CN105706251B - Backside protective sheet used for solar batteries - Google Patents

Backside protective sheet used for solar batteries Download PDF

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Publication number
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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types
protective sheet
layer
backside protective
sheet used
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CN105706251A (en
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森启太
猿渡昌隆
前田大辅
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Toyo Aluminum KK
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Toyo Aluminum KK
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered 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
    • B32B27/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/34Layered products comprising a layer of synthetic resin comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/04Semiconductor 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
    • H01L31/042PV modules or arrays of single PV cells
    • H01L31/048Encapsulation of modules
    • H01L31/049Protective back sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/12Photovoltaic modules
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

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  • 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

Backside protective sheet used for solar batteries
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.
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