CN105706251B - Backside protective sheet used for solar batteries - Google Patents
Backside protective sheet used for solar batteries Download PDFInfo
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- CN105706251B CN105706251B CN201480060567.6A CN201480060567A CN105706251B CN 105706251 B CN105706251 B CN 105706251B CN 201480060567 A CN201480060567 A CN 201480060567A CN 105706251 B CN105706251 B CN 105706251B
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- protective sheet
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- backside protective
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- 230000001681 protective effect Effects 0.000 title claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 97
- 239000011347 resin Substances 0.000 claims abstract description 97
- 238000002425 crystallisation Methods 0.000 claims abstract description 52
- 230000008025 crystallization Effects 0.000 claims abstract description 52
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 17
- 238000002835 absorbance Methods 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 18
- 239000011737 fluorine Substances 0.000 abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 abstract description 18
- 239000011521 glass Substances 0.000 abstract description 7
- 238000012216 screening Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 98
- 239000002033 PVDF binder Substances 0.000 description 32
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 32
- 239000010408 film Substances 0.000 description 21
- -1 Ethylene, ethylene-tetrafluoroethylene Chemical group 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 239000012790 adhesive layer Substances 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- 239000005038 ethylene vinyl acetate Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
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- 239000000178 monomer Substances 0.000 description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002620 polyvinyl fluoride Polymers 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 238000005382 thermal cycling Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
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- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 230000005611 electricity Effects 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920001691 poly(ether urethane) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
-
- 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
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- 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
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/12—Photovoltaic modules
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a kind of backside protective sheet used for solar batteries, and fluorine resin film is used in outermost layer, and inhibits fluorine resin film to turn yellow and generate and be cracked.Specifically, the present invention provides a kind of rear surface of solar cell screening glass, it configures the back side in solar cell device, it is characterized in that, (1) backside protective sheet used for solar batteries is at least laminated with the first resin layer and the second resin layer from outermost layer successively, when being bonded with the solar cell device, the innermost layer of the outermost layer opposite side is bonded with the solar cell device, (2) first resin layer contains Kynoar, it is by the obtained crystalline texture of the absorbance of the infrared absorption spectrum in the Kynoar, when setting the crystallization of α types and the crystallization of β types adds up to 100%, 30~70% crystallize for α types, remainder crystallizes for β types.
Description
Technical field
A kind of backside protective sheet used for solar batteries of back side the present invention relates to configuration in solar cell device.
Background technology
It is generally laminated with backside protective sheet used for solar batteries in the back side of solar cell device, they are combined
Commonly referred to as solar cell module.
In recent years, especially from the viewpoint of Global Environmental Problems, to directly converting the solar into the sun of electric energy
Energy battery is increased sharply as the expectation of the energy of new generation.It is to carry on the back solar cell device using the purpose of backside protective sheet
The protection and insulation in face.
Solar cell module is typically provided at outdoor, be exposed expose to wind and rain, the rugged environments such as periods of direct sunlight
In.For solar cell module, require it that there is the long-time service longevity more than 25 years under this rugged environment
Life, therefore for protecting the backside protective sheet of solar cell device that it is also required to have higher weatherability to natural environment.For
Meet the requirement, to a variety of materials of backside protective sheet use with compared with high-weatherability can material.
The universal layer structure of backside protective sheet used for solar batteries is shown in Fig. 1.Backside protective sheet 10 is according to the first tree
The sequence stacking of lipid layer 11, adhesive layer 12a, the second resin layer 13, adhesive layer 12b and the second resin layer 14.With the sun
When energy cell device fitting, solar cell device is bonded with the second resin layer 14.In other words, the first resin layer 11 is most
Outer layer, the second resin layer 14 are innermost layer (in the following, by " outermost layer " is known as away from the farthest layer of solar cell device).
As outermost first resin layer 11, fluorine resin film (Kynoar, poly- fluorine with weatherability are used
Ethylene, ethylene-tetrafluoroethylene copolymer), as the second resin layer 13, thickness (~250 μ being used to ensure that for the purpose of insulating properties
M) general polyethylene terephthalate (PET) film, as the second resin layer 14, it is common to use with solar cell member
Encapsulating material, that is, ethylene-vinyl acetate copolymer (EVA) film layer welding of part, alkene that fusing point is near 120 DEG C it is thin
Film.
As described above, in order to protect the back side of solar cell device, it is desirable that backside protective sheet used for solar batteries has
Higher weatherability is using the fluorine resin for being difficult to deteriorate in the presence of a harsh environment as outermost first resin layer
Film.Since the fluorine resin film has higher weatherability, even if assuming that the second resin layer (such as PET film) is bad
Change, the effect of the intensity and shape that maintain backside protective sheet can also be played.
As fluorine resin film, it is common to use polyvinyl fluoride (PVF) resin film, but for weatherability, soil resistance, resistance to
The viewpoints such as hot, compared to PVF resin films, using Kynoar (PVDF) resin film the case where is also more.About
PVDF resin films, for example, proposing following scheme in patent document 1：In order to inhibit residual shrinkage, using containing poly- inclined fluorine
Copolymer resins (the MS of vinyl resins and (methyl) acrylic ester monomer (MMA monomers) and styrene monomer (SM monomers)
Resin) film.
In addition, for rear surface of solar cell screening glass, major requirement weatherability, but since solar cell module is set
Situation about setting in the open air such as the roof in house is more, therefore appearance design is also particularly significant.In other words, for back-protective
Piece, not only requires weatherability, it is also required to be difficult to generate cosmetic variation (discoloration etc.) in long-term use.
Existing technical literature
Patent document
Patent document 1：Japanese Patent Publication 2011-018851 bulletins
Invention content
(1) technical problems to be solved
In the case where the outermost layer (the first resin layer) of backside protective sheet used for solar batteries uses fluorine resin film,
There are following two.
(1) due to the ingredient of adjacent adhesive layer, if its exposure for a long time under high temperature environment, fluorine resin film
It can turn yellow.
(2) due to outdoor temperature change drastically, cracking (crackle) can be generated in outermost fluorine resin film.Specifically
For, because of the change dramatically of high temperature/low temperature, thus expansion/contraction is generated cracking by fluorine resin film.It is particularly due to too
It is positive can cell device to have the thickness referred to as busbar be the metal wiring of 0.2mm or so, therefore there are the amount of the thickness of busbar,
Small difference in height can generate cracking if the outdoor temperature change existed drastically by starting point of the small segment difference.
The purpose of the present invention is to provide a kind of backside protective sheets used for solar batteries as a result, and fluorine is used in outermost layer
Based resin film, and inhibit fluorine resin film to turn yellow and generate and be cracked.
(2) technical solution
The present inventor has made intensive studies to reach above-mentioned purpose, as a result, finding to contain specifically in outermost layer
Above-mentioned purpose can be realized in the case of Kynoar, so far complete the present invention.
That is, the present invention relates to following backside protective sheets used for solar batteries and solar cell modules.
1. a kind of backside protective sheet used for solar batteries, configures the back side in solar cell device, feature exists
In,
(1) backside protective sheet used for solar batteries is at least laminated with the first resin layer and the second tree from outermost layer successively
Lipid layer, when being bonded with the solar cell device, by the innermost layer of the outermost layer opposite side and the solar cell
Element is bonded；
(2) first resin layer contains Kynoar, by the infrared absorption spectrum in the Kynoar
The obtained crystalline texture of absorbance is, when setting the crystallization of α types and the crystallization of β types adds up to 100%, 30~70% crystallize for α types,
Remainder crystallizes for β types.
2. in the backside protective sheet used for solar batteries described in above-mentioned technical proposal 1, first resin layer is relative to 100
The Kynoar of mass parts, the methacrylate containing 5~90 mass parts.
3. in the backside protective sheet used for solar batteries described in above-mentioned technical proposal 1 or 2, the thickness of first resin layer
Degree is 10~30 μm.
4. in the backside protective sheet used for solar batteries described in any one of above-mentioned technical proposal 1 to 3, second tree
Lipid layer contains selected from by polyethylene, polyolefin resin, (methyl) acrylic resin, polyvinyl chloride resin, polystyrene
Resinoid, polyvinylidene chloride resinoid, ethylene-vinyl acetate copolymer saponated material, polyvinyl alcohol, polycarbonate-based tree
Fat, fluorine resin, polyvinyl acetate resin, acetal-based resin, polyester resin, polyamide-based resin and polyphenylene oxide resin
At least one of group formed.
5. in the backside protective sheet used for solar batteries described in any one of above-mentioned technical proposal 1 to 4, second tree
Lipid layer is by two layers of composition described above.
6. a kind of solar cell module has the above-mentioned technical side of solar cell device and configuration in its back side
Backside protective sheet used for solar batteries described in any one of case 1 to 5.
(3) advantageous effect
Outermost first resin layer of the backside protective sheet used for solar batteries of the present invention contains Kynoar, by institute
The obtained crystalline texture of absorbance for stating the infrared absorption spectrum in Kynoar is to be crystallized with β types setting the crystallization of α types
When adding up to 100%, 30~70% crystallize for α types, and remainder crystallizes for β types, and thus, it is possible to inhibit long under high temperature environment
Flavescence after time exposure and the generation that is cracked caused by temperature change drastically.
Description of the drawings
Fig. 1 is the figure illustrated to the layer structure of the backside protective sheet used for solar batteries of the present invention.
Specific implementation mode
In the following, the present invention is described in detail.
Backside protective sheet used for solar batteries
The backside protective sheet used for solar batteries of the present invention configures at the back side of solar cell device,
It is characterized in that,
(1) backside protective sheet used for solar batteries is at least laminated with the first resin layer and the second tree from outermost layer successively
Lipid layer, when being bonded with the solar cell device, by the innermost layer of the outermost layer opposite side and the solar-electricity
Pond element fitting；
(2) first resin layer contains Kynoar (PVDF), by the infrared absorption spectrum in the PVDF
The obtained crystalline texture of absorbance is, when setting the crystallization of α types and the crystallization of β types adds up to 100%, 30~70% crystallize for α types,
Remainder crystallizes for β types.
The backside protective sheet used for solar batteries of the present invention as characterized above, outermost first resin layer contain
PVDF is to set the crystallization of α types and the crystallization of β types by the obtained crystalline texture of the absorbance of the infrared absorption spectrum in the PVDF
When adding up to 100%, 30~70% crystallize for α types, and remainder crystallizes for β types, and thus, it is possible to inhibit long under high temperature environment
Flavescence after time exposure and the generation that is cracked caused by temperature change drastically.
In the following, being illustrated to each layer for constituting backside protective sheet used for solar batteries.
First resin layer (outermost layer)
Contain PVDF in first resin layer, by the obtained crystalline texture of the absorbance of the infrared absorption spectrum in PVDF
For when setting the crystallization of α types and the crystallization of β types adds up to 100%, 30~70% crystallize for α types, and remainder crystallizes for β types.This
Outside, the α types, the difference of β types are the obtained crystalline texture of absorbance (crystallization of α types, β type knots by infrared absorption spectrum
It is brilliant) difference.It will inhibit thereby while outermost layer contains fluorine resin since the crystalline texture of PVDF is aforementioned proportion
Turn yellow after being exposed for a long time under hot environment, and inhibits the generation being cracked caused by temperature change drastically.
In the first resin layer, other than the PVDF of crystal type as the crystallization of α types, the crystallization of β types, it can also contain non-
The PVDF of crystal type.First resin layer either with or without non-crystalline type PVDF, as long as by the suction of the infrared absorption spectrum in PVDF
The obtained crystalline texture of luminosity is, when setting the crystallization of α types and the crystallization of β types adds up to 100%, 30~70% crystallize for α types, remain
Remaining part is divided into the crystallization of β types.Wherein, it preferably 40~70% is crystallized for α types, remainder crystallizes for β types.If in addition, crystallization
The ratio of α types crystallization in the PVDF of type and the crystallization of β types within the above range, even if if PVDF then containing non-crystalline type not
It can influence resistance to yellowing and to generating cracking the inhibition under hot environment.
Other than the PVDF in addition to crystal type in the case of PVDF also containing non-crystalline type, set crystal type with it is noncrystalline
When type adds up to 100%, crystal type is preferably 20%~60%, and more preferably 30%~50%.
The PVDF of the present invention refers to the homopolymer of vinylidene fluoride and using vinylidene fluoride as the inclined difluoro second of principal component
Alkene copolymer.As the comonomer of interpolymerized vinylidene fluoride monomer and formation copolymer, such as it there are hexafluoropropene, difluoro second
Alkene, tetrafluoroethene, chlorotrifluoroethylene, trifluoro-ethylene, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) bipolymer, chlorotrifluoroethylene-hexafluoro third
Alkene bipolymer etc..These comonomers can be used alone or be used as two or more mixtures.In addition, partially
The copolymerization ratios of the interpolymerized vinylidene fluoride monomer of fluoride copolymers are preferably 70 mass % of vinylidene fluoride copolymer entirety
More than, more preferably 80 mass % or more.
In addition, in order to improve to characteristics such as the processability of the first resin layer, impact resistance, cementability, heat resistances, remove
Other thermoplastic resins can also be contained except PVDF.For example, it is preferable to which the PVDF relative to 100 mass parts adds 5~90 matter
The methacrylate of part is measured, 5~50 mass parts are more preferably added.In addition, as methacrylate, such as can be appropriate
It uses polymethyl methacrylate (PMMA).
In the resin component of the first resin layer of 100 mass %, PVDF is preferably 50 mass % or more, more preferably
60~90 mass % or so.
First resin layer is single layer, and thickness is preferably 10~30 μm.It is thinner than 10 μm of feelings in the thickness of the first resin layer
Under condition, when manufacturing rear surface of solar cell screening glass, it is also easy to produce fold.In addition, in the case where being thicker than 30 μm, manufacturing too
When positive energy battery module, when carrying out the be bonded i.e. vacuum lamination of process with the encapsulating material (EVA) being layered on element, stripping
The shape of plate is transferred to the outermost layer of back sheet used for solar batteries, makes degraded appearance.If thickness is 10~30 μm, can
The appearance after flexibility (adaptability) of operation and vacuum lamination is kept well.
Second resin layer
It is required that the second resin layer has weatherability and electrical insulating property.
As the resin for constituting the second resin layer, such as polyethylene (PE) (such as high density polyethylene (HDPE) can be used
(HDPE), low density polyethylene (LDPE) (LDPE), linear low density polyethylene (LLDPE)), polypropylene (PP), the polyolefin such as polybutene
Resinoid, (methyl) acrylic resin, polyvinyl chloride resin, polystyrene resins, polyvinylidene chloride resinoid, second
Alkene-vinyl acetate copolymer saponated material, polyvinyl alcohol, polycarbonate resin, fluorine resin (Kynoar, poly- fluorine second
Alkene, ethylene-tetrafluoroethylene copolymer), polyvinyl acetate resin, acetal-based resin, polyester resin (poly terephthalic acid
Glycol ester (PET), polybutylene terephthalate (PBT), polyethylene naphthalate), polyamide-based resin, polyphenylene oxide tree
The films such as fat or sheet material.These films or sheet material can extend along uniaxial or two axis directions.
Second resin layer can be single layer, can also be made of two or more multilayers.It in the case of multiple layers, can be right
Backside protective sheet used for solar batteries assigns higher electrical insulating property and weatherability, meanwhile, it can also assign and as solar energy
The relatively high adhesiveness of the EVA of the encapsulating material of cell device.
Due to the second resin layer have to backside protective sheet used for solar batteries assign electrical insulating property, higher weatherability and
The effect of durability, therefore for the viewpoint, PET is used preferably in above-mentioned resin.In addition, being simple layer in the second resin layer
In the case of, for the viewpoint assigned with the relatively high adhesiveness of EVA, it is preferred to use 0.900~0.940g/cm of density3It is low close
Spend polyethylene (LDPE).
In the case where the second resin layer is multilayer, be preferably set as successively from outer layers towards inner layers pet layer and density 0.900~
0.940g/cm3Low density polyethylene layer (LDPE).By being formed as the sequence, make backside protective sheet used for solar batteries
With electrical insulating property and higher weatherability/durability, while backside protective sheet used for solar batteries and package material can be obtained
The relatively high adhesiveness of material.
Whether the thickness of simple layer or multiple layers, the second resin layer is preferably 50~350 μm.Its reason is：
If the thickness of the second resin layer can not obtain sufficient electrical insulating property less than 50 μm, if more than 350 μm, electrical insulating property is full
With.
Adhesive layer
It can be in the first resin layer and the interlayer of the second resin layer and/or being somebody's turn to do in the case where the second resin layer is multilayer
Interlayer has adhesive layer.For example, as the method for forming adhesive layer, may be used using bi-component curable polyurethane class
Adhesive, poly(ether-urethane) class bonding agent, polyesters bonding agent, polyester polyols alcohols bonding agent, polyester polyurethane polyol class are viscous
Connect the dry lamination method, coetrusion, Extrusion Coating method, the methods of the lamination methods using silane coupling agent of agent etc..
In the present invention, dry lamination method especially can be suitably used, which, which uses, contains aromatic series isocyanide
At least one polyurethanes bonding agent of acid esters or aliphatic isocyanates.
The general additive of each layer
For the purpose of absorbing or reflect ultraviolet light, can the first resin layer, the second resin layer and adhesive layer at least
The white pigments such as titanium oxide, barium sulfate are mixed into one layer.Furthermore it is also possible to be mixed into the well known ultraviolet light in addition to coloring pigment
Additive well known to absorbent, water absorbing agent (drier), deoxidier, antioxidant etc..Further, it is also possible to steady containing well known heat
Determine agent, antioxidant, light stabilizer, ultra-violet absorber, age resister, delustering agent, lubricant, nucleating agent, mechanical performance change
Kind agent etc..
Embodiment
In the following, showing that Examples and Comparative Examples are specifically explained the present invention.But the present invention is not limited to realities
Apply example.
Embodiment 1
To be to set the crystallization of α types as the obtained crystalline texture of the absorbance by infrared absorption spectrum of the first resin layer
With β types crystallization amount to 100% when, α types crystallization be 70%, β types crystallize be 30% thickness be 12 μm white PVDF thin film,
The clear PET film of 250 μm of the thickness as the second resin layer (outer layer side), as the thickness 50 of the second resin layer (internal layer side)
μm white linear low density polyethylene (LLDPE) film, respectively use dry lamination bonding agent, carried out with dry lamination method
It is bonded and is bonded, to make white backside protective sheet used for solar batteries.For bonding agent, using so that its solid constituent painting
Cloth amount is 10g/m2Mode come the bonding agent for preparing.
Embodiment 2
It is to set α types in addition to being used by the obtained crystalline texture of absorbance of infrared absorption spectrum in the first resin layer
Crystallization with β types crystallization add up to 100% when, α types crystallization be 60%, β types crystallize be 40% white PVDF thin film except, with
Embodiment 1 makes white backside protective sheet used for solar batteries in the same manner.
Embodiment 3
It is to set α types in addition to being used by the obtained crystalline texture of absorbance of infrared absorption spectrum in the first resin layer
Crystallization with β types crystallization add up to 100% when, α types crystallization be 50%, β types crystallize be 50% white PVDF thin film except, with
Embodiment 1 makes white backside protective sheet used for solar batteries in the same manner.
Embodiment 4
It is to set α types in addition to being used by the obtained crystalline texture of absorbance of infrared absorption spectrum in the first resin layer
Crystallization with β types crystallization add up to 100% when, α types crystallization be 40%, β types crystallize be 60% white PVDF thin film except, with
Embodiment 1 makes white backside protective sheet used for solar batteries in the same manner.
Embodiment 5
It is to set α types in addition to being used by the obtained crystalline texture of absorbance of infrared absorption spectrum in the first resin layer
Crystallization with β types crystallization add up to 100% when, α types crystallization be 30%, β types crystallize be 70% white PVDF thin film except, with
Embodiment 1 makes white backside protective sheet used for solar batteries in the same manner.
Comparative example 1
It is to set α types in addition to being used by the obtained crystalline texture of absorbance of infrared absorption spectrum in the first resin layer
Crystallization with β types crystallization add up to 100% when, α types crystallization be 80%, β types crystallize be 20% white PVDF thin film except, with
Embodiment 1 makes white backside protective sheet used for solar batteries in the same manner.
Comparative example 2
It is to set α types in addition to being used by the obtained crystalline texture of absorbance of infrared absorption spectrum in the first resin layer
Crystallization with β types crystallization add up to 100% when, α types crystallization be 20%, β types crystallize be 80% white PVDF thin film except, with
Embodiment 1 makes white backside protective sheet used for solar batteries in the same manner.
Comparative example 3
It is to set α types in addition to being used by the obtained crystalline texture of absorbance of infrared absorption spectrum in the first resin layer
Crystallization with β types crystallization add up to 100% when, α types crystallization be 2%, β types crystallize be 98% white PVDF thin film except, with
Embodiment 1 makes white backside protective sheet used for solar batteries in the same manner.
Test example 1 (making of solar cell module and evaluating characteristics)
By the white backside protective sheet used for solar batteries that will be made in Examples and Comparative Examples, according to solar-electricity
Pond is with tempered glass (thickness 3.2mm)/EVA (thickness 0.460mm)/busbar/crystal silicon element (0.25~0.30mm of thickness)/mother
The sequence of line/EVA (thickness 0.460mm)/white backside protective sheet used for solar batteries is laminated, and uses vacuum laminator
(Nano Plasma Ct Co., Ltd.'s system, LM-140X200S) is laminated, to make solar cell module.In addition, "/" indicates the interlayer of each layer.
For each solar cell module, measuring it, (temperature is 120 DEG C, humidity 100%, and air pressure is in PCT test
2atm × 96 hour) after yellowing degree, and to whether there are cracks after TC is tested generate investigate.In addition, PCT is finger pressure
Power pot is tested, and TC refers to thermal cycling test.
(test method 1) measures yellowing degree (△ b values)
In the measurement of yellowing degree, the Color whiteness meter (ProductName made by electricity Se Industrial Co., Ltd of Japan system：
NW11) outermost layer (resin layer 11) of the backside protective sheet used for solar batteries before and after above-mentioned PCT test is measured, will be tried
The difference for testing front and back yellow is indicated with △ b values.
The b values of sample before experiment are set as b1, when the b values of the sample after experiment are set as b2, the difference of b1 and b2 are set
For △ b=b2-b1.
Evaluation criteria is as described below.
·△b<3.0 ... qualified (A)：Discoloration is very small
B≤3.5 ... 3.0≤△ qualification (B)：Slightly change colour, but has no the problem in actual use
·3.5<△ b ... unqualified (C)：Yellowing degree is larger, and brown degree increases in appearance.
Whether there is or not generate to be cracked caused by temperature change drastically for (test method 2) verification
Using thermal cycling test (TC experiments) as whether there is or not the verifications that generation is cracked caused by temperature change drastically.
In thermal cycling test, the ARS-0680-J of Espec manufactures is used.Experimental condition is foundation with IEC61215 10.11.
By thermal cycle be set as 25 DEG C → -40 DEG C (41min), -40 DEG C keep (30min), -40 DEG C → 85 DEG C (75min),
85 DEG C keep (30min), 85 DEG C → 25 DEG C (30min).
In addition, in the state that above-mentioned temperature is more than or equal to 25 DEG C, by the maximum output operating current (Ipm) as module
Electric current be applied to solar cell module, to be tested.
The maximum output operating current (Ipm) applied to solar cell module is by using sun mould before TC is tested
Quasi- device (the rugged electrical system of rock, PXSS4K-1P) is measured power generation output characteristics to obtain measured value.
Solar cell module in being tested to TC using continuous-current plant (Kikusui systems, PAS20-18) applies electricity
Stream.
Whether there are cracks for rear surface of solar cell screening glass after validation test.
It confirmed that whether there are cracks after experiment.Flawless is set as A, has crackle to be set as B.
When confirming crackle, carries out visual confirmation and confirmed using magnifying glass.Magnifying glass has used East Sea industry strain
The manufacture of formula commercial firm must good magnifying glass (ピ ー ク ル ー ペ, Peak loupe) 10X, effective diameter is
Result above is indicated in table 1.
(table 1)
As shown in table 1, contain in the first resin layer when setting the crystallization of α types and the crystallization of β types adds up to 100%, the crystallization of α types is
30~70%, remainder is the backside protective sheet used for solar batteries of the PVDF of β types crystallization, and yellowing degree (△ b values) is no
Foot 3.5, and will not crack.
As comparative example 2,3, in the case that the ratio of the α types crystallization in PVDF is less than 30%, yellowing degree (△ b
Value) will be more than 3.5, when yellowing degree (△ b values) is more than 3.5, visually just know that brown degree increases, to which appearance design becomes non-
It is often poor.In addition, if the ratio of the α types crystallization in PVDF is more than 70%, temperature change drastically can not be born, is split to generate
Line.
Reference sign
10 back-protective films used for solar batteries
11 first resin layers (outermost layer)
12a adhesive layers
12b adhesive layers
13 second resin layers (outer layer side)
14 second resin layer (internal layer sides：The innermost layer of the form of Fig. 1)
Claims (4)
1. a kind of backside protective sheet used for solar batteries configures the back side in solar cell device, which is characterized in that
(1) backside protective sheet used for solar batteries is at least laminated with the first resin layer and the second resin from outermost layer successively
Layer, when being bonded with the solar cell device, by the innermost layer of the outermost layer opposite side and solar cell member
Part is bonded；
(2) first resin layer contains the Kynoar of crystal type and non-crystalline type, by the Kynoar of crystal type
The obtained crystalline texture of absorbance of infrared absorption spectrum be, when setting the crystallization of α types and adding up to 100% with the crystallization of β types,
60~70% crystallize for α types, and remainder crystallizes for β types, also, in the Kynoar for setting the crystal type and non-crystalline type
When adding up to 100%, the content of the Kynoar of crystal type is 20%~60%.
2. backside protective sheet used for solar batteries according to claim 1, which is characterized in that first resin layer is opposite
In the Kynoar of 100 mass parts, the methacrylate containing 5~90 mass parts.
3. backside protective sheet used for solar batteries according to claim 1 or 2, which is characterized in that first resin layer
Thickness be 10~30 μm.
4. a kind of solar cell module has solar cell device and configuration in the claims 1 to 3 of its back side
Backside protective sheet used for solar batteries described in any one.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-233341 | 2013-11-11 | ||
| JP2013233341 | 2013-11-11 | ||
| PCT/JP2014/079849 WO2015068849A1 (en) | 2013-11-11 | 2014-11-11 | Solar cell rear surface protective sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105706251A CN105706251A (en) | 2016-06-22 |
| CN105706251B true CN105706251B (en) | 2018-09-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201480060567.6A Expired - Fee Related CN105706251B (en) | 2013-11-11 | 2014-11-11 | Backside protective sheet used for solar batteries |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2015068849A1 (en) |
| CN (1) | CN105706251B (en) |
| TW (1) | TWI655787B (en) |
| WO (1) | WO2015068849A1 (en) |
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| CN107093646B (en) * | 2017-06-19 | 2023-10-31 | 江苏润达光伏无锡有限公司 | Photovoltaic crystalline silicon component and manufacturing method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103287044A (en) * | 2012-03-01 | 2013-09-11 | 佛山佛塑科技集团股份有限公司 | Polyvinylidene fluoride (PVDF) film for back board of solar battery and manufacturing method of PVDF film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2093804A1 (en) * | 2008-02-19 | 2009-08-26 | Helianthos B.V. | Solar cell system with encapsulant |
| CN101823355B (en) * | 2009-03-03 | 2013-09-25 | E.I.内穆尔杜邦公司 | Polymer laminated film and solar panel using laminated film |
| KR101334571B1 (en) * | 2009-04-20 | 2013-11-28 | 가부시끼가이샤 구레하 | Polyvinylidene fluoride resin composition, white resin film, and backsheet for solar cell module |
| CN101992571A (en) * | 2010-09-02 | 2011-03-30 | 常熟市冠日新材料有限公司 | Insulation backboard for solar photovoltaic module |
| CN202053621U (en) * | 2011-02-11 | 2011-11-30 | 蔡镇州 | Improved back board structure of solar module |
| US20140102533A1 (en) * | 2011-06-15 | 2014-04-17 | Kureha Corporation | Polyvinylidene Fluoride Resin Film, Multilayer Film, Backsheet for Solar Cell Module and Production Process of Film |
| JP6038804B2 (en) * | 2011-11-10 | 2016-12-07 | デンカ株式会社 | Fluorine resin film and solar cell module |
| CN103137732B (en) * | 2011-11-23 | 2016-08-03 | 比亚迪股份有限公司 | A kind of solar cell backboard and a kind of solar module |
-
2014
- 2014-11-11 CN CN201480060567.6A patent/CN105706251B/en not_active Expired - Fee Related
- 2014-11-11 JP JP2015546720A patent/JPWO2015068849A1/en active Pending
- 2014-11-11 TW TW103139052A patent/TWI655787B/en not_active IP Right Cessation
- 2014-11-11 WO PCT/JP2014/079849 patent/WO2015068849A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103287044A (en) * | 2012-03-01 | 2013-09-11 | 佛山佛塑科技集团股份有限公司 | Polyvinylidene fluoride (PVDF) film for back board of solar battery and manufacturing method of PVDF film |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015068849A1 (en) | 2015-05-14 |
| TW201535763A (en) | 2015-09-16 |
| CN105706251A (en) | 2016-06-22 |
| TWI655787B (en) | 2019-04-01 |
| JPWO2015068849A1 (en) | 2017-03-09 |
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