WO2015114983A1 - Composition de résine à base de fluor, film de résine, stratifié et feuille de support pour modules de cellules solaires - Google Patents

Composition de résine à base de fluor, film de résine, stratifié et feuille de support pour modules de cellules solaires Download PDF

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Publication number
WO2015114983A1
WO2015114983A1 PCT/JP2014/083537 JP2014083537W WO2015114983A1 WO 2015114983 A1 WO2015114983 A1 WO 2015114983A1 JP 2014083537 W JP2014083537 W JP 2014083537W WO 2015114983 A1 WO2015114983 A1 WO 2015114983A1
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mass
film
fluororesin
fluorine
resin
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PCT/JP2014/083537
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English (en)
Japanese (ja)
Inventor
日高知之
鈴木和元
石川勝之
赤津直人
會田光徳
村山利美
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株式会社クレハ
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    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • 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
    • B32B2419/00—Buildings or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • 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 fluorine resin composition suitable for uses such as a back sheet for a solar cell module, a resin film formed from the composition, a laminate including a layer made of the resin film, and a solar cell module Related to backsheet.
  • Fluoropolymers such as polyvinylidene fluoride are required to have long-term durability by taking advantage of their excellent weather resistance, heat resistance, contamination resistance, chemical resistance, solvent resistance, mechanical properties, and secondary processability.
  • a film made of fluororesin makes use of the cost merit of thinning, and as a protective material for various surfaces, materials for interior and exterior of buildings, container surface materials that require chemical resistance and organic solvent resistance, Is widely used for a surface protection material or a back surface protection material of a solar cell module, a fuel cell member, etc., in which long-term reliability is important.
  • Fluorine resin with excellent weather resistance, heat resistance, stain resistance, chemical resistance, solvent resistance, mechanical properties, and secondary workability is a single layer or laminated with other thermoplastic resin layers As a body, it has come to be used as a surface protection material or a back surface protection material of a solar cell module used for photovoltaic power generation.
  • a solar cell is a power generator that directly converts sunlight into electrical energy.
  • Solar cells are broadly classified into those using silicon semiconductors and those using compound semiconductors.
  • Silicon semiconductor solar cells include single crystal silicon solar cells, polycrystalline silicon solar cells, and amorphous silicon solar cells.
  • a typical module of a solar cell includes a surface protective material, a sealing material, a solar battery cell, a back surface protective material (hereinafter sometimes referred to as “back sheet”), and a frame.
  • a plurality of solar cells are arranged and connected in series by wiring, and a package using a surface protective material, a sealing material, and a back surface protective material is a solar cell module, or an end of the solar cell module or A frame is disposed on the peripheral edge. What connected several solar cell modules is called a solar cell array.
  • the surface protective material for example, a tempered glass plate, a transparent plastic plate, or a transparent plastic film is used.
  • a sealing material ethylene-vinyl acetate copolymer (EVA) is widely used.
  • EVA ethylene-vinyl acetate copolymer
  • back sheet for example, a plastic film, a plastic plate, a tempered glass plate, a metal plate (aluminum plate, painted steel plate, etc.) is used.
  • the frame for example, aluminum that is lightweight and excellent in environmental resistance is widely used.
  • the structure of the solar cell differs depending on the type of solar cell.
  • a silicon semiconductor solar cell typically has a structure in which n-type silicon and p-type silicon are joined and electrodes are arranged on each.
  • As another solar battery cell for example, there is one having a layer configuration of “collecting electrode / transparent conductive layer / semiconductor photoactive layer / reflective layer / conductive substrate”.
  • the semiconductor photoactive layer is, for example, an amorphous silicon semiconductor.
  • a solar cell module (the same applies to a solar cell array) is generally installed outdoors and then maintained in operation for a long period of time.
  • the surface protection material, the sealing material, and the back surface protection material (back sheet) of the solar cell module have a function of protecting solar cells over a long period of time in a harsh natural environment surrounding the solar cell module. Is required.
  • the back sheet for the solar cell module is directly exposed to the outdoors on the surface far from the solar cell (the outermost surface on the back side of the solar cell module).
  • the surface of the solar cell module backsheet close to the solar cells is exposed to sunlight through the gaps between the solar cells and the gaps between the solar cell modules.
  • the back sheet for solar cells has light resistance, weather resistance, heat resistance, moisture resistance, oxygen or water vapor barrier properties, electrical insulation, voltage resistance, mechanical properties, chemical resistance, salt resistance, antifouling properties. And various properties such as adhesion to a sealing material are required.
  • a back sheet for a solar cell module As a back sheet for a solar cell module, a single layer or multilayer plastic film, a plastic plate, a tempered glass plate, a metal plate, a composite of a plastic film and a metal plate, a composite of a plastic film and a metal foil, or the like is generally used. It has been.
  • the metal plate one having a synthetic resin coating film formed on the surface thereof is also used.
  • plastic film from the viewpoint of satisfying various properties such as light resistance, weather resistance, heat resistance, and antifouling properties required for the back sheet for the solar cell module, a fluorine resin film, a polyethylene terephthalate (PET) film, and These composite films are preferably used.
  • Patent Document 1 discloses, as an outer surface resin layer, an ethylene / tetrafluoroethylene copolymer, a terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride, and a polyfluoride.
  • a back surface protection sheet for solar cells is disclosed in which a fluorine-based resin such as vinyl, polyvinylidene fluoride, polychlorotrifluoroethylene, or tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer is melt-extruded and laminated.
  • Patent Document 2 discloses a back protective sheet for a solar cell provided with a film containing polyvinylidene fluoride and polymethyl methacrylate in the outermost layer.
  • the solar cell module backsheet has a beautiful appearance on the surface of the solar battery cell, and also efficiently reflects sunlight incident on the backsheet. It is required to have a function to If the incident light transmitted through the gaps between the solar cells can be efficiently reflected by the back sheet, the power conversion efficiency of the solar cells is improved by the reflected light. For this reason, the coloring backsheet for solar cell modules formed by mix
  • a white resin film in which an inorganic white pigment is blended with a thermoplastic resin is known in order to increase the reflectance of sunlight and increase the power generation efficiency of a solar cell.
  • Document 4 discloses that titanium oxide is particularly excellent in color tone and hiding power (light scattering property) among inorganic white pigments, and contributes to improvement in color tone and reflection characteristics of the white resin film.
  • a solar cell backsheet As a back sheet for a solar cell colored in a dark color, a sheet using carbon black, which is a black pigment, is generally used. However, carbon black absorbs sunlight and the temperature rises. As a result, not only the power generation efficiency of the battery but also the durability could decrease. Accordingly, it is also known to blend an inorganic pigment having infrared reflection characteristics or an infrared reflection black pigment as a solar cell backsheet colored in a dark color.
  • a fluororesin film made of a fluororesin composition in which a pigment is contained in a fluororesin such as polyvinylidene fluoride is used as a back sheet for a solar cell module, the appearance of the solar cell can be made beautiful. It is expected to contribute to the improvement of power conversion efficiency.
  • a large amount of pigment such as titanium oxide, for example, 100 parts by mass of a fluorine-based resin is used.
  • a fluororesin film including a sheet
  • a fluororesin composition containing 25 parts by mass or more of the resin the elongation of the resulting fluororesin film is reduced.
  • the fluororesin When the film is used as a back sheet for a solar cell module, the durability of the solar cell module may be insufficient, and the moldability may be deteriorated.
  • an acrylic rubber-containing methacrylate resin (disclosed as an impact resistance improver in Patent Literature 5, Patent Literature 6, etc.)
  • the draw resonance phenomenon does not occur, and it can be used for a solar cell module backsheet and the like.
  • a fluorine-based resin composition capable of efficiently forming a fluorine-based resin film having suitable elongation and other characteristics and excellent durability.
  • An object of the present invention is to provide a fluororesin composition in which a large amount of pigment is contained in a fluororesin in order to improve concealability and heat resistance, in which a draw resonance phenomenon does not occur, and a backsheet for a solar cell module, etc.
  • An object of the present invention is to provide a fluorine-based resin composition capable of efficiently forming a fluorine-based resin film having elongation and other characteristics suitable for applications and having excellent durability.
  • Another object of the present invention is to provide elongation and other characteristics suitable for applications such as a back sheet for a solar cell module, which is efficiently formed from a fluorine resin composition containing a large amount of pigment in a fluorine resin. It has it in providing the fluorine resin film which has and is excellent in durability, and also in providing the laminated body provided with the said fluorine resin film, and a solar cell module backsheet.
  • the present inventors have found that in a fluorine-based resin composition containing a large amount of pigment in a fluorine-based resin, (c) an acrylic rubber-containing methacrylate-based resin, ( It was found that the problem can be solved by containing a predetermined amount of d) high molecular weight acrylic processing aid and (e) calcium stearate, and the present invention has been completed.
  • a fluororesin composition containing (b) 25 to 75 parts by mass of pigment with respect to 100 parts by mass of fluororesin, and (C) Contains 1.5 to 15% by weight of acrylic rubber-containing methacrylate resin, (d) 0.8 to 6% by weight of high molecular weight acrylic processing aid, and (e) 0.05 to 1% by weight of calcium stearate
  • a fluororesin composition containing (b) 25 to 75 parts by mass of pigment with respect to 100 parts by mass of fluororesin, and (C) Contains 1.5 to 15% by weight of acrylic rubber-containing methacrylate resin, (d) 0.8 to 6% by weight of high molecular weight acrylic processing aid, and (e) 0.05 to 1% by weight of calcium stearate
  • a fluororesin composition containing (b) 25 to 75 parts by mass of pigment with respect to 100 parts by mass of fluororesin, and (C) Contains 1.5 to 15% by weight of acrylic rubber-containing methacrylate resin, (d) 0.8 to 6% by weight of
  • the following fluororesin compositions (1) to (8) are provided as embodiments thereof.
  • (1) (a) The said fluorine resin composition whose fluorine resin is a polyvinylidene fluoride.
  • the vinylidene fluoride copolymer has a vinylidene fluoride unit copolymerization ratio of 85 mol% or more, a vinylidene fluoride-hexafluoropropylene copolymer, a vinylidene fluoride-tetrafluoroethylene copolymer, Vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer, and vinylidene fluoride-chlorotrifluoroethylene-hexa
  • a fluororesin film formed from the above fluororesin composition.
  • the laminated body provided with the layer which consists of this fluororesin film, and the solar cell module backsheet provided with the layer which consists of this fluororesin film are provided.
  • a fluororesin composition containing (b) 25 to 75 parts by mass of a pigment with respect to 100 parts by mass of a fluororesin, and (C) Contains 1.5 to 15% by weight of acrylic rubber-containing methacrylate resin, (d) 0.8 to 6% by weight of high molecular weight acrylic processing aid, and (e) 0.05 to 1% by weight of calcium stearate
  • a fluorine-based resin composition characterized by Draw resonance phenomenon does not occur in fluororesin compositions containing a large amount of pigments in fluororesins in order to improve concealment and heat resistance, and elongation suitable for applications such as backsheets for solar cell modules
  • a fluorine-based resin composition capable of efficiently forming a fluorine-based resin film having various properties and excellent durability is provided.
  • the present invention by being a fluorine resin film formed from the above fluorine resin composition, it has elongation and other characteristics suitable for uses such as a back sheet for a solar cell module, and is durable. The effect that the fluororesin film excellent in property and formed efficiently is provided.
  • the present invention by being a laminate or a solar cell module backsheet comprising a layer made of the above-mentioned fluorine-based resin film, the elongation and other various properties suitable for use as a solar cell module backsheet and the like.
  • the effect of providing the laminated body or solar cell module backsheet which has a characteristic and is excellent in durability is show
  • the fluorine resin composition of the present invention is a fluorine resin composition containing (b) 25 to 75 parts by mass of pigment with respect to 100 parts by mass of (a) fluorine resin, and (C) Contains 1.5 to 15% by weight of acrylic rubber-containing methacrylate resin, (d) 0.8 to 6% by weight of high molecular weight acrylic processing aid, and (e) 0.05 to 1% by weight of calcium stearate (F) other such as (f) a polyalkylene glycol fatty acid ester, and / or (g) a thermal stabilizer, and / or a methacrylate resin.
  • Each of the thermoplastic resins is a fluorine-based resin composition containing a predetermined amount (total amount is 100% by mass).
  • (A) Fluorine Resin As the (a) fluorine resin contained in the fluorine resin composition of the present invention, a fluorine resin conventionally used for solar cell module backsheets and other uses should be used. Can do. Specifically, ethylene / tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene (TFE) / hexafluoropropylene (HFP) / vinylidene fluoride (VDF) terpolymer, polyvinyl fluoride (PVF) , Polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, and the like. From the viewpoints of appearance, heat resistance, durability, and melt moldability, polyvinylidene fluoride (PVDF) is preferred.
  • EFE ethylene / tetrafluoroethylene copolymer
  • TFE
  • PVDF Polyvinylidene fluoride
  • the polyvinylidene fluoride (PVDF) preferable as the (a) fluorine-based resin contained in the fluorine-based resin composition of the present invention includes a vinylidene fluoride homopolymer and a vinylidene fluoride-based copolymer containing vinylidene fluoride as a main component. Polymers can be mentioned and any of these or mixtures can be used.
  • vinylidene fluoride copolymer which is PVDF examples include vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, Vinylidene-trifluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer, vinylidene fluoride-chlorotrifluoroethylene-hexafluoropropylene terpolymer, and two or more of these Of the mixture.
  • the copolymerization ratio of vinylidene fluoride units is usually 85 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, that is, the comonomer copolymerization ratio is usually 15%. It is less than mol%, preferably less than 10 mol%, more preferably less than 5 mol%.
  • the copolymerization ratio of the comonomer is 15 mol% or less, the vinylidene fluoride copolymer becomes a thermoplastic resin having crystallinity.
  • the lower limit of the comonomer copolymerization ratio is not particularly limited, but is usually 1 mol%. If the copolymerization ratio of the comonomer becomes too high, the vinylidene fluoride copolymer may exhibit elastomeric properties, which may be undesirable for solar cell module backsheet applications.
  • At least one selected from the group consisting of a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer having a copolymerization ratio of 85 mol% or more of vinylidene fluoride can be preferably used.
  • vinylidene fluoride homopolymers and vinylidene fluoride-hexafluoropropylene copolymers having a copolymerization ratio of hexafluoropropylene units of 15 mol% or less are excellent in heat resistance, melt moldability, mechanical properties, It is particularly preferable from the viewpoints of soiling, solvent resistance, secondary workability and the like.
  • the intrinsic viscosity of PVDF is preferably in the range of 0.7 to 1.5 dl / g, more preferably 0.8 to 1.3 dl / g.
  • the intrinsic viscosity of PVDF is a logarithmic viscosity at 30 ° C. measured using a Ubbelohde viscometer for a solution in which 4 g of PVDF is dissolved in 1 liter of N, N-dimethylformamide.
  • the melting point of PVDF is usually 130 to 185 ° C., and in many cases 150 to 180 ° C.
  • the melting point of PVDF is a value measured by a differential scanning calorimeter (DSC).
  • (B) Pigment As the (b) pigment contained in the fluorine resin composition of the present invention, (a) the color tone and hiding power of the fluorine resin (h) so as to suit the use of a back sheet for a solar cell module, etc. There is no particular limitation as long as it does not impair the light scattering property, but it has excellent color tone and hiding power (light scattering property), so it has an inorganic white pigment such as titanium oxide, and reflection characteristics. Inorganic pigments and black pigments such as carbon black can be preferably used, inorganic white pigments such as titanium oxide are more preferable, and titanium oxide is particularly preferable.
  • Inorganic white pigments more preferably used as the (b) pigment contained in the fluororesin composition of the present invention include ZnO, TiO 2 , Al 2 O 3 .nH 2 O, [ZnS + BaSO 4. ], CaSO 4 ⁇ 2H 2 O, BaSO 4 , CaCO 3 , 2PbCO 3 ⁇ Pb (OH) 2 and the like.
  • inorganic white pigments color tone and hiding power (light scattering property) are extremely excellent, and titanium oxide (TiO 2 ) is particularly preferable because it can contribute to improvement of color tone and reflection characteristics of the white resin film.
  • Titanium oxide is widely used in two crystal forms, anatase and rutile. In the present invention, these two types of crystal forms can be used, but among these, since they are excellent in dispersibility in PVDF at high temperature and have extremely low volatility, oxidation having a rutile type crystal form is possible. Titanium is preferred.
  • the average particle diameter (average primary particle diameter) of titanium oxide by image analysis of transmission electron microscope images is usually in the range of 150 to 1000 nm, preferably 200 to 700 nm, more preferably 200 to 400 nm.
  • the average particle diameter of titanium oxide is too small, the hiding power is reduced. Since the average particle diameter of titanium oxide is within the above range, the refractive index is large and the light scattering property is strong, so that the hiding power as a white pigment is increased.
  • Titanium oxide is generally present in the form of secondary particles in which primary particles are aggregated.
  • the specific surface area of titanium oxide by the BET method is usually in the range of 1 to 15 m 2 / g, and in many cases 5 to 15 m 2 / g.
  • Titanium oxide can be improved in properties such as dispersibility, concealability, and weather resistance by surface treatment with a surface treatment agent.
  • the surface treatment agent include metal oxides such as aluminum, silicon, zirconium, tin, cerium, and bismuth; hydrated metal oxides such as zinc oxide; organometallic compounds such as organoaluminum compounds, organotitanium compounds, and organozirconium compounds; Examples thereof include organosilicon compounds such as silane coupling agents and polysiloxanes; phosphorus compounds such as aluminum phosphates and organophosphates; amine compounds.
  • Black pigment As the black pigment that can be used as the (b) pigment contained in the fluororesin composition of the present invention, carbon black is preferable. Usually, it is not particularly limited as long as it is a carbon black used for a solar battery backsheet or the like, and furnace black, channel black, acetylene black, thermal black, etc. can be used, and the surface is modified by a carboxyl group or the like. Carbon black can also be used.
  • the average particle size (average primary particle size) of carbon black by image analysis of transmission electron microscope images is usually in the range of 10 to 150 nm, preferably 13 to 100 nm, more preferably 15 to 40 nm. If the average particle size of the carbon black is too small, the carbon black is likely to aggregate and be difficult to handle.
  • BET specific surface area of carbon black is usually 20 ⁇ 250m 2 / g, preferably 50 ⁇ 200m 2 / g, more preferably in the range of 80 ⁇ 200m 2 / g.
  • the black pigment an inorganic pigment having infrared reflection characteristics can be used.
  • the pigment has a property of preventing heat storage by reflecting infrared rays of a specific wavelength even if it is colored black or chromatic in appearance, and has low heat deformation and excellent heat resistance. Even if it is used outdoors for a long time, it hardly resists hydrolysis and has excellent weather resistance. Therefore, when it is contained in a fluorine resin composition that forms a fluorine resin film used for a solar cell backsheet, the power generation efficiency of the solar cell is improved. It is possible to prevent a decrease, durability, and thermal decomposition or discoloration during molding.
  • Fe oxides containing at least two elements selected from Cr and Mn, for example, Fe (Fe, Cr) 2 O 4, (Co, Fe) (Fe, Cr) 2 O 4 , Cu (Cr, Mn) 2 O 4 , (Cu, Fe, Mn) (Fe, Cr, Mn) 2 O 4 , (Fe, Zn) (Fe, Cr) 2 O 4 , Cr 2 O 3 : Fe 2 O 3 , an oxide containing Co element and Ni element, specifically, (Ni, Co, Fe) (Fe, Cr) 2 O 4 etc., Fe, Co and Al, , Mg, Ca, Sr, Ba, Ti, Zn, Sn, Zr, Si, and a complex oxide containing one or more metals selected from Cu.
  • the content ratio of the (b) pigment in the fluororesin composition of the present invention is in the range of 25 to 75 parts by mass of (b) the pigment with respect to 100 parts by mass of the (a) fluororesin, preferably 28 to 70.
  • the amount is within the range of part by mass, more preferably 32 to 68 parts by mass, particularly preferably 35 to 65 parts by mass.
  • (B) When the content rate of a pigment is too small, it will become difficult to obtain the fluorine resin film which has the color tone, hiding power, and reflection efficiency which can be utilized as a solar cell module backsheet.
  • B When the content rate of a pigment is too large, manufacture of the fluorine resin film by an extrusion process will become difficult, and the mechanical strength of a fluorine resin film will fall.
  • Two or more types of pigments for example, an inorganic white pigment such as titanium oxide and a black pigment may be used in combination.
  • (C) Acrylic rubber-containing methacrylate-based resin The fluorine-based resin composition of the present invention contains (b) a pigment and (c) an acrylic rubber-containing methacrylate-based resin, whereby the resulting fluorine-based resin film has an elongation.
  • the fluororesin composition can be improved and the moldability can be improved.
  • (C) Acrylic rubber-containing methacrylate-based resin is a resin having a structure containing acrylic rubber as a rubber component phase in a hard component phase composed of a methacrylate-based resin.
  • a resin having a preferred structure is a core-shell structure (sometimes referred to as a “core-shell type”) in which a rubber component phase made of acrylic rubber is a core layer and the periphery of the core layer is coated with a hard component phase to form a shell layer. .)
  • the acrylic rubber as the rubber component phase may have a Tg (glass transition temperature) of ⁇ 30 ° C. or lower, preferably ⁇ 35 ° C. or lower, and includes n-butyl acrylate (BA), n-octyl acrylate, acrylic acid 2 A monomer such as ethylhexyl, if necessary, an alkyl acrylate such as methyl acrylate and ethyl acrylate; an alkyl ester such as methyl methacrylate (MMA), ethyl methacrylate and butyl methacrylate; divinylbenzene, Polymerized using a crosslinkable monomer such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate.
  • BA glass transition temperature
  • the acrylic rubber a silicone-acrylic composite rubber composed of a polyorganosiloxane rubber component and the above acrylic rubber component can also be used.
  • the acrylic rubber is preferably silicone-acrylic composite rubber or acrylic rubber obtained by polymerizing BA.
  • Use of a conjugated diene monomer such as butadiene is not preferable because it may be inferior in chemical resistance and durability, or may cause discoloration during molding.
  • the methacrylate resin which is a hard component phase has a Tg of 60 ° C. or higher, preferably 65 ° C. or higher, MMA alone or as a main component, and other monomers such as MMA such as ethyl methacrylate and butyl methacrylate.
  • MMA ethyl methacrylate
  • methacrylic acid alkyl ester acrylic acid alkyl ester such as methyl acrylate and ethyl acrylate
  • styrene monomer such as styrene and ⁇ -methylstyrene
  • nitrile monomer such as acrylonitrile and methacrylonitrile
  • Such a resin can be obtained by emulsion polymerization or suspension polymerization, and is preferably a monomer that polymerizes acrylic rubber and forms a methacrylate resin that is a hard component phase in the presence of the acrylic rubber. Can be obtained by polymerizing.
  • the acrylic rubber is the above-mentioned silicone / acrylic composite rubber, it can be obtained by adding a monomer for forming an acrylic rubber component to a pre-formed latex of a polyorganosiloxane rubber and polymerizing it.
  • the polymerization of the core layer and the shell layer may be performed in one stage, but may be performed in multiple stages.
  • the shell layer is polymerized in two or more stages, and the outermost layer is MMA. It is preferable to use a resin layer formed of
  • the ratio of the rubber component phase / hard component phase is 30 to 92% by mass / 70 to 8% by mass, preferably 35 to 90% by mass / 65 to 10% by mass, more preferably 40 to 85% by mass / 60 to 15% by mass. %.
  • the average particle size of the rubber component phase as the core layer is 1 ⁇ m or less, preferably 0. It is in the range of 05 to 0.8 ⁇ m, more preferably 0.1 to 0.6 ⁇ m. When the average particle diameter exceeds 1 ⁇ m, the mechanical properties of the obtained (c) acrylic rubber-containing methacrylate resin may be insufficient.
  • acrylic rubber-containing methacrylate resin in the present invention As (c) acrylic rubber-containing methacrylate resin in the present invention, Kaneace (registered trademark) FM manufactured by Kaneka Corporation, which is commercially available as an impact strength improver for vinyl chloride resin, ABS resin and other general-purpose molding resins. It is also possible to select from the series, Metablene (registered trademark) W series or S series manufactured by Mitsubishi Rayon Co., Ltd., Paraloid (registered trademark) EXL series manufactured by Rohm and Haas. (C) The acrylic rubber-containing methacrylate resin can be used alone or in combination of two or more.
  • the content of the acrylic rubber-containing methacrylate resin is 1.5 to 15% by mass, preferably 1.7 to 13% by mass, more preferably 1.9 to 11% by mass in the fluororesin composition. It is.
  • the fluororesin composition of the present invention is characterized by containing (d) a high molecular weight acrylic processing aid. That is, the fluororesin composition of the present invention further comprises (d) a high molecular weight acrylic processing aid, so that the fluororesin composition contains a large amount of pigment in the fluororesin composition. Sometimes a draw resonance phenomenon does not occur, and it is possible to efficiently form a fluorine resin film having elongation and other characteristics suitable for uses such as a back sheet for a solar cell module and having excellent durability.
  • the (d) high molecular weight acrylic processing aid contained in the fluororesin composition of the present invention is known per se as a molding processing aid for vinyl chloride resin, ABS resin and other general-purpose molding resins.
  • the acrylic polymer processing aid contains, as a main component, an ultra-high molecular weight acrylic polymer having a molecular weight of approximately 1,000,000 or more, preferably 1.5 million or more, more preferably 3 million or more.
  • the long chain of the acrylic polymer is entangled with the matrix resin (the above-mentioned general-purpose molding resin) to create a pseudo-crosslinked state and impart melt elasticity, thereby improving molding processability and It is said that it has the effect of improving the appearance.
  • the fluororesin composition of the present invention contains a predetermined amount of (d) a high molecular weight acrylic processing aid, but the exact mechanism of action is not clear, but a draw resonance phenomenon occurs during film forming processing. There is no effect, and the resulting fluorine-based resin film has elongation and other properties suitable for applications such as solar cell module backsheets, and has excellent durability. That is, it has an effect that cannot be directly expected as a molding processing aid.
  • the content of the high molecular weight acrylic processing aid is 0.8 to 6% by mass, preferably 0.9 to 5.8% by mass, more preferably 1 to 5.% in the fluororesin composition. 5% by mass.
  • the fluororesin composition of the present invention can improve the elongation of the resulting fluororesin film by containing (e) calcium stearate.
  • soap stearates such as calcium stearate and sodium stearate are used as a lubricant for the purpose of improving molding processability, but in the fluororesin composition of the present invention,
  • ( e) Calcium stearate has an effect as an elongation improver of the resulting fluororesin film, that is, a mechanical property improver.
  • the content of (e) calcium stearate is 0.05 to 1% by mass, preferably 0.07 to 0.8% by mass, more preferably 0.09 to 0%. .6% by mass.
  • the fluororesin composition of the present invention may further include an ultraviolet absorber, a stabilizer (thermal stabilizer, light stabilizer, etc.), a matting agent, a processability improver (lubricant, etc.), a tint, if desired.
  • Other additives selected from regulators, crystal nucleating agents, other mechanical property improving agents, and the like can be contained. These other additives are optionally used in proportions suitable for each, and in the fluororesin composition, each is preferably independently 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass. % Or less is used. When these additives are used, there is no particular lower limit of the content ratio, but in the fluorine-based resin composition, each is independently usually 0.001% by mass, and in many cases 0.01% by mass.
  • the fluororesin composition of the present invention preferably contains a processability improving agent as another additive.
  • the fluorine-based resin composition of the present invention can improve the dispersibility of the pigment (b) by containing a processability improving agent, and prevent the occurrence of pinholes when processing and forming films and the like. be able to.
  • the content of (e) calcium stearate can be reduced.
  • Processability improvers preferably used in the fluororesin composition of the present invention include fatty acid monohydric alcohol esters, polybasic acid monohydric alcohol esters, polyhydric alcohol fatty acid esters, and derivatives thereof, glycerin fatty acid esters. And the like, preferably a polyhydric alcohol fatty acid ester. From the viewpoint of improving the dispersibility of (b) pigments such as titanium oxide and (a) compatibility with fluorine-based resins, particularly preferred are (f) polyalkylene glycol fatty acid esters which are fatty acid esters of polyhydric alcohols.
  • Polyalkylene glycol fatty acid ester preferably used in the fluororesin composition of the present invention includes polyoxymethylene sorbitan monolaurate, polyoxymethylene sorbitan monopalinate, polyoxy Methylene sorbitan monostearate, polyoxymethylene sorbitan monooleate, polyethylene glycol behenate, polyethylene glycol dilaurate, polyethylene glycol distearate, polyoxymethylene sorbitan tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol mono Ethylphenol ether laurate and polyoxyethylene bisphenol A laurate Tell.
  • the most preferred (f) polyalkylene glycol fatty acid ester is polyoxyethylene bisphenol A lauric acid ester, which is commercially available as Exepal (registered trademark) BP-DL manufactured by Kao Corporation.
  • the fluororesin composition of the present invention further contains (f) a polyalkylene glycol fatty acid ester or the like as a processability improver
  • the content of the processability improver is usually 0.5 to 2% by mass, preferably Is in the range of 0.8 to 1.7% by mass, more preferably 1 to 1.5% by mass.
  • the fluororesin composition of the present invention preferably further contains a stabilizer, more specifically (g) a thermal stabilizer, as another additive.
  • the fluorine-based resin composition of the present invention contains (g) a heat stabilizer, thereby improving the heat resistance and suppressing thermal decomposition in the preparation of the fluorine-based resin composition and the molding process of the fluorine-based resin film. Can be played.
  • Thermal stabilizers preferably used in the fluororesin composition of the present invention include inorganic calcium compounds such as calcium carbonate and calcium hydroxide; metal oxides such as zinc oxide and magnesium oxide; calcium gluconate and the like. Polyhydroxymonocarboxylic acid calcium salt; and the like, and most preferably calcium carbonate.
  • a heat stabilizer can be used individually or in combination of 2 types or more, respectively.
  • the heat stabilizer is usually in the form of a powder.
  • an inorganic calcium compound such as calcium carbonate and a metal oxide such as zinc oxide have an average particle diameter (average primary particle diameter) in the range of 0.05 to 2 ⁇ m by image analysis of a transmission electron microscope image. Preferably there is.
  • the average particle diameter means a number average particle diameter (D 50 ) calculated as an integrated value of 50% of the primary particle diameter measured by the laser diffraction method.
  • D 50 a number average particle diameter calculated as an integrated value of 50% of the primary particle diameter measured by the laser diffraction method.
  • SALD particle diameter measuring instrument SALD manufactured by Shimadzu Corporation It can be measured using -3000J.
  • the content of (g) the heat stabilizer is preferably 0.1 to 10% by mass, more preferably 0.5 to It is in the range of 5% by mass, more preferably 1-3% by mass.
  • the content rate of a heat stabilizer is too small, the heat stabilization effect will become small and there exists a possibility that the thermal decomposition temperature of the (a) fluorine resin component in a fluorine resin composition may fall.
  • the content ratio of the thermal stabilizer is too large, the hiding power, color tone, mechanical properties, etc. of the fluororesin film may be adversely affected.
  • the content ratio of (g) the heat stabilizer is adjusted according to the content ratio of the (b) pigment in the fluororesin composition. It is preferable to do.
  • the content rate of a heat stabilizer is usually made smaller than the content rate of (b) a pigment.
  • the mass ratio of (b) pigment to (g) heat stabilizer is usually in the range of 200: 1 to 3: 1, preferably 100: 1 to 4: 1, more preferably 50: 1 to 5: 1. .
  • thermoplastic resins may contain only (a) a fluororesin as a resin component, but the processability, impact resistance and adhesion of the fluororesin composition In order to improve properties such as heat resistance and heat resistance, (h) another thermoplastic resin can be further contained as a resin component as desired.
  • thermoplastic resins include: polyolefins such as polyethylene and polypropylene; fluorine resins such as polytetrafluoroethylene and polyvinyl fluoride; polyamides such as nylon 6 and nylon 66; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate Polyester such as phthalate; methacrylate resin such as polymethyl methacrylate; polystyrene, polyacrylonitrile, polyvinyl chloride, polyoxymethylene, polycarbonate, polyphenylene oxide, polyester urethane, poly m-phenylene isophthalamide, poly p-phenylene terephthalamide, etc. Can be mentioned.
  • thermoplastic resin As another thermoplastic resin, (a) Methacrylate resin such as polymethyl methacrylate (PMMA) from the viewpoint of compatibility with PVDF particularly preferably used as a fluorine-based resin and adhesiveness to other members Is preferable, and PMMA is particularly preferable.
  • PMMA polymethyl methacrylate
  • the methyl methacrylate monomer as a structural unit exceeds 50 mol%, an acrylate monomer, and a methacrylate other than methyl methacrylate.
  • examples thereof include a copolymer containing less than 50 mol% of a monomer, and a mixture of two or more of these polymers.
  • the acrylate esters include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate.
  • methacrylic esters other than methyl methacrylate include ethyl methacrylate and propyl methacrylate.
  • the methacrylic acid alkyl ester can be illustrated.
  • thermoplastic resin preferably a methacrylate resin, particularly preferably PMMA
  • thermoplastic resins can be contained in a proportion of usually 10 to 30 parts by weight, preferably 10.5 to 29 parts by weight, more preferably 11 to 28 parts by weight.
  • the fluorine resin composition of the present invention comprises a predetermined amount of (a) a fluorine resin, (b) a pigment, (c) an acrylic rubber-containing methacrylate resin, and (d) a high molecular weight acrylic resin. Resin by uniformly mixing raw materials such as processing aid and (e) calcium stearate and (f) polyalkylene glycol fatty acid ester, (g) heat stabilizer and / or (h) other thermoplastic resin, if desired
  • the preparation method is not particularly limited as long as the composition can be obtained. For example, it can be prepared by a method of dry blending raw materials. Also, the fluororesin powder or pellets, together with other raw materials, can be supplied to an extruder and melt-kneaded, melt-extruded into a strand, cut and pelletized.
  • Fluorine-based resin film formed from a fluorine-based resin composition Fluorine-based resin film
  • the fluorine-based resin composition of the present invention can be formed into a fluorine-based resin film by being supplied to an extruder and melt-extruded into a film form from a T-die placed at the tip of the extruder. it can.
  • the film includes not only a film having a thickness of less than 250 ⁇ m but also a sheet (including a plate) having a thickness of 250 ⁇ m or more.
  • the thickness of the fluororesin film formed from the fluororesin composition of the present invention is not particularly limited, but is preferably 10 to 100 ⁇ m, more preferably 12 to 70 ⁇ m, and still more preferably 15 to 50 ⁇ m.
  • the lower limit of the thickness of the fluororesin film is not particularly limited, but is usually 1 ⁇ m, most often 3 ⁇ m, and in some cases about 5 ⁇ m.
  • the upper limit of the thickness of the fluororesin film is not particularly determined because it varies depending on the fluororesin film, but is usually 500 ⁇ m, most of which may be 300 ⁇ m, and in some cases 200 ⁇ m.
  • the thickness of the fluororesin film is too thin, it will be difficult to obtain a sufficient color tone and hiding power, and the mechanical properties will also deteriorate. If the thickness of the fluororesin film is too thick, flexibility may be impaired or weight reduction may be difficult.
  • the fluorine resin film formed from the fluorine resin composition of the present invention is a fluorine resin containing a large amount of 25 to 75 parts by mass of (b) a pigment such as titanium oxide with respect to 100 parts by mass of (a) fluorine resin. In spite of being formed from a resin-based resin composition, it is a fluorine-based resin film having improved elongation.
  • the elongation of the fluororesin film means the tensile fracture elongation measured according to JIS K7113.
  • the elongation is preferably at least 10%, more preferably at least 11%, particularly preferably at least 12% in both the longitudinal direction (MD) and the width direction (TD). It is.
  • the upper limit of the elongation of the fluororesin film of the present invention is not particularly limited, but is usually 250% and in many cases 230% or less. On the other hand, if the elongation of the fluororesin film is less than 10%, the flexibility of the film is insufficient, and for example, it is evaluated that it is inappropriate for uses such as a back sheet for a solar cell module. There is.
  • the fluorine resin film formed from the fluorine resin composition of the present invention can be produced by employing a resin film production method known per se by extrusion. Moreover, the fluorine resin film of the present invention may be an unstretched (unoriented) film.
  • the fluororesin composition is melt-kneaded and extruded into a sheet at a die temperature of 210 to 280 ° C., preferably 220 to 270 ° C., and 80 to 150
  • the fluororesin film of the present invention can be obtained by forming an unstretched sheet by quenching and solidifying with a cooling drum maintained at a surface temperature of 0 ° C., preferably 85 to 135 ° C.
  • the resin film of the present invention may be a stretched (oriented) film if desired.
  • the stretching temperature is 20 to 160 ° C., preferably 30 to 150 ° C.
  • the area magnification is 2 to 100 times. , Preferably 4 to 60 times, uniaxially or sequentially or simultaneously biaxially, and then at a temperature of 80 to 200 ° C., preferably 90 to 160 ° C., under tension or under 20% relaxation. Heat treatment.
  • what is necessary is just to select the optimal range for these temperature conditions and extending
  • the measurement and evaluation method for the presence or absence of the draw resonance phenomenon is as follows. That is, a fluorine-based resin film having a width of 200 mm and a thickness of 20 ⁇ m is manufactured by extrusion molding, and using a desk thickness meter manufactured by Yamabun Denki Co., Ltd., a 200 / The film thickness is measured over 2500 mm in the drawing direction (MD) of the film at a total of three positions (two points) separated by 3 mm. Based on the measurement result, the standard deviation of the thickness is calculated for each position (unit: ⁇ m), and the average value of the standard deviation of the thickness at the three positions is calculated as the standard deviation of the thickness of the film (hereinafter simply referred to as “standard deviation of thickness” ”).
  • the standard deviation of the thickness is 2 ⁇ m or less (corresponding to 10% or less of the average thickness), it can be evaluated that the film has a uniform thickness with no draw resonance phenomenon occurring. It can be said that the film is suitable for a sheet or the like. If the standard deviation of thickness is 1.8 ⁇ m or less, and further 1.5 ⁇ m or less, it can be evaluated that the thickness of the film is extremely uniform. On the other hand, when the thickness standard deviation exceeds 2 ⁇ m, the draw resonance phenomenon occurs. As a result, the film thickness is not uniform. In particular, when the thickness standard deviation exceeds 3 ⁇ m, the film thickness non-uniformity is visually observed. However, when the standard deviation of the thickness exceeds 5 ⁇ m, it can be visually observed that the film has a large thickness unevenness.
  • Laminate comprising a layer composed of a fluororesin film
  • the fluororesin film of the present invention can be used as a single layer fluororesin film, but is composed of a fluororesin film laminated with other resin films.
  • a laminated body having layers it can be used, for example, in fields where further improvement in mechanical strength such as impact resistance and flexibility is required.
  • resin films used for forming a laminate comprising a layer made of a fluorine resin film include polyolefins such as polyethylene and polypropylene; polyamides such as nylon 6 and nylon 66; polyethylene terephthalate (PET), polybutylene terephthalate, Polyester such as polyethylene naphthalate (PEN); methacrylate resin such as PMMA; polystyrene, polyacrylonitrile, polyvinyl chloride, polyoxymethylene, polycarbonate, polyphenylene oxide, polyphenylene sulfide, polyether ether ketone, polyester urethane, poly m-phenylene isophthal
  • examples of such films include amide and poly p-phenylene terephthalamide.
  • These other resin films can further contain other thermoplastic resins, compounding agents such as stabilizers, ultraviolet absorbers, pigments or dyes, if necessary.
  • a laminate comprising a layer made of a fluororesin film may be laminated with other layers in place of or in addition to the other resin films listed above, if desired, depending on the application. You can also.
  • other layers further laminated as desired include a metal plate and a barrier layer.
  • Specific examples of the barrier layer include a metal foil, a plastic film having a metal vapor deposition layer, and a barrier resin film such as an ethylene vinyl alcohol copolymer (hereinafter sometimes referred to as “EVOH”) film. .
  • the thickness of the laminate comprising a layer made of a fluororesin film is not particularly limited, but is usually 3 to 500 ⁇ m, preferably 7 to 400 ⁇ m, more preferably 10 to 300 ⁇ m, still more preferably 20 to 250 ⁇ m. If the thickness of the laminate is too small, the strength of the laminate is insufficient and the required mechanical properties may not be obtained. On the other hand, if the thickness of the laminated body is too large, the flexibility of the film as the laminated body may be insufficient, and weight reduction and thinning cannot be achieved.
  • the ratio of the thickness of the layer composed of the fluororesin film and the other thermoplastic resin film in the laminate is not particularly limited, but is preferably 1/99 to 90/10, more preferably 5/95 to 70/30. The ratio is more preferably 10/90 to 50/50, particularly preferably 15/85 to 40/60.
  • the back sheet for solar cell modules provided with the layer which consists of a fluorine resin film The fluorine resin film of this invention can be used as the back sheet for solar cell modules provided with the layer which consists of a fluorine resin film.
  • a back sheet for a solar cell module a single layer film of a fluororesin film formed from the fluororesin composition of the present invention, a composite of the fluororesin film and another resin film (for example, a PET film) Multilayer film (laminate), multilayer film (laminate) in which the fluororesin film and moisture-proof film are compounded, composite material (laminate) in which the fluororesin film and a tempered glass plate are compounded, A composite material (laminate) in which a fluorine resin film and a metal plate are combined, and the fluorine resin film and another resin film, a moisture-proof film, a barrier film, a tempered glass plate and the like are combined.
  • a composite material (laminated body) or the like is used.
  • a multilayer film and a composite material (laminated body) can arrange
  • surface of a base film are mentioned.
  • the commercially available moisture-proof film include CELLEL (registered trademark) manufactured by Kureha Corporation.
  • EVA is usually supplied as a sheet.
  • the solar battery cell can be sealed with EVA by sandwiching the solar battery cell between two EVA sheets and pressurizing and heating.
  • the EVA sheet can be supplied in the form of a composite with a fluorine resin film made of a fluorine resin composition.
  • the other resin film used for forming a back sheet for a solar cell module having a layer made of a fluorine resin film is not particularly limited, and a laminate having a layer made of the fluorine resin film described above is formed.
  • Other resin films used for the purpose can be used, and one or more of these may be selected in consideration of required mechanical strength, heat resistance, weather resistance, light resistance, and the like.
  • polyesters such as PET and PEN; thermoplastic resin films such as polycarbonate resins and methacrylate resins such as PMMA are preferably used.
  • Polyester films such as PET and PEN are particularly preferred, most preferably PET films are used, and among these, biaxially stretched PET films are preferred.
  • resin films used for forming a back sheet for a solar cell module having a layer made of a fluorine-based resin film if necessary, further other thermoplastic resins, stabilizers, ultraviolet absorbers, A compounding agent such as a pigment or a dye can be contained.
  • a pigment such as titanium oxide added for improving the concealability may be contained in another resin film.
  • the thickness of the back sheet for a solar cell module having a layer made of a fluororesin film is not particularly limited, but is usually 3 to 500 ⁇ m, preferably 7 to 400 ⁇ m, more preferably 10 to 300 ⁇ m, still more preferably 20 to 250 ⁇ m. It is. If the thickness of the back sheet for the solar cell module is too small, the strength of the back sheet for the solar cell module may be insufficient, and required mechanical characteristics may not be obtained. It becomes difficult to get. On the other hand, if the thickness of the back sheet for a solar cell module is too large, the film as a laminate may be insufficiently flexible, and the weight and thickness cannot be reduced.
  • the ratio of the thickness of the layer composed of the fluororesin film and the other thermoplastic resin film in the laminate is not particularly limited, but is preferably 1/99 to 90/10, more preferably 5/95 to 70/30.
  • the ratio is more preferably 10/90 to 50/50, particularly preferably 15/85 to 40/60.
  • the back sheet for a solar cell module including a layer made of the fluororesin film of the present invention for example, the following can be exemplified, but not limited thereto.
  • the back sheet having a multi-layer structure shows the surface near the solar battery cell (and the sealing material) as the right end.
  • Fluorine resin film that is, a back sheet for a single-layer solar cell module
  • Fluorine resin film / adhesive / EVA Fluorine resin film / other resin film
  • Other resin film / fluorine resin film 5) Fluorine resin film / adhesive / other resin film 6)
  • Other resin film / adhesive / fluorine resin film 7)
  • Fluorine resin film / other resin film / adhesive / EVA Other resin film / Fluorine resin film / Adhesive / EVA 9)
  • the solar cell module backsheet of the present invention is a laminate comprising a layer made of a fluorine resin film
  • the fluorine resin film is made adjacent to the sealing material (for example, EVA) layer directly or via an adhesive layer.
  • a solar cell module may be formed.
  • part in an Example and a comparative example means a mass part.
  • the measuring method of the characteristic of the fluorine resin film in an Example and a comparative example is as follows.
  • the standard deviation of the film thickness was measured by the following method. That is, while producing a fluorine-based resin film having a width of 200 mm and a thickness of 20 ⁇ m by extrusion molding, a table thickness gauge manufactured by Yamabun Denki Co., Ltd. was used, and the width of the film was changed from 200 to 200 in the width direction. Film thickness was measured over 2500 mm in the drawing direction (MD) of the film at a total of three positions (two points) separated by 3 mm. Based on the measurement result, the standard deviation of the film thickness was calculated for each position, and the standard deviation of thickness (unit: ⁇ m) was calculated as the average value of the standard deviation of the film thickness at the three positions.
  • Example 1 A material having the following composition as the fluororesin composition;
  • pigment (1) Titanium oxide [TI-PURE (registered trademark) R101 manufactured by DuPont; Rutile type titanium oxide, average particle size 0.29 ⁇ m, surface-treated product.
  • the pellets are supplied to a single screw extruder (manufactured by Pla Giken Co., Ltd.), melt extruded from a T die at a resin temperature of 240 ° C, and cooled with a cooling roll at a temperature of 90 ° C placed 2 cm below the die outlet.
  • a fluororesin film having a width of 303 mm and a thickness of 20 ⁇ m was produced under production conditions of a take-up speed of 7 m / min.
  • the standard deviation of the thickness of the film and the measurement results of the elongation of the obtained fluororesin film were used to determine the material composition of the fluororesin composition (the total amount is 100% by mass), (a) 100 mass of the fluororesin.
  • Content ratio of (b) pigment and (h) content ratio of other thermoplastic resin relative to parts are shown in Table 1.
  • Example 2 Example (c) Except for changing the content of acrylic rubber-containing methacrylate resin to 5.0% by mass and (h) changing the content of other thermoplastic resins to 12.2% by mass, respectively.
  • a fluororesin film was produced. The standard deviation of the thickness of the film and the measurement results of the elongation of the obtained fluororesin film are shown in Table 1 together with the contents of (b) and (h).
  • Example 3 (A) The content of fluorine resin is changed to 50.2% by mass, (c) the content of acrylic rubber-containing methacrylate resin is changed to 5.0% by mass, and (d) high molecular weight acrylic processing aid.
  • the agent was changed to METABRENE (registered trademark) P-530A manufactured by Mitsubishi Rayon Co., Ltd., with a molecular weight of 3 million (hereinafter sometimes referred to as “auxiliary (2)”).
  • Example except that (e) the content of calcium stearate was changed to 0.1% by mass and (h) the content of other thermoplastic resins was changed to 12.2% by mass
  • a fluororesin film was produced. The standard deviation of the thickness of the film and the measurement results of the elongation of the obtained fluororesin film are shown in Table 1 together with the contents of (b) and (h).
  • Example 4 The content of acrylic rubber-containing methacrylate resin is 6.0% by mass, (d) the content of high molecular weight acrylic processing aid is 1.7% by mass, and (h) other thermoplastic resins.
  • a fluororesin film was produced in the same manner as in Example 1 except that the content of was changed to 10.5% by mass. The standard deviation of the thickness of the film and the measurement results of the elongation of the obtained fluororesin film are shown in Table 1 together with the contents of (b) and (h).
  • Example 5 (A) Content of fluorine resin to 49.0 mass%, (c) Content of acrylic rubber-containing methacrylate resin to 6.0 mass%, (d) Content of high molecular weight acrylic processing aid (E) the content of calcium stearate to 0.2% by mass, and (h) the content of other thermoplastic resins to 10.0% by mass, and (F) Examples except that polyoxyethylene bisphenol A lauric acid ester (Exepar (registered trademark) BP-DL) 1.1% by mass was contained as a polyalkylene glycol fatty acid ester (Kao Corporation). In the same manner as in Example 1, a fluororesin film was produced. The standard deviation of the thickness of the film and the measurement results of the elongation of the obtained fluororesin film are shown in Table 1 together with the contents of (b) and (h).
  • Example 6 The content of acrylic rubber-containing methacrylate resin is 2.0% by mass, (d) the content of high molecular weight acrylic processing aid is 4.9% by mass, and (h) other thermoplastic resins.
  • a fluorine-based resin film was produced in the same manner as in Example 1 except that the content of each was changed to 11.3% by mass. The standard deviation of the thickness of the film and the measurement results of the elongation of the obtained fluororesin film are shown in Table 1 together with the contents of (b) and (h).
  • pigment (2) As a pigment, in addition to 21.0% by mass of the pigment (1), acetylene black [DENKA BLACK (registered trademark) manufactured by Denki Kagaku Kogyo Co., Ltd. Hereinafter, it may be referred to as “pigment (2)”. ] 0.02% by mass (corresponding to 38.1 parts by mass of pigment with respect to 100 parts by mass of PVDF), and (g) 2.5% by mass of heat stabilizer content [ In addition to the calcium carbonate (average particle size 0.15 ⁇ m) manufactured by Shiraishi Kogyo Co., Ltd.
  • Example 8 to 11 The composition of the fluororesin composition was changed to the composition shown in Table 1, and a fluororesin film was produced in the same manner as in Example 1. The standard deviation of the thickness of the film and the measurement results of the elongation of the obtained fluororesin film are shown in Table 1 together with the contents of (b) and (h).
  • thermoplastic resin film (D) Does not contain a high molecular weight acrylic processing aid, and (h) Except that the content of other thermoplastic resin was changed to 16.2% by mass, the same as in Example 6, A fluorine resin film was prepared. The standard deviation of the thickness of the film and the measurement results of the elongation of the obtained fluororesin film are shown in Table 1 together with the contents of (b) and (h).
  • a fluororesin composition containing (b) 25 to 75 parts by mass of pigment with respect to 100 parts by mass of fluororesin, and (C) Contains 1.5 to 15% by weight of acrylic rubber-containing methacrylate resin, (d) 0.8 to 6% by weight of high molecular weight acrylic processing aid, and (e) 0.05 to 1% by weight of calcium stearate
  • Each of the fluorine resin compositions of Examples 1 to 11 has a standard deviation of thickness of 2 ⁇ m or less, and a film having a uniform thickness is obtained without the occurrence of a draw resonance phenomenon. It has been found that both the MD direction and the TD direction have an elongation of 10% or more, and a fluorine-based resin film excellent in various properties suitable for applications such as a back sheet for a solar cell module can be obtained.
  • Example 3 when comparing the fluororesin compositions of Example 2 and Example 3 in which (d) a high molecular weight acrylic processing aid is used with processing aids having slightly different molecular weights (3.1 million and 3 million), Example 3
  • the fluororesin composition of (e) has a smaller standard deviation in thickness than that of the fluororesin composition of Example 2 even when the content of (e) calcium stearate is reduced to 0.1% by mass. It was found that a fluororesin film having a uniform thickness in which generation was further suppressed was obtained. From the results of the respective elongations of the films obtained from the fluororesin compositions of Example 2 and Example 3 (Example 2 has a significantly higher elongation than Example 3). From the viewpoint, it has been inferred that the effect as a molding processing aid and the effect of suppressing the occurrence of the draw resonance phenomenon are not directly linked.
  • the fluorine resin compositions of Comparative Examples 1 and 2 that do not contain a high molecular weight acrylic processing aid have a standard deviation of the film thickness of 1.4 ⁇ m.
  • the standard deviation of thickness exceeds 2 and the occurrence of the draw resonance phenomenon is observed. It was found that it cannot be said that a fluorine-based resin film having excellent characteristics and a uniform thickness can be obtained.
  • the fluorine resin composition of Comparative Example 3 not containing (d) the high molecular weight acrylic processing aid is compared with the fluorine resin composition of Example 1, the fluorine resin composition of Comparative Example 3 is compared.
  • the fluororesin composition of Comparative Example 4 in which the content of the high molecular weight acrylic processing aid is as small as 0.5% by mass has a standard deviation of thickness of 5.3 ⁇ m, and the draw resonance Since the occurrence of the phenomenon was noticeable, it was found that a fluorine resin film having a uniform thickness and excellent properties suitable for applications such as a back sheet for a solar cell module could not be obtained.
  • the fluororesin composition of the comparative example 4 has an effect as a shaping
  • the effect of suppressing the occurrence of the draw resonance phenomenon due to the fluorine resin composition of the present invention comprising (d) the high molecular weight acrylic processing aid is a unique action that cannot be expected as a molding processing aid. It was inferred that this was an effect.
  • the fluorine-based resin composition of Comparative Example 5 in which the content of (d) the high molecular weight acrylic processing aid is as large as 8.1% by mass has a standard deviation of thickness of 5.8 ⁇ m, Since the occurrence of resonance phenomenon is conspicuous, it has been found that a fluorine-based resin film having a uniform thickness and excellent properties suitable for applications such as a back sheet for a solar cell module cannot be obtained.
  • the fluororesin composition of Comparative Example 6 containing no high molecular weight acrylic processing aid and (h) other thermoplastic resin has a standard deviation of thickness of 11.0 ⁇ m, and draw resonance phenomenon It has been found that a fluorine resin film having a uniform thickness and excellent properties suitable for applications such as a back sheet for a solar cell module cannot be obtained.
  • the fluororesin composition of the present invention is (a) a fluororesin composition containing (b) 25 to 75 parts by mass of pigment with respect to 100 parts by mass of fluororesin, and (c) containing acrylic rubber. It contains 1.5 to 15% by mass of a methacrylate resin, (d) 0.8 to 6% by mass of a high molecular weight acrylic processing aid, and (e) 0.05 to 1% by mass of calcium stearate.
  • a draw resin phenomenon does not occur, and the fluorine resin has elongation and other characteristics suitable for applications such as a back sheet for a solar cell module, and has excellent durability. Since a film can be formed efficiently, industrial applicability is high.
  • the fluororesin film formed from the fluororesin composition of the present invention is used as a single film or as a laminate including a layer composed of the fluororesin film for applications such as a back sheet for a solar cell module. Since it is a fluororesin film having suitable elongation and other characteristics and excellent durability, it is highly applicable to the industry.

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Abstract

La présente invention concerne une composition de résine à base de fluor contenant, pour 100 parties en masse de (a) une résine à base de fluor telle que du polyfluorure de vinylidène, de 25 à 75 parties en masse de (b) un pigment tel que de l'oxyde de titane, et également, de 1,5 à 15 % en masse de (c) une résine méthacrylate contenant un caoutchouc acrylique, de 0,8 à 6 % en masse de (d) un adjuvant de traitement acrylique de masse moléculaire élevée et de 0,05 à 1 % en masse de (e) du stéarate de calcium et, le cas échéant, de 0,5 à 2 % en masse de (f) un ester d'acide gras de polyalkylène glycol, de 0,1 à 10 % en masse de (g) un agent de stabilisation thermique et (h) une autre résine thermoplastique telle qu'une résine méthacrylate ; un film de résine qui est formé à partir de cette composition ; et un stratifié et une feuille de support destinés à des modules de cellules solaires, chacun de ceux-ci comprenant une couche qui est formée de ce film de résine.
PCT/JP2014/083537 2014-01-29 2014-12-18 Composition de résine à base de fluor, film de résine, stratifié et feuille de support pour modules de cellules solaires WO2015114983A1 (fr)

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WO2019031378A1 (fr) * 2017-08-08 2019-02-14 パナソニックＩｐマネジメント株式会社 Module de cellule solaire et produit intermédiaire de module de cellule solaire
WO2019127315A1 (fr) * 2017-12-28 2019-07-04 珠海市盛西源机电设备有限公司 Matériau de surface solide acrylique hautement résistant aux taches et son procédé de préparation
CN112635599A (zh) * 2020-12-17 2021-04-09 浙江晶科能源有限公司 一种光伏组件背板用复合膜、光伏组件背板及光伏组件
WO2021117531A1 (fr) * 2019-12-11 2021-06-17 デンカ株式会社 Composition de résine et article moulé utilisant ladite composition
CN115558224A (zh) * 2021-12-29 2023-01-03 嘉兴高正新材料科技股份有限公司 一种光伏用聚偏氟乙烯膜及其制备方法和应用

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JP2011018851A (ja) * 2009-07-10 2011-01-27 Denki Kagaku Kogyo Kk フッ化ビニリデン系樹脂フィルムおよびそれを用いた太陽電池裏面保護シート
WO2012172876A1 (fr) * 2011-06-15 2012-12-20 株式会社クレハ Film de résine de fluorure de polyvinylidène, film multicouche, feuille de fond pour module de cellule solaire, et procédé de fabrication de film
JP2013043964A (ja) * 2011-08-26 2013-03-04 Kuraray Co Ltd アクリル系樹脂組成物よりなるフィルム
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JP2011018851A (ja) * 2009-07-10 2011-01-27 Denki Kagaku Kogyo Kk フッ化ビニリデン系樹脂フィルムおよびそれを用いた太陽電池裏面保護シート
WO2012172876A1 (fr) * 2011-06-15 2012-12-20 株式会社クレハ Film de résine de fluorure de polyvinylidène, film multicouche, feuille de fond pour module de cellule solaire, et procédé de fabrication de film
JP2013043964A (ja) * 2011-08-26 2013-03-04 Kuraray Co Ltd アクリル系樹脂組成物よりなるフィルム
WO2013108816A1 (fr) * 2012-01-17 2013-07-25 電気化学工業株式会社 Feuille multicouches, feuille de support arrière pour cellules solaires et module de cellules solaires

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019031378A1 (fr) * 2017-08-08 2019-02-14 パナソニックＩｐマネジメント株式会社 Module de cellule solaire et produit intermédiaire de module de cellule solaire
WO2019127315A1 (fr) * 2017-12-28 2019-07-04 珠海市盛西源机电设备有限公司 Matériau de surface solide acrylique hautement résistant aux taches et son procédé de préparation
WO2021117531A1 (fr) * 2019-12-11 2021-06-17 デンカ株式会社 Composition de résine et article moulé utilisant ladite composition
JP7560481B2 (ja) 2019-12-11 2024-10-02 デンカ株式会社 樹脂組成物及び当該組成物を用いた成形体
CN112635599A (zh) * 2020-12-17 2021-04-09 浙江晶科能源有限公司 一种光伏组件背板用复合膜、光伏组件背板及光伏组件
CN115558224A (zh) * 2021-12-29 2023-01-03 嘉兴高正新材料科技股份有限公司 一种光伏用聚偏氟乙烯膜及其制备方法和应用

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