WO2011129412A1 - 太陽電池モジュール用バックシートおよび太陽電池モジュール - Google Patents
太陽電池モジュール用バックシートおよび太陽電池モジュール Download PDFInfo
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- WO2011129412A1 WO2011129412A1 PCT/JP2011/059306 JP2011059306W WO2011129412A1 WO 2011129412 A1 WO2011129412 A1 WO 2011129412A1 JP 2011059306 W JP2011059306 W JP 2011059306W WO 2011129412 A1 WO2011129412 A1 WO 2011129412A1
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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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09D123/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
- H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
- H10F19/85—Protective back sheets
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
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- 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
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
Definitions
- the present invention relates to a solar cell module backsheet and a solar cell module having the backsheet.
- a solar cell module consists of a surface layer, a sealing material layer that seals solar cells, and a backsheet.
- a sealing material for forming the sealing material layer a copolymer of ethylene and vinyl acetate (hereinafter referred to as EVA) is usually used.
- EVA ethylene and vinyl acetate
- the back sheet is required to have various characteristics such as mechanical strength, weather resistance, waterproof / moisture resistance, and electrical insulation.
- the structure of a normal back sheet has a multilayer structure, for example, an electric insulating layer / waterproof / moisture proof layer / back surface layer located on the back side of the solar cell in order from the side in contact with the sealing material layer of the solar battery cell. .
- polyvinyl fluoride films are used for the electrical insulation layer and the back layer for reasons such as weather resistance, waterproof / moisture resistance, and electrical insulation, and polyethylene terephthalate (ethylene glycol) is used for the base sheet. And terephthalic acid copolymer, hereinafter referred to as PET).
- PET terephthalic acid copolymer
- a vapor deposition layer of a metal compound such as silica or a metal layer such as an aluminum foil is provided on the surface of the base sheet.
- the thickness of the back sheet is usually 20 to 100 ⁇ m in order to satisfy the required characteristics and various required characteristics such as durability and light shielding properties.
- demands for weight reduction and thinning have been made.
- a solar cell module back sheet has been proposed in which a cured coating film of a curable functional group-containing fluoropolymer coating is formed on at least one surface of a water-impermeable sheet (Patent Document 1).
- a curable tetrafluoroethylene (TFE) copolymer (Zeffle GK570, a trademark of Daikin Industries, Ltd.) is disclosed as the curable functional group-containing fluorine-containing polymer.
- TFE tetrafluoroethylene
- Zeffle GK570 a trademark of Daikin Industries, Ltd.
- the coating film of the curable functional group-containing fluorine-containing polymer paint has insufficient flexibility, adhesion to the substrate, and bending resistance, the coating film is cracked or cracked, It has been found that there are problems such as whitening and peeling, and problems of color unevenness due to poor dispersibility and poor curing due to poor dispersion of the hardener due to low dispersibility of pigments and hardeners.
- the adhesion of the coating film to the substrate is excellent, and there is a problem of cracks and cracks.
- a back sheet for a solar cell module that is light and excellent in productivity without causing any occurrence.
- the coating film of the coating composition containing the specific fluorine-containing copolymer (A) as an essential component on at least one side of the base sheet is the flexibility of the coating film, And it discovered that it was especially excellent in adhesiveness with a base material, and came to complete this invention. That is, the present invention includes the following [1] to [11].
- Fluorine-containing copolymer (A) having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene on at least one side of the substrate sheet, and a melting point of the fluorine-containing copolymer (A) or less
- the solar cell module backsheet which has the coating film formed from the composition for a coating containing the solvent which can melt
- the fluorine-containing copolymer (A) in the coating composition is obtained by precipitating from a solution in which the fluorine-containing polymer (A) is dissolved in the solvent.
- the solar cell module backsheet as described.
- the proportion of repeating units of monomers other than tetrafluoroethylene and ethylene in all repeating units in the fluorinated copolymer (A) is 0.1 to 30 mol% [1] or [2 ]
- the crosslinkable group is at least one selected from the group consisting of a carboxyl group, an acid anhydride group, and a carboxylic acid halide group.
- a back sheet for a solar cell module that is particularly excellent in adhesiveness, does not cause problems of cracks and cracks, is lightweight, and has excellent productivity. Moreover, the solar cell module provided with this back sheet is obtained.
- Sectional drawing of embodiment of the solar cell module of this invention Sectional drawing of embodiment by which the metal layer was provided among the solar cell modules of this invention. Sectional drawing of embodiment by which EVA layer was provided among the solar cell modules of this invention
- a repeating unit obtained directly by polymerization and a repeating unit obtained by further reacting the repeating unit obtained directly by polymerization are collectively referred to as “unit”.
- back sheet for a solar cell module of the present invention is a coating composition containing a fluorine-containing copolymer (A) on at least one side of a base sheet ( Hereinafter, it may be simply referred to as “coating composition”.
- the fluorinated copolymer (A) is not particularly limited as long as it is a fluorinated copolymer containing a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene.
- a fluorine-containing copolymer specifically, a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene (hereinafter sometimes referred to as “TFE”) are mainly contained in the copolymer. ETFE, etc., which is a simple repeating unit.
- ETFE may include a repeating unit based on a comonomer other than TFE and ethylene as a constituent unit of the copolymer. It is used as a general term for fluorine-containing copolymers having repeating units.
- the molar ratio of the repeating unit based on TFE / the repeating unit based on ethylene is preferably 70/30 to 30/70, more preferably 65/35 to 40/60. Most preferably, those of 60/40 to 40/60 are mentioned.
- the fluorine-containing copolymer (A) in the present invention includes a repeating unit based on a comonomer other than these in addition to TFE and ethylene in order to add various functions to the obtained copolymer. It is preferable that As a comonomer used with such TFE and ethylene, a monomer having no crosslinkable group (hereinafter referred to as “non-crosslinkable monomer”) and a monomer having a crosslinkable group (hereinafter referred to as “non-crosslinkable monomer”). And “crosslinkable monomer”).
- the crosslinkable group may contribute to adhesion to the substrate when chemically bonded to the substrate or interacts by hydrogen bonding or the like.
- chloroolefins such as vinyl chloride and vinylidene chloride.
- fluoroolefins particularly CF 2 ⁇ CH 2 is preferable from the viewpoint of improving the solubility of the fluorinated copolymer (A) in a solvent.
- polyfluoroalkylethylene particularly CF 3 CF 2 CF 2 CF 2 CH ⁇ CH 2 is preferred.
- These non-crosslinkable monomers may be used alone or in combination of two or more.
- crosslinkable group possessed by the crosslinkable monomer examples include a hydroxy group, a carboxylic acid group, a residue obtained by dehydration condensation of two carboxy groups in one molecule (hereinafter referred to as “acid anhydride group”), and a sulfonic acid group.
- acid anhydride group a residue obtained by dehydration condensation of two carboxy groups in one molecule
- sulfonic acid group Epoxy group, cyano group, carbonate group, isocyanate group, ester group, amide group, aldehyde group, amino group, hydrolyzable silyl group, carbon-carbon double bond, carboxylic acid halide group.
- the carboxylic acid group is a carboxy group or a salt thereof (—COOM 1 : M 1 is a metal atom or atomic group capable of forming a salt with a carboxylic acid), and the sulfonic acid group is a sulfo group or a salt thereof (— SO 3 M 2 : M 2 means a metal atom or atomic group capable of forming a salt with sulfonic acid. Most preferably, it is at least one selected from the group consisting of a hydroxy group, a carboxylic acid group, an acid anhydride group, and a carboxylic acid halide group.
- Examples of the crosslinkable monomer include a monomer having a hydroxyl group, an acid anhydride, a monomer having a carboxyl group, and a monomer having an epoxy group.
- Examples of the monomer having a hydroxyl group include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxy
- Examples include hydroxyl group-containing vinyl ethers such as pentyl vinyl ether and 6-hydroxyhexyl vinyl ether; and hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.
- hydroxyl group-containing vinyl ethers particularly 4-hydroxybutyl vinyl ether or 2-hydroxyethyl vinyl ether, are more preferable because they are easily available, have high polymerization reactivity, and have excellent crosslinkability of the crosslinkable group.
- the acid anhydride include itaconic anhydride, maleic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, and the like. Of these, itaconic anhydride is preferred.
- monomers having a carboxyl group acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, undecylenic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, phthalic acid
- unsaturated monocarboxylic acids such as vinyl
- unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid
- unsaturated dicarboxylic acid esters such as itaconic acid monoester, maleic acid monoester and fumaric acid monoester .
- Examples of the monomer having an epoxy group include monomers having an epoxy group such as glycidyl vinyl ether and glycidyl allyl ether. Among these, a monomer having a hydroxyl group or an acid anhydride is preferable from the viewpoint of obtaining a coating film having high hardness and enhancing the adhesion to the substrate.
- These crosslinkable monomers may be used alone or in combination of two or more. That is, two or more different types of crosslinkable groups may exist in one molecule of the fluorinated copolymer (A).
- the content ratio is preferably relative to all the monomer repeating units of the fluorine-containing copolymer (A). It is 0.1 to 10 mol%, more preferably 0.1 to 5 mol%.
- the total content is the total amount of the fluorine-containing copolymer (A).
- the amount is preferably 0.1 to 30 mol%, more preferably 0.1 to 25 mol%, still more preferably 0.1 to 20 mol%, and most preferably 0.1 to 30 mol% with respect to the body repeating unit. 1 to 15 mol%.
- the upper limit may be 50 mol% and a repeating unit based on a comonomer other than TFE and ethylene may be contained.
- the fluorine-containing copolymer (A) used for the coating composition in the present invention when the content of the repeating unit based on a comonomer other than TFE and ethylene is within this range, the composition is substantially composed of only TFE and ethylene. It is possible to impart functions such as high solubility, water repellency, oil repellency, curability and adhesion to a substrate without impairing the properties of ETFE.
- the fluorinated copolymer (A) used for the coating composition in the present invention has the crosslinkable group as a molecular group.
- the main chain or side chain is preferred.
- the crosslinkable group may be present at either the molecular end, the side chain or the main chain of the fluorine-containing copolymer (A).
- crosslinked group may be used individually by 1 type in the fluorine-containing copolymer (A), and 2 or more types may be used together.
- the type and content of the functional group having adhesiveness to the base material are appropriately determined depending on the type, shape, application, required adhesiveness, adhesion method, functional group introduction method, etc. of the base material on which the coating composition is applied. Selected.
- the coating composition in the present invention is a comonomer essential for the production of the fluorine-containing copolymer as the fluorine-containing copolymer (A) having the repeating unit based on ethylene and the repeating unit based on TFE. It is possible to use a copolymer obtained by copolymerizing certain ethylene and TFE with other comonomer described above which may optionally be included, but use what is obtained as a commercial item. You can also.
- one of these fluorine-containing copolymers (A) can be used alone, or two or more of them can be used in combination.
- the coating composition in the present invention contains a solvent together with the fluorine-containing copolymer (A).
- the solvent used for the coating composition in the present invention is a solvent capable of dissolving the fluorine-containing copolymer (A) at a temperature not higher than the melting point of the fluorine-containing copolymer (A). Furthermore, when the fluorine-containing copolymer (A) is precipitated from a solution in which the fluorine-containing copolymer (A) is dissolved in this solvent, the dispersion state can be maintained at least at normal temperature and pressure. Is preferred.
- the solvent used in the present invention various solvents can be mentioned as long as they meet the above conditions.
- the polarity of the solvent is preferably within a specific range.
- the following method is used, in which a solvent that satisfies the above conditions is selected as a solvent having a certain range of polarity based on Hansen solubility parameters (Hansen solubility parameters).
- the Hansen solubility parameter is obtained by dividing the solubility parameter introduced by Hildebrand into three components: a dispersion term ⁇ d, a polar term ⁇ p, and a hydrogen bond term ⁇ h, and representing it in a three-dimensional space.
- the dispersion term ⁇ d indicates the effect due to the dispersion force
- the polar term ⁇ p indicates the effect due to the force between the dipoles
- the hydrogen bond term ⁇ h indicates the effect due to the hydrogen bond force.
- Hansen solubility parameter The definition and calculation of the Hansen solubility parameter is described in CharlesCM. Hansen, Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007).
- the Hansen solubility parameter can be easily estimated by using the computer software Hansen Solubility Parameters in Practice (HSPiP).
- HSPiP Hansen Solubility Parameters in Practice
- the Hansen solubility parameter of a particular polymer can be determined by conducting a test to measure the solubility of a sample of the polymer in a number of different solvents for which the Hansen solubility parameter has been established. Specifically, a sphere in which all three-dimensional points of the solvent in which the polymer is dissolved among the solvents used in the solubility test are included inside the sphere, and the non-dissolved solvent points are outside the sphere. (Solubility sphere) is found and the center coordinate of the sphere is used as the Hansen solubility parameter of the polymer.
- the point indicated by the coordinates is the polymer. If it is encapsulated inside the solubility sphere, the solvent is considered to dissolve the polymer. On the other hand, if the coordinate point is outside the solubility sphere of the polymer, it is considered that this solvent cannot dissolve the polymer.
- the Hansen solubility parameter is used to dissolve the fluorine-containing copolymer (A) contained in the coating composition at a temperature below its melting point.
- a solvent group at a certain distance from the coordinates (15.7, 5.7, 4.3), which is the Hansen solubility parameter, is preferred with reference to diisopropyl ketone, which is an optimal solvent for dispersing the coalescence (A) as fine particles. It can be used as a solvent.
- R which is a value based on the Hansen solubility parameter represented by the following formula (1), was used as a solubility index for the fluorine-containing copolymer (A).
- R 4 ⁇ ( ⁇ d ⁇ 15.7) 2 + ( ⁇ p ⁇ 5.7) 2 + ( ⁇ h ⁇ 4.3) 2 (1)
- ⁇ d, ⁇ p, and ⁇ h represent a dispersion term, a polar term, and a hydrogen bond term in the Hansen solubility parameter, respectively, and the unit is (MPa) 1/2 .
- the solvent used in the present invention preferably has a solubility index (R) calculated by the above formula (1) of less than 25 using Hansen solubility parameter coordinates ( ⁇ d, ⁇ p, ⁇ h) of the solvent, and less than 16. More preferably.
- R solubility index
- a solvent having a Hansen solubility parameter in which R represented by the above formula (1) falls within this range has high affinity with the fluorine-containing copolymer (A), and the solubility and fluorine-containing copolymer (A) are High dispersibility in the case of fine particles.
- the value of R calculated based on the Hansen solubility parameter by the above formula (1), whether it is a solvent composed of one compound or a mixed solvent of two or more compounds, , And can be used as a solubility index for the fluorinated copolymer (A).
- a solubility index for the fluorinated copolymer (A) can be calculated using the Hansen solubility parameter.
- the boiling point of the solvent used in the present invention is preferably 210 ° C. or less, and more preferably 180 ° C. or less, from the viewpoints of handleability and solvent removal after coating. Further, if the boiling point of the solvent is too low, for example, there is a problem that bubbles are likely to be generated at the time of evaporation removal (hereinafter also referred to as drying) of the solvent after coating the composition. More preferably, it is 80 ° C. or higher.
- ketones having 3 to 10 carbon atoms, esters, carbonates, ethers and the like are preferable, and ketones and esters having 5 to 9 carbon atoms are more preferable.
- Specific examples include methyl ethyl ketone, 2-pentanone, methyl isopropyl ketone, 2-hexanone, methyl isobutyl ketone, pinacholine, 2-heptanone, 4-heptanone, diisopyrrole ketone, isoamyl methyl ketone, 2-octanone, 2-nonanone.
- the above solvents may be used alone or in admixture of two or more as long as they satisfy the above conditions of the present invention. Moreover, as long as the said conditions are satisfy
- the value of the solubility index (R) in the mixed solvent calculated from the Hansen solubility parameter of each solvent constituting the mixed solvent and the mixing ratio thereof is preferably less than 25, more preferably The blending amount is appropriately adjusted so as to be less than 16.
- the fluorine-containing copolymer (A) contained in the coating composition in the present invention may be present in a dissolved state, but is preferably present in a state dispersed in a solvent described below. .
- the fluorine-containing copolymer (A) is a fluorine-containing copolymer precipitated from a solution dissolved in a solvent described below. It is preferable that it is a coalescence (A).
- the fluorine-containing copolymer (A) is dispersed in the solvent in the form of fine particles by being precipitated from a solution dissolved in the solvent.
- the average particle size of the fine particles of the fluorinated copolymer (A) is preferably in the range of 0.005 to 2 ⁇ m as an average particle size measured by a small angle X-ray scattering method at 20 ° C. More preferably, it is 0.005 to 1 ⁇ m.
- the coating composition of the present invention if the average particle size of the fine particles of the fluorinated copolymer (A) is within this range, a coating film that is homogeneous and excellent in transparency, flatness, and adhesion can be formed. it can.
- the content of the fluorinated copolymer (A) in the coating composition in the present invention can be appropriately changed according to the film thickness of the target molded product.
- the content of the fluorinated copolymer (A) is preferably from 0.05 to 30% by mass, more preferably from 0.1 to 20% by mass, based on the total amount of the composition. When the content is within this range, it is excellent in handling properties such as viscosity, drying speed and film uniformity, and a homogeneous coating film comprising the fluorine-containing copolymer (A) can be formed.
- the content of the solvent in the coating composition in the present invention is preferably from 70 to 99.95% by mass, preferably from 80 to 99%, based on the total amount of the composition, from the viewpoint of moldability when a molded product is obtained using this. More preferably, it is 9% by mass.
- the coating composition is excellent in handleability at the time of application in coating film preparation, and the obtained coating film containing the fluorinated copolymer (A) is homogeneous and uniform. It can be.
- the method for producing a coating composition in the present invention preferably includes the following steps (1) and (2).
- a fluorine-containing copolymer (A) having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene is obtained at a temperature not higher than the melting point of the fluorine-containing copolymer (A).
- a step of dissolving (A) in a soluble solvent to form a solution hereeinafter referred to as “dissolution step”.
- a step of precipitating the fluorine-containing copolymer (A) as fine particles in the solvent in the solution to make the solution a dispersion in which the fine particles are dispersed in the solvent hereinafter referred to as “precipitation step”).
- the solvent used in the dissolution step is a solvent that satisfies the above conditions, that is, a solvent that can dissolve this fluorine-containing copolymer at a temperature not higher than the melting point of the fluorine-containing copolymer (A). Further, when the precipitation step is carried out to precipitate the fine particles of the fluorine-containing copolymer (A) from the solution in which the fluorine-containing copolymer is dissolved in this solvent, the solvent used is at least at room temperature and normal pressure. It is preferable that the fluorinated copolymer (A) can be stably dispersed as fine particles.
- the temperature, pressure, stirring, and other conditions in the dissolution step are not particularly limited as long as the fluorine-containing copolymer (A) is dissolved in the solvent, but the temperature conditions in the dissolution step are used.
- the temperature is preferably lower than the melting point of the fluorinated copolymer (A). Since the melting point of the fluorinated copolymer (A) used in the present invention is the highest and is approximately 275 ° C., the temperature of the step of dissolving it in the solvent is approximately 275 ° C. or less. preferable.
- the temperature at which the fluorinated copolymer (A) is dissolved in the solvent is more preferably 230 ° C. or less, and particularly preferably 200 ° C. or less.
- 0 degreeC is preferable and 20 degreeC is more preferable. If the temperature of the melting step is less than 0 ° C., a sufficient dissolved state may not be obtained, and if it exceeds 275 ° C., it may not be easily performed when performing actual work.
- conditions other than temperature are not particularly limited, and it is usually carried out under conditions of slight pressure of about normal pressure to about 0.5 MPa. Is preferred.
- conditions of slight pressure of about normal pressure to about 0.5 MPa.
- the type of the fluorine-containing copolymer (A) and the solvent when the boiling point of the solvent is lower than the temperature of the dissolution step, etc., in the pressure vessel, at least naturally occurring pressure or less, preferably 3 MPa or less, more preferably 2 MPa or less. More preferably, there is a method of dissolving under conditions of 1 MPa or less, most preferably under conditions of normal pressure or less, but in general, dissolution can be carried out under conditions of about 0.01 to 1 MPa. .
- the dissolution time depends on the content of the fluorinated copolymer (A) in the coating composition of the present invention, the shape of the fluorinated copolymer (A), and the like.
- the shape of the fluorine-containing copolymer (A) used is preferably in the form of a powder in terms of work efficiency for shortening the dissolution time, but in other shapes such as a pellet because of its availability. It is also possible to use.
- the dissolution means in the dissolution step is not special and may be a general method.
- the necessary amount of each component to be blended in the coating composition is weighed, preferably at a temperature not lower than the melting point of the fluorine-containing copolymer used at 0 ° C. or higher, more preferably 0 to 230 ° C., particularly preferably 20 to 200 ° C.
- These components may be mixed uniformly at a temperature of 1 and dissolved in the solvent.
- it is preferable in terms of efficiency to carry out the dissolution using a general stirring mixer such as a homomixer, a Henschel mixer, a Banbury mixer, a pressure kneader, a single screw or twin screw extruder.
- mixing and heating of various raw material components may be performed simultaneously, or after mixing various raw material components, heating may be performed while stirring as necessary.
- an apparatus such as an autoclave with a stirrer can be used.
- a marine propeller blade, a paddle blade, an anchor blade, a turbine blade, or the like is used.
- a magnetic stirrer or the like may be used.
- a composition containing the fluorine-containing copolymer (A) in a state dissolved in a solvent by a dissolution step can be used without performing a precipitation step.
- the fluorine-containing copolymer (A) is precipitated in the solvent from a solution obtained by dissolving the fluorine-containing copolymer (A) obtained in the dissolution step (1) in the solvent. Under conditions, generally, the fluorinated copolymer (A) is precipitated in the solvent by being kept at normal temperature and pressure. Specifically, when the (1) dissolution step is performed under heating, the resulting solution is cooled to a temperature not higher than the temperature at which the fluorinated copolymer (A) precipitates, usually to room temperature. Fine particles of the fluorine-containing copolymer (A) can be precipitated in the solvent. In this case, the cooling method is not particularly limited, and may be slow cooling or rapid cooling.
- the fluorine-containing copolymer (A) is usually precipitated as fine particles, and a composition in which the fine particles are dispersed in the solvent is obtained.
- the average particle size of the fluorine-containing copolymer (A) fine particles precipitated in the precipitation step is in the range of 0.005 to 2 ⁇ m as an average particle size measured by a small angle X-ray scattering method at 20 ° C. Preferably, it is 0.005 to 1 ⁇ m.
- the coating composition in the present invention can contain other optional components as needed within a range not impairing the effects of the present invention.
- optional components include a curing agent, a curing accelerator, an adhesion improver, a surface conditioner, an antioxidant, a light stabilizer, an ultraviolet absorber, a crosslinking agent, a lubricant, a plasticizer, a thickener, and a mat.
- Various additives such as an agent, a dispersion stabilizer, a filler (filler), a reinforcing agent, a leveling agent, a pigment, a dye, a flame retardant, an antistatic agent, and other resins.
- content of these arbitrary components which do not impair the effect of this invention content of 30 mass% or less can be mentioned with respect to the coating composition whole quantity.
- the coating composition in the present invention includes a step of dissolving the fluorine-containing copolymer (A) in a solvent to form a solution, the above additives are added as necessary as compared with a method such as melt-kneading. In large quantities and evenly. In addition, if a coating composition containing such an additive at a high concentration is used, a necessary function can be exerted with a thinner film thickness. Therefore, the fluorine-containing copolymer (A) The amount used can be reduced.
- a curing agent to cure the paint, but depending on the type of the crosslinkable group, it can be cured only by drying, so there is a case where addition of the curing agent is unnecessary. What is necessary is just to select a hardening
- curing agent suitably with the crosslinkable group contained in a fluorine-containing copolymer (A).
- the crosslinkable group is a hydroxyl group
- an isocyanate curing agent, a melamine resin, a silicate compound, an isocyanate-containing silane compound, or the like is selected.
- an amino curing agent or an epoxy curing agent is selected.
- a carbonyl-containing curing agent, an epoxy curing agent, and an acid anhydride curing agent are selected
- a carboxyl group is selected
- an isocyanate group a hydroxyl group is selected.
- Crosslinkable groups that do not require a curing agent include hydrolyzable silyl groups.
- a polyisocyanate is preferable as the curing agent, and among them, a non-yellowing polyisocyanate or a modified product of a non-yellowing polyisocyanate is more preferable.
- a non-yellowing modified polyisocyanate IPDI (isophorone diisocyanate), HMDI (hexamethylene diisocyanate), HDI (hexane diisocyanate), or a modified product thereof is preferable.
- modified products include epsilon caprolactam (E-CAP), methyl ethyl ketone oxime (MEK-OX), methyl isobutyl ketone oxime (MIBK-OX), pyraridine or triazine (TA), blocked isocyanate groups, and polyisocyanates
- E-CAP epsilon caprolactam
- MEK-OX methyl ethyl ketone oxime
- MIBK-OX methyl isobutyl ketone oxime
- TA triazine
- blocked isocyanate groups and polyisocyanates
- a uretdione bond and the like are preferably coupled.
- the curing accelerator for example, tin-based, other metal-based, organic acid-based, and amino-based curing accelerators can be used.
- the adhesion improver is not particularly limited, and for example, a silane coupling agent can be preferably used.
- silane coupling agents include aminoalkyls such as 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and ureidopropyltriethoxysilane.
- Silanes are preferred.
- Unsaturated alkylsilanes such as vinyltriethoxysilane, vinyltrimethoxysilane, 3- (trimethoxysilyl) propyl (meth) acrylate, 3- (triethoxysilyl) propyl (meth) acrylate;
- 2- Epoxysilanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, methyltriethoxy Orchids, methyl trimethoxy silane are preferred.
- the pigment has an effect of improving the aesthetics of the back sheet or increasing the light utilization efficiency by reflecting light.
- titanium oxide as a white pigment, calcium carbonate, carbon black as a black pigment, and composite metals are added.
- white pigment titanium oxide is known to decompose and degrade a coating film containing the pigment by photocatalysis. Therefore, as titanium oxide, in order from the inside, particles containing titanium oxide, a first coating layer containing cerium oxide covering the outside of the particles, and a second coating containing silicon oxide covering the outside of the first coating layer It is preferable to use a composite particle including a layer.
- the composite particle may have another coating layer inside or outside the cerium oxide coating layer and the silicon oxide coating layer. For example, it is preferable to have a silicon oxide coating layer between a particle containing titanium oxide and a first coating layer containing cerium oxide covering the outside of the particle.
- a metal compound different from the metal compound constituting the coating layer to the outermost coating layer of the composite particles according to the required characteristics of the composite particles.
- a metal compound different from the metal compound constituting the coating layer it is preferable to add zirconia for the purpose of hardening and preventing the pigment from collapsing, or alumina for the purpose of improving the hydrophilicity and improving the dispersibility.
- the outermost layer of the composite particles is the second layer containing the silicon oxide, it is preferable to add the zirconia and alumina to the silicon oxide.
- the amount in the case where a metal compound different from the metal compound constituting the coating layer is added to the coating layer is preferably 10 to 50% by mass, preferably 20 to 30% by mass with respect to the total mass of the metal compound constituting the coating layer. % Is more preferable.
- leveling agent for example, polyether-modified polydimethylsiloxane and polyether-modified siloxane are preferable.
- an ultraviolet absorber to the coating material containing the fluorinated copolymer (A) as an essential component to impart an ultraviolet absorbing function to the coating film.
- an ultraviolet absorber both organic and inorganic ultraviolet absorbers can be used. Examples of organic compound systems include salicylic acid ester systems, benzotriazole systems, benzophenone systems, cyanoacrylate systems, and external line absorbers, and inorganic systems include filler-type inorganic UV absorbers such as titanium oxide, zinc oxide, and cerium oxide. Etc. are preferable.
- titanium oxide When titanium oxide is used as the ultraviolet absorber, it is preferable to use titanium oxide as the composite particles.
- An ultraviolet absorber may be used individually by 1 type, and may be used in combination of 2 or more type.
- the amount of the ultraviolet absorber is preferably 0.1 to 15% by mass with respect to the total solid content of the fluorine-containing copolymer (A) in the coating. When the amount of the ultraviolet absorber is too small, the effect of improving the light resistance cannot be sufficiently obtained, and when the amount is too large, the effect is saturated.
- Examples of the light stabilizer include hindered amine-based light stabilizers and the like.
- Adekastab LA62, Adekastab LA67 (above, manufactured by Adeka Argus Chemical Co., Ltd., trade name), Tinuvin 292, Tinuvin 144, Tinuvin 123, Tinuvin 440 (above, Ciba Specialty Chemicals, trade name) and the like are preferable.
- the light stabilizer may be used alone or in combination of two or more kinds, and may be used in combination with an ultraviolet absorber.
- Examples of the thickener include a polyurethane-based associative thickener.
- As the matting agent a conventional inorganic or organic matting agent such as ultrafine powdered synthetic silica can be used.
- Other resins include non-fluorinated resins such as acrylic resins, polyester resins, acrylic polyol resins, polyester polyol resins, urethane resins, acrylic silicone resins, silicone resins, alkyd resins, epoxy resins, oxetane resins, amino resins, etc. It is done.
- the other resin may be a resin having a crosslinkable group and cured by being crosslinked by a curing agent.
- the content of the other resin is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the fluorinated copolymer (A).
- the concentration of the fluorinated copolymer (A) in the coating composition prepared as described above is preferably 1 to 50% by mass relative to the total mass of the paint.
- the material of the base sheet is not particularly limited, and polyolefins such as polyethylene and polypropylene; polyvinyl halides such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, and polyvinylidene fluoride; polyesters such as PET and polybutylene terephthalate Polyamides such as nylon 6, nylon 66 and MXD nylon (metaxylenediamine / adipic acid copolymer); polymers of olefins having substituents such as polyvinyl acetate, polyvinyl alcohol, and polymethyl methacrylate; EVA, A copolymer such as an ethylene / vinyl alcohol copolymer can be used. Among these, PET, EVA, polyvinyl alcohol, polyvinylidene chloride, nylon 6, nylon 66, or ethylene / vinyl alcohol copolymer is preferable.
- the back sheet of the present invention has a coating film and a base sheet, it has water and moisture resistance. However, higher waterproofness and moisture proofing may be required depending on the usage conditions of the solar cell.
- a layer hereinafter referred to as a “metal layer” consisting of a metal or a metal compound (hereinafter collectively referred to as “metals”) on one or both sides of the base sheet. It is preferable to provide a water-impermeable sheet.
- a metal layer can be provided by vapor-depositing a metal or a metal compound on the surface of a base material sheet, or bonding a metal or metal compound foil with an adhesive. The foil and the base sheet are preferably bonded via an adhesive layer formed by an adhesive.
- the metals those having excellent waterproof and moisture resistance and high corrosion resistance are preferable.
- the metal when providing a metal layer by vapor deposition, it can further select from the metal which can be vapor-deposited.
- the metal include a metal selected from the group consisting of silicon, magnesium, zirconium, zinc, tin, nickel, titanium, and aluminum, a compound of the metal, and stainless steel.
- silicon, aluminum, aluminum oxide, silicon oxide, silicon nitride oxide, or silicon nitride is preferable.
- one kind of metal may be used, or two or more kinds of metals may be used in combination.
- the metal when the metal foil is bonded with an adhesive aluminum, titanium, or stainless steel is preferable.
- the back sheet of this invention has the coating film formed from the composition for a coating which uses the said fluorine-containing copolymer (A) as an essential component on the single side
- the surface on the solar cell side of the base sheet is referred to as an inner surface
- the surface opposite to the solar cell is referred to as an outer surface.
- FIG. 1 shows an embodiment in which the coating film 5 is formed on one side of the base sheet 4, and the case where the coating film 5 is formed on the outer side is shown in FIG.
- the coating film is preferably formed only on the outer surface of the base sheet. That is, the preferred backsheet configuration is the base sheet and the configuration shown in FIG. 1-1 where the coating film is laminated on the outer surface of the base sheet.
- the base sheet has the metal layer 6, it is provided on one or both surfaces of the base sheet 4, but is usually provided only on one side from the economical viewpoint.
- the metal layer 6 is provided on the outer surface of the base sheet where moisture of the base sheet may enter (FIG. 2 (2-1). ) And FIG. (2-2) are preferred.
- the structure of the preferable back sheet in the case of having the metal layer 6 includes the base material sheet 4, the metal layer 6 laminated on the outer surface of the base material sheet, and the coating film 5 laminated on the outer surface of the metal layer. This is the configuration shown in FIG.
- a cured coating film may be directly formed, or a coating film may be formed after forming a primer layer.
- a coating composition containing the fluorine-containing copolymer (A) as an essential component is directly applied.
- a coating composition for primer is applied to the surface of a base sheet that may have a metal layer, and then a coating composition containing the fluorine-containing copolymer (A) as an essential component. Is preferably applied.
- the primer paint include epoxy resin, urethane resin, acrylic resin, silicone resin, and polyester resin.
- another polymer (hereinafter, also referred to as polymer (B)) layer 7 may be laminated on the outermost surface in contact with the inner side sealing material layer.
- the other polymer layer is preferably a layer made of a polymer different from the coating film, and polymers exemplified in the material of the base sheet can be employed.
- an EVA layer capable of improving the adhesiveness with a resin (hereinafter referred to as a sealing resin) that seals solar cells is preferable.
- the polymer layer may be provided directly on the base sheet of the back sheet, or provided on another layer through another layer such as a coating film between the polymer sheet and the base sheet. It may be done.
- FIG. 3 an embodiment in which the EVA layer 7 is provided on the surface in contact with the sealing material layer 2 on the inner side surface is shown in FIG. 3, which is shown in FIGS. 1-1 and 1-2, respectively.
- the backsheet include the embodiments shown in FIGS. (3-1) and (3-2) in which an EVA layer is formed on the surface of the inner surface in contact with the sealing material layer.
- the metal layer 6 may be provided on one side or both sides of the base sheet 4, and the metal layer 6 is preferably provided only on the outer side of the base sheet.
- an adhesive layer may be provided.
- an adhesive bond layer is provided between the base material sheet and metal foil in the case of forming the metal layer which consists of metal foil on the surface of a base material sheet.
- lifted is mention
- an adhesive layer may be provided on one side or both sides, preferably one side, of the other polymer (B) layer.
- an adhesive layer is preferably provided on the surface of the EVA layer opposite to the surface in contact with the sealing material layer.
- the other polymer layer is EVA and the encapsulant layer is made of EVA, they can be bonded together by pressure bonding.
- the adhesive can be appropriately changed depending on the material of the layer to be laminated, and examples thereof include polyester adhesives, acrylic adhesives, urethane adhesives, epoxy adhesives, polyamide adhesives, and polyimide adhesives.
- other layers may be formed on the surfaces described above, on the surface in contact with the sealing material, and on the outermost surface, if necessary.
- the back sheet of the present invention preferably has high electrical insulation.
- the layer constituting the back sheet is a layer made of a low dielectric constant material.
- an adhesive having a low dielectric constant is preferably used for the adhesive layer, and an epoxy adhesive, a polyamide adhesive, and a polyimide adhesive are more preferable from the viewpoint of low dielectric constant.
- the dielectric constant depends on the required characteristics of the solar cell module, the dielectric constant is preferably 3.5 or less, more preferably 3.3 or less, and most preferably 3.0 or less.
- the dielectric constant of the present invention is a value measured by a method according to JIS C-2151, and is a measured value at 23 ° C. and a frequency of 1 kHz.
- each layer constituting the backsheet can be appropriately changed according to the required performance.
- the coating film of the paint containing the fluorine-containing copolymer (A) as an essential component is preferably 1 to 75 ⁇ m.
- the metal layer is preferably 0.01 to 50 ⁇ m.
- the substrate sheet is preferably 25 to 200 ⁇ m.
- the other polymer (B) layer is preferably 50 to 200 ⁇ m.
- the adhesive layer is preferably 0.1 to 25 ⁇ m.
- the total film thickness of the backsheet of the present invention is preferably 30 to 300 ⁇ m.
- the backsheet of this invention comprises a solar cell module in combination with a photovoltaic cell.
- a surface sheet, a sealing layer in which solar cells are sealed with a resin, and a back sheet are sequentially laminated to form a solar cell module.
- an adhesive layer may be provided when the adhesion is insufficient in the lamination.
- a glass substrate is usually used, but a flexible material such as a resin sheet may be used for the top sheet. Since the back sheet of the present invention has a small film thickness and can be reduced in weight, it can be suitably used for a flexible solar cell.
- ETFE1 Coating Composition (A1) ⁇ Coating composition (A1)>
- ETFE1 Constituent monomer and molar ratio: tetrafluoroethylene / ethylene / hexafluoropropylene / 3,3,4,4,5,5 was used as the fluorine-containing copolymer (A).
- the average particle diameter of the fine particles of ETFE1 was 20 nm as an average particle diameter measured at 20 ° C. by the small angle X-ray scattering method. Further, when this dispersion was diluted to 0.05% by weight and observed with a transmission electron microscope, it was confirmed that the primary particle diameter was 20-30 nm.
- This dispersion was applied to a glass substrate by potting at room temperature and air-dried, and then heated and dried on a hot plate at 120 ° C. for 5 minutes to obtain a glass substrate on which a thin film of ETFE1 was formed.
- a glass substrate on which a thin film of ETFE1 was formed.
- the obtained thin film was observed with an optical microscope (50 times), it was confirmed to be a uniform and smooth film. Moreover, it was 3 micrometers when the film thickness was measured with the stylus type surface shape measuring device.
- the adhesion of the obtained ETFE1 film was evaluated, no peeling was observed.
- a sodium hydroxide solution was added to the aqueous dispersion, the solution was neutralized to pH 7 to 9, and cerium hydroxide was deposited on the surface of the titanium oxide pigment.
- the liquid containing the cerium hydroxide-coated particles was filtered, and the cerium hydroxide-coated particles were washed with water and dried.
- the lump of cerium hydroxide-coated particles was pulverized to obtain cerium hydroxide-coated particles.
- the cerium hydroxide-coated particles were added to 10 liters of pure water and dispersed for 1 hour with Desperm to obtain an aqueous dispersion. While the aqueous dispersion was heated to 80 ° C. and stirred, 348 g of No. 3 sodium silicate (silicon content: 28.5% by mass in terms of SiO 2 ) was added to the aqueous dispersion. At this time, dilute sulfuric acid is also added to maintain the pH of the liquid at 9 to 11, and stirring is continued for 1 hour. Then, sulfuric acid is added to adjust the pH of the liquid to 6 to 8, and the mixture is placed on the cerium hydroxide-coated particles. A second coating layer was formed.
- No. 3 sodium silicate silicon content: 28.5% by mass in terms of SiO 2
- the liquid containing the precursor particles was filtered, and the precursor particles were washed with water and dried.
- Precursor particles were pulverized to obtain precursor particles.
- the precursor particles were fired at a temperature of 500 ° C. for 2 hours, and the mass of particles was pulverized with a hammer mill to obtain composite particles (C) having an average particle diameter of 0.25 ⁇ m.
- the composite particles had a titanium oxide content of 72 mass%, a cerium oxide content of 10 mass%, and a silicon oxide content of 18 mass%. Therefore, the amount of cerium oxide with respect to 100 parts by mass of titanium oxide was 13.9 parts by mass, and the amount of silicon oxide with respect to 100 parts by mass of titanium oxide was 25.0 parts by mass.
- This pigment composition (B1) was applied to a polyethylene terephthalate (PET) film by potting at room temperature and air-dried, then dried by heating on a hot plate at 110 ° C. for 10 minutes, and a thin film of the pigment composition (B1) on the surface. A PET film with a formed was obtained. When the transmittance of visible light and UV of the obtained thin film was examined, it was 2% or less over the entire range of 200 to 800 nm.
- ⁇ Pigment composition (B1-a)> A pigment composition was used except that a methyl ethyl ketone dispersion (solid content concentration: 34%) of the composite particles (C) was used instead of the titanium oxide pigment (manufactured by Ishihara Sangyo Co., Ltd., CR97, average particle size: 0.25 ⁇ m).
- a pigment composition (B1-a) is obtained in the same manner as (B1).
- ⁇ Coating composition (D1-a)> A coating composition (D1-a) is obtained in the same manner as the coating composition D1, except that the pigment composition (B1-a) is used instead of the pigment composition (B1).
- a coating composition (D1-c) is obtained in the same manner as in D1.
- Coating compositions (D1), (D1-a), (D1-b), (D1-c), (D1-d), (D2), and (D3) are formed on one side of a PET film having a thickness of 50 ⁇ m. Paint to a thickness of 20 ⁇ m and dry at 80 ° C. for 1 hour. The bending properties and adhesion of the obtained two-layer sheet were evaluated and the results are shown in Table 1.
- An EVA sheet having a thickness of 100 ⁇ m is stacked on the surface of the two-layer sheet coated with fluorine paint, and is crimped at a load of 150 ° C. and 100 g / cm 2 . The adhesion between the fluororesin layer and the EVA layer was evaluated, and the results are shown in Table 1.
- Bendability evaluation-1 The crack of the coating film is confirmed when the two-layer structure sheet is bent 180 degrees along a cylindrical mandrel having a diameter of 2 mm so that the coated surface is on the outside. A state where there is no crack is indicated as “ ⁇ ”, and a state where the crack is present is indicated as “X”.
- Bendability evaluation-2 The two-layer structure sheet is folded so that the coated surface is on the outside, and a load of 50 g / cm 2 is applied for 1 minute, then the load is removed and cracking of the coating film is confirmed. A state where there is no crack is indicated as “ ⁇ ”, and a state where the crack is present is indicated as “X”.
- Adhesion evaluation The coating film is cut by 1 mm in width of 100 mm, cellophane tape is applied, and the adhesion property of the coating film to the ground is evaluated.
- the case where 91 squares or more are bonded is indicated by ⁇
- the case where 90-51 squares are adhered is indicated by ⁇
- the case where 50-0 squares or more are adhered is indicated by ⁇ .
- a 100 ⁇ m EVA sheet is stacked on the surface opposite to the coating film of the PET film via a polyester adhesive, and a back sheet is prepared by pressure bonding with a load of 150 ° C. and 100 g / cm 2 .
- a solar cell module is created with a configuration in which solar cells, an EVA sheet, and a glass plate are stacked on the EVA side of the backsheet.
- [Solar cell module 2] A coating composition (D1), (D1-a), (D1-b), (D1-c), (D1-d), (D2) via a polyester adhesive on both sides of a PET film having a thickness of 50 ⁇ m , (D3) are coated to a thickness of 20 ⁇ m and dried at 80 ° C. for 1 hour. Next, a 100 ⁇ m EVA sheet is stacked on one side coated with a coating film via a polyester-based adhesive, and a back sheet is prepared by pressure bonding at 150 ° C. and a load of 100 g / cm 2 .
- a solar cell module is created with a configuration in which solar cells, EVA sheets, and glass plates are stacked on the EVA sheet side of the backsheet.
- the coating film of the fluorine-containing copolymer (A) formed on at least one side of the base sheet is lightweight and excellent in productivity without causing problems of cracks, cracks, whitening and peeling.
- a back sheet for a solar cell module is provided.
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Abstract
Description
バックシートには、機械的強度、耐候性、防水・防湿性、電気絶縁性など、種々の特性が要求される。通常のバックシートの構成は多層構造になっており、たとえば太陽電池セルの封止材層と接する側から順に、電気絶縁層/防水・防湿層/太陽電池裏側に位置する裏面層からなっている。
一般的には電気絶縁層および裏面層には、耐候性、防水・防湿性、および電気絶縁性に優れる等の理由からポリフッ化ビニルのフィルムが用いられ、基材シートにはポリエチレンテレフタレート(エチレングリコールとテレフタル酸の共重合体であり、以下、PETという。)フィルムが用いられている。また、バックシートに高い防水・防湿効果が要求される場合には、基材シートの表面に、シリカなどの金属化合物の蒸着層、またはアルミニウム箔などの金属層、が設けられている。
前記バックシートの厚さは、前記要求特性や、耐久性、遮光性などの諸要求特性を満たすため、通常20~100μmとされる。しかし、近年、軽量化および薄膜化の要求がなされている。
水不透過性シートの少なくとも一方の面に硬化性官能基含有含フッ素ポリマー塗料の硬化塗膜が形成されてなる太陽電池モジュールのバックシートが提案されている(特許文献1)。該硬化性官能基含有含フッ素ポリマーとして硬化性テトラフルオロエチレン(TFE)系共重合体(ゼッフルGK570、ダイキン工業社商標)が開示されている。しかし、該硬化性官能基含有含フッ素ポリマー塗料の硬化塗膜は、塗膜の柔軟性、基材との密着性、および耐折曲げ性が不十分であるため、塗膜のヒビや割れ、白化、剥離等の問題を生じたり、顔料や硬化剤の分散性の低さから、分散性不良による色ムラや、硬化剤の分散不良による硬化不良を起こす問題があることが判明した。
すなわち、本発明は、次の[1]~[11]である。
[1]基材シートの少なくとも一方の側に、エチレンに基づく繰り返し単位とテトラフルオロエチレンに基づく繰り返し単位とを有する含フッ素共重合体(A)と、含フッ素共重合体(A)の融点以下の温度で含フッ素共重合体(A)を溶解可能な溶媒とを含有するコーティング用組成物から形成された塗膜を有する太陽電池モジュール用バックシート。
[2]前記コーティング用組成物中の含フッ素共重合体(A)が、含フッ素重合体(A)を前記溶媒に溶解させた溶液から析出させて得られたものである、[1]に記載の太陽電池用モジュール用バックシート。
[3]含フッ素共重合体(A)中の全繰り返し単位における、テトラフルオロエチレンおよびエチレン以外の単量体の繰り返し単位の割合が、0.1~30モル%である[1]または[2]に記載の太陽電池モジュール用バックシート。
[4]含フッ素共重合体(A)が、架橋性基を有する含フッ素共重合体である[1]~[3]のいずれかに記載の太陽電池モジュール用バックシート。
[5]前記架橋性基が、カルボキシル基、酸無水物基およびカルボン酸ハライド基からなる群から選ばれる少なくとも1種である、[4]に記載の太陽電池モジュール用バックシート。
[6]前記溶媒における、下記式(1)で示されるハンセン溶解度パラメータに基づく前記含フッ素共重合体(A)に対する溶解指標(R)が25未満である[1]~[5]のいずれかに記載の太陽電池モジュール用バックシート。
R=4×(δd-15.7)2+(δp-5.7)2+(δh-4.3)2 …(1)
(式(1)中、δd、δpおよびδhは、ハンセン溶解度パラメータにおける、分散項、極性項および水素結合項をそれぞれ示し、単位はいずれも(MPa)1/2である。)
[7]前記コーティング用組成物が、紫外線吸収剤を含有する[1]~[6]のいずれかに記載の太陽電池モジュール用バックシート。
[8]前記コーティング用組成物が、顔料を含有する[1]~[6]のいずれかに記載の太陽電池モジュール用バックシート。
[9]太陽電池セルと接する側のバックシートの最表面に、前記塗膜とは異なる重合体からなる層が設けられた[1]~[8]のいずれかに記載の太陽電池モジュール用バックシート。
[10]エチレンに基づく繰り返し単位とテトラフルオロエチレンに基づく繰り返し単位とを有する含フッ素共重合体(A)を、含フッ素共重合体(A)の融点以下の温度で含フッ素共重合体(A)を溶解可能な溶媒に溶解させたコーティング用組成物を基材シートの少なくとも一方の側に塗布した後に、溶媒を除去して塗膜を形成することを特徴とする太陽電池モジュール用バックシートの製造方法。
[11]表面シート、太陽電池セルが樹脂で封止されてなる封止層、および、[1]~[9]のいずれかに記載の太陽電池モジュール用バックシートが順に積層されてなる太陽電池モジュール。
含フッ素共重合体(A)としては、エチレンに基く繰り返し単位と、テトラフルオロエチレンに基づく繰り返し単位とを含有する含フッ素共重合体であれば、他に特に制限はない。このような含フッ素共重合体の例として具体的には、エチレンに基づく繰返し単位とテトラフルオロエチレン(以下、「TFE」と呼ぶことがある。)に基づく繰返し単位とを共重合体中の主な繰返し単位とするETFE等が挙げられる。ここで、本明細書において「ETFE」の用語は、TFEおよびエチレン以外の共単量体に基づく繰返し単位を共重合体の構成単位として含んでもよい、TFEおよびエチレンを共重合体中の主な繰返し単位とする含フッ素共重合体の総称として用いるものである。
こられの単量体の中でも、含フッ素共重合体(A)の溶媒への溶解性を向上させる観点からはフルオロオレフィン類、特にCF2=CH2が好ましい。また、含フッ素共重合体の靭性や耐ストレスクラック性を向上させる観点からは、ポリフルオロアルキルエチレン、特にCF3CF2CF2CF2CH=CH2が好ましい。
これらの非架橋性単量体は、単独でまたは2種以上を組み合わせて使用してもよい。
最も好ましくは、ヒドロキシ基、カルボン酸基、酸無水物基およびカルボン酸ハライド基からなる群から選ばれる少なくとも1種である。
水酸基を有する単量体としては、2-ヒドロキシエチルビニルエーテル、3-ヒドロキシプロピルビニルエーテル、2-ヒドロキシ-2-メチルプロピルビニルエーテル、4-ヒドロキシブチルビニルエーテル、4-ヒドロキシ-2-メチルブチルビニルエーテル、5-ヒドロキシペンチルビニルエーテル、6-ヒドロキシヘキシルビニルエーテル等の水酸基含有ビニルエーテル類;2-ヒドロキシエチルアリルエーテル、4-ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテル等の水酸基含有アリルエーテル類等が挙げられる。これらの中でも水酸基含有ビニルエーテル類、特に4-ヒドロキシブチルビニルエーテル、または2-ヒドロキシエチルビニルエーテルが入手容易性、重合反応性、架橋性基の架橋性が優れる点でより好ましい。
酸無水物としては、無水イタコン酸、無水マレイン酸、無水シトラコン酸、5-ノルボルネン-2,3-ジカルボン酸無水物等が挙げられる。これらの中でも無水イタコン酸が好ましい。
これらの中で硬度の高い塗膜を得るという観点や基材との密着性を高めるという観点から、水酸基を有する単量体または酸無水物が好ましい。
これらの架橋性単量体は、単独でまたは2種以上を組み合わせて使用してもよい。すなわち、架橋性基は、含フッ素共重合体(A)1分子中に異なる種類のものが2種類以上存在していてもよい。
含フッ素共重合体(A)が、架橋性単量体に基づく単位を含有する場合は、その含有割合は、含フッ素共重合体(A)の全単量体繰返し単位に対して、好ましくは0.1~10モル%であり、より好ましくは0.1~5モル%である。
本発明におけるコーティング用組成物に使用する含フッ素共重合体(A)において、TFEおよびエチレン以外の共単量体に基づく繰り返し単位の含有量がこの範囲にあると、ほぼTFEおよびエチレンのみで構成されるETFEが有する特性を損なうことなく、高い溶解性、撥水性、撥油性、硬化性、基材に対する接着性などの機能を付与することが可能になる。
本発明におけるコーティング用組成物は上記含フッ素共重合体(A)とともに溶媒を含有する。本発明におけるコーティング用組成物に用いる溶媒としては、上記含フッ素共重合体(A)の融点以下の温度でこの含フッ素共重合体(A)を溶解可能な溶媒である。さらにこの溶媒に含フッ素共重合体(A)を溶解した溶液から含フッ素共重合体(A)を析出させた際に、少なくとも常温常圧において、分散状態を維持することができるものであることが好ましい。
R=4×(δd-15.7)2+(δp-5.7)2+(δh-4.3)2 …(1)
(式(1)中、δd、δpおよびδhは、ハンセン溶解度パラメータにおける、分散項、極性項および水素結合項をそれぞれ示し、単位はいずれも(MPa)1/2である。)。
メチルエチルケトン、2-ペンタノン、メチルイソプロピルケトン、2-ヘキサノン、メチルイソブチルケトン、ピナコリン、2-ヘプタノン、4-ヘプタノン、ジイソピロピルケトン、イソアミルメチルケトン、2-オクタノン、2-ノナノン、ジイソブチルケトン、ギ酸イソプロピル、ギ酸イソブチル、ギ酸sec-ブチル、ギ酸t-ブチル、ギ酸アミル、ギ酸イソアミル、ギ酸ヘキシル、ギ酸ヘプチル、ギ酸オクチル、ギ酸2-エチルヘキシル、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸イソブチル、酢酸t-ブチル、酢酸アミル、酢酸イソアミル、酢酸ヘキシル、酢酸シクロヘキシル、酢酸ヘプチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸プロピル、プロピオン酸イソプロピル、プロピオン酸ブチル、プロピオン酸イソブチル、プロピオン酸sec-ブチル、プロピオン酸t-ブチル、プロピオン酸アミル、プロピオン酸イソアミル、プロピオン酸ヘキシル、プロピオン酸シクロヘキシル、酪酸メチル、酪酸エチル、酪酸プロピル、酪酸イソプロピル、酪酸ブチル、酪酸イソブチル、酪酸sec-ブチル、酪酸t-ブチル、酪酸アミル、酪酸イソアミル、イソ酪酸メチル、イソ酪酸エチル、イソ酪酸プロピル、イソ酪酸イソプロピル、イソ酪酸ブチル、イソ酪酸イソブチル、イソ酪酸sec-ブチル、イソ酪酸t-ブチル、イソ酪酸アミル、イソ酪酸イソアミル、吉草酸メチル、吉草酸エチル、吉草酸プロピル、吉草酸イソプロピル、吉草酸ブチル、吉草酸イソブチル、吉草酸sec-ブチル、吉草酸t-ブチル、イソ吉草酸メチル、イソ吉草酸エチル、イソ吉草酸プロピル、イソ吉草酸イソプロピル、イソ吉草酸ブチル、イソ吉草酸イソブチル、イソ吉草酸sec-ブチル、イソ吉草酸t-ブチル、ヘキサン酸メチル、ヘキサン酸エチル、ヘキサン酸プロピル、ヘキサン酸イソプロピル、ヘプタン酸メチル、ヘプタン酸エチル、オクタン酸メチル、シクロヘキサンカルボン酸メチル、シクロヘキサンカルボン酸エチル、シクロヘキサンカルボン酸プロピル、シクロヘキサンカルボン酸イソプロピル、酢酸2-プロポキシエチル、酢酸2-ブトキシエチル、酢酸2-ペンチルオキシエチル、1-エトキシ-2-アセトキシプロパン、1-プロポキシ-2-アセトキシプロパン、1-ブトキシ-2-アセトキシプロパン、酢酸3-エトキシブチル、酢酸3-プロポキシブチル、酢酸3-メトキシ-3-メチルブチル、酢酸3-エトキシ-3-メチルブチル、酢酸4-メトキシブチル、酢酸4-エトキシブチル、酢酸4-プロポキシブチル。なお、これらの溶媒はいずれも、上記式(1)から算出されるRが16未満の溶媒である。
本発明におけるコーティング用組成物に含有される含フッ素共重合体(A)は、溶解状態で存在していてもよいが、以下に説明する溶媒中に分散した状態で存在していることが好ましい。ここで、含フッ素共重合体(A)が分散した状態で存在する場合には、該含フッ素共重合体(A)は、以下に説明する溶媒に溶解させた溶液から析出した含フッ素共重合体(A)であることが好ましい。含フッ素共重合体(A)は、溶媒に溶解させた溶液から析出することにより微粒子の状態で溶媒に分散する。この場合の含フッ素共重合体(A)の微粒子の平均粒子径は、20℃において、小角X線散乱法で測定した平均粒子径として、0.005~2μmの範囲にあることが好ましく、0.005~1μmであることがより好ましい。本発明におけるコーティング用組成物において、含フッ素共重合体(A)の微粒子の平均粒子径が、この範囲にあれば均質で透明性、平坦性、密着性に優れた塗膜を形成することができる。
本発明におけるコーティング用組成物の製造方法について以下に説明する。本発明の製造方法は、具体的には、上に説明した本発明におけるコーティング用組成物を製造する方法として用いられる。
(1)エチレンに基づく繰り返し単位とテトラフルオロエチレンに基づく繰り返し単位とを有する含フッ素共重合体(A)を、前記含フッ素共重合体(A)の融点以下の温度で該含フッ素共重合体(A)を溶解可能な溶媒に溶解して溶液とする工程、(以下、「溶解工程」という。)
(2)前記溶液において前記溶媒中に前記含フッ素共重合体(A)を微粒子として析出させて、前記溶液を該微粒子が前記溶媒に分散した分散液とする工程(以下「析出工程」という。)
(1)溶解工程
溶解工程において使用する溶媒は、上記条件を満たす溶媒、すなわち、上記含フッ素共重合体(A)の融点以下の温度でこの含フッ素共重合体を溶解可能な溶媒である。さらに続いて析出工程を行って、この溶媒に含フッ素共重合体を溶解した溶液から含フッ素共重合体(A)の微粒子を析出させる場合には、使用する溶媒は、少なくとも常温常圧において、含フッ素共重合体(A)を安定して微粒子として分散させることができることが好ましい。
本発明におけるコーティング用組成物としては、析出工程を行わずに、溶解工程によって溶媒に溶解した状態の含フッ素共重合体(A)を含有する組成物を使用することもできる。
上記(1)溶解工程で得られた、上記含フッ素共重合体(A)を上記溶媒に溶解した溶液を、該含フッ素共重合体(A)が上記溶媒中に析出する条件下、一般的には常温常圧下におくことで、含フッ素共重合体(A)が上記溶媒中に析出する。具体的には、上記(1)溶解工程を加熱下で行った場合には、得られる溶液を含フッ素共重合体(A)が析出する温度以下の温度まで、通常は常温まで冷却することにより上記含フッ素共重合体(A)の微粒子を上記溶媒中に析出させることができる。この場合、冷却の方法は、特に制限されず、徐冷でもよく、急冷であってもよい。
本発明においては、コーティング用組成物として、微粒子として分散した状態の含フッ素共重合体(A)を含有する組成物を使用することが好ましい。
本発明におけるコーティング用組成物は、必要に応じてその他任意成分を本発明の効果を損なわない範囲で含有することができる。このような任意成分として、例えば、硬化剤、硬化促進剤、密着性改良剤、表面調整剤、酸化防止剤、光安定剤、紫外線吸収剤、架橋剤、滑剤、可塑剤、増粘剤、つや消し剤、分散安定剤、充填剤(フィラー)、強化剤、レベリング剤、顔料、染料、難燃剤、帯電防止剤、他の樹脂等の各種添加剤が挙げられる。また、本発明の効果を損なわないこれらの任意成分の含有量としては、コーティング用組成物全量に対して30質量%以下の含有量を挙げることができる。
たとえば、架橋性基が水酸基の場合にはイソシアネート系硬化剤、メラミン樹脂、シリケート化合物、イソシアネート含有シラン化合物などを選択し、カルボキシル基の場合にはアミノ系硬化剤、エポキシ系硬化剤を選択し、アミノ基の場合にはカルボニル含有硬化剤、エポキシ系硬化剤、酸無水物系硬化剤を選択し、エポキシ基の場合にはカルボキシル基を選択し、イソシアネート基の場合には水酸基を選択する。硬化剤が不要な架橋性基としては、加水分解性シリル基などがある。
無黄色変性ポリイソシアネートとしては、IPDI(イソホロンジイソシアネート)、HMDI(ヘキサメチレンジイソシアネート)、HDI(ヘキサンジイソシアネート)、またはこれらの変性体が好ましい。
変性体としては、イプシロンカプロラクタム(E-CAP)やメチルエチルケトンオキシム(MEK-OX)、メチルイソブチルケトンオキシム(MIBK-OX)、ピラリジンまたはトリアジン(TA)を用い、イソシアネート基をブロックしたもの、ポリイソシアネート同士をカップリングしてウレトジオン結合としたもの等が好ましい。
硬化促進剤としては、たとえばスズ系、その他金属系、有機酸系、アミノ系硬化促進剤などが使用できる。
顔料の中でも、白色顔料の酸化チタンは、光触媒作用により顔料が含まれている塗膜を分解劣化することが知られている。そこで酸化チタンとしては、内側から順に、酸化チタンを含む粒子、該粒子の外側を覆う酸化セリウムを含む第一の被覆層、および第一の被覆層の外側を覆う酸化ケイ素を含む第二の被覆層、とを含む複合粒子としたものを用いることが好ましい。
該複合粒子は、酸化セリウム被覆層、酸化ケイ素被覆層の内側または外側に他の被覆層を有していてもよい。たとえば酸化チタンを含む粒子と、該粒子の外側を覆う酸化セリウムを含む第一被覆層との間に、酸化ケイ素の被覆層を有することが好ましい。
紫外線吸収剤としては、有機系、無機系のいずれの紫外線吸収剤も用いることができる。有機化合物系では、たとえばサリチル酸エステル系、ベンゾトリアゾール系、ベンゾフェノン系、シアノアクリレート系、の外線吸収剤などがあげられ、無機系では酸化チタン、酸化亜鉛、酸化セリウムなどのフィラー型無機系紫外線吸収剤などが好ましい。
紫外線吸収剤として酸化チタンを用いる場合には、前記の複合粒子とした酸化チタンを用いることが好ましい。
紫外線吸収剤は1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。紫外線吸収剤の量は、塗料中の含フッ素共重合体(A)の固形分総質量に対して0.1~15質量%であることが好ましい。紫外線吸収剤の量が少なすぎる場合には、耐光性の改良効果が充分に得られず、また、多すぎても効果が飽和する。
光安定剤は1種または2種以上を組み合わせて用いてもよく、紫外線吸収剤と組み合わせて用いてもよい。
増粘剤としては、たとえばポリウレタン系会合性増粘剤などがあげられる。
つや消し剤としては、超微粉合成シリカ等など常用の無機または有機のつや消し剤を用いることができる。
本発明の塗料組成物に他の樹脂を配合する場合、他の樹脂の含有量は、含フッ素共重合体(A)の100質量部に対して1~200質量部が好ましい。
前記のように調製したコーティング用組成物中の含フッ素共重合体(A)の濃度は、塗料の全質量に対して1~50質量%であることが好ましい。
基材シートの材質は特に限定されず、ポリエチレン、ポリプロピレンなどのポリオレフィン類;ポリ塩化ビニル、ポリ塩化ビニリデン、ポリフッ化ビニル、ポリフッ化ビニリデンなどのポリハロゲン化ビニル類;PET、ポリブチレンテレフタレートなどのポリエステル類;ナイロン6、ナイロン66、MXDナイロン(メタキシレンジアミン/アジピン酸共重合体)などのポリアミド類;ポリ酢酸ビニル、ポリビニルアルコール、ポリメチルメタクリレートなどの置換基を有するオレフィン類の重合体;EVA、エチレン/ビニルアルコール共重合体などの共重合体などを用いることができる。
これらの中でも、PET、EVA、ポリビニルアルコール、ポリ塩化ビニリデン、ナイロン6、ナイロン66、またはエチレン/ビニルアルコール共重合体が好ましい。
金属層は、基材シート表面に金属もしくは金属化合物を蒸着する、または金属もしくは金属化合物の箔を接着剤によって接着することによって設けることができる。箔と基材シートとは、接着剤によって形成される接着剤層を介して接着されていることが好ましい。
該金属類としては、シリコン、マグネシウム、ジルコニウム、亜鉛、スズ、ニッケル、チタン、およびアルミニウムからなる群から選ばれる金属、もしくは該金属の化合物またはステンレスなどがあげられる。これらの中でも、蒸着に用いる金属類としてはシリコン、アルミニウム、酸化アルミ、酸化珪素、窒化酸化珪素、または窒化珪素が好ましい。蒸着においては、一種の金属類を用いてもよいし、2種以上の金属類を組み合わせて用いてもよい。
一方、金属類の箔を接着剤によって接着する場合の金属類としては、アルミニウム、チタン、またはステンレスが好ましい。
本発明のバックシートは、前記基材シートの片面または両面に、前記含フッ素共重合体(A)を必須成分とするコーティング用組成物から形成される塗膜を有する。以下、基材シートの太陽電池セル側の面を内側面と記し、太陽電池セルとは反対側の面を外側面と記す。
図1は、基材シート4の片面に塗膜5が形成された場合の態様を示し、外側面に形成された場合を図(1-1)に、基材シート4の両面に塗膜5が形成された場合を図(1-2)に示す。
塗膜5は、耐候性の観点から、基材シート4の外側面のみ、または基材シートの表面に形成されていることが好ましい。さらに、経済性および軽量化の観点から、塗膜は基材シートの外側面のみに形成されていることが好ましい。すなわち、好ましいバックシートの構成は、基材シート、および基材シートの外側面に塗膜が積層された図(1-1)の構成である。
さらに金属層を有していてもよい基材シート表面に塗膜を形成する際には、硬化塗膜を直接形成させてもよく、プライマー層を形成させたあとに塗膜を形成させてもよい。直接形成させる場合には、含フッ素共重合体(A)を必須成分とするコーティング用組成物を直接塗布する方法によるのが好ましい。プライマー層を形成させる場合には、プライマー用塗料を、金属層を有していてもよい基材シート表面に塗布し、つぎに含フッ素共重合体(A)を必須成分とするコーティング用組成物を塗布するのが好ましい。プライマー塗料としては、たとえばエポキシ樹脂、ウレタン樹脂、アクリル樹脂、シリコーン樹脂、ポリエステル樹脂などがあげられる。
重合体層は、バックシートの基材シートの上に直接設けれていてもよいし、基材シートとの間に塗膜のなどの別の層を介して、該別の層の上に設けられていてもよい。
たとえば、基材シートの表面に金属箔からなる金属層を形成する場合の基材シートと金属箔との間に接着剤層を設ける場合があげられる。また、他の重合体(B)層の接着性を改善するために、他の重合体(B)層の片面または両面、好ましくは片面に、接着剤層を設けてもよい。他の重合体(B)層がEVAである場合には、EVA層の封止材層と接する面と反対側の面に接着剤層を設けるのが好ましい。他の重合体層がEVAであり、封止材層がEVAからなる場合には、両者は、圧着により接着できる。接着剤としては、積層する層の材質によって適宜変更されうるが、ポリエステル系接着剤、アクリル系接着剤、ウレタン系接着剤、エポキシ系接着剤、ポリアミド系接着剤、ポリイミド系接着剤などがあげられる。
さらに、本発明のバックシートにおいては、上記で説明した各層の間、封止材と接する面、および最外側の面には、それぞれ必要に応じて他の層が形成されうる。
バックシートを構成する各層の厚さは、要求性能に応じて適宜変更されうる。たとえば含フッ素共重合体(A)を必須成分とする塗料の塗膜は1~75μmが好ましい。金属層は0.01~50μmが好ましい。基材シートは25~200μmが好ましい。他の重合体(B)層は50~200μmが好ましい。接着剤層が0.1~25μmが好ましい。さらに本発明のバックシートの総膜厚は30~300μmが好ましい。
本発明のバックシートは、太陽電池セルと組み合わせて太陽電池モジュールを構成する。通常は、表面シート、太陽電池セルが樹脂で封止されてなる封止層、およびバックシートが順に積層されて太陽電池モジュールとなる。さらに、積層において密着性が不充分である場合には、接着剤層を設けてもよい。
表面シートとしては、通常はガラス基板が用いられるが、表面シートに樹脂シートなどフレキシブルな材料を用いてもよい。本発明のバックシートは、膜厚が小であり、かつ、軽量化が可能であるため、フレキシブル太陽電池にも好適に用いうる。
[ETFE1のコーティング用組成物(A1)の製造]
<コーティング用組成物(A1)>
硼珪酸ガラス製耐圧反応器に、含フッ素共重合体(A)として、ETFE1(構成単量体およびモル比:テトラフルオロエチレン/エチレン/ヘキサフルオロプロピレン/3,3,4,4,5,5,6,6,6-ノナフルオロ-1-ヘキセン/無水イタコン酸=44.6/45.6/8.1/1.3/0.4、融点:192℃、以下、「ETFE1」という。)の2.40g、ジイソプロピルケトン(上記式(1)で算出されるR(以下、単に「R」と表す。)=0)の37.60gを入れ、撹拌しながら140℃に加熱したところ、均一で透明な溶液となった。
該反応器を徐々に室温まで冷却したところ、均一で沈降物のないETFE1の微粒子分散液(ETFE1の濃度6重量%)が得られた。ETFE1の微粒子の平均粒子径は、20℃において、小角X線散乱法で測定した平均粒子径として20nmであった。また、この分散液を0.05重量%に希釈して、透過型電子顕微鏡で観察したところ、1次粒子径は、20-30nmであることが確認できた。
溶媒としてシクロヘキサノン(R=25.6)を用いる以外はコーティング用組成物(A1)と同様にして、コーティング用組成物(A2)を得た。
<コーティング用組成物(A3)>
含フッ素共重合体(A)として、ETFE2(構成単量体およびモル比:テトラフルオロエチレン/エチレン/ヘキサフルオロプロピレン/3,3,4,4,5,5,6,6,6-ノナフルオロ-1-ヘキセン/無水イタコン酸=47.7/42.5/8.4/1.2/0.2、融点:188℃、以下、「ETFE2」という。)の1.20gを、溶媒として2-ヘキサノン(R=0.8)の38.80gを用いる以外はコーティング用組成物(A1)と同様にして、コーティング用組成物(A3)を得た。
<複合体粒子(C)の製造>
酸化チタン顔料(石原産業社製、CR50、平均粒子径:0.20μm)500gを純水10リットルに加え、デスパミル(ホソカワミクロン社製)で1時間分散させ、水分散液を得た。該水分散液を80℃に加熱および撹拌しながら、該水分散液に硝酸セリウム水溶液(セリウム含有量:CeO2換算で10質量%)264gを滴下した。該水分散液に水酸化ナトリウム溶液を添加し、該液をpH7~9に中和して、酸化チタン顔料表面に水酸化セリウムを沈積させた。水酸化セリウム被覆粒子を含む液をろ過し、水酸化セリウム被覆粒子を水洗、乾燥した。水酸化セリウム被覆粒子の塊を粉砕して、水酸化セリウム被覆粒子を得た。
前駆体粒子を温度500℃で2時間焼成し、粒子の塊をハンマーミルで粉砕して平均粒子径が0.25μmの複合体粒子(C)を得た。該複合粒子における酸化チタンの含有量は72質量%であり、酸化セリウムの含有量は10質量%であり、酸化ケイ素の含有量は18質量%であった。よって、酸化チタン100質量部に対する酸化セリウムの量は13.9質量部であり、酸化チタン100質量部に対する酸化ケイ素の量は25.0質量部であった。
<顔料組成物(B1)>
得られた含フッ素共重合体を含有するコーティング用組成物(A1)の40gに、酸化チタン顔料(石原産業社製、CR97、平均粒子径:0.25μm)のメチルエチルケトン分散液(固形分濃度:34.2%)の2.50gを加え、さらに、直径1mmのガラスビーズの40gを加えて、ペイントシェーカーで2時間撹拌した。撹拌後ろ過を行ってガラスビーズを取り除き、顔料組成物(B1)を得た。この顔料組成物(B1)をポリエチレンテレフタレート(PET)フィルム上に室温でポッティングにより塗布・風乾後、110℃のホットプレート上で10分間加熱して乾燥し、表面に顔料組成物(B1)の薄膜が形成されたPETフィルムを得た。得られた薄膜の可視光およびUVの透過率を調べたところ、200~800nmの全範囲で、2%以下でった。
<顔料組成物(B2)>
コーティング用組成物(A1)に代えて、コーティング用組成物(A2)を用いた他は、顔料組成物(B1)と同様にして、顔料組成物(B2)を得る。
<顔料組成物(B3)>
コーティング用組成物(A1)に代えて、コーティング用組成物(A3)を用いた他は、顔料組成物(B1)と同様にして、顔料組成物(B3)を得る。
酸化チタン顔料(石原産業社製、CR97、平均粒子径:0.25μm)に代えて、複合体粒子(C)のメチルエチルケトン分散液(固形分濃度:34%)を用いた他は、顔料組成物(B1)と同様にして、顔料組成物(B1-a)を得る。
<塗料組成物(D1)>
顔料組成物(B1)の40gに、コーティング用組成物(A1)の10gを加えて混合し、塗料組成物(D1)を得る。
<塗料組成物(D2)>
顔料組成物(B1)に代えて顔料組成物(B2)を用い、かつコーティング用組成物(A1)に代えて、コーティング用組成物(A2)を用いた他は、塗料組成物D1と同様にして、塗料組成物(D2)を得る。
<塗料組成物(D3)>
顔料組成物(B1)に代えて顔料組成物(B3)を用い、かつコーティング用組成物(A1)に代えて、コーティング用組成物(A3)を用いた他は、塗料組成物D1と同様にして、塗料組成物(D3)を得る。
<塗料組成物(D1-a)>
顔料組成物(B1)に代えて顔料組成物(B1-a)を用いた他は、塗料組成物D1と同様にして、塗料組成物(D1-a)を得る。
<塗料組成物(D1-b)>
顔料組成物(B1)に代えて顔料組成物(B1-a)を用い、チバスペシャルティケミカルズ社製紫外線吸収剤チヌビン384の10gおよびチヌビン400の3gを加えた他は、塗料組成物D1と同様にして、塗料組成物(D1-b)を得る。
<塗料組成物(D1-c)>
顔料組成物(B1)に代えて顔料組成物(B1-a)を用い、チバスペシャルティケミカルズ社製紫外線吸収剤チヌビン384の2.0gおよびチヌビン400の0.6gを加えた他は、塗料組成物D1と同様にして、塗料組成物(D1-c)を得る。
<塗料組成物(D1-d)>
顔料組成物(B1)に代えて顔料組成物(B1-a)を用い、コーティング用組成物(A1)に代えてメチルメタクリレート-ブチルメタクリレート共重合体(Aldrich社製、カタログ番号:474029、質量平均分子量:75000)のジイソプロピルケトン溶液(固形分濃度6%)の10gを加えた他は、塗料組成物D1と同様にして、塗料組成物(D1-d)を得る。
厚さ50μmのPETフィルムの片面に塗料組成物(D1)、(D1-a)、(D1-b)、(D1-c)、(D1-d)、(D2)、(D3)をそれぞれ膜厚20μmになるように塗装し80℃で1時間乾燥させる。得られた2層シートの折り曲げ性と密着性を評価し結果を表1に示す。
2層シートのフッ素塗料塗装面に100μmのEVAシートを重ね、150度、100g/cm2の荷重で圧着する。フッ素樹脂層とEVA層の接着性を評価し結果を表1に示す。
折り曲げ性評価-1:2層構造シートを塗装面が外側になるように直径2mmの円筒マンドレルに沿って180度折り曲げたときの塗膜の割れを確認する。割れがない状態を○、割れた状態を×とする。
折り曲げ性評価-2:2層構造シートを塗装面が外側になるように折り、50g/cm2の荷重をかけて1分間置いた後、荷重を取り除き塗膜の割れを確認する。割れがない状態を○、割れた状態を×とする。
密着性評価:塗膜に幅1mm100マスの切り込みを入れ、セロファンテープを張り、はがした際の塗膜の下地への密着性を評価する。91マス以上が接着していたものを○、90~51マス接着していたものを△、50~0マス以上が接着していたものを×とする。
厚さ50μmのPETフィルムの片面にポリエステル系接着剤を介して塗料組成物(D1)、(D1-a)、(D1-b)、(D1-c)、(D1-d)、(D2)、(D3)をそれぞれ膜厚20μmになるように塗装し80℃で1時間乾燥させる。PETフィルムの塗装膜と逆の面に、ポリエステル系接着剤を介して100μmのEVAシートを重ね、150度、100g/cm2の荷重で圧着しバックシートを作成する。このバックシートのEVA側に太陽電池セル、EVAシート、ガラス板を重ねた構成で太陽電池モジュールを作成する。
厚さ50μmのPETフィルムの両面にポリエステル系接着剤を介して塗料組成物(D1)、(D1-a)、(D1-b)、(D1-c)、(D1-d)、(D2)、(D3)をそれぞれ膜厚20μmになるように塗装し80℃で1時間乾燥させる。次に塗膜を塗装した片面に、ポリエステル系接着剤を介して100μmのEVAシートを重ね、150度、100g/cm2の荷重で圧着しバックシートを作成する。このバックシートのEVAシート側に太陽電池セル、EVAシート、ガラス板を重ねた構成で太陽電池モジュールを作成する。
なお、2010年4月16日に出願された日本特許出願2010-095210号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
2:封止材層
3:表面層
4:基材シート
5:塗膜
6:金属層
7:他の重合体層(EVA層など。)
Claims (11)
- 基材シートの少なくとも一方の側に、エチレンに基づく繰り返し単位とテトラフルオロエチレンに基づく繰り返し単位とを有する含フッ素共重合体(A)と、含フッ素共重合体(A)の融点以下の温度で含フッ素共重合体(A)を溶解可能な溶媒とを含有するコーティング用組成物から形成された塗膜を有する太陽電池モジュール用バックシート。
- 前記コーティング用組成物中の含フッ素共重合体(A)が、含フッ素重合体(A)を前記溶媒に溶解させた溶液から析出させて得られたものである、請求項1に記載の太陽電池用モジュール用バックシート。
- 含フッ素共重合体(A)中の全繰り返し単位における、テトラフルオロエチレンおよびエチレン以外の単量体の繰り返し単位の割合が、0.1~30モル%である請求項1または2に記載の太陽電池モジュール用バックシート。
- 含フッ素共重合体(A)が、架橋性基を有する含フッ素共重合体である請求項1~3のいずれかに記載の太陽電池モジュール用バックシート。
- 前記架橋性基が、カルボキシル基、酸無水物基およびカルボン酸ハライド基からなる群から選ばれる少なくとも1種である、請求項4に記載の太陽電池モジュール用バックシート。
- 前記溶媒における、下記式(1)で示されるハンセン溶解度パラメータに基づく前記含フッ素共重合体(A)に対する溶解指標(R)が25未満である請求項1~5のいずれかに記載の太陽電池モジュール用バックシート。
R=4×(δd-15.7)2+(δp-5.7)2+(δh-4.3)2 …(1)
(式(1)中、δd、δpおよびδhは、ハンセン溶解度パラメータにおける、分散項、極性項および水素結合項をそれぞれ示し、単位はいずれも(MPa)1/2である。) - 前記コーティング用組成物が、紫外線吸収剤を含有する請求項1~6のいずれかに記載の太陽電池モジュール用バックシート。
- 前記コーティング用組成物が、顔料を含有する請求項1~6のいずれかに記載の太陽電池モジュール用バックシート。
- 太陽電池セルと接する側のバックシートの最表面に、前記塗膜とは異なる重合体からなる層が設けられた請求項1~8のいずれかに記載の太陽電池モジュール用バックシート。
- エチレンに基づく繰り返し単位とテトラフルオロエチレンに基づく繰り返し単位とを有する含フッ素共重合体(A)を、含フッ素共重合体(A)の融点以下の温度で含フッ素共重合体(A)を溶解可能な溶媒に溶解させたコーティング用組成物を基材シートの少なくとも一方の側に塗布した後に、溶媒を除去して塗膜を形成することを特徴とする太陽電池モジュール用バックシートの製造方法。
- 表面シート、太陽電池セルが樹脂で封止されてなる封止層、および、請求項1~9のいずれかに記載の太陽電池モジュール用バックシートが順に積層されてなる太陽電池モジュール。
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| JP5234209B1 (ja) * | 2012-07-20 | 2013-07-10 | 東洋インキScホールディングス株式会社 | 太陽電池封止材用樹脂組成物 |
| WO2013173629A1 (en) * | 2012-05-16 | 2013-11-21 | Saint Gobain Performance Plastics Chaineux | Photovoltaic backsheet |
| JP2014128975A (ja) * | 2012-12-29 | 2014-07-10 | Shenzhen Futaihong Precision Industrial Co Ltd | セラミックとプラスチックとの複合体及びその製造方法 |
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| KR20140005963A (ko) * | 2011-01-25 | 2014-01-15 | 히타치가세이가부시끼가이샤 | Cmp 연마액 및 그의 제조 방법, 복합 입자의 제조 방법, 및 기체의 연마 방법 |
| CN104112783B (zh) * | 2013-04-22 | 2017-08-25 | 珠海兴业新能源科技有限公司 | 高性能绝缘太阳能光伏光热一体化板芯及其制备方法 |
| EP2824716B1 (en) * | 2013-07-09 | 2016-12-07 | Agfa-Gevaert | A backsheet for photovoltaic modules |
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| JP2017139334A (ja) * | 2016-02-03 | 2017-08-10 | 三菱電機株式会社 | 太陽電池モジュールおよび太陽電池モジュールの製造方法 |
| TWI610392B (zh) * | 2016-09-05 | 2018-01-01 | Daxin Materials Corp. | 光電元件的製備方法 |
| JP2017130685A (ja) * | 2017-03-27 | 2017-07-27 | 東洋インキScホールディングス株式会社 | 太陽電池用裏面保護シート、その製造方法および太陽電池モジュール |
| JP7206809B2 (ja) * | 2018-10-30 | 2023-01-18 | 大日本印刷株式会社 | 太陽電池モジュール用の透明保護シート |
| CN113748177B (zh) * | 2019-01-28 | 2023-10-03 | 科慕埃弗西有限公司 | 用于制造钝化层的组合物和使用所述组合物的钝化层 |
| CN113652121A (zh) * | 2021-07-30 | 2021-11-16 | 无锡尚德太阳能电力有限公司 | 一种高反射高粘接的光伏背板涂层及其制备方法 |
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| WO2013173629A1 (en) * | 2012-05-16 | 2013-11-21 | Saint Gobain Performance Plastics Chaineux | Photovoltaic backsheet |
| JP5234209B1 (ja) * | 2012-07-20 | 2013-07-10 | 東洋インキScホールディングス株式会社 | 太陽電池封止材用樹脂組成物 |
| JP2014128975A (ja) * | 2012-12-29 | 2014-07-10 | Shenzhen Futaihong Precision Industrial Co Ltd | セラミックとプラスチックとの複合体及びその製造方法 |
| US9855722B2 (en) | 2012-12-29 | 2018-01-02 | Shenzhen Futaihong Precision Industry Co., Ltd. | Composite article and method for making same |
Also Published As
| Publication number | Publication date |
|---|---|
| US20130037103A1 (en) | 2013-02-14 |
| CN102844884A (zh) | 2012-12-26 |
| KR20130077812A (ko) | 2013-07-09 |
| TW201141965A (en) | 2011-12-01 |
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