CN103534325B - Laminated chip adhesive composition and solar cell backside protective sheet - Google Patents
Laminated chip adhesive composition and solar cell backside protective sheet Download PDFInfo
- Publication number
- CN103534325B CN103534325B CN201280015206.0A CN201280015206A CN103534325B CN 103534325 B CN103534325 B CN 103534325B CN 201280015206 A CN201280015206 A CN 201280015206A CN 103534325 B CN103534325 B CN 103534325B
- Authority
- CN
- China
- Prior art keywords
- adhesive composition
- solar cell
- laminated chip
- acrylic polyol
- adhesion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000000853 adhesive Substances 0.000 title claims abstract description 51
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 51
- 230000001681 protective effect Effects 0.000 title claims abstract description 36
- -1 acrylic polyol Chemical class 0.000 claims abstract description 80
- 229920005862 polyol Polymers 0.000 claims abstract description 44
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 27
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 27
- 230000009477 glass transition Effects 0.000 claims abstract description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 238000003475 lamination Methods 0.000 claims description 16
- 239000010410 layer Substances 0.000 abstract description 39
- 239000007787 solid Substances 0.000 abstract description 36
- 239000002985 plastic film Substances 0.000 abstract description 24
- 229920006255 plastic film Polymers 0.000 abstract description 23
- 239000011229 interlayer Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 47
- 230000032683 aging Effects 0.000 description 35
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- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
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- 239000005357 flat glass Substances 0.000 description 4
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- 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
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- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
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- 150000002825 nitriles Chemical class 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
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- 229920000728 polyester Polymers 0.000 description 3
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- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IXAWXWACDBWEJF-UHFFFAOYSA-L C(CCCCCCC)[Sn+2]CCCCCCCC.C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].[Sn+4] Chemical compound C(CCCCCCC)[Sn+2]CCCCCCCC.C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].[Sn+4] IXAWXWACDBWEJF-UHFFFAOYSA-L 0.000 description 2
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- MASNVFNHVJIXLL-UHFFFAOYSA-N ethenyl(ethoxy)silicon Chemical compound CCO[Si]C=C MASNVFNHVJIXLL-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 210000000713 mesentery Anatomy 0.000 description 1
- JDQYWEMHMOYPTM-UHFFFAOYSA-N methylsilyl prop-2-enoate Chemical compound C[SiH2]OC(=O)C=C JDQYWEMHMOYPTM-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920005678 polyethylene based resin Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000000954 titration curve Methods 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
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-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
- 230000009466 transformation Effects 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- 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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
-
- 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
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S20/00—Supporting structures for PV modules
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/12—Photovoltaic modules
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Photovoltaic Devices (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a kind of laminated chip solid constituent and solar cell backside protective sheet; this adhesive composition; it demonstrates high adhesion at the interlayer comprising plastic film processing layer between various sheet component, particularly; even if also high adhesion can be maintained under being exposed to high-temperature high-humidity environment, be suitable for manufacturing solar cell backside protective sheet.Laminated chip adhesive composition of the present invention comprises acrylic polyol (A) and polymeric polyisocyanate (B), the number average molecular weight of acrylic polyol (A) is 10,000 ~ 100,000, and hydroxyl value is 1mgKOH/g ~ 100mgKOH/g, glass transition temperature (Tg) exceedes-40 DEG C and is less than 10 DEG C in addition.In addition, the hydroxyl being derived from acrylic polyol (A) is 0.1 ~ 3 with the equivalence ratio NCO/OH of the isocyanate group being derived from polymeric polyisocyanate (B).
Description
Technical field
The present invention relates to a kind of laminated chip adhesive composition and solar cell backside protective sheet.
Background technology
In recent years, multilayer (compound) laminate headed by multilayer (compound) film used in the such as barrier material of industrial applications, roof Material, solar cell panel material, window materials, outdoor floor material, illumination protecting materials, trolley part, signboard, label etc. outside faced chamber etc. obtains practical.Multilayer laminated boards body obtains by carrying out lamination (lamination) to metal system starting material or plastics system starting material etc.Metal system starting material can enumerate aluminium or the tinsel such as copper, steel plate, metal sheet, metal deposition film etc.Plastics system starting material can enumerate plastic film, plastic sheet, the plastic plate of polypropylene, polyvinyl chloride, polyester, fluoro-resin, acrylic resin etc., are formed with the plastic film etc. of the inorganic oxide layers such as silica steam plating film on surface.The solid used in the raw-material joint of metal system starting material or plastics system previously there will be a known poly-epoxy solid and polyurethane(s) system solid.
In patent documentation 1, describe a kind of back of solar cell sealing sheet, it comprises the laminate of being fitted by more than at least 2 layers base materials with polyurethane(s) system solid.More specifically, describe satisfied following condition and containing the polyurethane(s) system solid of solid with hydrolytic resistance: condition 1: as the highly accelerated stress screeningtest (highlyacceleratedstresstest of promotion evaluating apparatus utilizing steam under pressure, HAST) in room, 105 DEG C, preserve 168 hours under 1.05atm after lamination strength be at least more than 1N/15mm; Condition 2: as utilizing in the HAST room of promotion evaluating apparatus of steam under pressure, 105 DEG C, keep 168 hours under 1.05atm after, the protuberance between not producing along with the base material of delamination (delamination).Specifically, propose respectively relative to polyvalent alcohol A ~ this 6 type of polyvalent alcohol F polyvalent alcohol and combine the multiple polyurethane(s) system solid (with reference to claim the 2 ~ the 11st of patent documentation 1) of linking agent.
In patent documentation 2, describe a kind of solar cell module rear panel, it comprises the laminate of being fitted by least 2 base materials with acrylic acid series solid.More specifically, propose a kind of acrylic acid series solid as the acrylic acid series solid with hydrolytic resistance, resistance to insulativity and moisture barrier, described acrylic acid series solid contains the acrylic acid polymer (claim the 2 with reference to patent documentation 2) of the polymerizing monomer components made containing the monomer represented by general formula (I).
CH
2=C(R
1)-CO-OZ(I)
In formula, R
1represent hydrogen atom or methyl, Z represents that carbon number is the alkyl of 4 ~ 25.
In addition, as for patent documentation disclosed after becoming the previous application on the basis of right of priority, in patent documentation 3, patent documentation 4, describe a kind of adhesive composition being applicable to following purposes: for carrying out undressed of plastic film in sheet material then with other base materials.
[prior art document]
[patent documentation]
No. 2007-148754, [patent documentation 1] International Publication
[patent documentation 2] Japanese Patent Laid-Open 2009-246360 publication
[patent documentation 3] Japanese Patent Laid-Open 2011-105819 publication
[patent documentation 4] Japanese Patent Laid-Open 2011-111519 publication
Summary of the invention
In order under the rigor condition of outdoor through stably maintaining adhesion for a long time, even if importantly Bonding strength is in time through also stablizing.Recently, exploitation prevailing as shown in patent documentation 3 or patent documentation 4 can by do not carry out undressed of the plastics such as surface-treated polyester film with other base materials solid then well.The shortening of manufacturing step can be realized owing to not carrying out surface treatment, therefore can reduce costs.But with regard on the other hand, for also having used from previous used process for treating surface, the performance making adhesive composition original improves further and the demand synergistically with the adhesive composition of more excellent then characteristic also uprises.
The present invention forms in view of above-mentioned background; its object is to provide a kind of laminated chip adhesive composition and solar cell backside protective sheet; described laminated chip adhesive composition demonstrates high adhesion at the interlayer comprising plastic film processing layer between various sheet component, particularly; even if also high adhesion can be maintained under being exposed to high-temperature high-humidity environment, be suitable for manufacturing solar cell backside protective sheet.
Present inventor etc. the are artificial above-mentioned problem of solution and carried out making great efforts research, found that by laminated chip adhesive composition shown below and solves above-mentioned problem, thus completing the present invention.
That is, laminated chip adhesive composition of the present invention comprises acrylic polyol (A) and polymeric polyisocyanate (B), the number average molecular weight of described acrylic polyol (A) is 10,000 ~ 100,000, and hydroxyl value is 1mgKOH/g ~ 100mgKOH/g, glass transition temperature (Tg) exceedes-25 DEG C and is less than 10 DEG C in addition, and the hydroxyl being derived from described acrylic polyol (A) is 0.1 ~ 3 with the equivalence ratio NCO/OH of the isocyanate group being derived from described polymeric polyisocyanate (B).
The preference of described polymeric polyisocyanate (B) can enumerate comprise by alicyclic diisocyanate or aliphatic diisocyanate the example of polymeric polyisocyanate that derives.
The laminated chip adhesive composition of above-mentioned form uses in the manufacture of solar cell backside protective sheet comprising more than 2 layers sheet components, is applicable in following purposes: form adhesion agent layer in order to be engaged with each other by described sheet component at least partially.
Solar cell backside protective sheet of the present invention comprises: the adhesion agent layer formed by the laminated chip adhesive composition of above-mentioned form; And via described adhesion agent layer the sheet component of more than at least 2 layers of lamination.
[effect of invention]
Following excellent effect can be provided: a kind of laminated chip adhesive composition and solar cell backside protective sheet can be provided according to the present invention; described laminated chip adhesive composition demonstrates high adhesion at the interlayer comprising plastic film processing layer between various sheet component, particularly; even if also high adhesion can be maintained under being exposed to high-temperature high-humidity environment, be suitable for manufacturing solar cell backside protective sheet.
Embodiment
Below example of the present invention is described in detail.In addition, as long as aim according to the invention, other examples also can belong to category of the present invention.And in this manual, the record of " counting A ~ several B arbitrarily arbitrarily " is the scope representing several A and be greater than several A, and is number B and the scope being less than several B.And the record of " (methyl) acryloyl " described in this specification and claims book comprises any person of the compound being referred to as " acryloyl " and the compound being referred to as " methacryloyl ".And, define similarly in " (methyl) propenyl " and " (methyl) acrylate ".
< acrylic polyol (A) >
Acrylic polyol (A) preferably can use the multipolymer of list (methyl) acrylate monomer containing hydroxyl and not list (methyl) acrylate monomer of hydroxyl.List (methyl) acrylate monomer containing hydroxyl is the monomer containing 1 (methyl) acryl and more than 1 hydroxyl in 1 molecule.Preference can be enumerated by 2 yuan of alcohol and (methyl) acrylic acid reaction and list (methyl) acrylate monomer, 6-caprolactone upgrading (methyl) acrylic monomer etc. of gained.
If the number average molecular weight of acrylic polyol (A) is degree of the same race, then consider from the aspect improving adhesion, the part irrelevant with the copolymerization of list (methyl) acrylate monomer that is via ester bond with the part of (methyl) acrylate moiety bond (part such as alkyl or alkenyl.Hereinafter referred to as " pendant moiety ") carbon number preferably 1 ~ 17, more preferably 1 ~ 9, further more preferably 1 ~ 3.Described pendant moiety forms the side chain of acrylic polyol (A) after copolymerization.The carbon number of the described pendant moiety of single (methyl) acrylate monomer is generally about 1 ~ 30, if but the number average molecular weight of acrylic polyol (A) is equal extent, then described pendant moiety is shorter, and it is elongated that the main chain of acrylic polyol (A) gets over relativity.Its result, the mechanical properties (being specifically elongation) of the following layer after sclerosis improves, and adhesion improves.
Include, for example (methyl) 2-Hydroxy ethyl acrylate, (methyl) hydroxypropyl acrylate, BDO list (methyl) acrylate, (gathering) ethylene glycol list (methyl) acrylate etc. by list (methyl) acrylate monomer of 2 yuan of alcohol gained.
In addition, as such list (methyl) acrylate monomers of gained by the alcohol of more than 3 yuan such as (methyl) vinylformic acid-2,3-dihydroxyl propyl ester also can be used as list (methyl) acrylate monomer containing hydroxyl.
List (methyl) acrylate monomer of hydroxyl can not be suitable for selecting known free radical polymerization monomer since previously and use.Suitable example include, for example with (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid tri-n-butyl, (methyl) ethyl acrylate, (methyl) n-octyl, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) alkyl acrylate monomers such as (methyl) stearyl acrylate base ester are long-chain (methyl) acrylic monomer of representative, and vinyl cyanide etc.
In addition, except above-mentioned (methyl) acrylate monomer containing hydroxyl and list (methyl) acrylate monomer of not hydroxyl, all right other monomers of copolymerization, such as: (methyl) vinylformic acid, toxilic acid, maleic anhydride etc. are containing the monomer of carboxyl or its acid anhydrides, or the vinyl monomer etc. such as vinylbenzene.In addition, list (methyl) acrylate monomer of (methyl) acrylate monomer, not hydroxyl containing hydroxyl separately can use a kind of compound, also two or more compound combination can be used.About using the situation of other monomers too.
In the present invention, the number average molecular weight of acrylic polyol (A) is necessary for 10,000 ~ 100,000.Furthermore, preferably 10,000 ~ 70,000, more preferably 25,000 ~ 50,000.
Use laminated chip adhesive composition of the present invention (hereinafter also referred to " adhesive composition ") that the laminated chip of more than 2 sheet component laminations, such as solar cell backside protective sheet are such as can be passed through following step and obtain.The junction surface of a sheet component is coated with adhesive composition and makes it dry wherein.Secondly, other sheet components are overlapped in adhesion agent layer, by the step being called as " aging " about 2 days ~ 1 week of preservation under the environment of 40 DEG C ~ 60 DEG C, carry out the sclerosis of adhesion agent layer and obtain laminated chip.
In the number average molecular weight of acrylic polyol less than 10, during the situation of 000, there is the hypodynamic tendency of cohesion of the adhesion agent layer before Aging Step, and there is the anxiety that the adhesion before Aging Step diminishes.When the situation that industrialness is produced, the laminate being wound as the state of roll makes core for upper and lower vertical direction and carry out aging under normal conditions.If the adhesion before Aging Step is little, then when carrying out aging, winding easily scatters, and is not suitable for industrialness and produces.And, if less than 10,000, then there is the hypodynamic tendency of cohesion after Aging Step, be accompanied by this and there is humidity resistance step-down, produce the anxiety of delamination etc.
And if the number average molecular weight of acrylic polyol is more than 100,000, then the viscosity that there is solid uprises, and has problems in coating, to the tendency that the wettability of sheet component reduces, the anxiety that the adhesion before its result exists Aging Step diminishes.Although initial adhesion due to aging and with aging before Comparatively speaking becomes large, exist due to humidity resistance test thereafter and slowly reduce, after 3000 hours lower than the anxiety of use lower limit.
In addition, the number average molecular weight in the present invention is obtained by hydrogel permeation layer analyzer (GPC), carries out the value of polystyrene conversion.More specifically, the number average molecular weight in the present invention represents the value obtained by measuring method described in embodiment described later.And, about glass transition temperature, NCO/OH equivalence ratio, represent the value obtained by method described in embodiment described later similarly.
The hydroxyl value of acrylic polyol (A) is determined by the content of list (methyl) acrylate monomer containing hydroxyl, hydroxyl value is 1mgKOH/g ~ 100mgKOH/g in the present invention, preferably 1mgKOH/g ~ 50mgKOH/g, more preferably 1mgKOH/g ~ 15mgKOH/g.If less than 1mgKOH/g, then there is the tendency with the crosslinked reduction of isocyanate hardener, and there is the anxiety of humidity resistance reduction.And, if more than 100mgKOH/g, although then exist can show aging before adhesion, the tendency that uprises of cross-linking density after weathering, and exist and cannot show sufficient adhesion, the anxiety that adhesion reduces further in humidity resistance test thereafter.
And in the present invention, the glass transition temperature (Tg) of acrylic polyol (A) for exceeding-40 DEG C and be less than 10 DEG C due to reason described later, is preferredly above-25 DEG C and is less than 10 DEG C.
< polymeric polyisocyanate (B) >
Polymeric polyisocyanate (B) such as by known vulcabond the compound that derives, can unrestrictedly utilize known compound.Include, for example: by 2, 4-tolylene diisocyanate (another name: 2, 4-TDI), 2, 6-tolylene diisocyanate (another name: 2, 6-TDI), Xylene Diisocyanate (another name: XDI), diphenylmethanediisocyanate (another name: MDI), isophorone diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate (another name: HDI), two (4-isocyanate cyclohexyl) methane, or the vulcabond such as hydrogenated diphenyl methane diisocyanate the compound that derives, that is the isocyanic ester body of described vulcabond, trimethylolpropane adduct body, biuret form, there is the prepolymer (low-grade polymer by vulcabond and polyvalent alcohol gained) of isocyanate residue, there is urea two ketoboidies of isocyanate residue, allophanate body, or the mixture of those compounds, and blocked isocyanate.Polymeric polyisocyanate (B) can be used alone single compound or two or more combinationally used.
The viewpoint of the viscoelasticity of the hardened coating film after self-crosslinking is considered, polymeric polyisocyanate (B) preferably uses the polymeric polyisocyanate derivative by alicyclic diisocyanate or aliphatic diisocyanate.More specifically, alicyclic diisocyanate can enumerate isophorone diisocyanate, methyl-2,6-cyclohexyl diisocyanate etc.And aliphatic diisocyanate can enumerate hexamethylene diisocyanate, pentamethylene diisocyanate etc.And can enumerate: as the isocyanic ester body of the vulcabond of the derivative of aforesaid alicyclic diisocyanate and aliphatic diisocyanate compound, trimethylolpropane adduct body, biuret form, there is the prepolymer (low-grade polymer by vulcabond and polyvalent alcohol gained) of isocyanate residue, urea two ketoboidies with isocyanate residue, allophanate body or those mixture etc.
And, when paying attention to the situation of setting rate speed, preferably use as Xylene Diisocyanate (call: XDI) although there is aromatic nucleus, there is the isocyanic ester of alkylidene group between NCO and aromatic nucleus.If setting rate is fast, then can shorten digestion time in preferably.
And, the isocyanate group concentration preferably 5wt% ~ 30wt% in polymeric polyisocyanate (B).Isocyanate group concentration in polymeric polyisocyanate (B) is set to the scope of 5wt% ~ 30wt%.In addition, the isocyanate group concentration in polymeric polyisocyanate (B) is obtained by volumetry.Titration is evaluated by n-butylamine/hydrochloric titration.Specifically, after making sample dissolution in dry toluene, add superfluous di-n-butyl amine (dibutylamine) solution and make it react, the remaining di-n-butyl amine of back titration by hydrochloric acid, using the point of inflection on titration curve as terminal, according to until terminal titer and calculate isocyanate group containing ratio.
The usage quantity of polymeric polyisocyanate (B) can by the hydroxyl being derived from acrylic polyol (A) be derived from polymeric polyisocyanate (B) isocyanate group NCO/OH equivalence ratio and determine, NCO/OH equivalence ratio is set to 0.1 ~ 3.More preferably NCO/OH equivalence ratio is 1 ~ 3, further preferably 1.5 ~ 3.NCO/OH equivalence ratio can use following mathematical expression (1) and obtain.
NCO/OH ratio=polymeric polyisocyanate necessary amounts (weight part) × (561/OH value) × (NCO%/(42 × 100)) × (100/ polyvalent alcohol amount (solids by weight)) mathematical expression (1)
The people such as present inventor find out: by meeting following all conditions, can obtain the laminated chip adhesive composition of surprising excellent specific property.That is, find out by meeting following all conditions, (described adhesive composition is between various sheet component can to provide a kind of adhesive composition, particularly demonstrate high adhesion at the interlayer of the surface-treated layer comprising plastic film, even if also high adhesion can be maintained under being exposed to high-temperature high-humidity environment, be suitable for manufacturing solar cell backside protective sheet): use the above-mentioned number average molecular weight with (i) specified range, (ii) hydroxyl value of specified range, (iii) acrylic polyol (A) of the glass transition temperature (Tg) of specified range, the hydroxyl further (iv) being derived from acrylic polyol (A) is set as aforesaid specified range with the equivalence ratio NCO/OH of the isocyanate group being derived from polymeric polyisocyanate (B).Below, its reason is illustrated.
With the situation of the undressed plastic film of build-up surface Comparatively speaking, when lamination to carry out the situation of the plastic film processed with effects on surfaces such as corona discharges, require the value added of manufacturing step increase part.In adhesion, require the adhesion Comparatively speaking higher with the situation of the undressed plastic film of build-up surface.
If the Tg of acrylic polyol is too low, then the sclerosis of aging front adhesion agent layer is still insufficient, and the adhesion agent layer therefore formed by adhesive composition is soft.And, the adhesion that can show between sheet component to a certain degree due to its softness.But, after weathering, even if adhesion agent layer is fully hardened, also there is the not enough apparition of cohesive force of adhesion agent layer because the Tg of the acrylic polyol as raw material is low, become the tendency being difficult to guarantee large adhesion.In addition, if under laminate is placed in high-temperature high-humidity for a long time, then there is following tendency: the hypodynamic reason of the cohesion due to adhesion agent layer and cause adhesion slowly to reduce.
On the other hand, if the Tg of acrylic polyol is too high, then there is the tendency of the wettability deficiency to base material.Although the adhesion after aging and aging before Comparatively speaking become large a little, the sclerosis adhesion agent layer after crosslinked becomes really up to the mark, therefore there is the tendency that the adhesion after Aging Step worsens.
In the present invention, carry out studying and learn the reason obtaining above-mentioned excellent effect be due to: the Tg of acrylic polyol is set to not too low and not too high temperature range (specifically for exceed-40 DEG C and be less than 10 DEG C), be set to the scope of specific hydroxyl value, specific NCO/OH equivalence ratio and specific number average molecular weight on its basis further, excite the active degree of the motion of the acrylic polyol of molecular motion rank therefrom synergistically, thus make to improve the wettability of then object and anchoring.Particularly carry out studying and learn by by NCO/OH equivalence ratio control be 0.1 ~ 3 scope, particularly 1 ~ 3 scope, can realize appropriateness degree of crosslinking balance and after Aging Step, demonstrate high adhesion.And, even if find surprisingly also to show high adhesion before ageing.Find in addition: after Aging Step, also can maintain high adhesion being placed in after under high-temperature high-humidity.
When using tinsel, metal sheet or metal deposition film etc. to be the situation of base material, the viewpoint certainly making Bonding strength improve is considered, preferably laminated chip adhesive composition of the present invention contains silane coupling agent.
Silane coupling agent is not defined in following person, include, for example the vinyl silanes classes such as vinyl three ('beta '-methoxy oxyethyl group) silane, vinylethoxysilane and vinyltrimethoxy silane; (methyl) acryloxy silane classes such as γ-(methyl) acryloxypropyl Trimethoxy silane, γ-(methyl) acryloxypropyl triethoxyl silane and γ-(methyl) acryloxypropyl dimethoxymethylsilane; β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3,4-epoxycyclohexyl) methyltrimethoxy silane, β-(3,4-epoxycyclohexyl) the epoxy radicals silicone hydride class such as ethyl triethoxysilane, β-(3,4-epoxycyclohexyl) Union carbide A-162, γ-glycidoxypropyltrimewasxysilane and γ-glycidoxypropyl triethoxyl silane; The amino silicone alkanes such as N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl)-γ aminopropyltriethoxy silane, N-β-(amino-ethyl)-gamma-amino hydroxypropyl methyl diethoxy silicon silane, γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, N-phenyl-gamma-amino propyl trimethoxy silicane and N-phenyl-γ aminopropyltriethoxy silane; And the sulfuric silane such as γ mercaptopropyitrimethoxy silane and γ-Mercaptopropyltriethoxysilane class etc.Those compounds individually can use or two or more arbitrary combination are used.
The addition of silane coupling agent preferably 0.1 weight part ~ 5 weight part, more preferably 1 weight part ~ 3 weight part for acrylic polyol (A) 100 weight part.If less than 0.1 weight part, then the weak effect that the Bonding strength to tinsel brought owing to adding silane coupling agent improves; Even if add more than 5 weight parts, also there is the situation not finding that further performance improves.
Laminated chip adhesive composition of the present invention can be what is called 2 liquid mixed type solid host mixed with stiffening agent in use, also can be 1 liquid type solid host mixed with stiffening agent in advance.And acrylic polyol (A) or polymeric polyisocyanate (B) also can use multiple independently of one another.In addition, other hosts other than the above or stiffening agent also can use one or more independently of one another.Under normal circumstances, host comprises acrylic polyol (A), silane coupling agent, organic solvent, other additives, and stiffening agent comprises polymeric polyisocyanate (B), organic solvent, other additives.
As other additives, can without departing from the spirit and scope of the invention, in laminated chip solid of the present invention, allocate the various additive such as antioxidant, ultra-violet stabilizer, metal passivator, fire retardant, fluidizer, pigment dyestuff, mineral dye of viscosity increaser, reaction promotor, levelling agent, phosphorus system or phenol system.
When the situation using metal level (tinsel, metal sheet etc.) as sheet component, improve to make the metal adhesion of laminated chip adhesive composition of the present invention, phosphoric acid based compound can be added, the ester etc. of such as phosphoric acid, metaphosphoric acid, tetra-sodium, phosphorous acid or those acid.
And adhesive composition of the present invention, except preferably using as the solid in order to manufacture solar cell backside protective sheet, also can be used as solar cell laminated chip and increases glutinous coating-forming agent and use.When this situation, preferably put into anti-hard caking agent.]
In addition, the known additive as solid purposes can unrestrictedly be allocated without departing from the spirit and scope of the invention.Such as reaction promotor can be used.Specifically can enumerate the metal series catalysts such as dibutyltin diacetate, dibutyl tin laurate, tin dilaurate dioctyl tin, two dibutyitin maleate; 1,8-diaza-dicyclo [5.4.0] undecylene-7,1,5-diazabicyclo [4.3.0] nonene-5, tertiary amine such as 6-dibutylamino-1,8-diazabicyclo [5.4.0] undecylene-7 grade; Reactive tertiary amine etc. as trolamine.Reaction promotor can use a kind or be two kinds or more use.
In addition, in order to make laminated appearance improve, also known levelling agent or defoamer can be allocated in host.
Levelling agent include, for example polyethers upgrading polydimethylsiloxane, polyester upgrading polydimethylsiloxane, aralkyl upgrading gathers methyl alkyl siloxane, polyester upgrading hydroxyl polydimethylsiloxane, polyether ester upgrading hydroxyl polydimethylsiloxane, acrylic copolymer, methacryloyl based copolymer, polyethers upgrading gathers methyl alkyl siloxane, alkyl acrylate copolymer, methacrylate copolymer, Yelkin TTS, or the known levelling agent such as those mixture.
Defoamer can enumerate the known defoamer such as multipolymer or those mixture of silicone resin, silicone solution, alkyl vinyl ether and alkyl acrylate and alkyl methacrylate.When the situation of interpolation levelling agent, defoamer, a kind of compound can be used independently of one another also two or more compound at random can be combined and use.
And, as the known additive used in the present invention, the yellow of the yellow of process in time such as the solid caused in order to the ultraviolet suppressed further due to the sun etc., the solid that causes due to heat such as solar heats process in time, can allocate antioxidant, ultra-violet stabilizer, the metal passivator of known phosphorus system or phenol system in host.Those additives can be used alone, and also two or more arbitrary combination can be used.The scope of the phosphorus system used in the present invention or the antioxidant of phenol system, ultra-violet stabilizer, metal passivator preferably 0.05 weight part ~ 5 weight part for solids component 100 weight part of acrylic polyol (A), more preferably 0.1 weight part ~ 1 weight part.If addition is less than 0.05 weight part, then there is the anxiety that cannot obtain sufficient yellow inhibition; If more than 5 weight parts, then there is the anxiety worsened with making the large degree of the adhesion of solid.
As stiffening agent, except above-mentioned polymeric polyisocyanate (B), known oxazoline compound (such as 2 at random can be comprised in the scope not hindering effect of the present invention, 5-dimethyl-2-oxazoline or 2,2-(tetramethylene)-bis-(2-oxazoline)) or hydrazide compound (such as isophthalic dihydrazide, sebacic dihydrazide or adipic dihydrazide) etc.
The solvent used in the present invention, include, for example the ester classes such as ethyl acetate, butylacetate, cellosolve acetate; The ketones such as acetone, methyl ethyl ketone, isobutyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone; The ethers such as tetrahydrofuran (THF), dioxan; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; The halogenated hydrocarbons such as methylene dichloride, 1,2-ethylene dichloride; Dimethyl sulfoxide (DMSO), dimethyl sulfonamide etc.The solvent used can use a kind of solvent, also two or more arbitrary combination can be used.
The scope of the non-volatile composition (solids component) of solid of the present invention preferably 10wt% ~ 50wt%.This solid can use the adjustment carrying out solids component as the solvent as illustrated in above-mentioned.
Secondly, the method for solar cell backside protective sheet and an example of solar cell backside protective sheet that manufacture use laminated chip adhesive composition of the present invention are illustrated.In addition, the manufacture method of solar cell backside protective sheet or formation are not limited to following example, can adopt various manufacture method or formation according to object or needs.
As solar cell module, simple solar cell module to have in two faces of the solar battery cell as solar battery element lamination in turn and has the construction form of weighting agent and sheet glass.The transparency of sheet glass, weathering resistance, excellent scratch resistance, be therefore also generally used as the diaphragm seal of the sensitive surface side of solar cell module now.But; in the non-sensitive surface side without the need to the transparency; consider from the aspect of cost or security, processibility, develop the solar cell backside protective sheet (hereinafter referred to as backside protective sheet) beyond sheet glass by each company, those backside protective sheets replace sheet glass.
Solar cell backside protective sheet has lamination the solar cell backside protective sheet of following person: the plastic films such as polyester film, be provided with on polyester film etc. the evaporation layer of metal oxide or nonmetal oxide with the tinsel such as plastic film, aluminium foil of metal level, the plastic film etc. with silicon nitride layer.Laminated chip adhesive composition of the present invention can be used between each sheet component of institute's lamination and engage.The solar cell backside protective sheet that multilayer is formed gives various performance by this multilayered structure.Such as giving insulativity by using polyester film, giving weathering resistance by using fluorine mesentery, giving water vapor barrier by using aluminium foil.As for which kind of solar cell backside protective sheet of use, can according to using the product of solar cell module, purposes and suitablely to select.
Plastic film include, for example the polyester based resin film of polyethylene terephthalate, poly terephthalic acid naphthalene diester etc., polyethylene resin film, polypropylene-based resin film, polyvinyl chloride resin film, polycarbonate resin film, polysulfones resin film, poly-(methyl) acrylic resin film, the fluorine resin film etc. of fluorinated ethylene propylene, poly(vinylidene fluoride), polychlorotrifluoroethylene, polyethylene tetrafluoroethylene, tetrafluoroethylene, tetrafluoroethylene perfluoroalkyl vinyl ether multipolymer, tetrafluoraoethylene-hexafluoropropylene copolymer etc.
Can use and those plastic films are coated with the film of acrylic acid series, fluorine system coating as supporter, or by coextrusion the multilayer film etc. of lamination poly(vinylidene fluoride) or acrylic resin etc.In addition, the sheet component via multiple above-mentioned plastic films of lamination such as carbamate system adhesion agent layer can also be used.
Above-mentioned plastic film can be suitable for using and be handled as follows by effects on surface and make the plastic film of easy commissure: the physical treatment such as corona discharge, Cement Composite Treated by Plasma, flame treating, with acid or alkali etc., film surface is carried out to the chemical process of upgrading, be accompanied by fine concavo-convex on film surface, become the delustering processing etc. of so-called buckle condition.Certainly, also laminated chip adhesive composition of the present invention can be applicable in the starting material of surface free process.
Tinsel can enumerate aluminium foil or Copper Foil.The oxide compound of silicon, aluminium, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, yttrium etc. such as can be used as the metal oxide of institute's evaporation or nonmetallic inorganic oxide compound
Preferably in order to meet the performance such as weathering resistance, steam breathability, electric insulating quality, mechanical characteristics, packaging operation when using as solar cell module in those, lamination has and has the polyester based resin film such as polyethylene terephthalate, poly terephthalic acid naphthalene diester of tolerance, the solar cell backside protective sheet of polycarbonate resin film to temperature; The output that causes due to water mitigation to prevent solar battery cell reduces, and preferably lamination has the evaporation with water vapor barrier to have the solar cell backside protective sheet of the tinsels such as the plastic film of metal oxide or nonmetallic inorganic oxide compound or aluminium foil; In order to prevent the bad order because light deterioration produces; The preferably solar cell backside protective sheet of the lamination fluorine resin film that has weathering resistance good.
And; solar cell backside protective sheet is in order to protect solar cell module from the breakage applying to cause due to voltage; according to the generating capacity of solar battery cell, adopt require partial discharge voltage be 700V or 1000V tolerance and by electric insulating quality or comprise the formation that foaming layer makes partial discharge voltage improve.As the electric insulating quality of the method making partial discharge voltage improve, depend on the thickness of film or foaming layer, therefore there is the tendency that film or foaming layer become press mold.Recently, the formation adopting use 100 μm ~ about 300 μm persons more.
The formation of adhesion agent layer is such as take turns coating machine (commacoater) or dry adhered machine by unfilled corner to be coated on by adhesive composition on the one side of the sheet component of one of them plastic film etc., after making solvent evaporates, fit with another laminate substrate, at normal temperature or make it harden under heating and obtain.Or manufacture by such as under type: on any one sheet component, be coated with adhesive composition and carry out heat hardening, after forming adhesion agent layer, be coated with other sheet component formation masking liquid, form other sheet components by heat or active energy ray.As the device coated by adhesive composition on sheet component, unfilled corner wheel coating machine, dry adhered machine, rotor coating machine, mould painting machine, roller coating machine, rod coater, gravure roll coating machine, oppositely roller coating machine, knife coater (bladecoater), intaglio coating machine, miniature gravure coater etc. can be enumerated.The then dosage that laminate substrate is be coated with on the surface converts in drying, preferably 0.1g/m
2~ 50g/m
2left and right.More preferably 1g/m
2~ 50g/m
2left and right.As laminate substrate, any base material can be selected according to purposes with Arbitrary Digit, be set to more than 3 layers multilayer form time, can laminating each layer all or part of in use adhesive composition of the present invention.
As sheet component formation masking liquid, can enumerate can use in the formation of plastic film polyester based resin solution, polyethylene-based resin solution, polypropylene-based resin solution, polyvinyl chloride resin solution, polycarbonate-based resin solution, polysulfones system resin solution, poly-(methyl) acrylic resin solution, fluorine resin solution etc. are as preference.
Solar cell backside protective sheet can be considered as and the performance, price, productivity etc. that require, select various manufacture method or further those methods combined.
" embodiment "
Below, by embodiment, the present invention is described in more detail, but following embodiment does not impose any restrictions scope of authority of the present invention.In addition, each evaluation in embodiment is carried out according to following method.In addition, in an embodiment, part represents weight part, and % represents wt%, and hydroxyl value represents mgKOH/g.Number average molecular weight, glass transition temperature, hydroxyl value are obtained by such as under type.
< number average molecular weight >
The mensuration of number average molecular weight uses the GPC (hydrogel permeation layer analyzer) " HPC-8020 " of Dong Cao company manufacture, and tubing string uses SHODEXKF-806L2 root, KF-804L1 root, KF-8021 root, and solvent uses tetrahydrofuran (THF).Number average molecular weight converts by polystyrene standard and obtains.
< glass transition temperature (Tg) >
The DSC " RDC220 " that the mensuration of glass transition temperature (Tg) can use Seiko electronics limited-liability company to manufacture and carrying out.The sample that the acrylic polyol A-1 synthesized by the following gimmick ~ acrylic polyol A-21 solution of about 10mg is dry is measured in aluminum pot, be placed on after cooled with liquid nitrogen extremely-100 DEG C in DSC device, according to carrying out heating up with 10 DEG C/min, the DSC of gained schemes and obtains glass transition temperature.
< hydroxyl value >
Hydroxyl value is obtained by such as under type: after the sample dissolution of about 2g is in the pyridine of about 10m1, the volume ratio adding previously prepared diacetyl oxide/pyridine is the mixing solutions 5m1 of 15/85, places 20 hours.Thereafter, add water 1m1 and ethanol 10ml, carry out titration by the potassium hydroxide (ethanolic soln) of 0.1N and obtain.Indicator uses phenolphthalein.
The manufacture > of < acrylic polyol (A)
(synthesis example 1) loads ethyl acetate 100 weight part in 4 mouthfuls of flasks with condenser, nitrogen ingress pipe, dropping funnel and thermometer, is warming up to 80 DEG C.Then dripped with 2 hours monomer fluid butyl acrylate 42.7 weight part, β-dimethyl-aminoethylmethacrylate 51.0 weight part, 2-Hydroxy ethyl acrylate 1.8 weight part and azobisisobutylonitrile base nitrile 2.0 weight part are pre-mixed by dropping funnel.Thereafter make it react 1 hour, next adds azobisisobutylonitrile base nitrile 0.2 weight part makes it react 1 hour, carries out step as above until the transformation efficiency of monomer becomes more than 98%, is then cooled.Then, add ethyl acetate and obtain the solution that solids component is 50%.
(synthesis example 2 ~ synthesis example 21) be Molecular regulator amount by the addition of polymerization initiators azobisisobutylonitrile base nitrile, carries out and the acrylic polyol of the synthesis example 2 ~ synthesis example 21 shown in acquisition table 1 in addition in the same manner as synthesis example 1.In addition, about synthesis example 17, it is the acrylic polyol of the composition represented as synthesis example 1 in patent documentation 2.In addition, the abbreviation in table 1 is as described below.
BA: butyl acrylate, EMA: β-dimethyl-aminoethylmethacrylate, EA: ethyl propenoate, St: vinylbenzene, CHMA: cyclohexyl methacrylate, 2EHA: ethyl acrylate, HEA: 2-Hydroxy ethyl acrylate, 4HBA: vinylformic acid-4-hydroxybutyl, HEMA: hydroxyethyl methacrylate
[table 1]
The allotment example > of < adhesive composition
(embodiment 1 ~ embodiment 5, embodiment 7 ~ embodiment 17, reference example 1, comparative example 1 ~ comparative example 6) relative to the acrylic polyol as host (A) being 100 weight parts for solids component conversion, the polymeric polyisocyanate (B) allocated as stiffening agent using the allotment ratio shown in table 2, and allotment is as silane coupling agent (manufacture of chemical company of " KBM-403 " SHIN-ETSU HANTOTAI) 3.0 weight parts containing glycidyl of additive, and tin dilaurate dioctyl tin (" NEOSTANNU-810 ", day east changes into company and manufactures) 0.01 weight part, with ethyl acetate, solids component is adjusted to 30% further.
[table 2]
* 1 allotment ratio=host: stiffening agent (solids component ratio)
* 2 relative to (A) 100 for weight part (non-volatile composition), allotment KBM-403 (silane coupling agent) 3.0 weight part.
* 3 relative to (A) 100 for weight part (non-volatile composition), allotment U-8100.01 weight part is as reaction promotor.
* 4 stiffening agent A:TakenateD-160N (the TMP adducts upgrading thing of Mitsui Chemicals, Inc.'s manufacture, hexamethylene diisocyanate)
Stiffening agent B:TakenateD-178N (the allophanate upgrading thing of Mitsui Chemicals, Inc.'s manufacture, hexamethylene diisocyanate)
Stiffening agent C: the chlorinated isocyanurates upgrading thing of isophorone diisocyanate)
Stiffening agent D:SumidurN3200 (lives to change the biuret upgrading thing of the manufacture of Bayer Polyurethane (SumikaBayerUrethane) company, hexamethylene diisocyanate
The production example > of < laminated film 1
Use each adhesive composition of embodiment 1 ~ embodiment 5, embodiment 7 ~ embodiment 17, reference example 1 and comparative example 1 ~ comparative example 6, become 4g/m with drying coated amount
2~ 5g/m
2amount and by dry adhered machine, adhesive composition is coated the corona treatment face of polyester film [manufacture of Dong Li company, LumirrorX-10S, thickness are 50 μm].Then, after making solvent evaporates, be laminated on the corona treatment face of another 1 piece of polyester film [manufacture of Dong Li company, LumirrorX-10S, thickness are 50 μm].Thereafter, at 40 DEG C, carry out the hardening treatment (aging) of 3 days, make solid harden and make laminated film 1 thus.
The production example > of < laminated film 2
Use the adhesive composition of embodiment 1 ~ embodiment 4 and comparative example 1 ~ comparative example 3, according to the manufacture method of aforementioned laminated film 1, make the laminated film 2 becoming the formation of [corona treatment polyester film/adhesion agent layer/aluminium foil].
The production example > of < laminated film 3
Use the adhesive composition of embodiment 1 ~ embodiment 4 and comparative example 1 ~ comparative example 3, according to the manufacture method of aforementioned laminated film 1, make the mode that connects with adhesion agent layer with the evaporation layer of silica steam plating polyester film and become the laminated film 3 of the formation of [corona treatment polyester film/adhesion agent layer/silica steam plating polyester film].
In table 2, table 3, represent the combination of host in embodiment 1 ~ embodiment 5, embodiment 7 ~ embodiment 17, reference example 1, comparative example 1 ~ comparative example 6 and stiffening agent, and the initial adhesion of laminated film 1 with 85 DEG C, expose 1000 hours, 2000 hours and 3000 hours under the environment of humidity 85% after adhesion.
And, represent in table 4, table 5 use the laminated film 2 of embodiment 1 ~ embodiment 4, comparative example 1 ~ comparative example 3, the initial adhesion of laminated film 3 with 85 DEG C, expose 1000 hours, 2000 hours and 3000 hours under the environment of humidity 85% after adhesion.Below concrete evaluation method is illustrated.
Before < is aging, aging after adhesion test >
By before aging and aging after described laminated film 1, laminated film 2, laminated film 3 be cut to the size of 200mm × 15mm respectively, 25 DEG C, leave standstill 6 hours under the environment of humidity 65% after, tensile testing machine is used according to the test method(s) of ASTM-D1876-61,25 DEG C, under the environment of humidity 65%, be that 300mm/min carries out T-shaped stripping test with loaded speed.The stripping strength (N/15mm is wide) between PET film/PET film, between PET film/aluminium foil, between PET film/silica steam plating polyester film is represented with the mean value of 5 test pieces.
Adhesion test > after the test of < humidity resistance
Described laminate after aging is cut to respectively the size of 200mm × 15mm, 85 DEG C, leave standstill 1000 hours, 2000 hours, 3000 hours under the environment of humidity 85%.Thereafter, 25 DEG C, leave standstill 6 hours under the environment of humidity 65% after, use tensile testing machine according to the test method(s) of ASTM-D1876-61,25 DEG C, under the environment of humidity 65%, be that 300mm/min carries out T-shaped stripping test with loaded speed.The stripping strength (N/15mm is wide) between PET film/PET film, between PET film/aluminium foil, between PET film/silica steam plating polyester film is represented with the mean value of 5 test pieces.
< metewand >
[the adhesion test before aging]
◎ is excellent in practical: more than 3N/15mm
Zero practical region: 2N/15mm ~ 3N/15mm
Practical lower limit: the 1N/15mm ~ 2N/15mm of △
× can not be practical: less than 1N/15mm
[the adhesion test after the test after aging, humidity resistance test]
◎ is excellent in practical: more than 5N/15mm
Zero practical region: 4N/15mm ~ 5N/15mm
Practical lower limit: the 2N/15mm ~ 4N/15mm of △
× can not be practical: less than 2N/15mm
[table 3]
[table 4]
[table 5]
As shown in Table 3: the adhesive composition of embodiment aging before, aging after adhesion and adhesion after humidity resistance test excellent, can through maintaining Bonding strength for a long time.Therefore, the long-term humidity resistance towards outdoor application of the adhesive composition of those embodiments is excellent.
And, in JISC8917 (the envrionment test method of crystal system solar cell module and endurance test method), will 85 DEG C, humidity is defined as anti-moisture test B-2 in 85% time durable 1000 hours, is known as test method harsh especially.In the present embodiment, show more than 1000 hours, after 3000 hours long-time, also can maintain the characteristic of Bonding strength, adhesive composition of the present invention has long-term humidity resistance fully.
Solar cell backside protective sheet keeps sufficient interlayer Bonding strength (lamination strength) in this kind long-term hot resistance test; delamination is not produced between sheet layer; therefore can contribute to the protection of solar battery element, the maintenance of generating efficiency, the life of solar cell can be contributed to further.The life of solar cell and the universal relevant of solar battery system, certainly guarantee that the viewpoint of the energy beyond fossil oil is considered, also contribute to environment protection.
The multilayer laminated boards material (barrier material, outer wall material, roof Material, solar cell panel material (solar cell backside protective sheet, solar battery surface screening glass), window materials, outdoor floor material, illumination protecting materials, trolley part etc.) that adhesive composition of the present invention can be used as towards outdoor industrial applications such as buildingss provides strong Bonding strength with solid.And, the Bonding strength caused due to hydrolysis etc. when outdoor exposure can be suppressed to pass through in time and reduce, can through maintaining strong Bonding strength for a long time.
Comparative example 1 is the glass transition temperature of acrylic polyol (A) is 55 DEG C, higher than the example of 50 DEG C.The result evaluated obtains: there is no the wettability to base material, initial adhesion is little, the result that adhesion reduces in humidity resistance test.
Comparative example 2 is number average molecular weights of acrylic polyol (A) is 6,000, less than 10, and the example of 000.The result of known evaluation is that the cohesive force of the solid before Aging Step is not enough, and the adhesion before Aging Step is little.When the situation that industrialness is produced, the laminate being wound as the state of roll makes core for upper and lower vertical direction and carry out aging.If the adhesion before Aging Step is little, then reels when aging and easily scatter, be not suitable for industrialness and produce.
Comparative example 3 is number average molecular weights of acrylic polyol (A) is 150,000, is greater than 100, the example of 000.The result of known evaluation is not enough to the wettability of PET film, cannot obtain sufficient adhesion before ageing.Same with comparative example 2 is reel easily to scatter in aging process, is not suitable for industrialness and produces.And, cause adhesion slowly to reduce due to humidity resistance test, and adhesion is natively low, therefore obtains the result lower than practical lower limit after 3000 hours.
Comparative example 4 is that the glass transition temperature of acrylic polyol (A) is-50 DEG C, lower than the example of-40 DEG C.Even if the result of known evaluation is when the situation for surface treatment polyester film, even the adhesion of 3 (N/15mm) left and right also cannot show.
Comparative example 5 is OH values of acrylic polyol (A) is 110, is greater than the example of 100.The result of known evaluation obtains: be cross-linked and become superfluous thus become stone hardened coating film, the result of adherence difference.
Comparative example 6 is allotment amounts of polymeric polyisocyanate (B) is the example of NCO/OH=12.The result of known evaluation carries out the reaction with acrylic polyol (A) before the coating, produces jello, therefore cannot be coated with.
Subject application advocates the right of priority based on No. 2011-078188th, the Japanese patent application case of filing an application on March 31st, 2011, and the contents intact disclosed by this patent application case is incorporated in this specification sheets.
[utilizability in industry]
Laminated chip adhesive composition of the present invention engages the same or different raw-material body person that gets adhered, such as, can use aptly in the joint of the raw-material multilayer laminated boards body of plastics system starting material and metal system.Certainly, be also suitable for plastics system starting material each other, metal system starting material joint each other.Even if laminated chip adhesive composition of the present invention also can maintain high adhesion under being exposed to high-temperature high-humidity environment.Therefore, suitable with solid as the multilayer laminated boards material (barrier material, outer wall material, roof Material, solar cell panel material (solar cell backside protective sheet, solar battery surface screening glass), window materials, outdoor floor material, illumination protecting materials, trolley part etc.) towards outdoor industrial applications such as buildingss.Bonding strength can be maintained through passing through in time for a long time, being therefore particularly suitable for the purposes being strongly required environmental resistance, the such as formation of solar cell backside protective sheet.And, be also suitable for the formation of solar cell surface protective plate.And, laminated chip adhesive composition of the present invention particularly demonstrates high adhesion at the interlayer of the surface-treated layer comprising plastic film, but also can be applicable to aptly in the starting material (also comprising the plastic film of surface free process) of surface free process.
Claims (4)
1. a laminated chip adhesive composition, it comprises acrylic polyol (A) and polymeric polyisocyanate (B), the feature of described laminated chip adhesive composition is: the number average molecular weight of described acrylic polyol (A) is 10,000 ~ 100,000, and hydroxyl value is 1mgKOH/g ~ 100mgKOH/g, glass transition temperature (Tg) is more than-15 DEG C and is less than 10 DEG C in addition, and the hydroxyl being derived from described acrylic polyol (A) is 0.1 ~ 3 with the equivalence ratio NCO/OH of the isocyanate group being derived from described polymeric polyisocyanate (B).
2. laminated chip adhesive composition according to claim 1, is characterized in that: described polymeric polyisocyanate (B) comprises the polymeric polyisocyanate derived by alicyclic diisocyanate or aliphatic diisocyanate.
3. laminated chip adhesive composition according to claim 1 and 2; it is characterized in that: it uses in the manufacture of solar cell backside protective sheet comprising more than 2 layers sheet components, in following purposes: form adhesion agent layer in order to be engaged with each other by described sheet component at least partially.
4. a solar cell backside protective sheet, is characterized in that comprising: the adhesion agent layer formed by laminated chip adhesive composition according to any one of claim 1 to 3; And via described adhesion agent layer the sheet component of more than at least 2 layers of lamination.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-078188 | 2011-03-31 | ||
| JP2011078188 | 2011-03-31 | ||
| PCT/JP2012/000916 WO2012132193A1 (en) | 2011-03-31 | 2012-02-10 | Adhesive agent composition for laminate sheet, and back surface protecting sheet for solar cell |
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| CN103534325A CN103534325A (en) | 2014-01-22 |
| CN103534325B true CN103534325B (en) | 2015-11-25 |
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| CN201280015206.0A Active CN103534325B (en) | 2011-03-31 | 2012-02-10 | Laminated chip adhesive composition and solar cell backside protective sheet |
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| JP (2) | JP5003849B1 (en) |
| KR (1) | KR101850876B1 (en) |
| CN (1) | CN103534325B (en) |
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| JP6160241B2 (en) * | 2013-05-27 | 2017-07-12 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition for solar cell protective sheet |
| JP6241677B2 (en) * | 2014-03-31 | 2017-12-06 | 荒川化学工業株式会社 | Undercoat agent for substrate with copper thin film, substrate with copper thin film and method for producing the same, and conductive film and electrode film |
| JP6491864B2 (en) * | 2014-12-05 | 2019-03-27 | ヘンケルジャパン株式会社 | Adhesive for laminated sheet |
| DE102015224734A1 (en) * | 2015-12-09 | 2017-06-14 | Tesa Se | Composition for the production of pressure-sensitive adhesives |
| JP6726027B2 (en) * | 2016-05-26 | 2020-07-22 | ヘンケルジャパン株式会社 | Adhesive for laminated sheets |
| WO2018092172A1 (en) * | 2016-11-15 | 2018-05-24 | 信越化学工業株式会社 | High efficiency solar cell and method for manufacturing high efficiency solar cell |
| JP6919529B2 (en) * | 2017-11-28 | 2021-08-18 | 株式会社デンソー | Curable resin composition and electrical components using it |
| CN108624216B (en) * | 2018-06-05 | 2021-05-04 | 广州慧谷化学有限公司 | Water-based laser aluminizing transfer coating and preparation method thereof |
| JP7174877B1 (en) | 2022-04-22 | 2022-11-17 | 第一工業製薬株式会社 | Two-component curable polyurethane resin composition |
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| CN101479855A (en) * | 2006-06-21 | 2009-07-08 | 凸版印刷株式会社 | Sheet for sealing rear surface of solar cell |
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| JPH0198612A (en) * | 1987-10-13 | 1989-04-17 | Hitachi Chem Co Ltd | Resin composition for self-adhesive |
| JP2000328035A (en) * | 1999-05-24 | 2000-11-28 | Toyo Ink Mfg Co Ltd | Pressure-sensitive adhesive composition |
| JP2004070296A (en) * | 2002-06-14 | 2004-03-04 | Toray Ind Inc | Polarizing plate protective sheet and polarizing plate |
| JP2005350513A (en) * | 2004-06-08 | 2005-12-22 | Sekisui Chem Co Ltd | Highly weather-resistant elastic adhesive |
| JP2006199842A (en) * | 2005-01-21 | 2006-08-03 | Toyo Ink Mfg Co Ltd | Adhesive composition and adhesive sheet |
| JP5120587B2 (en) * | 2006-05-30 | 2013-01-16 | Ｄｉｃ株式会社 | Adhesive composition |
| US20090116132A1 (en) * | 2006-09-28 | 2009-05-07 | Yuka Hiwatashi | Adhesive composition for optical filter, optical filter and display device |
| WO2009113318A1 (en) * | 2008-03-13 | 2009-09-17 | 株式会社日本触媒 | Solar cell module backsheet |
| JP5531190B2 (en) * | 2009-02-27 | 2014-06-25 | 綜研化学株式会社 | Acrylic adhesive, adhesive sheet for polarizing film and adhesive polarizing film using the same |
| JPWO2011004872A1 (en) * | 2009-07-09 | 2012-12-20 | リンテック株式会社 | Protection sheet for solar cell module |
| TWI545014B (en) * | 2009-09-17 | 2016-08-11 | 東洋油墨製造股份有限公司 | Back protection sheet for solar cell, its manufacturing method and solar cell module |
| JP5423332B2 (en) * | 2009-11-16 | 2014-02-19 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition for laminated sheet |
| JP5504848B2 (en) * | 2009-11-26 | 2014-05-28 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition for laminated sheet |
| KR101403535B1 (en) * | 2010-07-07 | 2014-06-10 | 토요잉크Sc홀딩스주식회사 | Highly-adhesive agent for a solar-cell back-side protective sheet, solar-cell back-side protective sheet, and solar cell module |
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| JP5690583B2 (en) * | 2010-12-28 | 2015-03-25 | ヘンケルジャパン株式会社 | Adhesive for solar battery backsheet |
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| CN101479855A (en) * | 2006-06-21 | 2009-07-08 | 凸版印刷株式会社 | Sheet for sealing rear surface of solar cell |
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| JP5003849B1 (en) | 2012-08-15 |
| CN103534325A (en) | 2014-01-22 |
| TWI548104B (en) | 2016-09-01 |
| WO2012132193A1 (en) | 2012-10-04 |
| JP5935502B2 (en) | 2016-06-15 |
| JP2012214805A (en) | 2012-11-08 |
| TW201242054A (en) | 2012-10-16 |
| KR20140022811A (en) | 2014-02-25 |
| KR101850876B1 (en) | 2018-04-23 |
| JP2012214703A (en) | 2012-11-08 |
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