WO2012017553A1 - Composition de revêtement et stratifié - Google Patents

Composition de revêtement et stratifié Download PDF

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Publication number
WO2012017553A1
WO2012017553A1 PCT/JP2010/063403 JP2010063403W WO2012017553A1 WO 2012017553 A1 WO2012017553 A1 WO 2012017553A1 JP 2010063403 W JP2010063403 W JP 2010063403W WO 2012017553 A1 WO2012017553 A1 WO 2012017553A1
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WIPO (PCT)
Prior art keywords
coating composition
mass
resin
parts
acrylate
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PCT/JP2010/063403
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English (en)
Japanese (ja)
Inventor
田坂　道久
弘康 管野
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リケンテクノス株式会社
ビーエーエスエフ ソシエタス・ヨーロピア
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Priority to PCT/JP2010/063403 priority Critical patent/WO2012017553A1/fr
Publication of WO2012017553A1 publication Critical patent/WO2012017553A1/fr

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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • 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
    • 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
    • C09D5/32—Radiation-absorbing 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • 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
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2031/00—Use of polyvinylesters or derivatives thereof as moulding material
    • B29K2031/04—Polymers of vinyl acetate, e.g. PVAc, i.e. polyvinyl acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0085—Copolymers
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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 in particular, excellent adhesion to glass, polycarbonate resin, polyester resin, cellulosic resin, liquid crystal polymer, and ethylene-vinyl acetate copolymer, particularly heat resistant adhesiveness.
  • the present invention also relates to a coating composition and a laminate having excellent water resistance 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,
  • an object of the present invention is to provide a coating composition and a laminate having heat-resistant adhesion and excellent water resistance and weather resistance.
  • the present invention is as follows. 1. (A) 45 to 95 parts by mass of a fluororesin, (B) 2 to 35 parts by mass of a block copolymer or polyvinyl acetal resin comprising a block (A) mainly composed of methacrylic acid ester and a block (B) mainly composed of acrylic acid ester, (C) vinyl ester resin or unsaturated polyester resin 2 to 50 parts by mass (provided that the total of the components (a) to (c) is 100 parts by mass), and (d) an initiator The component (a) to A coating composition comprising 0.1 to 15 parts by mass with respect to 100 parts by mass in total of (c). 2. 2.
  • 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.
  • the (b) polyvinyl acetal resin is a polyvinyl butyral resin.
  • a coating composition according to claim 1. 10.
  • a glass coating composition comprising the coating composition according to any one of 1 to 10 above.
  • a coating composition for a solar battery backsheet comprising the coating composition according to any one of 1 to 10 above. 13.
  • 14 A laminate obtained by coating the substrate with the coating composition according to any one of 1 to 10 above. 15.
  • 15. The laminate according to 14, wherein the substrate is at least one selected from glass, polycarbonate resin, polyester resin, cellulose resin, and liquid crystal polymer. 16. 10.
  • An extrusion composition comprising the coating composition according to any one of 1 to 9 above.
  • the coating composition of the present invention contains the components (a), (b), (c) and (d) in a specific quantitative relationship, glass, polycarbonate resin, polyester resin, cellulose It has excellent adhesiveness, especially heat-resistant adhesiveness, and water resistance and weather resistance to resin, liquid crystal polymer, and ethylene-vinyl acetate copolymer. 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 white light reflecting material a black material, an infrared absorbing material, an ultraviolet absorbing material, an antistatic material, and an electromagnetic shielding material, and / or (g) a book containing 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.
  • the laminate of the present invention is coated with a coating composition (solvent coating or melting) containing the components (a), (b), (c) and (d) in a specific quantitative relationship. Extrusion coating), it has excellent adhesion to glass, polycarbonate resin, polyester resin, cellulose resin, liquid crystal polymer, ethylene-vinyl acetate copolymer, especially heat resistant adhesive, 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.
  • Polyvinyl acetal resin Component (b) used in the present invention that is, a polyvinyl acetal resin, is generally obtained by polymerizing a vinyl acetate monomer to produce a polyvinyl acetate resin, and then saponifying the 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.
  • Component (c) of the coating composition of the present invention is a vinyl ester resin or an unsaturated polyester resin.
  • the vinyl ester resin is specifically selected from a urethane (meth) acrylate resin, an epoxy (meth) acrylate resin, and a polyester (meth) acrylate resin, and more preferably has excellent flexibility and impact resistance.
  • urethane (meth) acrylate resins that are excellent in adhesion between different materials can be used.
  • the (meth) acrylate referred to in the present invention refers to acrylate or methacrylate.
  • Such urethane (meth) acrylate resin is preferably obtained by reaction of polyol, polyisocyanate and (meth) acrylate having one or more hydroxyl groups in one molecule, and two or more (meth) acrylates in one molecule. ) It has an acryloyl group.
  • the polyol used in the urethane (meth) acrylate resin preferably has a number average molecular weight of 200 to 3000, particularly preferably 400 to 2000.
  • Typical examples of the polyol include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, and the like. These polyols are used alone or in combination of two or more.
  • the polyether polyol may include a polyol obtained by adding the alkylene oxide to bisphenol A and bisphenol F, in addition to a polyalkylene oxide such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • the polyester polyol is a condensation polymer of dibasic acids and polyhydric alcohols or a ring-opening polymer of a cyclic ester compound such as polycaprolactone.
  • Dibasic acids used here are, for example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, Hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2 , 3-naphthalenedicarboxylic acid, 2,3-naphthal
  • Polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3 -Butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, adducts of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, Glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cycl Hexane dimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin
  • Examples of the polyisocyanate used in the urethane (meth) acrylate resin include 2,4-TDI and its isomer or a mixture of isomers, MDI, HDI, IPDI, XDI, hydrogenated XDI, dicyclohexylmethane diisocyanate, tolidine diisocyanate, and naphthalene.
  • MDI, HDI, IPDI, XDI, hydrogenated XDI, dicyclohexylmethane diisocyanate, tolidine diisocyanate, and naphthalene examples of the polyisocyanate used in the urethane (meth) acrylate resin.
  • Examples of the (meth) acrylate (hydroxyl group-containing (meth) acrylate) having one or more hydroxyl groups per molecule used in the urethane (meth) acrylate resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Mono (meth) acrylates such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanuric acid di (meth) acrylate, And polyvalent (meth) acrylates such as pentaerythritol tri (meth) acrylate.
  • the epoxy (meth) acrylate resin used as the vinyl ester resin preferably has two or more (meth) acryloyl groups in one molecule, and is an esterification catalyst for epoxy resin and unsaturated monobasic acid. It is obtained by reacting in the presence of.
  • Examples of the epoxy resin mentioned here include a bisphenol type or novolac type epoxy resin alone, or a resin in which a bisphenol type and a novolac type epoxy resin are mixed, and the average epoxy equivalent is preferably 150 to It is in the range of 450.
  • the bisphenol type epoxy resin a glycidyl ether type epoxy resin substantially having two or more epoxy groups in one molecule obtained by the reaction of epichlorohydrin and bisphenol A or bisphenol F is used.
  • An epoxy resin a methyl glycidyl ether-type epoxy resin obtained by reaction of methyl epichlorohydrin and bisphenol A or bisphenol F, an epoxy resin obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or methyl epichlorohydrin, or the like.
  • Typical examples of the novolak type epoxy resin include an epoxy resin obtained by a reaction of phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.
  • Typical examples of unsaturated monobasic acids used for epoxy (meth) acrylate resins include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, and monoester maleate. (2-ethylhexyl) or sorbic acid. These unsaturated monobasic acids may be used alone or in combination of two or more.
  • the reaction between the epoxy resin and the unsaturated monobasic acid is preferably carried out using an esterification catalyst at a temperature of 60 to 140 ° C., particularly preferably 80 to 120 ° C.
  • esterification catalyst known catalysts such as tertiary amines such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane, triphenylphosphine or diethylamine hydrochloride Can be used as is.
  • the polyester (meth) acrylate resin used as the vinyl ester resin is a saturated or unsaturated polyester having two or more (meth) acryloyl groups in one molecule, and (meth) acrylic at the end of the saturated or unsaturated polyester. A compound is reacted.
  • the number average molecular weight of such a resin is preferably 500 to 5,000.
  • the saturated polyester used in the present invention is a condensation reaction between a saturated dibasic acid and a polyhydric alcohol
  • the unsaturated polyester is a dibasic acid containing an ⁇ , ⁇ -unsaturated dibasic acid and a polyhydric alcohol. It is obtained by the condensation reaction.
  • the resin which made the terminal of unsaturated polyester react with the (meth) acryl compound shall be contained in vinyl ester resin in this invention, and shall be distinguished from the unsaturated polyester resin demonstrated below.
  • saturated dibasic acid examples include the compounds shown in the above-mentioned polyester polyol, and examples of the ⁇ , ⁇ -unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, and itaconic acid. And itaconic anhydride.
  • the compound shown to the term of the said polyester polyol can be mentioned also about polyhydric alcohol.
  • the (meth) acrylic compound of the polyester (meth) acrylate resin used as the vinyl ester resin includes unsaturated glycidyl compounds, various unsaturated monobasic acids such as acrylic acid or methacrylic acid, and glycidyl esters thereof. is there.
  • glycidyl (meth) acrylate is used.
  • the unsaturated polyester resin is obtained by polycondensing an acid component and an alcohol component by a known method, and the kind thereof is not particularly limited as long as it is known as a thermosetting resin.
  • the acid component for example, unsaturated dibasic acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid are used. If necessary, use a saturated dibasic acid such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid, and acids other than dibasic acids such as benzoic acid and trimellitic acid. be able to.
  • the alcohol component include polyhydric alcohols shown in the above-mentioned polyester polyol section.
  • the coating composition of the present invention comprises (d) an initiator as an essential component.
  • the oligomer component for example, vinyl ester resin or unsaturated polyester resin (c)
  • a thermal polymerization initiator for example, a photopolymerization initiator
  • it can be easily cured in a short time by ultraviolet irradiation or electron beam irradiation using an ultraviolet fluorescent lamp or a high-pressure mercury lamp.
  • ultraviolet irradiation is preferred.
  • the coating composition of the present invention When the coating composition of the present invention is cured by heating, it can be cured by heating at a room temperature to about 90 ° C.
  • the thermal polymerization initiator include benzoyl peroxide, lauroyl peroxide, succinic acid peroxide, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, and cyclohexanone peroxide. Is mentioned. For example, when the (1 minute) half-life temperature of the peroxides is 100 ° C. to 180 ° C., sufficient curability can be obtained at 80 ° C. ⁇ 10 minutes to 160 ° C. ⁇ 5 minutes.
  • photopolymerization initiator examples include benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin-n- Butyl ether, benzoin isobutyl ether, benzyl-1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl 1-phenylpropan-1-one, benzyl sulfide, thioxanthone Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-chlorothixant and the like.
  • the coating composition of the present invention may further contain (e) 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), (b) and (c).
  • the blending amount is preferably 5 to 40 parts by mass with respect to 100 parts by mass in total of the components (a), (b) and (c).
  • 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 components (a), (b) and (c).
  • 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 a total of 100 parts by mass of the components (a), (b) and (c). 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 the desired infrared absorptivity.
  • the blending amount of the infrared absorbing material is 0.1 with respect to a total of 100 parts by mass of the components (a), (b) and (c). A range of up to 30 parts by mass can be mentioned.
  • the ultraviolet absorbing material examples 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.
  • the blending amount of the ultraviolet absorbing material is 0.1 with respect to a total of 100 parts by mass of the components (a), (b) and (c). A range of up to 30 parts by mass can be mentioned.
  • 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.
  • the blending amount of the antistatic material is 0.1% with respect to a total of 100 parts by mass of the components (a), (b) and (c). A range of up to 30 parts by mass can be mentioned.
  • the electromagnetic wave 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, 60 to 90 mass with respect to a total of 100 mass parts of the components (a), (b) and (c). A range of parts.
  • the coating composition of the present invention can further contain (f) an organic solvent.
  • an organic solvent 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 boiling points 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-butan
  • preferred examples of the solvent (f-1) are those having poor volatility but easily dissolving the component (a), such as 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 dissolve component (a), such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK).
  • MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone
  • the coating composition of the present invention can further contain (g) 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 has a total of (a) fluorine-based resin, (b) block copolymer or polyvinyl acetal resin, (c) vinyl ester resin or unsaturated polyester resin, 100 parts by mass, From the viewpoint of adhesion to a specific substrate and heat-resistant adhesion, and further from the viewpoint of water resistance and weather resistance, component (a) 45 to 95 parts by mass, component (b) 2 to 35 parts by mass, (c) 2 to 50 A part by mass is blended.
  • the component (a) is preferably 60 to 90 parts by mass, the component (b) is 5 to 30 parts by mass, and the component (c) is 5 to 20 parts by mass.
  • the compounding amount of the component (a) exceeds 95 parts by mass, the adhesion to the specific substrate is deteriorated. Also, the flexibility deteriorates. When the amount of component (a) is less than 45 parts by mass, water resistance and weather resistance are deteriorated. When the compounding amount of component (b) exceeds 35 parts by mass, water resistance and weather resistance are deteriorated. When the compounding amount of the component (b) is less than 2 parts by mass, the adhesion to the specific substrate is deteriorated. Also, the flexibility deteriorates. When the compounding amount of component (c) exceeds 50 parts by mass, water resistance and weather resistance are deteriorated. When the amount of component (c) is less than 2 parts by mass, the adhesion and flexibility are deteriorated.
  • the component (d) is a total of 100 components (a) to (c) from the viewpoint of practical photocuring time (irradiation intensity of 500 mJ / cm 2 and irradiation for 10 seconds or less). 0.1 to 15 parts by mass based on the mass is blended.
  • the amount of the component (d) is more preferably 1 to 10 parts by mass, particularly preferably 2 to 5 parts by mass in terms of practical photocuring time (irradiation intensity of 500 mJ / cm 2 for 3 seconds or less). Part.
  • the compounding amount of the component (d) exceeds 15 parts by mass, flexibility, adhesiveness and impact resistance are lowered.
  • it is less than 0.1 mass part since photocuring is inadequate, it is inferior to adhesiveness.
  • the same compounding quantity as the above may be sufficient.
  • the blending amount thereof is preferably 400 to 900 parts by mass with respect to 100 parts by mass in total of the components (a), (b) and (c). If the blending amount of component (f) exceeds 900 parts by mass, it will be too thin, so that it will be necessary to apply several times and work efficiency will deteriorate. When the compounding amount of the component (f) is 400 parts by mass or more, the viscosity is further reduced and the film forming property is improved.
  • the blending amount is preferably 1 to 20 parts by mass with respect to 100 parts by mass in total of the components (a), (b) and (c). If the amount of component (g) exceeds 20 parts by mass, the leveling (smoothness) will deteriorate. If the amount of component (g) is less than 1 part by mass, the amount added is too small to obtain the desired flame retardancy. A more preferable amount of component (g) is 3 to 10 parts by mass with respect to a total of 100 parts by mass of components (a), (b) and (c).
  • 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 above components (a), (b), (c) and (d) or, if necessary, the above component (e) and other various additives are added to a container equipped with a stirrer. It can 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 organic solvent (f) is added to the coating composition of the present invention, and the obtained paint is applied to a substrate 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 (e) 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.
  • spin coating method As coating methods, spin coating method, (doctor) knife coating method, micro gravure coating method, direct gravure coating method, offset gravure method, reverse gravure method, reverse roll coating method, (Meyer) bar coating method, die coating method, Methods such as spray coating and 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 to 50 ⁇ m, preferably about 5 to 30 ⁇ m, and more preferably about 8 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),
  • Component (d) Component Initiator (i) Photopolymerization initiator CIBA, IRGACURE TM 819, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (ii) Thermal polymerization initiator NOF Corporation Perhexa 25B (1 minute half-life: 179 ° C.), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
  • each component except the component (d) is put into a normal plastic kneader, kneaded at a kneading temperature of 180 ° C. to 220 ° C. and pelletized did.
  • 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.
  • the composition was applied by spin coating (application thickness 15 to 20 ⁇ m) and dried.
  • a layer (A) of the composition was formed on the substrate.
  • the layer (A) of the composition was cured by irradiating ultraviolet rays having an energy of 500 mJ / cm 2 under air to prepare a laminate.
  • a thermal polymerization initiator if necessary, 0 to 0.05 part by mass of 6% naphthenic cobalt is added to the composition and cured by heat treatment at 100 ° C. for 10 minutes to prepare a laminate. did.
  • Each base material used is as follows. ⁇ Glass (slide glass for microscope preparation) ⁇ Polyethylene terephthalate PET (Unitika Polyester MA-2103 made by Unitika) ⁇ Polybutylene terephthalate PBT (Mitsubishi Engineering Plastics, trade name Nova Duran 5010R5) ⁇ Polycarbonate PC (trade name Panlite L-1225L, manufactured by Teijin Chemicals Ltd.) ⁇ Liquid crystal polymer LCP (manufactured by Sumitomo Chemical Co., Ltd., trade name Sumika Super E5008L) ⁇ Triacetylcellulose TAC (Fuji Film Co., Ltd., trade name FUJITAC (with UV))
  • 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.
  • the coating compositions of the examples of the present invention contain the components (a), (b), (c) and (d) in a specific quantitative relationship, glass Excellent adhesion to polycarbonate resin, polyester resin, cellulose resin, liquid crystal polymer, and ethylene-vinyl acetate copolymer, particularly heat-resistant adhesive, water resistance, and weather resistance. Moreover, it was confirmed that the desired functionality was imparted to the system to which the functional material was added. On the other hand, in Comparative Examples 1 to 4 and 7 to 15, the compounding amounts of the components (a) to (d) are outside the range defined by the present invention. , Water resistance and weather resistance could not be satisfied at all. In Comparative Examples 5 to 6, since the component (b) is a component outside the range of the present invention, the adhesion to the specific substrate, the heat-resistant adhesion, and the water resistance deteriorated.

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Abstract

La présente invention concerne une composition de revêtement caractérisée en ce qu'elle contient : (a) de 45 à 95 parties en poids d'une résine fluorée ; (b) de 2 à 35 parties en poids d'une résine acétal de polyvinyle ou d'un copolymère séquencé composé d'une séquence (A) comprenant principalement un ester de méthacrylate et d'une séquence (B) comprenant principalement un ester d'acrylate ; (c) de 2 à 50 parties en poids d'une résine d'ester de vinyle ou d'une résine de polyester insaturée (la somme des composants (a) à (c) étant égale à 100 parties en poids) ; et (d) de 0,1 à 15 parties en poids d'un initiateur pour 100 parties en poids de la totalité des constituants (a) à (c).
PCT/JP2010/063403 2010-08-06 2010-08-06 Composition de revêtement et stratifié WO2012017553A1 (fr)

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JP2014141626A (ja) * 2012-12-28 2014-08-07 Konica Minolta Inc 塗布液、反射膜、反射シート、太陽電池モジュール、ｌｅｄ照明装置および実装用基板
WO2018154630A1 (fr) * 2017-02-21 2018-08-30 三菱電機株式会社 Composition de revêtement, film de revêtement et climatiseur l'utilisant

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JP2000188412A (ja) * 1998-10-13 2000-07-04 Dainippon Printing Co Ltd 太陽電池モジュ―ル用保護シ―トおよびそれを使用した太陽電池モジュ―ル
JP2002338707A (ja) * 2001-05-18 2002-11-27 Kanegafuchi Chem Ind Co Ltd 金属板被覆用フィルムおよびこれを用いた被覆金属板
JP2007231072A (ja) * 2006-02-28 2007-09-13 Three M Innovative Properties Co コーティング組成物及びそれを使用した物品
JP2010526886A (ja) * 2007-04-23 2010-08-05 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フルオロポリマー被膜フィルム、それの形成方法、およびフルオロポリマー液体組成物
WO2009104423A1 (fr) * 2008-02-22 2009-08-27 有限会社サンサーラコーポレーション Composition de polymère et article moulé obtenu à partir de la composition
JP2010138310A (ja) * 2008-12-12 2010-06-24 Dic Corp ２液型紫外線吸収着色塗料組成物

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* Cited by examiner, † Cited by third party
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JP2014141626A (ja) * 2012-12-28 2014-08-07 Konica Minolta Inc 塗布液、反射膜、反射シート、太陽電池モジュール、ｌｅｄ照明装置および実装用基板
WO2018154630A1 (fr) * 2017-02-21 2018-08-30 三菱電機株式会社 Composition de revêtement, film de revêtement et climatiseur l'utilisant
JPWO2018154630A1 (ja) * 2017-02-21 2019-07-04 三菱電機株式会社 コーティング組成物、コーティング膜及びそれを有する空気調和機
CN110300781A (zh) * 2017-02-21 2019-10-01 三菱电机株式会社 涂布组合物、涂膜及具有其的空调机

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