WO2015146780A1 - 太陽電池バックシート及び太陽電池モジュール - Google Patents
太陽電池バックシート及び太陽電池モジュール Download PDFInfo
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- 239000005341 toughened glass Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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- 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
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- 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
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/712—Weather resistant
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
- B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2457/12—Photovoltaic modules
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a solar cell back sheet that is a member for a solar cell module that is excellent in adhesive strength and environmental resistance with a sealing material that can withstand use in a severe outdoor environment for a long period of time, and a solar cell using the solar cell back sheet It is about modules.
- Solar cells used for photovoltaic power generation constitute the heart of a photovoltaic power generation system that directly converts sunlight energy into electrical energy, and are made of semiconductors such as silicon.
- solar cell elements are wired in series or in parallel, and various packaging is performed to protect the elements over a long period of about 20 years, thereby forming a unit.
- the unit incorporated in this package is called a solar cell module.
- the surface exposed to sunlight is covered with glass, the gap is filled with a resin sealing material, and the back surface is protected with a resin sheet called a solar cell back sheet. It has become the composition.
- the sealing material ethylene-vinyl acetate copolymer resin (hereinafter referred to as EVA resin) is often used because of its high transparency and excellent moisture resistance.
- EVA resin ethylene-vinyl acetate copolymer resin
- the solar cell backsheet has mechanical strength, weather resistance, heat resistance, water resistance, chemical resistance, light reflectivity, water vapor barrier, adhesion to sealing material, design, outermost terminal box Properties such as adhesion to a silicone resin adhesive for mounting are required.
- Conventionally used solar battery back sheets include a white polyvinyl fluoride film (for example, DuPont Co., Ltd., trade name: “Tedlar” (registered trademark)) excellent in weather resistance on both surfaces of a polyester film and polyurethane.
- a solar battery back sheet bonded with an adhesive typified by a resin.
- a solar battery back sheet having a laminated structure in which a polyester film is sandwiched between the films is widely used in such applications.
- the structure which bonded together the polyester-type film excellent in the weather resistance and gas barrier property with the adhesive agent is also disclosed (patent document 1).
- a general-purpose polyester resin film has a molecular weight that is reduced by hydrolysis, and since embrittlement progresses and mechanical properties are lowered, improvement thereof, that is, improvement of heat and moisture resistance is required. Therefore, various studies have been made to suppress hydrolysis of the polyester resin. For example, with respect to a biaxially oriented polyester film, studies have been made to improve the moisture and heat resistance by increasing the molecular weight of the resin of the film and controlling the degree of plane orientation (Patent Document 3).
- polyester film especially polyester film with ethylene terephthalate unit as the main constituent, is highly functional for weather resistance, which is important for maintaining a stable protective function over a long period of time. Therefore, when other components (for example, an ultraviolet absorber, inorganic particles, etc.) are mixed, there is a problem that deterioration due to hydrolysis or the like proceeds at the time of melt kneading at the time of use or at the time of use. Moreover, although the function of the component to add is expressed, there existed a problem that heat-and-moisture resistance fell.
- other components for example, an ultraviolet absorber, inorganic particles, etc.
- the adhesive strength with the sealing material layer and the weather resistance of the polyvinyl fluoride film bonded to both surfaces is not limited.
- the hydrolysis reaction proceeds when exposed to heat and humidity over a long period of time.
- a sufficient protection function cannot be maintained, for example, causing a decrease in mechanical strength, and it is a problem that it is expensive.
- An object of the present invention is to provide a solar battery back sheet that is excellent in weather resistance against light irradiation from the back side and excellent in thermal curl characteristics.
- an object relating to the second invention is to provide a solar cell back sheet in which the adhesive strength between the solar cell back sheet and the sealing material and the durability of the adhesive strength are enhanced.
- the first invention adopts the following configuration in order to solve such a problem.
- the C layer is mainly composed of an acrylic resin and is disposed on one outermost surface of the back sheet.
- the base film has an A layer and a B layer,
- the A layer contains a polyester resin as a main component
- the white layer in the A layer is contained in an amount of 5.0% by mass or more and 25% by mass or less, has a thickness of 5 ⁇ m or more, and is disposed on the other outermost surface of the backsheet.
- the B layer includes a polyester resin as a main component, and includes 1.0% by mass or more and less than 5.0% by mass of a white pigment in all components of the B layer, and a thickness of 70% or more of the entire back sheet. Back sheet.
- the solar cell backsheet wherein the C layer is obtained from a C layer forming raw material composition (I) containing an acrylic resin having a hydroxyl group, an isocyanate compound, and a pigment.
- the second invention adopts the following configuration in order to solve such a problem.
- the C layer is disposed on one outermost surface of the backsheet,
- the said C layer is a solar cell backsheet which is obtained from the following raw material composition (II) for C layer formation.
- the raw material composition (II) for forming the C layer includes an acrylic resin having a functional group having reactivity with an isocyanate group and two or more isocyanate compounds, and the isocyanate group is protected by a blocking group.
- the blocked isocyanate compound and the isocyanate compound in which the isocyanate group is not protected by the blocking group are included.
- the C layer of the solar battery backsheet of the present invention faces the back side sealing material, so that the light receiving surface side protective base material, the light receiving surface side sealing material, the cell, the back side sealing material, and the solar battery backsheet However, the solar cell modules arranged in this order.
- the C layer of the solar battery backsheet of the present invention faces the back side sealing material, so that the light receiving surface side protective base material, the light receiving surface side sealing material, the cell, the back side sealing material, and the solar battery backsheet Are arranged in this order and heated, a method for manufacturing a solar cell module.
- a solar battery back sheet excellent in adhesive strength with a sealing material, light reflection characteristics, productivity, and weather resistance that can withstand use in a harsh outdoor environment for a long time can be obtained.
- the solar cell backsheet of this invention is used, the solar cell module excellent in the adhesive strength of a sealing material and a solar cell backsheet, a weather resistance, and the solar cell element protection performance over a long term will be obtained.
- a solar cell back sheet excellent in adhesion strength to a sealing material that can withstand use in a severe outdoor environment for a long period of time can be obtained.
- the solar cell backsheet of this invention is used, the solar cell module excellent in the interface adhesive strength of a sealing material and a solar cell backsheet will be obtained.
- the cross-sectional schematic of an example of the solar cell backsheet of this invention The cross-sectional schematic of an example of the solar cell backsheet of this invention.
- the cross-sectional schematic of an example of the solar cell backsheet of this invention The cross-sectional schematic of the solar cell module of this invention.
- the solar cell backsheet of 1st invention and 2nd invention is demonstrated in detail below.
- the solar cell backsheet of this invention has a base film and C layer.
- the solar cell module in which the solar cell backsheet of the first invention and the second invention is used includes a glass (5) that is a light-receiving surface side protective substrate that receives sunlight (S), and The solar cell (3) connected in series with the sealing material (6), the wiring material (9), and the solar battery back sheet (1) are overlapped and integrated.
- the integration is usually performed through a heating / compression process called vacuum lamination.
- the wiring member (9) is pulled out to the outside on the back side of the module, and electric power is taken out through a terminal box attached with an adhesive.
- the long side and the short side of a rectangular solar cell module are attached to a frame (10) using a material typified by aluminum via an adhesive (4) to form a solar cell module. *
- the solar battery back sheet (1) has a C layer (11) bonded to a sealing material when constituting the solar cell module of the base film (2).
- C layer (11) contains an acrylic resin.
- FIG. 2 is a schematic view of the solar cell backsheet of the first invention.
- the solar battery back sheet (1) is composed of a base film (2) made of a single polyester film including the A layer (30) and the B layer (20), and a sealing material when constituting a solar cell module. And C layer (11) to be bonded together.
- a solar cell backsheet (1) is a base film (2) composed of one polyester film including an A layer (30), a B layer (20) and a D layer (40), and When configuring the solar cell module, the solar cell module has a C layer (11) bonded to the sealing material.
- Base film In common with the first invention and the second invention, as the base film constituting the solar battery back sheet, a polyester film having excellent mechanical strength, dimensional stability, thermal stability and relatively inexpensive is used. Can do. Specific examples include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Among them, a PET film containing polyethylene terephthalate as a main component is particularly preferable because it is excellent as a target for imparting mechanical strength, dimensional stability, thermal stability, processability, and weather resistance.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- the polyester film used for the base film in common with the first invention and the second invention is preferably excellent in hydrolysis resistance. Since the solar cell module is used in an environment that is directly exposed to the outside air, the long-term durability of the adhesive strength with the back side sealing material, the interface of each layer in the solar cell backsheet configuration (in the first invention, A The interface between the layer and the B layer (the interface between the base film and the C layer in common with the first and second inventions) and the interlayer adhesive strength between the solar cell backsheet and the sealing material Is important. This is because, in order to maintain such adhesive strength, it is considered preferable that the wet heat deterioration of the polyester resin constituting the base film is smaller.
- a polyester film is formed from a polymer obtained by polycondensation of monomers, but an oligomer typified by a cyclic trimer, which is positioned between the monomer and the polymer, is 1.5 to 2 mass in the film. About% is included.
- the hydrolysis resistant film contains a polyester resin obtained by polymerization by a solid phase polymerization method, and the cyclic trimer oligomer is 1.0% by mass or less in the polyester resin.
- the polyester resin constituting the base film used in the first and second inventions preferably has a number average molecular weight in the range of 10,000 to 40,000.
- a resin having 5 ⁇ 10 ⁇ 5 m 3 / g or more is preferable. Such a molecular weight provides high hydrolysis resistance.
- the thickness of the base film of the present invention is not particularly limited, but the solar cell back affects the withstand voltage characteristics, partial discharge voltage characteristics, and handling properties in the solar cell module assembly process of the solar cell backsheet. Considering the stiffness and cost of the sheet, the range of 75 to 300 ⁇ m is preferable.
- the base film of the present invention preferably contains 1% by mass or more and 25% by mass or less of a white pigment in the base film regardless of whether it is a single layer or a multilayer.
- the white pigment is not particularly limited, and any organic or inorganic white pigment can be used.
- inorganic white pigments such as zinc oxide, antimony trioxide, and titanium oxide are preferred in consideration of long-term color stability, durability, and ultraviolet absorption.
- titanium oxide is preferable in consideration of ultraviolet resistance.
- rutile type titanium oxide is preferable. It is also preferable to use titanium oxide of the type in which the surface of titanium oxide is coated with an inorganic oxide such as alumina or silica.
- the base film may contain additives such as an antistatic agent, an ultraviolet absorber, a stabilizer, an antioxidant, a plasticizer, a lubricant, a filler, and a coloring pigment as necessary. Can be contained.
- the solar cell backsheet of the first invention has only one base film. And the base film of 1st invention has A layer and B layer.
- the A layer contains a polyester resin as a main component, includes 5.0% by mass to 25% by mass of a white pigment in all components of the A layer, has a thickness of 5 ⁇ m or more, and is different from the C layer of the backsheet. It is arranged on the outermost surface.
- the B layer contains a polyester resin as a main component, and contains 1.0% by mass or more and less than 5.0% by mass of a white pigment in all components of the B layer, and the thickness occupies 70% or more of the entire back sheet.
- the base film in the first invention has at least an A layer and a B layer. And A layer is a layer arrange
- the A layer is arranged on the outermost surface of the solar cell module. It becomes.
- A is the back side of the solar cell module.
- the layers are also exposed to ultraviolet light that scatters in the atmosphere or reflects off the ground.
- the solar cell backsheet will gradually undergo UV degradation, and the protection function provided by the solar cell backsheet will be maintained. There is a concern that this will cause trouble.
- the weather resistance of the A layer is extremely important.
- the A layer is mainly composed of polyester resin.
- the polyester resin is the main component” means that 50% by mass or more and 100% by mass or less of the polyester resin is included in 100% by mass of all the components of the layer.
- the upper limit is preferably 95% by mass or less.
- the A layer preferably contains 5.0% by mass or more and 25% by mass or less of white pigment in the A layer.
- Examples and preferred examples of the white pigment include those described in the above [Base film] column.
- the number average primary particle diameter obtained by observation with a white pigment by an electron microscope is preferably 0.1 to 1.0 ⁇ m, and the dispersibility of the white pigment in the polyester resin in the layer A From the viewpoint of cost, it is more preferably 0.2 to 0.5 ⁇ m.
- the white pigment is dispersed in an island shape in the polyester resin, and the polyester resin can form a sea-like continuous phase, thereby exhibiting sufficient cohesive strength.
- the polyester resin which is the main component of the A layer.
- the polyester resin is deteriorated by ultraviolet rays on the backmost surface of the solar battery back sheet, and there is a possibility that problems such as yellowing, a decrease in mechanical strength, a decrease in film thickness, or generation of cracks may occur.
- the content of the white pigment in the layer A is too large, the ultraviolet absorption performance is sufficiently expressed, but since the ratio of the white pigment in the polyester resin is high, the toughness of the layer A and the film strength in the thickness direction are high. May decrease.
- a terminal box is bonded to the A layer to be disposed on the outermost surface using an adhesive typified by a silicone resin.
- the adhesive tape that is attached to fix the cable to the A layer is peeled off so that the cable will not be uncovered during transportation, the A layer may coherently break down. is there.
- the thickness of the A layer is preferably 5 ⁇ m or more.
- the preferable content of the white pigment contained in the A layer is as described above.
- the various required properties required for the solar cell backsheet the properties of mechanical strength and electrical insulation and the durability thereof are mainly borne by the layer B described later, which has a high proportion of the total thickness. Therefore, the A layer preferably has a function of protecting the B layer from ultraviolet rays that cause ultraviolet degradation and a function of protecting from humidity (water vapor) in the outside air that causes hydrolysis reaction.
- the function of protecting from ultraviolet rays is the ultraviolet shielding function by the A layer, and therefore the content of the white pigment in the A layer is preferably in the range of 5.0% by mass to 25% by mass, and the unit thickness Considering the perimeter ultraviolet shielding factor, the thickness of the A layer is preferably 5 ⁇ m or more.
- the function of protecting from water vapor in the outside air it is known that the water vapor permeability of the polyester resin layer is inversely proportional to the thickness of the polyester resin layer. Therefore, the layer A preferably has a thickness of 5 ⁇ m or more from the viewpoint of the water vapor barrier property per thickness of the polyethylene terephthalate resin or polyethylene naphthalate resin.
- the base film used for the back sheet of the first invention has at least an A layer and a B layer having different components and ratios. Economically, it is preferable to form a base film by melt-extrusion of two kinds of raw materials from two extruders and co-stretching. In such a process, it is difficult to stably form a film having an extremely thin A layer so that the film thickness unevenness is reduced. From that viewpoint, the thickness of the A layer is preferably 5 ⁇ m or more. On the other hand, the upper limit of the thickness of the A layer is not particularly limited. If the thickness of the A layer is too large, the ratio of the B layer to the total thickness may have to be reduced. In that case, the hydrolysis resistance of the solar battery backsheet may be lowered, and therefore the thickness of the A layer is preferably 70 ⁇ m or less.
- the base film of 1st invention has A layer (30) and B layer (20) as above-mentioned. And B layer occupies 70% or more of the thickness of the whole backsheet. B layer can give mechanical strength and electrical insulation with respect to a back sheet because the thickness of B layer occupies 70% or more of the whole back sheet.
- B layer will be described.
- the B layer is made mainly of polyester resin.
- the main component of the polyester resin means that 50% by mass or more and 100% by mass or less of the polyester resin is included in 100% by mass of all the components of the layer. About an upper limit, Preferably it is 99 mass% or less.
- the moisture and heat resistance of the solar cell backsheet is important from the viewpoint of durability. It is. It is known that moisture in the atmosphere is adsorbed on the surface layer of the solar cell backsheet, diffuses in the thickness direction of the solar cell backsheet, and enters the module. It is known that each layer constituting the solar cell backsheet acts with moisture, and particularly a hydrolysis reaction proceeds with respect to the polyester resin. When a hydrolysis reaction occurs in the polyester resin, the molecular weight decreases, for example, the mechanical strength decreases.
- the polyester resin constituting the solar battery backsheet is formed of a polyester resin having a cyclic trimer content of 1.0% by mass or less obtained by polymerization by a solid phase polymerization method as a raw material.
- a hydrolyzable polyester film or the like is preferably used.
- the inventors have found that when the content of the white pigment in the layer present in the polyester resin film is less than 5.0% by mass, good hydrolysis resistance can be maintained. That is, the B layer of the base film used for the back sheet of the first invention contains 1.0% by mass or more and less than 5.0% by mass of the white pigment in all the components of the B layer.
- the white pigment of the B layer constituting the solar cell backsheet of the first invention is too much, the light reflectance of the solar cell backsheet is improved due to the visible light reflection characteristics of the white pigment. The hydrolyzability may be inferior.
- the concern which produces a micro air hole (void) around a white pigment increases.
- the polyester resin which is a main component constituting the base film, can maintain the inherent hydrolysis resistance, and air holes (voids). There is no concern that there will be a significant increase in concerns about
- the content of the white pigment in the B layer is too small, the amount of the pigment having the light reflection performance is too small in the B layer occupying 70% or more of the total thickness in the solar cell backsheet of the first invention. Therefore, the light reflection characteristics that contribute to the power generation characteristics of the solar cell module may be inferior.
- the B layer occupies 70% or more of the total thickness of the solar cell backsheet of the first invention, practically sufficient light reflection characteristics are expressed by the amount of the white pigment in the B layer, The mechanical strength of the entire solar battery back sheet, electrical insulation, and their heat and humidity resistance are realized.
- the thickness of the B layer is smaller than the total thickness of the back sheet, the ratio of the thickness of the A layer or the C layer having a high white pigment concentration increases, and the heat and moisture resistance and mechanical strength may decrease. Also, the cost may increase.
- sheet is preferable.
- the thickness of B layer is 50 micrometers or more from a viewpoint of the mechanical characteristic of a base film, electrical insulation, and durability of the said characteristic.
- the A layer and the B layer of the base film constituting the solar cell backsheet of the first invention may include, for example, an antistatic agent, an ultraviolet absorber, a stabilizer, an oxidation agent as necessary.
- Additives such as an inhibitor, a plasticizer, a lubricant, a filler, and a color pigment can be added within a range that does not impair the effects of the first invention.
- a well-known method can be used about the film-forming method of the base film which has A layer and B layer characterized by the solar cell backsheet of 1st invention.
- the polyester resin which is the main component of the A layer and B layer, is dried as necessary, and the polyester resin fed from different flow paths using two or more extruders is converted into a multi-manifold die, field block, static mixer, A method of laminating in multiple layers using pinol or the like can be used. Moreover, you may combine these arbitrarily.
- the sheets stacked in multiple layers discharged from the die are extruded onto a cooling body such as a casting drum, and cooled and solidified to obtain a casting sheet.
- a cooling body such as a casting drum
- Biaxial stretching refers to stretching in the longitudinal direction and the transverse direction. Stretching may be sequentially biaxially stretched or simultaneously stretched in two directions. Further, re-stretching may be performed in the longitudinal and / or transverse direction.
- a known technique can be used as a method of dispersing the white pigment in the film layer so as to have a constant content.
- a method of adding a white pigment having a number average primary particle size of 0.1 to 1 ⁇ m to the base film and dispersing it uniformly in the film will be described.
- the method of adding the white pigment is preferably a compound method. Specifically, a method of adding a large amount (for example, 50% by mass) of a titanium oxide pigment to a polyester resin to prepare a master chip and diluting to a target concentration is preferable.
- a dispersion aid can be used, and polyalkylene glycol or a copolymer thereof can be used. Specifically, polyethylene glycol, polypropylene glycol, polybutylene terephthalate-polytetramethylene glycol copolymer and the like are preferably used.
- the base film may be provided with a layer such as a metal thin film or an inorganic oxide by vapor deposition for the purpose of imparting a water vapor barrier property.
- a layer such as a metal thin film or an inorganic oxide by vapor deposition for the purpose of imparting a water vapor barrier property.
- the base film may be subjected to surface treatment such as discharge treatment such as corona discharge or plasma discharge, or acid treatment, if necessary.
- the solar cell backsheet of 1st invention and 2nd invention has a base film and C layer. And this C layer is arrange
- C layer will be bonded together with a back side sealing material.
- Such a C layer will be described below.
- C layer is a layer mainly composed of acrylic resin.
- the main component of the acrylic resin means that 50% by mass or more and 100% by mass or less of the acrylic resin is included in 100% by mass of all the components of the layer.
- a lower limit it is preferable to set it as 60 mass%.
- an upper limit it is preferable to set it as 90 mass% or less in all the components of a layer.
- the C layer of the solar battery back sheet is often used by adhering to the back side sealing material in the solar battery module, the light including ultraviolet rays passing through the gap between the solar battery cell and the solar battery cell is the back of the solar battery. It will reach the C layer surface of the sheet. Depending on the wavelength of the reached light, the composition forming the C layer, and the binding energy of each bond included in the repeating structure, the layer may cause a photodegradation reaction. Further, when light passes through the sealing material and the C layer, there is a concern that a photodegradation reaction may occur in the base film layer adjacent to the C layer.
- the resin constituting the C layer is selected in consideration of weather resistance and adhesiveness. Therefore, in the first invention and the second invention, in addition to the polyester resin, the olefin resin, and the urethane resin, an acrylic resin having a relatively excellent weather resistance as a main component is preferably used as a main component.
- the acrylic resin has an advantage that it is easy to improve the adhesive strength with the base film and the dispersibility or compatibility with other polymers by optimizing the selection, combination and blending ratio of monomers.
- Sealing materials used for solar cell modules are generally transparent sheet members mainly composed of EVA resin, but the material is often Contains a UV absorber. Also, normally, when configuring a solar cell module, two sealing materials are used, and solar cells connected in series by a wiring material are sandwiched between the two to protect and fill the solar cells. To do. As described above, in a solar cell module using two encapsulants containing an ultraviolet absorber and having a thickness of about 400 to 600 ⁇ m, the amount of ultraviolet rays reaching the solar cell back sheet surface from the light receiving surface side is the light received from glass or the like.
- the solar cell module in which the solar cell back sheet of the first invention is bonded to the outermost surface is installed outdoors for a long period of time and power is generated, ultraviolet rays reach even if the transmittance is 10% or less. Will continue. Accordingly, the C layer itself is excellent in weather resistance, and if the C layer is not shielded from ultraviolet rays, there is a concern that the ultraviolet rays reach the polyester film which is the underlayer of the C layer and cause the ultraviolet degradation of the polyester resin.
- the C layer transmits light having a wavelength of 350 nm more than 50%
- the base film mainly deteriorates due to ultraviolet rays and discolors, and the color tone change of the C layer surface of the C layer solar battery backsheet increases.
- the mechanical strength of a solar cell backsheet may also fall.
- the amount of light transmitted through the C layer is 50% or less at a wavelength of 350 nm, it is possible to suppress the light deterioration of the polyester film, and as a result, discoloration and a decrease in mechanical strength are less likely to occur.
- the phenomenon that light having a wavelength of 350 nm is transmitted through the C layer does not contribute to the development of these functions in any of the solar cell backsheet and the solar cell module.
- the amount of light having a wavelength of 350 nm may be 0%. That is, in the solar cell backsheet of the first invention, it is preferable that the C layer has a light transmittance of a wavelength of 350 nm of 0% or more and 50% or less.
- an ultraviolet absorber is contained in the C layer in order to make the transmittance of light having a wavelength of 350 nm of the C layer 50% or less.
- Organic UV absorbers can be used. However, in the case of an organic ultraviolet absorber, it is assumed that the organic ultraviolet absorber moves to the sealing material layer, so that it is relatively difficult to move to another layer, and an inorganic ultraviolet ray having long-term stability. It is preferable to use a polymer type ultraviolet absorber chemically bonded to the absorber or polymer.
- the inorganic ultraviolet absorber metal oxides such as titanium oxide, zinc oxide, and cerium oxide are preferable from the viewpoint of ultraviolet absorption performance, durability, and versatility, but they have a particularly high refractive index and excellent concealability. Further, it is preferable to use rutile type titanium oxide having good weather resistance. That is, it is preferable that the C layer of the solar cell backsheet of the first invention and the second invention contains an ultraviolet absorber.
- the content of the ultraviolet absorber is preferably in the range of 10% by mass to 50% by mass with respect to all components of the C layer.
- the content of the ultraviolet absorber is within the above range, not only can the ultraviolet shielding effect and sealing material adhesion be compatible, but also includes an inorganic ultraviolet absorber having a large specific gravity compared to the acrylic resin, which will be described later. If the C layer is formed by this method, the film formation stability is also excellent.
- the acrylic resin preferably used for the C layer is a polymer containing a component derived from at least one acrylic monomer in its repeating structure. That is, the acrylic resin refers to a polymer obtained from at least one acrylic monomer, and may be a copolymer polymer obtained from a plurality of monomers including at least one acrylic monomer.
- An acrylic monomer means acrylic acid and its ester, and methacrylic acid and its ester.
- acrylic acid esters and methacrylic acid esters include methyl methacrylate, methyl acrylate, and ethyl acrylate, and methyl methacrylate and methyl acrylate are particularly preferable from the viewpoints of versatility, cost, and light stability.
- Copolymerization monomers that can be used to produce acrylic resins in addition to acrylic monomers include unsaturated carboxylic acids such as maleic acid and itaconic acid, unsaturated carboxylic acid anhydrides such as maleic anhydride, and butadiene And unsaturated hydrocarbons such as ethylene and vinyl esters such as vinyl acetate.
- the C layer can introduce a crosslinked functional structure by introducing a reactive functional group and adding a crosslinking agent capable of reacting with the reactive functional group.
- the solar cell backsheet of the first invention is exposed to high temperature treatment in the solar cell module manufacturing process.
- a white pigment may be blended for the purpose of improving the ultraviolet shielding property of the C layer, etc. In order to suppress embrittlement of the C layer caused by the blending and to improve the toughness and strength of the C layer. .
- Examples of the reactive functional group introduced into the C layer for this purpose include a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, a silyl group, and the like. Therefore, it is selected as appropriate in accordance with the reaction mode. Among these, those reactive with an isocyanate compound described later, that is, reactive with an isocyanate group are preferable.
- a hydroxyl group, a cyano group, a glycidyl group and a silyl group are preferable from the viewpoint of good reactivity, and a hydroxyl group is particularly preferable from the viewpoint of easy availability of the resin and good reactivity.
- the C layer preferably contains an acrylic resin having a functional group reactive with an isocyanate group, particularly an acrylic resin having a hydroxyl group, and the C layer is obtained using a composition containing an acrylic resin having a hydroxyl group. It is preferable that it is a layer to be formed.
- the acrylic resin having a hydroxyl group reacts with an isocyanate compound to become an acrylic resin containing a urethane bond.
- a monomer used for obtaining an acrylic resin having a hydroxyl group will be described.
- monomers used for introducing hydroxyl groups into the acrylic resin include hydroxyl group-containing acrylic monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl, and the like.
- examples include hydroxyl group-containing vinyl ethers such as vinyl ether, and hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether.
- the hydroxyl value of the acrylic resin having a hydroxyl group is preferably 2 to 100 mgKOH / g in terms of solid content. It is preferably 2 to 50 mgKOH / g, more preferably 2 to 30 mgKOH / g.
- the hydroxyl value of the acrylic resin is too large, the degree of cross-linking of the C layer becomes dense, and the adhesive strength to the base film tends to decrease.
- the hydroxyl value is too small, the degree of cross-linking of the C layer is lowered, and thus the heat and moisture resistance is lowered.
- crosslinking agent that can be contained in the composition for forming a C layer composed of an acrylic resin composition
- This crosslinking agent forms a crosslinked structure by bonding with the functional group of the acrylic resin having a reactive functional group in the composition.
- the heat resistance improvement and embrittlement of the coating film can be suppressed.
- the effect of improving the adhesive strength between the base film and the C layer can be obtained by the inclusion of the crosslinking agent.
- the C layer is preferably a layer obtained using a C layer forming raw material composition containing an acrylic resin having a hydroxyl group, an isocyanate compound, and a white pigment added as necessary.
- an isocyanate compound suitable as a crosslinking agent a compound having two or more isocyanate groups is preferable.
- Suitable isocyanate compounds include aromatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.
- a resin obtained from an isocyanate containing an aromatic ring having an absorption band of light in the ultraviolet region in the resin skeleton is easily yellowed with ultraviolet irradiation, and thus has an alicyclic polyisocyanate and an aliphatic polyisocyanate as a main component. It is preferable to use a crosslinking agent.
- Each is a compound using a diisocyanate compound shown below as a raw material.
- diisocyanate used as a raw material for the alicyclic polyisocyanate examples include 1,4-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), and the like.
- diisocyanate used as a raw material for the aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and the like.
- polyisocyanate As a raw material of polyisocyanate, it is also possible to use a combination of these diisocyanates in combination, or to use modified products such as a burette modified product and a nurate modified product.
- a curing process in which heat is applied is usually employed.
- the curing conditions differ depending on the combination of the type of acrylic resin and the type of isocyanate compound, it is, for example, about 50 ° C. and about 3 days.
- the crosslinking reaction proceeds between the isocyanate compound and the hydroxyl group in the acrylic resin having a hydroxyl group, and an acrylic resin having a urethane bond is formed, whereby the strength and toughness of the C layer is improved.
- the C layer forming raw material is protected with a blocked isocyanate compound and a blocking group.
- the isocyanate compound which is not made is included. That is, the raw material for forming the C layer includes two or more isocyanate compounds, and the isocyanate compound is a blocked isocyanate compound in which an isocyanate group is protected by a blocking group, and an isocyanate compound in which the isocyanate group is not protected by a blocking group.
- it contains two or more kinds of isocyanate compounds.
- the blocked isocyanate compound is obtained by blocking an isocyanate group in the isocyanate compound with a blocking group, and the blocking group is eliminated by heating, and an isocyanate group is generated, so that a crosslinking reaction proceeds. Therefore, below the temperature necessary for elimination of the blocking group, no reactivity is exhibited, the characteristics of the resin layer are stable, and the storage stability is good.
- the isocyanate compound contains two or more isocyanate compounds, and the isocyanate compound is a blocked isocyanate compound in which an isocyanate group is protected by a blocking group, and an isocyanate compound in which the isocyanate group is not protected by a blocking group.
- the C layer in the resulting backsheet is a layer containing an acrylic resin having a hydroxyl group, an acrylic resin having a urethane bond, an isocyanate compound (block isocyanate compound), and a white pigment.
- the isocyanate compound in which the isocyanate group in the raw material for forming the C layer is not protected by the blocking group forms a crosslinking reaction with the acrylic resin to form an acrylic resin having a urethane bond. It becomes.
- the blocked isocyanate compound is contained in the C layer without being reacted. Therefore, it is preferable that C layer of a solar cell backsheet is a layer containing the acrylic resin which has a hydroxyl group, the acrylic resin which has a urethane bond, an isocyanate compound (block isocyanate compound), and a white pigment.
- the blending ratio of the blocked isocyanate compound in which the isocyanate group is protected with a blocking group is preferably in the range of 0.1 to 20 parts by mass with respect to 1 part by mass of the isocyanate compound in which the isocyanate group is not protected with a blocking group.
- the raw material composition for forming the C layer can contain a solvent.
- the acrylic resin is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more with respect to the component excluding the solvent in the C layer forming raw material composition (referred to as “solid content” in this paragraph). . Moreover, 90 mass% or less is preferable.
- the C layer forming raw material composition contains an isocyanate compound, the content is preferably in the range of 0.1 to 5 isocyanate groups with respect to one hydroxyl group of the acrylic resin.
- an isocyanate compound is added, the range of 0.01 to 5% by mass with respect to the solid content of the C layer forming raw material composition is preferred.
- the C layer contains a white pigment, it should be contained in an amount of 10 to 50% by mass, further 10 to 45% by mass, and further 10 to 40% by mass with respect to the solid content of the raw material composition for forming the C layer. Is preferred.
- Examples of the blocking agent for the isocyanate group used in the blocked isocyanate compound include ⁇ -caprolactam, phenol, cresol, oxime, alcohol and the like, but are not limited thereto.
- the blocked isocyanate compounds a non-yellowing blocked isocyanate compound that does not have an isocyanate group directly bonded to an aromatic ring is preferable from the viewpoint of preventing yellowing of the C layer.
- the solar cell module in which the solar cell module of the first invention and the second invention is used is such that the C layer of the solar cell back sheet faces the back side sealing material,
- the light-receiving surface side sealing material, the cell, the back side sealing material, and the back sheet are arranged in this order and are obtained by laminating.
- vacuum lamination is generally performed, but heat necessary for detachment of the block group is applied when the lamination is performed in this vacuum lamination process.
- elimination of blocking groups, generation of isocyanate groups, and cross-linking reactions with components contained in the sealant occur, and after the durability test from the beginning, it is strong and stable under actual outdoor exposure. It shows the adhesive strength.
- the method for forming the C layer includes a method of laminating or coating a raw material composition for forming a C layer ((I) or (II)) that has been melted or dispersed in water in the film forming process of the base film, and C layer formation
- a method of laminating or coating a raw material composition for forming a C layer ((I) or (II)) that has been melted or dispersed in water in the film forming process of the base film, and C layer formation
- Any of the methods of applying a coating to a base film as a coating solution using water or an organic solvent as a medium is possible.
- the method of forming the C layer using a method of applying a coating solution in which the raw material for forming the C layer is dispersed or dissolved in an organic solvent as a medium is excellent in productivity and quality stability of the C layer.
- the C layer is provided by applying a coating solution
- it is applied to the base film, then heated and dried, and in some cases, cured by ultraviolet irradiation or the like.
- a coating method known coating methods such as gravure coating and roll coating can be applied.
- the temperature of the drying oven is set to a high temperature of 150 ° C. or higher in the drying process after coating, and the C layer is formed by heating and drying. The heat shrinkage rate of the battery back sheet can also be reduced, which is economically useful.
- examples of the solvent for the coating solution include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and water.
- the properties of the coating liquid may be either an emulsion type or a dissolution type.
- the thickness of the C layer is not particularly limited, but is preferably 0.2 ⁇ m or more and less than 3 ⁇ m.
- the thickness of the C layer is in the range of 0.2 ⁇ m or more and less than 3 ⁇ m, especially when the C layer is formed by a wet coating method, appearance defects such as pinholes are not likely to occur, and relatively little diluting solvent is volatilized. Since coating can be performed under conditions, it is excellent in drying efficiency, can easily increase the coating speed, and is economically advantageous.
- the solar cell backsheets of the first invention and the second invention are such that when the sheet cut into a size of 20 cm in length and 20 cm in width is heated at 150 ° C. for 30 minutes, the rise of the four corners of the sheet is 30 mm or less.
- the solar cell module is such that the sealing material adhesion surface of the solar cell back sheet faces the back side sealing material side, the light receiving surface side protective base material, the light receiving surface side sealing material, the cell, the back side
- the laminate is manufactured by a method of laminating the laminated body after carrying it into a device called a vacuum laminator having a heating plate capable of heating, a vacuum pump, etc. .
- the hot plate temperature is lowered and the heating to the laminate becomes uneven or uneven.
- unevenness occurs in the degree of crosslinking of the sealing material. As a result, it may cause a difference in the quality of the solar cell module. Therefore, a means for preheating the laminated body and then transporting it into the vacuum laminator is used.
- the solar battery back sheet curled on the lower lid of the apparatus that is lowered causes problems such as bending.
- the solar battery backsheet configured by bonding two or three films
- the solar battery backsheet is wound on the side of the film having a large heat shrinkage ratio by heating. This force causes curling.
- each film constituting the solar cell backsheet is previously reduced in heat shrinkage ratio and then bonded with an adhesive to form a solar cell backsheet.
- the process including the transport process is performed a plurality of times, defects such as scratches may occur, and the number of processes increases, resulting in poor productivity and economy.
- the solar cell backsheet of the present invention by constituting with only one base film, there is no fear of curling at the time of heating due to the difference in heat shrinkage rate between the films, and in the solar cell module manufacturing process, Defects are reduced.
- the surface layer cohesive strengths of the A layer and the C layer measured according to ISO 2409 (2013 version) are preferably class 0.
- the A layer and the C layer forming the outermost surface may rub against other members in the solar cell module assembly process.
- there are processes such as attaching the terminal box via an adhesive or sticking an adhesive tape to temporarily fix the cable, and peeling off the temporary fixing tape when the solar cell module is installed. Therefore, it is preferable that the A layer and the C layer of the solar cell module of the first invention have a surface layer cohesive strength that can withstand physical stress when the rubbing or the adhesive tape is peeled off.
- the C layer and the C layer preferably have a high surface layer cohesive strength.
- the surface layer cohesive strength of a practically sufficient surface layer in the manufacturing process and use environment of the solar cell module that is, the surface layer cohesive strength of the A layer and the C layer measured according to the description of ISO 2409 (2013 edition) to class 0
- the following embodiments are preferred.
- the solar cell backsheet of the first invention has only one base film and a C layer, and the base film has an A layer and a B layer, which are A layer / B layer / C. Although they exist in the order of the layers, another layer may exist between the A layer and the B layer or between the B layer and the C layer. That is, the solar cell backsheet of the first invention has an A layer, a B layer, and a C layer, as long as the C layer is disposed on one outermost surface and the A layer is disposed on the other outermost surface. There may be another layer inside. As shown in FIG. 3, for example, a layer (D layer (40)) containing a polyester resin as a main component may be further provided between the C layer (11) and the B layer (29).
- the D layer having a higher white pigment content than the B layer is used as the C layer and the B layer.
- the design formed between the two is effective.
- the white pigment is included in the D layer, the content of the white pigment is preferably 5% by mass or more and 20% by mass or less with respect to 100% by mass of all components of the D layer.
- the solar cell module of the present invention is such that the C layer of the solar cell backsheet obtained as described above faces the back side sealing material side,
- the light-receiving surface side protective base material, the light-receiving surface-side sealing material, the cell, the back-side sealing material, and the back sheet are arranged in this order, and are obtained by heating and laminating.
- the heating temperature in the laminating step is preferably in the range of 120 ° C. or higher and 180 ° C. or lower, more preferably in the range of 130 ° C. or higher and 170 ° C. or lower in consideration of the crosslinking reaction of the sealing material layer and the blocking group elimination reaction of the blocked isocyanate compound.
- Examples of the sealing material (light-receiving surface side sealing material, back side sealing material) used for the solar cell module include EVA resin, polyvinyl butyral, and modified polyolefin, but the present invention is limited to these. It is not a thing. Among these, EVA resin is preferable from the viewpoint of weather resistance, heat resistance, and member cost.
- the use of the solar cell backsheet of the present invention is not limited by the type of power generation layer, and can be suitably used in any type of solar cell module.
- part means “part by mass” unless otherwise noted.
- Thickness of each layer The total thickness was measured according to JIS C2151 (1990), and the laminated section was pretreated by cutting the section in the thickness direction with a microtome, and then a field emission scanning electron microscope (FE) manufactured by Hitachi, Ltd. -SEM) Using S-800, the thickness section was imaged at a magnification ( ⁇ 1000) at which the entire image was taken, and the thickness of the section photograph was measured.
- FE field emission scanning electron microscope
- Titanium oxide content in each layer Using the solar cell backsheet as a sample, the elemental amount of titanium, which is an element peculiar to titanium oxide, was determined by a fluorescent X-ray elemental analyzer (manufactured by Horiba, MESA-500W type). . The titanium oxide content was converted from the titanium element amount.
- C layer transmittance (C layer light transmittance of 350 nm wavelength)
- both the standard white plate opening and the test piece opening were made of alumina oxide as the standard white plate, and the test piece opening was tilted at an angle of 10 ° at 300 to 350 nm, and there was no sample.
- the state transmittance was measured (A0), and the transmittance at that time was 100%.
- a film with less absorption in the ultraviolet light region hereinafter referred to as “ETFE film”) (50 ⁇ m, transparent) is placed on the front surface of the incident light, and the transmittance at 300 to 350 nm is measured every 5 nm, and the transmittance at 350 nm.
- T (%) Tetfe / c (%) / Tetfe (%) ⁇ 100.
- the tested pseudo solar cell module sample is obtained by stacking an EVA sheet on the C layer surface of the produced solar cell back sheet, further stacking a semi-tempered glass with a thickness of 0.3 mm thereon, and after reducing the pressure using a commercially available vacuum laminator, What was press-treated for 15 minutes under a load of 1 atm under a 142 ° C. heating condition was used.
- the EVA sheet a 450 ⁇ m-thick sheet (Fast cure type) manufactured by Sanvic Co., Ltd. was used.
- the width of the test piece of the adhesive strength test was 10 mm, and each of the two test pieces was measured once, and the average value of the two measured values was taken as the value of the adhesive strength.
- the test piece which measured the adhesive strength with a sealing material by said method was processed for 2000 hours under the conditions of the temperature of 85 degreeC and the relative humidity of 85% RH in the constant temperature and humidity oven by Espec Co., Ltd. After that, the adhesive strength with the sealing material after the wet heat test was measured according to the above method. It was judged that the adhesive strength was 30 N / 10 mm or more at a level where there was no practical problem.
- the produced solar cell backsheet was cut into a size of 1 cm ⁇ 20 cm and pulled at a chucking distance of 5 cm and a pulling speed of 300 mm / min.
- Elongation at break (%) E1 / E0 ⁇ 100
- the obtained elongation retention was determined as follows. When the elongation at break is 50% or more: A When the elongation at break is 40% or more and less than 50%: B When the elongation at break is 30% or more and less than 40%: C When the elongation at break is less than 30%: D.
- the solar battery backsheet cut into a size of 20 cm in length and 20 cm in width is laid flat on a heatable plate so that the C layer is in contact with the plate, and the plate is heated to 150 ° C. And left for 30 minutes. At that time, the solar cell back sheet was evaluated by the height of the four corners (vertical distance between each of the four corners and the hot plate). The rise of all four corners of the sheet is 10 mm or less: A Not applicable to either A or C: B The rise of any of the four corners of the sheet exceeds 30 mm: C.
- PET polymer a 100 parts of terephthalic acid as a dicarboxylic acid component) is mixed with 64 parts of ethylene glycol, 0.1 parts of zinc acetate and 0.03 part of antimony trioxide are added as catalysts, and transesterification is performed at the reflux temperature of ethylene glycol. did.
- this PET was put into a rotary vacuum apparatus (rotary vacuum dryer) having a high polymerization temperature of 220 ° C. and a vacuum degree of 0.5 mmHg, and heated for 10 hours while stirring to solid-phase polymerize to obtain a PET polymer. It was.
- a rotary vacuum apparatus rotary vacuum dryer
- PET polymer b high concentration titanium oxide masterbatch
- the PET polymer a produced by the above method and titanium oxide (rutile type, average particle size 200 nm) were compounded to obtain a master chip with 50% by mass of titanium oxide.
- This master chip was designated as PET polymer b.
- the density of the master chip was 2.5 g / cm 3 .
- the chip shape of the master chip was a cylindrical chip shape having a length of 2.40 to 4.60 mm, a width of 3.20 to 4.80 mm, and a height of 1.70 to 2.30 mm.
- PET polymers cm Preparation of PET polymers cm
- the PET polymer a and the PET polymer b produced by the above method were mixed at the blending ratio shown in Table 1 to obtain polyester film-forming resin raw materials PET polymers cm.
- a titanium oxide pigment having an average particle diameter of 100 nm is blended with this solution so that the mass ratio to the resin solid content is 30 mass%, and ethyl acetate and methyl isobutyl ketone (1 to 1 mass ratio) are added as a mixed dilution solvent. Then, the concentration was adjusted so that the total solid content mass was 50% by mass of the solution to obtain a titanium oxide-containing acrylic polymer solution (C2).
- hexamethylene polyisocyanate (HDI) -containing curing agent solution “N-3200” manufactured by Sumika Bayer Urethane Co., Ltd. as a polyisocyanate curing agent is added to 100 parts of the above-mentioned titanium oxide-containing acrylic polymer solution (C2).
- methyl isobutyl ketone was further blended and the concentration was adjusted so that the total solid content was 20% by mass to obtain a C layer forming raw material composition (C3).
- C layer forming raw material composition C6 The acrylic polymer solution (C1) obtained by the above method was diluted with methyl isobutyl ketone to adjust the total solid content concentration to 50% by mass. 1 part of the above-mentioned hexamethylene polyisocyanate (HDI) -containing curing agent solution “N-3200” is blended with 100 parts of the acrylic polymer solution, and then methylisobutylketone is additionally blended, so that the total solid mass is 30 masses. The concentration was adjusted to be% and a C layer forming raw material composition (C6) was obtained.
- HDI hexamethylene polyisocyanate
- a titanium oxide pigment having an average particle diameter of 100 nm is blended so that the mass ratio with respect to the resin solid content is 30% by mass, and ethyl acetate and methyl isobutyl ketone are added as a diluent solvent to give a total solid mass of 50% of the solution.
- the concentration was adjusted to be mass% to obtain a titanium oxide-containing acrylic polymer solution (C7).
- hexamethylene polyisocyanate (HDI) -containing curing agent solution “N-3200” manufactured by Sumika Bayer Urethane Co., Ltd. as a polyisocyanate curing agent is added to 100 parts of the above-mentioned titanium oxide-containing acrylic polymer solution (C7).
- methyl isobutyl ketone was further blended and the concentration was adjusted so that the total solid content was 20% by mass, to obtain a C layer forming raw material composition (C8).
- Example 1 The PET polymer e shown in Table 1 was used as the A layer forming raw material, and the PET polymer k was used as the B layer forming raw material so as to be B layer / A layer. As shown in Table 2, the thickness of the layer A was 50 ⁇ m, the thickness of the layer B was 200 ⁇ m, and the total thickness was 250 ⁇ m. The thickness was controlled by adjusting the discharge amount of the extruder. An unstretched sheet obtained by cooling and solidifying a sheet-like molded product discharged from a T-die with a cooling drum having a surface temperature of 25 ° C.
- the C layer forming raw material C3 was applied to the B layer surface of the base film using a wire bar, dried at 180 ° C. for 60 seconds, and the C layer was provided so that the coating thickness after drying was 2 ⁇ m. .
- the sheet thus obtained was aged at 40 ° C. for 3 days to produce a solar battery back sheet, BS1.
- Example 2 Except that a base film made of a biaxially stretched polyester film was formed in the same manner as in Example 1 so that the A layer and the B layer had a predetermined thickness using the respective PET polymer raw materials shown in Table 2.
- Example 6 Using a PET polymer raw material shown in Table 2, a base film made of a biaxially stretched polyester film was formed in the same manner as in Example 1 so that the A layer and the B layer had a predetermined thickness. .
- C layer forming raw material composition C5 is applied to the surface of layer B of the base film using a wire bar, dried at 180 ° C. for 60 seconds, and dried so that the coating thickness is 0.5 ⁇ m.
- a layer was provided.
- the sheet thus obtained was aged at 40 ° C. for 3 days to produce a solar battery back sheet BS6 having a laminated structure shown in Table 2.
- Example 7 The PET polymer f shown in Table 1 is laminated as a raw material for forming the A layer and the D layer, and the PET polymer j is laminated as a raw material for forming the B layer so as to be a three layer composite of A layer / B layer / D layer through a laminating apparatus, Molded into a sheet from a T-die.
- the laminated structure was laminated by adjusting the discharge amount of the extruder so that the thickness of the A layer and the D layer was 35 ⁇ m, the thickness of the B layer was 170 ⁇ m, and the total thickness was 240 ⁇ m.
- An unstretched sheet obtained by cooling and solidifying a sheet-like molded product discharged from a T-die with a cooling drum having a surface temperature of 25 ° C. is led to a roll group heated to 85 to 98 ° C., and stretched 3.3 times in the longitudinal direction, and 21 to It cooled with the roll group of 25 degreeC. Subsequently, the film was stretched by 3.6 times in the direction perpendicular to the longitudinal direction in an atmosphere heated to 130 ° C. while being guided to a tenter while holding both ends of the longitudinally stretched film with clips. Thereafter, heat setting was performed at 220 ° C. in a tenter, and after uniform cooling, the solution was cooled to room temperature to obtain a base film made of a biaxially stretched polyester film having a winding thickness of 250 ⁇ m.
- C layer forming raw material C5 is applied to the surface of layer D of this base film using a wire bar, dried at 180 ° C. for 60 seconds, and after drying, layer C is formed so that the coating thickness becomes 0.5 ⁇ m.
- the sheet thus obtained was aged at 40 ° C. for 3 days to produce a solar battery back sheet BS7 having a laminated structure shown in Table 2.
- Example 8 Three layer composite of A layer / B layer / D layer in the same manner as described in Example 7 so that each of the PET polymer raw materials shown in Table 2 has a predetermined thickness for layer A, layer B and layer D A base film made of a biaxially stretched polyester film was formed.
- the C layer forming raw material C5 is applied to the surface of the D layer of the two base films using a wire bar, dried at 180 ° C. for 60 seconds, and after drying, the C layer is formed to have a coating thickness of 0.5 ⁇ m.
- the sheet thus obtained was aged at 40 ° C. for 3 days to produce a solar battery back sheet BS8 having a laminated structure shown in Table 2.
- Example 9 As shown in Table 2, a solar cell back sheet BS9 having a laminated structure shown in Table 2 was produced in the same manner as in Example 1 except that the B layer was formed using PET polymer i. In addition, the titanium oxide density
- Example 10 Similar to the method described in Example 1, except that the C layer forming raw material C8 shown in Table 2 was used instead of the C layer forming raw material C3, and the C layer was formed so that the thickness after drying was 2.0 ⁇ m. Thus, a solar battery back sheet BS10 having a laminated structure shown in Table 2 was produced.
- Example 1 A base film made of a biaxially stretched polyester film was formed in the same manner as in Example 1 so that the A layer and the B layer had a predetermined thickness using the respective PET polymer raw materials shown in Table 2. In addition, the density
- the C layer forming raw material C3 is applied to the surface of the B layer of the biaxially stretched polyester film using a wire bar, dried at 180 ° C. for 60 seconds, and the C layer is formed so that the coating thickness after drying is 2 ⁇ m. Provided.
- the sheet thus obtained was aged at 40 ° C. for 3 days to produce a solar battery back sheet BS11 having a laminated structure shown in Table 2.
- Example 2 A solar cell backsheet BS12 having a laminated structure shown in Table 2 was produced in the same manner as in Example 1 except that the A layer was formed using PET polymer c as shown in Table 2. In addition, the titanium oxide density
- Example 3 As shown in Table 2, a solar battery back sheet BS13 having a laminated structure shown in Table 2 was produced in the same manner as in Example 1 except that the B layer was formed using PET polymer m. In addition, the titanium oxide density
- Example 4 As shown in Table 2, the same procedure as described in Example 1 was applied, except that the thickness of the A layer was 100 ⁇ m, the thickness of the B layer was 150 ⁇ m, and the discharge amount of the extruder was adjusted so that the total thickness was 250 ⁇ m. T A solar battery back sheet BS14 was produced.
- Example 5 Similar to the method described in Example 1, except that the C layer forming raw material C6 is used instead of the C layer forming raw material C3 shown in Table 2, and the C layer is formed so that the thickness after drying becomes 2.9 ⁇ m. Thus, a solar battery back sheet BS15 having a laminated structure shown in Table 2 was produced.
- the solar cell backsheet BS16 is a backsheet of a type in which three films are bonded together.
- Examples 1 to 8 and Example 10 belong to the first invention.
- the breaking elongation retention is high and the change in color tone is small.
- Examples 1 to 9 belong to the second invention. The thing of these Examples is excellent in durability with respect to sealing material adhesive strength and sealing material adhesive strength.
- the solar cell sealing sheet of the present invention is excellent in adhesive strength to sealant, storage stability, productivity and environmental resistance, and is preferably used in a solar cell module.
- a stop sheet and a solar cell module using the same are useful.
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Abstract
Description
前記C層は、アクリル樹脂を主たる成分とし、バックシートの一方の最表面に配置され、
前記基材フィルムは、A層及びB層を有し、
前記A層は、ポリエステル樹脂を主たる成分とし、A層中に白色顔料を5.0質量%以上25質量%以下含み、厚さが5μm以上であり、バックシートの他方の最表面に配置され、
前記B層は、ポリエステル樹脂を主たる成分とし、B層の全成分中に白色顔料を1.0質量%以上5.0質量%未満含み、厚さがバックシート全体の70%以上である
太陽電池バックシート。
基材フィルム及びC層を有し、
前記C層は、バックシートの一方の最表面に配置され、
前記C層は下記C層形成用原料組成物(II)から得られたものである太陽電池バックシート。
ここで、C層形成用原料組成物(II)はイソシアネート基と反応性を有する官能基を有するアクリル樹脂ならびに2種以上のイソシアネート化合物を含み、当該イソシアネート化合物が、イソシアネート基がブロック基で保護されたブロックイソシアネート化合物及びイソシアネート基がブロック基で保護されていないイソシアネート化合物を含む。
本発明の太陽電池バックシートのC層が、裏側封止材の側を向くようにして、受光面側保護基材、受光面側封止材、セル、裏側封止材、及び太陽電池バックシートが、この順に配置された太陽電池モジュール。
第一の発明および第二の発明の太陽電池バックシートを以下に詳細に説明する。本発明の太陽電池バックシートは、基材フィルム及びC層を有する。
図2は第一の発明の太陽電池バックシートの概略図である。太陽電池バックシート(1)は、A層(30)及びB層(20)を含む1枚のポリエステルフィルムからな基材フィルム(2)、並びに、太陽電池モジュールを構成する際には封止材と貼り合されるC層(11)を有する。
第一の発明、第二の発明に共通して、太陽電池バックシートを構成する基材フィルムとしては、機械強度、寸法安定性、熱安定性に優れ、比較的安価であるポリエステルフィルムを用いることができる。具体的には、ポリエチレンテレフタレート(PET)やポリエチレンナフタレート(PEN)などのポリエステルフィルムが例示できる。中でも機械強度、寸法安定性、熱安定性や加工適性、耐候性付与の対象として優れていることからポリエチレンテレフタレートを主な成分とするPETフィルムが特に好ましい。
第一の発明の太陽電池バックシートは、基材フィルムを1枚のみ有する。そして第一の発明の基材フィルムは、A層およびB層を有する。
第一の発明における基材フィルムは、A層及びB層を少なくとも有する。そしてA層は、バックシートの一方の最表面に配置される層である。まずはこのA層について説明する。
第一の発明の基材フィルムは、上述のとおりA層(30)及びB層(20)を有する。そしてB層は、その厚さがバックシート全体の厚さの70%以上を占める。B層の厚さがバックシート全体の70%以上を占めることで、B層はバックシートに対して機械強度および電気絶縁性を付与することができる。以下、B層について説明する。
第一の発明の太陽電池バックシートで特徴付けられるA層およびB層を有する基材フィルムの製膜方法については公知の方法を用いることができる。A層およびB層の主たる成分であるポリエステル樹脂を必要に応じて乾燥し、2台以上の押出機を用いて異なる流路から送り出されたポリエステル樹脂を、マルチマニホールドダイやフィールドブロックやスタティックミキサー、ピノール等を用いて多層に積層する方法等を使用することができる。また、これらを任意に組み合わせても良い。
第一の発明および第二の発明の太陽電池バックシートは、基材フィルム及びC層を有する。そしてこのC層は、バックシートの一方の最表面に配置される。このように最表面に配置されることで、太陽電池バックシートを用いて太陽電池モジュールを製造する際に、C層は裏側封止材と貼り合わされることとなる。このようなC層について、以下に説明する。
(i)第一の発明の太陽電池バックシートは、太陽電池モジュール製造工程において、高温処理に曝されることから、C層の耐熱性を向上するため。
(ii)C層の紫外線遮蔽性向上の目的などのため白色顔料の配合を行う場合があるが、その配合により生じるC層の脆化を抑制し、C層の靭性や強度の向上をするため。
第一の発明および第二の発明に共通して、本発明の太陽電池モジュールは、上述のようにして得た太陽電池バックシートのC層が、裏側封止材の側を向くようにして、受光面側保護基材、受光面側封止材、セル、裏側封止材、及びバックシートを、この順に配置して、加熱してラミネートすることで得られる。ラミネート工程における加熱温度は封止材層の架橋反応及びブロックイソシアネート化合物のブロック基脱離反応を考慮すると、120℃以上180℃以下の範囲が好ましく、130℃以上170℃以下の範囲がさらに好ましい。
本実施例で用いた特性の評価方法は、下記のとおりである。
全体の厚みをJIS C2151(1990年)に準じて測定し、積層断面をミクロトームで厚み方向に断面を切る前処理をしたのち、日立製作所製電界放射型走査電子顕微鏡(FE-SEM)S-800を用い、厚み断面を全体像が写る倍率(×1000)で撮像し、その断面写真の厚みを採寸した。
前記(1)の方法で各層厚みを断面写真から採寸した結果から下式に基づいてB層の厚み比率を算出した。
B層の厚み比率[%]=(B層の厚み)/(全体の厚み)×100 。
太陽電池バックシートをサンプルとし、蛍光X線元素分析装置(堀場製作所製、MESA-500W型)により、酸化チタン特有の元素であるチタンの元素量を求めた。そのチタン元素量から酸化チタン含有量を換算した。
日立製分光光度計U-3310を用い、標準白色板用開口部および試験片開口部ともに標準白色板として硫酸バリウムを用いた。試験片の開口部の傾斜角度を10°として560nmで拡散反射率を測定し(T0)とし、そのときの反射率を100%とした。その後、試験片開口部の標準白色版を試験片に取り替え560nmで拡散反射率を測定した。その後、下記式により、相対反射率(R)に換算した。
R(%)=T1/T0×100
T0:標準白色板の反射率
T1:試験片の反射率。
日立分光光度計U-3310を用い、標準白色板用開口部と試験片開口部ともに標準白色板として酸化アルミナを用いて300~350nmで試験片開口部の傾斜角度を10°付けて試料のない状態の透過率を測定し(A0)とし、そのときの透過率を100%とした。その後、入射光前面に、紫外光領域に吸収が少ないフィルム(以下「ETFEフィルムという。)(50μm、透明)を配置し、300~350nmの透過率を波長5nmおきに測定し、350nmにおける透過率Tetfeを得た。次に前記ETFEフィルムにC層を形成したフィルムを配置し、同様に350nmにおける透過率Tetfe/cを測定した。これら2つの透過率から下式のとおり波長350nmにおけるC層の透過率T(%)を求めた。
T(%)=Tetfe/c(%)/Tetfe(%)×100 。
作製した太陽電池バックシートの両表面(A層およびC層)についてISO2409(2013年版)に記載の方法でクロスカットテストを行い、ISO2409に記載の「Table 1 Classification of test results」にしたがって特性分類をした。
JIS K6854-2(1999年版)に基づいて、太陽電池バックシートと封止材として用いたEVAシートと接着強度を測定した。試験した疑似太陽電池モジュールサンプルは、作製した太陽電池バックシートのC層面にEVAシートを重ね、さらにその上に厚さ0.3mmの半強化ガラスを重ね、市販の真空ラミネーターを用いて減圧後に、142℃加熱条件下1気圧の荷重で15分プレス処理をしたものを用いた。EVAシートは、サンビック(株)製の450μm厚さのシート(Fast cureタイプ)を用いた。接着強度試験の試験片の幅は10mmとし、2つの試験片について各々測定を1回行い、2つの測定値の平均値を接着強度の値とした。
また、上記の方法で封止材との接着強度を測定した試験片を、エスペック(株)製恒温恒湿オーブンにて、温度85℃、相対湿度85%RHの条件下にて2000時間処理を行い、その後上記の方法にしたがって湿熱試験後の封止材との接着強度を測定した。
接着強度は30N/10mm以上あることが実用上問題ないレベルと判断した。
JIS C 2151(2006年版)に基づいて、オーブン内で150℃で30分間の熱処理を行い、加熱処理前後の寸法変化を、作製した太陽電池バックシートの長手方向(MD)および幅方向(TD)について評価した。測定した寸法変化値から下式にしたがって加熱収縮率を算出した。
加熱収縮率[%]={(加熱処理前の長さ-加熱処理後の長さ)/加熱処理前の長さ}×100
(9)破断伸度の測定
ASTM-D882(ANNUAL BOOK OF ASTM STANDARDS1999年版)に基づいて破断伸度を測定した。なお作製した太陽電池バックシートを1cm×20cmの大きさに切り出し、チャック間5cm、引っ張り速度300mm/minにて引っ張ったものである。サンプル数はn=5とし、太陽電池バックシートの長手方向について測定し、その結果を初期破断伸度E0とした。
試料を測定片の形状(1cm×20cm)に切り出した後、エスペック(株)製恒温恒湿オーブンにて、温度85℃、相対湿度85%RHの条件下にて2000時間処理を行い、その後上記(9)項にしたがって破断伸度を測定した。なお、測定はn=5とし、また、太陽電池バックシートの長手方向について測定した後、その平均値を破断伸度E1とした。上記(9)項にしたがって測定した初期破断伸度E0と耐湿熱試験後の破断伸度E1を用いて、次の式により破断伸度保持率を算出した。
破断伸度保持率(%)=E1/E0×100
得られた伸度保持率について、以下のように判定した。
破断伸度保持率が50%以上の場合:A
破断伸度保持率が40%以上50%未満の場合:B
破断伸度保持率が30%以上40%未満の場合:C
破断伸度保持率が30%未満の場合:D。
作製した太陽電池バックシートを7cm×20cmの形状に切り出し、スガ試験機(株)製キセノン耐候性試験装置“SX-75”にて、ブラックパネル温度65℃、相対湿度50%RH、照度180W/m2(光源:キセノンランプ、波長範囲:300~400nm)の条件とし、下記のサイクル1、2を繰り返して3000時間照射し、その後、紫外線照射試験済み試験片から1cm×20cmの短冊状サンプルに切り出した後、上記(9)項にしたがって破断伸度を測定した。
サイクル1 紫外線照射のみを108分間行う。
サイクル2 紫外線照射と水噴霧とを12分間行う(この間は湿度制御無し)。
なお、測定はn=5とし、また、フィルムの長手方向について測定した後、その平均値を破断伸度E2とした。上記(9)項にしたがって測定した初期破断伸度E0と耐候性試験後の破断伸度E2を用いて、次の式により破断伸度保持率を算出した。
破断伸度保持率(%)=E2/E0×100
得られた伸度保持率について、以下のように判定した。
破断伸度保持率が50%以上の場合:A
破断伸度保持率が40%以上50%未満の場合:B
破断伸度保持率が30%以上40%未満の場合:C
破断伸度保持率が30%未満の場合:D 。
太陽電池バックシートのA層およびC層について、耐候性試験に伴う色調変化を、JISK 7105(2006年度版)に基づいて、スガ試験機社製カラーメータSMカラーコンピューターSM-6を使用して、表色系b値を測定し、試験前後のb値の差であるΔb(b値(試験後)-b値(試験前))を求めた。n数は2で評価を実施した。b値が高いほど黄色の度合いが強く、Δb値が大きいほど試験前に比べて黄色に変化していることを意味する。
縦20cm、横20cmのサイズに切り出した本太陽電池バックシートのC層が熱板に接する向きになるように加熱可能な熱板上に平置きし、熱板を150℃に加熱して30分間放置した。その際、太陽電池バックシートの4角の立ち上がり高さ(4角それぞれと熱板との垂直距離)で評価した。
シートの4角の全ての立ち上がりが10mm以下:A
AおよびCのいずれにも該当しない:B
シートの4角のいずれかの立ち上がりが30mmを超える:C 。
ジカルボン酸成分としてテレフタル酸100部)にエチレングリコール64部を混合し、さらに触媒として酢酸亜鉛を0.1部および三酸化アンチモン0.03部を添加し、エチレングリコールの環流温度でエステル交換を実施した。
の温度で5時間重合を行った。得られたポリエチレンテレフタレートの固有粘度は0.5
5であった。該ポリマーを長さ4mmのチップ状に切断した。
前記の方法で作製したPETポリマーaと酸化チタン(ルチル型、平均粒子径200nm)をコンパウンドして酸化チタンが50質量%のマスターチップとした。このマスターチップをPETポリマーbとした。マスターチップの密度は2.5g/cm3であった。マスターチップのチップ形状を長さ:2.40~4.60mm、幅:3.20~4.80mm、高さ:1.70~2.30mmの円柱形のチップ形状とした。
前記の方法で作製したPETポリマーaおよびPETポリマーbを表1に示す配合比で混合し、ポリエステルフィルム形成用樹脂原料PETポリマーc~mを得た。
冷却管、撹拌装置、温度計、窒素導入管を備えた4つ口フラスコに、メチルメタクリレート18部、n-ブチルメタクリレート80部、2-ヒドロキシエチルメタクリレート2部、トルエン100部を仕込み、窒素雰囲気下で撹拌しながら100℃まで昇温した。次いで、アゾビスイソブチロニトリルを0.15部加えて2時間重合反応を行った。続いて、アゾビスイソブチロニトリルを0.07部加えてさらに2時間重合反応を行い、更に0.07部のアゾビスイソブチロニトリルを加えてさらに2時間重合反応を行うことにより、メタクリル系共重合体溶液を得た。
前記の方法で得た酸化チタン含有アクリルポリマー溶液(C2)を50部量りとり、紫外線吸収剤および光安定化剤をポリマーの繰り返し構造中に含むアクリル樹脂を成分とする株式会社日本触媒製“ハルスハイブリット”(登録商標)ポリマーUV-G13、50部を配合して酸化チタン含有アクリルポリマー溶液(C4)を得た。次に酸化チタン含有アクリルポリマー溶液(C4)100部に、ポリイソシアネート硬化剤として住化バイエルウレタン社製ヘキサメチレンポリイソシアネート(HDI)含有硬化剤溶液N-3200を1部配合した後、メチルイソブチルケトンを追加配合して、全固形分質量が10質量%となるように濃度を調整して、C層形成用原料組成物(C5)を得た。
前記の方法で得たアクリルポリマー溶液(C1)をメチルイソブチルケトンで希釈して全固形分濃度が50質量%になるように調整した。そのアクリルポリマー溶液100部に対して前記のヘキサメチレンポリイソシアネート(HDI)含有硬化剤溶液“N-3200”を1部配合した後、メチルイソブチルケトンを追加配合して、全固形分質量が30質量%となるように濃度調整して、C層形成用原料組成物(C6)を得た。
冷却管、撹拌装置、温度計、窒素導入管を備えた4つ口フラスコに、メチルメタクリレート18部、n-ブチルメタクリレート80部、2-ヒドロキシエチルメタクリレート2部、トルエン100部を仕込み、窒素雰囲気下で撹拌しながら100℃まで昇温した。次いで、アゾビスイソブチロニトリルを0.15部加えて2時間重合反応を行った。続いて、アゾビスイソブチロニトリルを0.07部加えてさらに2時間重合反応を行い、更に0.07部のアゾビスイソブチロニトリルを加えてさらに2時間重合反応を行うことにより、メタクリル系共重合体溶液を得た。
表1に示すPETポリマーeをA層形成用原料として、PETポリマーkをB層形成用原料としてB層/A層となるように積層装置を通して積層し、Tダイよりシート状に成形した。積層構成は、表2に示すとおりA層の厚みが50μm、B層の厚みが200μmで総厚みが250μmとなるようにした。厚みは押出機の吐出量の調整により制御した。Tダイより吐出したシート状成形物を表面温度25℃の冷却ドラムで冷却固化した未延伸シートを85~98℃に加熱したロール群に導き、長手方向に3.3倍縦延伸し、21~25℃のロール群で冷却した。続いて、縦延伸したフィルムの両端をクリップで把持しながらテンターに導き130℃に加熱された雰囲気中で長手に垂直な方向に3.6倍横延伸した。その後テンター内で220℃の熱固定を行い、均一に徐冷後、室温まで冷やして巻き取り厚み250μmの2軸延伸ポリエステルフィルムからなる基材フィルムを得た。
表2に示すPETポリマー原料をそれぞれ用いてA層およびB層を所定の厚みになるように実施例1に記載の方法と同様にして2軸延伸ポリエステルフィルムからなる基材フィルムを製膜した以外は、実施例1に記載の方法と同様にして表2に示す積層構成の太陽電池バックシートBS2~BS5をそれぞれ製造した。
表2に示すPETポリマー原料をそれぞれ用いてA層およびB層を所定の厚みになるように、実施例1に記載の方法と同様にして2軸延伸ポリエステルフィルムからなる基材フィルムを製膜した。
表1に示すPETポリマーfをA層およびD層形成用原料として、PETポリマーjをB層形成用原料としてA層/B層/D層の3層複合となるように積層装置を通して積層し、Tダイよりシート状に成形した。積層構成は、表2に示すとおりA層およびD層の厚みが35μm、B層の厚みが170μmで総厚みが240μmとなるように押出機の吐出量を調整して積層した。Tダイより吐出したシート状成形物を表面温度25℃の冷却ドラムで冷却固化した未延伸シートを85~98℃に加熱したロール群に導き、長手方向に3.3倍縦延伸し、21~25℃のロール群で冷却した。続いて、縦延伸したフィルムの両端をクリップで把持しながらテンターに導き130℃に加熱された雰囲気中で長手に垂直な方向に3.6倍横延伸した。その後テンター内で220℃の熱固定を行い、均一に徐冷後、室温まで冷やして巻き取り厚み250μmの2軸延伸ポリエステルフィルムからなる基材フィルムを得た。
表2に示すPETポリマー原料をそれぞれ用いてA層、B層およびD層を所定の厚みになるように実施例7に記載の方法と同様にしてA層/B層/D層の3層複合2軸延伸ポリエステルフィルムからなる基材フィルムを製膜した。
表2に示すとおりB層をPETポリマーiを用いて形成した以外は実施例1に記載の方法と同様にして、表2に示す積層構成の太陽電池バックシートBS9を製造した。なお、このフィルムのB層の酸化チタン濃度は6質量%であった。
表2に示すC層形成用原料C3の代わりにC層形成用原料C8を用いて、乾燥後厚みが2.0μmとなるようにC層を形成した以外は実施例1に記載の方法と同様にして表2に示す積層構成の太陽電池バックシートBS10を製造した。
表2に示すPETポリマー原料をそれぞれ用いてA層およびB層を所定の厚みになるように実施例1に記載の方法と同様にして2軸延伸ポリエステルフィルムからなる基材フィルムを製膜した。なお、このフィルムのA層の酸化チタンの濃度は4.5質量%であった。
A層を表2に示すとおりPETポリマーcを用いて形成した以外は実施例1に記載の方法と同様にして、表2に示す積層構成の太陽電池バックシートBS12を製造した。なお、このフィルムのA層の酸化チタン濃度は28質量%であった。
表2に示すとおりB層をPETポリマーmを用いて形成した以外は実施例1に記載の方法と同様にして、表2に示す積層構成の太陽電池バックシートBS13を製造した。なお、このフィルムのB層の酸化チタン濃度は0.5質量%であった。
表2に示すとおりA層の厚みが100μm、B層の厚みが150μmで総厚みが250μmとなるように押出機の吐出量を調整して積層した以外は実施例1に記載の方法と同様にして。太陽電池バックシートBS14を製造した。
表2に示すC層形成用原料C3の代わりにC層形成用原料C6を用いて、乾燥後厚みが2.9μmとなるようにC層を形成した以外は実施例1に記載の方法と同様にして表2に示す積層構成の太陽電池バックシートBS15を製造した。
酸化チタン粒子を含有する白色EVAフィルム(50μm)と透明ポリエチレンテレフタレートフィルム“ルミラー”(登録商標)S10(東レ(株)製、210μm)および白色顔料を含有する白色ポリエチレンテレフタレートフィルム“ルミラー”(登録商標)MX11(東レ(株)製、50μm)を用意した。また、DIC(株)製ドライラミネート剤 ディックドライ(登録商標)LX-903を16部、硬化剤としてDIC(株)製KL-75を2部、および酢酸エチルを29.5部量りとり、15分間攪拌することにより固形分濃度20%のドライラミネート用接着剤を得た。
(考察)
実施例1~8、実施例10は第一の発明に属するものである。第一の発明の特性を有するA層およびB層を有することにより、耐光性試験を行っても破断伸度保持率が高く、色調の変化が少ない。実施例1~9は第二の発明に属するものである。これら実施例のものは対封止材接着強度及び対封止材接着強度の耐久性に優れている。
2 基材フィルム
3 太陽電池セル
4 接着剤
5 受光面側保護基材
6 封止材
7 端子箱
8 接着剤
9 配線材
10 フレーム
11 C層
20 B層
30 A層
40 D層
50 封止材接着面
Claims (13)
- 1枚のみの基材フィルム及びC層を有し、
前記C層は、アクリル樹脂を主たる成分とし、バックシートの一方の最表面に配置され、
前記基材フィルムは、A層及びB層を有し、
前記A層は、ポリエステル樹脂を主たる成分とし、A層中に白色顔料を5.0質量%以上25質量%以下含み、厚さが5μm以上であり、バックシートの他方の最表面に配置され、
前記B層は、ポリエステル樹脂を主たる成分とし、B層の全成分中に白色顔料を1.0質量%以上5.0質量%未満含み、厚さがバックシート全体の70%以上である
太陽電池バックシート。 - 白色顔料が酸化チタンである請求項1に記載の太陽電池バックシート。
- 前記C層が、水酸基を有するアクリル樹脂、イソシアネート化合物、及び白色顔料を含むC層形成用原料組成物(I)から得られたものである請求項1または2に記載の太陽電池バックシート。
- 前記C層形成用原料(I)が、2種以上のイソシアネート化合物を含み、
当該イソシアネート化合物が、イソシアネート基がブロック基で保護されたブロックイソシアネート化合物、及び、イソシアネート基がブロック基で保護されていないイソシアネート化合物を含む請求項3に記載の太陽電池バックシート。 - 前記C層が、水酸基を有するアクリル樹脂、ウレタン結合を有するアクリル樹脂、イソシアネート化合物、及び白色顔料を含む請求項1~4のいずれかに記載の太陽電池バックシート。
- 基材フィルム及びC層を有し、
前記C層は、バックシートの一方の最表面に配置され、
前記C層は下記C層形成用原料組成物(II)から得られたものである太陽電池バックシート。
ここで、C層形成用原料組成物(II)はイソシアネート基と反応性を有する官能基を有するアクリル樹脂ならびに2種以上のイソシアネート化合物を含み、当該イソシアネート化合物が、イソシアネート基がブロック基で保護されたブロックイソシアネート化合物及びイソシアネート基がブロック基で保護されていないイソシアネート化合物を含む。 - イソシアネート基と反応性を有する官能基が水酸基である請求項6記載の太陽電池バックシート。
- C層形成用原料組成物(II)がさらに白色顔料を含有する請求項6または7に記載の太陽電池バックシート。
- 縦20cm、横20cmのサイズに切り出したシートを、150℃で30分間加熱した後に、シートの四隅の立ち上がりがいずれも30mm以下である請求項1~8いずれかに記載の太陽電池バックシート。
- 前記C層が、波長350nmの光の透過率が50%以下である請求項1~9のいずれかに記載の太陽電池バックシート。
- ISO2409(2013年版)の記載にしたがって測定したA層及びC層の表層凝集強度が、クラス0であることを特徴とする、請求項1~5のいずれかに記載の太陽電池バックシート。
- 請求項1~11のいずれかに記載の太陽電池バックシートのC層が、裏側封止材の側を向くようにして、受光面側保護基材、受光面側封止材、セル、裏側封止材、及び太陽電池バックシートが、この順に配置された太陽電池モジュール。
- 請求項1~11のいずれかに記載の太陽電池バックシートのC層が、裏側封止材の側を向くようにして、受光面側保護基材、受光面側封止材、セル、裏側封止材、及び太陽電池バックシートを、この順に配置し、加熱することを特徴とする太陽電池モジュールの製造方法。
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2015
- 2015-03-19 WO PCT/JP2015/058232 patent/WO2015146780A1/ja active Application Filing
- 2015-03-19 KR KR1020167028040A patent/KR20160138104A/ko not_active Application Discontinuation
- 2015-03-19 JP JP2015515336A patent/JP6627504B2/ja active Active
- 2015-03-19 US US15/127,542 patent/US10074760B2/en active Active
- 2015-03-19 CN CN201580015472.7A patent/CN106104816B/zh not_active Expired - Fee Related
- 2015-03-20 TW TW104108894A patent/TWI676298B/zh not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011249756A (ja) * | 2010-04-29 | 2011-12-08 | Mitsubishi Plastics Inc | 太陽電池裏面保護材用積層ポリエステルフィルム |
WO2012043000A1 (ja) * | 2010-09-27 | 2012-04-05 | 三菱樹脂株式会社 | 太陽電池裏面保護材用ポリエステルフィルム |
JP2013251427A (ja) * | 2012-06-01 | 2013-12-12 | Toray Ind Inc | 太陽電池モジュール裏面封止シート用フィルム |
Also Published As
Publication number | Publication date |
---|---|
TWI676298B (zh) | 2019-11-01 |
JPWO2015146780A1 (ja) | 2017-04-13 |
US20170133530A1 (en) | 2017-05-11 |
CN106104816A (zh) | 2016-11-09 |
TW201539775A (zh) | 2015-10-16 |
KR20160138104A (ko) | 2016-12-02 |
JP6627504B2 (ja) | 2020-01-08 |
CN106104816B (zh) | 2018-05-11 |
US10074760B2 (en) | 2018-09-11 |
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