WO2012029733A1 - 太陽電池モジュール用裏面保護シートおよびそれを用いた太陽電池モジュール - Google Patents
太陽電池モジュール用裏面保護シートおよびそれを用いた太陽電池モジュール Download PDFInfo
- Publication number
- WO2012029733A1 WO2012029733A1 PCT/JP2011/069514 JP2011069514W WO2012029733A1 WO 2012029733 A1 WO2012029733 A1 WO 2012029733A1 JP 2011069514 W JP2011069514 W JP 2011069514W WO 2012029733 A1 WO2012029733 A1 WO 2012029733A1
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- WIPO (PCT)
- Prior art keywords
- solar cell
- film
- cell module
- adhesive
- weight
- Prior art date
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 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
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
-
- 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 back surface protection sheet for a solar cell module and a solar cell module using the same, and more particularly, particularly excellent in electrical insulation, heat resistance and dimensional stability, and Even when used in high-temperature and high-humidity environments by using an adhesive with excellent weather resistance in the backside protection sheet that has two or more kinds of plastic films with excellent mechanical strength, weather resistance, water resistance, etc.
- Back surface protection sheet for solar cell modules that can suppress a decrease in adhesive strength between plastic films and can suppress a decrease in breaking strength of the back surface protection sheet by using a polyethylene terephthalate film having excellent hydrolysis resistance. And a solar cell module using the same.
- a solar cell module uses a solar cell element such as a crystalline silicon solar cell element or an amorphous silicon solar cell element, a surface protection sheet, a filler sheet such as ethylene / vinyl acetate copolymer resin, solar
- the battery element, the filler sheet, and the back surface protection sheet layer are laminated in this order, and are manufactured by a method of vacuum suction, thermocompression bonding, and integration.
- a back surface protection sheet constituting a solar cell module a plastic base material that is light in weight and excellent in electrical characteristics and strength has been generally used.
- the back surface protection sheet constituting the solar cell module is strength, weather resistance, heat resistance, water resistance, light resistance, chemical resistance, light reflectivity, light diffusibility, moisture resistance, antifouling property, and design. Etc., and these do not need to change over time.
- a back surface protection sheet using a polyester film such as polyethylene terephthalate having excellent weather resistance and electrical insulation has been developed as a back surface protection sheet for a solar cell module.
- a polyester film such as polyethylene terephthalate having excellent weather resistance and electrical insulation
- the amount of cyclic oligomer in a system containing a UV absorber (Patent Document 1) and a polyester film (Patent Documents 2 and 3), or the molecular weight of a polyester film (Patent Document) 4) etc. are disclosed.
- polyester films and other materials are bonded together and used as a laminate, it is important to select an adhesive for bonding, and any one of carbodiimide compounds, oxazoline compounds, and epoxy compounds can be used as a polyurethane-based adhesive.
- any one of carbodiimide compounds, oxazoline compounds, and epoxy compounds can be used as a polyurethane-based adhesive.
- the thing containing this is known (patent documents 5 and 6).
- An object of the present invention is to provide a back surface protection sheet for a solar cell module with little decrease in adhesive strength even when used under long-term high temperature and high humidity conditions.
- the present inventors have improved the weather resistance (hydrolysis resistance) as a base film and weather resistance (hydrolysis resistance) to the adhesive to be bonded. It has been found that an excellent back surface protection sheet for a solar cell module with little decrease in adhesive strength and breaking strength can be obtained over a long period of time even under high temperature and high humidity.
- the present invention is a back protective sheet for a solar cell module in which a hydrolysis-resistant polyethylene terephthalate film is laminated with another laminate or film and an adhesive, and the adhesive is 100 parts by weight of polyester polyol (a). 5 to 30 parts by weight of epoxy resin (b), 5 to 30 parts by weight of polycarbonate polyol (c), 1 to 10 parts by weight of carbodiimide compound (d), and 10 to 30 parts by weight of polyisocyanate compound (e) It is a back surface protection sheet for solar cell modules characterized by being blended.
- the back surface protection sheet for solar cell modules of the present invention is a back surface protection sheet for solar cell modules in which a hydrolysis-resistant polyethylene terephthalate film is laminated with another laminate or film and an adhesive.
- a back protective sheet for a solar cell module in which a polyethylene film, a white plastic film, and a polyethylene terephthalate film having hydrolysis resistance are sequentially laminated, or a polyethylene film, a black plastic film, and polyethylene having hydrolysis resistance.
- Solar cell module backside protective sheet with laminated terephthalate film sequentially, or white polyethylene film and hydrolysis-resistant polyethylene terephthalate film, further white polypropylene film and hydrolysis-resistant polyethylene terephthalate film laminated
- a battery module back surface protection sheet or the like is configured according to various requirements.
- an adhesive containing a polyester polyol, an epoxy resin, a polycarbonate polyol, a carbodiimide compound, and a polyisocyanate compound is used for adhesion between the films.
- FIG. 1, FIG. 2 and FIG. 3 are cross-sectional views showing an example of the layer structure of the back surface protective sheet for solar cell module of the present invention.
- FIG. 4 is a cross-sectional view showing an example of the layer structure of a solar cell module using the back surface protective sheet for a solar cell module of the present invention.
- the back surface protective sheet (11) for solar cell modules in the present invention comprises a polyethylene film (1), a white plastic film (2), and a hydrolysis-resistant polyethylene terephthalate film (3), an adhesive layer (4), (5 ),
- (5), the back protective sheet for solar cell modules (17), or the white polyethylene film or white polypropylene film (12) and the hydrolysis-resistant polyethylene terephthalate film (14) are adhesive layers.
- the hydrolysis-resistant polyethylene terephthalate film used in the present invention (hereinafter abbreviated as hydrolysis-resistant PET film) has a breaking strength after being treated at 120 ° C. and 100% RH for 48 hours, when it is untreated. 10% or more (break strength retention is 10% or more), and the elongation at break after treatment at 120 ° C. and 100% RH for 48 hours is 10% or more when not treated. It is preferably maintained (breaking elongation retention is 10% or more).
- the retention ratios of breaking strength and breaking elongation are more preferably 60% or more, and most preferably 80% or more.
- the hydrolysis-resistant PET film is preferably a biaxially stretched film from the viewpoint of mechanical strength, heat resistance, voltage resistance, dimensional stability, chemical resistance, weather resistance, and the like.
- the thickness of the hydrolysis-resistant PET film is preferably 50 to 300 ⁇ m, and 75 to 250 ⁇ m is preferable from the standpoint of the film, the voltage resistance, the cost of the solar battery back surface protection sheet, and the suitability for processing in the production of solar cells. More preferred.
- the hydrolysis-resistant PET film is a polyethylene terephthalate comprising at least 90 mol% of ethylene terephthalate units and containing any one of polymerization catalyst metal compounds selected from antimony, germanium, and titanium compounds.
- a polyethylene terephthalate composition in which the amount of catalytic metal compound is 0.2 to 1 mol / ton as a metal with respect to the polyethylene terephthalate and the ethylene terephthalate cyclic trimer content is 0.5% by weight or less based on the whole. Is done.
- the above polyethylene terephthalate may copolymerize various dicarboxylic acids or ester-forming derivatives thereof and diols as other copolymerization components within 10 mol%.
- examples of the alicyclic dicarboxylic acid component that can be copolymerized include 1,4-cyclohexanedicarboxylic acid.
- diol component examples include ethylene glycol, 1,2-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, , 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2-bis (4'- ⁇ -hydroxyethoxyphenyl) propane, etc. And aliphatic, alicyclic, and aromatic diols. These components may be used alone or in combination of two or more.
- Polyethylene terephthalate that is preferably used as the hydrolysis-resistant PET film in the present invention can be produced according to a conventionally known polyester production method. That is, it is produced by using a dialkyl ester as an acid component, transesterifying it with a diol component, and then heating the product of this reaction under reduced pressure to perform polycondensation while removing excess diol component. can do.
- the hydrolysis-resistant PET film of the present invention has an intrinsic viscosity [ ⁇ ] using terephthalic acid as the dicarboxylic acid component and ethylene glycol as the diol component, and is more preferably 0. .75-1.00 polyethylene terephthalate can be obtained as a biaxially stretched film.
- the intrinsic viscosity [ ⁇ ] is a value measured by dissolving a polyethylene terephthalate film using o-chlorophenol as a solvent and a temperature of 25 ° C., and the viscosity is proportional to the degree of polymerization of polyethylene terephthalate. In order to improve hydrolysis resistance, it is important to increase the degree of polymerization of polyethylene terephthalate.
- a method for increasing the degree of polymerization a method in which the polymerization time is allowed to proceed while removing ethylene glycol at the time of polymerization under reduced pressure to allow the polymerization to proceed.
- a so-called solid-phase polymerization method in which the polyethylene terephthalate resin once subjected to the above-mentioned polymerization is crystallized and then heat-treated under high pressure at a high temperature to further increase the degree of polymerization.
- intrinsic viscosity [ ⁇ ] Can be set to a desired value.
- the intrinsic viscosity is 0.70 or more, it is easy to impart hydrolysis resistance and heat resistance, and this is preferable because the hydrolysis resistance of the back surface protection sheet and further the solar cell module is improved.
- An intrinsic viscosity of 1.20 or less is preferable because the melt viscosity becomes low, melt extrusion molding becomes easy, and the film-forming property of the film is improved.
- the polyethylene terephthalate is dried as necessary, supplied to a known melt extruder, the sheet is extruded from a slit-shaped die, and the metal drum is formed. It is made to adhere and it cools to the temperature below the glass transition point of this polyethylene terephthalate, and an unstretched film is obtained.
- a biaxially stretched film can be obtained from the unstretched film by a known method such as a simultaneous biaxial stretching method or a sequential biaxial stretching method. As the conditions in this case, the stretching temperature can be selected arbitrarily from the glass transition point Tg to Tg + 100 ° C.
- the physical properties of the film finally obtained in the temperature range of 80 to 170 ° C. From the viewpoint of productivity.
- the stretching ratio can be selected in the range of 1.6 to 5.0 times, preferably 1.7 to 4.5 times in both the longitudinal direction and the width direction of the film.
- the stretching speed is preferably 1000 to 200000% / min.
- the film is heat-treated after stretching. However, the film can be heat-treated continuously in a heat-treating chamber following the tenter that extends in the width direction, heated in another oven, or heat-treated with a heating roll. As heat treatment conditions, a temperature of 120 to 245 ° C. and a time of 1 to 60 seconds are usually used. Relaxing treatment may be performed for the purpose of improving thermal dimensional stability in the width direction and the longitudinal direction during heat treatment.
- the adhesive used for laminating the hydrolysis-resistant PET film to another film or laminate is 5 to 30 parts by weight of the epoxy resin (b) with respect to 100 parts by weight of the polyester polyol (a). And 5 to 30 parts by weight of polycarbonate polyol (c), 1 to 10 parts by weight of carbodiimide compound (d), and 10 to 30 parts by weight of polyisocyanate compound (e) as a curing agent To do.
- a weather-resistant adhesive it is possible to obtain a back protective sheet for a solar cell module that is excellent in weather resistance and has little decrease in adhesive strength over time.
- the polyester polyol (a), which is the main component of the adhesive, is obtained by condensation polymerization of dicarboxylic acid and polyhydric alcohol
- polyester diol obtained by condensation polymerization of dicarboxylic acid and diol is representative.
- Dicarboxylic acids include malonic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and other aliphatic dicarboxylic acids, fumaric acid, maleic anhydride and other unsaturated dicarboxylic acids, phthalic acid, dimethyl Aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid and dimethyl terephthalic acid.
- polyhydric alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, neopentyl glycol, 1,5 -Pentanediol, 1,6-hexanediol, 3-methyl 1,5-pentanediol, 2-ethyl 1,3-hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 1,8-octane Diol, aliphatic glycol such as 1,10-decanediol, cyclohexanediol, cyclohexanedimethanol, alicyclic glycol such as hydrogenated bisphenol A, xylene glycol, bishydroxyethoxybenzene, bishydroxyethyl terephthalate, etc.
- Aromatic glycol, trimethylol propane, and aliphatic triols such as glycerin can be exemplified.
- Various known polyester polyol resins based on these combinations can be used, but those having a number average molecular weight in the range of 1,000 to 40,000 are preferable, and those having a hydroxyl value of 1 to 30 mg KOH / g can be used. If the number average molecular weight is less than 1000, the adhesive strength is insufficient, and if it exceeds 40000, the workability, the coating film appearance and the solubility are inferior.
- the epoxy resin (b) used for the adhesive in the present invention a bisphenol type epoxy resin which is a copolymer of bisphenol A or bisphenol F and epichlorohydrin can be used, and the number average molecular weight is 500 to 1500. Is preferred. When the number average molecular weight is 500 or more, the heat-and-moisture resistance as an adhesive can be improved, and when the number-average molecular weight is 1500 or less, the solubility in the coating agent can be improved.
- the epoxy resin (b) for example, a bisphenol A type epoxy resin having a number average molecular weight of about 1000 is used.
- the addition amount of the epoxy resin (b) used in the adhesive in the present invention is not sufficient moisture and heat resistance if the blending amount is small, and if the blending amount is large, poor coating due to wetting and repelling of the adhesive occurs. It is important to add 5 to 30 parts by weight per 100 parts by weight of the polyester polyol (a).
- the polycarbonate polyol (c) used for the adhesive in the present invention is generally a polycarbonate diol composed of a diol and a carbonate, and has a number average molecular weight of 500 to 3000 and a hydroxyl value of 20 to 200 mgKOH / g in order to maintain weather resistance and adhesive strength. Is selected.
- diol for producing the polycarbonate diol examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, Diols having no side chain, such as 1,8-octanediol, 1,9-nanodiol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,8-octane Diol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2, 4-diethyl-1,5-pentanediol, 2-butyl
- dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate and dibutyl carbonate
- diaryl carbonates such as diphenyl carbonate, ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate
- alkylene carbonates such as 1,3-butylene carbonate and 1,2-pentylene carbonate.
- polycarbonate diols composed of aliphatic diols (1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, etc.) and ethylene carbonate are preferably used.
- the addition amount of the polycarbonate polyol resin (c) used in the adhesive in the present invention is not sufficient moisture and heat resistance if the blending amount is small, and if the blending amount is large, the heat and humidity resistance is obtained, but the adhesive strength decreases. It is important to blend 5 to 30 parts by weight with respect to 100 parts by weight of the polyester polyol (a).
- the carbodiimide compound (d) is added to the adhesive in the present invention in order to seal a carboxyl group that remains in the adhesive composition or is generated by hydrolysis and promotes hydrolysis.
- carbodiimide compound examples include dicyclohexylcarbodiimide, diisopropylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, octyldecylcarbodiimide, di-t-butylcarbodiimide, dibenzylcarbodiimide, diphenylcarbodiimide, N-octadecyl-N′-phenylcarbodiimide, and N-benzylcarbodiimide.
- bis (2,6-diisopropylphenyl) carbodiimide and 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide are preferred from the viewpoints of reactivity and stability.
- a commercially available polycarbodiimide compound as the polycarbodiimide compound can be suitably used without the need for synthesis.
- various grades sold under the trade name “Carbodilite” marketed by Nisshinbo Chemical Co., Ltd. can be used.
- the carbodiimide compound (d) has a carbodiimide equivalent (molecular weight / number of carbodiimide groups contained in the molecule) of 100 to 1000, and it is important to blend 1 to 10 parts by weight with respect to 100 parts by weight of the polyester polyol (a). is there. If it is less than 1 part by weight, the hydrolysis resistance is insufficient, and if it exceeds 10 parts by weight, the hue becomes yellowish, which causes a problem in appearance.
- the polyisocyanate compound (e) which is a curing agent component of the adhesive in the present invention is one or more selected from aliphatic, alicyclic, araliphatic and aromatic, such as hexamethylene diisocyanate, Aliphatic isocyanates such as pentamethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, cyclohexane diisocyanate, methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, and the like, and araliphatic isocyanates such as xylylene diisocyanate, tetramethylxylylene diisocyanate, Examples include aromatic isocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate. In addition, adducts, dimers, trimers, carbodiimide-modified products, allophanate-modified products, burette-modified products, nurate
- isocyanate curing agents hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate systems that are excellent in weather resistance and coating film performance are preferred. Easy and preferred.
- the adhesive is not sufficiently cured when the blending amount is small, and the adhesive strength is lowered when the blending amount is large, so that the polyester polyol (a) constituting the main component is added to 100 parts by weight. On the other hand, it is important to add 10 to 30 parts by weight.
- the solvent used for the adhesive in the present invention is preferably a solvent having no active hydrogen such as esters, ketones, aliphatics, and aromatics.
- esters include ethyl acetate, propyl acetate, and butyl acetate.
- ketones include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- aliphatic group include n-heptane, n-hexane, cyclohexane and the like.
- aromatics include toluene and xylene. Of these, ethyl acetate, propyl acetate, and methyl ethyl ketone are particularly preferable from the viewpoints of solubility and coating suitability.
- the thickness of the adhesive layer is preferably 0.1 to 10 ⁇ m, and more preferably 2 to 6 ⁇ m from the viewpoint of cost and adhesiveness.
- Examples of the method for producing a laminate in the present invention include, for example, a gravure roll coating method, a roll coating method, a reverse coating method, a kiss coating method, a coating method such as other methods on a hydrolysis-resistant PET film, or Other laminates or films can be laminated using a known technique such as dry lamination in which an adhesive is applied using a printing method or the like.
- the hydrolysis-resistant PET film can be subjected to a surface treatment for improving adhesion such as corona treatment or plasma treatment, if necessary.
- FIG. 3 shows a schematic sectional side view of an example in which a solar cell module is produced.
- the hydrolysis-resistant PET film is laminated with the other laminate or film and the adhesive of the present invention by the above-mentioned method.
- preferred embodiments as the other laminate or film will be described.
- the polyethylene film used as an element of a preferred laminate of the present invention preferably has a density of 0.910 to 0.945 g / cm 3 and a melting point of 110 ° C. or higher. Further, the polyethylene film used in the present invention itself has adhesiveness with an ethylene / vinyl acetate copolymer sheet (hereinafter abbreviated as EVA sheet) used as a filling sheet of a solar cell module.
- EVA sheet ethylene / vinyl acetate copolymer sheet
- an adhesive resin layer made of polyethylene resin or the like is provided, the adhesive surface side with the EVA sheet, or a terminal A surface treatment such as a corona treatment or a plasma treatment may be performed on each surface on the adhesion surface side with the box.
- a surface treatment such as a corona treatment or a plasma treatment may be performed on each surface on the adhesion surface side with the box.
- the film When the density is 0.945 g / cm 3 or more, the film is stiff and excellent in slipperiness, but on the other hand, in the secondary processing such as lamination, the film is torn or the surface of the film is rubbed with a driving roll. This is undesirable because it produces powder and scratches the appearance.
- the polyethylene resin of the polyethylene film may be a polymer of ethylene alone or a copolymer with another monomer which is an ⁇ -olefin having 4 to 8 carbon atoms. It is also possible to further strengthen the adhesion to the EVA sheet using polyethylene obtained by graft polymerization of carboxylic acid such as maleic anhydride.
- the thickness of the sheet made of polyethylene resin is preferably in the range of 10 ⁇ m to 1000 ⁇ m from the viewpoint of weather resistance, moisture resistance and moldability, and more preferably in the range of 25 ⁇ m to 150 ⁇ m from the viewpoint of price.
- the polyethylene film can be molded by a generally known method, and specifically, a molding method such as calendar molding, extrusion molding or press molding is preferable.
- an ultraviolet shielding agent an ultraviolet absorber, or an antioxidant to the above polyethylene film in order to increase the reliability of its performance.
- UV absorbers, UV absorbers and antioxidants all disperse in the resin and exhibit more effective weather resistance.
- Typical examples of the ultraviolet shielding agent include titanium oxide, zinc oxide, and carbon black.
- titanium oxide having a rutile crystal structure is desirable because it is less colored due to deterioration in weather resistance.
- Titanium oxide improves the weather resistance mainly because it blocks ultraviolet rays, so the addition amount is preferably 1 to 10% by weight. This is because if the amount is less than 1% by weight, the effect of the shielding rate is insufficient, and if it exceeds 10% by weight, the improvement of the shielding effect is reduced.
- antioxidants and the ultraviolet absorber those usually used for plastic sheets and films can be used, and as the antioxidant, there are phenol derivatives, allylamine derivatives, phosphites and the like.
- organic UV absorbers and inorganic UV absorbers are preferred in this application, and more specifically, benzophenone derivatives, salicylic acid esters, benzotriazole derivatives, piperidine derivatives. Benzoate derivatives, tin organic compounds, thiazolidone and the like.
- a hindered amine-based or phenol-based radical scavenger may be used in combination.
- the white plastic film used as an element of the preferred laminate of the present invention is a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a polyolefin film such as polyethylene or polypropylene, a polystyrene film, a polyamide film, a polyvinyl chloride film, a polycarbonate film, A film obtained by adding a white colorant to an acrylonitrile film, a polyimide film, or the like, or a film formed with a foamed layer.
- white colorants include basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white, zinc sulfide, lithopone, antimony trioxide, anatase titanium oxide, rutile titanium oxide, silica, and aluminum oxide.
- white pigments such as magnesium oxide, calcium carbonate, barium sulfate and the like can be used.
- the amount of the white colorant used is desirably 10% by weight to 30% by weight with respect to the plastic film.
- a white polyethylene terephthalate film is more preferably selected from the viewpoint of processability, heat resistance and economy.
- a white colorant can be kneaded into a biaxially stretched film of polyethylene terephthalate, or a white layer can be formed by forming a foamed layer on the film.
- the biaxially stretched film of polyethylene terephthalate is colored white to reflect or diffuse sunlight, thereby returning the sunlight to the solar cells and reusing them, thereby improving the power generation efficiency. .
- the thickness of the white plastic film is preferably 5 to 200 ⁇ m, and more preferably in the range of 25 to 125 ⁇ m from the light reflectivity of sunlight, the cost of the solar battery back surface protection sheet, and the processing suitability in the production of solar cells. .
- the black plastic film used as an element of the preferred laminate of the present invention is a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a polyolefin film such as polyethylene or polypropylene, a polystyrene film, a polyamide film, a polyvinyl chloride film, a polycarbonate film, A black colorant is added to an acrylonitrile film, a polyimide film, or the like.
- a typical black colorant is carbon black, and the average secondary particle diameter of carbon black particles is preferably 0.1 to 3.0 ⁇ m.
- the amount of carbon black particles used is desirably 0.5% to 35% by weight with respect to the plastic film.
- the black plastic film is more preferably a black polyethylene terephthalate film, and a biaxially stretched film of polyethylene terephthalate is more preferable in terms of processability, transparency, heat resistance, and cost.
- a biaxially stretched film of polyethylene terephthalate By adding carbon black particles to a biaxially stretched film of polyethylene terephthalate, it can be colored black.
- the biaxially stretched film of polyethylene terephthalate is colored black, when it is installed as a solar cell module, there is an effect that the design is improved.
- the thickness of the black plastic film is preferably 5 to 200 ⁇ m.
- the thickness of the black plastic film is 25 to 125 ⁇ m because of the design properties when installed as a solar cell module, the cost of the solar cell back surface protection sheet, and the processing suitability when manufacturing solar cells. A range is more preferred.
- the above-mentioned polyethylene film and white plastic film, or polyethylene film and black plastic film are bonded with an adhesive having the same composition as the adhesive of the present invention.
- a laminate is preferred.
- the adhesive strength between the polyethylene film and the white plastic film or between the polyethylene film and the black plastic film is preferably 2N / 15 mm or more.
- the adhesive strength between these films is 2 N / 15 mm or more, sufficient interlayer strength of the laminated films is obtained, and delamination does not easily occur during processing of a solar cell module or an accelerated test, and is 6 N / 15 mm or more. Is more preferable.
- Examples of a method for producing a laminate in which a polyethylene film and a white plastic film or a polyethylene film and a black plastic film are bonded with an adhesive include, for example, a gravure roll coat method, a roll coat on the above other laminate or film.
- the film can be laminated by a known method such as dry lamination in which the above-mentioned adhesive is applied using a coating method such as a coating method, a reverse coating method, a kiss coating method, or the like, or a printing method.
- the other laminate or the film side can be subjected to surface treatment for improving adhesion such as corona treatment or plasma treatment, if necessary.
- the white polyethylene film bonded to the hydrolysis-resistant polyethylene terephthalate film of the present invention is, for example, a film having a three-layer structure of A1 layer / B1 layer / C1 layer, and the A1 layer has a density of 0.92 g / cm 3 to 0. .95 g / cm 3 of ethylene / ⁇ -olefin copolymer as a main component, a resin composition in which low density polyethylene and a propylene resin are blended, and the B1 layer has 100 parts by weight of the resin component and an average particle size of 0.2.
- the main component is an ethylene / ⁇ -olefin copolymer containing 5 to 30 parts by weight of rutile-type titanium oxide particles coated with an inorganic oxide of about 0.5 ⁇ m, and the C1 layer has a density of 0.92 g / cm 3.
- a multilayer white polyethylene film composed of a resin composition containing organic particles can be exemplified, but is not limited to this configuration, and titanium oxide, silica, alumina, Add 5-30 parts by weight of fine particles such as calcium carbonate and barium sulfate with respect to 100 parts by weight of the resin component, or add a whitening agent such as thiophene diyl to 100 parts by weight of the resin component to further increase the whiteness. And 0.01 to 1 part by weight added.
- the thickness of the white polyethylene film used in the present invention is preferably in the range of 25 ⁇ m to 1000 ⁇ m from the viewpoint of weather resistance, moisture resistance and molding processability, and more preferably in the range of 50 ⁇ m to 300 ⁇ m from the viewpoint of price.
- the white polypropylene film to be bonded to the hydrolysis-resistant polyethylene terephthalate film of the present invention is, for example, a film composed of three layers of A2 layer / B2 layer / C2 layer, and the A2 layer is composed of a mixture of polyethylene and propylene resin.
- the B2 layer is made of a propylene-based resin containing 5 to 50% by weight of a white colorant, and the white polypropylene-based multilayer film in which the C2 layer is made of a propylene-based resin can be exemplified.
- the thickness of the white polypropylene film used in the present invention is preferably in the range of 25 ⁇ m to 1000 ⁇ m from the viewpoint of weather resistance, moisture resistance and molding processability, and more preferably in the range of 50 ⁇ m to 300 ⁇ m from the price aspect.
- the adhesive strength between the hydrolysis-resistant PET film of the present invention and another laminate or film is preferably 2N / 15 mm or more.
- the adhesive strength is 2N / 15 mm or more, the interlayer strength of the laminated film is sufficient, the delamination does not easily occur during processing of the solar cell module or by an accelerated test, and the adhesive strength may be 6 N / 15 mm or more. More preferred.
- the adhesive strength of the laminate according to the present invention is 2 N / 15 mm after storage for 1000 hours under the conditions of 85 ° C. and 85% RH in order to prevent delamination of the solar cell back surface protection sheet at any bonding part. It is preferable to maintain the above adhesive strength.
- the back surface protection sheet for a solar cell module of the present invention has a breaking strength after 48 hours at 120 ° C. and 100% RH of 60% or more of the breaking strength before the test.
- the back surface protection sheet (11) for the solar cell module of the invention is sequentially laminated, and if necessary, other materials are optionally laminated between the respective layers, and then these are integrated by vacuum suction or the like.
- a solar cell module is manufactured by using a conventional molding method such as a lamination method for thermocompression bonding and thermocompression-molding each of the above-mentioned layers as an integral molded body and mounting a frame.
- the surface protection sheet (8) for the solar cell module constituting the solar cell module has the sunlight transmission property, insulation property, weather resistance, heat resistance, light resistance, water resistance, moisture resistance, It preferably has physical or chemical strength such as soiling.
- the surface protective sheet include glass plates, polyamide resins (various nylons), polyester resins, cyclic polyolefin resins, polystyrene resins, (meth) acrylic resins, polycarbonate resins.
- Various resin films or sheets such as acetal resin and others can be used.
- the filler layer (10) laminated under the surface protection sheet for the solar cell module preferably has weather resistance, heat resistance and transparency.
- the filler layer for example, ethylene / vinyl acetate copolymer, ionomer resin, ethylene / acrylic acid copolymer, or acid-modified polyolefin resin, polyvinyl butyral resin, It is possible to use a mixture of one or more resins such as silicone resins, epoxy resins, (meth) acrylic resins and others.
- the solar cell element (9) as a photovoltaic element constituting the solar cell module is a conventionally known one, for example, a crystalline silicon solar electron such as a single crystal silicon type solar cell element or a polycrystalline silicon type solar cell element.
- amorphous silicon solar cell element of single junction type or tandem structure type III-V group compound semiconductor solar electronic element such as gallium arsenide (GaAs) or indium phosphorus (InP), cadmium tellurium (CdTe) or copper indium serena II-VI group compound semiconductor solar electronic devices such as id (CuInSe 2 ), organic solar cell devices, and the like can be used.
- a thin film polycrystalline silicon solar cell element, a thin film microcrystalline silicon solar cell element, a hybrid element of a thin film crystalline silicon solar cell element and an amorphous silicon solar cell element, or the like can also be used.
- the filler layer (18) laminated under the photovoltaic element constituting the solar cell module is made of the same material as the filler layer laminated under the surface protection sheet for the solar cell module. Can be used.
- the filler layer preferably has adhesiveness to the back surface protection sheet.
- the filler layer has thermoplasticity in order to perform the function of maintaining the smoothness of the back surface of the solar cell element as the photovoltaic element, and further, the protection of the solar cell element as the photovoltaic element. Therefore, it is preferable to be excellent in scratch resistance, shock absorption and the like.
- An aluminum mold is suitable for the frame of the solar cell module.
- Table 1 shows the back surface protective sheet member for the solar cell module and the adhesive constituent components.
- Adhesive strength Cut the back protection sheet for solar cell module to 15mm width, peel it between each layer of laminate film, and measure peel strength using ORIENTEC's Tensilon PTM-50 with peel angle of 180 ° and peel speed of 100mm / min. This value was used as the initial adhesive strength.
- the back protective sheet for solar cell module was cut to a width of 15 mm and stored for 1000 hours in a temperature and humidity environment of 85 ° C. and humidity of 85% using a constant temperature and humidity chamber PR-2KPH manufactured by ESPEC.
- the adhesive strength was measured by the method.
- the back protective sheet for solar cell module was cut to a length of 100 mm in the longitudinal direction and a width of 10 mm in the width direction, and the EASTEC HAST chamber EHS-221MD was used in a temperature 120 ° C., humidity 100% RH environment.
- the back protective sheet for solar cell module was cut to a length of 100 mm in the longitudinal direction and a width of 10 mm in the width direction, and the EASTEC HAST chamber EHS-221MD was used in a temperature 120 ° C., humidity 100% RH environment.
- a hydrolytic resistant PET film or non-hydrolytic resistant PET film is cut to a length of 100 mm in the longitudinal direction and 10 mm in the width direction, and measured using a universal tensile compression tester TCM-50 manufactured by Minebea. Was set to 55 mm, the length of the sample at the time of breaking at a tensile speed of 300 mm / min was measured, and the percentage of the sample length with respect to the measurement distance of 55 mm was defined as the initial breaking elongation (%). .
- the back protective sheet for solar cell module was cut to a length of 100 mm in the longitudinal direction and a width of 10 mm in the width direction, and the EASTEC HAST chamber EHS-221MD was used in a temperature 120 ° C., humidity 100% RH environment.
- the elongation at break (%) was measured by the above method (PCT test).
- the breaking elongation value after storage for 48 hours of PCT was divided by the initial breaking elongation value and multiplied by 100 to calculate the breaking elongation retention rate (%).
- Example 1 Resin component of adhesive to white plastic film (“Lumirror” (registered trademark) E20F, 50 ⁇ m, manufactured by Toray Industries, Inc.) using a dry laminator (“dry laminator with one-color printing” manufactured by Okazaki Kikai Kogyo Co., Ltd.) OG / DL-130TA-AF) Is 100 parts by weight of “Dick Dry” LX-71A (manufactured by DIC) having a polyester polyol, number average molecular weight of 5000 and hydroxyl value of 11 mgKOH / g, and 10 parts by weight of “Epiclon” 1050 (manufactured by DIC) as an epoxy resin.
- “Dick Dry” LX-71A manufactured by DIC
- Epiclon 1050 manufactured by DIC
- the main component mixed with 15 parts by weight of “Placcel” CD210 (manufactured by Daicel Chemical Industries) having a number average molecular weight of 1000 and a hydroxyl value of 110 mg KOH / g as a polycarbonate polyol, and “Desmo” which is a nurate modified hexamethylene diisocyanate as an isocyanate curing agent.
- “Placcel” CD210 manufactured by Daicel Chemical Industries
- “Desmo” which is a nurate modified hexamethylene diisocyanate as an isocyanate curing agent.
- the biaxially stretched plastic film having resistance to hydrolysis (“Lumirror” (registered trademark) X10S, 125 ⁇ m, manufactured by Toray Industries, Inc.) and the white plastic film surface of the laminated film were similarly bonded with the above-mentioned dry laminator.
- Limirror registered trademark
- X10S 125 ⁇ m
- a biaxially stretched plastic film having resistance to hydrolysis (“Lumirror” (registered trademark) X10S, 125 ⁇ m, manufactured by Toray Industries, Inc.) is fractured when the fracture strength after treatment at 120 ° C. and 100% RH for 48 hours is untreated. The strength is maintained at 80% (break strength retention: 80%), and the elongation at break after treatment for 48 hours at 120 ° C. and 100% RH is maintained at 95% when not treated (break elongation at break). Degree retention rate 95%).
- the laminated film was aged at a temperature of 40 ° C. for 72 hours to cause a curing reaction of the two layers of the adhesive, thereby producing a back protective sheet for a solar cell module of the present invention.
- the resin component of the adhesive is polyester polyol, “Eritel” XO-0276 (manufactured by Unitika) having a number average molecular weight of 20000 and a hydroxyl value of 4 mgKOH / g, and 7 parts by weight of “Epiclon” 1050 as an epoxy resin, is a carbodiimide compound.
- a back protective sheet for a solar cell module was prepared in the same manner as in Example 1 except that “Carbodilite” V-07 was changed to 4 parts by weight.
- the resin component of the adhesive is polyester polyol, “Beckolite” M-6180-50 (manufactured by DIC) having a number average molecular weight of 6000 and a hydroxyl value of 21 mg KOH / g, and “Epiclon” 1050 as an epoxy resin is 25 parts by weight.
- Example 1 except that 10 parts by weight of “Placcel” CD210 as polycarbonate polyol, 25 parts by weight of “Desmodur” N3300 as isocyanate curing agent, and 7 parts by weight of “Carbodilite” V-07 as carbodiimide compound The back surface protection sheet for solar cell modules was produced similarly to.
- Example 4 The resin component of the adhesive was polyester polyol, and “Aron Melt” PES-375SE50 (manufactured by Toagosei Co., Ltd.) having a number average molecular weight of 13,000 and a hydroxyl value of 11 mg KOH / g was mixed with 25 parts by weight of “Placcel” CD210 as polycarbonate polyol.
- a back protective sheet for a solar cell module was prepared in the same manner as in Example 1 except that 13 parts by weight of “Desmodule” N3300 as the main component and isocyanate curing agent and 4 parts by weight of “Carbodilite” V-07 as the carbodiimide compound were prepared. did.
- Example 5 Solar cell module as in Example 1 except that the resin component of the adhesive was 17 parts by weight of “Desmodule” N3200 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), which is a burette modified product of hexamethylene diisocyanate as an isocyanate curing agent. A back protective sheet was prepared.
- “Desmodule” N3200 manufactured by Sumitomo Bayer Urethane Co., Ltd.
- Example 6 A back protective sheet for a solar cell module was produced in the same manner as in Example 3 except that the resin component of the adhesive was 25 parts by weight of “Desmodule” N3200 as an isocyanate curing agent.
- Example 7 Example 1 except that the film to be laminated with an unstretched polyethylene film (Toray Film Processing Co., Ltd., type name 4801 50 ⁇ m) is a black plastic film (“Lumirror” (registered trademark) X30, 50 ⁇ m manufactured by Toray Industries, Inc.). Thus, a back surface protection sheet for the solar cell module of the present invention was produced.
- an unstretched polyethylene film Toray Film Processing Co., Ltd., type name 4801 50 ⁇ m
- a black plastic film (“Lumirror” (registered trademark) X30, 50 ⁇ m manufactured by Toray Industries, Inc.).
- Example 8 A back protective sheet for a solar cell module was produced in the same manner as in Example 1 except that the film to be bonded to the hydrolysis-resistant PET film was a white polyethylene film (manufactured by Toray Film Processing Co., Ltd., type name 4806W, 150 ⁇ m).
- the above 4806W is a film having a three-layer structure of A1 layer / B1 layer / C1 layer.
- the A1 layer has a density of 0.93 g / cm 3 and an MFR of 5 g / 10 min.
- Low-density polyethylene 100 parts by weight Density 0.90 g / cm 3 , MFR 7 g / 10 min
- the B1 layer has an average particle size of 0.3 ⁇ m and inorganic oxidation with respect to 100 parts by weight of linear low density polyethylene with a density of 0.92 g / cm 3 and MFR of 5 g / 10 min.
- the C1 layer is the same resin composition as the A1 layer, and the average particle diameter is 2 ⁇ m. (“Silton” JC30, manufactured by Mizusawa Chemical Co., Ltd.) was added to make the addition amount of aluminum silicate 0.3 wt%. Using this resin composition, A1 / B1 / C1 The layer thickness ratio was 20/70/10, and a molded product by a known coextrusion method was prepared.
- Example 9 A white polypropylene film was used as a film to be bonded to the hydrolysis-resistant PET film.
- This white polypropylene film is a film having a three-layer structure of A2 / B2 / C2 layers.
- As a resin used for the A2 layer 1-butene is copolymerized, melting point 127 ° C., density 0.94 g / cm 3. 3 and 15 parts by weight of low density polyethylene having a melting point of 112 ° C.
- the resin used for the B2 layer is a titanium oxide master batch (60 wt. Of titanium oxide with respect to the base homopolypropylene) with respect to 100 wt. Parts of homopolypropylene having a melting point of 160 ° C. and a density of 0.90 g / cm 3. % Resin) was used. The amount of titanium oxide added is 6.4% by weight.
- an ethylene / propylene block copolymer resin having a melting point of 160 ° C. and a density of 0.900 g / cm 3 was used as the resin used for the C2 layer.
- the ratio of the thickness of the A2 / B2 / C2 layer was 20/70/10 and the total thickness was 150 ⁇ m, which was molded by a known coextrusion method.
- a back protective sheet for a solar cell module was prepared in the same manner as in Example 2 except that the resin component of the adhesive was polyester polyol, “Beckolite” M-6180-50, and the epoxy resin and the polycarbonate polyol component were not mixed. did.
- Example 2 A back protective sheet for a solar cell module was prepared in the same manner as in Example 2 except that the resin component of the adhesive was “Dick Dry” LX-71A as the polyester polyol and the epoxy resin component was not mixed.
- Example 3 A back protection sheet for a solar cell module was prepared in the same manner as in Example 2 except that the resin component of the adhesive was “Beccolite” M-6180-50 as the polyester polyol and 50 parts by weight of “Epiclon” 1050 as the epoxy resin. did.
- Example 7 A back protective sheet for a solar cell module was prepared in the same manner as in Example 1 except that the resin component of the adhesive was 5 parts by weight of “Desmodule” N3300 as an isocyanate curing agent.
- the laminated film was aged at a temperature of 40 ° C. for 72 hours. However, since the curing reaction of the two adhesive layers was insufficient, the breaking strength and the adhesive strength could not be evaluated.
- Biaxially stretched polyethylene terephthalate film without hydrolysis resistance (“Lumirror” (registered trademark) T60, 125 ⁇ m, manufactured by Toray Industries, Inc.) has a breaking strength after treatment at 120 ° C. and 100% RH for 48 hours. 5% or less of the breaking strength (breaking strength retention is 5% or less), the breaking elongation after 48 hours of treatment at 120 ° C. and 100% RH is 5% or less of the breaking elongation when not treated (breaking elongation) Degree retention was 5% or less).
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Abstract
Description
上記耐加水分解性PETフィルムは、機械強度、耐熱性、耐電圧性、寸法安定性、耐薬品性、耐候性などの面から二軸延伸フィルムであることが好ましい。
接着剤組成分試料1g中に含まれる水酸基をアセチル化するために要する水酸化カリウムのmg数を水酸基価(mgKOH/g)とした。
(太陽電池モジュール用裏面保護シート構成)
太陽電池モジュール用裏面保護シート部材および接着剤構成成分を表1に示す。
太陽電池モジュール用裏面保護シートを15mm幅にカットし、ラミネートフィルム各層間にて剥離し、ORIENTEC社製テンシロンPTM-50を用いて、剥離角度180°、剥離スピード100mm/minで剥離強さを測定し、この数値を初期接着強度とした。
太陽電池モジュール用裏面保護シートをシートの長手方向に100mm長、巾方向に10mm幅にカットし、ミネベア社製万能引張圧縮試験機TCM-50を用いて、測定距離が55mmになるように設置し、引張スピード300mm/minによる破断時の荷重を測定し、単位断面積当たりの当該荷重を初期破断強度(MPa(=N/mm2))とした。
耐加水分解性PETフィルムあるいは耐加水分解性のないPETフィルムをシートの長手方向に100mm長、巾方向に10mm幅にカットし、ミネベア社製万能引張圧縮試験機TCM-50を用いて、測定距離が55mmになるように設置し、引張スピード300mm/minによる破断時の荷重を測定し、単位断面積当たりの当該荷重を初期破断強度(MPa(=N/mm2))とした。
耐加水分解性PETフィルムあるいは耐加水分解性のないPETフィルムをシートの長手方向に100mm長、巾方向に10mm幅にカットし、ミネベア社製万能引張圧縮試験機TCM-50を用いて、測定距離が55mmになるように設置し、引張スピード300mm/minによる破断時のサンプルが伸びた長さを測定し、測定距離55mmに対するサンプルが伸びた長さの百分率を初期破断伸度(%)とした。
接着強度及び破断強度の評価結果を総合して、太陽電池モジュール用裏面保護シートとして、接着強度および破断強度の両方が以下の条件を満たす場合はA、接着強度および破断強度の片方または両方が以下の条件を満たさない場合をBとした。総合評価結果を表2に示す。
接着強度が、いずれの接着部分においても2N/15mm以上、85℃×85%RH条件下にて1000時間保管後に2N/15mm以上を保持。
120℃×100%RHで48時間促進試験後の破断強度が、試験前の破断強度の60%以上を保持。
ドライラミネーター(岡崎機械工業社製“一色印刷付きドライラミネーター”OG/DL-130TA-AF)により、白色プラスチックフィルム(東レ社製「ルミラー」(登録商標)E20F、50μm)へ、接着剤の樹脂成分がポリエステルポリオール、数平均分子量5000、水酸基価11mgKOH/gである“ディックドライ”LX-71A(DIC社製)100重量部に対し、エポキシ樹脂として“エピクロン”1050(DIC社製)10重量部及びポリカーボネートポリオールとして数平均分子量1000、水酸基価110mgKOH/gである“プラクセル”CD210(ダイセル化学社製)15重量部混合させた主剤と、イソシアネート系硬化剤としてヘキサメチレンジイソシアネートのヌレート変性体である“デスモジュール”N3300(住友バイエルウレタン社製)を17重量部と、カルボジイミド化合物としてカルボジイミド基当量200の“カルボジライト”V-07(日清紡ケミカル社製)を2重量部混合し、固形分塗布厚さ5μmに塗布、乾燥し、無延伸ポリエチレンフィルム(東レフィルム加工社製、タイプ名4801、50μm)と60N/cmのニップ圧でラミネートを実施した。
接着剤の樹脂成分をポリエステルポリオールとして、数平均分子量20000、水酸基価4mgKOH/gである“エリーテル”XO-0276(ユニチカ社製)とし、エポキシ樹脂として“エピクロン”1050を7重量部とし、カルボジイミド化合物として “カルボジライト”V-07を4重量部に変更した以外は実施例1と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分をポリエステルポリオールとして、数平均分子量6000、水酸基価21mgKOH/gである“ベッコライト”M-6180-50(DIC社製)とし、エポキシ樹脂として“エピクロン”1050を25重量部とし、ポリカーボネートポリオールとして “プラクセル”CD210を10重量部とし、イソシアネート系硬化剤として“デスモジュール”N3300を25重量部とし、カルボジイミド化合物として “カルボジライト”V-07を7重量部とした以外は実施例1と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分がポリエステルポリオールとして、数平均分子量13000、水酸基価11mgKOH/gである“アロンメルト”PES-375SE50(東亞合成社製)とし、ポリカーボネートポリオールとして “プラクセル”CD210を25重量部混合させた主剤とイソシアネート系硬化剤として“デスモジュール”N3300を13重量部と、カルボジイミド化合物として“カルボジライト”V-07を4重量部とした以外は実施例1と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分がイソシアネート系硬化剤としてヘキサメチレンジイソシアネートのビューレット変性体である“デスモジュール”N3200(住友バイエルウレタン社製)を17重量部とした以外は実施例1と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分がイソシアネート系硬化剤として“デスモジュール”N3200を25重量部とした以外は実施例3と同様に太陽電池モジュール用裏面保護シートを作製した。
無延伸ポリエチレンフィルム(東レフィルム加工社製、タイプ名4801 50μm)とラミネートするフィルムが黒色プラスチックフィルム(東レ社製「ルミラー」(登録商標)X30、50μm)であること以外は実施例1と同様にして、本発明の太陽電池モジュール用裏面保護シートを作製した。
耐加水分解性PETフィルムと貼り合わせるフィルムを、白色ポリエチレンフィルム(東レフィルム加工社製、タイプ名4806W、150μm)とした以外は実施例1と同様に太陽電池モジュール用裏面保護シートを作製した。
耐加水分解性PETフィルムと貼り合わせるフィルムとして白色ポリプロピレンフィルムを用いた。この白色ポリプロピレンフィルムは、A2層/B2層/C2層の3層構成からなるフィルムであり、A2層に使用する樹脂として、1-ブテンを共重合し、融点127℃、密度0.94g/cm3であってメルトフローレート5g/10分の直鎖状低密度ポリエチレン85重量部に対し、融点112℃、密度0.91g/cm3の低密度ポリエチレンを15重量部、及びプロピレン系樹脂として、融点150℃、密度0.900g/cm3のエチレン・プロピレンランダム共重合体80重量部を混合した樹脂混合物を用いた。
(比較例1)
接着剤の樹脂成分がポリエステルポリオールとして、“ベッコライト”M-6180-50とし、エポキシ樹脂とポリカーボネートポリオール成分を混合しないものとした以外は実施例2と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分が、ポリエステルポリオールとして“ディックドライ”LX-71Aとし、エポキシ樹脂成分を混合しないものとした以外は実施例2と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分がポリエステルポリオールとして “ベッコライト”M-6180-50とし、エポキシ樹脂として“エピクロン”1050を50重量部とした以外は実施例2と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分がポリエステルポリオールとして“ベッコライト”M-6180-50とし、エポキシ樹脂として“エピクロン”1050を18重量部及びポリカーボネートポリオールとして“プラクセル”CD210を50重量部とした以外は実施例2と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分がポリエステルポリオールとして“ベッコライト”M-6180-50とし、エポキシ樹脂として“エピクロン”1050を10重量部及びポリカーボネートポリオールとして“プラクセル”CD210を2重量部とした以外は実施例2と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分がポリカーボネートポリオールとして“プラクセル”CD210を15重量部とし、イソシアネート系硬化剤として“デスモジュール”N3300を40重量部とした以外は実施例1と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分がイソシアネート系硬化剤として“デスモジュール”N3300を5重量部とした以外は実施例1と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分がカルボジイミド化合物を添加しなかった以外は実施例1と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分がポリエステルポリオールとして“ベッコライト”M-6180-50とし、カルボジイミド化合物として“カルボジライト”V-07を15重量部とした以外は実施例1と同様に太陽電池モジュール用裏面保護シートを作製した。
接着剤の樹脂成分がエポキシ樹脂の代わりに、エポキシ化合物としてネオペンチルグリコールジグリシジルエーテル(東京化成工業社製)10重量部とした以外は実施例1と同様にして、本発明の太陽電池モジュール用裏面保護シートを作製した。
白色プラスチックフィルムと無延伸ポリエチレンフィルムとをラミネートした2層フィルムへ、続いてラミネートするフィルムが耐加水分解性のない二軸延伸ポリエチレンテレフタレートフィルム(東レ社製「ルミラー」(登録商標)T60、125μm)であること以外は実施例1と同様にして、本発明の太陽電池モジュール用裏面保護シートを作製した。
2:白色プラスチックフィルム
3、14:耐加水分解性ポリエチレンテレフタレートフィルム
4、5、15:接着剤層
8:太陽電池モジュール用表面保護シート
9:太陽電池素子
10、18:充填材層
7、11、13、17:太陽電池裏面保護シート
12:白色ポリエチレンフィルムまたは白色ポリプロピレンフィルム
16:黒色プラスチックフィルム
Claims (8)
- 耐加水分解性ポリエチレンテレフタレートフィルムが他の積層体あるいはフィルムと接着剤により積層された太陽電池モジュール用裏面保護シートであって、該接着剤がポリエステルポリオール(a)100重量部に対して、エポキシ樹脂(b)5~30重量部、カルボジイミド化合物(d)1~10重量部、ポリイソシアネート化合物(e)10~30重量部、及びポリカーボネートポリオール(c)5~30重量部が配合されてなることを特徴とする太陽電池モジュール用裏面保護シート。
- ポリエチレンフィルムと白色プラスチックフィルムと耐加水分解性ポリエチレンテレフタレートフィルムが、前記接着剤によりこの順に積層されてなることを特徴とする請求項1に記載の太陽電池モジュール用裏面保護シート。
- ポリエチレンフィルムと黒色プラスチックフィルムと耐加水分解性ポリエチレンテレフタレートフィルムが、前記接着剤によりこの順に積層されてなることを特徴とする請求項1に記載の太陽電池モジュール用裏面保護シート。
- 白色ポリエチレンフィルムと耐加水分解性ポリエチレンテレフタレートフィルムが、前記接着剤により積層されてなることを特徴とする請求項1に記載の太陽電池モジュール用裏面保護シート。
- 白色ポリプロピレンフィルムと耐加水分解性ポリエチレンテレフタレートフィルムが、前記接着剤により積層されてなることを特徴とする請求項1に記載の太陽電池モジュール用裏面保護シート。
- 積層体の接着強度が、いずれの接着部分においても2N/15mm以上であり、85℃×85%RH条件下にて1000時間保管後に2N/15mm以上を保持し、120℃×100%RHで48時間促進試験後の破断強度が試験前の破断強度の60%以上を保持す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モジュール用裏面保護シート。
- 前記耐加水分解性ポリエチレンテレフタレートフィルムの、120℃100%RHで48時間処理した後の破断強度が、未処理の時の破断強度の10%以上を維持し、かつ未処理の時の破断伸度の10%以上を維持することを特徴とする請求項1~6のいずれかに記載の太陽電池モジュール用裏面保護シート。
- 請求項1~7のいずれかに記載の太陽電池モジュール用裏面保護シートを使用した太陽電池モジュール。
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US13/819,841 US9064995B2 (en) | 2010-08-31 | 2011-08-30 | Back-face protection sheet for solar cell module, and solar cell module using same |
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CN201180041796.XA CN103098230B (zh) | 2010-08-31 | 2011-08-30 | 太阳能电池模块用背面保护片材及使用其的太阳能电池模块 |
JP2011541001A JP5804326B2 (ja) | 2010-08-31 | 2011-08-30 | 太陽電池モジュール用裏面保護シートおよびそれを用いた太陽電池モジュール |
KR1020137004990A KR20130143004A (ko) | 2010-08-31 | 2011-08-30 | 태양전지 모듈용 이면 보호 시트 및 그것을 사용한 태양전지 모듈 |
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JP2016089035A (ja) * | 2014-11-05 | 2016-05-23 | Dic株式会社 | ポリエステルポリイソシアネート、これを用いる2液型ウレタン系接着剤用硬化剤、2液型ウレタン系接着剤、積層フィルム及び太陽電池のバックシート |
JP2016089034A (ja) * | 2014-11-05 | 2016-05-23 | Dic株式会社 | ポリエステルポリイソシアネート、これを用いる2液型ウレタン系接着剤用硬化剤、2液型ウレタン系接着剤、積層フィルム及び太陽電池のバックシート |
JP2019536271A (ja) * | 2016-11-11 | 2019-12-12 | ディーエスエム アイピー アセッツ ビー.ブイ.Dsm Ip Assets B.V. | 背面封止材に面しているポリオレフィンをベースとする機能層を含むバックシート |
US11764321B2 (en) | 2016-11-11 | 2023-09-19 | Endurance Solar Solutions B.V. | Backsheet comprising a polyolefine based functional layer facing the back encapsulant |
JP2019047071A (ja) * | 2017-09-06 | 2019-03-22 | ダイヤプラスフィルム株式会社 | 太陽電池裏面保護シート用フィルム、太陽電池裏面保護シート、及び太陽電池モジュール |
JP2019047070A (ja) * | 2017-09-06 | 2019-03-22 | ダイヤプラスフィルム株式会社 | 太陽電池裏面保護シート用フィルム、太陽電池裏面保護シート、及び太陽電池モジュール |
JP7009123B2 (ja) | 2017-09-06 | 2022-01-25 | ダイヤプラスフィルム株式会社 | 太陽電池裏面保護シート用フィルム、太陽電池裏面保護シート、及び太陽電池モジュール |
JP7009124B2 (ja) | 2017-09-06 | 2022-01-25 | ダイヤプラスフィルム株式会社 | 太陽電池裏面保護シート用フィルム、太陽電池裏面保護シート、及び太陽電池モジュール |
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JPWO2012029733A1 (ja) | 2013-10-28 |
US20150249174A1 (en) | 2015-09-03 |
CN103098230A (zh) | 2013-05-08 |
TWI527705B (zh) | 2016-04-01 |
US20140144488A1 (en) | 2014-05-29 |
US9537035B2 (en) | 2017-01-03 |
US9064995B2 (en) | 2015-06-23 |
TW201219227A (en) | 2012-05-16 |
KR20130143004A (ko) | 2013-12-30 |
EP2613363A4 (en) | 2016-08-24 |
CN103098230B (zh) | 2016-03-16 |
EP2613363A1 (en) | 2013-07-10 |
JP5804326B2 (ja) | 2015-11-04 |
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