WO2012004962A1 - 太陽電池裏面保護シート用易接着剤、及び太陽電池裏面保護シート、ならびに太陽電池モジュール - Google Patents
太陽電池裏面保護シート用易接着剤、及び太陽電池裏面保護シート、ならびに太陽電池モジュール Download PDFInfo
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- WO2012004962A1 WO2012004962A1 PCT/JP2011/003793 JP2011003793W WO2012004962A1 WO 2012004962 A1 WO2012004962 A1 WO 2012004962A1 JP 2011003793 W JP2011003793 W JP 2011003793W WO 2012004962 A1 WO2012004962 A1 WO 2012004962A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S10/00—PV power plants; Combinations of PV energy systems with other systems for the generation of electric power
- H02S10/30—Thermophotovoltaic systems
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
- H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
- H10F19/804—Materials of encapsulations
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
- H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
- H10F19/85—Protective back sheets
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F77/00—Constructional details of devices covered by this subclass
- H10F77/30—Coatings
- H10F77/306—Coatings for devices having potential barriers
- H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/322—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of solar panels
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2887—Adhesive compositions including addition polymer from unsaturated monomer including nitrogen containing polymer [e.g., polyacrylonitrile, polymethacrylonitrile, etc.]
Definitions
- solar cells have been attracting attention as a clean energy source free from environmental pollution due to an increase in awareness of environmental problems, and earnestly researched and put into practical use from the viewpoint of using solar energy as a useful energy resource.
- solar cell elements include a crystalline silicon solar cell element, a polycrystalline silicon solar cell element, an amorphous silicon solar cell element, a copper indium selenide solar cell element, and a compound semiconductor solar. Battery elements and the like are known.
- polycrystalline silicon solar cell elements, amorphous silicon solar cell elements, and compound semiconductor solar cell elements are relatively low cost and can be increased in area. It has been broken.
- the adhesion with the sealant and the adhesion durability are basic and important performance requirements. If the adhesiveness with the sealant is insufficient, the back surface protective sheet is peeled off, and the solar cell cannot be protected from moisture or external factors, leading to deterioration of the output of the solar cell.
- JP 2009-246360 A Japanese Patent Laid-Open No. 2004-200322 JP 2004-223925 A Japanese Patent Laid-Open No. 2001-119051 JP 2006-152013 A JP 2007-136911 A JP 2010-114154 A JP 2010-263193 A JP 2011-18872 A
- the present invention has a glass transition temperature of 10 to 60 ° C., a number average molecular weight of 25,000 to 250,000, a hydroxyl value of 2 to 100 (mgKOH / g), and has no (meth) acryloyl group (meth).
- the content of the compound (B) having a (meth) acryloyl group is 0.1 to 20 parts by weight with respect to 100 parts by weight of the acrylic copolymer (A) having no (meth) acryloyl group. preferable.
- the present invention relates to a solar cell surface protective material (I) located on the light receiving surface side of the solar cell, a sealant (II) located on the light receiving surface side of the solar cell, a solar cell (III), The solar cell back surface protection sheet (V) which is located on the non-light-receiving surface side and is formed from the sealing agent (IV) containing an organic peroxide and the solar cell back surface protection sheet (V ′) according to claim 4.
- a solar cell module comprising: The solar cell module is characterized in that the hard adhesive layer (D) of the hard adhesive layer (D ′) is in contact with the non-light-receiving surface side sealing agent (IV).
- the sealing agent (IV) on the non-light-receiving surface side contains an organic peroxide.
- the sealant on the non-light-receiving surface side is preferably composed mainly of an ethylene-vinyl acetate copolymer (EVA).
- the easy adhesive for solar cell back surface protective sheet of the present invention By using the easy adhesive for solar cell back surface protective sheet of the present invention, the easy adhesive for solar cell back surface protective sheet, the solar cell back surface protective sheet, and the solar cell back surface protective sheet excellent in adhesion and adhesion durability It has the outstanding effect that the solar cell module to be used can be provided.
- the solar cell back surface protective sheet of the present invention it is possible to provide a solar cell module having a small output drop even when exposed to a high temperature and high humidity environment for a long time.
- a numerical range specified using “to” includes numerical values described before and after “to” as ranges of the lower limit value and the upper limit value.
- film and “sheet” are not distinguished by thickness.
- the “sheet” in this specification includes a thin film-like material
- the “film” in this specification includes a thick sheet-like material.
- FIG. 1 is a schematic cross-sectional view of a solar cell module according to the present invention.
- the solar cell module 100 includes a solar cell surface protective material (I), a light-receiving surface side sealant (II), a solar cell (III), a non-light-receiving surface side sealant (IV), and a solar cell back surface protection. At least the sheet (V) is included.
- the light receiving surface side of the solar battery cell (III) is protected by the solar cell surface protecting material (I) through the sealant (II) on the light receiving surface side.
- the non-light-receiving surface side of the solar battery cell (III) is protected by the solar battery back surface protective sheet (V) through the sealant (IV) on the non-light-receiving surface side.
- an easy adhesive layer made of an easy adhesive for the solar cell back surface protective sheet is laminated.
- the easy-adhesive layer (D ′) formed by the easy-adhesive for solar cell back surface protective sheet of the present invention undergoes a cross-linking reaction using a thermocompression bonding process when the solar cell module 100 is formed.
- the easy-adhesive layer before the thermocompression bonding step is distinguished as the easy-adhesive layer (D ′)
- the cross-linked easy-adhesive layer after the thermocompression-bonding step is distinguished as the easy-adhesive layer (D).
- the solar cell back surface protection sheet before the thermocompression bonding step is distinguished as a solar cell back surface protection sheet (V ′), and the solar cell back surface protection sheet after the thermocompression bonding step is distinguished as a solar cell back surface protection sheet (V).
- the glass transition temperature of the (meth) acrylic copolymer (A) exceeds 60 ° C., the coating film of the easy-adhesive agent becomes hard and the adhesive force to the sealing agent decreases. When the temperature is lower than 10 ° C., tackiness occurs on the surface of the coating film of the easy-adhesive agent. Therefore, when the solar cell back surface protective sheet is formed into a roll after production, blocking easily occurs.
- the glass transition temperature of the (meth) acrylic copolymer (A) is more preferably 20 to 50 ° C.
- the glass transition temperature here is a glass transition temperature measured by differential scanning calorimetry (DSC) for a resin obtained by drying the (meth) acrylic copolymer (A) to a solid content of 100%.
- the glass transition temperature an aluminum pan with a sample weighed about 10 mg and an aluminum pan without a sample are set in a DSC apparatus, and this is set to ⁇ 50 using liquid nitrogen in a nitrogen stream. A rapid cooling treatment is performed until the temperature is increased to 100 ° C. at 20 ° C./min, and a DSC curve is plotted. The slope of the DSC curve on the low temperature side (the DSC curve portion in the temperature region where no transition or reaction occurs in the test piece) is extended to the high temperature side, and the slope of the step change portion of the glass transition is maximized. From the intersection with the tangent drawn at such a point, the extrapolated glass transition start temperature (Tig) can be determined, and this can be determined as the glass transition temperature.
- the glass transition temperature of this invention has described the value measured by said method.
- the number average molecular weight of the (meth) acrylic copolymer (A) exceeds 250,000, the adhesive force to the sealant is reduced. The wet heat resistance of the film is lowered, and the adhesive force to the sealant is lowered after the wet heat test.
- the number average molecular weight of the (meth) acrylic copolymer (A) is preferably 25,000 to 150,000, more preferably 25,000 to 100,000, and more preferably 25,000 to More preferably, it is 80,000.
- said number average molecular weight is the value of polystyrene conversion by the gel permeation chromatography (GPC) of a (meth) acrylic-type copolymer (A).
- the temperature of the columns (KF-805L, KF-803L, and KF-802 manufactured by Showa Denko KK) is 40 ° C.
- THF is used as an eluent
- the flow rate is 0.2 ml / min
- the detection is RI
- the sample concentration was 0.02%
- polystyrene was used as a standard sample.
- the number average molecular weight of the present invention describes the value measured by the above method.
- the hydroxyl value of the (meth) acrylic copolymer (A) is 2 to 100 mgKOH / g, preferably 2 to 50 mgKOH / g, more preferably 2 to 30 mgKOH / g in terms of solid content. It is more preferable.
- the hydroxyl value of the (meth) acrylic copolymer (A) exceeds 100 mgKOH / g, the cross-linking of the easy-adhesive coating film becomes dense and the adhesive force to the plastic film (E) is reduced. Even if it is initially bonded, the crosslinking reaction may proceed during the moist heat test, and the adhesive strength may decrease after the moist heat test.
- Such a (meth) acrylic copolymer (A) can be obtained by polymerizing various monomers.
- the monomer include a (meth) acrylic monomer having an alkyl group, a (meth) acrylic monomer having a hydroxyl group, a (meth) acrylic monomer having a carboxyl group, and a (meth) acrylic monomer having a glycidyl group.
- Other examples include vinyl acetate, maleic anhydride, vinyl ether, vinyl propionate, and styrene.
- Examples of the (meth) acrylic monomer having an alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, normal butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate.
- Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- Examples of the (meth) acrylic monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and citraconic acid.
- Examples of the (meth) acrylic monomer having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether.
- the polymerization of the above monomers ordinary radical polymerization can be used.
- the reaction method there is no limitation on the reaction method, and it can be carried out by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, etc., but solution polymerization is preferable because the control of the reaction is easy and the next operation can be directly performed.
- the monomer used may be one type or a mixture of a plurality of types.
- the solvent is not particularly limited as long as the resin can be dissolved in the present invention, such as methyl ethyl ketone, methyl isobutyl ketone, toluene, cellosolve, ethyl acetate, butyl acetate, and a single solvent or a plurality of solvents may be mixed.
- polymerization initiators used in the polymerization reaction are organic peroxides such as benzoyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, and azo initiators such as azobisisobutyronitrile. There is no particular limitation.
- the compound (B) having a (meth) acryloyl group used in the present invention may be any compound as long as it has at least one (meth) acryloyl group in the molecule, for example, trimethylolpropane.
- (Meth) acrylates of polyhydric alcohols such as tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di
- examples thereof include epoxy (meth) acrylates such as (meth) acrylate and di (meth) acrylate of polyethylene glycol diglycidyl ether.
- the compound (B) having a (meth) acryloyl group preferably has 2 or more (meth) acryloyl groups in the molecule, and more preferably 3 or more in the molecule. Is preferred.
- the compound (B) having a (meth) acryloyl group a hydroxyl group or a group such that the crosslinking between the acrylic copolymer (A) having no (meth) acryloyl group and the polyisocyanate compound (C) is not inhibited.
- Other functional groups may be included.
- the sealing agent (II) located on the light receiving surface side of the solar cell and the sealing agent (IV) located on the non-light receiving surface side are not particularly limited, and known materials can be suitably applied. Suitable materials include EVA (ethylene-vinyl acetate copolymer), polyvinyl butyral, polyurethane, polyolefin and the like. Of these, EVA is mainly used from the viewpoint of cost.
- EVA ethylene-vinyl acetate copolymer
- polyvinyl butyral polyurethane
- polyolefin polyolefin
- EVA ethylene-vinyl acetate copolymer
- a sheet including a film
- the sealing agent (II) located on the light receiving surface side and the sealing agent (IV) located on the non-light receiving surface side may contain an organic peroxide.
- the sealing agent (II) is crosslinked or sealed by a radical reaction.
- Crosslinking the agent (II) and the sealant (IV) or crosslinking the sealant (IV) can be performed with high efficiency.
- the (meth) acryloyl group in the easy-adhesive layer (D ′) before the curing treatment is used during heat sealing.
- the organic peroxide acts, radical polymerization occurs, and the non-light-receiving surface side sealing agent (IV) and the easy-adhesive layer (D ′) before the curing treatment can be cross-linked or easily cured. Since the adhesive layer (D ′) is cross-linked, it is considered that the adhesive force is improved.
- the “curing treatment” in the present specification refers to a treatment for bonding the encapsulant (IV) and the solar cell back surface protective sheet (V) after they are overlapped.
- the organic peroxide contained in the sealant is preferably used in an amount of 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the sealant resin.
- Specific examples of the organic peroxide include tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-2-ethylhexyl isopropyl carbonate, tert-butyl peroxyacetate, tert-butylcumyl peroxide, 2,5-dimethyl- 2,5-di (tert-butylperoxy) hexane, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2, 5-dimethyl- 2,5-di (tert-butylperoxy) hexane, 1,1-di (tert-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (
- the compound (B) having a (meth) acryloyl group may be contained at a ratio of 0.1 to 20 parts by weight with respect to 100 parts by weight of the acrylic copolymer (A) having no (meth) acryloyl group.
- the ratio is preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight. If the proportion is less than 0.1 parts by weight, a sufficient effect of improving the adhesive strength cannot be expected. If the proportion is more than 20 parts by weight, the cross-linking between the compounds (B) having a (meth) acryloyl group becomes dense. Adhesive strength to materials and sealants is reduced.
- the polyisocyanate compound (C) reacts with the hydroxyl group of the (meth) acrylic copolymer (A) to crosslink the copolymers, thereby imparting moisture and heat resistance to the coating film and constituting a back protective sheet. It is possible to improve the adhesion with a sealing agent such as EVA which is a sealing agent (IV) on the plastic film (E) or the non-light-receiving surface side. Therefore, it is important that the polyisocyanate compound (C) has two or more isocyanate groups in one molecule, and examples thereof include aromatic polyisocyanates, chain aliphatic polyisocyanates, and alicyclic polyisocyanates. It is done.
- the polyisocyanate compound (C) may be used alone or in combination of two or more compounds.
- Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate. Range isocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 " -Triphenylmethane triisocyanate and the like.
- chain aliphatic polyisocyanates examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
- alicyclic polyisocyanates examples include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl- Examples include 2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.
- IPDI 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate
- 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate
- 1,4-cyclohexane diisocyanate examples include 2,4-cyclohexane diisocyanate
- an adduct of the polyisocyanate and a polyol compound such as trimethylolpropane, a burette or isocyanurate of the polyisocyanate, and further, the polyisocyanate and a known polyether polyol or polyester polyol, Examples thereof include adducts with acrylic polyol, polybutadiene polyol, polyisoprene polyol and the like.
- polyisocyanate compounds (C) a low yellowing type aliphatic or alicyclic polyisocyanate is preferable from the viewpoint of design, and an isocyanurate body is preferable from the viewpoint of heat and moisture resistance. More specifically, hexamethylene diisocyanate (HDI) isocyanurate and 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) isocyanurate are preferred.
- HDI hexamethylene diisocyanate
- IPDI 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate
- the blocked polyisocyanate compound (B1) can be obtained by reacting almost all of the isocyanate groups of the polyisocyanate compound (C) with the blocking agent.
- the polyisocyanate compound (C) is preferably a blocked polyisocyanate compound (C1).
- the blocking agent examples include phenols such as phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol, chlorophenol, oximes such as acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, methanol, ethanol, n- Alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-pentanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol , Pyrazo such as 3,5-dimethylpyrazole, 1,2-pyrazole, etc.
- phenols such as phenol, thiophenol, methylthiophenol, xylenol, cresol, res
- Triazoles such as 1,2,4-triazole, halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol, ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -Lactams such as propyl lactam, and active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate, and ethyl malonate.
- Other examples include amines, imides, mercaptans, imines, ureas, and diaryls.
- One blocking agent may be used, or two or more blocking agents may be used in combination.
- these blocking agents those having a dissociation temperature of 80 to 150 ° C. are preferable.
- the dissociation temperature is less than 80 ° C., when the easy-adhesive is applied and the solvent is volatilized, the curing reaction proceeds and the adhesiveness to the filler may be reduced.
- the dissociation temperature exceeds 150 ° C., the curing reaction does not proceed sufficiently in the vacuum thermocompression bonding step when forming the solar cell module, and the adhesion with the filler is lowered.
- Examples of the blocking agent having a dissociation temperature of 80 ° C. to 150 ° C. include methyl ethyl ketone oxime (dissociation temperature: 140 ° C., the same applies hereinafter), 3,5-dimethylpyrazole (120 ° C.), diisopropylamine (120 ° C.), and the like.
- the amount of the polyisocyanate compound (C) in the easy-adhesive of the present invention is such that the isocyanate group exists in the range of 0.1 to 5 isocyanate groups per hydroxyl group in the (meth) acrylic copolymer (A). It is necessary that the amount is such that it is preferably in the range of 0.5 to 4. If it is less than 0.1, the crosslinking density is too low and the heat and moisture resistance is not sufficient, and if it is more than 5, excess isocyanate reacts with moisture in the air during the moist heat test and the coating becomes hard. Moreover, it becomes a cause of the adhesive force fall with sealing agent with the plastic film (E) which comprises a back surface protection sheet, EVA etc. which are sealing agent (IV) by the side of a non-light-receiving surface.
- the plastic film (E) which comprises a back surface protection sheet, EVA etc. which are sealing agent (IV) by the side of a non-light-receiving surface.
- the easy-adhesive of the present invention can contain 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, of organic particles or inorganic particles described later with respect to 100 parts by weight of the solid content. Parts can be contained. By containing these particles, tackiness on the surface of the easy-adhesive layer (D ′) before the curing treatment can be reduced. If the content is less than 0.01 parts by weight, the tack on the surface of the easy-adhesive layer (D ′) before the curing treatment cannot be sufficiently reduced. On the other hand, when the above-mentioned various particles increase, the adhesion between the easy-adhesive layer (D ′) and the sealant before the curing treatment may be hindered, resulting in a decrease in adhesive strength.
- organic particles having a melting point or softening point of 150 ° C. or higher can be preferably used. If the melting point or softening point of the organic particles is lower than 150 ° C., the particles may be softened in the vacuum thermocompression bonding process when constituting the solar cell module, and the adhesion with the sealant may be hindered.
- organic particles include polymethyl methacrylate resin, polystyrene resin, nylon (registered trademark) resin, melamine resin, guanamine resin, phenol resin, urea resin, silicon resin, methacrylate resin, acrylate resin and other polymer particles, Alternatively, cellulose powder, nitrocellulose powder, wood powder, waste paper powder, rice husk powder, starch and the like can be mentioned. One type of organic particles may be used, or two or more types may be used in combination.
- the polymer particles can be obtained by a polymerization method such as an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a soap-free polymerization method, a seed polymerization method, or a micro suspension polymerization method.
- the organic particles may contain impurities to the extent that the characteristics are not impaired.
- the shape of the particles may be any shape such as powder, granule, granule, flat plate, and fiber.
- inorganic particles include magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, antimony, titanium, and other metal oxides, hydroxides, sulfates, carbonates, silicates, etc. Inorganic particles to be used.
- silica gel aluminum oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, zinc oxide, lead oxide, diatomaceous earth, zeolite, aluminosilicate, talc, white carbon, mica Glass fiber, glass powder, glass beads, clay, wollastonite, iron oxide, antimony oxide, titanium oxide, lithopone, pumice powder, aluminum sulfate, zirconium silicate, barium carbonate, dolomite, molybdenum disulfide, iron sand, carbon black, etc.
- inorganic particles One type of inorganic particles may be used, or two or more types may be used in combination.
- the inorganic particles may contain impurities to such an extent that the characteristics are not impaired.
- the shape of the particles may be any shape such as powder, granule, granule, flat plate, and fiber.
- a cross-linking accelerator may be added to the easy-adhesive agent in the present invention, if necessary, within a range that does not interfere with the effects of the present invention.
- the cross-linking accelerator plays a role as a catalyst for promoting the urethane bond reaction by the hydroxyl group of the (meth) acrylic copolymer (A) and the isocyanate of the polyisocyanate compound (C).
- Examples of the crosslinking accelerator include tin compounds, metal salts, bases and the like.
- tin octylate dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, tin chloride, iron octylate, cobalt octylate, and naphthenic acid.
- Zinc, triethylamine, triethylenediamine and the like can be mentioned. These can be used alone or in combination.
- the easy-adhesive in the present invention includes, if necessary, a filler, a thixotropy imparting agent, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, and a heat conduction, as long as the effects of the present invention are not hindered.
- Various additives such as property improvers, plasticizers, anti-sagging agents, antifouling agents, antiseptics, bactericides, antifoaming agents, leveling agents, curing agents, thickeners, pigment dispersants, silane coupling agents It may be added.
- the easy-adhesive used in the present invention contains a solvent.
- a solvent As the solvent, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether, diethylene glycol methyl ether, Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Hydrocarbons such as hexane, heptane, octane, Aromatics such as benzene, toluene, xylene, cumene, Among the esters such as ethyl acetate and butyl acetate, those suitable for the composition of the resin composition can be used, but those having a boiling point of 50 ° C.
- the boiling point is lower than 50 ° C., the solvent easily evaporates when applying the easy-adhesive agent, and the solid content becomes high, making it difficult to apply with a uniform film thickness.
- the boiling point is higher than 200 ° C., it is difficult to dry the solvent. Two or more solvents may be used.
- the easy-adhesive agent of the present invention is a solar cell back surface protective sheet that has good adhesion to the sealant (IV) by coating the plastic film (E) to form an easy-adhesive layer (D ′). (V ′) can be produced.
- the easy-adhesive layer (D ′) before the curing treatment can be formed by applying the easy-adhesive by these methods and volatilizing the solvent by heat drying.
- the thickness of the easy-adhesive layer (D ′) before the curing treatment is preferably 0.01 to 30 ⁇ m, and more preferably 0.1 to 10 ⁇ m.
- plastic film (E) examples include polyester resin films such as polyethylene terephthalate, polybutylene terephthalate, and polynaphthalene terephthalate, olefin films such as polyethylene, polypropylene, and polycyclopentadiene, polyvinyl fluoride, polyvinylidene fluoride film, and polytetra Fluoro-based films such as fluoroethylene films and ethylene-tetrafluoroethylene copolymer films, acrylic films, and triacetyl cellulose films can be used. From the viewpoint of film rigidity and cost, a polyester resin film is preferable, and among these, a polyethylene terephthalate film is preferable.
- polyester resin films such as polyethylene terephthalate, polybutylene terephthalate, and polynaphthalene terephthalate
- olefin films such as polyethylene, polypropylene, and polycyclopentadiene
- polyvinyl fluoride polyvinylidene flu
- the plastic film (E) may have a single layer or a multilayer structure of two or more layers. Furthermore, the plastic film (E) may be laminated with a deposited film or the like on which a metal oxide or a non-metallic inorganic oxide is deposited.
- metal oxide or non-metal inorganic oxide to be deposited examples include oxides such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, and yttrium. Alkali metal and alkaline earth metal fluorides can also be used, and these can be used alone or in combination. These metal oxides or non-metal inorganic oxides can be deposited using a conventionally known PVD method such as vacuum deposition, ion plating, sputtering, or the like, or a CVD method such as plasma CVD or microwave CVD.
- PVD method such as vacuum deposition, ion plating, sputtering, or the like
- CVD method such as plasma CVD or microwave CVD.
- the plastic film (E) may be colorless or may contain coloring components such as pigments or dyes.
- Examples of the method of containing the coloring component include a method of kneading the coloring component in advance at the time of film formation, a method of printing the coloring component on a colorless transparent film substrate, and the like. Further, a colored film and a colorless transparent film may be bonded together.
- the solar cell back surface protective sheet (V ′) is formed on the surface of the plastic film (E) where the easy-adhesive layer (D ′) is not formed, such as a metal foil (F) or a weather resistant resin layer (G).
- a film layer or a coat layer may be provided as a single layer or a plurality of layers.
- the metal foil (F) aluminum foil, iron foil, zinc plywood and the like can be used, and among these, aluminum foil is preferable from the viewpoint of corrosion resistance.
- the thickness is preferably 10 ⁇ m to 100 ⁇ m, more preferably 20 ⁇ m to 50 ⁇ m.
- Various conventionally known adhesives can be used for laminating the metal foil (F).
- Examples of the weather resistant resin layer (G) include those obtained by laminating polyester resin films such as polyvinylidene fluoride film, polyethylene terephthalate, polybutylene terephthalate, and polynaphthalene terephthalate using various conventionally known adhesives, Asahi Glass Co., Ltd. ) And a coating layer formed by applying a highly weather-resistant paint such as Lumiflon.
- polyester resin films such as polyvinylidene fluoride film, polyethylene terephthalate, polybutylene terephthalate, and polynaphthalene terephthalate using various conventionally known adhesives, Asahi Glass Co., Ltd.
- a coating layer formed by applying a highly weather-resistant paint such as Lumiflon.
- the solar cell module 100 seals the solar cell surface protection material (I) positioned on the light receiving surface side of the solar cell with respect to the solar cell (III) before the curing process positioned on the light receiving surface side of the solar cell.
- the solar cell back surface protection sheet (V ′) before curing treatment is laminated via the sealing agent (IV) before curing treatment positioned on the non-light-receiving surface side of the solar battery cell. It can be obtained by hot pressing under reduced pressure.
- the solar cell surface protective material (I) is not particularly limited, but suitable examples include glass plates, polycarbonate and polyacrylate plastic plates, and the like. In view of transparency, weather resistance, toughness and the like, a glass plate is preferable. Furthermore, white glass with high transparency is preferable among the glass plates.
- Sealants such as EVA used as sealants (II) and (IV) include UV absorbers and light stabilizers for improving weather resistance, organic peroxides for crosslinking EVA itself, etc.
- the additive may be contained.
- the easy-adhesive layer (D ′) of the present invention seals the (meth) acryloyl group of the compound (B) having a (meth) acryloyl group by a radical reaction in a high-temperature thermocompression bonding step when forming a solar cell module.
- the adhesive force with the sealing agent (IV) is improved by crosslinking with the agent (IV) or by crosslinking with the compound (B) having a (meth) acryloyl group.
- this crosslinking reaction is promoted, so that the effect of the present invention is exhibited to the maximum. Therefore, it is preferable that sealing agent (IV) located in the non-light-receiving surface side contains an organic peroxide.
- an electrode is provided on a photoelectric conversion layer such as crystalline silicon, amorphous silicon, and a compound semiconductor represented by copper indium selenide, and further, these are laminated on a substrate such as glass. Etc. can be illustrated.
- ⁇ (Meth) acrylic copolymer A1 solution> A four-necked flask equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube was charged with 18 parts of methyl methacrylate, 80 parts of n-butyl methacrylate, 2 parts of 2-hydroxyethyl methacrylate, and 100 parts of toluene under a nitrogen atmosphere. The temperature was raised to 100 ° C. with stirring. Subsequently, 0.15 part of azobisisobutyronitrile was added and a polymerization reaction was performed for 2 hours.
- the number average molecular weight, glass transition temperature, acid value, and hydroxyl value were measured as described below.
- Mn number average molecular weight
- Tg glass transition temperature
- S Amount of sample collected
- a Consumption of 0.1N alcoholic potassium hydroxide solution
- F Potency of 0.1N alcoholic potassium hydroxide solution
- ⁇ Measurement of hydroxyl value (OHV)> About 1 g of a sample (resin solution: about 50%) is accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol 2/1) mixed solution is added and dissolved. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds.
- the hydroxyl value was determined by the following formula.
- the hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
- ⁇ (Meth) acrylic copolymer A2 solution> A four-necked flask equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube was charged with 18 parts of methyl methacrylate, 80 parts of n-butyl methacrylate, 2 parts of 2-hydroxyethyl methacrylate, and 100 parts of toluene under a nitrogen atmosphere. The temperature was raised to 100 ° C. with stirring, and 0.3 part of azobisisobutyronitrile was added to conduct a polymerization reaction for 2 hours.
- ⁇ (Meth) acrylic copolymer A3 solution> A four-necked flask equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube was charged with 18 parts of methyl methacrylate, 80 parts of n-butyl methacrylate, 2 parts of 2-hydroxyethyl methacrylate, and 100 parts of toluene under a nitrogen atmosphere. The temperature was raised to 80 ° C. while stirring, and 0.075 part of azobisisobutyronitrile was added to conduct a polymerization reaction for 2 hours.
- ⁇ (Meth) acrylic copolymer A4 solution> A four-necked flask equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube was charged with 98 parts of n-butyl methacrylate, 2 parts of 2-hydroxylethyl methacrylate, and 100 parts of toluene, and stirred while stirring in a nitrogen atmosphere. The temperature was raised to 0 ° C., 0.15 part of azobisisobutyronitrile was added, and a polymerization reaction was carried out for 2 hours.
- ⁇ (Meth) acrylic copolymer A6 solution A four-necked flask equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introducing tube was charged with 20 parts of methyl methacrylate, 65 parts of n-butyl methacrylate, 15 parts of 2-hydroxylmethacrylate, and 100 parts of toluene, under a nitrogen atmosphere. The temperature was raised to 100 ° C. while stirring, and 0.15 part of azobisisobutyronitrile was added to conduct a polymerization reaction for 2 hours.
- ⁇ (Meth) acrylic copolymer A8 solution> A four-necked flask equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube was charged with 20 parts of methyl methacrylate, 57 parts of n-butyl methacrylate, 23 parts of 2-hydroxylmethacrylate, and 100 parts of toluene, under a nitrogen atmosphere. The temperature was raised to 100 ° C. with stirring at 0.13 parts, 0.13 parts of azobisisobutyronitrile was added and the polymerization reaction was carried out for 2 hours, and then 0.07 parts of azobisisobutyronitrile was added, and another 2 hours. A polymerization reaction was performed.
- ⁇ (Meth) acrylic copolymer A10 solution> A four-necked flask equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube was charged with 18 parts of methyl methacrylate, 80 parts of n-butyl methacrylate, 2 parts of 2-hydroxyethyl methacrylate, and 100 parts of toluene under a nitrogen atmosphere. The temperature was raised to 100 ° C. with stirring, and 0.6 parts of azobisisobutyronitrile was added to conduct a polymerization reaction for 2 hours.
- ⁇ (Meth) acrylic copolymer A11 solution> A four-necked flask equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube was charged with 63 parts of n-butyl methacrylate, 66 parts of 2-ethylhexyl methacrylate, 2 parts of 2-hydroxyethyl methacrylate, and 100 parts of toluene, and nitrogen was added. While stirring in an atmosphere, the temperature was raised to 100 ° C., 0.15 part of azobisisobutyronitrile was added, and a polymerization reaction was performed for 2 hours.
- ⁇ (Meth) acrylic copolymer A12 solution> A four-necked flask equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube was charged with 64 parts of methyl methacrylate, 34 parts of n-butyl methacrylate, 2 parts of 2-hydroxyethyl methacrylate, and 100 parts of toluene under a nitrogen atmosphere. The temperature was raised to 100 ° C. while stirring, and 0.15 part of azobisisobutyronitrile was added to conduct a polymerization reaction for 2 hours.
- a (meth) acrylic copolymer (A) solution, a compound (B) having a (meth) acryloyl group, an allyl group-containing compound (H), and a polyisocyanate compound (C) solution were mixed in the composition shown in Table 2. Furthermore, 0.01 parts by weight of dioctyltin laurate as a catalyst was blended with 100 parts by weight of the solid content of the (meth) acrylic copolymer (A) solution to obtain easy adhesive solutions 1 to 31. .
- a polyester adhesive “Dyna Leo VA-3020 / HD-701” (manufactured by Toyochem Co., Ltd., blending ratio 100/7, the same shall apply hereinafter) is applied to the surface of the polyester film-deposited PET laminate on the deposited PET side by a gravure coater. It was applied, the solvent was dried, and an adhesive layer having an application amount of 10 g / square meter was provided, and a polyvinyl fluoride film (manufactured by DuPont, Tedlar, thickness 50 ⁇ m) was overlaid on the adhesive layer. Thereafter, aging treatment was performed at 50 ° C. for 4 days to cure the adhesive layer, and a polyester film-deposited PET-polyvinyl fluoride film laminate was produced.
- the easy adhesive solution 1 is applied to the polyester film surface of the polyester film-deposited PET-polyvinyl fluoride film laminate by a gravure coater, the solvent is dried, and an easy adhesive layer with a coating amount of 1 g / square meter is provided.
- the solar cell back surface protective sheet 1 was produced.
- solar cell back surface protective sheets 2 to 31 were prepared using the easy-adhesive solutions 2 to 31.
- Adhesive Strength Evaluation Samples 2 through 31 were prepared using the solar cell back surface protective sheets 2 through 31.
- the white plate glass, the EVA film, and the solar cell back surface protection sheet 32 are stacked in order so that the polyester film side surface of the solar cell back surface protection sheet 32 is in contact with the EVA film, and the adhesive strength evaluation is performed in the same manner as in the sample 1 for adhesive strength evaluation.
- Sample 32 was prepared.
- Example 1 Using the adhesive strength evaluation sample 1, the adhesiveness of the easy-adhesive layer to the EVA film and the wet heat resistance test (1000 hours and 2000 hours) were evaluated by the method described later.
- ⁇ Adhesion measurement> One surface of the solar cell back surface protection sheet of the adhesive strength evaluation sample 1 is cut into a width of 15 mm with a cutter, and the adhesive force between the easy-adhesive layer formed on the solar cell back surface protection sheet 1 and the EVA film as a sealant is measured. did.
- a tensile tester was used, and a 180 degree peel test was performed at a load speed of 100 mm / min.
- the obtained measurement values were evaluated as follows. ⁇ : 50N / 15mm or more ⁇ : 30N / 15mm or more to less than 50N / 15mm ⁇ : 10N / 15mm or more to less than 30N / 15mm ⁇ : Less than 10N / 15mm
- Examples 2 to 19 In the same manner as in Example 1, the adhesive strength evaluation samples 2 to 19 were used to evaluate the adhesiveness of the easy adhesive layer to the EVA film and the adhesiveness after the wet heat resistance test.
- the back surface protection sheet for solar cells using the easy-adhesive agent of the present invention has sufficient adhesion to the EVA film and adhesion after the wet heat resistance test.
- Comparative Example 1 since the OH value of the (meth) acrylic copolymer (A) is smaller than 2, the crosslinking is not sufficient and the adhesiveness is inferior.
- Comparative Example 2 the molecular weight of the (meth) acrylic copolymer (A) is too low and the adhesiveness after the wet heat resistance test is poor.
- Comparative Example 3 is inferior in adhesiveness because the Tg of the (meth) acrylic copolymer (A) is too low and the cohesive force is small, and Comparative Example 4 is Tg of the (meth) acrylic copolymer (A). Is too high and the easy-adhesive layer (D ′) becomes hard, resulting in poor adhesion.
- Comparative Example 5 the (meth) acrylic copolymer (A) has an OH value greater than 100, so that crosslinking is excessive and the adhesiveness is poor.
- Comparative Example 11 the polyisocyanate compound (C) was not used, and since the NCO / OH ratio of the curing agent and the acrylic copolymer (A) was 0, the crosslinking reaction did not occur and the adhesiveness after the wet heat resistance test was poor.
- Comparative Example 12 since the NCO / OH ratio is 10, crosslinking is excessive, and the adhesiveness and the adhesiveness after the wet heat resistance test are inferior.
- Comparative Example 21 Except for using the solar cell back surface protection sheet 32 instead of the solar cell back surface protection sheet 1 and laminating so that the surface of the polyester film of the solar cell back surface protection sheet 32 is in contact with the sealant (IV) on the non-light-receiving surface side, In the same manner as in Example 20, a solar cell module 19 was produced, and the photoelectric conversion efficiency (initial, after wet heat resistance test) was measured. This was designated as Comparative Example 21. The results are shown in Table 4.
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Abstract
Description
太陽電池素子には様々な形態があり、その代表的なものとして、結晶シリコン太陽電池素子、多結晶シリコン太陽電池素子、非晶質シリコン太陽電池素子、銅インジウムセレナイド太陽電池素子、化合物半導体太陽電池素子等が知られている。この中でも多結晶シリコン太陽電池素子や、非晶質シリコン太陽電池素子、化合物半導体太陽電池素子は、比較的低コストであり、大面積化が可能であるため、各方面で活発に研究開発が行われている。また、これらの太陽電池素子の中でも、導体金属基板上にシリコンを積層し、更にその上に透明導電層を形成した非晶質シリコン太陽電池素子に代表される薄膜太陽電池素子は、軽量であり、耐衝撃性やフレキシブル性に富んでいるので、太陽電池における将来の形態として有望視されている。
多層構造の裏面保護シートは、その多層構造により、さまざまな性能を付与することができる。例えば、ポリエステルフィルムを用いることで絶縁性を、アルミニウム箔を用いることで水蒸気バリア性を付与することができる(特許文献2~4参照)。
どのような裏面保護シートを用いるかは、太陽電池モジュールが用いられる製品・用途によって、適宜選択され得る。
しかし、前者のコロナ処理などの表面処理は、初期の接着性は確保されるが、接着耐久性に劣ることが問題となっている。
後者の易接着コート処理の場合に用いられる易接着剤が特許文献1、5、6に開示されている。
しかしながら、この例におけるEVAシートとの接着力は、20mm幅で10~20N(即ち、15mm幅ならば7.5~15N)程度である(同文献の表2参照)。封止剤-裏面保護シート間の接着性は太陽電池の出力劣化に大きく影響するため、市場ではより高い接着性が求められ、より厳しい条件下における接着性能の信頼性が求められるようになってきており、20mm幅で20N程度の接着力ではそのような市場の要求に応えられない。特許文献1においては、接着力は改善されるが、市場では、より高性能の易接着剤が求められている。
しかし、このようなフィルムは一般的に数十μmの厚みがあるため、上記の易接着処理に比べてコストが高くなってしまう。
<化1> CH2=C(R1)-CO-OZ
但し、R1は、水素原子またはメチル基、Zは炭素数4~25の炭化水素基を示す。
また、特許文献9には、フッ素系共重合体、アクリル系共重合体、又はポリウレタン系共重合体(重合体a)と、光硬化のためのエチレン性不飽和基を1個以上有する重合性モノマー及び/又はオリゴマー(モノマーb)、及び/又は分子内に1個以上のエチレン性不飽和基と2個以上のイソシアネート基を含有する化合物(ポリイソシアネートc)とからなるプライマー層を有する太陽電池素子の裏面保護シートが開示されている。
(メタ)アクリロイル基を有する化合物(B)と、
前記アクリル系共重合体(A)中の水酸基1個に対して、イソシアネート基が0.1~5個の範囲であるポリイソシアネート化合物(C)とを含有する太陽電池裏面保護シート用易接着剤に関する。
易接着剤層(D')の硬化した易接着剤層(D)が、前記非受光面側封止剤(IV)に接していることを特徴とする太陽電池モジュールに関する。
(メタ)アクリル系共重合体(A)は、ガラス転移温度が10~60℃、数平均分子量が25,000~250,000、水酸基価が2~100(mgKOH/g)である。
なお、ここでのガラス転移温度とは、(メタ)アクリル系共重合体(A)を乾燥させて固形分100%にした樹脂について、示差走査熱量分析(DSC)によって計測したガラス転移温度のことを示す。例えば、ガラス転移温度は、試料約10mgを秤量したサンプルを入れたアルミニウムパンと、試料を入れていないアルミニウムパンとをDSC装置にセットし、これを窒素気流中で、液体窒素を用いて-50℃まで急冷処理し、その後、20℃/分で100℃まで昇温し、DSC曲線をプロットする。このDSC曲線の低温側のベースライン(試験片に転移および反応を生じない温度領域のDSC曲線部分)を高温側に延長した直線と、ガラス転移の階段状変化部分の曲線の勾配が最大になるような点で引いた接線との交点から、補外ガラス転移開始温度(Tig)を求め、これをガラス転移温度として求めることができる。本発明のガラス転移温度は、上記の方法により測定した値を記載している。
なお、上記の数平均分子量は、(メタ)アクリル系共重合体(A)のゲルパーミエーションクロマトグラフィ(GPC)によるポリスチレン換算の値である。例えば、カラム(昭和電工(株)製KF-805L、KF-803L、及びKF-802)の温度を40℃として、溶離液としてTHFを用い、流速を0.2ml/minとし、検出をRI、試料濃度を0.02%とし、標準試料としてポリスチレンを用いて行ったものである。本発明の数平均分子量は、上記の方法により測定した値を記載している。
溶剤としては、メチルエチルケトン、メチルイソブチルケトン、トルエン、セロソルブ、酢酸エチル、酢酸ブチルなど、本発明で樹脂が溶解するものであれば何ら制限は無く、単独でも、複数の溶媒を混合しても良い。また、重合反応の際に使用される重合開始剤もベンゾイルパーオキサイド、アセチルパーオキサイド、メチルエチルケトンパーオキサイド、ラウロイルパーオキサイドなどの有機過酸化物、アゾビスイソブチロニトリルなどのアゾ系開始剤など公知のものを用いることができ、特に制限は無い。
本発明で使用される(メタ)アクリロイル基を有する化合物(B)は、分子中に少なくとも1個以上の(メタ)アクリロイル基を有していればどのようなものでも良く、例えば、トリメチロールプロパントリ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレートなどの多価アルコールの(メタ)アクリレート、ビスフェノールAジグリシジルエーテルのジ(メタ)アクリレート、ポリエチレングリコールジグリシジルエーテルのジ(メタ)アクリレートなどのエポキシ(メタ)アクリレートなどが挙げられる。
これらの中でも、反応性の観点から、(メタ)アクリロイル基を有する化合物(B)は分子中に2個以上の(メタ)アクリロイル基を有することが好ましく、さらには分子中に3個以上有することが好ましい。
また、(メタ)アクリロイル基を有する化合物(B)としては、(メタ)アクリロイル基を有しないアクリル系共重合体(A)とポリイソシアネート化合物(C)との架橋を阻害しない程度にヒドロキシル基や他の官能基を含んでいても良い。
受光面側に位置する封止剤(II)及び非受光面側に位置する封止剤(IV)には、有機過酸化物が含まれていてもよい。有機過酸化物を含有させることによって、封止剤(II)及び(IV)で太陽電池セル(III)を挟み、加熱する際、ラジカル反応により封止剤(II)を架橋させたり、封止剤(II)と封止剤(IV)とを架橋させたり、封止剤(IV)を架橋させたりすることを高効率に行うことができる。
非受光面側の封止剤(IV)中に有機過酸化物を含有させることによって、加熱封止の際、硬化処理前の易接着剤層(D')中の(メタ)アクリロイル基合にも有機過酸化物が作用し、ラジカル重合が生起され、非受光面側の封止剤(IV)と硬化処理前の易接着剤層(D')とを架橋させたり、硬化処理前の易接着剤層(D')を架橋させたりするので、接着力が向上するものと考察される。なお、本明細書における「硬化処理」とは、封止剤(IV)と太陽電池裏面保護シート(V)とを重ね合わせた後に、これらを接合するための処理を云う。
ポリイソシアネート化合物(C)は、(メタ)アクリル系共重合体(A)の水酸基と反応し、共重合体同士を架橋させることで、塗膜に耐湿熱性を付与すると共に、裏面保護シートを構成するプラスチックフィルム(E)や非受光面側の封止剤(IV)であるEVA等の封止剤との密着性を向上させることができる。そのため、ポリイソシアネート化合物(C)は、一分子中に2つ以上のイソシアネート基を有することが重要であり、例えば、芳香族ポリイソシアネート、鎖式脂肪族ポリイソシアネート、脂環族ポリイソシアネート等が挙げられる。ポリイソシアネート化合物(C)は、1種類でも2種類以上の化合物を併用してもよい。
溶剤としては、メタノール、エタノール、プロパノール、ブタノール、エチレングリコールメチルエーテル、ジエチレングリコールメチルエーテル等のアルコール類、
アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、
テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル等のエーテル類、
ヘキサン、ヘプタン、オクタン等の炭化水素類、
ベンゼン、トルエン、キシレン、クメン等の芳香族類、
酢酸エチル、酢酸ブチル等のエステル類、などの内から樹脂組成物の組成に応じ適当なものを使用できるが、沸点が50℃~200℃のものを好ましく用いることができる。沸点が50℃よりも低いと、易接着剤を塗布する際に溶剤が揮発しやすく、固形分が高くなって均一な膜厚で塗布することが難しくなる。沸点が200℃よりも高いと、溶剤を乾燥しづらくなる。なお、溶剤は2種以上用いてもよい。
硬化処理前の易接着剤層(D')の厚みは、0.01~30μmであることが好ましく、0.1~10μmであることがより好ましい。
これらの金属酸化物もしくは非金属無機酸化物は、従来公知の真空蒸着、イオンプレーティング、スパッタリングなどのPVD方式や、プラズマCVD、マイクロウェーブCVDなどのCVD方式を用いて蒸着することができる。
太陽電池モジュール100は、太陽電池セル(III)に対し、太陽電池セルの受光面側に位置する太陽電池表面保護材(I)を太陽電池セルの受光面側に位置する硬化処理前の封止剤(II)を介して積層し、硬化処理前の太陽電池裏面保護シート(V')を太陽電池セルの非受光面側に位置する硬化処理前の封止剤(IV)を介して積層し、減圧下で高温加熱圧着することによって得ることができる。
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、数平均分子量が36,000、水酸基価が9.0(mgKOH/g)、Tgが31℃、固形分50%の(メタ)アクリル系共重合体A1溶液を得た。
Mnの測定は、前述したGPC(ゲルパーミエーションクロマトグラフィー)によって求めた
ガラス転移温度の測定は、前述した示差走査熱量測定(DSC)法により求めた。
なお、Tg測定用の試料は、上記のアクリル樹脂溶液を150℃で約15分、加熱し、乾固させたものを用いた。
共栓三角フラスコ中に試料(樹脂の溶液:約50%)約1gを精密に量り採り、トルエン/エタノール(容量比:トルエン/エタノール=2/1)混合液100mlを加えて溶解する。これに、フェノールフタレイン試液を指示薬として加え、30秒間保持する。その後、溶液が淡紅色を呈するまで0.1Nアルコール性水酸化カリウム溶液で滴定する。酸価は次式により求めた。酸価は樹脂の乾燥状態の数値とした(単位:mgKOH/g)。
酸価(mgKOH/g)={(5.611×a×F)/S}/(不揮発分濃度/100)
ただし、S:試料の採取量(g)
a:0.1Nアルコール性水酸化カリウム溶液の消費量(ml)
F:0.1Nアルコール性水酸化カリウム溶液の力価
共栓三角フラスコ中に試料(樹脂の溶液:約50%)約1gを精密に量り採り、トルエン/エタノール(容量比:トルエン/エタノール=2/1)混合液100mlを加えて溶解する。更にアセチル化剤(無水酢酸25gをピリジンで溶解し、容量100mlとした溶液)を正確に5ml加え、約1時間攪拌した。これに、フェノールフタレイン試液を指示薬として加え、30秒間持続する。その後、溶液が淡紅色を呈するまで0.1Nアルコール性水酸化カリウム溶液で滴定する。
水酸基価は次式により求めた。水酸基価は樹脂の乾燥状態の数値とした(単位:mgKOH/g)。
水酸基価(mgKOH/g)
=[{(b-a)×F×28.25}/S]/(不揮発分濃度/100)+D
ただし、S:試料の採取量(g)
a:0.1Nアルコール性水酸化カリウム溶液の消費量(ml)
b:空実験の0.1Nアルコール性水酸化カリウム溶液の消費量(ml)
F:0.1Nアルコール性水酸化カリウム溶液の力価
D:酸価(mgKOH/g)
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、アゾビスイソブチロニトリルを0.3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0.05部加えてさらに2時間重合反応を行い、更に0.05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、数平均分子量が25,000、水酸基価が8.2(mgKOH/g)、Tgが33℃、固形分50%の(メタ)アクリル系共重合体A2溶液を得た。
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80℃まで昇温し、アゾビスイソブチロニトリルを0.075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、数平均分子量が76,000、水酸基価が8.0(mgKOH/g)、Tgが34℃、固形分50%の(メタ)アクリル系共重合体A3溶液を得た。
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、n-ブチルメタクリレート98部、2-ヒドロキシル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、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、数平均分子量が35,000、水酸基価が8.8(mgKOH/g)、Tgが19℃、固形分50%の(メタ)アクリル系共重合体A4溶液を得た。
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41部、n-ブチルメタクリレート57部、2-ヒドロキシル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、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、数平均分子量が40,000、水酸基価が7.9(mgKOH/g)、Tgが51℃、固形分50%の(メタ)アクリル系共重合体A5溶液を得た。
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20部、n-ブチルメタクリレート65部、2-ヒドロキシルエチルメタクリレート15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、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、数平均分子量が45,000、水酸基価が62.1(mgKOH/g)、Tgが40℃、固形分50%の(メタ)アクリル系共重合体A6溶液を得た。
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78部、2-ヒドロキシルエチルメタクリレート4部、酢酸エチル100部を仕込み、窒素雰囲気下で撹拌しながら77℃まで昇温し、アゾビスイソブチロニトリルを0.05部加えて2時間重合反応を行った。次に、酢酸エチル22部、および0.05部のアゾビスイソブチロニトリルを加えて2時間重合反応を行い、更に、酢酸エチル22部、および0.05部のアゾビスイソブチロニトリルを加えて2時間重合反応を行った。その後、酢酸エチル36部および0.05部のアゾビスイソブチロニトリルを加えて2時間重合反応を行い、さらに0.05部のアゾビスイソブチロニトリルを加えて2時間重合反応を行い、数平均分子量が244,000、水酸基価が16.0(mgKOH/g)、Tgが35℃、固形分35%の(メタ)アクリル系共重合体溶液A7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20部、n-ブチルメタクリレート57部、2-ヒドロキシルエチルメタクリレート23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、アゾビスイソブチロニトリルを0.13部加えて2時間重合反応を行い、次に、アゾビスイソブチロニトリルを0.07部加えてさらに2時間重合反応を行った。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時間重合反応を行い、数平均分子量が42,000、水酸基価が97.5(mgKOH/g)、Tgが44℃、固形分50%のアクリル樹脂溶液A8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82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、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、数平均分子量が42,000、水酸基価が0(mgKOH/g)、Tgが36℃、固形分50%の(メタ)アクリル系共重合体A7溶液を得た。
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、アゾビスイソブチロニトリルを0.6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0.05部加えてさらに2時間重合反応を行い、更に0.05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、数平均分子量が12,000、水酸基価が8.6(mgKOH/g)、Tgが33℃、固形分50%の(メタ)アクリル系共重合体A8溶液を得た。
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、n-ブチルメタクリレート63部、2-エチルヘキシルメタクリレート66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、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0.307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、数平均分子量が36,000、水酸基価が9.2(mgKOH/g)、Tgが2℃、固形分50%の(メタ)アクリル系共重合体A9溶液を得た。
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64部、n-ブチルメタクリレート34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、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、数平均分子量が38,000、水酸基価が8.2(mgKOH/g)、Tgが69℃、固形分50%の(メタ)アクリル系共重合体A10溶液を得た。
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20部、n-ブチルメタクリレート55部、2-ヒドロキシエチルメタクリレート25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、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、数平均分子量が37,000、水酸基価が109(mgKOH/g)、Tgが44℃、固形分50%の(メタ)アクリル系共重合体A11溶液を得た。
(メタ)アクリロイル基を有する化合物B1~B6には、表2に記載した化合物をそのまま用いた。
アリル基含有化合物H1~H4には、表2に記載した化合物をそのまま用いた。
3,5-ジメチルピラゾールでブロックされた、ヘキサメチレンジイソシアネートのイソシアヌレート体を、酢酸エチルで75%に希釈し、ポリイソシアネート化合物(C)溶液を得た。
(メタ)アクリル系共重合体(A)溶液、(メタ)アクリロイル基を有する化合物(B)、アリル基含有化合物(H)、ポリイソシアネート化合物(C)溶液を表2に示す組成にて混合し、さらに(メタ)アクリル系共重合体(A)溶液の固形分100重量部に対して、いずれも触媒としてジオクチル錫ラウレートを0.01重量部配合し、易接着剤溶液1~31を得た。
ポリエステルフィルム(帝人デュポンフィルム(株)製、テトロン(登録商標)S、厚み188μm、)の両面にコロナ処理し、一方の面にポリエステル接着剤「ダイナレオVA-3020/HD-701」(トーヨーケム(株)製、配合比100/7、以下同)をグラビアコーターによって塗布し、溶剤を乾燥させ、塗布量:10g/平方メートルの接着剤層を設け、該接着剤層に、下記の蒸着PET(三菱樹脂(株)製、テックバリアLX、厚み12μm)の蒸着面を重ね合わせた。その後、50℃、4日間、エージング処理し、接着剤層を硬化させ、ポリエステルフィルム-蒸着PET積層体を作製した。
白板ガラス、酢酸ビニル-エチレン共重合体フィルム(サンビック(株)製、スタンダードキュアタイプ、以下EVAフィルム)、太陽電池裏面保護シート1を、太陽電池裏面保護シート1の易接着剤層がEVAフィルムに接するように順に重ねた。その後、この積層体を真空ラミネーターに入れ、1Torr程度に真空排気して、プレス圧力0.1MPaで、150℃30分間加熱後、さらに150℃で30分間加熱し、10cm×10cm角の接着力評価用サンプル1を作製した。
接着力評価用サンプル1を用い、後述する方法で、易接着剤層のEVAフィルムへの接着性、耐湿熱試験後(1000時間後、2000時間後)接着性の評価を行った。
接着力評価用サンプル1の太陽電池裏面保護シート1面をカッターで15mm幅に切り、太陽電池裏面保護シート1に形成された易接着剤層と封止剤であるEVAフィルムとの接着力を測定した。測定には、引っ張り試験機を用い、荷重速度100mm/minで180度剥離試験を行った。得られた測定値に対して、以下のように評価した。
◎:50N/15mm以上
○:30N/15mm以上~50N/15mm未満
△:10N/15mm以上~30N/15mm未満
×:10N/15mm未満
接着力評価用サンプル1を、温度85℃、相対湿度85%RHの環境条件で1000時間、2000時間静置した後、接着性測定と同様にして、耐湿熱試験後接着性の評価を行った。
実施例1と同様にして、接着力評価用サンプル2~19を用い、易接着剤層のEVAフィルムへの接着性、耐湿熱試験後接着性の評価を行い、実施例2~19とした。
実施例1と同様にして、接着力評価用サンプル20~31を用い、易接着剤層のEVAフィルムへの接着性、耐湿熱試験後接着性の評価を行い、比較例1~12とした。
実施例1と同様にして、接着力評価用サンプル32を用い、ポリエステルフィルム表面とEVAフィルムとの接着性、耐湿熱試験後接着性の評価を行い、比較例13とした。
以上の結果を表2、又は表3に示す。
比較例2は、(メタ)アクリル系共重合体(A)の分子量が低すぎて耐湿熱試験後接着性に劣る。
比較例3は、(メタ)アクリル系共重合体(A)のTgが低すぎて凝集力が小さいために接着性に劣り、比較例4は(メタ)アクリル系共重合体(A)のTgが高すぎて易接着剤層(D')が硬くなるために接着性に劣る。
また、比較例5は、(メタ)アクリル系共重合体(A)のOH価が100より大きいために架橋が過剰になって接着性に劣る。
<太陽電池モジュールの作製>
白板ガラス・・・太陽電池表面封止剤(I)
EVAフィルム・・・受光面側の封止剤(II)
多結晶シリコン太陽電池素子・・・太陽電池セル(III)
EVAフィルム・・・非受光面側の封止剤(IV)
上記(I)~(IV)及び太陽電池裏面保護シート1を、太陽電池裏面保護シート1の易接着層が非受光面側の封止剤(IV)に接するように順に重ねた後、真空ラミネーターに入れ、1Torr程度に真空排気して、プレス圧力としては大気圧の圧力をかけた状態で、150℃30分間加熱後、さらに150℃で30分間加熱し、10cm×10cm角の光電変換効率評価用太陽電池モジュール1を作製した。
得られた太陽電池モジュール1の太陽電池出力を測定し、JIS C8912に従って、ソーラーシュミレーター(英弘精機製、SS-100XIL)を用いて光電変換効率を測定した。
さらに、温度85℃、相対湿度85%RHの環境条件で500時間、1000時間、1500時間、2000時間静置した後の耐湿熱試験後の光電変換効率を、同様にして測定した。初期の光電変換効率に対する、耐湿熱試験後の光電変換効率の低下の割合を計算し、以下のように評価した。
○:出力の低下が10%未満
△:出力の低下が10%以上~15%未満
×:出力の低下が20%以上
実施例20と同様にして、太陽電池裏面保護シート2~11を用いて太陽電池モジュール2~11(実施例21~30)、太陽電池裏面保護シート20~26を用いて太陽電池モジュール12~18(比較例14~20)を作製し、光電変換効率(初期、耐湿熱試験後)を測定した。
太陽電池裏面保護シート1の代わりに太陽電池裏面保護シート32を用い、太陽電池裏面保護シート32のポリエステルフィルムの表面が非受光面側の封止剤(IV)に接するように積層した以外は、実施例20と同様にして、太陽電池モジュール19を作製し、光電変換効率(初期、耐湿熱試験後)を測定した。これを比較例21とした。
以上の結果を表4に示す。
II 太陽電池セルの受光面側に位置する封止剤
III 太陽電池セル
IV 太陽電池セルの非受光面側に位置する封止剤
V 太陽電池裏面保護シート
Claims (8)
- ガラス転移温度が10~60℃、数平均分子量が25,000~250,000、水酸基価が2~100(mgKOH/g)であり、(メタ)アクリロイル基を有しないアクリル系共重合体(A)と、
(メタ)アクリロイル基を有する化合物(B)と、
前記(メタ)アクリル系共重合体(A)中の水酸基1個に対して、イソシアネート基が0.1~5個の範囲であるポリイソシアネート化合物(C)とを含有する太陽電池裏面保護シート用易接着剤。 - 前記(メタ)アクリロイル基を有しないアクリル系共重合体(A)100重量部に対して、(メタ)アクリロイル基を有する化合物(B)を0.1~20重量部含有する、請求項1に記載の太陽電池裏面保護シート用易接着剤。
- 前記ポリイソシアネート化合物(C)がブロック化ポリイソシアネート(C1)である、請求項1又は2に記載の太陽電池裏面保護シート用易接着剤。
- 前記(メタ)アクリロイル基を有する化合物(B)は、分子中に2個以上の(メタ)アクリロイル基を有することを特徴とする請求項1~3いずれか1項に記載の太陽電池裏面保護シート用易接着剤。
- 請求項1~4いずれか1項に記載の太陽電池裏面保護シート用易接着剤によって形成される硬化処理前の易接着剤層と、プラスチックフィルムとを具備する太陽電池裏面保護シート。
- 太陽電池セルと、
受光面側に配設され、受光面側の封止剤を介して前記太陽電池セルを保護する太陽電池表面保護材と、
非受光面側に配設され、非受光面側の封止剤を介して前記太陽電池セルを保護する太陽電池裏面保護シートと、を具備し、
前記太陽電池裏面保護シートは、プラスチックフィルムと、請求項1~4のいずれか1項に記載の太陽電池裏面保護シート用易接着剤から形成された硬化処理前の易接着剤層とを具備する太陽電池裏面保護シートを、前記易接着剤層が、前記非受光面側の封止剤と接するように配置して、前記太陽電池裏面保護シート用易接着剤層を硬化することにより得たものである太陽電池モジュール。 - 前記非受光面側の封止剤は、有機過酸化物が含有されていることを特徴とする請求項6に記載の太陽電池モジュール。
- 前記非受光面側の封止剤は、エチレン-酢酸ビニル共重合体(EVA)を主成分とすることを特徴とする請求項6又は7に記載の太陽電池モジュール。
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| JP2012214805A (ja) * | 2011-03-31 | 2012-11-08 | Toyo Ink Sc Holdings Co Ltd | 積層シート用接着剤組成物 |
| JP2013117021A (ja) * | 2011-10-31 | 2013-06-13 | Toyo Ink Sc Holdings Co Ltd | 太陽電池裏面保護シート用易接着剤、及び太陽電池裏面保護シート、ならびに太陽電池モジュール |
| JP2013136665A (ja) * | 2011-12-28 | 2013-07-11 | Toyo Ink Sc Holdings Co Ltd | 太陽電池表面保護シート用易接着剤、太陽電池表面保護シート、ならびに太陽電池モジュール |
| JP2013187349A (ja) * | 2012-03-08 | 2013-09-19 | Toyo Ink Sc Holdings Co Ltd | 太陽電池モジュール、太陽電池モジュールの製造方法、及び太陽電池セル用保護シート |
| JP2014136730A (ja) * | 2013-01-16 | 2014-07-28 | Dic Corp | 易接着剤組成物、積層ポリエステル樹脂フィルム及び太陽電池バックシート |
| JP2014152335A (ja) * | 2013-02-07 | 2014-08-25 | Sumika Technology Co Ltd | 接着性ポリマー組成物及びその適用 |
| JP2013251530A (ja) * | 2013-03-27 | 2013-12-12 | Henkel Japan Ltd | 太陽電池バックシート用接着剤 |
| JP2013251531A (ja) * | 2013-03-27 | 2013-12-12 | Henkel Japan Ltd | 太陽電池バックシート用接着剤 |
| WO2015012134A1 (ja) * | 2013-07-25 | 2015-01-29 | 株式会社Adeka | 熱硬化型粘着性組成物 |
| JPWO2015012134A1 (ja) * | 2013-07-25 | 2017-03-02 | 株式会社Adeka | 熱硬化型粘着性組成物 |
| JPWO2015025701A1 (ja) * | 2013-08-20 | 2017-03-02 | 株式会社Adeka | 難燃性合成樹脂組成物 |
| JP2014015619A (ja) * | 2013-08-22 | 2014-01-30 | Henkel Japan Ltd | 太陽電池バックシート用接着剤 |
| JP2013251576A (ja) * | 2013-08-22 | 2013-12-12 | Henkel Japan Ltd | 太陽電池バックシート用接着剤 |
| JP2016053112A (ja) * | 2014-09-03 | 2016-04-14 | 東洋インキScホールディングス株式会社 | 熱硬化性樹脂組成物、および太陽電池裏面保護シート |
| CN104393076A (zh) * | 2014-10-24 | 2015-03-04 | 无锡中洁能源技术有限公司 | 改性丙烯酸太阳能电池背板及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201213479A (en) | 2012-04-01 |
| TWI465536B (zh) | 2014-12-21 |
| KR20130036021A (ko) | 2013-04-09 |
| EP2592125A4 (en) | 2013-12-18 |
| CN103003380A (zh) | 2013-03-27 |
| CN103003380B (zh) | 2014-08-27 |
| JP4924780B2 (ja) | 2012-04-25 |
| KR101405450B1 (ko) | 2014-06-10 |
| JPWO2012004962A1 (ja) | 2013-09-02 |
| EP2592125A1 (en) | 2013-05-15 |
| US20130098441A1 (en) | 2013-04-25 |
| US9321943B2 (en) | 2016-04-26 |
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