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WO2012004849A1 - Composition de revêtement et stratifié - Google Patents

Composition de revêtement et stratifié Download PDF

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Publication number
WO2012004849A1
WO2012004849A1 PCT/JP2010/061400 JP2010061400W WO2012004849A1 WO 2012004849 A1 WO2012004849 A1 WO 2012004849A1 JP 2010061400 W JP2010061400 W JP 2010061400W WO 2012004849 A1 WO2012004849 A1 WO 2012004849A1
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WO
WIPO (PCT)
Prior art keywords
coating composition
mass
component
parts
composition according
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
Application number
PCT/JP2010/061400
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English (en)
Japanese (ja)
Inventor
田坂　道久
弘康 管野
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.)
BASF SE
Riken Technos Corp
Original Assignee
BASF SE
Riken Technos 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 BASF SE, Riken Technos Corp filed Critical BASF SE
Priority to PCT/JP2010/061400 priority Critical patent/WO2012004849A1/fr
Publication of WO2012004849A1 publication Critical patent/WO2012004849A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C03C17/324—Polyesters
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09D5/32—Radiation-absorbing paints
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/804—Materials of encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/85—Protective back sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2369/00—Polycarbonates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a coating composition and a laminate, and more specifically, has excellent adhesion to glass, polycarbonate resin, polyester resin, cellulose resin, liquid crystal polymer, and ethylene-vinyl acetate copolymer, and also has water resistance.
  • the present invention relates to a coating composition and a laminate having excellent properties and weather resistance.
  • the coating composition of the present invention is particularly useful as a coating composition for glass and a coating composition for solar battery backsheet.
  • Patent Document 1 discloses a technique in which a pressure-sensitive adhesive layer is provided on one side of a plastic film such as polyethylene terephthalate, and this is adhered to glass. In such a technique, various characteristics required for the window glass are disclosed. Therefore, improvement was demanded.
  • the conventional pressure-sensitive adhesive layer is usually a two-component room-temperature-curing pressure-sensitive adhesive in which an epoxy resin is diluted with a solvent, and takes a long time (for example, 1 hour or more) until volatile organic compound (VOC) and odor are generated and dried. There were problems such as.
  • a single photovoltaic element is not used as it is, and generally several to several tens of photovoltaic elements are wired in series or in parallel, and the element is extended over a long period of time.
  • various packaging is performed, and a unit is formed as a solar cell module.
  • a solar cell module has an upper transparent material made of glass or transparent plastic on the surface that is exposed to sunlight, and a sealing material layer made of a thermoplastic resin such as an ethylene vinyl acetate copolymer (hereinafter referred to as EVA).
  • EVA ethylene vinyl acetate copolymer
  • the solar battery backsheet has excellent mechanical strength and excellent properties such as weather resistance, heat resistance, water resistance, light resistance, and chemical resistance to protect the contents of solar cells and leads.
  • a high gas barrier property that prevents intrusion of moisture, oxygen and the like is required.
  • the adhesion and adhesion stability with a sealing material layer such as EVA are important. This is because separation of the sealing material layer, discoloration, and corrosion of the wiring occur due to moisture permeation from the interface, which may affect the output of the module itself.
  • the inner surface is required to be white because of its contribution to improving power generation efficiency.
  • a fluororesin having good weather resistance, flame retardancy, and EVA which is often used as a sealing material, such as polyvinyl fluoride (PVF) and polyvinylidene fluoride (PVDF).
  • PVDF polyvinyl fluoride
  • the fluororesin simplex sheet has problems such as water vapor barrier properties, transparency, weather resistance, and flame retardancy.
  • Patent Document 2 discloses a film for sealing a back surface of a solar cell, which is a laminate of a polybutylene terephthalate (PBT) film containing a titanium oxide produced by a chlorine method.
  • PBT polybutylene terephthalate
  • adhesiveness with a sealing material layer such as EVA is inferior.
  • the present invention has been made in view of the above problems, and its purpose is to provide excellent adhesion to glass, polycarbonate resin, polyester resin, cellulose resin, liquid crystal polymer, and ethylene-vinyl acetate copolymer. It is providing the coating composition and laminated body which are excellent in water resistance and a weather resistance while having it.
  • the present invention is as follows. 1. (A) 45 to 90 parts by mass of a fluororesin, and (b) a block copolymer or polyvinyl acetal resin 10 comprising a block (A) mainly composed of a methacrylic ester and a block (B) mainly composed of an acrylate ester. 55 parts by mass (however, the total of the components (a) and (b) is 100 parts by mass)
  • a coating composition comprising: 2.
  • 3. 3 The coating composition as described in 1 or 2 above, wherein the (b) block copolymer has a triblock structure. 4).
  • the (b) block copolymer is a block copolymer having an ABA type triblock structure (provided that the A block component is a methacrylic ester and the B block component is an acrylate ester). 4.
  • the (b) block copolymer has the following general formula-(A1)-(B)-(A2)- (Wherein (A1) and (A2) each represent a block component composed of a methacrylic acid alkyl ester, and (B) represents a block component composed of an acrylic acid alkyl ester). 5.
  • a glass coating composition comprising the coating composition according to any one of 1 to 9 above.
  • a coating composition for a solar battery backsheet comprising the coating composition according to any one of 1 to 9 above.
  • 12 The solar cell backsheet coating composition as described in 11 above, wherein the backsheet substrate is a polyester resin or a polycarbonate resin.
  • 13 A laminate obtained by coating the substrate with the coating composition according to any one of 1 to 9 above.
  • 14 14. The laminate according to 13, wherein the substrate is at least one selected from glass, polycarbonate resin, polyester resin, cellulose resin, and liquid crystal polymer. 15.
  • An extrusion composition comprising the coating composition according to any one of 1 to 8 above.
  • the organic solvent (d) is at least one selected from N-methylpyrrolidone (NMP), propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), methyl isobutyl ketone (MIBK) and methyl ethyl ketone (MEK).
  • NMP N-methylpyrrolidone
  • PC propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • MIBK methyl isobutyl ketone
  • MEK methyl ethyl ketone
  • the organic solvent (d) is at least one selected from N-methylpyrrolidone (NMP), propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), methyl isobutyl ketone (MIBK) and methyl ethyl ketone (MEK).
  • NMP N-methylpyrrolidone
  • PC propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • MIBK methyl isobutyl ketone
  • MEK methyl ethyl ketone
  • the coating composition of the present invention since the components (a) and (b) are blended in a specific quantitative relationship, glass, polycarbonate resin, polyester resin, cellulose resin, liquid crystal polymer, ethylene- It has excellent adhesion to vinyl acetate copolymer and is excellent in water resistance and weather resistance. Since the coating composition of the present invention has the above properties, it is particularly useful as a glass coating composition and a solar battery backsheet coating composition.
  • a book containing (c) at least one functional material selected from (c) white light reflecting material, black material, infrared absorbing material, ultraviolet absorbing material, antistatic material and electromagnetic shielding material and / or (e) a flame retardant.
  • the coating composition of the present invention of the invention can effectively impart desired functionality to a glass or solar cell backsheet. Since the laminate of the present invention is formed by coating a substrate with a coating composition containing the components (a) and (b) in a specific quantitative relationship, glass, polycarbonate resin It has excellent adhesion to polyester resins, cellulose resins, liquid crystal polymers, and ethylene-vinyl acetate copolymers, as well as excellent water resistance and weather resistance. Since the laminated body of this invention has said property, it is especially useful as a window glass and a solar cell backsheet.
  • Fluorine-based resin Component (a) of the composition of the present invention is a fluorine-based resin.
  • fluororesins examples include polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), polyethylene tetrafluoroethylene (ETFE), polytetrafluoroethylene (PTFE), and tetrafluoroethylene perfluoro.
  • PFA polyvinyl fluoride
  • PVDF polyvinylidene fluoride
  • PCTFE polychlorotrifluoroethylene
  • EFE polyethylene tetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • tetrafluoroethylene perfluoro examples include polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), polyethylene tetrafluoroethylene (ETFE), polytetrafluoroethylene (PTFE), and tetrafluoroethylene perfluoro.
  • solvent-soluble fluororesins include copolymers of fluoroolefins and hydrocarbon monomers such as vinyl ethers and vinyl esters, such as hydroxyl groups, carboxylic acid groups, hydrolyzable silyl groups, and epoxy groups.
  • the fluorine-containing polymer having the reactive group is employed.
  • the fluoropolymer include chlorotrifluoroethylene, cyclohexyl vinyl ether, alkyl vinyl ether, hydroxyalkyl vinyl ether copolymer, chlorotrifluoroethylene, alkyl vinyl ether, allyl alcohol copolymer, chlorotrifluoroethylene, and aliphatic carboxylic acid.
  • Examples include vinyl esters and copolymers of hydroxyalkyl vinyl esters. These are marketed under names such as Lumiflon (Asahi Glass) and Cefal Coat (Central Glass). For example, Lumiflon LF-550, LF-552, LF-554, LF-600, LF-601, LF-602, LF-100, LF-200, LF-302, LF-400, LF-700, LF-916 LF-936 and the like.
  • solvent solubility, adhesiveness to various substrates such as glass, polycarbonate resin, polyester resin, cellulose resin, liquid crystal polymer, ethylene-vinyl acetate copolymer (hereinafter sometimes referred to as specific substrate)
  • substrates such as glass, polycarbonate resin, polyester resin, cellulose resin, liquid crystal polymer, ethylene-vinyl acetate copolymer (hereinafter sometimes referred to as specific substrate)
  • PVDF polyvinylidene fluoride
  • PVDF polyvinyl fluoride
  • PVF polyvinyl fluoride
  • ECTFE chlorotrifluoroethylene / ethylene copolymer
  • PCTFE polychlorotrifluoroethylene
  • fluoroolefin / vinyl ether copolymer More preferred are polyvinylidene fluoride (PVDF) and fluoroolefin / vinyl ether copolymers.
  • Fluorine-based resin is a composition with properties such as heat resistance, cold resistance, chemical resistance, flame resistance, electrical properties, low friction, non-adhesiveness, weather resistance, UV-cutting properties, low refractive index properties, etc. Can be granted.
  • the (a) fluororesin having a melting point of 230 ° C. or lower is preferable in terms of solvent solubility, cold resistance, and flexibility.
  • a more preferable melting point is 100 to 200 ° C.
  • the component (b) used in the present invention is a block copolymer comprising a block (A) mainly composed of a methacrylic ester and a block (B) mainly composed of an acrylate ester, Either a linear structure or a radial structure may be used. Moreover, any of block structures, such as AB, ABA, and ABAB, may be sufficient.
  • the component (b) of the present invention has a function of imparting to the composition adhesiveness to a specific substrate, particularly glass, polycarbonate resin, polyester resin, and ethylene-vinyl acetate copolymer (EVA). From the viewpoint of adhesiveness, the block copolymer (b) preferably has a triblock structure (hereinafter, sometimes referred to as component (b-1)). Moreover, it is preferable that it is a linear structure.
  • the component (b-1) is an ABA type triblock copolymer in which the ABA type A block component is a methacrylic ester and the B block component is an acrylate ester, preferably the ABA type It is a block copolymer having a triblock structure.
  • methacrylic acid ester examples include methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, isobutyl methacrylate, methacrylic acid-tert-butyl, methacrylic acid- n-pentyl, methacrylate-n-hexyl, cyclohexyl methacrylate, methacrylate-n-heptyl, methacrylate-n-octyl, methacrylate-2-ethylhexyl, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, methacrylic acid Phenyl, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-
  • acrylic ester examples include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-tert-butyl, acrylic acid- n-pentyl, acrylate-n-hexyl, cyclohexyl acrylate, acrylate-n-heptyl, acrylate-n-octyl, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, acrylic acid Phenyl, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, A Glycidyl silylate, 2-a
  • the component (b-1) is preferably represented by the following general formula-(A1)-(B)-(A2)- (Wherein (A1) and (A2) each represent a block component composed of an alkyl methacrylate, and (B) represents a block component composed mainly of an alkyl acrylate ester). It is what has.
  • methacrylic acid alkyl ester examples include methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, isobutyl methacrylate, methacrylic acid-tert-butyl, methacrylic acid.
  • acrylic acid alkyl ester examples include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-tert-butyl, and acrylic acid.
  • an ABA type triblock copolymer comprising polymethyl methacrylate and polyacrylic acid-n-butyl is preferable in terms of heat-bonding with a polyester resin and flexibility.
  • An ABA type triblock copolymer in which the segment is polymethyl methacrylate and the soft segment is polyacrylic acid-n-butyl is preferable.
  • the weight average molecular weight (Mw) of the (b) block copolymer in the present invention is, for example, 10,000 to 1,000,000, preferably 30,000 to 500,000, and particularly 50,000 to 150. More preferably, it is 1,000.
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (b) block copolymer is preferably 1.0 to 1.8, particularly 1 It is preferably 1 to 1.5.
  • examples of the polymerization method of the block copolymer (b) in the present invention include living anion polymerization and living radical polymerization.
  • Examples of such an acrylic ABA triblock copolymer include LA polymers 2140E and 2250 manufactured by Kuraray, and NABSTAR manufactured by Kaneka. Among these, LA polymer manufactured by Kuraray Co., Ltd. synthesized by living anionic polymerization is preferable from the viewpoint of adhesion to the specific substrate.
  • Kuraray's LA polymers 2140E and 2250 have a triblock structure represented by the general formula-(A1)-(B)-(A2)-, and (A1) and (A2) are polymethyl methacrylates.
  • (B) is poly-n-butyl acrylate
  • the weight average molecular weight is 80,000
  • the JIS-A hardness is 32 and 65, respectively.
  • the component (b) used in the present invention is generally obtained by polymerizing a vinyl acetate monomer to produce a polyvinyl acetate resin, and then producing a polyvinyl alcohol obtained by saponification. Produced by reacting with an aldehyde. That is, the polyvinyl acetal resin is a resin having a vinyl acetal group, a vinyl alcohol group, and a vinyl acetate group, a reaction product with formaldehyde is a polyvinyl formal resin, and a reaction product with butyraldehyde is called a polyvinyl butyral resin.
  • polyvinyl acetal resin examples include polyvinyl acetoacetal, polyvinyl propyl acetal, and the like. Among them, a polyvinyl butyral resin is preferably used from the viewpoint of adhesion to the specific substrate. Furthermore, what made the polyvinyl acetal resin contain the carboxyl group is used suitably. The carboxyl group is desirably about 0.1 to 5 mol%, preferably about 0.2 to 3 mol% in the polyvinyl acetal resin.
  • a polyvinyl acetal resin containing a carboxyl group for example, a method of producing a polyvinyl acetal resin by a conventional method from copolymerization of vinyl acetate and an unsaturated carboxylic acid, or an aldehyde containing a carboxyl group when acetalizing polyvinyl alcohol It is obtained by reacting with.
  • the average degree of polymerization of the polyvinyl acetal resin used in the present invention is not particularly limited, but is preferably in the range of 300 to 5,000, particularly preferably 500 or more, from the viewpoint of adhesion to the specific substrate.
  • the hydroxyl group content is preferably 10 to 30% by mass.
  • the acetic acid group content is preferably 1 to 4% by mass.
  • the coating composition of the present invention may further contain (c) at least one functional material selected from a white light reflecting material, a black material, an infrared absorbing material, an ultraviolet absorbing material, an antistatic material and an electromagnetic shielding material. it can. Thereby, a desired function can be effectively provided by coating the coating composition of the present invention on various substrates.
  • the white light reflecting material examples include inorganic pigment components.
  • inorganic pigment components For example, basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white (specific gravity 5.47 to 5.61), zinc sulfide (specific gravity 4. 1), lithopone, antimony triacid antimony (specific gravity 5.5 to 5.6), diacid titanium (specific gravity 4.2), graphite (specific gravity 3.3). These components may be used alone or in combination of two or more.
  • the inorganic pigment component it is preferable to use titanium dioxide or zinc sulfide as a main component. Particularly preferred is titanium dioxide. Titanium dioxide is particularly preferable because it has a strong action of removing ultraviolet rays (light having a wavelength of 400 nm or less) and a function of removing visible light.
  • the shape of the inorganic pigment component may be a spherical structure, an elliptical structure, a needle-like structure, a polygonal structure, or an amorphous structure.
  • the particle diameter of the inorganic pigment component is not particularly limited as long as it is smaller than the coating thickness of the coating composition of the present invention.
  • the white light reflecting material which is an optional component, is contained, it is preferably blended in an amount of 5 to 40 parts by mass with respect to a total of 100 parts by mass of the components (a) and (b).
  • the blending amount is preferably 5 to 40 parts by mass with respect to 100 parts by mass in total of the component (a) and the component (b).
  • the compounding amount of the white light reflecting material exceeds 40 parts by mass, the film forming property and the adhesion to the specific substrate may be deteriorated. Moreover, there is a risk of deterioration of flexibility. If the blending amount of the white light reflecting material is less than 10 parts by mass, the addition amount is too small and the desired effect may not be exhibited.
  • a more preferable amount of the white light reflecting material is 10 to 20 parts by mass with respect to a total of 100 parts by mass of the component (a) and the component (b).
  • the black material has a function of absorbing ultraviolet rays, and examples thereof include carbon black. Examples thereof include furnace black, channel black, acetylene black, and thermal black. These components may be used alone or in combination of two or more.
  • the blending amount is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass as a total of the components (a) and (b). If the blending amount of the black material exceeds 5 parts by mass, the film forming property and the adhesion to the specific substrate may be deteriorated. Moreover, there is a risk of deterioration of flexibility. If the amount of the black material is less than 0.5 parts by mass, the amount added is too small to achieve the desired effect.
  • infrared absorbing materials include carbon nanotubes, zinc oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, cesium-containing tungsten oxide, ATO (antimony-tin composite oxide or antimony-doped tin oxide), ITO (indium-tin composite oxide). Thing) etc. are mentioned.
  • the blending amount of the infrared absorbing material may be appropriately determined in consideration of a desired infrared absorptivity. A range of parts.
  • Examples of the ultraviolet absorbing material include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based organic compounds, the carbon nanotubes described above, zinc oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and titanium dioxide.
  • Inorganic compounds such as hybrid inorganic powder obtained by complexing cerium oxide and titanium dioxide fine particles with iron oxide, and hybrid inorganic powder obtained by coating the surface of cerium oxide fine particles with amorphous silica.
  • the blending amount of the ultraviolet absorbing material may be appropriately determined in consideration of the desired infrared absorptivity. A range of parts.
  • the antistatic material examples include metal oxides and metal salts.
  • the metal oxide include zinc oxide, aluminum doped zinc oxide, gallium doped zinc oxide, ATO, ITO, tin oxide, and antimony pentoxide described above. , Zirconium oxide, titanium oxide, aluminum oxide and the like.
  • the carbon nanotube mentioned above can also be utilized.
  • the blending amount of the antistatic material may be appropriately determined in consideration of a desired antistatic property, and examples thereof include a range of 0.1 to 30% by mass in the paint of the present invention.
  • the blending amount of the antistatic material may be appropriately determined in consideration of the desired infrared absorptivity. For example, 0.1 to 30 masses per 100 mass parts of the total of the component (a) and the component (b). A range of parts.
  • the electromagnetic shielding material examples include conductive particles such as (1) carbon particles or powder; (2) nickel, indium, chromium, gold, vanadium, tin, cadmium, silver, platinum, aluminum, copper, titanium, cobalt , Particles or powders of lead or other metals or alloys or conductive oxides thereof; (3) a coating layer of the conductive material (1) or (2) above is formed on the surface of plastic particles such as polystyrene or polyethylene; And the like.
  • the blending amount of the electromagnetic shielding material may be appropriately determined in consideration of desired electromagnetic shielding properties. For example, the blending amount is in the range of 60 to 90 parts by mass with respect to 100 parts by mass in total of the components (a) and (b). Is mentioned.
  • the coating composition of the present invention can further contain (d) an organic solvent.
  • organic solvents include aromatic hydrocarbons such as toluene, xylene, or benzene; aliphatic hydrocarbons such as n-heptane, n-hexane, or n-octane; petroleum benzine, petroleum ether, ligroin Hydrocarbon mixtures with a boiling point in the range of 30-300 ° C, such as mineral split, petroleum naphtha or kerosene; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane or ethylcyclohexane; methanol, ethanol, n- Propanol, isopropanol, n-butanol, isobutanol, tert-
  • preferred examples of the solvent (d-1) are those that are poorly volatile but easily dissolve the component (a).
  • N-methylpyrrolidone (NMP), ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC) N-methylpyrrolidone (NMP) and propylene carbonate (PC) are more preferable.
  • solvents that are excellent in volatility but slightly difficult to dissolve component (a) include methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK).
  • the coating composition of the present invention can further contain (e) a flame retardant.
  • a flame retardant include phosphorus flame retardant, bromine flame retardant, chlorine flame retardant, aluminum hydroxide, zinc borate and the like.
  • the coating composition of the present invention is further water resistant from the viewpoint of adhesion to the specific substrate when the total of (a) the fluororesin and (b) the block copolymer or the polyvinyl acetal resin is 100 parts by mass.
  • the component (a) is 45 to 90 parts by mass, and the component (b) is 10 to 55 parts by mass.
  • the component (a) is preferably 65 to 85 parts by mass, and the component (b) is 15 to 30 parts by mass.
  • the blending amount thereof is preferably 400 to 900 parts by mass with respect to 100 parts by mass in total of the component (a) and the component (b).
  • the blending amount of the component (d) exceeds 900 parts by mass, it becomes too thin so that it needs to be applied several times and work efficiency deteriorates.
  • the blending amount of the component (d) is less than 400 parts by mass, the viscosity becomes too high and the film forming property is deteriorated.
  • the blending amount thereof is preferably 1 to 20 parts by mass with respect to 100 parts by mass in total of the component (a) and the component (b).
  • the compounding quantity of a component exceeds 20 mass parts, leveling (smoothness) property will deteriorate.
  • the amount of component (e) is less than 1 part by mass, the amount added is too small to obtain the desired flame retardancy.
  • a more preferable blending amount of the component (e) is 3 to 10 parts by mass with respect to a total of 100 parts by mass of the component (a) and the component (b).
  • the coating composition of the present invention may contain various known additives such as a refractive index adjuster, a light stabilizer, a leveling agent, a viscosity adjuster, etc., if necessary. Is possible.
  • the coating composition of the present invention comprises the above components (a) and (b) or, if necessary, the above component (c) and various other additives in an ordinary plastic kneader (biaxial kneader or mixer type kneader). ) (Kneading temperature 180 ° C. to 220 ° C.), for example, pelletized.
  • said (d) component it can prepare by adding the obtained pellet to the container provided with the stirrer with (d) component, and mixing by a conventional method.
  • the said (d) component add said (a) and (b) or the said (c) component and other various additives as needed with (d) to the container provided with the stirrer, It can also be prepared by mixing by a conventional method.
  • the coating composition of the present invention has excellent adhesion to glass, polycarbonate resin, polyester resin, cellulose resin, liquid crystal polymer, and ethylene-vinyl acetate copolymer, and is excellent in water resistance and weather resistance. Since the coating composition of the present invention has the above properties, it is particularly useful as a glass coating composition and a solar battery backsheet coating composition.
  • the back sheet base material include polyester resins (particularly polyethylene terephthalate (PET) or polycarbonate resins) from the viewpoint of obtaining strong adhesiveness.
  • PET polyethylene terephthalate
  • the glass is not particularly limited, and examples thereof include hard and light soda lime glass, quartz glass having a high refractive index and transparency, and borosilicate glass having a low transparency but being hard and light.
  • polycarbonate resin examples include polycarbonate (PC) and modified polycarbonate.
  • polyester resin examples include polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate (PBT), and polyethylene naphthalate film.
  • cellulose resin examples include diacetyl cellulose and triacetyl cellulose.
  • Liquid crystal polymers include polycondensates of ethylene terephthalate and parahydroxybenzoic acid (type I), polycondensates of phenol and phthalic acid with parahydroxybenzoic acid (type II), 2,6-hydroxynaphthoic acid and para And polycondensates with hydroxybenzoic acid (type III). The thickness of these base materials is, for example, 0.5 mm to 3 mm.
  • the laminated body of this invention can be obtained through the process formed by coating the coating composition of this invention on a base material.
  • the substrate include substrates made of glass, polycarbonate resin, polyester resin, cellulose resin, liquid crystal polymer, and ethylene-vinyl acetate copolymer as described above.
  • a coating method it is preferable to employ one of two methods of solvent coating and coating using an extruder.
  • the solvent coating a predetermined amount of the above-mentioned (d) organic solvent is added to the coating composition of the present invention, and the obtained coating material is applied on a base material by spin coating, (doctor) knife coating, or micro gravure coating.
  • the coating using the extruder include a method in which the coating composition of the present invention is charged into a commercially available hot melt extruder and extruded onto a substrate using, for example, a T-type die. In this form, the coating composition of the present invention can be used as an extrusion composition. As another form, a method in which the coating composition of the present invention is formed into a sheet, and then adhered to the substrate and thermally laminated using a heating roll can be exemplified.
  • the thickness of the layer of the coating composition of the present invention is preferably 10 ⁇ m to 200 ⁇ m, more preferably 15 ⁇ m to 100 ⁇ m, from the viewpoint of the effect of the present invention.
  • the laminate of the present invention is useful as a window glass from the viewpoint of excellent adhesion to glass, water resistance, weather resistance, transparency, surface smoothness, and flexibility.
  • the window glass is not particularly limited, and examples thereof include window glass for buildings such as ordinary houses and buildings, vehicles such as automobiles and railways, window glass for vehicles such as airplanes and ships, and viewing windows in mechanical equipment.
  • the window glass for buildings is preferable from a viewpoint that said various characteristics are excellent.
  • the laminate of the present invention is a solar cell from the viewpoint that it has excellent adhesion to polycarbonate resins and polyester resins and is excellent in water resistance, weather resistance, transparency, surface smoothness, and flexibility.
  • Useful as a backsheet when utilizing the laminated body in this invention as a solar cell backsheet, it is preferable to add said (c) functional material, especially white light reflection material to the coating composition of this invention.
  • the manufacturing method of the solar cell backsheet may be a conventional manufacturing method, and is not particularly limited. For example, first, a layer of the coating composition is applied on the substrate.
  • Coating methods include spin coating, (doctor) knife coating, micro gravure coating, direct gravure coating, offset gravure, reverse gravure, reverse roll coating, (Meyer) bar coating, and die coating
  • a method such as spray coating or dip coating can be preferably applied.
  • a manual spinner ASS-301 type manufactured by Able Co., Ltd.
  • the thickness of the coating composition layer is not particularly limited, but is about 2 ⁇ m to 50 ⁇ m, preferably about 5 ⁇ m to 30 ⁇ m, and more preferably about 8 ⁇ m to 20 ⁇ m.
  • Solar cells are included in the encapsulant layer.
  • the method for forming the sealing material layer may be a conventionally known method, and is not particularly limited, but is laminated in the order of tempered glass / EVA sheet / solar battery cell / EVA sheet / the above solar battery back sheet, and vacuum lamination. Heat bonding using the method.
  • the above solar cell backsheet preparation method and solar cell module preparation method are merely examples, and those skilled in the art can make various modifications.
  • Raw materials used The raw materials used in Examples and Comparative Examples are as follows. (1) (a) Fluorine resin (a-1) SOLEF21216 / 1001 (Product of Solvay Solexis Co., Ltd., Polyvinylidene fluoride (PVDF), high purity PVDF, melting point 160 ° C.) (A-2) Lumiflon LF-200 (Asahi Glass Co., Ltd.
  • Halar 6014 product of Solvay Solexis Co., Ltd., chlorotrifluoroethylene / ethylene copolymer (ECTFE), melting point 225 ° C.
  • Algoflon 25 CAR B product of Solvay Solexis, polytetrafluoroethylene (PTFE), melting point 190 ° C.
  • Block copolymer or polyvinyl acetal resin (b-1) LA polymer 2140E (Kuraray product, compound name: acrylic block copolymer, polymerization method: living anion polymerization, JIS-A hardness 32 ) (B-2) LA polymer 2250 (Kuraray Co., Ltd., compound name: acrylic block copolymer, polymerization method: living anion polymerization, JIS-A hardness 65) (B-3) NABSTAR F700KS (Kaneka Corporation, compound name: acrylic block copolymer, polymerization method: living radical polymerization, JIS-A hardness 22) (B-4) Mowital SB 70 HH (Kuraray Co., Ltd., polyvinyl butyral, non-volatile content: 97.5% by mass or more, hydroxyl group content: 12-14% by mass, acetate group content: 1-4% by mass (B-5) Parapet GF (Kuraray Co., Ltd., polymethyl methacrylate (PMMA),
  • each component except the component (d) was placed in a normal plastic kneader, kneaded at a kneading temperature of 180 ° C. to 220 ° C., and pelletized. Next, the pellet was added to a container equipped with a stirrer together with the component (d) and mixed by a conventional method to obtain a coating composition. The viscosity (mPa ⁇ s) at 25 ° C. of the obtained composition was measured.
  • composition was applied by spin coating (coating thickness: 15 to 20 ⁇ m) on each of the substrates (dimensions: 150 mm ⁇ 25 mm ⁇ thickness 1 mm) shown in Tables 1 to 8, dried, and coated on the substrate.
  • a laminate having a layer (A) of the composition was prepared.
  • Each base material used is as follows.
  • Adhesion test for different materials was performed by measuring the shear adhesive force as shown below.
  • layer (B1) of polyethylene terephthalate PET (trade name EMC307 manufactured by Toyobo Co., Ltd.) having dimensions of 150 mm ⁇ 1 mm thickness ⁇ 25 mm width
  • the above composition was applied by a spin coating method (application thickness: 15 to 20 ⁇ m).
  • a layer (A) is formed, and an ethylene-vinyl acetate copolymer EVA (trade name KA-30 manufactured by Sumitomo Chemical Co., Ltd., vinyl acetate content 28 having the same dimensions as (B1) shown in the table is formed thereon. %)
  • EVA ethylene-vinyl acetate copolymer
  • Layer (B2) was pressure-bonded to prepare a laminate. Thereafter, the layer (B2) was pulled in a direction parallel to the bonding surface of the layer (A), and the tensile strength at break was measured. The results are shown in the table as PET vs EVA (MPa).
  • the visible light transmittance was determined by the average transmittance for a D light source at a wavelength of 380 to 780 nm in a spectral transmittance curve by a U-4000 type self-recording spectrophotometer (manufactured by Hitachi, Ltd.) according to JIS R-3106.
  • the ultraviolet transmittance was obtained as an average transmittance at a wavelength of 300 to 380 nm by the same means as described above according to the ISO / DIS 13837 B method.
  • Infrared transmittance An average transmittance of 780 nm to 2000 nm was determined in the same manner as described above according to the ISO / DIS 13837 B method.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne une composition de revêtement qui est caractérisée en ce qu'elle comprend (a) 45 à 90 parties en masse d'une fluororésine et (b) 10 à 55 parties en masse d'une résine de polyacétal de vinyle ou d'un copolymère séquencé comprenant une séquence (A) contenant principalement un ester méthacrylique et une séquence (B) contenant principalement un ester acrylique (le total de (a) et (b) étant de 100 parties en masse).
PCT/JP2010/061400 2010-07-05 2010-07-05 Composition de revêtement et stratifié Ceased WO2012004849A1 (fr)

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JP2013144746A (ja) * 2012-01-13 2013-07-25 Hitachi Chemical Co Ltd 熱放射性塗料及び放熱部材
WO2014024933A1 (fr) * 2012-08-09 2014-02-13 旭硝子株式会社 Stratifié en résine de fluor en feuille de verre
WO2014046119A1 (fr) * 2012-09-18 2014-03-27 ダイキン工業株式会社 Composition de revêtement, film de revêtement durci, feuille arrière pour module photovoltaïque, et module photovoltaïque
CN106867158A (zh) * 2015-10-01 2017-06-20 三菱铅笔株式会社 氟系树脂的非水系分散体、含氟系树脂的热固化树脂组合物和其固化物以及粘接剂组合物
JP2020122112A (ja) * 2019-01-31 2020-08-13 株式会社クラレ インキ用又は塗料用バインダー及びその用途
WO2022058689A1 (fr) * 2020-09-17 2022-03-24 Melchior Material And Life Science France Composition fluide pour revetement de surface pour absorption et diffusion de composes volatils
WO2022058690A1 (fr) * 2020-09-17 2022-03-24 Ceva Sante Animale Composition fluide pour revetement de surface pour absorption et diffusion de composes volatils

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JP2013144746A (ja) * 2012-01-13 2013-07-25 Hitachi Chemical Co Ltd 熱放射性塗料及び放熱部材
WO2014024933A1 (fr) * 2012-08-09 2014-02-13 旭硝子株式会社 Stratifié en résine de fluor en feuille de verre
JPWO2014024933A1 (ja) * 2012-08-09 2016-07-25 旭硝子株式会社 ガラスシートフッ素樹脂積層体
WO2014046119A1 (fr) * 2012-09-18 2014-03-27 ダイキン工業株式会社 Composition de revêtement, film de revêtement durci, feuille arrière pour module photovoltaïque, et module photovoltaïque
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CN106867158A (zh) * 2015-10-01 2017-06-20 三菱铅笔株式会社 氟系树脂的非水系分散体、含氟系树脂的热固化树脂组合物和其固化物以及粘接剂组合物
CN106867158B (zh) * 2015-10-01 2021-01-26 三菱铅笔株式会社 氟系树脂的非水系分散体、含氟系树脂的热固化树脂组合物和其固化物以及粘接剂组合物
JP2020122112A (ja) * 2019-01-31 2020-08-13 株式会社クラレ インキ用又は塗料用バインダー及びその用途
WO2022058689A1 (fr) * 2020-09-17 2022-03-24 Melchior Material And Life Science France Composition fluide pour revetement de surface pour absorption et diffusion de composes volatils
WO2022058690A1 (fr) * 2020-09-17 2022-03-24 Ceva Sante Animale Composition fluide pour revetement de surface pour absorption et diffusion de composes volatils

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