KR102063055B1 - Curable pressure sensitive adhesive composition, solar cell module comprising encapsulating layer having the same, and preparing process of the solar cell - Google Patents
Curable pressure sensitive adhesive composition, solar cell module comprising encapsulating layer having the same, and preparing process of the solar cell Download PDFInfo
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- KR102063055B1 KR102063055B1 KR1020160010825A KR20160010825A KR102063055B1 KR 102063055 B1 KR102063055 B1 KR 102063055B1 KR 1020160010825 A KR1020160010825 A KR 1020160010825A KR 20160010825 A KR20160010825 A KR 20160010825A KR 102063055 B1 KR102063055 B1 KR 102063055B1
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- Prior art keywords
- solar cell
- meth
- cell module
- acrylate
- parts
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- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000008393 encapsulating agent Substances 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 77
- 239000000178 monomer Substances 0.000 claims description 38
- -1 acryl Chemical group 0.000 claims description 18
- 239000002998 adhesive polymer Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000001723 curing Methods 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 7
- 239000012963 UV stabilizer Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000000016 photochemical curing Methods 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000001029 thermal curing Methods 0.000 claims description 2
- 238000004383 yellowing Methods 0.000 abstract description 5
- 238000010924 continuous production Methods 0.000 abstract description 4
- 238000010030 laminating Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 19
- 239000005038 ethylene vinyl acetate Substances 0.000 description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229940117969 neopentyl glycol Drugs 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 description 1
- YVAACGXAZGGQSM-UHFFFAOYSA-N 2,2-dimethylpropaneperoxoic acid Chemical compound CC(C)(C)C(=O)OO YVAACGXAZGGQSM-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- YCPMSWJCWKUXRH-UHFFFAOYSA-N 2-[4-[9-[4-(2-prop-2-enoyloxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethyl prop-2-enoate Chemical compound C1=CC(OCCOC(=O)C=C)=CC=C1C1(C=2C=CC(OCCOC(=O)C=C)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YCPMSWJCWKUXRH-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- LWZNQGJGMBRAII-UHFFFAOYSA-N 2-methylhexyl prop-2-enoate Chemical compound CCCCC(C)COC(=O)C=C LWZNQGJGMBRAII-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920007925 Ethylene chlorotrifluoroethylene (ECTFE) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VIBDJEWPNNCFQO-UHFFFAOYSA-N ethane-1,1,2-triol Chemical compound OCC(O)O VIBDJEWPNNCFQO-UHFFFAOYSA-N 0.000 description 1
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical group C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- UOMUPDCRXJLVGR-UHFFFAOYSA-N propane-1,2,2-triol Chemical compound CC(O)(O)CO UOMUPDCRXJLVGR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- 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
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- 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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- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- 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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- 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
Abstract
본 출원은 경화성 점착제 조성물, 상기 조성물을 포함하는 봉지재층을 포함하는 태양전지 모듈 및 그 제조방법에 관한 것으로, 예시적인 점착제 조성물에 의하면 황변현상이 억제되고, 전면 부재와의 접착력이 우수한 봉지재층을 포함하는 태양전지 모듈을 제공할 수 있다. 또한, 본 출원의 예시적인 태양전지 모듈의 제조방법에 의하면, 진공, 고온, 고압의 라미네이팅 공정을 생략하고 롤 투 롤(Roll to Roll) 연속 공정이 가능하여 생산속도 및 생산효율을 향상시킬 수 있다.The present application relates to a curable pressure-sensitive adhesive composition, a solar cell module including an encapsulant layer including the composition, and a method of manufacturing the same. According to an exemplary pressure-sensitive adhesive composition, a yellowing phenomenon is suppressed, and an encapsulant layer having excellent adhesion to a front member is provided. It can provide a solar cell module comprising. In addition, according to the exemplary method of manufacturing the solar cell module of the present application, it is possible to omit the laminating process of vacuum, high temperature, high pressure and to perform a roll to roll continuous process to improve production speed and production efficiency. .
Description
본 출원은 경화성 점착제 조성물, 이를 포함하는 봉지재층을 포함하는 태양전지 모듈 및 그 제조방법에 관한 것이다.The present application relates to a curable pressure-sensitive adhesive composition, a solar cell module including an encapsulant layer including the same, and a manufacturing method thereof.
태양광 발전은 태양광으로부터 전기를 생산하는 청정 발전 기술이다. 태양광 발전 시설은 태양광을 받아 전기를 발생하는 태양전지(모듈)와 발생된 직류 전기를 교류로 변환시키는 전력 조절 장치 및 주간에 생선된 전기를 저장하는 축전지 등으로 구성된다. 전기를 발생시키는 모듈은 일반적으로 유리, 봉지재, 태양전지 및 이면시트로 구성되어 있다.Solar power generation is a clean power generation technology that produces electricity from sunlight. The photovoltaic power generation facility is composed of a solar cell (module) that generates electricity by receiving sunlight, a power control device that converts the generated direct current electricity into alternating current, and a storage battery that stores electricity generated during the day. Modules for generating electricity generally consist of glass, encapsulant, solar cell and backsheet.
현재 봉지재로 쓰이는 EVA(에틸렌-비닐아세테이트 공중합체)는 습기에 취약한 태양전지 소자를 보호하기 위해 태양전지 전후면과 표면재 사이에 삽입되는 물질이다. EVA는 투과율, 접착력 및 탄성 등의 특성을 어느 정도 만족시키나, 진공 및 고온에서 별도 가교 공정이 필요하여 태양전지 모듈의 생산속도 및 생산효율을 저하시킬 수 있다. 또한, EVA는 가교 시 발생하는 산 등의 부식성 물질과 장기간 자외선 노출에 따른 황변 현상으로 인해 태양전지 모듈의 효율을 저하시키는 문제점이 있다.EVA (ethylene-vinylacetate copolymer), which is currently used as an encapsulant, is a material inserted between the solar cell front and back and the surface material to protect the solar cell device vulnerable to moisture. EVA satisfies characteristics such as transmittance, adhesion, and elasticity to some extent, but a separate crosslinking process is required at vacuum and high temperature, thereby lowering the production speed and production efficiency of the solar cell module. In addition, EVA has a problem of lowering the efficiency of the solar cell module due to corrosive substances such as acids generated during crosslinking and yellowing due to long-term UV exposure.
본 출원은 상기한 문제점을 해결하기 위한 것으로, 경화성 점착제 조성물, 이를 포함하는 봉지재층을 포함하는 태양전지 모듈 및 그 제조방법을 제공하는 것을 목적으로 한다.The present application is to solve the above problems, an object of the present invention to provide a curable pressure-sensitive adhesive composition, a solar cell module comprising a sealing material layer comprising the same and a method of manufacturing the same.
본 출원은 무용제형의 경화성 점착제 조성물에 관한 것이다. 예시적인 상기 봉지재 조성물은 시트(sheet) 형태의 EVA와 같이 진공 압착등의 가교 공정(약 15분 소요)을 요구하지 않는다. 또한, 상기 조성물은 점착액 자체를 도포해 수 분 동안의 열 경화를 진행하여 롤 투 롤(Roll to Roll) 연속 공정이 가능하므로 생산속도 및 생산 효율이 우수하다. 또한, 내습에 강한 소재를 사용하여 EVA 봉지재보다 내습성이 우수하며, EVA와 달리 가교시 산이 발생하지 않아 그로 인한 광전소자의 부식이 없고, UV cut-off 특성을 향상시켜 황변 현상을 억제하였다.The present application relates to a solvent-free curable pressure-sensitive adhesive composition. Exemplary encapsulant compositions do not require a crosslinking process (such as about 15 minutes), such as vacuum pressing, in sheet form EVA. In addition, the composition is applied to the adhesive liquid itself to proceed the heat curing for several minutes to roll to roll (Roll to Roll) continuous process is excellent because the production speed and production efficiency. In addition, using moisture resistant material, it has better moisture resistance than EVA encapsulant, and unlike EVA, it does not generate acid when crosslinking, so there is no corrosion of optoelectronic device, and it improves UV cut-off characteristic to suppress yellowing phenomenon. .
이하에서 본 출원의 점착제 조성물, 이를 포함하는 봉지재층을 포함하는 태양전지 모듈 및 그 제조방법을 첨부된 도면을 참조하여 구체적으로 설명하지만 첨부된 도면은 예시적인 것으로서, 상기 태양전지 모듈이 예시된 도면에 의하여 제한되는 것은 아니다.Hereinafter, a pressure-sensitive adhesive composition of the present application, a solar cell module including an encapsulant layer including the same, and a method of manufacturing the same will be described in detail with reference to the accompanying drawings, but the accompanying drawings are illustrative and the solar cell module is illustrated. It is not limited by.
본 출원에 있어서, 「(메트)아크릴레이트」는 아크릴레이트(Acrylate) 또는 메타크릴레이트(Methacrylate)를 의미한다.In the present application, "(meth) acrylate" means acrylate (Acrylate) or methacrylate (Methacrylate).
본 출원에 있어서, 「Y.I」 값은 황변지수를 의미하며, ASTM D1003에 의해 측정된 값을 의미한다.In the present application, the "Y.I" value means a yellowing index and means a value measured by ASTM D1003.
본 출원에 있어서, 「투과율」 값은 ASTM D1003에 의해 측정된 값을 의미한다.In the present application, the "transmittance" value means a value measured by ASTM D1003.
본 출원에 있어서, 「Haze」 값은 ASTM D1003에 의해 측정된 값을 의미한다.In this application, a "Haze" value means the value measured by ASTM D1003.
본 출원에 있어서 「봉지재층의 박리력」은 이면시트에 대한 박리력을 의미하며, ASTM D903에 의해 측정된 값을 의미한다.In the present application, "peel force of the encapsulant layer" means a peel force to the back sheet, and means a value measured by ASTM D903.
본 출원의 예시적인 무용제형의 경화성 점착제 조성물은 (메트)아크릴레이트 점착성 중합체, 반응형 자외선 안정제, (메트)아크릴레이트 단량체 및 이소시아네이트계 경화제를 포함한다. 상기에서 「무용제형」은 점착제 조성물이 용제를 실질적으로 포함하지 않는 것을 말한다. 「용제를 실질적으로 포함하지 않는다」란 예를 들어, 용제의 함유량이 전체 조성물에서 1중량% 이하, 0.5중량% 이하 또는 0.1중량% 이하인 것을 의미할 수 있다.Exemplary solvent-free curable pressure-sensitive adhesive compositions of the present application include a (meth) acrylate adhesive polymer, a reactive ultraviolet stabilizer, a (meth) acrylate monomer, and an isocyanate-based curing agent. As used above, "solvent-free" means that the pressure-sensitive adhesive composition contains substantially no solvent. "Does not substantially contain a solvent" may mean, for example, that the content of the solvent is 1% by weight or less, 0.5% by weight or less, or 0.1% by weight or less in the total composition.
하나의 예시에서, (메트)아크릴레이트 점착성 중합체는 가교성 관능기를 포함하는 (메트)아크릴레이트 단량체와 (메트)아크릴레이트 단량체의 공중합체일 수 있다. 가교성 관능기를 포함하는 (메트)아크릴레이트 단량체의 가교성 관능기는 히드록시기일 수 있다. 히드록시기를 포함하는 (메트)아크릴레이트 단량체는 2-히드록시에틸 (메트)아크릴레이트, 2-히드록시프로필(메트)아크릴레이트, 4-히드록시부틸 (메트)아크릴레이트, 6-히드록시헥실 (메트)아크릴레이트 또는 8-히드록시옥틸 (메트)아크릴레이트 등의 히드록시알킬 (메트)아크릴레이트; 또는 2-히드록시에틸렌글리콜 (메트)아크릴레이트 또는 2-히드록시프로필렌글리콜 (메트)아크릴레이트 등의 히드록시알킬렌글리콜 (메트)아크릴레이트 등이 사용될 수 있으나, 이에 제한되는 것은 아니다.In one example, the (meth) acrylate tacky polymer may be a copolymer of a (meth) acrylate monomer and a (meth) acrylate monomer comprising a crosslinkable functional group. The crosslinkable functional group of the (meth) acrylate monomer containing a crosslinkable functional group may be a hydroxy group. The (meth) acrylate monomers containing hydroxy groups include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl ( Hydroxyalkyl (meth) acrylates such as meth) acrylate or 8-hydroxyoctyl (meth) acrylate; Or hydroxyalkylene glycol (meth) acrylate, such as 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate, and the like, may be used, but is not limited thereto.
본 발명의 일 구현예에 있어서, 가교성 관능기를 포함하는 (메트)아크릴레이트 단량체는 점착성 중합체 100 중량부 대비 5 내지 30 중량부, 7 내지 25 중량부 또는 10 내지 20 중량부로 포함될 수 있다. 상기 함량 범위에서, 점착제 조성물로 형성한 봉지층이 우수한 경화도 및 모듈러스 특성을 나타낼 수 있다.In one embodiment of the present invention, the (meth) acrylate monomer containing a crosslinkable functional group may be included in 5 to 30 parts by weight, 7 to 25 parts by weight or 10 to 20 parts by weight relative to 100 parts by weight of the adhesive polymer. In the above content range, the encapsulation layer formed of the pressure-sensitive adhesive composition may exhibit excellent curing and modulus properties.
하나의 예시에서, (메트)아크릴레이트 점착성 중합체의 공중합 단위인 (메트)아크릴레이트 단량체는 알킬(메트)아크릴레이트를 사용할 수 있다. 알킬 (메트)아크릴레이트는 단독 중합체를 형성한 경우 단독 중합체의 유리전이온도가 0℃ 미만인 단량체를 형성할 수 있는 알킬 (메트)아크릴레이트 단량체이면 그 종류는 특별히 제한되지 않으나, 예를 들어 응집력, 유리전이온도 및 점착성의 조절 등을 고려하여, 탄소수 1 내지 20, 탄소수 4 내지 16 또는 탄소수 6 내지 12의 알킬기를 가지는 알킬 (메트)아크릴레이트를 사용할 수 있다. 상기에서 알킬기는, 예를 들면, 직쇄형, 분지쇄형 또는 고리형일 수 있다. 이러한 단량체의 예로는 메틸 아크릴레이트, 에틸 아크릴레이트, n-프로필 아크릴레이트, 이소프로필 아크릴레이트, n-부틸 아크릴레이트, sec-부틸 아크릴레이트, 2-메틸 헵실 아크릴레이트, 펜틸 아크릴레이트, 2-에틸헥실 (메트)아크릴레이트, 2-에틸부틸 (메트)아크릴레이트, n-옥틸 (메트)아크릴레이트 등을 들 수 있고, 상기 중 일종 또는 이종 이상을 선택하여 사용할 수 있지만 이에 제한되는 것은 아니다. 또한, (메트)아크릴레이트 점착성 중합체는 유리전이온도가 25℃ 이상인 단독 중합체를 형성할 수 있는 단량체(이하, 단순히 하드 단량체로 호칭할 수 있다)를 공중합 단위로 포함할 수 있다. 하드 단량체는 상기 알킬 (메트)아크릴산 에스테르 단량체와 공중합될 수 있고, 단독 중합체를 형성한 때에 상기 범위의 유리전이온도를 나타낼 수 있는 것이라면 어떠한 종류도 사용할 수 있다. 이러한 단량체가 중합체에 포함됨으로써, 예를 들어, 점착제가 고온 조건에 유지되는 경우에도 적합한 물성을 유지할 수 있다.In one example, the (meth) acrylate monomer which is a copolymerization unit of the (meth) acrylate adhesive polymer may use an alkyl (meth) acrylate. The alkyl (meth) acrylate is not particularly limited as long as it is an alkyl (meth) acrylate monomer capable of forming a monomer having a glass transition temperature of less than 0 ° C. when the homopolymer is formed, for example, cohesion, In consideration of the control of glass transition temperature, adhesiveness, etc., an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, 4 to 16 carbon atoms or 6 to 12 carbon atoms can be used. In the above, the alkyl group may be, for example, linear, branched or cyclic. Examples of such monomers are methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, 2-methyl hexyl acrylate, pentyl acrylate, 2-ethyl Hexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) acrylate, etc. can be mentioned, One or more types of these can be selected and used, but it is not limited to these. In addition, the (meth) acrylate adhesive polymer may include a monomer (hereinafter, simply referred to as a hard monomer) capable of forming a homopolymer having a glass transition temperature of 25 ° C. or more as a copolymerization unit. The hard monomer may be copolymerized with the alkyl (meth) acrylic acid ester monomer, and any kind may be used as long as it can exhibit the glass transition temperature in the above range when forming the homopolymer. By including such a monomer in the polymer, for example, suitable physical properties can be maintained even when the pressure-sensitive adhesive is maintained at high temperature conditions.
하드 단량체로는, 예를 들면, 메틸 (메트)아크릴레이트, 에틸 (메트)아크릴레이트, n-부틸 (메트)아크릴레이트, iso-부틸 (메트)아크릴레이트, tert-부틸 (메트)아크릴레이트, 이소보닐(메트)아크릴레이트, 아크릴아미드 및 n,n-디메틸아크릴아미드 등을 들 수 있고, 상기 중 일종 이상을 선택하여 사용할 수 있지만 이에 제한되는 것은 아니다.As a hard monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, Isobornyl (meth) acrylate, acrylamide, n, n-dimethylacrylamide, and the like, and one or more of the above may be selected and used, but is not limited thereto.
상기 알킬 (메트)아크릴레이트 단량체는 상기 점착성 중합체 100 중량부에 대하여 40 내지 90 중량부, 45 내지 85 중량부 또는 55 내지 75 중량부로 포함될 수 있다. 상기 하드 단량체는 상기 점착성 중합체 100 중량부에 대하여 5 내지 35 중량부, 10 내지 30 중량부 또는 15 내지 25 중량부로 포함될 수 있다. 상기와 같은 범위에서, 점착제 조성물의 작업성 및 접착력을 확보할 수 있다.The alkyl (meth) acrylate monomer may be included in 40 to 90 parts by weight, 45 to 85 parts by weight or 55 to 75 parts by weight based on 100 parts by weight of the adhesive polymer. The hard monomer may be included in 5 to 35 parts by weight, 10 to 30 parts by weight or 15 to 25 parts by weight based on 100 parts by weight of the adhesive polymer. In the range as described above, the workability and adhesion of the pressure-sensitive adhesive composition can be ensured.
본 출원의 점착제 조성물은 반응형 자외선 안정제를 포함한다. 하나의 예시에서, 반응형 자외선 안정제는 하기 화학식 1로 나타내어지는 아크릴계 단량체일 수 있다.The pressure-sensitive adhesive composition of the present application includes a reactive ultraviolet stabilizer. In one example, the reactive UV stabilizer may be an acrylic monomer represented by Formula 1 below.
[화학식 1] [Formula 1]
화학식 1에 있어서, R1은 수소 또는 메틸기이고, X는 단일 결합 또는 탄소수 1 내지 5 또는 탄소수 1 내지 3의 알킬렌기이며, R2는 방향족기로 치환된 페닐기, 방향족기로 치환된 히드록시페닐기, 헤테로방향족기로 치환된 페닐기 또는 헤테로방향족기로 치환된 히드록시페닐기이고, 하나의 구체적인 예시에서 R2는 벤조트리아졸기로 치환된 히드록시페닐기일 수 있다.In Formula 1, R 1 is hydrogen or a methyl group, X is a single bond or an alkylene group having 1 to 5 carbon atoms or 1 to 3 carbon atoms, R 2 is a phenyl group substituted with an aromatic group, a hydroxyphenyl group substituted with an aromatic group, hetero A phenyl group substituted with an aromatic group or a hydroxyphenyl group substituted with a heteroaromatic group, and in one specific example, R 2 may be a hydroxyphenyl group substituted with a benzotriazole group.
상기 반응형 자외선 안정제의 함량은 점착성 중합체 100 중량부에 대하여 0.1 내지 10 중량부, 0.3 내지 5 중량부 또는 0.8 내지 3 중량부일 수 있다. 상기와 같은 자외선 안정제의 함량 범위에서 점착제 조성물로 제조한 봉지층이 자외선에 장시간 노출되어도 황변현상이 억제되는 한편, 우수한 광투과율 및 헤이즈 특성을 확보할 수 있다.The content of the reactive UV stabilizer may be 0.1 to 10 parts by weight, 0.3 to 5 parts by weight or 0.8 to 3 parts by weight based on 100 parts by weight of the adhesive polymer. Even if the encapsulation layer made of the pressure-sensitive adhesive composition in the content range of the UV stabilizer as described above is exposed to ultraviolet rays for a long time, yellowing is suppressed, and excellent light transmittance and haze characteristics can be secured.
본 발명의 일 구현예에 있어서, 점착제 조성물에 점착성 중합체, 반응형 자외선 안정제 및 이소시아네이트계 경화제와 함께 포함되는 (메트)아크릴레이트 단량체는 희석 모노머이다. 하나의 예시에서, (메트)아크릴레이트 단량체는 하기 화학식 2로 나타내어질 수 있다.In one embodiment of the present invention, the (meth) acrylate monomer included in the pressure sensitive adhesive composition together with the adhesive polymer, the reactive ultraviolet stabilizer and the isocyanate curing agent is a dilution monomer. In one example, the (meth) acrylate monomer may be represented by the following formula (2).
[화학식 2][Formula 2]
화학식 2에 있어서, R3는 수소 또는 메틸기이고, Y는 탄소수 1 내지 5의 알킬기, 탄소수 1 내지 3의 알킬기이다.In formula (2), R 3 is hydrogen or a methyl group, Y is an alkyl group having 1 to 5 carbon atoms and an alkyl group having 1 to 3 carbon atoms.
상기 (메트)아크릴레이트 단량체는 점착성 중합체 100 중량부 대비 1 내지 20 중량부, 2 내지 9 중량부 또는 3.7 내지 8 중량부로 점착제 조성물에 포함된다. (메트)아크릴레이트 단량체가 상기 함량범위로 포함될 경우, 본 출원의 점착제 조성물로 제조한 봉지층을 포함하는 태양전지 모듈이 1.9 이하, 1.7 이하 또는 1.5 이하의 우수한 Y.I 값을 나타내면서, 우수한 물리적 특성을 확보할 수 있다.The (meth) acrylate monomer is included in the pressure-sensitive adhesive composition in 1 to 20 parts by weight, 2 to 9 parts by weight or 3.7 to 8 parts by weight relative to 100 parts by weight of the adhesive polymer. When the (meth) acrylate monomer is included in the above content range, the solar cell module including the encapsulation layer made of the pressure-sensitive adhesive composition of the present application exhibits excellent YI values of 1.9 or less, 1.7 or 1.5 or less, and has excellent physical properties. It can be secured.
본 출원의 점착제 조성물에는 광가교제가 추가로 포함될 수 있다. 하나의 예시에서, 광가교제는 다관능성 아크릴레이트일 수 있다. 다관능성 아크릴레이트는 예를 들면, 1,4-부탄디올디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 네오펜틸글리콜아디페이트의 디(메트)아크릴레이트, 히드록시피발산네오펜틸글리콜디(메트)아크릴레이트, 디시클로펜타닐디(메트)아크릴레이트, 카프로락톤 변성 디시클로펜테닐디(메트)아크릴레이트, 에틸렌옥사이드 변성 인산디(메트)아크릴레이트, 디(메트)아크릴옥시에틸이소시아누레이트, 알릴화시클로헥실디(메트)아크릴레이트, 트리시클로데칸디메탄올디(메트)아크릴레이트, 디메틸올디시클로펜탄디(메트)아크릴레이트, 에틸렌옥사이드 변성 헥사히드로프탈산디(메트)아크릴레이트, 네오펜틸글리콜 변성 트리메틸올프로판디(메트)아크릴레이트, 아다만탄디(메트)아크릴레이트, 9,9-비스[4-(2-아크릴로일옥시에톡시)페닐]플루오렌 등의 2관능형; 트리메틸올프로판트리(메트)아크릴레이트, 디펜타에리트리톨트리(메트)아크릴레이트, 프로피온산 변성 디펜타에리트리톨트리(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트, 프로필렌옥사이드 변성 트리메틸올프로판트리(메트)아크릴레이트, 트리스(메트)아크릴옥시에틸이소시아누레이트 등의 3관능형; 디글리세린테트라(메트)아크릴레이트, 펜타에리트리톨테트라(메트)아크릴레이트 등의 4관능형; 프로피온산 변성 디펜타에리트리톨펜타(메트)아크릴레이트 등의 5관능형; 및 디펜타에리트리톨헥사(메트)아크릴레이트, 카프로락톤 변성 디펜타에리트리톨헥사(메트)아크릴레이트 등의 6관능형 다관능 (메트)아크릴레이트계 모노머의 1종 단독 또는 2종 이상의 조합을 들 수 있다.The pressure-sensitive adhesive composition of the present application may further include a photocrosslinking agent. In one example, the photocrosslinker may be a multifunctional acrylate. The polyfunctional acrylate is, for example, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentyl glycoldi (meth) acrylate, polyethylene glycol di (meth) Acrylate, di (meth) acrylate of neopentylglycol adipate, neopentylglycol di (meth) acrylate of hydroxy pivalate, dicyclopentanyldi (meth) acrylate, caprolactone modified dicyclopentenyldi (meth) Acrylate, ethylene oxide modified phosphate di (meth) acrylate, di (meth) acryloxyethyl isocyanurate, allylated cyclohexyldi (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dimethyl Aldicyclopentanedi (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, neopentyl glycol modified trimethylolpropanedi (meth) acrylate, Ada Bifunctional types such as mantandi (meth) acrylate and 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene; Trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane Trifunctional types such as tri (meth) acrylate and tris (meth) acryloxyethyl isocyanurate; Tetrafunctional types such as diglycerin tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate; 5-functional types, such as propionic acid modified dipentaerythritol penta (meth) acrylate; And one or a combination of two or more of six functional polyfunctional (meth) acrylate monomers such as dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Can be.
광가교제의 함량은 점착성 중합체 100 중량부에 대하여 0.1 내지 10 중량부, 0.3 내지 5 중량부 또는 0.5 내지 2 중량부일 수 있다. 광가교제가 상기 함량 범위로 점착제 조성물에 포함될 때, 점착제 조성물로 제조한 봉지층이 우수한 모듈러스 특성, 목적하는 경화도 및 우수한 박리강도를 확보할 수 있다. The content of the photocrosslinker may be 0.1 to 10 parts by weight, 0.3 to 5 parts by weight or 0.5 to 2 parts by weight based on 100 parts by weight of the tacky polymer. When the optical crosslinking agent is included in the pressure-sensitive adhesive composition in the above content range, the encapsulation layer made of the pressure-sensitive adhesive composition can secure excellent modulus properties, desired curing degrees, and excellent peel strength.
본 출원은 또한, 전술한 점착제 조성물을 이용하여 제조한 봉지재층을 포함하는 태양전지 모듈에 관한 것이다.The present application also relates to a solar cell module including an encapsulant layer manufactured by using the above-described pressure-sensitive adhesive composition.
상기 태양전지 모듈에 있어서 이면시트는 고분자 필름일 수 있으며, 예를 들어 폴리에틸렌(PE), 폴리프로필렌(PP), 폴리에틸렌테레프탈레이트(PET), 폴리페닐렌설파이드(PPS), 폴리에틸렌나프탈레이트(PEN), 폴리비닐플루오라이드(PVF), 폴리비닐리덴플루오라이드(PVDF), 에틸렌테트라플루오르에틸렌(ETFE), 폴리클로로트리플루오로에틸렌(PCTFE), 에틸렌클로로트리플루오로에틸렌(ECTFE)로 이루어진 군에서 선택한 어느 하나이다.In the solar cell module, the back sheet may be a polymer film. For example, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyethylene naphthalate (PEN) , Polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), ethylene tetrafluoroethylene (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE) Which one.
상기 태양전지 모듈에 있어서, 봉지재층을 제조하는데 이용되는 점착제 조성물에 관한 구체적인 내용은 전술한 점착제 조성물에 관한 부분에서 설명한 바와 동일하므로, 생략하기로 한다.In the solar cell module, detailed descriptions of the pressure-sensitive adhesive composition used to prepare the encapsulant layer are the same as those described in the above-described pressure-sensitive adhesive composition, and will be omitted.
상기 점착제 조성물을 이용하여 제조한 태양전지 모듈은 봉지재층의 이면시트에 대한 박리력(ASTM D903)이 800gf/in 내지 1200gf/in, 900gf/in 내지 1100gf/in 또는 970gf/in 내지 1030gf/in이다. 상기와 같은 박리력 범위에서, 태양전지 모듈은 장기간 수분 및 직사광선에 노출되어도 봉지재층의 들뜸이 억제될 수 있으며, 점착제 조성물의 공정성을 확보할 수 있다.The solar cell module manufactured using the pressure-sensitive adhesive composition has a peel force (ASTM D903) on the back sheet of the encapsulant layer of 800 gf / in to 1200 gf / in, 900 gf / in to 1100 gf / in or 970 gf / in to 1030 gf / in . In the above peeling force range, the solar cell module can be prevented from lifting of the encapsulant layer even when exposed to moisture and direct sunlight for a long time, it can ensure the fairness of the pressure-sensitive adhesive composition.
본 출원은 또한, 전술한 점착제 조성물을 이용하여 태양전지 모듈을 제조하는 방법에 관한 것이다.The present application also relates to a method of manufacturing a solar cell module using the above-described pressure-sensitive adhesive composition.
상기 제조방법에 있어서, 점착제 조성물에 관한 구체적인 내용은 전술한 점착제 조성물에 관한 부분에서 설명한 바와 동일하므로, 생략하기로 한다.In the above production method, the specific content of the pressure-sensitive adhesive composition is the same as described in the above-described portion of the pressure-sensitive adhesive composition, it will be omitted.
본 출원의 태양전지 모듈의 제조방법에 따른 일 구현예에 있어서 태양전지 모듈의 제조방법은, 전술한 점착제 조성물을 이면시트에 도포하고, 상기 도포된 점착제 조성물에 30초 내지 6분, 1분 내지 5분 또는 2분 내지 4분 동안 자외선(A영역 기준 5mW)을 조사하여 광경화한 후, 추가적인 열 경화(110℃)를 수행하는 단계를 포함한다. 자외선 경화에 이어 추가적으로 열 경화를 수행함으로써, 가교밀도를 향상시켜 롤 투 롤(Roll to Roll) 연속 공정이 가능해 생산속도 및 생산효율을 향상시킬 수 있다.In one embodiment according to the manufacturing method of the solar cell module of the present application, the manufacturing method of the solar cell module, the above-described pressure-sensitive adhesive composition is applied to the back sheet, 30 seconds to 6 minutes, 1 minute to the applied pressure-sensitive adhesive composition Irradiating ultraviolet rays (5 mW based on the A region) for 5 minutes or 2 to 4 minutes for photocuring, and then performing additional thermal curing (110 ° C.). In addition to UV curing, heat curing is performed to further increase the crosslinking density, thereby enabling a roll to roll continuous process to improve production speed and production efficiency.
본 출원에 따른 경화성 점착제 조성물은 조성물 자체를 도포하여 자외선 경화를 진행한 후에 추가적인 열 경화를 진행해 가교밀도를 향상시킬 수 있어 롤 투 롤(Roll to Roll) 연속 공정이 가능하다. 따라서, 생산속도 및 생산효율이 향상된다. 또한, 본 출원에 따른 경화성 점착제 조성물은 반응형 자외선 안정제와 (메트)아크릴레이트 단량체를 포함하여 우수한 물성 및 광학적 특성을 확보하였다.The curable pressure-sensitive adhesive composition according to the present application may further improve the crosslinking density by performing an additional heat curing after applying the composition itself to UV curing, thereby enabling a roll to roll continuous process. Therefore, production speed and production efficiency are improved. In addition, the curable pressure-sensitive adhesive composition according to the present application, including a reactive ultraviolet stabilizer and a (meth) acrylate monomer to secure excellent physical and optical properties.
도 1은 본 출원의 구현예에 따른 태양전지 모듈을 예시적으로 보여주는 도면이다.
도 2는 본 출원의 실시예에 따라 제조된 적층체를 간략히 보여주는 도면이다.1 is a view showing a solar cell module according to an embodiment of the present application by way of example.
2 is a view briefly showing a laminate produced according to an embodiment of the present application.
이하, 본 발명을 실시예에 의해 보다 자세하게 설명하지만, 아래의 실시예는 본 발명을 단지 상세하게 설명하기 위한 것이며 본 발명의 범주를 한정하기 위한 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are only for illustrating the present invention in detail and are not intended to limit the scope of the present invention.
도 2와 같이 유리(210), 봉지재층(220) 및 이면시트(230)로 이루어진 적층체(200)를 제조하였다. 적층체를 제조하는데 있어서, 점착제 조성물이 포함하는 희석 모노머의 함량에 따른 봉지재층의 물성 및 광학적 특성을 측정하였다.As shown in FIG. 2, a laminate 200 including a
실시예Example
내부에 질소가스가 환류되고 온도 조절이 용이하도록 냉각 장치를 설치한 2L 반응기에 2-에틸헥실 아크릴레이트(HEA) 65 중량부, 이소보닐 아크릴레이트(IBOA) 20 중량부 및 하이드록시에틸 아크릴레이트(HEA) 15 중량부를 투입하였다. 산소 제거를 위하여 질소 가스를 60분 동안 퍼지(purging)한 후, 온도를 67℃로 승온한 상태에서 반응 개시제인 아조비스이소부티로니트릴(AIBN) 0.2 중량부 및 2,4-디페닐-4-메틸-1-펜텐 0.2 중량부를 반응기에 투입하여 반응을 개시시켰다. 이후, 약 2시간 반응을 시킨 반응물에 초기 단량체 투입 비율의 혼합액을 전체 초기 투입량 대비 50%로 첨가하면서, 산소를 주입하여 점착성 중합체(UV-EIH)를 제조하였다.65 parts by weight of 2-ethylhexyl acrylate (HEA), 20 parts by weight of isobornyl acrylate (IBOA), and hydroxyethyl acrylate (2 L reactor equipped with a refrigeration device for reflux of nitrogen gas and easy temperature control) HEA) 15 parts by weight was added. Nitrogen gas was purged for 60 minutes to remove oxygen, and then 0.2 parts by weight of azobisisobutyronitrile (AIBN) and 2,4-diphenyl-4 as reaction initiators were heated at a temperature of 67 ° C. 0.2 parts by weight of -methyl-1-pentene was added to the reactor to initiate the reaction. Thereafter, oxygen was injected to the reactants reacted for about 2 hours while adding a mixture of the initial monomer input ratio of 50% of the total initial input amount, thereby preparing an adhesive polymer (UV-EIH).
상기 점착성 중합체(UV-EIH) 100 중량부에 대하여 희석 모노머로서 메틸 아크릴레이트(MA)를 하기 표 1과 같이 1 내지 20 중량부, 광가교제로서 펜타에리트리톨 트리아크릴레이트(PETA) 1 중량부, 반응형 자외선 안정제로서 오츠카 케미컬사의 RUVA-93 1 중량부, 광개시제로서 BASF사의 Irgacure 819 0.5 중량부 및 미츠이 케미컬 사의 TAKENATE D-110N 이소시아네이트 가교제 0.5 중량부를 균일하게 혼합하여 경화성 조성물을 제조하였다.1 to 20 parts by weight of methyl acrylate (MA) as a diluting monomer based on 100 parts by weight of the adhesive polymer (UV-EIH), 1 part by weight of pentaerythritol triacrylate (PETA) as a photocrosslinking agent, A curable composition was prepared by uniformly mixing 1 part by weight of RUVA-93 from Otsuka Chemical, 0.5 part by weight of Irgacure 819 from BASF as a photoinitiator, and 0.5 part by weight of TAKENATE D-110N isocyanate crosslinker from Mitsui Chemical.
상기에서 제조된 경화성 조성물을 TOYOBO사의 A4300 PET 일면에 블레이드 코트로 두께가 약 120μm 정도가 되도록 코팅한 후, 산소 공급을 차단하기 위해 질소 분위기 하에서 코팅층에 블랙 라이트 자외선 램프(UV 조사 장치, 가나텍)로 자외선(A 영역 기준 5mW 3분 조사 광량)을 조사하였다. 이후, 110℃ 오븐에서 3분간 건조하여 코팅층을 경화시켰다. 마지막으로 경화된 코팅층 상에 다시 SKC Haas사의 RF02N 필름을 라미네이트하여 점착제 층을 형성하였고, 유리 위에 이형 처리된 PET 필름을 박리하여 적층체를 제조해 샘플을 얻었다.After coating the curable composition prepared above to a thickness of about 120μm with a blade coat on one surface of TOYOBO's A4300 PET, black light UV lamp (UV irradiation apparatus, Ganatech) to the coating layer under a nitrogen atmosphere to block oxygen supply Ultraviolet rays (5mW 3-minute irradiation amount based on the A area) were irradiated. Thereafter, the coating layer was cured by drying in an oven at 110 ° C. for 3 minutes. Finally, a pressure-sensitive adhesive layer was formed by laminating an RF02N film of SKC Haas Co., Ltd. again on the cured coating layer, and peeling off the release-treated PET film on glass to prepare a laminate.
상기 샘플에 대해 경화도, 모듈러스, 박리력 및 광학적 특성을 측정한 결과는 아래 표 1과 같다.Hardness, modulus, peel force, and optical properties of the sample were measured, and the results are shown in Table 1 below.
(중량부)Diluted monomer
(Part by weight)
(%)Curing degree
(%)
(Pa)Modulus
(Pa)
(gf/in)Peel force
(gf / in)
상기 표 1에서, 본 출원에 따른 점착제 조성물을 이용해 제조한 태양전지 모듈용 봉지재층은 우수한 물리적 특성 및 광학적 특성을 가지는 것을 알 수 있다. 또한, 비교적 짧은 경화 시간을 통해 우수한 경화도를 가지는 봉지재층을 제조할 수 있는 것을 알 수 있다.In Table 1, it can be seen that the encapsulant layer for a solar cell module manufactured using the pressure-sensitive adhesive composition according to the present application has excellent physical and optical properties. In addition, it can be seen that an encapsulant layer having an excellent degree of curing can be produced through a relatively short curing time.
100: 태양전지 모듈
110: 이면시트
120: 봉지재층
130: 전면 부재
140: 태양전지셀
200: 적층체
210: 유리
220: 봉지재층
230: 이면시트100: solar cell module
110: back sheet
120: encapsulant layer
130: front member
140: solar cell
200: laminate
210: glass
220: encapsulant layer
230: back sheet
Claims (14)
상기 봉지재층은, (메트)아크릴레이트 점착성 중합체; 반응형 자외선 안정제; 상기 점착성 중합체 100 중량부 대비 1 내지 20 중량부의 (메트)아크릴레이트 단량체; 및 이소시아네이트계 경화제를 포함하는 무용제형 경화성 점착제 조성물의 경화물을 포함하고,
상기 봉지재층의 이면시트에 대한 박리력(ASTM D903)이 800gf/in 내지 1200gf/in이며,
상기 봉지재층은 Y.I(ASTM D1003) 값이 1.9 이하이고,
상기 반응형 자외선 안정제는 하기 화학식 1로 나타내어지는 아크릴계 단량체인, 태양전지 모듈:
[화학식 1]
화학식 1에 있어서, R1은 수소 또는 메틸기이고, X는 단일 결합 또는 탄소수 1 내지 5의 알킬렌기이며, R2는 방향족기로 치환된 페닐기, 방향족기로 치환된 히드록시페닐기, 헤테로방향족기로 치환된 페닐기 또는 헤테로방향족기로 치환된 히드록시페닐기이다.Front member; An encapsulant layer formed on the front member and encapsulating the solar cell; And a back sheet formed on the encapsulant layer,
The encapsulant layer is a (meth) acrylate adhesive polymer; Reactive ultraviolet stabilizers; 1 to 20 parts by weight of (meth) acrylate monomer relative to 100 parts by weight of the adhesive polymer; And a cured product of the solvent-free curable pressure-sensitive adhesive composition containing an isocyanate-based curing agent,
Peel force (ASTM D903) for the back sheet of the encapsulant layer is 800gf / in to 1200gf / in,
The encapsulant layer has a YI (ASTM D1003) value of 1.9 or less,
The reactive UV stabilizer is an acryl-based monomer represented by Formula 1, a solar cell module:
[Formula 1]
In Formula 1, R 1 is hydrogen or a methyl group, X is a single bond or an alkylene group having 1 to 5 carbon atoms, R 2 is a phenyl group substituted with an aromatic group, a hydroxyphenyl group substituted with an aromatic group, a phenyl group substituted with a heteroaromatic group Or a hydroxyphenyl group substituted with a heteroaromatic group.
Y.I(ASTM D1003) 값이 1.5이하인, 태양전지 모듈.The method of claim 1,
Solar cell module, YI (ASTM D1003) value is less than 1.5.
(메트)아크릴레이트 점착성 중합체는 가교성 관능기를 포함하는 (메트)아크릴레이트 단량체와 (메트)아크릴레이트 단량체의 공중합체인, 태양전지 모듈.The method of claim 1,
The (meth) acrylate adhesive polymer is a copolymer of a (meth) acrylate monomer and a (meth) acrylate monomer containing a crosslinkable functional group.
가교성 관능기는 히드록시기인, 태양전지 모듈.The method of claim 3, wherein
The crosslinkable functional group is a hydroxyl group, solar cell module.
가교성 관능기를 포함하는 (메트)아크릴레이트 단량체의 함량은 점착성 중합체 100 중량부 대비 5 내지 30 중량부인, 태양전지 모듈.The method of claim 3, wherein
The content of the (meth) acrylate monomer including a crosslinkable functional group is 5 to 30 parts by weight based on 100 parts by weight of the tacky polymer, solar cell module.
반응형 자외선 안정제의 함량은 점착성 중합체 100 중량부에 대하여 0.1 내지 10 중량부인, 태양전지 모듈.The method of claim 1,
The content of the reactive UV stabilizer is 0.1 to 10 parts by weight based on 100 parts by weight of the adhesive polymer, solar cell module.
(메트)아크릴레이트 단량체는 하기 화학식 2로 나타내어지는 (메트)아크릴레이트 단량체인, 태양전지 모듈:
[화학식 2]
화학식 2에 있어서, R3는 수소 또는 메틸기이고, Y는 탄소수 1 내지 5의 알킬기이다.The method of claim 1,
The (meth) acrylate monomer is a (meth) acrylate monomer represented by the following formula (2), a solar cell module:
[Formula 2]
In formula (2), R 3 is hydrogen or a methyl group, and Y is an alkyl group having 1 to 5 carbon atoms.
(메트)아크릴레이트 단량체의 함량이 3.7 내지 8 중량부인, 태양전지 모듈.The method of claim 2,
The solar cell module, wherein the content of the (meth) acrylate monomer is 3.7 to 8 parts by weight.
광가교제를 추가로 포함하는, 태양전지 모듈.The method of claim 1,
A solar cell module further comprising an optical crosslinking agent.
광가교제는 다관능성 아크릴레이트인, 태양전지 모듈.The method of claim 10,
The photocrosslinker is a polyfunctional acrylate, solar cell module.
광가교제의 함량은 점착성 중합체 100 중량부에 대하여 0.1 내지 10 중량부인, 태양전지 모듈.The method of claim 10,
The content of the photocrosslinker is 0.1 to 10 parts by weight based on 100 parts by weight of the tacky polymer, solar cell module.
상기 무용제형의 경화성 점착제 조성물을 이면시트에 도포하는 단계;
상기 도포된 조성물에 30초 내지 6분 동안 자외선을 조사하여 광경화하는 단계; 및
상기 광경화 후 추가적인 열 경화를 수행하는 단계를 포함하는 태양전지 모듈의 제조방법.Method for manufacturing a solar cell module according to claim 1,
Applying the solvent-free curable pressure-sensitive adhesive composition to the back sheet;
Photocuring by irradiating the applied composition with ultraviolet light for 30 seconds to 6 minutes; And
Method of manufacturing a solar cell module comprising the step of performing additional thermal curing after the photocuring.
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