CA2791015A1 - Photovoltaic module with stabilized polymer - Google Patents
Photovoltaic module with stabilized polymer Download PDFInfo
- Publication number
- CA2791015A1 CA2791015A1 CA2791015A CA2791015A CA2791015A1 CA 2791015 A1 CA2791015 A1 CA 2791015A1 CA 2791015 A CA2791015 A CA 2791015A CA 2791015 A CA2791015 A CA 2791015A CA 2791015 A1 CA2791015 A1 CA 2791015A1
- Authority
- CA
- Canada
- Prior art keywords
- poly
- vinyl butyral
- solar cell
- encapsulant
- methyl
- 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.)
- Abandoned
Links
- 229920000642 polymer Polymers 0.000 title claims description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 170
- -1 poly(vinyl butyral) Polymers 0.000 claims abstract description 106
- 239000004332 silver Substances 0.000 claims abstract description 72
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052709 silver Inorganic materials 0.000 claims abstract description 71
- 239000008393 encapsulating agent Substances 0.000 claims description 82
- 238000000034 method Methods 0.000 claims description 35
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 30
- 239000010408 film Substances 0.000 claims description 29
- 239000010409 thin film Substances 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 27
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 24
- 150000001412 amines Chemical class 0.000 claims description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 21
- 238000003475 lamination Methods 0.000 claims description 19
- 230000001681 protective effect Effects 0.000 claims description 19
- 125000001424 substituent group Chemical group 0.000 claims description 19
- 239000004014 plasticizer Substances 0.000 claims description 18
- 239000006096 absorbing agent Substances 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 150000001565 benzotriazoles Chemical class 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000002845 discoloration Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000003017 thermal stabilizer Substances 0.000 claims description 8
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000002738 chelating agent Substances 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 5
- 239000004611 light stabiliser Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 4
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 3
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 229910021424 microcrystalline silicon Inorganic materials 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- AXWLKJWVMMAXBD-UHFFFAOYSA-N 1-butylpiperidine Chemical compound CCCCN1CCCCC1 AXWLKJWVMMAXBD-UHFFFAOYSA-N 0.000 claims description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- IENXJNLJEDMNTE-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical compound CC(O)=O.NCCN IENXJNLJEDMNTE-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims description 2
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 claims description 2
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 claims description 2
- OUDSFQBUEBFSPS-UHFFFAOYSA-N ethylenediaminetriacetic acid Chemical compound OC(=O)CNCCN(CC(O)=O)CC(O)=O OUDSFQBUEBFSPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 2
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 claims 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 claims 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 claims 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- 239000012964 benzotriazole Substances 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- 238000004383 yellowing Methods 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 235000012431 wafers Nutrition 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 238000000429 assembly Methods 0.000 description 8
- 230000000712 assembly Effects 0.000 description 8
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 7
- FRQDZJMEHSJOPU-UHFFFAOYSA-N Triethylene glycol bis(2-ethylhexanoate) Chemical compound CCCCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CCCC FRQDZJMEHSJOPU-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 5
- 229920002313 fluoropolymer Polymers 0.000 description 5
- 239000004811 fluoropolymer Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 4
- MVXVYAKCVDQRLW-UHFFFAOYSA-N 1h-pyrrolo[2,3-b]pyridine Chemical compound C1=CN=C2NC=CC2=C1 MVXVYAKCVDQRLW-UHFFFAOYSA-N 0.000 description 4
- HRYKDUPGBWLLHO-UHFFFAOYSA-N 8-azaadenine Chemical compound NC1=NC=NC2=NNN=C12 HRYKDUPGBWLLHO-UHFFFAOYSA-N 0.000 description 4
- 239000011358 absorbing material Substances 0.000 description 4
- 238000006359 acetalization reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229920002620 polyvinyl fluoride Polymers 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- SSKNCQWPZQCABD-UHFFFAOYSA-N 2-[2-[2-(2-heptanoyloxyethoxy)ethoxy]ethoxy]ethyl heptanoate Chemical compound CCCCCCC(=O)OCCOCCOCCOCCOC(=O)CCCCCC SSKNCQWPZQCABD-UHFFFAOYSA-N 0.000 description 3
- TZFOEYRGARRRGO-UHFFFAOYSA-N 2h-triazole-4,5-dicarboxylic acid Chemical compound OC(=O)C1=NNN=C1C(O)=O TZFOEYRGARRRGO-UHFFFAOYSA-N 0.000 description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N 4-methyl-1h-indole Chemical compound CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 3
- 229930024421 Adenine Natural products 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- 229960000643 adenine Drugs 0.000 description 3
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 3
- 239000005329 float glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 2
- 150000000177 1,2,3-triazoles Chemical class 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- 150000000182 1,3,5-triazines Chemical class 0.000 description 2
- NZFLWVDXYUGFAV-UHFFFAOYSA-N 1-methyl-2-acetylpyrrole Chemical compound CC(=O)C1=CC=CN1C NZFLWVDXYUGFAV-UHFFFAOYSA-N 0.000 description 2
- HGIJKQXOOIWWGO-UHFFFAOYSA-N 1-prop-2-ynylbenzotriazole Chemical compound C1=CC=C2N(CC#C)N=NC2=C1 HGIJKQXOOIWWGO-UHFFFAOYSA-N 0.000 description 2
- QMNUDYFKZYBWQX-UHFFFAOYSA-N 1H-quinazolin-4-one Chemical compound C1=CC=C2C(=O)N=CNC2=C1 QMNUDYFKZYBWQX-UHFFFAOYSA-N 0.000 description 2
- ADZUEEUKBYCSEY-UHFFFAOYSA-N 1h-indole-5-carbaldehyde Chemical compound O=CC1=CC=C2NC=CC2=C1 ADZUEEUKBYCSEY-UHFFFAOYSA-N 0.000 description 2
- OXQOBQJCDNLAPO-UHFFFAOYSA-N 2,3-Dimethylpyrazine Chemical compound CC1=NC=CN=C1C OXQOBQJCDNLAPO-UHFFFAOYSA-N 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- FKHNZQFCDGOQGV-UHFFFAOYSA-N 2,3-dimethylquinoxaline Chemical compound C1=CC=C2N=C(C)C(C)=NC2=C1 FKHNZQFCDGOQGV-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 2
- LCZUOKDVTBMCMX-UHFFFAOYSA-N 2,5-Dimethylpyrazine Chemical compound CC1=CN=C(C)C=N1 LCZUOKDVTBMCMX-UHFFFAOYSA-N 0.000 description 2
- 239000001934 2,5-dimethylpyrazine Substances 0.000 description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2,5-dimethylpyridine Chemical compound CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 2
- HJFZAYHYIWGLNL-UHFFFAOYSA-N 2,6-Dimethylpyrazine Chemical compound CC1=CN=CC(C)=N1 HJFZAYHYIWGLNL-UHFFFAOYSA-N 0.000 description 2
- LNIMMWYNSBZESE-UHFFFAOYSA-N 2-Ethyl-3-methylpyrazine, 9CI Chemical compound CCC1=NC=CN=C1C LNIMMWYNSBZESE-UHFFFAOYSA-N 0.000 description 2
- IGJQUJNPMOYEJY-UHFFFAOYSA-N 2-acetylpyrrole Chemical compound CC(=O)C1=CC=CN1 IGJQUJNPMOYEJY-UHFFFAOYSA-N 0.000 description 2
- HNXQXTQTPAJEJL-UHFFFAOYSA-N 2-aminopteridin-4-ol Chemical compound C1=CN=C2NC(N)=NC(=O)C2=N1 HNXQXTQTPAJEJL-UHFFFAOYSA-N 0.000 description 2
- GLKCOBIIZKYKFN-UHFFFAOYSA-N 2-aminopteridine-4,7-diol Chemical compound N1=CC(O)=NC2=NC(N)=NC(O)=C21 GLKCOBIIZKYKFN-UHFFFAOYSA-N 0.000 description 2
- QMQDJVIJVPEQHE-UHFFFAOYSA-N 2-methoxy-3-(1-methylpropyl) pyrazine Chemical compound CCC(C)C1=NC=CN=C1OC QMQDJVIJVPEQHE-UHFFFAOYSA-N 0.000 description 2
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 2
- AQSRRZGQRFFFGS-UHFFFAOYSA-N 2-methylpyridin-3-ol Chemical compound CC1=NC=CC=C1O AQSRRZGQRFFFGS-UHFFFAOYSA-N 0.000 description 2
- GNCLPNMQEGMNTG-UHFFFAOYSA-N 2-methylpyridin-4-amine Chemical compound CC1=CC(N)=CC=N1 GNCLPNMQEGMNTG-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- ALHUXMDEZNLFTA-UHFFFAOYSA-N 2-methylquinoxaline Chemical compound C1=CC=CC2=NC(C)=CN=C21 ALHUXMDEZNLFTA-UHFFFAOYSA-N 0.000 description 2
- NURQLCJSMXZBPC-UHFFFAOYSA-N 3,4-dimethylpyridine Chemical compound CC1=CC=NC=C1C NURQLCJSMXZBPC-UHFFFAOYSA-N 0.000 description 2
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 2
- GUSWJGOYDXFJSI-UHFFFAOYSA-N 3,6-dichloropyridazine Chemical compound ClC1=CC=C(Cl)N=N1 GUSWJGOYDXFJSI-UHFFFAOYSA-N 0.000 description 2
- MFEIKQPHQINPRI-UHFFFAOYSA-N 3-Ethylpyridine Chemical compound CCC1=CC=CN=C1 MFEIKQPHQINPRI-UHFFFAOYSA-N 0.000 description 2
- MVRGLMCHDCMPKD-UHFFFAOYSA-N 3-amino-1h-1,2,4-triazole-5-carboxylic acid Chemical compound NC1=NNC(C(O)=O)=N1 MVRGLMCHDCMPKD-UHFFFAOYSA-N 0.000 description 2
- AGJCUQSNRFXRDU-UHFFFAOYSA-N 3-amino-1h-1,2,4-triazole-5-carboxylic acid;hydrate Chemical compound O.NC1=NNC(C(O)=O)=N1 AGJCUQSNRFXRDU-UHFFFAOYSA-N 0.000 description 2
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 2
- UXFSPRAGHGMRSQ-UHFFFAOYSA-N 3-isobutyl-2-methoxypyrazine Chemical compound COC1=NC=CN=C1CC(C)C UXFSPRAGHGMRSQ-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 2
- XCZPDOCRSYZOBI-UHFFFAOYSA-N 5,6,7,8-Tetrahydroquinoxaline Chemical compound C1=CN=C2CCCCC2=N1 XCZPDOCRSYZOBI-UHFFFAOYSA-N 0.000 description 2
- MBNDVRNZPXEYHL-UHFFFAOYSA-N 5-[(3-amino-1h-1,2,4-triazol-5-yl)methyl]-1h-1,2,4-triazol-3-amine Chemical compound NC1=NNC(CC=2NN=C(N)N=2)=N1 MBNDVRNZPXEYHL-UHFFFAOYSA-N 0.000 description 2
- CQLOYHZZZCWHSG-UHFFFAOYSA-N 5-methylquinoxaline Chemical compound C1=CN=C2C(C)=CC=CC2=N1 CQLOYHZZZCWHSG-UHFFFAOYSA-N 0.000 description 2
- ONYNOPPOVKYGRS-UHFFFAOYSA-N 6-methylindole Natural products CC1=CC=C2C=CNC2=C1 ONYNOPPOVKYGRS-UHFFFAOYSA-N 0.000 description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XQVZDADGTFJAFM-UHFFFAOYSA-N Indole-7-carboxaldehyde Chemical compound O=CC1=CC=CC2=C1NC=C2 XQVZDADGTFJAFM-UHFFFAOYSA-N 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001374 small-angle light scattering Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NVMNEWNGLGACBB-UHFFFAOYSA-N sodium;1,2-diaza-4-azanidacyclopenta-2,5-diene Chemical compound [Na+].C=1N=C[N-]N=1 NVMNEWNGLGACBB-UHFFFAOYSA-N 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- RCRHNFLCSMGSSF-UHFFFAOYSA-N st50284608 Chemical compound C1CCC2=NN=C3CCCC4=NN=C1C2=C43 RCRHNFLCSMGSSF-UHFFFAOYSA-N 0.000 description 1
- SJFPWKLCYPPTQM-UHFFFAOYSA-N st50563754 Chemical compound C1=CC2=CC=CC=C2C2=C1C1=NNC(C)=C1N=N2 SJFPWKLCYPPTQM-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- XOXHILFPRYWFOD-UHFFFAOYSA-N sulfachloropyridazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=CC=C(Cl)N=N1 XOXHILFPRYWFOD-UHFFFAOYSA-N 0.000 description 1
- FFJIWWBSBCOKLS-UHFFFAOYSA-N sulfaethoxypyridazine Chemical compound N1=NC(OCC)=CC=C1NS(=O)(=O)C1=CC=C(N)C=C1 FFJIWWBSBCOKLS-UHFFFAOYSA-N 0.000 description 1
- VLYWMPOKSSWJAL-UHFFFAOYSA-N sulfamethoxypyridazine Chemical compound N1=NC(OC)=CC=C1NS(=O)(=O)C1=CC=C(N)C=C1 VLYWMPOKSSWJAL-UHFFFAOYSA-N 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- MFWLMNXHLBAYTJ-UHFFFAOYSA-N sulfuric acid;5,7,7-trimethyl-2,3,5,6-tetrahydropyrrolo[1,2-a]imidazole Chemical compound OS(O)(=O)=O.C1CN2C(C)CC(C)(C)C2=N1 MFWLMNXHLBAYTJ-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OYTCZOJKXCTBHG-UHFFFAOYSA-N terbutylazine-2-hydroxy Chemical compound CCNC1=NC(=O)N=C(NC(C)(C)C)N1 OYTCZOJKXCTBHG-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- XWUFRDJEUOAMNW-UHFFFAOYSA-N tert-butyl 1,2,4-triazole-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1C=NC=N1 XWUFRDJEUOAMNW-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- BJORNXNYWNIWEY-UHFFFAOYSA-N tetrahydrozoline hydrochloride Chemical compound Cl.N1CCN=C1C1C2=CC=CC=C2CCC1 BJORNXNYWNIWEY-UHFFFAOYSA-N 0.000 description 1
- 229940021790 tetrahydrozoline hydrochloride Drugs 0.000 description 1
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 description 1
- JIVZKJJQOZQXQB-UHFFFAOYSA-N tolazoline Chemical compound C=1C=CC=CC=1CC1=NCCN1 JIVZKJJQOZQXQB-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- CAPORZWUTKSILW-UHFFFAOYSA-N triazolealanine Chemical compound OC(=O)C(N)CC1=NC=NN1 CAPORZWUTKSILW-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WPSPBNRWECRRPK-UHFFFAOYSA-N trimethyl(1,2,4-triazol-1-yl)silane Chemical compound C[Si](C)(C)N1C=NC=N1 WPSPBNRWECRRPK-UHFFFAOYSA-N 0.000 description 1
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 1
- NYVOYAFUSJONHU-UHFFFAOYSA-K trisodium;1,3,5-triazine-2,4,6-trithiolate Chemical compound [Na+].[Na+].[Na+].[S-]C1=NC([S-])=NC([S-])=N1 NYVOYAFUSJONHU-UHFFFAOYSA-K 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10678—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising UV absorbers or stabilizers, e.g. antioxidants
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
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- H—ELECTRICITY
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0376—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including amorphous semiconductors
- H01L31/03762—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including amorphous semiconductors including only elements of Group IV of the Periodic Table
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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- 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
- H01L31/06—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 characterised by potential barriers
- H01L31/075—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 characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
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- 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
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- B32B2457/12—Photovoltaic modules
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y02E10/548—Amorphous silicon PV cells
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Abstract
The present invention provides a photovoltaic device comprising metal and a poly(vinyl butyral) layer that incorporates a suitable amount of lH-benzotriazole. When electrical bias is applied to the photovoltaic device, lH-benzotriazole forms a barrier layer at the metal/poly(vinyl butyral) interface, which, for example, unexpectedly virtually eliminated the yellowing of poly(vinyl butyral) in photovoltaic devices comprising silver components.
Description
TITLE OF THE INVENTION
SOLAR CELL MODULES WITH POLY(VINYL BUTYRAL) ENCAPSULANT COMPRISING
UNSATURATED HETEROCYCLIC COMPOUND
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority under 35 U.S.C. 120 to U.S. Provisional Appln. Nos.
61/146,535, filed on January 22, 2009, 61/221,771, filed on June 30, 2009, and 61/226,435, filed on July 17, 2009, each of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The invention is directed to a solar cell module comprising an improved poly(vinyl butyral) composition useful as an encapsulant material for solar cell assemblies. In particular, the improved poly(vinyl butyral) composition is resistant to yellowing upon prolonged contact with components of the assemblies that comprise elemental silver and alloys of elemental silver.
BACKGROUND OF THE INVENTION
Several patents and publications are cited in this description in order to more fully describe the state of the art to which this invention pertains. The entire disclosure of each of these patents and publications is incorporated by reference herein.
Because solar cells provide a sustainable energy resource, their use is rapidly expanding. Solar cells can typically be categorized into two types based on the light absorbing material used, i.e., bulk or wafer-based solar cells and thin film solar cells.
Monocrystalline silicon (c-Si), poly- or multi-crystalline silicon (poly-Si or me-Si) and ribbon silicon are the materials used most commonly in forming the more traditional wafer-based solar cells. Solar cell modules derived from wafer-based solar cells often comprise a series of about 180 and about 240 pm thick self-supporting wafers (or cells) that are soldered together. Such a panel of solar cells, along with a layer of conductive paste and/or connecting wires deposited on its surface, may be referred to as a solar cell assembly and encapsulated by or sandwiched or laminated between polymeric encapsulants, which may be further sandwiched between two protective outer layers to form a weather resistant module. The protective outer layers may be formed of glass, metal sheets or films, or plastic sheets or films. In general, however, the outer layer that faces to the sunlight should be sufficiently transparent to allow photons reach the solar cells.
In the increasingly important alternative, thin film solar cells, the commonly used materials include amorphous silicon (a-Si), microcrystalline silicon (pc-Si), cadmium telluride (CdTe), copper indium selenide (CulnSe2 or CIS), copper indium/gallium diselenide (CulnXGa(,_ x)Se2 or GIGS), light absorbing dyes, organic semiconductors, etc. By way of example, thin film solar cells are described in U.S. Patent Nos. 5,507,881; 5,512,107; 5,948,176;
5,994,163;
hNSDOCID: <WO_20100e5664A1_I >
6,040,521; 6, 123,824; 6,137,048; 6,288,325; 6,258,620; 6,613,603; and 6,784,301; and U.S.
Patent Publication Nos. 20070298590; 20070281090; 20070240759; 20070232057;
20070238285;20070227578;20070209699; 20070079866; 20080223436; and 20080271675.
Thin film solar cells with a typical thickness of less than 2 pm are produced by depositing the semiconductor materials onto a substrate in multi-layers. Further, connecting wires, metal conductive coatings, and/or metal reflector films may be deposited over the surface of the thin film solar cells to constitute part of the thin film solar cell assembly. The substrate may be formed of glass or a flexible film and may also be referred to as superstrate in those modules in which it faces to the sunlight. Similarly to the wafer-based solar cell modules, the thin film solar cell assemblies are further encapsulated by or laminated or sandwiched between polymeric encapsulants, which are further laminated or sandwiched between protective outer layers. In certain solar cell modules, the thin film solar cell assembly may be only partially encapsulated by the encapsulant, so that only the side of the thin film solar cell assembly that is opposite from the substrate (or superstrate) is laminated to a polymeric encapsulant and then a protective outer layer. In such a construction, the thin film solar cell assembly is sandwiched between the substrate (or superstrate) and the encapsulant on the opposite side.
Within the solar cell modules, some components (such as connecting wires, conductive paste (used in wafer-based solar cell modules), conductive coatings (used in thin film solar cells) and back reflector films) may comprise oxidizable silver or a silver alloy. When in contact with an oxidizable silver component, an encapsulant comprising poly(vinyl butyral) (PVB) tends to discolor over time. Discoloration is not desirable in the photovoltaic industry, because it decreases the transmission of light, and because it may be considered aesthetically unpleasing.
Thus, there is a need to develop a PVB composition that is useful as an encapsulant material for solar cell modules and that has improved resistance to discoloration when in prolonged contact with oxidizable silver components.
SUMMARY OF THE INVENTION
A solar cell module comprising a solar cell assembly encapsulated by poly(vinyl butyral) and containing a silver component, wherein the silver component is at least partially in contact with the poly(vinyl butyral) and the poly(vinyl butyral) comprises about 15 to about 45 wt% of plasticizer and about 0.5 to about 2 wt%, preferably about 0.1 to about 2 wt%, of unsaturated heterocyclic compound, based on the total weight of the poly(vinyl butyral).
An assembly for preparing a solar cell module comprising a solar cell assembly, which comprises a silver component, and a poly(vinyl butyral) sheet having a thickness of about 0.25 mm to about 1.2 mm and comprising about 15 to about 45 wt% of plasticizer and about 0.5 to about 2 wt%, preferably about 0.1 to about 2 wt%, of unsaturated heterocyclic compound, based on the total weight of the poly(vinyl butyral) sheet.
SOLAR CELL MODULES WITH POLY(VINYL BUTYRAL) ENCAPSULANT COMPRISING
UNSATURATED HETEROCYCLIC COMPOUND
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority under 35 U.S.C. 120 to U.S. Provisional Appln. Nos.
61/146,535, filed on January 22, 2009, 61/221,771, filed on June 30, 2009, and 61/226,435, filed on July 17, 2009, each of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The invention is directed to a solar cell module comprising an improved poly(vinyl butyral) composition useful as an encapsulant material for solar cell assemblies. In particular, the improved poly(vinyl butyral) composition is resistant to yellowing upon prolonged contact with components of the assemblies that comprise elemental silver and alloys of elemental silver.
BACKGROUND OF THE INVENTION
Several patents and publications are cited in this description in order to more fully describe the state of the art to which this invention pertains. The entire disclosure of each of these patents and publications is incorporated by reference herein.
Because solar cells provide a sustainable energy resource, their use is rapidly expanding. Solar cells can typically be categorized into two types based on the light absorbing material used, i.e., bulk or wafer-based solar cells and thin film solar cells.
Monocrystalline silicon (c-Si), poly- or multi-crystalline silicon (poly-Si or me-Si) and ribbon silicon are the materials used most commonly in forming the more traditional wafer-based solar cells. Solar cell modules derived from wafer-based solar cells often comprise a series of about 180 and about 240 pm thick self-supporting wafers (or cells) that are soldered together. Such a panel of solar cells, along with a layer of conductive paste and/or connecting wires deposited on its surface, may be referred to as a solar cell assembly and encapsulated by or sandwiched or laminated between polymeric encapsulants, which may be further sandwiched between two protective outer layers to form a weather resistant module. The protective outer layers may be formed of glass, metal sheets or films, or plastic sheets or films. In general, however, the outer layer that faces to the sunlight should be sufficiently transparent to allow photons reach the solar cells.
In the increasingly important alternative, thin film solar cells, the commonly used materials include amorphous silicon (a-Si), microcrystalline silicon (pc-Si), cadmium telluride (CdTe), copper indium selenide (CulnSe2 or CIS), copper indium/gallium diselenide (CulnXGa(,_ x)Se2 or GIGS), light absorbing dyes, organic semiconductors, etc. By way of example, thin film solar cells are described in U.S. Patent Nos. 5,507,881; 5,512,107; 5,948,176;
5,994,163;
hNSDOCID: <WO_20100e5664A1_I >
6,040,521; 6, 123,824; 6,137,048; 6,288,325; 6,258,620; 6,613,603; and 6,784,301; and U.S.
Patent Publication Nos. 20070298590; 20070281090; 20070240759; 20070232057;
20070238285;20070227578;20070209699; 20070079866; 20080223436; and 20080271675.
Thin film solar cells with a typical thickness of less than 2 pm are produced by depositing the semiconductor materials onto a substrate in multi-layers. Further, connecting wires, metal conductive coatings, and/or metal reflector films may be deposited over the surface of the thin film solar cells to constitute part of the thin film solar cell assembly. The substrate may be formed of glass or a flexible film and may also be referred to as superstrate in those modules in which it faces to the sunlight. Similarly to the wafer-based solar cell modules, the thin film solar cell assemblies are further encapsulated by or laminated or sandwiched between polymeric encapsulants, which are further laminated or sandwiched between protective outer layers. In certain solar cell modules, the thin film solar cell assembly may be only partially encapsulated by the encapsulant, so that only the side of the thin film solar cell assembly that is opposite from the substrate (or superstrate) is laminated to a polymeric encapsulant and then a protective outer layer. In such a construction, the thin film solar cell assembly is sandwiched between the substrate (or superstrate) and the encapsulant on the opposite side.
Within the solar cell modules, some components (such as connecting wires, conductive paste (used in wafer-based solar cell modules), conductive coatings (used in thin film solar cells) and back reflector films) may comprise oxidizable silver or a silver alloy. When in contact with an oxidizable silver component, an encapsulant comprising poly(vinyl butyral) (PVB) tends to discolor over time. Discoloration is not desirable in the photovoltaic industry, because it decreases the transmission of light, and because it may be considered aesthetically unpleasing.
Thus, there is a need to develop a PVB composition that is useful as an encapsulant material for solar cell modules and that has improved resistance to discoloration when in prolonged contact with oxidizable silver components.
SUMMARY OF THE INVENTION
A solar cell module comprising a solar cell assembly encapsulated by poly(vinyl butyral) and containing a silver component, wherein the silver component is at least partially in contact with the poly(vinyl butyral) and the poly(vinyl butyral) comprises about 15 to about 45 wt% of plasticizer and about 0.5 to about 2 wt%, preferably about 0.1 to about 2 wt%, of unsaturated heterocyclic compound, based on the total weight of the poly(vinyl butyral).
An assembly for preparing a solar cell module comprising a solar cell assembly, which comprises a silver component, and a poly(vinyl butyral) sheet having a thickness of about 0.25 mm to about 1.2 mm and comprising about 15 to about 45 wt% of plasticizer and about 0.5 to about 2 wt%, preferably about 0.1 to about 2 wt%, of unsaturated heterocyclic compound, based on the total weight of the poly(vinyl butyral) sheet.
2 BNSDOCID: WO_2010085664A1_I_>
A process of preventing discoloration of poly(vinyl butyral) encapsulant in a solar cell module comprising a solar cell assembly that comprises a silver component in complete or partial contact with the polyvinyl butyral) encapsulant, comprising providing a polyvinyl butyral) comprising about 15 to about 45 wt% of plasticizer and about 0.5 to about 2 wt%, preferably about 0.1 to about 2 wt%, of unsaturated heterocyclic compound, based on the total weight of the poly(vinyl butyral), and encapsulating a solar cell assembly with the poly(vinyl butyral).
A process of preventing discoloration of poly(vinyl butyral) encapsulant in a solar cell module comprising a solar cell assembly that comprises a silver component in complete or partial contact with the poly(vinyl butyral) encapsulant, comprising providing a poly(vinyl butyral) sheet having a thickness of about 0.25 mm to about 1.2 comprising about 15 to about 45 wt% of plasticizer and about 0.5 to about 2 wt%, preferably about 0.1 to about 2 wt%, of unsaturated heterocyclic compound, based on the total weight of the poly(vinyl butyral), and forming a solar cell module including the step of laminating the solar cell assembly to the poly(vinyl butyral) sheet.
DETAILED DESCRIPTION OF THE INVENTION
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the specification, including definitions, will control.
Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, suitable methods and materials are described herein.
Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.
When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.
When the term "about" is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to.
As used herein, the terms "comprises," "comprising," "includes," "including,"
"containing,"
"characterized by," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
A process of preventing discoloration of poly(vinyl butyral) encapsulant in a solar cell module comprising a solar cell assembly that comprises a silver component in complete or partial contact with the polyvinyl butyral) encapsulant, comprising providing a polyvinyl butyral) comprising about 15 to about 45 wt% of plasticizer and about 0.5 to about 2 wt%, preferably about 0.1 to about 2 wt%, of unsaturated heterocyclic compound, based on the total weight of the poly(vinyl butyral), and encapsulating a solar cell assembly with the poly(vinyl butyral).
A process of preventing discoloration of poly(vinyl butyral) encapsulant in a solar cell module comprising a solar cell assembly that comprises a silver component in complete or partial contact with the poly(vinyl butyral) encapsulant, comprising providing a poly(vinyl butyral) sheet having a thickness of about 0.25 mm to about 1.2 comprising about 15 to about 45 wt% of plasticizer and about 0.5 to about 2 wt%, preferably about 0.1 to about 2 wt%, of unsaturated heterocyclic compound, based on the total weight of the poly(vinyl butyral), and forming a solar cell module including the step of laminating the solar cell assembly to the poly(vinyl butyral) sheet.
DETAILED DESCRIPTION OF THE INVENTION
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the specification, including definitions, will control.
Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, suitable methods and materials are described herein.
Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.
When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.
When the term "about" is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to.
As used herein, the terms "comprises," "comprising," "includes," "including,"
"containing,"
"characterized by," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
3 ONSDOCID <WO_2010085664A1_I_,
4 PCT/US2010/021829 The term "or", as used herein, is inclusive; that is, the phrase "A or B"
means "A, B, or both A and B". Exclusive "or" is designated herein by terms such as "either A
or B" and "one of A or B", for example.
The transitional phrase "consisting essentially of' limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the claimed invention.
Where applicants have defined an invention or a portion thereof with an open-ended term such as "comprising," it should be readily understood that unless otherwise stated the description should be interpreted to also describe such an invention using the terms "consisting essentially of and "consisting of'.
The articles "a" and "an" may be employed in connection with various elements and components of compositions, processes or structures described herein. This is merely for convenience and to give a general sense of the compositions, processes or structures. Such a description includes "one or at least one" of the elements or components.
Moreover, as used herein, the singular articles also include a description of a plurality of elements or components, unless it is apparent from a specific context that the plural is excluded.
As used herein, the term "copolymer" refers to polymers comprising copolymerized units resulting from copolymerization of two or more comonomers. Such copolymers include dipolymers, terpolymers or higher order copolymers. In this connection, a copolymer may be described herein with reference to its constituent comonomers or to the amounts of its constituent comonomers, for example "a copolymer comprising ethylene and 18 weight % of acrylic acid", or a similar description. Such a description may be considered informal in that it does not refer to the comonomers as copolymerized units; in that it does not include a conventional nomenclature for the copolymer, for example International Union of Pure and Applied Chemistry (IUPAC) nomenclature; in that it does not use product-by-process terminology; or for another reason. As used herein, however, a description of a copolymer with reference to its constituent comonomers or to the amounts of its constituent comonomers means that the copolymer contains copolymerized units (in the specified amounts when specified) of the specified comonomers. It follows as a corollary that a copolymer is not the product of a reaction mixture containing given comonomers in given amounts, unless expressly stated in limited circumstances to be such.
An improved poly(vinyl butyral) (PVB) composition useful as an encapsulant material in solar cell modules comprises (a) a PVB polymer at a level of about 85 wt%, or about 80 wt%, or about 75 to about 55 wt%, or about 65 wt%, or about 70 wt%; (b) one or more plasticizers at a level of about 15 wt%, or about 20 wt%, or about 25 wt% to about 45 wt%, or about 35 wt%, or about 30 wt%, based on the total weight of the PVB composition, and (c) one or more unsaturated heterocyclic compounds at a level of about 0.1 wt%, or about 0.15 wt%, or about 0.1 wt% to about 2 wt%, or about 0.2 wt% to about 1 wt%, or about 0.5 wt% to about 2 wt%, or BNSDOCID: <WO_20100B5664A1_I_n about 0.8 wt%, or about 0.75 wt%, or about 0.5 wt%, or about 0.4 wt%, or about 0.3 wt% based on the total weight of the PVB composition. The amount of PVB resin may be adjusted by subtracting the weight percentage of the heterocyclic compound(s) and of any other additives described herein, so that the sum of the weight percentages of the components of the improved PVB composition is 100 wt%. The improved PVB composition exhibits reduced yellowing after prolonged contact with silver-containing components of the solar cell module.
PVB is a vinyl resin resulting from the condensation of poly(vinyl alcohol) with butyraldehyde. The PVB may be produced by aqueous or solvent acetalization. In a solvent process, acetalization is carried out in the presence of sufficient solvent to dissolve the PVB and produce a homogeneous solution at the end of acetalization. The PVB is separated from solution by precipitation of solid particles with water, which are then washed and dried.
Solvents used are lower aliphatic alcohols such as ethanol. In an aqueous process, acetalization is carried out by adding butyraldehyde to a water solution of poly(vinyl alcohol) at a temperature of about 20 C to about 100 C, in the presence of an acid catalyst, agitating the mixture to cause an intermediate PVB to precipitate in finely divided form and continuing the agitation while heating until the reaction mixture has proceeded to the desired end point, followed by neutralization of the catalyst, separation, stabilization and drying of the PVB. For example, PVB can be produced as described in U.S. Patent Nos. 3,153,009 and 4,696,971.
Suitable PVB resins have a weight average molecular weight of about 30,000 Da, or about 45,000 Da, or about 200,000 Da to about 600,000 Da, or about 300,000 Da, as determined by size exclusion chromatography using low angle laser light scattering. The PVB
may comprise about 12 wt%, or about 14 wt%, or about 15 wt%, to about 23 wt%, or about 21 wt%, or about 19.5 wt%, or about 19 wt% of hydroxyl groups calculated as polyvinyl alcohol (PVOH). The hydroxyl number can be determined according to standard methods, such as ASTM D1396-92 (1998). In addition, the PVB used here may include up to about 10%, or up to about 3% of residual ester groups, calculated as polyvinyl ester, typically acetate groups, with the balance being butyraldehyde acetal. The PVB may further comprise a minor amount of acetal groups other than butyral, for example, 2-ethyl hexanal, as described in U.S. Patent No.
means "A, B, or both A and B". Exclusive "or" is designated herein by terms such as "either A
or B" and "one of A or B", for example.
The transitional phrase "consisting essentially of' limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the claimed invention.
Where applicants have defined an invention or a portion thereof with an open-ended term such as "comprising," it should be readily understood that unless otherwise stated the description should be interpreted to also describe such an invention using the terms "consisting essentially of and "consisting of'.
The articles "a" and "an" may be employed in connection with various elements and components of compositions, processes or structures described herein. This is merely for convenience and to give a general sense of the compositions, processes or structures. Such a description includes "one or at least one" of the elements or components.
Moreover, as used herein, the singular articles also include a description of a plurality of elements or components, unless it is apparent from a specific context that the plural is excluded.
As used herein, the term "copolymer" refers to polymers comprising copolymerized units resulting from copolymerization of two or more comonomers. Such copolymers include dipolymers, terpolymers or higher order copolymers. In this connection, a copolymer may be described herein with reference to its constituent comonomers or to the amounts of its constituent comonomers, for example "a copolymer comprising ethylene and 18 weight % of acrylic acid", or a similar description. Such a description may be considered informal in that it does not refer to the comonomers as copolymerized units; in that it does not include a conventional nomenclature for the copolymer, for example International Union of Pure and Applied Chemistry (IUPAC) nomenclature; in that it does not use product-by-process terminology; or for another reason. As used herein, however, a description of a copolymer with reference to its constituent comonomers or to the amounts of its constituent comonomers means that the copolymer contains copolymerized units (in the specified amounts when specified) of the specified comonomers. It follows as a corollary that a copolymer is not the product of a reaction mixture containing given comonomers in given amounts, unless expressly stated in limited circumstances to be such.
An improved poly(vinyl butyral) (PVB) composition useful as an encapsulant material in solar cell modules comprises (a) a PVB polymer at a level of about 85 wt%, or about 80 wt%, or about 75 to about 55 wt%, or about 65 wt%, or about 70 wt%; (b) one or more plasticizers at a level of about 15 wt%, or about 20 wt%, or about 25 wt% to about 45 wt%, or about 35 wt%, or about 30 wt%, based on the total weight of the PVB composition, and (c) one or more unsaturated heterocyclic compounds at a level of about 0.1 wt%, or about 0.15 wt%, or about 0.1 wt% to about 2 wt%, or about 0.2 wt% to about 1 wt%, or about 0.5 wt% to about 2 wt%, or BNSDOCID: <WO_20100B5664A1_I_n about 0.8 wt%, or about 0.75 wt%, or about 0.5 wt%, or about 0.4 wt%, or about 0.3 wt% based on the total weight of the PVB composition. The amount of PVB resin may be adjusted by subtracting the weight percentage of the heterocyclic compound(s) and of any other additives described herein, so that the sum of the weight percentages of the components of the improved PVB composition is 100 wt%. The improved PVB composition exhibits reduced yellowing after prolonged contact with silver-containing components of the solar cell module.
PVB is a vinyl resin resulting from the condensation of poly(vinyl alcohol) with butyraldehyde. The PVB may be produced by aqueous or solvent acetalization. In a solvent process, acetalization is carried out in the presence of sufficient solvent to dissolve the PVB and produce a homogeneous solution at the end of acetalization. The PVB is separated from solution by precipitation of solid particles with water, which are then washed and dried.
Solvents used are lower aliphatic alcohols such as ethanol. In an aqueous process, acetalization is carried out by adding butyraldehyde to a water solution of poly(vinyl alcohol) at a temperature of about 20 C to about 100 C, in the presence of an acid catalyst, agitating the mixture to cause an intermediate PVB to precipitate in finely divided form and continuing the agitation while heating until the reaction mixture has proceeded to the desired end point, followed by neutralization of the catalyst, separation, stabilization and drying of the PVB. For example, PVB can be produced as described in U.S. Patent Nos. 3,153,009 and 4,696,971.
Suitable PVB resins have a weight average molecular weight of about 30,000 Da, or about 45,000 Da, or about 200,000 Da to about 600,000 Da, or about 300,000 Da, as determined by size exclusion chromatography using low angle laser light scattering. The PVB
may comprise about 12 wt%, or about 14 wt%, or about 15 wt%, to about 23 wt%, or about 21 wt%, or about 19.5 wt%, or about 19 wt% of hydroxyl groups calculated as polyvinyl alcohol (PVOH). The hydroxyl number can be determined according to standard methods, such as ASTM D1396-92 (1998). In addition, the PVB used here may include up to about 10%, or up to about 3% of residual ester groups, calculated as polyvinyl ester, typically acetate groups, with the balance being butyraldehyde acetal. The PVB may further comprise a minor amount of acetal groups other than butyral, for example, 2-ethyl hexanal, as described in U.S. Patent No.
5,137, 954.
Plasticizers suitable for the PVB compositions may be any of those that known within the art (see, e.g., U.S. Patent Nos. 3,841,890; 4,144,217; 4,276,351; 4,335,036;
4,902,464;
5,013,779; and 5,886,075). Among those commonly used plasticizers are esters of a polybasic acid or a polyhydric alcohol. Specific examples of suitable plasticizers include, but are not limited to, diesters obtained from the reaction of triethylene glycol or tetraethylene glycol with aliphatic carboxylic acids having from 6 to 10 carbon atoms; diesters obtained from the reaction of sebacic acid with aliphatic alcohols having from 1 to 18 carbon atoms;
oligoethylene glycol di-2-ethylhexanoate; tetraethylene glycol di-n-heptanoate; dihexyl adipate;
dioctyl adipate;
dibutoxy ethyl adipate; mixtures of heptyl and nonyl adipates; dibutyl sebacate; tributoxyethyl-BNSDOCID: cWO_2010085664A1 I >
phosphate; isodecylphenylphosphate; triisopropylphosphite; polymeric plasticizers, such as, the oil-modified sebacid alkyds; mixtures of phosphates and adipates; mixtures of adipates and alkyl benzyl phthalates; and combinations of two or more of the above.
Preferred plasticizers include triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, and combinations of two or more thereof. More preferred plasticizers include triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-n-heptanoate, and combination of two or more thereof. A plasticizer of note is triethylene glycol di-2-ethylhexanoate.
The PVB composition further comprises one or more unsaturated heterocylic compounds. As used herein, the term "unsaturated heterocylic compounds"
includes 1 H-benzotriazole and non-2H substituted benzotriazole derivatives having a formula of:
R
R N
N
R N
\
R R
1,2,3-triazole and 1,2,3-triazole derivatives having a formula of:
R
R i/N
R
1,2,4-triazole and 1,2,4-triazole derivatives having a formula of:
R
N
R'/ `11 N
R
imidazole and imidazole derivatives having a formula of:
R
R N R
{
pyrrole and pyrrole derivatives having a formula of:
R R
/
R N R
Plasticizers suitable for the PVB compositions may be any of those that known within the art (see, e.g., U.S. Patent Nos. 3,841,890; 4,144,217; 4,276,351; 4,335,036;
4,902,464;
5,013,779; and 5,886,075). Among those commonly used plasticizers are esters of a polybasic acid or a polyhydric alcohol. Specific examples of suitable plasticizers include, but are not limited to, diesters obtained from the reaction of triethylene glycol or tetraethylene glycol with aliphatic carboxylic acids having from 6 to 10 carbon atoms; diesters obtained from the reaction of sebacic acid with aliphatic alcohols having from 1 to 18 carbon atoms;
oligoethylene glycol di-2-ethylhexanoate; tetraethylene glycol di-n-heptanoate; dihexyl adipate;
dioctyl adipate;
dibutoxy ethyl adipate; mixtures of heptyl and nonyl adipates; dibutyl sebacate; tributoxyethyl-BNSDOCID: cWO_2010085664A1 I >
phosphate; isodecylphenylphosphate; triisopropylphosphite; polymeric plasticizers, such as, the oil-modified sebacid alkyds; mixtures of phosphates and adipates; mixtures of adipates and alkyl benzyl phthalates; and combinations of two or more of the above.
Preferred plasticizers include triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, and combinations of two or more thereof. More preferred plasticizers include triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-n-heptanoate, and combination of two or more thereof. A plasticizer of note is triethylene glycol di-2-ethylhexanoate.
The PVB composition further comprises one or more unsaturated heterocylic compounds. As used herein, the term "unsaturated heterocylic compounds"
includes 1 H-benzotriazole and non-2H substituted benzotriazole derivatives having a formula of:
R
R N
N
R N
\
R R
1,2,3-triazole and 1,2,3-triazole derivatives having a formula of:
R
R i/N
R
1,2,4-triazole and 1,2,4-triazole derivatives having a formula of:
R
N
R'/ `11 N
R
imidazole and imidazole derivatives having a formula of:
R
R N R
{
pyrrole and pyrrole derivatives having a formula of:
R R
/
R N R
6 BNSDOCID: cWO 2010085664A1 I
pyrazine and pyrazine derivatives having a formula of:
R IN R
R N R
pyrimidine and pyrimidine derivatives having a formula of:
R
R N
R N' 'R
pyridine and pyridine derivatives having a formula of:
R
R R
R N R
pyridizine and pyridizine derivatives having a formula of, R ~N
R R
R
thiazole and thiazole derivatives having a formula of:
R \ y_NR
S
R
benzoxazole and benzoxazole derivatives having a formula of:
R
R O
/ N~R
R
R
benzothiazole and benzothiazole derivatives having a formula of:
pyrazine and pyrazine derivatives having a formula of:
R IN R
R N R
pyrimidine and pyrimidine derivatives having a formula of:
R
R N
R N' 'R
pyridine and pyridine derivatives having a formula of:
R
R R
R N R
pyridizine and pyridizine derivatives having a formula of, R ~N
R R
R
thiazole and thiazole derivatives having a formula of:
R \ y_NR
S
R
benzoxazole and benzoxazole derivatives having a formula of:
R
R O
/ N~R
R
R
benzothiazole and benzothiazole derivatives having a formula of:
7 BNSDOCID: cWO_2010065664A1_I_>
R
R
/>-R
R \ N
R
1,3,5-triazine and 1,3,5-triazine derivatives having a formula of:
R` R
--N
NT
R
2,2'-bipyridine and 2,2'-bipyridine derivatives having a formula of:
R
R R R
R I N
N R
R
R
wherein R represents a hydrogen atom or a substituent (also referred to herein as an "R group"
or "substituent R"); and wherein, when the unsaturated heterocyclic compound comprises more than one substituent, the substituents may be identical or different. Each substituent is independently selected from the group consisting of alkyl groups that are branched or unbranched, linear or cyclic; other non-aromatic hydrocarbon groups, such as alkenyl groups and alkynyl groups, that are also unbranched or branched, linear or cyclic, that are singly or multiply unsaturated and that contain C=C (double) or C=C (triple) bonds;
substituted or unsubstituted aromatic hydrocarbon groups, including aryl groups (e.g., phenyl and naphthyl groups); amino groups; hydroxyl groups; alkoxy groups; and halogens (e.g., F, Cl, Br, or I, preferably Cl or Br). In addition, one or more of the hydrogen atoms on one or more of the R
groups may optionally be substituted with a halogen atom or a branched or unbranched alkyl group comprising 1 to 4 carbon atoms. When more than one of the hydrogen atoms of the R
group(s) are substituted, these substituents may also be the same or different.
Preferred substituents R include branched alkyl groups, unbranched alkyl groups, cyclic alkyl groups, unsaturated hydrocarbon groups, substituted aryl groups, unsubstituted aryl groups, and halogen atoms. Branched or linear alkyl groups comprising I to 4 carbon atoms, and in particular methyl groups, are more preferred substituents R. Other examples of suitable substituents R are found below in the lists of specific examples of unsaturated heterocyclic compounds.
More specifically with respect to benzotriazole, it is well known that this compound exists as two tautomers, 1 H-benzotriazole (numbered structure (1), below) and 2H-benzotriazole (numbered structure (ii), below). Because of symmetry, 3H-benzotriazole is equivalent to 1 H-
R
R
/>-R
R \ N
R
1,3,5-triazine and 1,3,5-triazine derivatives having a formula of:
R` R
--N
NT
R
2,2'-bipyridine and 2,2'-bipyridine derivatives having a formula of:
R
R R R
R I N
N R
R
R
wherein R represents a hydrogen atom or a substituent (also referred to herein as an "R group"
or "substituent R"); and wherein, when the unsaturated heterocyclic compound comprises more than one substituent, the substituents may be identical or different. Each substituent is independently selected from the group consisting of alkyl groups that are branched or unbranched, linear or cyclic; other non-aromatic hydrocarbon groups, such as alkenyl groups and alkynyl groups, that are also unbranched or branched, linear or cyclic, that are singly or multiply unsaturated and that contain C=C (double) or C=C (triple) bonds;
substituted or unsubstituted aromatic hydrocarbon groups, including aryl groups (e.g., phenyl and naphthyl groups); amino groups; hydroxyl groups; alkoxy groups; and halogens (e.g., F, Cl, Br, or I, preferably Cl or Br). In addition, one or more of the hydrogen atoms on one or more of the R
groups may optionally be substituted with a halogen atom or a branched or unbranched alkyl group comprising 1 to 4 carbon atoms. When more than one of the hydrogen atoms of the R
group(s) are substituted, these substituents may also be the same or different.
Preferred substituents R include branched alkyl groups, unbranched alkyl groups, cyclic alkyl groups, unsaturated hydrocarbon groups, substituted aryl groups, unsubstituted aryl groups, and halogen atoms. Branched or linear alkyl groups comprising I to 4 carbon atoms, and in particular methyl groups, are more preferred substituents R. Other examples of suitable substituents R are found below in the lists of specific examples of unsaturated heterocyclic compounds.
More specifically with respect to benzotriazole, it is well known that this compound exists as two tautomers, 1 H-benzotriazole (numbered structure (1), below) and 2H-benzotriazole (numbered structure (ii), below). Because of symmetry, 3H-benzotriazole is equivalent to 1 H-
8 BNSOOCIL: cW0_201GD85664A1_I_>
triazole; however, asymmetrical substitution with one or more non-hydrogen R
groups will destroy this equivalence.
H
7 I N\N 7 `NH 2 (i) (ii) 5 Moreover, as used herein, the term "non-2H-substituted" refers to benzotriazole derivatives having no hydrogen atom or other substituent bound to nitrogen atom 2. Stated alternatively, the term "non-2H-substituted" includes the 1 H and 3H tautomers of benzotriazole and derivatives of these tautomers in which there is a hydrogen atom or a substituent R bound to nitrogen atom 1 of I H-benzotriazole or to nitrogen atom 3 of 3H-benzotriazole. 2H-Benzotriazole and derivatives of this tautomer in which there is a hydrogen atom or a substituent R bound to nitrogen atom 2 are not included. For example, 1-propargyl-1 H-benzotriazole (structure (i), below) is a non-2H-substituted benzotriazole;
therefore, it is within the definition of "unsaturated heterocyclic compounds," as that term is used herein. In contrast, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol (structure (ii), below) is a 2H-substituted benzotriazole; therefore, it is not included in the definition of "unsaturated heterocyclic compounds".
N He W~
N
C_zCH (i) CH3 (ii) In summary, benzotriazole compounds are included in or excluded from the definition of "unsaturated heterocyclic compounds" based solely on their "non-2H
substituted" structure. In this connection, the definition of "non-2H substituted" set forth above is not to be superceded by principles of nomenclature that may be inconsistent with the structural descriptions herein.
Accordingly, examples of suitable benzotriazole derivatives include, but are not limited to, 1-methyl-1 H-benzotriazole, 5-methyl-1 H-benzotriazole, 1-aminobenzotriazole, 4-hydroxy-1 H-benzotriazole, 1-cyanobenzotriazole, 1H-benzotriazole-1-carboxaldehyde, 1,6-dimethyl-1H-1,2,3-benzotriazole, 1H-benzotriazole-1-methanol, 1-hydroxybenzotriazole hydrate, 5-chlorobenzotriazole, 1-propargyl-1 H-benzotriazole, 1 H-benzotriazol-1-ylmethyl isocyanide, 1 H-benzotriazole-l-acetonitrile, I-allylbenzotriazole, benzotriazole-1-carboxamide, benzotriazole-5-carboxylic acid, 1-(methoxymethyl)-1 H-benzotriazole, 5,6-dimethyl-1 H-benzotriazole monohydrate, 1-(chloromethyl)-1H-benzotriazole, 6-chloro-1-hydroxybenzotriazole dehydrate, 1-(2-methyl-allyl) -1 H-benzotriazole, n-(1 H-benzotriazol-1-ylmethyl)formamide, n,n-dimethylbenzotriazole-methanamine, 1 H-1,2,3-benzotriazole-l-ylacetic acid, 1-methyl-5-nitro-
triazole; however, asymmetrical substitution with one or more non-hydrogen R
groups will destroy this equivalence.
H
7 I N\N 7 `NH 2 (i) (ii) 5 Moreover, as used herein, the term "non-2H-substituted" refers to benzotriazole derivatives having no hydrogen atom or other substituent bound to nitrogen atom 2. Stated alternatively, the term "non-2H-substituted" includes the 1 H and 3H tautomers of benzotriazole and derivatives of these tautomers in which there is a hydrogen atom or a substituent R bound to nitrogen atom 1 of I H-benzotriazole or to nitrogen atom 3 of 3H-benzotriazole. 2H-Benzotriazole and derivatives of this tautomer in which there is a hydrogen atom or a substituent R bound to nitrogen atom 2 are not included. For example, 1-propargyl-1 H-benzotriazole (structure (i), below) is a non-2H-substituted benzotriazole;
therefore, it is within the definition of "unsaturated heterocyclic compounds," as that term is used herein. In contrast, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol (structure (ii), below) is a 2H-substituted benzotriazole; therefore, it is not included in the definition of "unsaturated heterocyclic compounds".
N He W~
N
C_zCH (i) CH3 (ii) In summary, benzotriazole compounds are included in or excluded from the definition of "unsaturated heterocyclic compounds" based solely on their "non-2H
substituted" structure. In this connection, the definition of "non-2H substituted" set forth above is not to be superceded by principles of nomenclature that may be inconsistent with the structural descriptions herein.
Accordingly, examples of suitable benzotriazole derivatives include, but are not limited to, 1-methyl-1 H-benzotriazole, 5-methyl-1 H-benzotriazole, 1-aminobenzotriazole, 4-hydroxy-1 H-benzotriazole, 1-cyanobenzotriazole, 1H-benzotriazole-1-carboxaldehyde, 1,6-dimethyl-1H-1,2,3-benzotriazole, 1H-benzotriazole-1-methanol, 1-hydroxybenzotriazole hydrate, 5-chlorobenzotriazole, 1-propargyl-1 H-benzotriazole, 1 H-benzotriazol-1-ylmethyl isocyanide, 1 H-benzotriazole-l-acetonitrile, I-allylbenzotriazole, benzotriazole-1-carboxamide, benzotriazole-5-carboxylic acid, 1-(methoxymethyl)-1 H-benzotriazole, 5,6-dimethyl-1 H-benzotriazole monohydrate, 1-(chloromethyl)-1H-benzotriazole, 6-chloro-1-hydroxybenzotriazole dehydrate, 1-(2-methyl-allyl) -1 H-benzotriazole, n-(1 H-benzotriazol-1-ylmethyl)formamide, n,n-dimethylbenzotriazole-methanamine, 1 H-1,2,3-benzotriazole-l-ylacetic acid, 1-methyl-5-nitro-
9 BNSDOCID; <WO_2010085664A1_I->
1 H-1,2,3-benzotriazole, 2-methyl-4-nitro-2H-1,2,3-benzotriazole, benzotriazole-I -carbonyl chloride, 1-(2-butenoyl)-1H-benzotriazole, 1-(trimethylsilyl)-1H-benzotriazole, 1-(alpha-chloroacetyl)-1 H-benzotriazole, 1-(methylsulfonyl)-1 H-benzotriazole, 1 H-benzotriazole-4-sulfonic acid, 1-(1-ethoxy-2-propynyl)-1 H-benzotriazole, (1-pyrrolidinylmethyl) benzotriazole, (1-ethoxy-2-propenyl)benzotriazole, 1-(2,2,2-trimethylacetyl)-1 H-benzotriazole, benzotriazole- 1-acetic ethyl ester, 3-(1H-1,2,3-benzotriazole-1-yl)propanohydrazide, 1-[(trimethylsilyl)methyl]
benzotriazole, 5-aminobenzotriazole dihydrochloride, 5,6-dinitro-1 H-benzotriazole, 1-benzyl-1 H-benzotriazole, 1-(3-chloropropionyl)-1 H-benzotriazole, 1-(2-pyrrolecarbonyl)benzotriazole, 1-(2-furoyl)-1 H-benzotriazole, 1 -(trifluoromethyl)acetylbenzotriazole, (4-morpholinyl-methyl)benzotriazole, 1-benzoyl-1 H-benzotriazole, 1-(2-pyridylcarbonyl) benzotriazole, 1-(4-pyridylcarbonyl)benzotriazole, N-Phenylbenzotriazole-methanamine, 1-(phenoxymethyl)-1 H-benzotriazole, 1-(9-amino-3H-(1,2,3)#riazolo(4,5-f)quinolin-8-yl)ethanone, 2-benzotriazol-1-yl-ethanesulfonyl fluoride, 1-(2-thienylcarbonyl)-1 H-benzotriazole, 1-(2,2-dichloroacetyl)-1 H-benzotriazole, [1-(4-morpholinyl)ethyl]benzotriazole, benzotriazol-1-ylpyrrolidin-1-ylmethanethione, n-(1H-1,2,3-benzotriazol-1-ylmethyl)-3-methylaniline, alpha-methyl-n-phenyl-1 H-benzotriazole-1-methanamine, N-(1 H-1,2,3-benzotriazol-1-ylmethyl)-2-methylaniline, N-methyl-N-phenylbenzotriazolemethana mine, phenyl-1 H-1,2,3-benzotriazole-5-carboxyl ate, 1-(benzoyloxy)-1 H-1,2,3-benzotriazole, 3-(benzotriazol-1-ylmethoxy)-phenylamine, 1-(4-fluorobenzoyl)-1 H-benzotriazole, 1-[(phenylthio)methyl]-1 H-benzotriazole, [1-(4-morpholinyl)propyl]benzotriazole, 1-(3-phenyl-2-propenoyl)-1H-1,2,3-benzotriazole, n-(1H-benzotriazol-1 -ylmethyl)benzamide, benzotriazol-1-ylmethyl-(2-ethyl-phenyl)-amine, n-(1 H-1,2,3-benzotriazol-1-ylmethyl)-2,4-dimethylaniline, 4-(1 H-1,2,3-benzotriazol-1 -ylcarbonyl)phenyl methyl ether, 1-(benzyloxycarbonyl)benzotriazole, 2-benzotriazol-1-yl-n-pyridin-2-yl-acetamide, benzotriazol-1-ylmethyl-(2-methoxy-phenyl)-amine, n-(1 H-1,2,3-benzotriazol-1 -ylmethyl)-4-methoxyaniline, 1-O-tolylsulfanylmethyl-1 H-benzotriazole, n'-(2-(1 H-1,2,3-benzotriazole-1-yl)-1-methylethylidene)-2-cyanoacetohydrazide, methyl 3-(1 H-1,2,3-benzotriazol-4-yl(methyl) amino)-2-cyanoacrylate, 1-(4-ohlorobenzoyl)-1 H-benzotriazole, n-(1 H-1,2,3-benzotriazol-l-ylmethyl)-2-chloroaniline, benzotriazol-1-ylmethyl-(3-chloro-phenyl)-amine, n-(1H-1,2,3-benzotriazol-1-ylmethyl)-4-chloro-aniline, 1-(phenylsulfonyl)-1H-benzotriazole, and benzotriazol-1-ylmethyl-(2,5-difluoro-phenyl)-amine.
Examples of suitable 1,2,3-triazole derivatives include, but are not limited to, 5-nitro-1H-1,2,3-triazole, 1H-1,2,3-triazolo[4,5-b]pyridine, 1-hydroxy-7-azabenzotriazole solution, 3H-(1,2,3)triazolo(4,5-d)pyrimidi n-7-ylamine, 8-azaadenine, 8-azaguanine, 8-azaxanthine monohydrate, 1,2,3-triazole-4,5-dicarboxylic acid, n-phenyl-IH-1,2,3-triazol-5-amine, 1-acetyl-1 H-1,2,3-triazolo[4,5-b]pyridine, 3-methyl-8-azaguanine, 3H-1,2,3,4,5,7,7a-heptaaza-s-indacen-8-ol, 4,6-dimethyl-I H-v-triazolo(4,5-d)pyrimidine-5,7(4H,6H)-dione, 1,2,3-triazole-4,5-dicarboxylic acid, monopotassium salt of 1,2,3-triazole-4,5-dicarboxylic acid, 5-amino-1,4-diphenyl-1,2,3-triazole, 5-anilino-4-phenyl-lH-1,2,3-triazole, and rufinamide.
BNSDOCID: cWO 2010085664A1_I_>
Examples of suitable 1,2,4-triazole derivatives include, but are not limited to, 3-amino-1,2,4-triazole, 1H-1,2,4-triazol-5-amine, 1,2,4-triazolylsodium, 1 -vinyl-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-1,2,4-triazole-3-thiol, 1,2,4-triazole-3-carboxylic acid, 3-nitro-1H-1,2,4-triazole, 3-amino-1,2,4-triazole-5-thiol, 1,2,4-triazolo[1,5-a]pyrimidine, 3-acetamido-1 H-1,2,4-triazole, methyl-IH-1,2,4-triazole-3-carboxylate, 5-amino-4H-(1,2,4)triazole-3-carboxylic acid, 5-amino-1 H-(1,2,4)triazole-3-carboxylic acid, 3-amino-1 H-1,2,4-triazole-5-carboxylic acid, 3-amino-5-methylthio-1H-1,2,4-triazole, 5-methyl-s-triazolo (1,5-a)pyrimidine, 1-trimethylsilyl-1,2,4-triazole, 5-amino-1 H-[1,2,4]-triazole-3-carboxylic acid methyl ester, 3-methyl-5-(2-oxido-2-oxohydrazino)-1H-1,2,4-triazole, 3-amino-1,2,4-triazole-5-carboxylic acid hydrate, 1H-1,2,4-triazole-1-carboxamidine hydrochloride, 5,7-dimethyl-s-triazolo[1,5-a]pyrimidine, 7-hydroxy-5-methyl[1,2,4]triazolo[1,5-a]pyrimidine, 5-methyl(1,2,4)triazolo(4,3-a)pyrimidin-7-ol, 7-amino-s-triazolo(1,5-a)pyrimidin-5(4H)-one, 5-(trifluoromethyl)-4H-1,2,4-triazol-3-ylamine, oxo(1H-1,2,4-triazol-5-ylamino)acetic acid, 3-(1,2,4-triazol-1-yl)-L-alanine, 5-amino-1 H-(1,2,4)triazole-3-carboxylic acid ethyl ester, beta-(1,2,4-triazol-3-yl)-DL-alanine, 1 -amino-5-propyl-1 H-1,2,4-triazol-3-yl hydrosulfide, 2-(2-aminophenyl)-1 H-1,3,4-triazole, 2-chloro-n-(4H-(1,2,4)triazol-3-yl)-acetamide, (5-dihydroxymethyl-2H-(1,2,4)triazol-3-yl)-methanediol, 1,1'-carbonyl-di-(1,2,4-triazole), 5,5'-dimethyl-1H,1'H-(3,3')BI((1,2,4)triazolyl), 1H,1'H-(3,3')Bl((1,2,4)triazolyl)-5,5'-diamine, 2H,2'H-(3,3')BI((1,2,4)triazolyl)-5,5'-diamine, 3,3'-bis(5-amino-4H-1,2,4-tria), 3-OXO-N-(1H-1,2,4-triazol-5-yl)butanamide, 7-chloro-5-methyl-(1,2,4)triazolo(1,5-a)pyrimidine, 1-(tert-butoxycarbonyl)1 H-1,2,4-triazole, s-triazolo(4,3-a)quinoline, 6,7,8,9-tetrahydro-5H-(1,2,4)triazolo (1,5-a)azepin-2-yl hydrosulfide, 2-(3-nitro-(1,2,4)triazol-1-yl)-acetamide, (3-nitro-(1,2,4)triazol-1-yl)-acetic acid, benzylidene-(1,2,4)triazol-4-Y, 4-(benzylideneamino)-4H-1,2,4-triazole, n-(4-pyrid inylmethylene)-4H-1,2,4-triazol-4-amine, (4-methyl-4H-(1,2,4)triazol-3-ylsulfanyl)-acetic acid, 3-methylamino-5-phenyl-1,2,4-triazole, 3-(3-pyridylmethylamino)-1,2,4-triazole, (1,2,4)triazolo (3,4-B)(1,3)benzothiazole, 3H-1,2,3,4,5,7,7A-heptaaza-S-indacen-8-OL, 1-phenyl-I H-(1,2,4)triazole-3-thiol, 5-phenyl-1 H-1,2,4-triazole-3-thiol, 5-propyl-(1,2,4)triazolo (1,5-A)pyrimidin-7-OL, 5-(4-pyridyl)-lH-1,2,4-triazole-3-thiol, 6-nitro-(1,2,4)triazolo (1,5-A)pyrimidin-2-ylamine, 5-((5-amino-4H-1,2,4-triazol-3-yl)methyl)-4H-1,2,4-triazol-3-ylamine, 3-((5-amino-1 H-1,2,4-triazol-3-yl)methyl)-1H-1,2,4-triazol-5-ylamine, 5,7-dimethyl-(1,2,4)triazolo (1,5-A)pyrimidine-2-thiol, hydrochloride of 3-phenyl-4H-(1,2,4)triazole, 3-mercapto-5-methyl-8H-(1,2,4)triazolo(4,3-A)pyrimidin-7-one, 5-amino-1H-(1,2,4)triazole-3-carboxylic acid butyl ester, and 3-(4-pyridinyl)-6,7-dihydro-5H-pyrrolo (2,1-C)(1,2,4)triazole.
Examples of suitable imidazoles include, but are not limited to, 2-methyl-2-imidazoline, 2-phenyl-2-imidazoline, 3-(4,5-dihydro-2-imidazolyl)pyridine, 8-methyl-2,3,7,8-tetrahydroimidazo(1,2-A)pyrimidin-5(6H)-one, (4,5-dihydro-1 H-imidazol-2-ylthio)acetic acid, 2-benzylimidazoline, 4-(4,5-dihydro-1 H-imidazol-2-yl)phenylamine, 2-(4,5-dihydro-1 H-imidazol-2-yl)phenol, 4-(4,5-dihydro-1 H-imidazol-2-yl)phenol, 3-(4,5-dihydro-1 H-imidazol-2-yl)phenol, 2-chloro-1,3-dimethylimidazolidinium chloride, 3A,4,5,6,7,7A-hexahydro-1 H-benzimidazol-2-yl BNSDOCID: cWO_2010085664A1_I_>
methyl sulfide, hydrochloride of imidazo(1,2-A)pyridin-2-one, 2,3-dihydro-5H-imidazo(2,1-A)isoindol-5-one, 2-amino-5,5-bis(hydroxymethyl)-1-methyl-l,5-dihydro-4H-imidazol-4-one, 4-(4-methyl-4,5-dihydro-1 H-imidazol-2-yl)phenylamine, 4-(4-methyl-4,5-dihydro-1 H-imidazol-2-yl)phenol, 2-(4-methyl-4,5-dihydro-1 H-imidazol-2-yl)phenol, 3-(4-methyl-4,5-dihydro-1 H-imidazol-2-yl)phenol, 2-amino-1-methyl-2-imidazoline hydrobromide, 2-mercapto-3-phenyl-3,5-dihydro-imidazol-4-one, 2-(4-methoxystyryl)-2-imidazoline, 2,10-dihydro-10-ethylimidazo(2,1-B)quinazoline-5(3H)-one, 2-methyl-4,5-di hydro-imidazole-1-carbothioic acid phenylamide, 2-chloro-1,3-dimethylimidazolidinium tetrafluoroborate, 2-(4-bromophenyl)-4,5-dihydro-1 H-imidazole, 2-(methylamino)-2-midazoline hydriodide, 2-(3-nitrophenyl)-4,5-dihydro-1 H-imidazole hydrochloride, 2-(4,5-dihydro-1 H-imidazol-2-yl)quinoline hydrochloride, 5-butoxy-2-(4,5-dihydro-I H-imidazol-2-yl)phenol, 3-(1,3-dimethyl-2,6-dioxo-1,2,3,4,5,6-hexahydro-9H-purin-9-yl)propanenitrile, tetrahydrozoline hydrochloride, idazoxan hydrochloride, tetramisole hydrochloride, levamisol hydrochloride, 1,3-diisopropylimidazolinium tetrafluoroborate, 2-(4,5-dihydro-IH-imidazol-2-yl)-1-benzofuran-5-yl thiocyanate, 2-methylthio-2-imidazoline hydriodide, 4,5-dihydro-1 H-imidazol-2-yl 2-fluorobenzyl sulfide hydrochloride, naphazoline hydrochloride, 4-chloro-alpha-(2-imidazolin-2-yl)benzyl alcohol hydrochloride, 5A, 11A-dihydronaphtho[2',3':4,5]imidazo[1,2-A]pyrid ine-6,11-dione, 2,3,6,7-tetrahydro-5,7,7-trimethyl-5H-pyrrolo(1,2-a)imidazole, 3-(4,5-dihydro-1H-imidazol-2-yl)aniline dihydrochloride hydrate, efaroxan hydrochloride, cirazoline hydrochloride, 1 -bityl-4,5-d i hyd ro-3-ethyl-8-hyd roxyxa nth ine, imidacloprid solution, 2-(4-fluorobenzylidene)-2,5,6,7,8,9-hexahydro-3H-imidazo(1,2-a)azepin-3-one, imidacloprid-d4, imazapyr, 9-benzyl-2-chloro-5,9-dihydro-4H-purin-6-ylamine, 2-fluoro-1,3-dimethylimidazolidinium hexafluorophosphate, 2-(4,5-dihydro-1H-imidazol-2-yl)-(hexyloxy)phenol, 3-phenyl-2-(4-toluidino)-3,5-dihydro-4H-imidazol-4-one, clonidine hydrochloride, n-(3-chlorophenyl)-n'-(i-methyl-4-oxo-4,5-dihydro-1 H-imidazol-2-yl)urea, 2,4,5-tri-(2-furyl)-2-imidazoline, 5-(benzyloxy)-2-(4,5-dihydro-1 H-imidazol-2-yl)phenol, 1,3-ditert-butyl-4,5-dihydro-1 H-imidazol-3-ium tetrafluoroborate, n-allyl-n-(2,6-dichlorophenyl)-4,5-dihydro-1 H-imidazol-2-amine, 2-(4,5-dihydro-1 H-imidazol-2-yl)-2,3-dihydro-l,4-benzodioxin-2-yl methyl ether hydrochloride, 2-(4,5-dihydro-1 H-imidazol-2-yl)-2,3-dihydro-l,4-benzodioxin-2-yl methyl ether, 3-(3,4-dihydroxyphenyl)-5,6-dihydroimidazo(2,1-B)thiazole hydrochloride, 2-methyl-n-(3-(trifluoromethyl)phenyl)-2-imidazoline-l-carboxamide, nitric acid compound with 2-(1-naphthylmethyl)-4,5-dihydro-1 H-imidazole (1:1), 2-benzyl-2-imidazoline thiosulfate, 1-[3-(triethoxysilyl)propyl]-4,5-dihydro-1 H-imidazole, 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1 H-imidazol-2-yl)-5-methylnicotinic acid, 2-[(E)-2-(2-methylphenyl)ethenyl]-4,5-dihydro-1 H-imidazole ethanedioate nonahydrochtoride, 6,6-diphenyl-2,3,6,7-tetrahydro-5H-pyrrolo(1,2-a)imidazol-5-one, 10-benzyl-2,3-dihydroimidazo(2,1-b)quinazolin-5(10H)-one, n-(4-chloro-6-methoxy-2-methyl-5-pyrimidinyl)-n-(4,5-dihydro-1H-imidazol-2-yl)amine hydrochloride, n-(4-chloro-6-methoxy-2-methyl-5-pyrimidinyl)-n-(4,5-dihydro-1H-imidazol-2-yl)amine hydrochloride, 2-chloro-1,3-dimethyl-4,5-dihydro-1 H-imidazol-3-ium hexafluorophosphate, 2,3,5,6,7,8-BNSDOCID: <WO 2010085664A1J_>
hexahydro-8-methylimidazo (1,2-a)pyrimidin-5-imine hydriodide, 3,7-dimethyl-1-(5-oxo-hexyl)-3,7-dihydro-purine-2,6-dione, 3,7-dimethyl-l-(5-oxohexyl)-3,7-dihydro-1 H-purine-2,6-dione, 2-(4-tert-butyl-2,6-dim ethyl benzyl)-4,5-dihydro-1 H-imidazole hydrochloride, 8-methyl-2,3,7,8-tetrahydroimidazo(1,2-a)pyrimidin-5(6H)-one hydriodide, 2,6-dichloro-N(1)-(4,5-dihydro-1 H-imidazol-2-yl)-1,4-benzenediamine hydrochloride, 3-(4-chlorophenyl)-2-ethyl-2,3,5,6-tetra-hydroimidazo(2, 1-b)thiazol-3-ol, 5-(4-chlorophenyl)-2,5-dihydro-3H-imidazo[2,1-a]isoindol-5-ol, 2-(4-nitrobenzylidene}2,5,6,7,8,9-hexahydro-3H-imidazo(1,2-a)azepin-3-one, 2-(2-nitrobenzylidene)-2,5,6,7,8,9-hexahydro-3H-imidazo(1,2-a)azepin-3-one, 9,13b-dihydro-1 H-dibenzo[c,f]imidazo[1,5-a]azepin-3-ylamine hydrochloride, 2-(4,5-dihydro-1 H-imidazol-2-ylthio)-n-(4-methylphenyl)acetamide hydrochloride, 2-(4,5-dihydro-1H-imidazol-2-ylthio)-n-(2-methylphenyl)acetamide hydrochloride, methyl 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1 H-imidazol-2-yl)-4-methylbenzoate, hydrobromide of 3-thiophen-2-yl-5,6-2H-imidazo(2,1-B)thiazole, 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)nicotinic acid, n-(5-chloro-2,1,3-benzothiadiazol-4-yl)-n-(4,5-dihydro-1 H-imidazol-2-yl)amine hydrochloride, 2-(4,5-dihydro-1 H-imidazol-2-yl)-5-(octyloxy)phenol, 5-bromo-N-(4,5-dihydro-1 H-imidazol-2-yl)-6-quinoxalinamine, 5-benzylidene-2-methylsulfanyl-3-phenyl-3,5-dihydro-imidazol-4-one, 5-benzyl idene-2-mercapto-3-(2-methylphenyl)-3, 5-dihydro-4H-imidazol-4-one, 6-tert-butyl-3-(4,5-dihydro-lH-imidazol-2-ylmethyl)-2,4-dimethylphenol hydrochloride, and DL-isoamarine.
Examples of suitable pyrrole derivatives include, but are not limited to, I H-pyrrole-d5, 1-methyl-1 H-pyrrole, 3-methyl-1 H-pyrrole, 1 H-pyrrole-2-carbonitrile, 1 H-pyrrole-2-carbaldehyde, 2,5-dimethyl-1 H-pyrrole, 2-ethyl-1 H-pyrrole, 2,4-dimethyl-1 H-pyrrole, 1 -(1 H-pyrrol-2-yl)ethanone, 1-methyl-1 H-pyrrole-2-carbaldehyde, 1,2,5-trimethyl-1 H-pyrrole, 1 H-pyrrole-2-carbaldehydehyde oxime, N,N-dimethyl-1 H-pyrrol-1-amine, 1 H-pyrrole-2-carboxylic acid, 1 H-indole, 1 H-pyrrolo[2,3-b]pyridine, 1,5-dimethyl-1 H-pyrrole-2-carbonitrile, 3-(1 H-pyrrol-1 -yl)propanenitrile, 3-(1 H-pyrrol-2-yl)-2-propenal, 4,5,6,7-tetrahydro-1 H-indole, 1 H-pyrrole-2,5-dicarbaldehyde, 1-(1-methyl-1 H-pyrrol-2-yl)ethanone, 3,5-dimethyl-1 H-pyrrole-2-carbaldehyde, 1-(1-methyl-1 H-pyrrol-3-yl)ethanone, 1-(4-methyl-1 H-pyrrol-3-yl)ethanone, 3-ethyl-2,4-dimethyl-1H-pyrrole, 1-(1H-pyrrol-2-yl)ethanone oxime, 1H-indole-d7, methyl 1H-pyrrole-1-carboxylate, 1-methyl-1H-pyrrole-2-carboxylic acid, 2,3-dihydro-6H-[1,4]dioxino[2,3-c]pyrrole, methyl 1 H-pyrrole-3-carboxylate, methyl 1 H-pyrrole-2-carboxylate, 3-chloro-1 H-pyrrole-2-carbaldehyde, 4-methyl-1 H-indole, 2-methyl-1 H-indole, 3-methyl-1 H-indole, 1-methyl-1 H-indole, 5-methyl-1 H-indole, 7-methyl-1 H-indole, 6-methyl-1 H-indole, 1 H-indol-5-amine, 1 H-indol-7-amine, 1 H-indol-6-amine, 1 H-indol-4-amine, 1 H-indol-4-ol, I H-indol-5-ol, 1 H-indol-6-ol, 5-fluoro-1 H-indole, 4-fluoro-1 H-indole, 6-fluoro-1 H-indole, 1,5,6,7-tetrahydro-4H-indol-4-one, 4-(1 H-pyrrol-2-yl)-3-buten-2-one, formic acid (2-pyrrolylmethylene)hydrazide, 1-(2,4-dimethyl-1 H-pyrrol-3-yl)ethanone, 1-(4-ethyl-1 H-pyrrol-3-yl)ethanon e, ethyl I H-pyrrole-2-carboxylate, 2-methyl-2,3-dihydro-6H-[1,4]dioxino[2,3-c]pyrrole, 3-(1 H-pyrrol-1 -yl)propanoic acid, 2-(1H-pyrrol-2-yl)acetohydrazide, 1 H-indole-4-carbonitrile, 1 H-indole-5-carbonitrile, 2-(1 H-pyrrol-2-BNSDOCID: cWO _2010095664A1 I >
ylmethylene)maIononitrile, 1-phenyl-1H-pyrrole, 1H-indole-3-carbaldehyde, 1H-indole-5-carbaldehyde, 1 H-indole-7-carbaldehyde, 1 H-indole-2-carbaldehyde, 1 H-indole-4-carbaldehyde, 1 H-indole-6-carbaldehyde, 2,5-dimethyl-1 H-indole, 1,3-dimethylindole, 1,2-dimethyl-1 H-indole, 7-ethyl-1 H-indole, 2,3-dimethyl-1 H-indole, 3-chloro-1 H-pyrrole-2-carboxylic acid, 1 H-pyrrolo[2,3-b]pyridine-3-carbaldehyde, 2-(1H -pyrrol-2-yl m ethyl)- 1H-pyrrole, 1 H-indol-5-ylmethanamine, 2-methyl-1 H-indol-5-amine, 1 H-indol-3-ylmethanol, 1 H-indol-5-yl methyl ether, 1 H-indol-2-ylmethanol, 1 H-indol-7-yl methyl ether, 1 H-indol-6-yl methyl ether, 1 H-indol-4-yl methyl ether, 1-(2-furylmethyl)-1 H-pyrrole, 5-formyl-3,4-dimethyl-1 H-pyrrole-2-carbonitrile, methyl 1 H-pyrrolo[2,3-c]pyrid in-5-yl ether, methyl 7H-pyrrolo(2,3-d)pyrimidin-4-yl ether, 2-methyl-7H-pyrrolo (2,3-d)pyrimidin-4-ol, 5-fluoro-2-methyl-1H-indole, 1-(1H-pyrrol-2-yl)-1-penten-3-one, 2-amino-7H-pyrrolo[2, 3-d]pyrimidin-4-ol, 2,5-dimethyl-1 H-pyrrole-3,4-dicarbaldehyde, 3-(1 H-pyrrol-3-yl)-acrylic acid methyl ester, and 3,4-dimethyl-2,5-pyrroledicarboxaldehyde.
Examples of suitable pyrazine derivatives include, but are not limited to, pyrazine-d4, 2-methylpyrazine, 2-pyrazinamine, 2-pyrazinecarbonitrile, 2,3-dimethylpyrazine, 2-ethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2-methoxypyrazine, 2-chloropyrazine, sodium salt of pyrazinol, imidazo[1,2-a]pyrazine, 1-(2-pyrazinyl)ethanone, 2-ethyl-3-methylpyrazine, 2,3,5-trimethyl pyrazine, 2-pyrazinecarboxamide, 2-pyrazinecarboxylic acid, 2-methoxy-3-methylpyrazine, 2-(methylsulfanyl)pyrazine, 2,3-pyrazinedicarbonitrile, quinoxaline, 5,6,7,8-tetrahydroquinoxaline, 5-methyl-6,7-dihydro-5H-cyclopenta[b]pyrazine, 1-(3-methyl-2-pyrazinyl)ethanone, 2,3,5,6-tetramethylpyrazine, 2,3-diethylpyrazine, methyl 2-pyrazinecarboxylate, 5-methyl-2-pyrazinecarboxylic acid, 2-ethyl-3-methoxypyrazine, 2-ethoxy-3-methylpyrazine, 3-amino-2-pyrazinecarboxylic acid, 5-hydroxy-2-pyrazinecarboxylic acid, 2-methyl-3-(methylsulfanyl)pyrazine, 2-(2-pyrazinyl)ethanethiol, 3-chloro-2,5-dimethylpyrazine, 5-methyl-2,3-pyrazinedicarbonitrile, 2-methylquinoxaline, 5-methylquinoxaline, 2-quinoxalinol, 2,6-dichioropyrazine, 2,3-dichioropyrazine, furo[3,4-b]pyrazine-5,7-dione, 1-(3-ethyl-2-pyrazinyl)etha none, 1-(3,5-dimethyl-2-pyrazinyl)ethanone, 2,3-diethyl-5-methylpyrazine, 2-isobutyl-3-methylpyrazine, 2-(2-(dimethylamino)ethyl)pyrazine, 2-isopropyl-3-methoxypyrazine, 2-methyl-6-propoxy-pyrazine, methyl 3-amino-2-pyrazinecarboxylate, 5,6-dimethyl-2,3-pyrazinedicarbonitrile, 2,3-dimethylquinoxaline, 6,7-dimethylquinoxa line, 2,3-dimethylpyrido (2,3-b)pyrazine, 5,6-diamino-2,3-pyrazinedicarbonitrile, 6,7-dimethylpteridine, 2,3-quinoxalinediol, pyrido[2,3-b]pyrazine-2,3-diol, 2-amino-4(3H)-pteridinone, 2,4-pteridinediol, 3-hydroxy-5,6-dimethyl-1 H-pyrazolo-(3,4b)-pyrazine, 2-chloroquinoxaline, 2,3-pyrazinedicarboxamide, 2-isobutyl-3-methoxypyrazine, 2-sec-butyl-3-methoxypyrazine, 2,3-pyrazinedicarboxylic acid, quinoxaline-2-carbaldehyde oxime, 2-quinoxalinecarboxylic acid, 2-methylquinoxaline-1,4-dioxide, 4-hydroxy-6,7-dimethylpteridine, hydrate of 2,3-dimethyl-quinoxaline, isoxanthopterin, phenazine, 3-amino-6-(chloromethyl)-2-pyrazinecarbonitrile 4-oxide, n-methyl-n'-quinoxalin-2-ylmethylene-hydrazine, 2,3-diethylquinoxaline, 2,3,6,7-tetramethylquinoxa line, 1-(3,5-diamino-6-chloro-2-pyrazinyl)ethanone, 3,5-diamino-6-chloro-2-BNSDOCID: <WO_2010065664A11>
WO 20101085664 PCT/US2014)/021829 pyrazinecarboxamide, 2-hydroxy-3,6,7-trimethylquinoxaline, 1,2,3,4,6,7,8,9-octahydrophenazine, 5-bromo-2,3-pyrazinediamine, 2-(nitromethyl)quinoxaline, 3-hydroxy-2-quinoxalinecarboxylic acid, 6,7-dimethyl-2,3-quinoxalinediol, 2,4-diamino-6,7-dimethylpteridine, 2-amino-6,7-dimethyl-4-pteridinol, 6,7-dimethyl-2,4-pteridinediol, (2,4-diamino-6-pteridinyl)methanol, 2-quinoxalinecarbonyl chloride, 2-amino-6-methyl-4,7-pteridinediol, 2-amino- I,5-dihydro-4,6-pteridinedione hydrate, 3-bromoimidazo[1,2-a]pyrazine, 2,6-dichloroquinoxaline, 2,3-dichloroquinoxaline, and ethyl 2-q uinoxalinecarboxylate.
Examples of suitable pyrimidine derivatives include, but are not limited to, 4-methylpyrimidine, 5-methylpyrimidine, 2-methylpyrimidine, 4-pyrimidinamine, 5-pyrimidinamine, pyrimidine 1-oxide, 2-pyrimidine-carbonitrile, 4,6-dimethylpyrimidine, 4-methyl-2-pyrimidinamine, 4,5-pyrimidinediamine, 2,4-pyrimidinediamine, 4,6-pyrimidinediol, 2,4-dihydroxypyrimidine, 2-pyrimidinethiol, 5-fluoro-2-pyrimidinol, 5-fluoro-pyrimidin-4-ol, 2-chloropyrimidine, 2,4-difluoropyrimidine, 9H-purine, 4-amino-5-pyrimidinecarbonitrile, n-(2-pyrimidinyl)-formamide, 4,6-dimethyl-2-pyrimidinamine, 2,6-dimethyl-4-pyrimidinol, 4,6-diamino-2-methylpyrimidine, 2-amino-6-methyl-4-pyrimidinol, 4-amino-6-hydroxy-2-methylpyrimidine, 6-methoxy-pyrimidinamine, 2,4,6-pyrimidinetriamine, 6-methyl-2,4(1 H,3H)-pyrimidinedione, 2-methyl-4,6-pyrimidinediol, 6-methyl-pyrimidine-4,5-diol, 5-methyl-4,6-pyrimidinediol, 2,6-diamino-4-pyrimidinol, 6-hydrazino-4-pyrimidinol, 6-methyl-4-pyrimidinethiol, 2-amino-4,6-pyrimidinediol, dihydro-2,4,5(3H)-pyrimidinetrione, 5-fluoro-6-methyl-pyrimidin-4-ol, 2-thioxo-2,3-dihydro-4(1 H)-pyrimidinone, 4-sulfanyl-2-pyrimidinol, 2-chloro-4-pyrimidinamine, 5-chloro-2-pyrimidinamine, 5-fluoro-pyrimidine-4-thiol, quinazoline, 2-chloro-5-fluoropyrimidine, 2-pyrimidinol hydrochloride, 4,5,6-trifluoropyrimidine, 2-amino-6-methyl-4(3H)-pteridinone, 4-amino-2-methyl-pyrimidine-5-carbonitrile, 6-methyl-9H-purine, 1H-pyrazolo[3,4-d]pyrimidin-4-amine, 7H-purin-2-amine, 9H-purin-6-amine, 5-cyano-2,4-diaminopyrimidine, 9H-purin-6-amine, 1,5-dihydro-4H-pyrazolo[3,4-d]pyrimidin-4-one, 3H-(1,2,3)triazolo(4,5-d)pyrimidin-7-ylamine, 1H-[1,2,3]triazolo[4,5-d]pyrimidin-7-amine, 9H-purin-6-amine, 2-acetamidopyrimidine, methyl 5-pyrimidinecarboxylate, 4,6-diamino-5-nitrosopyrimidine, 2-amino-5,6-dimethyl-4-pyrimidinol, 4-methoxy-6-methyl-2-pyrimidinamine, 6-hydroxy-4-pyrimidinecarboxylic acid, 5-nitro-2-pyrimidinamine, 5,6-dimethyl-2,4(1 H,3H)-pyrimidinedione, 5-methyoxy-2-methyl-pyrimidin-4-ol, 2,4-dimethoxypyrimidine, 5-amino-4-hydroxy-6-(methylamino)pyrimidine, 4,6-dimethyl-2-pyrimidinethiol, 4-methyl-2-(methylsulfanyl)pyri mid ine, 2-amino-4,6-dihydroxy-5-methylpyrimidine, 2-amino-5-methyoxy-pyrimidin-4, 5-amino-2,4-dihydroxy-6-methylpyrimidine, 4-amino-2-hydroxy-5-(hydroxymethyl) pyrimidine, 2-amino-6-methyl-4,5-pyrimidinediol, 4-amino-2-mercapto-6-methylpyrimidine, 6-methyl-2-thioxo-2,3-dihydro-4(1 H)-pyrimidinone, 2-methylsulfanyl-pyrimidin-5-ol, 2-methylsulfanyl-pyrimidin-4-ol, 2,4-diamino-6-mercaptopyrimidine, 4,5-diamino-2-mercaptopyrimidine, 2-chloro-5-ethylpyrimidine, 6-a mino-5-fluoro-2-methyl-pyri mid in-4-ol, 4-amino-2-hydroxy-6-mercaptopyrimidine, 4-chloro-6-methyl-2-pyrimidinamine, 2-thioxodihydro-4,6(1 H,5H)-pyrimidinedione, 2-chloro-5-methoxypyrimidine, 2-chloro-4-methoxypyrimidine, 6-BNSDOCID: <WO_2010085664A1_I_>
chloro-2-methyl-4-pyrimidinol, 6-chloro-2,4-pyrimidinediamine, 7H-purine-6-carbonitrile, 5-fluoro-6-fluoromethyl-pyrimidin-4-ol, 4(3H)-quinazolinone, and 4-methyl-2(1H)-pyrimidinone hydrochloride.
Examples of suitable pyridine derivatives include, but are not limited to, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-pyridinamine, 4-pyridinamine, 3-pyridinamine, pyridine 1-oxide, 2-pyridinol, 3-pyridinol, 4(1 H)-pyridinone, 4-methylpyridine-d3, 2-fluoropyridine, 3-fluoropyridine, pyridine hydrofluoride, 2-pyridinamine-d6, 2-methylpyridine-d7, 2-ethynylpyridine, 2-pyridinecarbonitrile, nicotinonitrile, isonicotinonitrile, 2-vinylpyridine, 4-vinylpyridine, 2-pyridinecarbaldehyde, nicotinaldehyde, isonicotinaldehyde, 2,5-dimethylpyridine, 4-ethylpyridine, 2,3-dimethylpyridine, 3,4-dimethylpyridine, 3-ethylpyridine, 2-ethylpyridine, 2,4-dimethylpyridine, 3,5-dimethylpyridine, 2,6-dimethylpyridine, N-methyl-N-(4-pyridinyl)amine, N-methyl-N-(2-pyridinyl)a mine, 2-methyl-3-pyrid ina mine, 4-pyridinylmethanamine, 2-methyl-4-pyridinamine, 3-methyl-2-pyridinamine, 4-methyl-2-pyridinamine, 5-methyl-3-pyridinamine, 3-pyridinylmethanamine, 2-pyridinylmethanamine, 5-methyl-2-pyridinamine, 6-methyl-2-pyridinamine, 6-methyl-3-pyridinamine, 4-methyl-3-pyridinamine, 2-methyl-4-pyridinamine, 3-methyl-2(1 H)-pyridinone, 4-methoxypyridine, 5-methyl-2-pyridinol, 2-methoxypyridine, 6-methyl-2-pyridinol, 3-pyridinylmethanol, 2-pyridinylmethanol, 6-methyl-3-pyridinot, 4-methyl-2-pyridinol, 4-pyridinylmethanol, 3-methoxypyridine, 2-methyl-3-pyridinol, 2,5-pyridinediamine, 2-hydrazinopyridine, 2,3-pyridinediamine, 3,4-pyridinediamine, 2,6-pyridinediamine, 2-amino-3-pyridinol, 2,4-pyridinediol, 2,3-pyridinediol, 2-fluoro-3-methylpyridine, 2-fluoro-6-methylpyridine, 2-fluoro-5-methylpyridine, 2-fluoro-4-methylpyridine, 2-pyridinethiol, 4-pyridinethiol, 5-fluoro-2-pyridinamine, 3-chloropyridine, 2-chloropyridine, 2,6-difluoropyridine, pyridine hydrochloride, 4-methyl-2-pyridinecarbonitrile, 6-methyl-2-pyridinecarbonitrile, 3-methyl-2-pyridinecarbonitrile, 1H-pyrrolo[2,3-b]pyridine, 3-pyridinylacetonitrile, 2-pyridinylacetonitrile, 5-methylnicotinonitrile, 1 H-imidazo[4,5-b]pyridine, and 2-aminonicotinonitrile.
Examples of suitable pyridizine derivatives include, but are not limited to, 3-methylpyridazine, 4-methylpyridazine, 3-pyridazinamine, pyridazine 1-oxide, 1,2-dihydro-3,6-pyridazinedione, 3,6-pyridazinediol, 4-pyridazinecarboxylic acid, 4-methyl-3,6-pyridazinediol, 3-chloro-6-methylpyridazine, 3-chloro-6-methoxypyridazine, 3-chloro-6-hydrazinopyridazine, 4-chloro-3,6-dihydroxypyridazine, 3,6-dichloropyridazine, 3,6-dichloropyridazine, 3-chloro-6-ethoxypyridazine, 6-chloro-3-methoxy-4-pyridazinamine, phthalazine-1,4-diamine, 3-chloro-6-(methylthio)pyridazine, 3,6-dichloro-4-methylpyridazine, 3,6-dichloro-4-pyridazinamine, 1-chlorophthalazine, 3-amino-5,6-dimethyl-4-pyridazinecarboxamide, cinnoline hydrochloride hydrate, 3-chloro-5,6-dimethyl-4-pyridazinecarbonitrile, 4-cinnolinecarboxylic acid, 5-amino-1,4-phthalazinediol, 1,4,5-timethyl-1H-pyrazolo[3,4-c]pyridazin-3-amine, 3,6-dichloro-N-methyl-4-pyridazinamine, 5-chloro-8-methyl-phthalazine, benzo(C)cinnoline, 3-chloro-6-phenylpyridazine, 3-chloro-6-(methylsulfonyl)pyridazine, 3,6-dichloro-4-pyridazinecarboxylic acid, 6-amino-1,4-phthalazinediol hydrate, 1,4-dichlorophthalazine, 4-amino-3-methyl-6-nitrocinnoline, 3-chloro-6-BNSDOCID: <WO_2010065664A1_I_>
methyl-4-phenylpyridazine, N-(3,6-dichloro-4-pyridazinyl)acetamide, 1-ethoxyphthalazine hydrochloride, 1,2,3,6,7,8-hexahydrocinnolino (5,4,3-CDE)cinnoline, 3-chloro-6-(4-methoxyphenyl)pyridazine, acetone O-(6-{[(1-methylethylidene) amino]oxy}-3-pyridazinyl)oxime, 4-((6-methoxy-3-pyridazinyl)amino)-4-oxo-2-butenoic acid, 4-styrylcinnoline, 3,6-diphenylpyridazine, 1-methyl-3H-benzo(H)pyrazolo (4,3-C)cinnoline, 1-chloro-4-phenylphthalazine, 8-chloro-4-hydroxy-3-cinnolinecarboxylic acid hydrate, 6-(phenylsulfinyl) tetraazolo[1,5-b]pyridazine, 6-methyl-3,4-diphenylpyridazine, 4-methyl-3,6-diphenylpyridazine, 4,5-dimethyl-N-[(E)-phenylmethylidene]-1H-pyrazolo[3,4-c]pyridazin-3-amine, 3,4,7-trimethyl-2-P-tolyl-2H-pyrazolo(3,4-D)pyridazine, 1,2,5,6-tetrathia-3,4,7,8-tetraazacyclopenta (FG)acenaphthylene, cyclopentanone (4-chloro-1-phthalazinyl)hydrazone, 3,6-bis(1,1,2,2-tetramethylpropyl)pyridazin e, 3-methyl-6-[3-(trifluoromethyl) phenyl][1,2,4]triazolo[4,3-b]pyridazine, 3,4-dihydro-1(2H)-naphthalenone (1, 2,4)triazolo(4,3-B)pyridazin-6-ylhydrazone, 4-amino-N-(6-methoxy-3-pyridazinyl)benzenesulfonamide, 1,4-dihydrazinophthalazine dihydro-chloride monohydrate, benzaldehyde (4-chloro-1-phthalazinyl)hydrazone, nicotinaldehyde (4-chloro-l-phthalazinyl)hydrazone, 4-amino-N-(6-chloro-3-pyridazinyl)benzenesulfonamide, 1-(3-hydroxy-5,6-diphenyl-4-pyridazinyl)ethanone, 2-((6-chloro-pyridazin-3-yi)-hydrazonomethyl)-4-nitro-phenol, 2-((6-chloro-pyridazin-3-yl)-hydrazonomethyl)-6-nitro-phenol, 4-amino-N-(6-ethoxy-3-pyridazinyl)benzenesulfonamide, 4-[(1-phthal-azinylsulfanyl)methyl]benzoic acid, 4-methylbenzaldehyde (4-chloro-1-phthalazinyl)hydrazone, 1-phenylethanone (4-chloro-1-phthalazinyl) hydrazone, 2-methylbenzaldehyde (4-chloro-1 -phthalazinyl)hydrazone, (1 R,5S)-3-(6-chloro-3-pyridazinyl)-3,8-diazabicyclo[3.2.1 ]octane di hydrochloride, and 4-methyl-N-[2-(4-morpholinyl)ethyl]-6-phenyl-3-pyridazinamine dihydrochloride.
Examples of suitable thiazole derivatives include, but are not limited to, 5-methyl-1,3-thiazole, 4-methyl-1,3-thiazole, 1,3-thiazol-2-amine, 1,3-thiazole-5-carbaldehyde, 1,3-thiazole-2-carbaldehyde, 4,5-dimethyl-1,3-thiazole, 2,4-dimethyl-1,3-thiazole, 4-methyl-1,3-thiazol-2-amine, and 5-methyl-1,3-thiazol-2-amine.
Examples of suitable benzoxazole derivatives include, but are not limited to, 2-methyl-1,3-benzoxazole, 2-hydrazinobenzoxazole, 6-fluoro-2-methyl-1,3-benzoxazole, 1,3-benzoxazol-2-yl hydrosulfide, 2-chloro-1,3-benzoxazole, 5-chioro-1,3-benzoxazole, 2,5,6-trimethylbenzoxazole, 5-methyoxy-2-methylbenzoxazole, 2-(methylthio)benzoxazole, 5-chloro-2-methyl-1,3-benzoxazole, 5-chloro-l,3-benzoxazol-2-amine, 1-(2-benzoxazolyl)-guanidine, 2-methyl-6-nitrobenzoxazole, 5-chloro-2,6-dimethylbenzoxazole, 2-methylnaphth (2,1-D)oxazole, 5-aceta m ido-2-m ethyl benzoxazole, 2-phenyl-1,3-benzoxazole, 5-phenyl-benzooxazole, 2-methyl-5-phenyl-1,3-benzoxazole, 2-phenyl-1,3-benzoxazol-5-amine, 4-(1,3-benzoxazol-2-yl)aniline, 2-(1,3-benzoxazol-2-yl)phenol, 5-cyclohexyl-2-methylbenzoxazole, 2-(2-methyiphenyl)-1,3-benzoxazol-5-amine, 5-(1,3-benzoxazol-2-yl)-2-methylaniline, 3-(6-methyl-1,3-benzoxazol-2-yl)phenylamine, 3-(5-methyl-1,3-benzoxazol-2-yl)phenylamine, 4-(5-methyl-1,3-benzoxazol-2-yl)phenylamine, 2-(5-methyl-1,3-benzoxazol-2-yl)phenol, N-benzooxazol-2-yl-BNSDOGID: <WO_2010085664A1_I_>
N'-furan-2-ylmethylene-hydrazine, 3-(5,6-dimethyl-1,3-benzoxazol-2-yl)aniline, 2-methyl-5-(6-methyl-1,3-benzoxazol-2-yl)aniline, 2-(4-ethylphenyl)-1,3-benzoxazol-5-amine, 2-methyl-5-(5-methyl-1,3-benzoxazol-2-yl)aniline, 2-(3-nitrophenyl)-1,3-benzoxazole, 3-(1,3-benzoxazol-2-yl)-4-chloroaniline, 2-(4-chlorophenyl)-1,3-benzoxazol-5-amine, 2-(2-chlorophenyl)-1,3-benzoxazol-5-amine, 2-(3-chlorophenyl)-1,3-benzoxazol-5-amine, 3-(5-chloro-1,3-benzoxazol-yl)phenylamine, 4-(5-chloro-1,3-benzoxazol-2-yl)phenylamine, 4-benzooxazol-2-yl-quinoline, methyl naphtho(1,2-D)(1,3)oxazol-2-yl sulfone, 2-(benzooxazol-2-yl-hydrazonomethyl)-phenol, 4-(benzooxazol-2-yl-hydrazonomethyl)-phenol, 4-chloro-3-(5-methyl-1,3-benzoxazol-2-yl)aniline, 4-chloro-3-(6-methyl-1,3-benzoxazol-2-yl)aniline, 4-benzooxazol-2-yl-2-methyl-quinoline, 2-(1-naphthyl)-1,3-benzoxazol-5-amine, 4-amino-2-(5-chloro-1,3-benzoxazol-2-yl)phenol, 5-amino-2-(5-chloro-1,3-benzoxazol-2-yl)phenol, 1,3-benzoxazol-2-yl phenoxyacetate, 2-chloro-3-ethyl-1,3-benzoxazol-3-ium tetrafluoroborate, ethyl 2-cyano-3-((2-methyl-1,3-benzoxazol-yl)amino)acrylate, 2-(4-methyoxy-benzylsulfanyl)-benzooxazole, 2-(((5-nitro-2-furyl)methyl)thio)-1,3-benzoxazole, 4-chloro-3-(5-chloro-1,3-benzoxazol-2-yl)aniline, 2-(2,4-dichlorophenyl)-1,3-benzoxazol-5-amine, 2-(2,5-dichlorophenyl)-1,3-benzoxazol-5-amine, 2-(3,4-dichlorophenyl)-1,3-benzoxazol-5-amine, 3-(1,3-benzoxazol-2-yl)-7-hydroxy-2H-chromen-2-one, N-[3-(1,3-benzoxazol-2-yl)phenyl}2-methylpropanamide, 4-(dimethylamino) benzaldehyde 1,3-benzoxazol-2-ylhydrazone, N-benzooxazol-2-yl-N'-(4-nitro-benzylidene)-hydrazine, 3-hydroxy-4-methoxybenzaldehyde 1,3-benzoxazol-2-ylhydrazone, N-(benzooxazoi-2-ylsulfanylmethyl)-benzamide, 4-methyoxy-thiobenzoic acid S-benzooxazoi-2-yl ester, 2-(4-nitro-benzylsulfanyl)-benzooxazole, 2-(1,1'-biphenyl)-4-yl-1,3-benzoxazol-5-amine, 2-(4-bromophenyl)-1,3-benzoxazol-5-amine, 2-(2-bromophenyl)-1,3-benzoxazol-5-amine, 2-(3-bromophenyl)-1,3-benzoxazol-5-amine, 3-chloro-thiobenzoic acid S-benzooxazoi-2-yl ester, 3-(1,3-benzoxazol-2-yl)-N-(4-methyl phenyl)-2-oxopropanamide, 2-(1,3-benzoxazol-2-ylthio)-1-(4-hydroxy-2-methylphenyl)ethanone, 2-((1,3-benzoxazol-2-ylthio)methyl)-4-nitrophenol, 3-(1,3-benzoxazol-2-yl)-7-hydroxy-2-oxo-2H-chromene-4-carbonitrile, diethyl 2-(2-benzoxazolyl)-2-ethyl m al on ate, 2-(3,5-dichloro-4-methoxyphenyl)-1,3-benzoxazol-5-amine, 2-(1,3-benzoxazol-2-yl)phenyl benzoate, N-benzooxazol-2-yl-N'-(4-bromo-benzylidene)-hydrazine, 2-(2,4-dinitrophenylth io)benzoxazole, toluene-4-sulfonic acid 1-benzooxazoi-2-yl-ethyl ester, 2-(3-bromo-4-methoxyphenyl)-1,3-benzoxazol-5-ylamine, 3-(1,3-benzoxazol-2-yl)-2-oxo-chromen-7-yl acetate, 2-(5-bromo-2-chlorophenyl)-1,3-benzoxazol-5-ylamine, 4-(5-(l ,3-benzoxazol-2-yl)-1 H-benzimidazol-2-yl)phenylamine, N-(4-acetyl-phenyl)-2-(benzooxazol-2-yl sulfanyl)-acetamide, 4-(2-(benzooxazoi-2-ylsulfanyl)-acetylamino)-benzoic acid, 3-(1,3-benzoxazol-2-yl)-N-(3-chloro-2-methylphenyl)-2-oxopropanamide, 4-(5-chloro-2-(2-chlorophenyl)-1,3-benzoxazol-7-yl)-3-butyn-2-ol, 2-(3-phenoxy-benzylsulfanyl)-benzooxazole, and 2-{4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy}propanoic acid.
Examples of suitable 1,3,5-triazine derivatives include, but are not limited to, 1,3,5-triazine-d3, 2-amino-1,3,5-triazine, 2,4-diamino-1,3,5-triazine, 1,3,5-triazine-2,4-diamine, 6-BNSDOCIO: <WO_2010085664A 1_I_>
methyl-1,3,5-triazine-2,4-diamine, 1,3,5-triazine-2,4,6-triamine, 4,6-diamino-1,3,5-triazin-2-ol, 1,3,5-triaz-inane-2,4,6-trione, 2,4,6-trifluoro-1,3,5-triazine, 4-amino-2-dimethylamino-1,3,5-triazine, 4-methoxy-6-methyl-1,3,5-triazin-2-amine, 6-chloro-1,3,5-triazine-2,4-diamine, 1,3,5-triazine-2,4,6-triamine hydrofluoride, N-(4-methoxy-6-methyl-1,3,5-triazin-2-yi)-N-methylamine, 4-chloro-N-ethyl-6-(hydroxyamino)-1,3,5-triazin-2-amine, 1,3,5-triazine-2,4,6-triol compound with hydrazine (1:1), N(2)-cyclopropyl-1,3,5-triazine-2,4,6-triamine, N(2)-ethyl-6-methoxy-1,3,5-triazine-2,4-diamine, 4-chloro-6-(hydroxyamino)-N-isopropyl-1,3,5-triazin-2-amine, 6-ethoxy-N(2)-methyl-1,3,5-triazine-2,4-diamine, 2,4,6-trimethoxy-1,3,5-triazine, 2-chloro-N-(1,3,5)triazin-2-yl-acetamide, 6-chloro-N(2)-ethyl-1,3,5-triazine-2,4-diamine, 2-chloro-4,6-dimethoxy-1,3,5-triazine, 1,3,5-triazine-2,4,6-trithiol, 4,6-dichloro-1,3,5-triazine, 4,6-dichloro-1,3,5-triazin-2-yl methyl ether, 2,4-diamino-6-isobutyryl-1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine, 6-phenyl-1,3,5-triazine-2,4-diamine, 2,4,6-trichloro-1,3,5-triazine, 6-chloro-N(2)-isopropyl-1,3,5-triazine-2,4-diamine, 4,6-diamino-gamma-oxo-1,3,5-triazine-2-butyronitrile, N-methyl-6-trifluoromethyl-(1, 3,5)triazine-2,4-diamine, 2-amino-4-cyclohexylamino-1,3,5-triazine, potassium 4,6-dioxo-1,4,5,6-tetrahydro-1,3,5-triazine-2-carboxylate, N(2)-(tert-butyl)-6-methoxy-1,3,5-triazine-2,4-diamine, 2,4-diamino-6-(m-tolyl)-1,3,5-triazine, N(2)-(2-methylphenyl)-1,3,5-triazine-2,4-diamine, N(2)-(4-methylphenyl)-1,3,5-triazine-2,4-diamine, N(2)-(sec-butyl)-6-chloro-1,3,5-triazine-2,4-diamine, 6-chloro-N(2),N(4)-diethyl-1,3,5-triazine-2,4-diamine, 6-chloro-N(2),N(4)-diethyl-1,3,5-triazine-2,4-diamine, N(2)-(tert-butyl)-6-chloro-1,3,5-triazine-2,4-diamine, 6-(3-fluorophenyl)-1,3,5-triazine-2,4-diamine, 6-(4-fluorophenyl)-1,3,5-triazine-2,4-diamine, 6-(2-fluorophenyl)-1,3,5-triazine-2,4-diamine, N(2),N(2),N(4),N(4), N(6),N(6)-hexamethyl-1,3,5-triazine-2,4,6-triamine, 4,6-bis(isopropylamino)-1,3,5-triazin-2-ol, 4-(tert-butylamino)-6-(ethylamino)-1,3,5-triazin-2-ol, N(2)-ethyl-N(4)-isopropyl-6-methoxy-1,3,5-triazine-2,4-diamine, 6-chloro-N(2),N(4)-diethyl-1,3,5-triazine-2,4-diamine-dl0, N(2),N(4)-diethyl-6-(methyl-sulfanyl)-1,3,5-triazine-2,4-diamine, 2,4-diamino-6-(2,3-xylyl)-1,3,5-triazine, 6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine, 6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine, 6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine, N(2)-(2-methyoxy-phenyl)-1,3,5-triazine-2,4-diamine, 6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diamine, 2-chloro-4-ethyl-d5-amino-6-isopropylamino-1,3,5-triazine, 4,6-dichloro-N,N-diethyl-1,3,5-triazin-2-amine, 2-amino-4-(4-chloroanilino)-1,3,5-triazine, 2-(2-chlorophenyl)-4,6-diamino-1,3,5-triazine, 6-(4-chloro-phenyl)-1,3,5-triazine-2,4-diamine, 2-N-butoxy-4,6-dichloro-l,3,5-triazine, 6-(3,5-difluorophenyl)-1,3,5-triazine-2,4-diamine, 2-amino-4-phenylamino-I,3,5-triazine hydrochloride, 1-[4-amino-6-(methylsulfanyl)-1,3,5-triazin-2-yl]-3-isopropyl-l ,2-triazadien-2-ium, N(2),N(4)-diisopropyl-6-methoxy-1,3,5-triazine-2,4-diamine, N(2)-(sec-butyl)-N(4)-ethyl-6-methoxy-1,3,5-triazine-2,4-diamine, N(2)-(tert-butyl)-N(4)-ethyl-6-methoxy-1,3,5-triazine-2,4-diamine, N(2)-methyl-6-(2-phenylvinyl)-1,3,5-triazine-2,4-diamine, 6-(ethylthio)-N(2)-isopropyl-N(4)-methyl-1,3,5-triazine-2,4-diamine, N(2)-ethyl-N(4)-isopropyl-6-(methylsulfanyl)-1,3,5-triazine-2,4-diamine, 6-chloro-N (2)-cyclopropyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine, 2,4-diamino-6-phenylacetyl-1,3,5-BNSDOCID: cWO_2010085664A1_ , triazine, N(2),N(4),N(6)-trichloro-1,3,5-triazine-2,4,6-triamine, 6-chloro-N,N'-dipropyl-(1,3,5)triazine -2,4-diamine, N(2)-(sec-butyl)-6-chloro-N(4)-ethyl-1,3,5-triazine-2,4-diamine, 6-chloro-N(2),N(4)-diisopropyl-1,3,5-triazine-2,4-diamine, 6-chloro-N(2),N(2), N(4)-triethyl-1,3,5-triazine-2,4-diamine, 4-(1,2,4)triazol-4-yl-6-trifluoromethyl-(1,3,5)triazin-2-ylamine, 2,4-diamino-6-(3-nitrophenyl)-1,3,5-triazine, 2-amino-4-anilino-6-(chloromethyl)-1,3,5-triazine, 4-chloro-2-(4,6-diamino-1,3,5-triazin-2-yl)phenol, 5,7-bis(ethylamino)(1,2,4)triazolo(4,3-A)(1,3,5)triazine-3-thiol, 2-{[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino}-2-m ethylpropanenitrile, N(2),N(4)-diisopropyl-6-(methylsulfanyl)-1,3,5-triazine-2,4-diamine, N(2)-(tert-butyl)-N(4)-ethyl-6-(methylsulfanyi)-1,3,5-triazine-2,4-diamine, 4,6-dichloro-1,3,5-triazin-2-yl phenyl ether, 1,3,5-Triazine-2,4,6-trithiol trisodium salt, N(2)-(sec-butyl)-6-chloro-N(4)-isopropyl-1,3,5-triazine-2,4-diamine, 2,4,6-tris(allyloxy)-1,3,5-triazine, and N(4-amino-S-triazin-2-yl)-sulfanilic acid.
Examples of suitable 2,2'-bipyridine derivatives include, but are not limited to, 2,2'-bipyridine, 6-methyl-2,2'-bipyridine, 2-(2-pyridinyl)pyridine 1-oxide, 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 6,6'-dimethyl-2,2'-bipyridine, 2,2'-bipyridine-3,3'-diol, 2,2'-bipyridineN,N'-dioxide, and 2-(2-pyridinyl)quinoline.
1 H-Benzotriazole, non-2H-substituted benzotriazole derivatives, imidazole, and imidazole derivatives are preferred unsaturated heterocyclic compounds.
Specific examples of preferred unsaturated heterocyclic compounds include, without limitation, I H-benzotriazole; 5-methyl-1 H-benzotriazole; imidazole; 2-methyl imidazole; and 1 H-1,2,3-triazole. 1H-Benzotriazole is a more preferred unsaturated heterocyclic compound.
Moreover, the PVB composition may further comprise one or more UV absorbers at a level ranging from about 0.01 wt%, or about 0.05 wt%, or about 0.08 wt% to about 1 wt%, or about 0.8 wt%, or about 0.5 wt%, based on the total weight of the PVB
composition. UV
absorbers are well-known in the art, and any known UV absorber may find utility within the PVB
composition. Examples of suitable UV absorbers include, but are not limited to, benzotriazole derivatives, hydroxybenzophenones, hydroxyphenyl triazines, esters of substituted and unsubstituted benzoic acids, and mixtures of any two or more of these suitable UV absorbers.
Significantly, the benzotriazole derivatives that are useful as UV absorbers are 2-H substituted benzotriazole derivatives. Therefore, they are not included in the definitions of non-2-H
substituted benzotriazole derivatives and of unsaturated heterocyclic compounds that are set forth above. Suitable commercially available UV absorbers include, but are not limited to, TinuvinTM P, TinuvinT"" 1130, TinuvinTM 326, TinuvinTM 327, TinuvinT"' 328, TinuvinTM 571, TinuvinTM 99-DW, or Chimassobs"d 81, manufactured by Ciba, UvinuIT" 3000, UvinulTM 3008, UvinuIT" 3040, or UvinuITM 3050, manufactured by BASF (Germany), and CyasorbT"" 5411, manufactured by Cytec Industries, Inc.
The PVB composition may further comprise one or more thermal stabilizers at a level ranging from about 0.01 wt%, or about 0.05 wt%, or about 0.08 wt% to about 1 wt%, or about 0.8 wt%, or about 0.5 wt%, based on the total weight of the PVB composition.
The thermal BNSOOCID: <WO 2010085664A7 I->
stabilizers used here may also be referred to as phenolic antioxidants and are well known in the industry. Examples of suitable thermal stabilizers include, but are not limited to, IrganoxT'"
1010, IrganoxTM 1035, IrganoxTM 1076, IrganoxT"" 1081, IrganoxT"' 1098, IrganoxTM 1135, IrganoxTM 1330, IrganoxTM 1425 WL, lrganoxTM 1520, IrganoxTM 245, IrganoxTM
3114, trganoxTM
565, IrganoxTM E 201, or IrganoxTM MD 1024 manufactured by Ciba, LowinoxTM
1790, LowinoxTM 22M46, LowinoxTM 44B25, LowinoxT"" CA22, LowinoxTM CPL, LowinoxTM HD
98, LowinoxTM MD24, LowinoxTM TBM-6, or LowinoxTM WSP, manufactured by Chemtura (Middlebury, CT), CyanoxTM 1741, CyanoxTM 2246, or CyanoxTM 425, manufactured by Cytec, or mixtures of any thereof. Thermal stabilizers of note include LowinoxTM
1790, LowinoxTM
22M46, LowinoxTM 44B25, Lowinox"'A CA22, LowinoxTM CPL, LowinoxTM HD 98, LowinoxTM
MD24, LowinoxTM TBM-6, or LowinoxTM WSP, or mixtures of any thereof. One preferred thermal stabilizer is octylphenol. Another preferred thermal stabilizer is butylated hydoxytoluene (BHT).
The PVB composition may further comprise one or more hindered amines at a level of up to 1 wt %. Alternatively, the hindered amines may be present at a level ranging from about 0.08 wt%, or about 0.1 wt%, or greater than 0.1 wt%, to about 1 wt%, to about 0.8 wt%, or up to about 0.5 wt%, based on the total weight of the PVB composition. The hindered amines may be secondary or tertiary hindered amines. Examples of suitable secondary hindered amines include, but are not limited to, 2,2,6,6-Tetramethyl-piperadine, 2,2,6,6-Tetramethylpiperadinol, and mixtures thereof. Examples of suitable tertiary hindered amines include, but are not limited to, N-butyl piperidine, N,N-diethyl cyclohexyfamine, and mixtures of any two or more thereof. In some preferred PVB compositions, the hindered amines are hindered amine light stabilizers (HALS), which are typically secondary, tertiary, acetylated, N hydrocarbyloxy substituted, hydroxy substituted N-hydrocarbyloxy substituted, or other substituted cyclic amines which further incorporate steric hindrance, generally derived from aliphatic substitution on the carbon atoms adjacent to the amine function. As used herein, the terms "hindered amines" and "hindered amine light stabilizers" refer to compounds that are completely saturated, except for substituents that include a carbonyl group. Therefore, these terms do not refer to any of the unsaturated heterocyclic compounds described above. Hindered amine light stabilizers are also well known within the art and commercially available. For example, TinuvinTM 111, TinuvinTM 123, TinuvinTM 144, TinuvinTM 152, TinuvinTM 292, TinuvinTM 622, TinuvinTM 765, TinuvinTM 770, TinuvinTM 783,TinuvinTM 791, ChimassorbT"' 119, ChimassorbTM
2020, or ChimassorbTM 944, manufactured by Ciba (Tarrytown, NY), CyasorbTM 3346 or CyasorbTM
3853S manufactured by (Cytec Industries, Inc., Paterson, NJ), or a combination of any two or more thereof can be used in the PVB composition. Further information regarding suitable hindered amines and their use in encapsulant compositions may be found in U.S.
Provisional Appin. No. 61/146,522, filed on January 22, 2009 (Attorney Docket No. PP0086).
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The PVB composition may further comprise one or more chelating agents at a level ranging from about 0.01 wt%, or about 0.05 wt%, or about 0.08 wt% to about 1 wt%, or about 0.8 wt%, or about 0.5 wt%, based on the total weight of the PVB composition.
Examples of suitable chelating agents include, but are not limited to, ethylenediaminetetraacetic acid (EDTA), ethylenediamine monoacetic acid, ethylenediamine diacetic acid, ethylenediamine triacetic acid, ethylene diamine, tris(2-aminoethyl) amine, diethylenetriaminepentacetic acid, or mixtures of any thereof. As used herein, the term "chelating agent" does not include 2,2'-bipyridine or its derivatives. Further information regarding suitable chelating agents and their use in encapsulant compositions may be found in U.S. Provisional Appin. No.
61/146,547, filed on January 22, 2009 (Attorney Docket No. PP0088).
In addition to the plasticizer and the additives listed above, the PVB
composition may further comprise one or more of any other suitable additives, including, but not limited to, adhesion control additives, surface tension controlling agents, processing aids, flow enhancing additives, lubricants, pigments, dyes, flame retardants, impact modifiers, nucleating agents, anti-blocking agents such as silica, dispersants, surfactants, coupling agents, reinforcement additives, such as glass fiber, fillers and the like. These additives, suitable concentrations of the additives, and methods for incorporating them into the PVB compositions are described in the Kirk Othmer Encyclopedia of Chemical Technology, 51h Edition, John Wiley &
Sons (New Jersey, 2004), for example.
Further provided herein is a solar cell module that comprises a solar cell assembly, wherein (A) the solar cell assembly comprises at least one solar cell and a silver component; (B) the solar cell assembly is fully or partially encapsulated by a PVB
encapsulant layer or layers comprising the PVB composition described above; and (C) the silver component is at least partially in contact with the PVB encapsulant layer or layers.
The term "solar cell" as used herein includes any article that converts light into electrical energy. Solar cells useful in the solar cell assemblies and modules described herein include, but are not limited to, wafer-based solar cells (e.g., c-Si or me-Si based solar cells), thin film solar cells (e.g., a-Si, pc-Si, CdTe, or CI(G)S based solar cells), and organic solar cells. In principle, however, any type of solar cell known in the art is suitable for use in the solar cell modules described herein. The solar cells may include, but are not limited to, those described in U.S. Patent Nos. 4,017,332; 4,179,702; 4,292,416; 6,123,824; 6,288,325;
6,613,603; and 6,784,361, U.S. Patent Publication Nos. 2006/0213548; 2008/0185033;
2008/0223436;
2008/0251120; and 2008/0271675; and PCT Patent Application Nos. W02004/084282 and 2007/103598.
By "fully encapsulated", it is meant that the solar cell assembly is laminated or sandwiched between two encapsulant layers comprising the PVB composition.
Generally, the area of the largest surface of the solar cell assembly is smaller than that of some other components of the solar cell module, such as, for example, the substrate or superstrate, or the 6NSDOCID: cWO 201 0085 66 4A1_1_>
front or back protecting layers, or the encapsulant layer(s) before or after lamination. Therefore, in modules comprising fully encapsulated assemblies, the two PVB encapsulant layers may come in contact with each other over the edges of the solar cell assembly and form a seal around the edges of the solar cell module. When the area of the largest surface of the encapsulant layers is larger than that of the solar cell assembly, the contact between them may be established in the stacked, unlaminated solar cell module. Alternatively, when the greatest two-dimensional surface area of the encapsulant layers is smaller than that of the solar cell assembly, the contact between them may not be established until the encapsulant layers melt and flow under the heat and pressure of the solar cell module lamination process. Those of skill in the art will be able to take account of the changes necessitated in the above description by solar cell assemblies having a significant thickness.
By "partially encapsulated", it is meant that the solar cell assembly, which comprises solar cells (such as thin film solar cells) and is deposited on a substrate (or superstrate), has one side that is opposite from the substrate (or superstrate) laminated to an encapsulant layer comprising the PVB composition so that the solar cell assembly is sandwiched between the substrate (or superstrate) and the PVB encapsulant layer. In modules comprising partially encapsulated assemblies, the PVB encapsulant layer may come in contact with the substrate (or superstrate) of the solar cell assembly over the edges of the solar cell module and form a seal around the edges of the solar cell assembly. Again, depending on the relative surface areas of the substrate (superstrate), the solar cell assembly and the encapsulant layer, the edge seal may form before or after the lamination process that forms the solar cell module.
In one solar cell module, for example, the PVB encapsulant layer(s) are formed from PVB sheets and the encapsulated solar cell assembly is formed by laminating one or both sides of the solar cell assemblies to the PVB sheet(s). The PVB sheets may have a thickness of about 0.25 to about 1.2 mm.
It has been found that, within a solar cell module, when a prior art PVB
encapsulant is in complete or partial contact with a silver component (such as a component comprising silver or silver alloy), the prior art PVB encapsulant tends to discolor or yellow over time.
Without wishing to be bound by theory, it is believed that such discoloration results when Ago comprised in the silver component is oxidized, under high voltage and high moisture conditions, to form Ag+ ions that migrate into the PVB encapsulant. Once in the PVB
encapsulant, the Ag' ions are then reduced to metallic silver (Ag ). The metallic silver, which may be in the form of nano-sized silver particles, is believed to cause the discoloration. By adding the unsaturated heterocyclic compounds and optionally the other additives described above into the PVB encapsulants, however, the formation of the elemental silver is prevented, and the resulting discoloration of the PVB encapsulant is mitigated.
More specifically, when the PVB encapsulant described herein is in prolonged contact with one or more silver components, the yellowness index (YI) change of the PVB encapsulant BNSDOCID: <WO_2010085664A1_I_>
is reduced or minimized. The YI for a PVB encapsulant can be determined in accordance with ASTM E313-05, using a 20 observer and using Illuminant C as a light source.
These conditions may also be described as "2 /C". The YI is reported in unitless numbers and must be normalized to a particular sample pathlength for direct comparison. In general, the Yl of PVB
encapsulants described herein remains about 60 or less, or about 55 or less, or about 50 or less, or 40 or less, or about 30 or less, or about 20 or less, for a sample having a pathlength of 1.0 cm.
The YI of the PVB encapsulant in a solar cell module is difficult to measure in situ, as the yellowness of the other components in the module, such as the coatings, is difficult to deconvolute from that of the encapsulant. In order to avoid this obstacle, it is generally necessary to delaminate the module, isolating the PVB encapsulant.
Delamination is also an inconvenient procedure, however. Therefore, the Yl of the PVB encapsulant is generally measured using a model system. Both solid encapsulants and polymer solutions may be used as model systems for the Yl of PVB encapsulants in solar cell modules.
When a solid encapsulant is used as a model, it is laminated to the silvered side of silver-coated glass sheet, then held under a bias of 1,000 V for 1000 hours at 85 C and at 85%
relative humidity (RH). The solid encapsulants used as models herein have a constant plasticizer concentration, for the validity of the comparison of the encapsulants' Yl. The total amount of the other additives (unsaturated heterocyclic compound, UV absorber, thermal stabilizer, hindered amine and the like) is typically about 1 % or less of the amount of plasticizer in the solid encapsulants; accordingly, changes in Yl due to variation in the amounts of the additives is deemed to be insignificant.
When a polymer solution is used as a model system, a stock solution of neat PVB resin (10g) in methanol (100g) is combined with a stock solution of a silver salt in methanol and with stock solutions of any additives that are included in the solution model. The solution samples are incubated at 60 C in a hot water bath for 2 to 8 hours, until the yellow color of a negative control sample becomes apparent to the naked eye. The samples are transferred to cuvettes having a pathlength of 1.0 cm, and their spectra are obtained according to the standard method.
The concentrations of the PVB and of the silver (calculated as silver ions) in the solution samples are held constant, again for validity of comparison of the solutions' Yl.
The term "silver component", as used herein, refers to a constituent part or to any sub-combination of the constituent parts of the solar cell assembly or of the solar cell module that comprises elemental silver. The terms "elemental silver", "metallic silver", and "Ag " are synonymous and are used interchangeably herein. The elemental silver may be present in substantially neat or pure form, for example as it is used in a reflector film. Alternatively, it may be compounded, for example with a non-metallic material such as a carrier or a filler, or it may be present in a solid solution, in an alloy, in crystalline form, as a powder or as a flake, as the continuous or dispersed phase of a dispersion, or in any other morphology. For example, the BNSDOCID: <WO2010085664A1_I_>
solder material used in some connecting wires is a silver and aluminum alloy containing as little as about 2 wt% of silver.
The silver component may be any one or more of the conductive paste, the connecting wires, the metal conductive coatings, and the metal reflector films.
The conductive paste, which is typically used in wafer-based solar cells, is a conductive film deposited on the front sun-facing or back non-sun-facing side of solar cells to efficiently contact the solar cells and transport the photo-generated current. The front conductive paste, for example, may comprise elemental silver.
The term "connecting wires" as used herein also includes the solder materials used to connect the individual wires together or to anchor the wires onto the solar cells. The connecting wires, which may be included in both wafer-based solar cells and thin film solar cells, are typically soldered on the surface of the solar cells to provide electrical connections between individual solar cells and to lead the photo-generated current out of the modules. In certain solar cell modules, the connecting wires (including its solder material), and especially the solder material, may comprise silver or a silver alloy.
During the construction of thin film solar cells, a first conductive layer (e.g., a transparent conductive oxide (TCO) or metal coating) is first coated on the substrate before the photon absorbing materials is deposited thereon. Further, during the construction of the solar cells, a second conductive layer (e.g., a TCO or metal coating) is further deposited on the photon absorbing materials. The silver component may be one or both of these two metal conductive coatings.
Metal back reflector films are often incorporated in thin film solar cells to reflect the photons that have passed around or through the solar cells back onto the solar cells, thereby improving power generating efficiency. In certain solar cell modules, the metal back reflector film is formed by sputtering a silver layer or a silver comprising layer on the solar cells.
Moreover, the silver component may be completely or partially in contact with the PVB
encapsulant. For example, "partially in contact with" indicates that the silver at least about 3.6 x10-5% of the silver component's surface area is in contact with the PVB
encapsulant. This amount corresponds to the calculated area of scribe lines in a thin film cell, although it is also used herein to indicate a minimum surface area of contact for other silver components and in different types of solar cell modules. In contrast, the silver component is completely in contact with PVB, for example in a solar cell module in which substantially 100% of the surface area of a reflector film is in contact with the PVB encapsulant. When used without modification, however, as in the term "the silver component is in contact with the PVB
encapsulant," for example, any non-zero level of contact is indicated. Stated alternatively, any non-zero percentage of the component's surface area may be in contact with the PVB
encapsulant.
In one module, the solar cells are wafer-based solar cells, and the silver component may be a conductive paste deposited thereon, or it may be one or more connecting wires. The silver BNSDOCID: <WO 2010085664A1_I_>
component is in contact with the PVB encapsulant. Further, the solar cell assembly, which comprises the wafer-based solar cells and the silver component, and which is encapsulated by the PVB encapsulant, may be further sandwiched between two protective outer layers (which are also referred to as the front and back sheets).
The protective outer layers of the solar cell modules may be formed of any suitable sheets or films. Suitable sheets include glass sheets, metal sheets such as aluminum, steel, galvanized steel, ceramic plates, or plastic sheets, such as polycarbonates, acrylics, polyacrylates, cyclic polyolefins (e.g., ethylene norbornene polymers), polystyrenes (preferably polystyrenes prepared in the presence of metallocene catalysts), polyamides, polyesters, fluoropolymers, or combinations of two or more thereof.
Suitable films include metal films, such as aluminum foil, or polymeric films such as those comprising polyesters (e.g., poly(ethylene terephthalate) and poly(ethylene naphthalate)), polycarbonate, polyolefins (e.g., polypropylene, polyethylene, and cyclic polyolefins), norbornene polymers, polystyrene (e.g., syndiotactic polystyrene), styrene-acrylate copolymers, acrylonitrile-styrene copolymers, polysulfones (e.g., polyethersulfone, polysulfone, etc.), nylons, poly(urethanes), acrylics, cellulose acetates (e.g., cellulose acetate, cellulose triacetates, etc.), cellophane, silicones, poly(vinyl chlorides) (e.g., poly(vinylidene chloride)), fluoropolymers (e.g., polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethyl en e-tetrafl u oroethylene copolymers, etc.), or combinations of two or more thereof. The polymeric film may be non-oriented, or uniaxially oriented, or biaxially oriented. Some specific examples of suitable polymeric films include, but are not limited to, polyester films (e.g., poly(ethylene terephthalate) films), fluoropolymer films (e.g., Tedlar , Tefzel(D, and Teflon films available from E. I. du Pont de Nemours and Company (DuPont), Wilmington, DE). Further, the films may be in the form of a multi-layer film, such as a fluoropolymer/ polyester/fluoropolymer multilayer film (e.g., Tedlar /PET/Tedlar or TPT laminate film available from Isovolta AG., Austria or Madico, Woburn, MA).
In another module, the solar cells are thin film solar cells, and the silver component may be selected from connecting wires, conductive coatings, or back reflector films, or a combination of two or more thereof. In one particular thin film solar cell, the silver component is a conductive coating comprising silver or silver alloy. The silver component may also be a back reflector film comprising silver or silver alloy. Similarly to the above described wafer-based solar cell modules, the thin film solar cell assembly is fully or partially encapsulated by the PVB
encapsulant, and the silver component is in contact with the PVB encapsulant.
Again, the fully or partially encapsulated thin film solar cell assembly may be further sandwiched between two additional protective outer layers, such as a front or back sheet.
Alternatively, the thin film solar cell assembly maybe partially encapsulated by the PVB encapsulant, i.e., in which the side that is opposite from the substrate (or superstrate) is laminated to the PVB
encapsulant, and in which the PVB encapsulant is further laminated to a protective outer layer.
Also preferably, the BNSDOCID: WO 2010085664A1 _I_o thin film solar cell assembly comprises a reflector film which, in turn, comprises silver and which is in contact with the PVB encapsulant.
In a preferred thin film solar cell module, the light absorbing materials are deposited on a substrate in layers. The substrate may be made of glass, or any suitable metal, or polymeric sheets or films as described above for the protective outer layers. The thin film solar cells may be single junction or multi-junction (including tandem junction) thin film solar cells. As the spectrum of solar radiation provides photons of varying energies, multi-junction solar cells were developed in which the sunlight passes serially through several solar cell layers. Each separate layer of the multi-junction solar cell is tailored to convert photons of a specific wavelength efficiently to electrical energy. The multi junction solar cells are usually constructed with layers of different energy gaps. The layers having greater energy gaps are adjacent to the surface through which the light enters the module. The layers having lesser energy gaps are positioned further towards the interior or back of the module.
Further provided is a solar cell array comprising two or more of the solar cell modules described above.
Further provided is a process for converting light energy to electricity, said process comprising the step of exposing a solar cell assembly or a solar cell module to electromagnetic radiation Further provided is a process for converting solar energy to electricity, said process comprising the step of exposing a solar cell assembly or a solar cell module to solar radiation.
Any suitable process may be used in preparing the solar cell modules described herein.
In particular, any suitable lamination process known within the art (such as an autoclave or a non-autoclave process) may be used to prepare the solar cell modules. For example, in a typical lamination process, the solar cells are first stacked between the PVB
encapsulants (e.g., in the form of PVB sheets), and further between two protective films or sheets, and this pre-lamination assembly is then subjected to the lamination process. Further, in the preparation of thin film solar cell modules, the solar cells, which are deposited over a substrate, are first stacked over the PVB encapsulant (e.g., in the form of a PVB sheet) and then a protective film or sheet, to form a pre-lamination assembly.
Accordingly, further provided herein is a pre-lamination assembly for preparing a solar cell module. The pre-lamination assembly comprises a solar cell assembly, which in turn comprises a solar cell, an oxidizable metal component, and a poly(vinyl butyral) sheet comprising the PVB composition described herein. Preferably, the poly(vinyl butyral) sheet has a thickness of about 0.25 mm to about 1.2 mm and a yellowness index of about 60 or less in accordance with ASTM E313-05 after 1000 hours at 85% relative humidity (RH) and at 85 C
with a bias of 1,000 V. The pre-lamination assembly may further comprise one or more additional layers selected from the group consisting of: a second poly(vinyl butyral) sheet that may be the same as or different from the poly(vinyl butyral) sheet, said second poly(vinyl BNSDOCID <WO 2010065664A11>
butyral) sheet being in contact with the solar cell assembly; a protective outer layer that is in contact with the poly(vinyl butyral) sheet; a second protective outer layer that may be the same as or different from the protective outer layer, said second protective outer layer in contact with the second poly(vinyl butyral) sheet; and a substrate or a superstrate that is in contact with the solar cell assembly and with the poly(vinyl butyral) sheet.
In one suitable process, the pre-lamination assembly is placed into a bag capable of sustaining a vacuum ("a vacuum bag"), the air is drawn out of the bag by a vacuum line or other means, the bag is sealed while the vacuum is maintained (e.g., at least about 27-28 in Hg (689-711 mm Hg)), and the sealed bag is placed in an autoclave at a pressure of about 150 to about 250 psi (about 11.3 to about 18.8 bar), a temperature of about 130 C to about 180 C, or about 120 C to about 160 C, or about 135 C to about 160 C, or about 145 C to about 155 C, for about 10 to about 50 min, or about 20 to about 45 min, or about 20 to about 40 min, or about 25 to about 35 min. A vacuum ring may be substituted for the vacuum bag. One type of suitable vacuum bag is described in U.S. Patent No. 3,311,517. Following the heat and pressure cycle, the air in the autoclave is cooled without adding additional gas to maintain pressure in the autoclave. After about 20 min of cooling, the excess air pressure is vented and the laminates are removed from the autoclave.
Alternatively, the pre-lamination assembly may be heated in an oven at about 80 C to about 120 C, or about 90 C to about 100 C, for about 20 to about 40 min, and thereafter, the heated assembly is passed through a set of nip rolls so that the air in the void spaces between the individual layers may be squeezed out, and the edge of the assembly sealed. The assembly at this stage is referred to as a pre-press.
The pre-press may then be placed in an air autoclave where the temperature is raised to about 120 C to about 160 C, or about 135 C to about 160 C, at a pressure of about 100 to about 300 psi (about 6.9 to about 20.7 bar), or preferably about 200 psi (13.8 bar). These conditions are maintained for about 15 to about 60 min, or about 20 to about 50 min, and after which, the air is cooled while no more air is added to the autoclave. After about 20 to about 40 min of cooling, the excess air pressure is vented and the laminated products are removed from the autoclave.
The solar cell modules may also be produced through non-autoclave processes.
Suitable non-autoclave processes are described, e.g., in U.S. Patent Nos.
3,234,062;
3,852,136; 4,341,576; 4,385,951; 4,398,979; 5,536,347; 5,853,516; 6,342,116;
and 5,415,909, U.S. Patent Publication No. 20040182493, European Patent No. EP1235683 B1, and PCT
Patent Publication Nos. W09101880 and W003057478. Generally, the non-autoclave processes include heating the pre-lamination assembly and the application of vacuum, pressure or both. For example, the assembly may be successively passed through heating ovens and nip rolls.
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These examples of lamination processes are not intended to be limiting.
Essentially any lamination process that is operative may be used.
The Examples below are provided to describe the invention in further detail.
These Examples, which set forth a preferred mode presently contemplated for carrying out the invention, are intended to illustrate and not to limit the invention.
EXAMPLES
Control Example CE1 A commercially available Butacite PVB sheet from DuPont, which comprises 72.97 wt% of poly(vinyl butyral), 26.7 wt% of triethyleneglycol di-2-ethyl-hexanoate, 0.1 wt% of TinuvinTM P Benzotriazole UV Absorber (Ciba), 0.003 wt% of TinuvinTM 123 hindered amine light stabilizer (HALS) (Ciba), and 0.22 wt% octylphenol, based on the total weight of the PVB
composition, was laminated to a silver coated glass sheet at the silver coated side. After 1000 hours of conditioning at 85% RH, 85 C and under a bias of 1000 V, the PVB
sheet changed color from near water white to dark brown.
In connection with Control Example CE1, TinuvinTMP is a 2-H substituted derivative of benzotriazole. Accordingly, it is not an unsaturated heterocyclic compound as the term is defined herein.
Control Examples CE2 to CE7 and Examples El to E5 Solutions of dried neat PVB resin (6.9 x 10-5 mol), silver nitrate (1.2 x 10-5 mol), and additive(s) were prepared by mixing a solution of silver nitrate and additives in methanol with a solution of PVB flake in methanol. The PVB resin had a residual OH level of 18.8 wt%, as determined by ASTM E222-00(2005)el (Standard Test Methods for Hydroxyl Groups Using Acetic Anhydride Acetylation, Test B, Reflux Method), and a molecular weight of greater than 125,000 Da, as determined by size exclusion chromatography.
Two control solutions (CE2 and CE3), one with PVB in methanol without additives and one with PVB and silver nitrate in methanol without additives, were also prepared. The solutions were then heated at 60 C for two to eight hours. Their color change was monitored by measurement with a HunterLab Ultrascan Colorimeter (Hunter Labs, Reston, VA).
Yellowness index (YI) was calculated by ASTM E313-05, using a 2 observer and Illuminant C (2 /C), and normalized to a 1.0 cm pathlength. The results are summarized in Table 1.
BNSDOCID: <WO_2010005664A1_1_>
TABLE I
Sample Unsaturated UV Absorber Other Additives Yl Heterocyclic Compound CE2* --- --- -- 6*
CE3 -- -- -- 290.1 Tinuvin P
CE4 --- Benzotriazole UV --- 139.7 Absorber**
2.6 x 10-5 mol**
Tinuvin 326 CE5 Benzotriazole UV --- 175.8 Absorber"*
6.1 x 10-6 mol CE6 - _- Octylphenol*** 197.6 2.88 x 10 mol N,N-CE7 -- --- Diethylcyclohexylamine*** 151.2 1.3 x 10-3 cool E1 Benzotriazole'** -- 22.9 1.64 x 10" mol Tinuvin P
Benzotriazole*** Benzotriazole UV
E2 Absorber** -- 7.8 1.64 x 10-3 mol 8.9 x 10-6 mol Tinuvin 770 Low Benzotriazole*** Molecular Weight Hindered Amine Light E3 1.64 x 10-3 mol Stabilizer (HALS)** 11.1 5.7 x 10-6 mol Tinuvin P Tinuvin 770 Low Benzotriazole UV Molecular Weight Benzotriazole*** Hindered Amine Light E4 Absorber** Stabilizer (HALS)** 10.2 1.1 x 10-3 mol 8.9 x 10-6 mol s 5.7x10- mol Imidazole***
E5 8.6 x 10'4 mol -- -- 9.6 Notes: *A solution of PVB in methanol without silver nitrate;
**Ciba, Tarrytown, NY;
***Sigma Aldrich, St. Louis, MO.
BNSDOCID: <WO_2010085664A1_I_>
The data in Table 1 show that, as a result of the addition of silver nitrate to the PVB/methanol solution, the yellowness index (Yl) was changed from 6 (in Control Example CE2) to 290.1 (in Control Example CE3). Upon addition of an unsaturated heterocyclic compound (benzotriazole in Examples El to E4 and imidazole in Example E5), the Yl was reduced significantly compared to the PVB/silver nitrate/methanol control solutions (Control Examples CE3 to CE7). Addition of optional UV absorbers (e.g., TinuvinTMP, as in Example E2), hindered amines (e.g., TinuvinTM 770, as in Example E3), or both (as in Example E4) can provide a further reduction of YI.
Control Example CE8 and Example E6 In Example E6, 72.46 wt% of the dried neat PVB resin used in Examples El to E5 was blended with a solution of 0.5 wt% 1 H-benzotriazole, 0.12 wt% TinuvinTM P, and 0.22 wt%
octylphenol in 26.7 wt% triethylene glycol di-2-ethylhexanoate. This blend was fed into a single screw extruder and melted at a temperature of 200 C, nominally. The resulting melt was pressed into a 30 mil thick sheet, and the sheet was laminated between a first float glass sheet and a second float glass sheet. The second float glass sheet had a silver coating (200 nm thick) on the side that was laminated in contact with the PVB sheet. The laminate of Control Example CE8 had the same structure, except that the PVB sheet was comprised of 72.96 wt%
PVB resin, 26.7 wt% triethylene glycol di-2-ethylhexanoate, 0.12 wt% TinuvinTM
P, and 0.22 wt% octylphenol.
The laminates of Control Example CE8 and Example E6 were placed into a chamber held at 85 C and 85% relative humidity (RH) for 1000 hours and subjected to a bias of 1000 V.
After this exposure, the PVB sheet in the laminate of Control Example CE8 was dark brown, while the PVB sheet in the laminate of Example E6 was only lightly yellowed.
This result demonstrates that the addition of the 0.5 wt% of 1 H-benzotriazole mitigates the yellowing of a PVB sheet that is in contact with silver.
While certain of the preferred embodiments of the present invention have been described and specifically exemplified above, it is not intended that the invention be limited to such embodiments. Various modifications may be made without departing from the scope and spirit of the present invention, as set forth in the following claims.
Bt SDOCID: <WO_2010085664A1_I_>
1 H-1,2,3-benzotriazole, 2-methyl-4-nitro-2H-1,2,3-benzotriazole, benzotriazole-I -carbonyl chloride, 1-(2-butenoyl)-1H-benzotriazole, 1-(trimethylsilyl)-1H-benzotriazole, 1-(alpha-chloroacetyl)-1 H-benzotriazole, 1-(methylsulfonyl)-1 H-benzotriazole, 1 H-benzotriazole-4-sulfonic acid, 1-(1-ethoxy-2-propynyl)-1 H-benzotriazole, (1-pyrrolidinylmethyl) benzotriazole, (1-ethoxy-2-propenyl)benzotriazole, 1-(2,2,2-trimethylacetyl)-1 H-benzotriazole, benzotriazole- 1-acetic ethyl ester, 3-(1H-1,2,3-benzotriazole-1-yl)propanohydrazide, 1-[(trimethylsilyl)methyl]
benzotriazole, 5-aminobenzotriazole dihydrochloride, 5,6-dinitro-1 H-benzotriazole, 1-benzyl-1 H-benzotriazole, 1-(3-chloropropionyl)-1 H-benzotriazole, 1-(2-pyrrolecarbonyl)benzotriazole, 1-(2-furoyl)-1 H-benzotriazole, 1 -(trifluoromethyl)acetylbenzotriazole, (4-morpholinyl-methyl)benzotriazole, 1-benzoyl-1 H-benzotriazole, 1-(2-pyridylcarbonyl) benzotriazole, 1-(4-pyridylcarbonyl)benzotriazole, N-Phenylbenzotriazole-methanamine, 1-(phenoxymethyl)-1 H-benzotriazole, 1-(9-amino-3H-(1,2,3)#riazolo(4,5-f)quinolin-8-yl)ethanone, 2-benzotriazol-1-yl-ethanesulfonyl fluoride, 1-(2-thienylcarbonyl)-1 H-benzotriazole, 1-(2,2-dichloroacetyl)-1 H-benzotriazole, [1-(4-morpholinyl)ethyl]benzotriazole, benzotriazol-1-ylpyrrolidin-1-ylmethanethione, n-(1H-1,2,3-benzotriazol-1-ylmethyl)-3-methylaniline, alpha-methyl-n-phenyl-1 H-benzotriazole-1-methanamine, N-(1 H-1,2,3-benzotriazol-1-ylmethyl)-2-methylaniline, N-methyl-N-phenylbenzotriazolemethana mine, phenyl-1 H-1,2,3-benzotriazole-5-carboxyl ate, 1-(benzoyloxy)-1 H-1,2,3-benzotriazole, 3-(benzotriazol-1-ylmethoxy)-phenylamine, 1-(4-fluorobenzoyl)-1 H-benzotriazole, 1-[(phenylthio)methyl]-1 H-benzotriazole, [1-(4-morpholinyl)propyl]benzotriazole, 1-(3-phenyl-2-propenoyl)-1H-1,2,3-benzotriazole, n-(1H-benzotriazol-1 -ylmethyl)benzamide, benzotriazol-1-ylmethyl-(2-ethyl-phenyl)-amine, n-(1 H-1,2,3-benzotriazol-1-ylmethyl)-2,4-dimethylaniline, 4-(1 H-1,2,3-benzotriazol-1 -ylcarbonyl)phenyl methyl ether, 1-(benzyloxycarbonyl)benzotriazole, 2-benzotriazol-1-yl-n-pyridin-2-yl-acetamide, benzotriazol-1-ylmethyl-(2-methoxy-phenyl)-amine, n-(1 H-1,2,3-benzotriazol-1 -ylmethyl)-4-methoxyaniline, 1-O-tolylsulfanylmethyl-1 H-benzotriazole, n'-(2-(1 H-1,2,3-benzotriazole-1-yl)-1-methylethylidene)-2-cyanoacetohydrazide, methyl 3-(1 H-1,2,3-benzotriazol-4-yl(methyl) amino)-2-cyanoacrylate, 1-(4-ohlorobenzoyl)-1 H-benzotriazole, n-(1 H-1,2,3-benzotriazol-l-ylmethyl)-2-chloroaniline, benzotriazol-1-ylmethyl-(3-chloro-phenyl)-amine, n-(1H-1,2,3-benzotriazol-1-ylmethyl)-4-chloro-aniline, 1-(phenylsulfonyl)-1H-benzotriazole, and benzotriazol-1-ylmethyl-(2,5-difluoro-phenyl)-amine.
Examples of suitable 1,2,3-triazole derivatives include, but are not limited to, 5-nitro-1H-1,2,3-triazole, 1H-1,2,3-triazolo[4,5-b]pyridine, 1-hydroxy-7-azabenzotriazole solution, 3H-(1,2,3)triazolo(4,5-d)pyrimidi n-7-ylamine, 8-azaadenine, 8-azaguanine, 8-azaxanthine monohydrate, 1,2,3-triazole-4,5-dicarboxylic acid, n-phenyl-IH-1,2,3-triazol-5-amine, 1-acetyl-1 H-1,2,3-triazolo[4,5-b]pyridine, 3-methyl-8-azaguanine, 3H-1,2,3,4,5,7,7a-heptaaza-s-indacen-8-ol, 4,6-dimethyl-I H-v-triazolo(4,5-d)pyrimidine-5,7(4H,6H)-dione, 1,2,3-triazole-4,5-dicarboxylic acid, monopotassium salt of 1,2,3-triazole-4,5-dicarboxylic acid, 5-amino-1,4-diphenyl-1,2,3-triazole, 5-anilino-4-phenyl-lH-1,2,3-triazole, and rufinamide.
BNSDOCID: cWO 2010085664A1_I_>
Examples of suitable 1,2,4-triazole derivatives include, but are not limited to, 3-amino-1,2,4-triazole, 1H-1,2,4-triazol-5-amine, 1,2,4-triazolylsodium, 1 -vinyl-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-1,2,4-triazole-3-thiol, 1,2,4-triazole-3-carboxylic acid, 3-nitro-1H-1,2,4-triazole, 3-amino-1,2,4-triazole-5-thiol, 1,2,4-triazolo[1,5-a]pyrimidine, 3-acetamido-1 H-1,2,4-triazole, methyl-IH-1,2,4-triazole-3-carboxylate, 5-amino-4H-(1,2,4)triazole-3-carboxylic acid, 5-amino-1 H-(1,2,4)triazole-3-carboxylic acid, 3-amino-1 H-1,2,4-triazole-5-carboxylic acid, 3-amino-5-methylthio-1H-1,2,4-triazole, 5-methyl-s-triazolo (1,5-a)pyrimidine, 1-trimethylsilyl-1,2,4-triazole, 5-amino-1 H-[1,2,4]-triazole-3-carboxylic acid methyl ester, 3-methyl-5-(2-oxido-2-oxohydrazino)-1H-1,2,4-triazole, 3-amino-1,2,4-triazole-5-carboxylic acid hydrate, 1H-1,2,4-triazole-1-carboxamidine hydrochloride, 5,7-dimethyl-s-triazolo[1,5-a]pyrimidine, 7-hydroxy-5-methyl[1,2,4]triazolo[1,5-a]pyrimidine, 5-methyl(1,2,4)triazolo(4,3-a)pyrimidin-7-ol, 7-amino-s-triazolo(1,5-a)pyrimidin-5(4H)-one, 5-(trifluoromethyl)-4H-1,2,4-triazol-3-ylamine, oxo(1H-1,2,4-triazol-5-ylamino)acetic acid, 3-(1,2,4-triazol-1-yl)-L-alanine, 5-amino-1 H-(1,2,4)triazole-3-carboxylic acid ethyl ester, beta-(1,2,4-triazol-3-yl)-DL-alanine, 1 -amino-5-propyl-1 H-1,2,4-triazol-3-yl hydrosulfide, 2-(2-aminophenyl)-1 H-1,3,4-triazole, 2-chloro-n-(4H-(1,2,4)triazol-3-yl)-acetamide, (5-dihydroxymethyl-2H-(1,2,4)triazol-3-yl)-methanediol, 1,1'-carbonyl-di-(1,2,4-triazole), 5,5'-dimethyl-1H,1'H-(3,3')BI((1,2,4)triazolyl), 1H,1'H-(3,3')Bl((1,2,4)triazolyl)-5,5'-diamine, 2H,2'H-(3,3')BI((1,2,4)triazolyl)-5,5'-diamine, 3,3'-bis(5-amino-4H-1,2,4-tria), 3-OXO-N-(1H-1,2,4-triazol-5-yl)butanamide, 7-chloro-5-methyl-(1,2,4)triazolo(1,5-a)pyrimidine, 1-(tert-butoxycarbonyl)1 H-1,2,4-triazole, s-triazolo(4,3-a)quinoline, 6,7,8,9-tetrahydro-5H-(1,2,4)triazolo (1,5-a)azepin-2-yl hydrosulfide, 2-(3-nitro-(1,2,4)triazol-1-yl)-acetamide, (3-nitro-(1,2,4)triazol-1-yl)-acetic acid, benzylidene-(1,2,4)triazol-4-Y, 4-(benzylideneamino)-4H-1,2,4-triazole, n-(4-pyrid inylmethylene)-4H-1,2,4-triazol-4-amine, (4-methyl-4H-(1,2,4)triazol-3-ylsulfanyl)-acetic acid, 3-methylamino-5-phenyl-1,2,4-triazole, 3-(3-pyridylmethylamino)-1,2,4-triazole, (1,2,4)triazolo (3,4-B)(1,3)benzothiazole, 3H-1,2,3,4,5,7,7A-heptaaza-S-indacen-8-OL, 1-phenyl-I H-(1,2,4)triazole-3-thiol, 5-phenyl-1 H-1,2,4-triazole-3-thiol, 5-propyl-(1,2,4)triazolo (1,5-A)pyrimidin-7-OL, 5-(4-pyridyl)-lH-1,2,4-triazole-3-thiol, 6-nitro-(1,2,4)triazolo (1,5-A)pyrimidin-2-ylamine, 5-((5-amino-4H-1,2,4-triazol-3-yl)methyl)-4H-1,2,4-triazol-3-ylamine, 3-((5-amino-1 H-1,2,4-triazol-3-yl)methyl)-1H-1,2,4-triazol-5-ylamine, 5,7-dimethyl-(1,2,4)triazolo (1,5-A)pyrimidine-2-thiol, hydrochloride of 3-phenyl-4H-(1,2,4)triazole, 3-mercapto-5-methyl-8H-(1,2,4)triazolo(4,3-A)pyrimidin-7-one, 5-amino-1H-(1,2,4)triazole-3-carboxylic acid butyl ester, and 3-(4-pyridinyl)-6,7-dihydro-5H-pyrrolo (2,1-C)(1,2,4)triazole.
Examples of suitable imidazoles include, but are not limited to, 2-methyl-2-imidazoline, 2-phenyl-2-imidazoline, 3-(4,5-dihydro-2-imidazolyl)pyridine, 8-methyl-2,3,7,8-tetrahydroimidazo(1,2-A)pyrimidin-5(6H)-one, (4,5-dihydro-1 H-imidazol-2-ylthio)acetic acid, 2-benzylimidazoline, 4-(4,5-dihydro-1 H-imidazol-2-yl)phenylamine, 2-(4,5-dihydro-1 H-imidazol-2-yl)phenol, 4-(4,5-dihydro-1 H-imidazol-2-yl)phenol, 3-(4,5-dihydro-1 H-imidazol-2-yl)phenol, 2-chloro-1,3-dimethylimidazolidinium chloride, 3A,4,5,6,7,7A-hexahydro-1 H-benzimidazol-2-yl BNSDOCID: cWO_2010085664A1_I_>
methyl sulfide, hydrochloride of imidazo(1,2-A)pyridin-2-one, 2,3-dihydro-5H-imidazo(2,1-A)isoindol-5-one, 2-amino-5,5-bis(hydroxymethyl)-1-methyl-l,5-dihydro-4H-imidazol-4-one, 4-(4-methyl-4,5-dihydro-1 H-imidazol-2-yl)phenylamine, 4-(4-methyl-4,5-dihydro-1 H-imidazol-2-yl)phenol, 2-(4-methyl-4,5-dihydro-1 H-imidazol-2-yl)phenol, 3-(4-methyl-4,5-dihydro-1 H-imidazol-2-yl)phenol, 2-amino-1-methyl-2-imidazoline hydrobromide, 2-mercapto-3-phenyl-3,5-dihydro-imidazol-4-one, 2-(4-methoxystyryl)-2-imidazoline, 2,10-dihydro-10-ethylimidazo(2,1-B)quinazoline-5(3H)-one, 2-methyl-4,5-di hydro-imidazole-1-carbothioic acid phenylamide, 2-chloro-1,3-dimethylimidazolidinium tetrafluoroborate, 2-(4-bromophenyl)-4,5-dihydro-1 H-imidazole, 2-(methylamino)-2-midazoline hydriodide, 2-(3-nitrophenyl)-4,5-dihydro-1 H-imidazole hydrochloride, 2-(4,5-dihydro-1 H-imidazol-2-yl)quinoline hydrochloride, 5-butoxy-2-(4,5-dihydro-I H-imidazol-2-yl)phenol, 3-(1,3-dimethyl-2,6-dioxo-1,2,3,4,5,6-hexahydro-9H-purin-9-yl)propanenitrile, tetrahydrozoline hydrochloride, idazoxan hydrochloride, tetramisole hydrochloride, levamisol hydrochloride, 1,3-diisopropylimidazolinium tetrafluoroborate, 2-(4,5-dihydro-IH-imidazol-2-yl)-1-benzofuran-5-yl thiocyanate, 2-methylthio-2-imidazoline hydriodide, 4,5-dihydro-1 H-imidazol-2-yl 2-fluorobenzyl sulfide hydrochloride, naphazoline hydrochloride, 4-chloro-alpha-(2-imidazolin-2-yl)benzyl alcohol hydrochloride, 5A, 11A-dihydronaphtho[2',3':4,5]imidazo[1,2-A]pyrid ine-6,11-dione, 2,3,6,7-tetrahydro-5,7,7-trimethyl-5H-pyrrolo(1,2-a)imidazole, 3-(4,5-dihydro-1H-imidazol-2-yl)aniline dihydrochloride hydrate, efaroxan hydrochloride, cirazoline hydrochloride, 1 -bityl-4,5-d i hyd ro-3-ethyl-8-hyd roxyxa nth ine, imidacloprid solution, 2-(4-fluorobenzylidene)-2,5,6,7,8,9-hexahydro-3H-imidazo(1,2-a)azepin-3-one, imidacloprid-d4, imazapyr, 9-benzyl-2-chloro-5,9-dihydro-4H-purin-6-ylamine, 2-fluoro-1,3-dimethylimidazolidinium hexafluorophosphate, 2-(4,5-dihydro-1H-imidazol-2-yl)-(hexyloxy)phenol, 3-phenyl-2-(4-toluidino)-3,5-dihydro-4H-imidazol-4-one, clonidine hydrochloride, n-(3-chlorophenyl)-n'-(i-methyl-4-oxo-4,5-dihydro-1 H-imidazol-2-yl)urea, 2,4,5-tri-(2-furyl)-2-imidazoline, 5-(benzyloxy)-2-(4,5-dihydro-1 H-imidazol-2-yl)phenol, 1,3-ditert-butyl-4,5-dihydro-1 H-imidazol-3-ium tetrafluoroborate, n-allyl-n-(2,6-dichlorophenyl)-4,5-dihydro-1 H-imidazol-2-amine, 2-(4,5-dihydro-1 H-imidazol-2-yl)-2,3-dihydro-l,4-benzodioxin-2-yl methyl ether hydrochloride, 2-(4,5-dihydro-1 H-imidazol-2-yl)-2,3-dihydro-l,4-benzodioxin-2-yl methyl ether, 3-(3,4-dihydroxyphenyl)-5,6-dihydroimidazo(2,1-B)thiazole hydrochloride, 2-methyl-n-(3-(trifluoromethyl)phenyl)-2-imidazoline-l-carboxamide, nitric acid compound with 2-(1-naphthylmethyl)-4,5-dihydro-1 H-imidazole (1:1), 2-benzyl-2-imidazoline thiosulfate, 1-[3-(triethoxysilyl)propyl]-4,5-dihydro-1 H-imidazole, 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1 H-imidazol-2-yl)-5-methylnicotinic acid, 2-[(E)-2-(2-methylphenyl)ethenyl]-4,5-dihydro-1 H-imidazole ethanedioate nonahydrochtoride, 6,6-diphenyl-2,3,6,7-tetrahydro-5H-pyrrolo(1,2-a)imidazol-5-one, 10-benzyl-2,3-dihydroimidazo(2,1-b)quinazolin-5(10H)-one, n-(4-chloro-6-methoxy-2-methyl-5-pyrimidinyl)-n-(4,5-dihydro-1H-imidazol-2-yl)amine hydrochloride, n-(4-chloro-6-methoxy-2-methyl-5-pyrimidinyl)-n-(4,5-dihydro-1H-imidazol-2-yl)amine hydrochloride, 2-chloro-1,3-dimethyl-4,5-dihydro-1 H-imidazol-3-ium hexafluorophosphate, 2,3,5,6,7,8-BNSDOCID: <WO 2010085664A1J_>
hexahydro-8-methylimidazo (1,2-a)pyrimidin-5-imine hydriodide, 3,7-dimethyl-1-(5-oxo-hexyl)-3,7-dihydro-purine-2,6-dione, 3,7-dimethyl-l-(5-oxohexyl)-3,7-dihydro-1 H-purine-2,6-dione, 2-(4-tert-butyl-2,6-dim ethyl benzyl)-4,5-dihydro-1 H-imidazole hydrochloride, 8-methyl-2,3,7,8-tetrahydroimidazo(1,2-a)pyrimidin-5(6H)-one hydriodide, 2,6-dichloro-N(1)-(4,5-dihydro-1 H-imidazol-2-yl)-1,4-benzenediamine hydrochloride, 3-(4-chlorophenyl)-2-ethyl-2,3,5,6-tetra-hydroimidazo(2, 1-b)thiazol-3-ol, 5-(4-chlorophenyl)-2,5-dihydro-3H-imidazo[2,1-a]isoindol-5-ol, 2-(4-nitrobenzylidene}2,5,6,7,8,9-hexahydro-3H-imidazo(1,2-a)azepin-3-one, 2-(2-nitrobenzylidene)-2,5,6,7,8,9-hexahydro-3H-imidazo(1,2-a)azepin-3-one, 9,13b-dihydro-1 H-dibenzo[c,f]imidazo[1,5-a]azepin-3-ylamine hydrochloride, 2-(4,5-dihydro-1 H-imidazol-2-ylthio)-n-(4-methylphenyl)acetamide hydrochloride, 2-(4,5-dihydro-1H-imidazol-2-ylthio)-n-(2-methylphenyl)acetamide hydrochloride, methyl 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1 H-imidazol-2-yl)-4-methylbenzoate, hydrobromide of 3-thiophen-2-yl-5,6-2H-imidazo(2,1-B)thiazole, 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)nicotinic acid, n-(5-chloro-2,1,3-benzothiadiazol-4-yl)-n-(4,5-dihydro-1 H-imidazol-2-yl)amine hydrochloride, 2-(4,5-dihydro-1 H-imidazol-2-yl)-5-(octyloxy)phenol, 5-bromo-N-(4,5-dihydro-1 H-imidazol-2-yl)-6-quinoxalinamine, 5-benzylidene-2-methylsulfanyl-3-phenyl-3,5-dihydro-imidazol-4-one, 5-benzyl idene-2-mercapto-3-(2-methylphenyl)-3, 5-dihydro-4H-imidazol-4-one, 6-tert-butyl-3-(4,5-dihydro-lH-imidazol-2-ylmethyl)-2,4-dimethylphenol hydrochloride, and DL-isoamarine.
Examples of suitable pyrrole derivatives include, but are not limited to, I H-pyrrole-d5, 1-methyl-1 H-pyrrole, 3-methyl-1 H-pyrrole, 1 H-pyrrole-2-carbonitrile, 1 H-pyrrole-2-carbaldehyde, 2,5-dimethyl-1 H-pyrrole, 2-ethyl-1 H-pyrrole, 2,4-dimethyl-1 H-pyrrole, 1 -(1 H-pyrrol-2-yl)ethanone, 1-methyl-1 H-pyrrole-2-carbaldehyde, 1,2,5-trimethyl-1 H-pyrrole, 1 H-pyrrole-2-carbaldehydehyde oxime, N,N-dimethyl-1 H-pyrrol-1-amine, 1 H-pyrrole-2-carboxylic acid, 1 H-indole, 1 H-pyrrolo[2,3-b]pyridine, 1,5-dimethyl-1 H-pyrrole-2-carbonitrile, 3-(1 H-pyrrol-1 -yl)propanenitrile, 3-(1 H-pyrrol-2-yl)-2-propenal, 4,5,6,7-tetrahydro-1 H-indole, 1 H-pyrrole-2,5-dicarbaldehyde, 1-(1-methyl-1 H-pyrrol-2-yl)ethanone, 3,5-dimethyl-1 H-pyrrole-2-carbaldehyde, 1-(1-methyl-1 H-pyrrol-3-yl)ethanone, 1-(4-methyl-1 H-pyrrol-3-yl)ethanone, 3-ethyl-2,4-dimethyl-1H-pyrrole, 1-(1H-pyrrol-2-yl)ethanone oxime, 1H-indole-d7, methyl 1H-pyrrole-1-carboxylate, 1-methyl-1H-pyrrole-2-carboxylic acid, 2,3-dihydro-6H-[1,4]dioxino[2,3-c]pyrrole, methyl 1 H-pyrrole-3-carboxylate, methyl 1 H-pyrrole-2-carboxylate, 3-chloro-1 H-pyrrole-2-carbaldehyde, 4-methyl-1 H-indole, 2-methyl-1 H-indole, 3-methyl-1 H-indole, 1-methyl-1 H-indole, 5-methyl-1 H-indole, 7-methyl-1 H-indole, 6-methyl-1 H-indole, 1 H-indol-5-amine, 1 H-indol-7-amine, 1 H-indol-6-amine, 1 H-indol-4-amine, 1 H-indol-4-ol, I H-indol-5-ol, 1 H-indol-6-ol, 5-fluoro-1 H-indole, 4-fluoro-1 H-indole, 6-fluoro-1 H-indole, 1,5,6,7-tetrahydro-4H-indol-4-one, 4-(1 H-pyrrol-2-yl)-3-buten-2-one, formic acid (2-pyrrolylmethylene)hydrazide, 1-(2,4-dimethyl-1 H-pyrrol-3-yl)ethanone, 1-(4-ethyl-1 H-pyrrol-3-yl)ethanon e, ethyl I H-pyrrole-2-carboxylate, 2-methyl-2,3-dihydro-6H-[1,4]dioxino[2,3-c]pyrrole, 3-(1 H-pyrrol-1 -yl)propanoic acid, 2-(1H-pyrrol-2-yl)acetohydrazide, 1 H-indole-4-carbonitrile, 1 H-indole-5-carbonitrile, 2-(1 H-pyrrol-2-BNSDOCID: cWO _2010095664A1 I >
ylmethylene)maIononitrile, 1-phenyl-1H-pyrrole, 1H-indole-3-carbaldehyde, 1H-indole-5-carbaldehyde, 1 H-indole-7-carbaldehyde, 1 H-indole-2-carbaldehyde, 1 H-indole-4-carbaldehyde, 1 H-indole-6-carbaldehyde, 2,5-dimethyl-1 H-indole, 1,3-dimethylindole, 1,2-dimethyl-1 H-indole, 7-ethyl-1 H-indole, 2,3-dimethyl-1 H-indole, 3-chloro-1 H-pyrrole-2-carboxylic acid, 1 H-pyrrolo[2,3-b]pyridine-3-carbaldehyde, 2-(1H -pyrrol-2-yl m ethyl)- 1H-pyrrole, 1 H-indol-5-ylmethanamine, 2-methyl-1 H-indol-5-amine, 1 H-indol-3-ylmethanol, 1 H-indol-5-yl methyl ether, 1 H-indol-2-ylmethanol, 1 H-indol-7-yl methyl ether, 1 H-indol-6-yl methyl ether, 1 H-indol-4-yl methyl ether, 1-(2-furylmethyl)-1 H-pyrrole, 5-formyl-3,4-dimethyl-1 H-pyrrole-2-carbonitrile, methyl 1 H-pyrrolo[2,3-c]pyrid in-5-yl ether, methyl 7H-pyrrolo(2,3-d)pyrimidin-4-yl ether, 2-methyl-7H-pyrrolo (2,3-d)pyrimidin-4-ol, 5-fluoro-2-methyl-1H-indole, 1-(1H-pyrrol-2-yl)-1-penten-3-one, 2-amino-7H-pyrrolo[2, 3-d]pyrimidin-4-ol, 2,5-dimethyl-1 H-pyrrole-3,4-dicarbaldehyde, 3-(1 H-pyrrol-3-yl)-acrylic acid methyl ester, and 3,4-dimethyl-2,5-pyrroledicarboxaldehyde.
Examples of suitable pyrazine derivatives include, but are not limited to, pyrazine-d4, 2-methylpyrazine, 2-pyrazinamine, 2-pyrazinecarbonitrile, 2,3-dimethylpyrazine, 2-ethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2-methoxypyrazine, 2-chloropyrazine, sodium salt of pyrazinol, imidazo[1,2-a]pyrazine, 1-(2-pyrazinyl)ethanone, 2-ethyl-3-methylpyrazine, 2,3,5-trimethyl pyrazine, 2-pyrazinecarboxamide, 2-pyrazinecarboxylic acid, 2-methoxy-3-methylpyrazine, 2-(methylsulfanyl)pyrazine, 2,3-pyrazinedicarbonitrile, quinoxaline, 5,6,7,8-tetrahydroquinoxaline, 5-methyl-6,7-dihydro-5H-cyclopenta[b]pyrazine, 1-(3-methyl-2-pyrazinyl)ethanone, 2,3,5,6-tetramethylpyrazine, 2,3-diethylpyrazine, methyl 2-pyrazinecarboxylate, 5-methyl-2-pyrazinecarboxylic acid, 2-ethyl-3-methoxypyrazine, 2-ethoxy-3-methylpyrazine, 3-amino-2-pyrazinecarboxylic acid, 5-hydroxy-2-pyrazinecarboxylic acid, 2-methyl-3-(methylsulfanyl)pyrazine, 2-(2-pyrazinyl)ethanethiol, 3-chloro-2,5-dimethylpyrazine, 5-methyl-2,3-pyrazinedicarbonitrile, 2-methylquinoxaline, 5-methylquinoxaline, 2-quinoxalinol, 2,6-dichioropyrazine, 2,3-dichioropyrazine, furo[3,4-b]pyrazine-5,7-dione, 1-(3-ethyl-2-pyrazinyl)etha none, 1-(3,5-dimethyl-2-pyrazinyl)ethanone, 2,3-diethyl-5-methylpyrazine, 2-isobutyl-3-methylpyrazine, 2-(2-(dimethylamino)ethyl)pyrazine, 2-isopropyl-3-methoxypyrazine, 2-methyl-6-propoxy-pyrazine, methyl 3-amino-2-pyrazinecarboxylate, 5,6-dimethyl-2,3-pyrazinedicarbonitrile, 2,3-dimethylquinoxaline, 6,7-dimethylquinoxa line, 2,3-dimethylpyrido (2,3-b)pyrazine, 5,6-diamino-2,3-pyrazinedicarbonitrile, 6,7-dimethylpteridine, 2,3-quinoxalinediol, pyrido[2,3-b]pyrazine-2,3-diol, 2-amino-4(3H)-pteridinone, 2,4-pteridinediol, 3-hydroxy-5,6-dimethyl-1 H-pyrazolo-(3,4b)-pyrazine, 2-chloroquinoxaline, 2,3-pyrazinedicarboxamide, 2-isobutyl-3-methoxypyrazine, 2-sec-butyl-3-methoxypyrazine, 2,3-pyrazinedicarboxylic acid, quinoxaline-2-carbaldehyde oxime, 2-quinoxalinecarboxylic acid, 2-methylquinoxaline-1,4-dioxide, 4-hydroxy-6,7-dimethylpteridine, hydrate of 2,3-dimethyl-quinoxaline, isoxanthopterin, phenazine, 3-amino-6-(chloromethyl)-2-pyrazinecarbonitrile 4-oxide, n-methyl-n'-quinoxalin-2-ylmethylene-hydrazine, 2,3-diethylquinoxaline, 2,3,6,7-tetramethylquinoxa line, 1-(3,5-diamino-6-chloro-2-pyrazinyl)ethanone, 3,5-diamino-6-chloro-2-BNSDOCID: <WO_2010065664A11>
WO 20101085664 PCT/US2014)/021829 pyrazinecarboxamide, 2-hydroxy-3,6,7-trimethylquinoxaline, 1,2,3,4,6,7,8,9-octahydrophenazine, 5-bromo-2,3-pyrazinediamine, 2-(nitromethyl)quinoxaline, 3-hydroxy-2-quinoxalinecarboxylic acid, 6,7-dimethyl-2,3-quinoxalinediol, 2,4-diamino-6,7-dimethylpteridine, 2-amino-6,7-dimethyl-4-pteridinol, 6,7-dimethyl-2,4-pteridinediol, (2,4-diamino-6-pteridinyl)methanol, 2-quinoxalinecarbonyl chloride, 2-amino-6-methyl-4,7-pteridinediol, 2-amino- I,5-dihydro-4,6-pteridinedione hydrate, 3-bromoimidazo[1,2-a]pyrazine, 2,6-dichloroquinoxaline, 2,3-dichloroquinoxaline, and ethyl 2-q uinoxalinecarboxylate.
Examples of suitable pyrimidine derivatives include, but are not limited to, 4-methylpyrimidine, 5-methylpyrimidine, 2-methylpyrimidine, 4-pyrimidinamine, 5-pyrimidinamine, pyrimidine 1-oxide, 2-pyrimidine-carbonitrile, 4,6-dimethylpyrimidine, 4-methyl-2-pyrimidinamine, 4,5-pyrimidinediamine, 2,4-pyrimidinediamine, 4,6-pyrimidinediol, 2,4-dihydroxypyrimidine, 2-pyrimidinethiol, 5-fluoro-2-pyrimidinol, 5-fluoro-pyrimidin-4-ol, 2-chloropyrimidine, 2,4-difluoropyrimidine, 9H-purine, 4-amino-5-pyrimidinecarbonitrile, n-(2-pyrimidinyl)-formamide, 4,6-dimethyl-2-pyrimidinamine, 2,6-dimethyl-4-pyrimidinol, 4,6-diamino-2-methylpyrimidine, 2-amino-6-methyl-4-pyrimidinol, 4-amino-6-hydroxy-2-methylpyrimidine, 6-methoxy-pyrimidinamine, 2,4,6-pyrimidinetriamine, 6-methyl-2,4(1 H,3H)-pyrimidinedione, 2-methyl-4,6-pyrimidinediol, 6-methyl-pyrimidine-4,5-diol, 5-methyl-4,6-pyrimidinediol, 2,6-diamino-4-pyrimidinol, 6-hydrazino-4-pyrimidinol, 6-methyl-4-pyrimidinethiol, 2-amino-4,6-pyrimidinediol, dihydro-2,4,5(3H)-pyrimidinetrione, 5-fluoro-6-methyl-pyrimidin-4-ol, 2-thioxo-2,3-dihydro-4(1 H)-pyrimidinone, 4-sulfanyl-2-pyrimidinol, 2-chloro-4-pyrimidinamine, 5-chloro-2-pyrimidinamine, 5-fluoro-pyrimidine-4-thiol, quinazoline, 2-chloro-5-fluoropyrimidine, 2-pyrimidinol hydrochloride, 4,5,6-trifluoropyrimidine, 2-amino-6-methyl-4(3H)-pteridinone, 4-amino-2-methyl-pyrimidine-5-carbonitrile, 6-methyl-9H-purine, 1H-pyrazolo[3,4-d]pyrimidin-4-amine, 7H-purin-2-amine, 9H-purin-6-amine, 5-cyano-2,4-diaminopyrimidine, 9H-purin-6-amine, 1,5-dihydro-4H-pyrazolo[3,4-d]pyrimidin-4-one, 3H-(1,2,3)triazolo(4,5-d)pyrimidin-7-ylamine, 1H-[1,2,3]triazolo[4,5-d]pyrimidin-7-amine, 9H-purin-6-amine, 2-acetamidopyrimidine, methyl 5-pyrimidinecarboxylate, 4,6-diamino-5-nitrosopyrimidine, 2-amino-5,6-dimethyl-4-pyrimidinol, 4-methoxy-6-methyl-2-pyrimidinamine, 6-hydroxy-4-pyrimidinecarboxylic acid, 5-nitro-2-pyrimidinamine, 5,6-dimethyl-2,4(1 H,3H)-pyrimidinedione, 5-methyoxy-2-methyl-pyrimidin-4-ol, 2,4-dimethoxypyrimidine, 5-amino-4-hydroxy-6-(methylamino)pyrimidine, 4,6-dimethyl-2-pyrimidinethiol, 4-methyl-2-(methylsulfanyl)pyri mid ine, 2-amino-4,6-dihydroxy-5-methylpyrimidine, 2-amino-5-methyoxy-pyrimidin-4, 5-amino-2,4-dihydroxy-6-methylpyrimidine, 4-amino-2-hydroxy-5-(hydroxymethyl) pyrimidine, 2-amino-6-methyl-4,5-pyrimidinediol, 4-amino-2-mercapto-6-methylpyrimidine, 6-methyl-2-thioxo-2,3-dihydro-4(1 H)-pyrimidinone, 2-methylsulfanyl-pyrimidin-5-ol, 2-methylsulfanyl-pyrimidin-4-ol, 2,4-diamino-6-mercaptopyrimidine, 4,5-diamino-2-mercaptopyrimidine, 2-chloro-5-ethylpyrimidine, 6-a mino-5-fluoro-2-methyl-pyri mid in-4-ol, 4-amino-2-hydroxy-6-mercaptopyrimidine, 4-chloro-6-methyl-2-pyrimidinamine, 2-thioxodihydro-4,6(1 H,5H)-pyrimidinedione, 2-chloro-5-methoxypyrimidine, 2-chloro-4-methoxypyrimidine, 6-BNSDOCID: <WO_2010085664A1_I_>
chloro-2-methyl-4-pyrimidinol, 6-chloro-2,4-pyrimidinediamine, 7H-purine-6-carbonitrile, 5-fluoro-6-fluoromethyl-pyrimidin-4-ol, 4(3H)-quinazolinone, and 4-methyl-2(1H)-pyrimidinone hydrochloride.
Examples of suitable pyridine derivatives include, but are not limited to, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-pyridinamine, 4-pyridinamine, 3-pyridinamine, pyridine 1-oxide, 2-pyridinol, 3-pyridinol, 4(1 H)-pyridinone, 4-methylpyridine-d3, 2-fluoropyridine, 3-fluoropyridine, pyridine hydrofluoride, 2-pyridinamine-d6, 2-methylpyridine-d7, 2-ethynylpyridine, 2-pyridinecarbonitrile, nicotinonitrile, isonicotinonitrile, 2-vinylpyridine, 4-vinylpyridine, 2-pyridinecarbaldehyde, nicotinaldehyde, isonicotinaldehyde, 2,5-dimethylpyridine, 4-ethylpyridine, 2,3-dimethylpyridine, 3,4-dimethylpyridine, 3-ethylpyridine, 2-ethylpyridine, 2,4-dimethylpyridine, 3,5-dimethylpyridine, 2,6-dimethylpyridine, N-methyl-N-(4-pyridinyl)amine, N-methyl-N-(2-pyridinyl)a mine, 2-methyl-3-pyrid ina mine, 4-pyridinylmethanamine, 2-methyl-4-pyridinamine, 3-methyl-2-pyridinamine, 4-methyl-2-pyridinamine, 5-methyl-3-pyridinamine, 3-pyridinylmethanamine, 2-pyridinylmethanamine, 5-methyl-2-pyridinamine, 6-methyl-2-pyridinamine, 6-methyl-3-pyridinamine, 4-methyl-3-pyridinamine, 2-methyl-4-pyridinamine, 3-methyl-2(1 H)-pyridinone, 4-methoxypyridine, 5-methyl-2-pyridinol, 2-methoxypyridine, 6-methyl-2-pyridinol, 3-pyridinylmethanol, 2-pyridinylmethanol, 6-methyl-3-pyridinot, 4-methyl-2-pyridinol, 4-pyridinylmethanol, 3-methoxypyridine, 2-methyl-3-pyridinol, 2,5-pyridinediamine, 2-hydrazinopyridine, 2,3-pyridinediamine, 3,4-pyridinediamine, 2,6-pyridinediamine, 2-amino-3-pyridinol, 2,4-pyridinediol, 2,3-pyridinediol, 2-fluoro-3-methylpyridine, 2-fluoro-6-methylpyridine, 2-fluoro-5-methylpyridine, 2-fluoro-4-methylpyridine, 2-pyridinethiol, 4-pyridinethiol, 5-fluoro-2-pyridinamine, 3-chloropyridine, 2-chloropyridine, 2,6-difluoropyridine, pyridine hydrochloride, 4-methyl-2-pyridinecarbonitrile, 6-methyl-2-pyridinecarbonitrile, 3-methyl-2-pyridinecarbonitrile, 1H-pyrrolo[2,3-b]pyridine, 3-pyridinylacetonitrile, 2-pyridinylacetonitrile, 5-methylnicotinonitrile, 1 H-imidazo[4,5-b]pyridine, and 2-aminonicotinonitrile.
Examples of suitable pyridizine derivatives include, but are not limited to, 3-methylpyridazine, 4-methylpyridazine, 3-pyridazinamine, pyridazine 1-oxide, 1,2-dihydro-3,6-pyridazinedione, 3,6-pyridazinediol, 4-pyridazinecarboxylic acid, 4-methyl-3,6-pyridazinediol, 3-chloro-6-methylpyridazine, 3-chloro-6-methoxypyridazine, 3-chloro-6-hydrazinopyridazine, 4-chloro-3,6-dihydroxypyridazine, 3,6-dichloropyridazine, 3,6-dichloropyridazine, 3-chloro-6-ethoxypyridazine, 6-chloro-3-methoxy-4-pyridazinamine, phthalazine-1,4-diamine, 3-chloro-6-(methylthio)pyridazine, 3,6-dichloro-4-methylpyridazine, 3,6-dichloro-4-pyridazinamine, 1-chlorophthalazine, 3-amino-5,6-dimethyl-4-pyridazinecarboxamide, cinnoline hydrochloride hydrate, 3-chloro-5,6-dimethyl-4-pyridazinecarbonitrile, 4-cinnolinecarboxylic acid, 5-amino-1,4-phthalazinediol, 1,4,5-timethyl-1H-pyrazolo[3,4-c]pyridazin-3-amine, 3,6-dichloro-N-methyl-4-pyridazinamine, 5-chloro-8-methyl-phthalazine, benzo(C)cinnoline, 3-chloro-6-phenylpyridazine, 3-chloro-6-(methylsulfonyl)pyridazine, 3,6-dichloro-4-pyridazinecarboxylic acid, 6-amino-1,4-phthalazinediol hydrate, 1,4-dichlorophthalazine, 4-amino-3-methyl-6-nitrocinnoline, 3-chloro-6-BNSDOCID: <WO_2010065664A1_I_>
methyl-4-phenylpyridazine, N-(3,6-dichloro-4-pyridazinyl)acetamide, 1-ethoxyphthalazine hydrochloride, 1,2,3,6,7,8-hexahydrocinnolino (5,4,3-CDE)cinnoline, 3-chloro-6-(4-methoxyphenyl)pyridazine, acetone O-(6-{[(1-methylethylidene) amino]oxy}-3-pyridazinyl)oxime, 4-((6-methoxy-3-pyridazinyl)amino)-4-oxo-2-butenoic acid, 4-styrylcinnoline, 3,6-diphenylpyridazine, 1-methyl-3H-benzo(H)pyrazolo (4,3-C)cinnoline, 1-chloro-4-phenylphthalazine, 8-chloro-4-hydroxy-3-cinnolinecarboxylic acid hydrate, 6-(phenylsulfinyl) tetraazolo[1,5-b]pyridazine, 6-methyl-3,4-diphenylpyridazine, 4-methyl-3,6-diphenylpyridazine, 4,5-dimethyl-N-[(E)-phenylmethylidene]-1H-pyrazolo[3,4-c]pyridazin-3-amine, 3,4,7-trimethyl-2-P-tolyl-2H-pyrazolo(3,4-D)pyridazine, 1,2,5,6-tetrathia-3,4,7,8-tetraazacyclopenta (FG)acenaphthylene, cyclopentanone (4-chloro-1-phthalazinyl)hydrazone, 3,6-bis(1,1,2,2-tetramethylpropyl)pyridazin e, 3-methyl-6-[3-(trifluoromethyl) phenyl][1,2,4]triazolo[4,3-b]pyridazine, 3,4-dihydro-1(2H)-naphthalenone (1, 2,4)triazolo(4,3-B)pyridazin-6-ylhydrazone, 4-amino-N-(6-methoxy-3-pyridazinyl)benzenesulfonamide, 1,4-dihydrazinophthalazine dihydro-chloride monohydrate, benzaldehyde (4-chloro-1-phthalazinyl)hydrazone, nicotinaldehyde (4-chloro-l-phthalazinyl)hydrazone, 4-amino-N-(6-chloro-3-pyridazinyl)benzenesulfonamide, 1-(3-hydroxy-5,6-diphenyl-4-pyridazinyl)ethanone, 2-((6-chloro-pyridazin-3-yi)-hydrazonomethyl)-4-nitro-phenol, 2-((6-chloro-pyridazin-3-yl)-hydrazonomethyl)-6-nitro-phenol, 4-amino-N-(6-ethoxy-3-pyridazinyl)benzenesulfonamide, 4-[(1-phthal-azinylsulfanyl)methyl]benzoic acid, 4-methylbenzaldehyde (4-chloro-1-phthalazinyl)hydrazone, 1-phenylethanone (4-chloro-1-phthalazinyl) hydrazone, 2-methylbenzaldehyde (4-chloro-1 -phthalazinyl)hydrazone, (1 R,5S)-3-(6-chloro-3-pyridazinyl)-3,8-diazabicyclo[3.2.1 ]octane di hydrochloride, and 4-methyl-N-[2-(4-morpholinyl)ethyl]-6-phenyl-3-pyridazinamine dihydrochloride.
Examples of suitable thiazole derivatives include, but are not limited to, 5-methyl-1,3-thiazole, 4-methyl-1,3-thiazole, 1,3-thiazol-2-amine, 1,3-thiazole-5-carbaldehyde, 1,3-thiazole-2-carbaldehyde, 4,5-dimethyl-1,3-thiazole, 2,4-dimethyl-1,3-thiazole, 4-methyl-1,3-thiazol-2-amine, and 5-methyl-1,3-thiazol-2-amine.
Examples of suitable benzoxazole derivatives include, but are not limited to, 2-methyl-1,3-benzoxazole, 2-hydrazinobenzoxazole, 6-fluoro-2-methyl-1,3-benzoxazole, 1,3-benzoxazol-2-yl hydrosulfide, 2-chloro-1,3-benzoxazole, 5-chioro-1,3-benzoxazole, 2,5,6-trimethylbenzoxazole, 5-methyoxy-2-methylbenzoxazole, 2-(methylthio)benzoxazole, 5-chloro-2-methyl-1,3-benzoxazole, 5-chloro-l,3-benzoxazol-2-amine, 1-(2-benzoxazolyl)-guanidine, 2-methyl-6-nitrobenzoxazole, 5-chloro-2,6-dimethylbenzoxazole, 2-methylnaphth (2,1-D)oxazole, 5-aceta m ido-2-m ethyl benzoxazole, 2-phenyl-1,3-benzoxazole, 5-phenyl-benzooxazole, 2-methyl-5-phenyl-1,3-benzoxazole, 2-phenyl-1,3-benzoxazol-5-amine, 4-(1,3-benzoxazol-2-yl)aniline, 2-(1,3-benzoxazol-2-yl)phenol, 5-cyclohexyl-2-methylbenzoxazole, 2-(2-methyiphenyl)-1,3-benzoxazol-5-amine, 5-(1,3-benzoxazol-2-yl)-2-methylaniline, 3-(6-methyl-1,3-benzoxazol-2-yl)phenylamine, 3-(5-methyl-1,3-benzoxazol-2-yl)phenylamine, 4-(5-methyl-1,3-benzoxazol-2-yl)phenylamine, 2-(5-methyl-1,3-benzoxazol-2-yl)phenol, N-benzooxazol-2-yl-BNSDOGID: <WO_2010085664A1_I_>
N'-furan-2-ylmethylene-hydrazine, 3-(5,6-dimethyl-1,3-benzoxazol-2-yl)aniline, 2-methyl-5-(6-methyl-1,3-benzoxazol-2-yl)aniline, 2-(4-ethylphenyl)-1,3-benzoxazol-5-amine, 2-methyl-5-(5-methyl-1,3-benzoxazol-2-yl)aniline, 2-(3-nitrophenyl)-1,3-benzoxazole, 3-(1,3-benzoxazol-2-yl)-4-chloroaniline, 2-(4-chlorophenyl)-1,3-benzoxazol-5-amine, 2-(2-chlorophenyl)-1,3-benzoxazol-5-amine, 2-(3-chlorophenyl)-1,3-benzoxazol-5-amine, 3-(5-chloro-1,3-benzoxazol-yl)phenylamine, 4-(5-chloro-1,3-benzoxazol-2-yl)phenylamine, 4-benzooxazol-2-yl-quinoline, methyl naphtho(1,2-D)(1,3)oxazol-2-yl sulfone, 2-(benzooxazol-2-yl-hydrazonomethyl)-phenol, 4-(benzooxazol-2-yl-hydrazonomethyl)-phenol, 4-chloro-3-(5-methyl-1,3-benzoxazol-2-yl)aniline, 4-chloro-3-(6-methyl-1,3-benzoxazol-2-yl)aniline, 4-benzooxazol-2-yl-2-methyl-quinoline, 2-(1-naphthyl)-1,3-benzoxazol-5-amine, 4-amino-2-(5-chloro-1,3-benzoxazol-2-yl)phenol, 5-amino-2-(5-chloro-1,3-benzoxazol-2-yl)phenol, 1,3-benzoxazol-2-yl phenoxyacetate, 2-chloro-3-ethyl-1,3-benzoxazol-3-ium tetrafluoroborate, ethyl 2-cyano-3-((2-methyl-1,3-benzoxazol-yl)amino)acrylate, 2-(4-methyoxy-benzylsulfanyl)-benzooxazole, 2-(((5-nitro-2-furyl)methyl)thio)-1,3-benzoxazole, 4-chloro-3-(5-chloro-1,3-benzoxazol-2-yl)aniline, 2-(2,4-dichlorophenyl)-1,3-benzoxazol-5-amine, 2-(2,5-dichlorophenyl)-1,3-benzoxazol-5-amine, 2-(3,4-dichlorophenyl)-1,3-benzoxazol-5-amine, 3-(1,3-benzoxazol-2-yl)-7-hydroxy-2H-chromen-2-one, N-[3-(1,3-benzoxazol-2-yl)phenyl}2-methylpropanamide, 4-(dimethylamino) benzaldehyde 1,3-benzoxazol-2-ylhydrazone, N-benzooxazol-2-yl-N'-(4-nitro-benzylidene)-hydrazine, 3-hydroxy-4-methoxybenzaldehyde 1,3-benzoxazol-2-ylhydrazone, N-(benzooxazoi-2-ylsulfanylmethyl)-benzamide, 4-methyoxy-thiobenzoic acid S-benzooxazoi-2-yl ester, 2-(4-nitro-benzylsulfanyl)-benzooxazole, 2-(1,1'-biphenyl)-4-yl-1,3-benzoxazol-5-amine, 2-(4-bromophenyl)-1,3-benzoxazol-5-amine, 2-(2-bromophenyl)-1,3-benzoxazol-5-amine, 2-(3-bromophenyl)-1,3-benzoxazol-5-amine, 3-chloro-thiobenzoic acid S-benzooxazoi-2-yl ester, 3-(1,3-benzoxazol-2-yl)-N-(4-methyl phenyl)-2-oxopropanamide, 2-(1,3-benzoxazol-2-ylthio)-1-(4-hydroxy-2-methylphenyl)ethanone, 2-((1,3-benzoxazol-2-ylthio)methyl)-4-nitrophenol, 3-(1,3-benzoxazol-2-yl)-7-hydroxy-2-oxo-2H-chromene-4-carbonitrile, diethyl 2-(2-benzoxazolyl)-2-ethyl m al on ate, 2-(3,5-dichloro-4-methoxyphenyl)-1,3-benzoxazol-5-amine, 2-(1,3-benzoxazol-2-yl)phenyl benzoate, N-benzooxazol-2-yl-N'-(4-bromo-benzylidene)-hydrazine, 2-(2,4-dinitrophenylth io)benzoxazole, toluene-4-sulfonic acid 1-benzooxazoi-2-yl-ethyl ester, 2-(3-bromo-4-methoxyphenyl)-1,3-benzoxazol-5-ylamine, 3-(1,3-benzoxazol-2-yl)-2-oxo-chromen-7-yl acetate, 2-(5-bromo-2-chlorophenyl)-1,3-benzoxazol-5-ylamine, 4-(5-(l ,3-benzoxazol-2-yl)-1 H-benzimidazol-2-yl)phenylamine, N-(4-acetyl-phenyl)-2-(benzooxazol-2-yl sulfanyl)-acetamide, 4-(2-(benzooxazoi-2-ylsulfanyl)-acetylamino)-benzoic acid, 3-(1,3-benzoxazol-2-yl)-N-(3-chloro-2-methylphenyl)-2-oxopropanamide, 4-(5-chloro-2-(2-chlorophenyl)-1,3-benzoxazol-7-yl)-3-butyn-2-ol, 2-(3-phenoxy-benzylsulfanyl)-benzooxazole, and 2-{4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy}propanoic acid.
Examples of suitable 1,3,5-triazine derivatives include, but are not limited to, 1,3,5-triazine-d3, 2-amino-1,3,5-triazine, 2,4-diamino-1,3,5-triazine, 1,3,5-triazine-2,4-diamine, 6-BNSDOCIO: <WO_2010085664A 1_I_>
methyl-1,3,5-triazine-2,4-diamine, 1,3,5-triazine-2,4,6-triamine, 4,6-diamino-1,3,5-triazin-2-ol, 1,3,5-triaz-inane-2,4,6-trione, 2,4,6-trifluoro-1,3,5-triazine, 4-amino-2-dimethylamino-1,3,5-triazine, 4-methoxy-6-methyl-1,3,5-triazin-2-amine, 6-chloro-1,3,5-triazine-2,4-diamine, 1,3,5-triazine-2,4,6-triamine hydrofluoride, N-(4-methoxy-6-methyl-1,3,5-triazin-2-yi)-N-methylamine, 4-chloro-N-ethyl-6-(hydroxyamino)-1,3,5-triazin-2-amine, 1,3,5-triazine-2,4,6-triol compound with hydrazine (1:1), N(2)-cyclopropyl-1,3,5-triazine-2,4,6-triamine, N(2)-ethyl-6-methoxy-1,3,5-triazine-2,4-diamine, 4-chloro-6-(hydroxyamino)-N-isopropyl-1,3,5-triazin-2-amine, 6-ethoxy-N(2)-methyl-1,3,5-triazine-2,4-diamine, 2,4,6-trimethoxy-1,3,5-triazine, 2-chloro-N-(1,3,5)triazin-2-yl-acetamide, 6-chloro-N(2)-ethyl-1,3,5-triazine-2,4-diamine, 2-chloro-4,6-dimethoxy-1,3,5-triazine, 1,3,5-triazine-2,4,6-trithiol, 4,6-dichloro-1,3,5-triazine, 4,6-dichloro-1,3,5-triazin-2-yl methyl ether, 2,4-diamino-6-isobutyryl-1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine, 6-phenyl-1,3,5-triazine-2,4-diamine, 2,4,6-trichloro-1,3,5-triazine, 6-chloro-N(2)-isopropyl-1,3,5-triazine-2,4-diamine, 4,6-diamino-gamma-oxo-1,3,5-triazine-2-butyronitrile, N-methyl-6-trifluoromethyl-(1, 3,5)triazine-2,4-diamine, 2-amino-4-cyclohexylamino-1,3,5-triazine, potassium 4,6-dioxo-1,4,5,6-tetrahydro-1,3,5-triazine-2-carboxylate, N(2)-(tert-butyl)-6-methoxy-1,3,5-triazine-2,4-diamine, 2,4-diamino-6-(m-tolyl)-1,3,5-triazine, N(2)-(2-methylphenyl)-1,3,5-triazine-2,4-diamine, N(2)-(4-methylphenyl)-1,3,5-triazine-2,4-diamine, N(2)-(sec-butyl)-6-chloro-1,3,5-triazine-2,4-diamine, 6-chloro-N(2),N(4)-diethyl-1,3,5-triazine-2,4-diamine, 6-chloro-N(2),N(4)-diethyl-1,3,5-triazine-2,4-diamine, N(2)-(tert-butyl)-6-chloro-1,3,5-triazine-2,4-diamine, 6-(3-fluorophenyl)-1,3,5-triazine-2,4-diamine, 6-(4-fluorophenyl)-1,3,5-triazine-2,4-diamine, 6-(2-fluorophenyl)-1,3,5-triazine-2,4-diamine, N(2),N(2),N(4),N(4), N(6),N(6)-hexamethyl-1,3,5-triazine-2,4,6-triamine, 4,6-bis(isopropylamino)-1,3,5-triazin-2-ol, 4-(tert-butylamino)-6-(ethylamino)-1,3,5-triazin-2-ol, N(2)-ethyl-N(4)-isopropyl-6-methoxy-1,3,5-triazine-2,4-diamine, 6-chloro-N(2),N(4)-diethyl-1,3,5-triazine-2,4-diamine-dl0, N(2),N(4)-diethyl-6-(methyl-sulfanyl)-1,3,5-triazine-2,4-diamine, 2,4-diamino-6-(2,3-xylyl)-1,3,5-triazine, 6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine, 6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine, 6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine, N(2)-(2-methyoxy-phenyl)-1,3,5-triazine-2,4-diamine, 6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diamine, 2-chloro-4-ethyl-d5-amino-6-isopropylamino-1,3,5-triazine, 4,6-dichloro-N,N-diethyl-1,3,5-triazin-2-amine, 2-amino-4-(4-chloroanilino)-1,3,5-triazine, 2-(2-chlorophenyl)-4,6-diamino-1,3,5-triazine, 6-(4-chloro-phenyl)-1,3,5-triazine-2,4-diamine, 2-N-butoxy-4,6-dichloro-l,3,5-triazine, 6-(3,5-difluorophenyl)-1,3,5-triazine-2,4-diamine, 2-amino-4-phenylamino-I,3,5-triazine hydrochloride, 1-[4-amino-6-(methylsulfanyl)-1,3,5-triazin-2-yl]-3-isopropyl-l ,2-triazadien-2-ium, N(2),N(4)-diisopropyl-6-methoxy-1,3,5-triazine-2,4-diamine, N(2)-(sec-butyl)-N(4)-ethyl-6-methoxy-1,3,5-triazine-2,4-diamine, N(2)-(tert-butyl)-N(4)-ethyl-6-methoxy-1,3,5-triazine-2,4-diamine, N(2)-methyl-6-(2-phenylvinyl)-1,3,5-triazine-2,4-diamine, 6-(ethylthio)-N(2)-isopropyl-N(4)-methyl-1,3,5-triazine-2,4-diamine, N(2)-ethyl-N(4)-isopropyl-6-(methylsulfanyl)-1,3,5-triazine-2,4-diamine, 6-chloro-N (2)-cyclopropyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine, 2,4-diamino-6-phenylacetyl-1,3,5-BNSDOCID: cWO_2010085664A1_ , triazine, N(2),N(4),N(6)-trichloro-1,3,5-triazine-2,4,6-triamine, 6-chloro-N,N'-dipropyl-(1,3,5)triazine -2,4-diamine, N(2)-(sec-butyl)-6-chloro-N(4)-ethyl-1,3,5-triazine-2,4-diamine, 6-chloro-N(2),N(4)-diisopropyl-1,3,5-triazine-2,4-diamine, 6-chloro-N(2),N(2), N(4)-triethyl-1,3,5-triazine-2,4-diamine, 4-(1,2,4)triazol-4-yl-6-trifluoromethyl-(1,3,5)triazin-2-ylamine, 2,4-diamino-6-(3-nitrophenyl)-1,3,5-triazine, 2-amino-4-anilino-6-(chloromethyl)-1,3,5-triazine, 4-chloro-2-(4,6-diamino-1,3,5-triazin-2-yl)phenol, 5,7-bis(ethylamino)(1,2,4)triazolo(4,3-A)(1,3,5)triazine-3-thiol, 2-{[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino}-2-m ethylpropanenitrile, N(2),N(4)-diisopropyl-6-(methylsulfanyl)-1,3,5-triazine-2,4-diamine, N(2)-(tert-butyl)-N(4)-ethyl-6-(methylsulfanyi)-1,3,5-triazine-2,4-diamine, 4,6-dichloro-1,3,5-triazin-2-yl phenyl ether, 1,3,5-Triazine-2,4,6-trithiol trisodium salt, N(2)-(sec-butyl)-6-chloro-N(4)-isopropyl-1,3,5-triazine-2,4-diamine, 2,4,6-tris(allyloxy)-1,3,5-triazine, and N(4-amino-S-triazin-2-yl)-sulfanilic acid.
Examples of suitable 2,2'-bipyridine derivatives include, but are not limited to, 2,2'-bipyridine, 6-methyl-2,2'-bipyridine, 2-(2-pyridinyl)pyridine 1-oxide, 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 6,6'-dimethyl-2,2'-bipyridine, 2,2'-bipyridine-3,3'-diol, 2,2'-bipyridineN,N'-dioxide, and 2-(2-pyridinyl)quinoline.
1 H-Benzotriazole, non-2H-substituted benzotriazole derivatives, imidazole, and imidazole derivatives are preferred unsaturated heterocyclic compounds.
Specific examples of preferred unsaturated heterocyclic compounds include, without limitation, I H-benzotriazole; 5-methyl-1 H-benzotriazole; imidazole; 2-methyl imidazole; and 1 H-1,2,3-triazole. 1H-Benzotriazole is a more preferred unsaturated heterocyclic compound.
Moreover, the PVB composition may further comprise one or more UV absorbers at a level ranging from about 0.01 wt%, or about 0.05 wt%, or about 0.08 wt% to about 1 wt%, or about 0.8 wt%, or about 0.5 wt%, based on the total weight of the PVB
composition. UV
absorbers are well-known in the art, and any known UV absorber may find utility within the PVB
composition. Examples of suitable UV absorbers include, but are not limited to, benzotriazole derivatives, hydroxybenzophenones, hydroxyphenyl triazines, esters of substituted and unsubstituted benzoic acids, and mixtures of any two or more of these suitable UV absorbers.
Significantly, the benzotriazole derivatives that are useful as UV absorbers are 2-H substituted benzotriazole derivatives. Therefore, they are not included in the definitions of non-2-H
substituted benzotriazole derivatives and of unsaturated heterocyclic compounds that are set forth above. Suitable commercially available UV absorbers include, but are not limited to, TinuvinTM P, TinuvinT"" 1130, TinuvinTM 326, TinuvinTM 327, TinuvinT"' 328, TinuvinTM 571, TinuvinTM 99-DW, or Chimassobs"d 81, manufactured by Ciba, UvinuIT" 3000, UvinulTM 3008, UvinuIT" 3040, or UvinuITM 3050, manufactured by BASF (Germany), and CyasorbT"" 5411, manufactured by Cytec Industries, Inc.
The PVB composition may further comprise one or more thermal stabilizers at a level ranging from about 0.01 wt%, or about 0.05 wt%, or about 0.08 wt% to about 1 wt%, or about 0.8 wt%, or about 0.5 wt%, based on the total weight of the PVB composition.
The thermal BNSOOCID: <WO 2010085664A7 I->
stabilizers used here may also be referred to as phenolic antioxidants and are well known in the industry. Examples of suitable thermal stabilizers include, but are not limited to, IrganoxT'"
1010, IrganoxTM 1035, IrganoxTM 1076, IrganoxT"" 1081, IrganoxT"' 1098, IrganoxTM 1135, IrganoxTM 1330, IrganoxTM 1425 WL, lrganoxTM 1520, IrganoxTM 245, IrganoxTM
3114, trganoxTM
565, IrganoxTM E 201, or IrganoxTM MD 1024 manufactured by Ciba, LowinoxTM
1790, LowinoxTM 22M46, LowinoxTM 44B25, LowinoxT"" CA22, LowinoxTM CPL, LowinoxTM HD
98, LowinoxTM MD24, LowinoxTM TBM-6, or LowinoxTM WSP, manufactured by Chemtura (Middlebury, CT), CyanoxTM 1741, CyanoxTM 2246, or CyanoxTM 425, manufactured by Cytec, or mixtures of any thereof. Thermal stabilizers of note include LowinoxTM
1790, LowinoxTM
22M46, LowinoxTM 44B25, Lowinox"'A CA22, LowinoxTM CPL, LowinoxTM HD 98, LowinoxTM
MD24, LowinoxTM TBM-6, or LowinoxTM WSP, or mixtures of any thereof. One preferred thermal stabilizer is octylphenol. Another preferred thermal stabilizer is butylated hydoxytoluene (BHT).
The PVB composition may further comprise one or more hindered amines at a level of up to 1 wt %. Alternatively, the hindered amines may be present at a level ranging from about 0.08 wt%, or about 0.1 wt%, or greater than 0.1 wt%, to about 1 wt%, to about 0.8 wt%, or up to about 0.5 wt%, based on the total weight of the PVB composition. The hindered amines may be secondary or tertiary hindered amines. Examples of suitable secondary hindered amines include, but are not limited to, 2,2,6,6-Tetramethyl-piperadine, 2,2,6,6-Tetramethylpiperadinol, and mixtures thereof. Examples of suitable tertiary hindered amines include, but are not limited to, N-butyl piperidine, N,N-diethyl cyclohexyfamine, and mixtures of any two or more thereof. In some preferred PVB compositions, the hindered amines are hindered amine light stabilizers (HALS), which are typically secondary, tertiary, acetylated, N hydrocarbyloxy substituted, hydroxy substituted N-hydrocarbyloxy substituted, or other substituted cyclic amines which further incorporate steric hindrance, generally derived from aliphatic substitution on the carbon atoms adjacent to the amine function. As used herein, the terms "hindered amines" and "hindered amine light stabilizers" refer to compounds that are completely saturated, except for substituents that include a carbonyl group. Therefore, these terms do not refer to any of the unsaturated heterocyclic compounds described above. Hindered amine light stabilizers are also well known within the art and commercially available. For example, TinuvinTM 111, TinuvinTM 123, TinuvinTM 144, TinuvinTM 152, TinuvinTM 292, TinuvinTM 622, TinuvinTM 765, TinuvinTM 770, TinuvinTM 783,TinuvinTM 791, ChimassorbT"' 119, ChimassorbTM
2020, or ChimassorbTM 944, manufactured by Ciba (Tarrytown, NY), CyasorbTM 3346 or CyasorbTM
3853S manufactured by (Cytec Industries, Inc., Paterson, NJ), or a combination of any two or more thereof can be used in the PVB composition. Further information regarding suitable hindered amines and their use in encapsulant compositions may be found in U.S.
Provisional Appin. No. 61/146,522, filed on January 22, 2009 (Attorney Docket No. PP0086).
BNSDOCID: <WO^2 01 008 5 66 4A1_I_>
The PVB composition may further comprise one or more chelating agents at a level ranging from about 0.01 wt%, or about 0.05 wt%, or about 0.08 wt% to about 1 wt%, or about 0.8 wt%, or about 0.5 wt%, based on the total weight of the PVB composition.
Examples of suitable chelating agents include, but are not limited to, ethylenediaminetetraacetic acid (EDTA), ethylenediamine monoacetic acid, ethylenediamine diacetic acid, ethylenediamine triacetic acid, ethylene diamine, tris(2-aminoethyl) amine, diethylenetriaminepentacetic acid, or mixtures of any thereof. As used herein, the term "chelating agent" does not include 2,2'-bipyridine or its derivatives. Further information regarding suitable chelating agents and their use in encapsulant compositions may be found in U.S. Provisional Appin. No.
61/146,547, filed on January 22, 2009 (Attorney Docket No. PP0088).
In addition to the plasticizer and the additives listed above, the PVB
composition may further comprise one or more of any other suitable additives, including, but not limited to, adhesion control additives, surface tension controlling agents, processing aids, flow enhancing additives, lubricants, pigments, dyes, flame retardants, impact modifiers, nucleating agents, anti-blocking agents such as silica, dispersants, surfactants, coupling agents, reinforcement additives, such as glass fiber, fillers and the like. These additives, suitable concentrations of the additives, and methods for incorporating them into the PVB compositions are described in the Kirk Othmer Encyclopedia of Chemical Technology, 51h Edition, John Wiley &
Sons (New Jersey, 2004), for example.
Further provided herein is a solar cell module that comprises a solar cell assembly, wherein (A) the solar cell assembly comprises at least one solar cell and a silver component; (B) the solar cell assembly is fully or partially encapsulated by a PVB
encapsulant layer or layers comprising the PVB composition described above; and (C) the silver component is at least partially in contact with the PVB encapsulant layer or layers.
The term "solar cell" as used herein includes any article that converts light into electrical energy. Solar cells useful in the solar cell assemblies and modules described herein include, but are not limited to, wafer-based solar cells (e.g., c-Si or me-Si based solar cells), thin film solar cells (e.g., a-Si, pc-Si, CdTe, or CI(G)S based solar cells), and organic solar cells. In principle, however, any type of solar cell known in the art is suitable for use in the solar cell modules described herein. The solar cells may include, but are not limited to, those described in U.S. Patent Nos. 4,017,332; 4,179,702; 4,292,416; 6,123,824; 6,288,325;
6,613,603; and 6,784,361, U.S. Patent Publication Nos. 2006/0213548; 2008/0185033;
2008/0223436;
2008/0251120; and 2008/0271675; and PCT Patent Application Nos. W02004/084282 and 2007/103598.
By "fully encapsulated", it is meant that the solar cell assembly is laminated or sandwiched between two encapsulant layers comprising the PVB composition.
Generally, the area of the largest surface of the solar cell assembly is smaller than that of some other components of the solar cell module, such as, for example, the substrate or superstrate, or the 6NSDOCID: cWO 201 0085 66 4A1_1_>
front or back protecting layers, or the encapsulant layer(s) before or after lamination. Therefore, in modules comprising fully encapsulated assemblies, the two PVB encapsulant layers may come in contact with each other over the edges of the solar cell assembly and form a seal around the edges of the solar cell module. When the area of the largest surface of the encapsulant layers is larger than that of the solar cell assembly, the contact between them may be established in the stacked, unlaminated solar cell module. Alternatively, when the greatest two-dimensional surface area of the encapsulant layers is smaller than that of the solar cell assembly, the contact between them may not be established until the encapsulant layers melt and flow under the heat and pressure of the solar cell module lamination process. Those of skill in the art will be able to take account of the changes necessitated in the above description by solar cell assemblies having a significant thickness.
By "partially encapsulated", it is meant that the solar cell assembly, which comprises solar cells (such as thin film solar cells) and is deposited on a substrate (or superstrate), has one side that is opposite from the substrate (or superstrate) laminated to an encapsulant layer comprising the PVB composition so that the solar cell assembly is sandwiched between the substrate (or superstrate) and the PVB encapsulant layer. In modules comprising partially encapsulated assemblies, the PVB encapsulant layer may come in contact with the substrate (or superstrate) of the solar cell assembly over the edges of the solar cell module and form a seal around the edges of the solar cell assembly. Again, depending on the relative surface areas of the substrate (superstrate), the solar cell assembly and the encapsulant layer, the edge seal may form before or after the lamination process that forms the solar cell module.
In one solar cell module, for example, the PVB encapsulant layer(s) are formed from PVB sheets and the encapsulated solar cell assembly is formed by laminating one or both sides of the solar cell assemblies to the PVB sheet(s). The PVB sheets may have a thickness of about 0.25 to about 1.2 mm.
It has been found that, within a solar cell module, when a prior art PVB
encapsulant is in complete or partial contact with a silver component (such as a component comprising silver or silver alloy), the prior art PVB encapsulant tends to discolor or yellow over time.
Without wishing to be bound by theory, it is believed that such discoloration results when Ago comprised in the silver component is oxidized, under high voltage and high moisture conditions, to form Ag+ ions that migrate into the PVB encapsulant. Once in the PVB
encapsulant, the Ag' ions are then reduced to metallic silver (Ag ). The metallic silver, which may be in the form of nano-sized silver particles, is believed to cause the discoloration. By adding the unsaturated heterocyclic compounds and optionally the other additives described above into the PVB encapsulants, however, the formation of the elemental silver is prevented, and the resulting discoloration of the PVB encapsulant is mitigated.
More specifically, when the PVB encapsulant described herein is in prolonged contact with one or more silver components, the yellowness index (YI) change of the PVB encapsulant BNSDOCID: <WO_2010085664A1_I_>
is reduced or minimized. The YI for a PVB encapsulant can be determined in accordance with ASTM E313-05, using a 20 observer and using Illuminant C as a light source.
These conditions may also be described as "2 /C". The YI is reported in unitless numbers and must be normalized to a particular sample pathlength for direct comparison. In general, the Yl of PVB
encapsulants described herein remains about 60 or less, or about 55 or less, or about 50 or less, or 40 or less, or about 30 or less, or about 20 or less, for a sample having a pathlength of 1.0 cm.
The YI of the PVB encapsulant in a solar cell module is difficult to measure in situ, as the yellowness of the other components in the module, such as the coatings, is difficult to deconvolute from that of the encapsulant. In order to avoid this obstacle, it is generally necessary to delaminate the module, isolating the PVB encapsulant.
Delamination is also an inconvenient procedure, however. Therefore, the Yl of the PVB encapsulant is generally measured using a model system. Both solid encapsulants and polymer solutions may be used as model systems for the Yl of PVB encapsulants in solar cell modules.
When a solid encapsulant is used as a model, it is laminated to the silvered side of silver-coated glass sheet, then held under a bias of 1,000 V for 1000 hours at 85 C and at 85%
relative humidity (RH). The solid encapsulants used as models herein have a constant plasticizer concentration, for the validity of the comparison of the encapsulants' Yl. The total amount of the other additives (unsaturated heterocyclic compound, UV absorber, thermal stabilizer, hindered amine and the like) is typically about 1 % or less of the amount of plasticizer in the solid encapsulants; accordingly, changes in Yl due to variation in the amounts of the additives is deemed to be insignificant.
When a polymer solution is used as a model system, a stock solution of neat PVB resin (10g) in methanol (100g) is combined with a stock solution of a silver salt in methanol and with stock solutions of any additives that are included in the solution model. The solution samples are incubated at 60 C in a hot water bath for 2 to 8 hours, until the yellow color of a negative control sample becomes apparent to the naked eye. The samples are transferred to cuvettes having a pathlength of 1.0 cm, and their spectra are obtained according to the standard method.
The concentrations of the PVB and of the silver (calculated as silver ions) in the solution samples are held constant, again for validity of comparison of the solutions' Yl.
The term "silver component", as used herein, refers to a constituent part or to any sub-combination of the constituent parts of the solar cell assembly or of the solar cell module that comprises elemental silver. The terms "elemental silver", "metallic silver", and "Ag " are synonymous and are used interchangeably herein. The elemental silver may be present in substantially neat or pure form, for example as it is used in a reflector film. Alternatively, it may be compounded, for example with a non-metallic material such as a carrier or a filler, or it may be present in a solid solution, in an alloy, in crystalline form, as a powder or as a flake, as the continuous or dispersed phase of a dispersion, or in any other morphology. For example, the BNSDOCID: <WO2010085664A1_I_>
solder material used in some connecting wires is a silver and aluminum alloy containing as little as about 2 wt% of silver.
The silver component may be any one or more of the conductive paste, the connecting wires, the metal conductive coatings, and the metal reflector films.
The conductive paste, which is typically used in wafer-based solar cells, is a conductive film deposited on the front sun-facing or back non-sun-facing side of solar cells to efficiently contact the solar cells and transport the photo-generated current. The front conductive paste, for example, may comprise elemental silver.
The term "connecting wires" as used herein also includes the solder materials used to connect the individual wires together or to anchor the wires onto the solar cells. The connecting wires, which may be included in both wafer-based solar cells and thin film solar cells, are typically soldered on the surface of the solar cells to provide electrical connections between individual solar cells and to lead the photo-generated current out of the modules. In certain solar cell modules, the connecting wires (including its solder material), and especially the solder material, may comprise silver or a silver alloy.
During the construction of thin film solar cells, a first conductive layer (e.g., a transparent conductive oxide (TCO) or metal coating) is first coated on the substrate before the photon absorbing materials is deposited thereon. Further, during the construction of the solar cells, a second conductive layer (e.g., a TCO or metal coating) is further deposited on the photon absorbing materials. The silver component may be one or both of these two metal conductive coatings.
Metal back reflector films are often incorporated in thin film solar cells to reflect the photons that have passed around or through the solar cells back onto the solar cells, thereby improving power generating efficiency. In certain solar cell modules, the metal back reflector film is formed by sputtering a silver layer or a silver comprising layer on the solar cells.
Moreover, the silver component may be completely or partially in contact with the PVB
encapsulant. For example, "partially in contact with" indicates that the silver at least about 3.6 x10-5% of the silver component's surface area is in contact with the PVB
encapsulant. This amount corresponds to the calculated area of scribe lines in a thin film cell, although it is also used herein to indicate a minimum surface area of contact for other silver components and in different types of solar cell modules. In contrast, the silver component is completely in contact with PVB, for example in a solar cell module in which substantially 100% of the surface area of a reflector film is in contact with the PVB encapsulant. When used without modification, however, as in the term "the silver component is in contact with the PVB
encapsulant," for example, any non-zero level of contact is indicated. Stated alternatively, any non-zero percentage of the component's surface area may be in contact with the PVB
encapsulant.
In one module, the solar cells are wafer-based solar cells, and the silver component may be a conductive paste deposited thereon, or it may be one or more connecting wires. The silver BNSDOCID: <WO 2010085664A1_I_>
component is in contact with the PVB encapsulant. Further, the solar cell assembly, which comprises the wafer-based solar cells and the silver component, and which is encapsulated by the PVB encapsulant, may be further sandwiched between two protective outer layers (which are also referred to as the front and back sheets).
The protective outer layers of the solar cell modules may be formed of any suitable sheets or films. Suitable sheets include glass sheets, metal sheets such as aluminum, steel, galvanized steel, ceramic plates, or plastic sheets, such as polycarbonates, acrylics, polyacrylates, cyclic polyolefins (e.g., ethylene norbornene polymers), polystyrenes (preferably polystyrenes prepared in the presence of metallocene catalysts), polyamides, polyesters, fluoropolymers, or combinations of two or more thereof.
Suitable films include metal films, such as aluminum foil, or polymeric films such as those comprising polyesters (e.g., poly(ethylene terephthalate) and poly(ethylene naphthalate)), polycarbonate, polyolefins (e.g., polypropylene, polyethylene, and cyclic polyolefins), norbornene polymers, polystyrene (e.g., syndiotactic polystyrene), styrene-acrylate copolymers, acrylonitrile-styrene copolymers, polysulfones (e.g., polyethersulfone, polysulfone, etc.), nylons, poly(urethanes), acrylics, cellulose acetates (e.g., cellulose acetate, cellulose triacetates, etc.), cellophane, silicones, poly(vinyl chlorides) (e.g., poly(vinylidene chloride)), fluoropolymers (e.g., polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethyl en e-tetrafl u oroethylene copolymers, etc.), or combinations of two or more thereof. The polymeric film may be non-oriented, or uniaxially oriented, or biaxially oriented. Some specific examples of suitable polymeric films include, but are not limited to, polyester films (e.g., poly(ethylene terephthalate) films), fluoropolymer films (e.g., Tedlar , Tefzel(D, and Teflon films available from E. I. du Pont de Nemours and Company (DuPont), Wilmington, DE). Further, the films may be in the form of a multi-layer film, such as a fluoropolymer/ polyester/fluoropolymer multilayer film (e.g., Tedlar /PET/Tedlar or TPT laminate film available from Isovolta AG., Austria or Madico, Woburn, MA).
In another module, the solar cells are thin film solar cells, and the silver component may be selected from connecting wires, conductive coatings, or back reflector films, or a combination of two or more thereof. In one particular thin film solar cell, the silver component is a conductive coating comprising silver or silver alloy. The silver component may also be a back reflector film comprising silver or silver alloy. Similarly to the above described wafer-based solar cell modules, the thin film solar cell assembly is fully or partially encapsulated by the PVB
encapsulant, and the silver component is in contact with the PVB encapsulant.
Again, the fully or partially encapsulated thin film solar cell assembly may be further sandwiched between two additional protective outer layers, such as a front or back sheet.
Alternatively, the thin film solar cell assembly maybe partially encapsulated by the PVB encapsulant, i.e., in which the side that is opposite from the substrate (or superstrate) is laminated to the PVB
encapsulant, and in which the PVB encapsulant is further laminated to a protective outer layer.
Also preferably, the BNSDOCID: WO 2010085664A1 _I_o thin film solar cell assembly comprises a reflector film which, in turn, comprises silver and which is in contact with the PVB encapsulant.
In a preferred thin film solar cell module, the light absorbing materials are deposited on a substrate in layers. The substrate may be made of glass, or any suitable metal, or polymeric sheets or films as described above for the protective outer layers. The thin film solar cells may be single junction or multi-junction (including tandem junction) thin film solar cells. As the spectrum of solar radiation provides photons of varying energies, multi-junction solar cells were developed in which the sunlight passes serially through several solar cell layers. Each separate layer of the multi-junction solar cell is tailored to convert photons of a specific wavelength efficiently to electrical energy. The multi junction solar cells are usually constructed with layers of different energy gaps. The layers having greater energy gaps are adjacent to the surface through which the light enters the module. The layers having lesser energy gaps are positioned further towards the interior or back of the module.
Further provided is a solar cell array comprising two or more of the solar cell modules described above.
Further provided is a process for converting light energy to electricity, said process comprising the step of exposing a solar cell assembly or a solar cell module to electromagnetic radiation Further provided is a process for converting solar energy to electricity, said process comprising the step of exposing a solar cell assembly or a solar cell module to solar radiation.
Any suitable process may be used in preparing the solar cell modules described herein.
In particular, any suitable lamination process known within the art (such as an autoclave or a non-autoclave process) may be used to prepare the solar cell modules. For example, in a typical lamination process, the solar cells are first stacked between the PVB
encapsulants (e.g., in the form of PVB sheets), and further between two protective films or sheets, and this pre-lamination assembly is then subjected to the lamination process. Further, in the preparation of thin film solar cell modules, the solar cells, which are deposited over a substrate, are first stacked over the PVB encapsulant (e.g., in the form of a PVB sheet) and then a protective film or sheet, to form a pre-lamination assembly.
Accordingly, further provided herein is a pre-lamination assembly for preparing a solar cell module. The pre-lamination assembly comprises a solar cell assembly, which in turn comprises a solar cell, an oxidizable metal component, and a poly(vinyl butyral) sheet comprising the PVB composition described herein. Preferably, the poly(vinyl butyral) sheet has a thickness of about 0.25 mm to about 1.2 mm and a yellowness index of about 60 or less in accordance with ASTM E313-05 after 1000 hours at 85% relative humidity (RH) and at 85 C
with a bias of 1,000 V. The pre-lamination assembly may further comprise one or more additional layers selected from the group consisting of: a second poly(vinyl butyral) sheet that may be the same as or different from the poly(vinyl butyral) sheet, said second poly(vinyl BNSDOCID <WO 2010065664A11>
butyral) sheet being in contact with the solar cell assembly; a protective outer layer that is in contact with the poly(vinyl butyral) sheet; a second protective outer layer that may be the same as or different from the protective outer layer, said second protective outer layer in contact with the second poly(vinyl butyral) sheet; and a substrate or a superstrate that is in contact with the solar cell assembly and with the poly(vinyl butyral) sheet.
In one suitable process, the pre-lamination assembly is placed into a bag capable of sustaining a vacuum ("a vacuum bag"), the air is drawn out of the bag by a vacuum line or other means, the bag is sealed while the vacuum is maintained (e.g., at least about 27-28 in Hg (689-711 mm Hg)), and the sealed bag is placed in an autoclave at a pressure of about 150 to about 250 psi (about 11.3 to about 18.8 bar), a temperature of about 130 C to about 180 C, or about 120 C to about 160 C, or about 135 C to about 160 C, or about 145 C to about 155 C, for about 10 to about 50 min, or about 20 to about 45 min, or about 20 to about 40 min, or about 25 to about 35 min. A vacuum ring may be substituted for the vacuum bag. One type of suitable vacuum bag is described in U.S. Patent No. 3,311,517. Following the heat and pressure cycle, the air in the autoclave is cooled without adding additional gas to maintain pressure in the autoclave. After about 20 min of cooling, the excess air pressure is vented and the laminates are removed from the autoclave.
Alternatively, the pre-lamination assembly may be heated in an oven at about 80 C to about 120 C, or about 90 C to about 100 C, for about 20 to about 40 min, and thereafter, the heated assembly is passed through a set of nip rolls so that the air in the void spaces between the individual layers may be squeezed out, and the edge of the assembly sealed. The assembly at this stage is referred to as a pre-press.
The pre-press may then be placed in an air autoclave where the temperature is raised to about 120 C to about 160 C, or about 135 C to about 160 C, at a pressure of about 100 to about 300 psi (about 6.9 to about 20.7 bar), or preferably about 200 psi (13.8 bar). These conditions are maintained for about 15 to about 60 min, or about 20 to about 50 min, and after which, the air is cooled while no more air is added to the autoclave. After about 20 to about 40 min of cooling, the excess air pressure is vented and the laminated products are removed from the autoclave.
The solar cell modules may also be produced through non-autoclave processes.
Suitable non-autoclave processes are described, e.g., in U.S. Patent Nos.
3,234,062;
3,852,136; 4,341,576; 4,385,951; 4,398,979; 5,536,347; 5,853,516; 6,342,116;
and 5,415,909, U.S. Patent Publication No. 20040182493, European Patent No. EP1235683 B1, and PCT
Patent Publication Nos. W09101880 and W003057478. Generally, the non-autoclave processes include heating the pre-lamination assembly and the application of vacuum, pressure or both. For example, the assembly may be successively passed through heating ovens and nip rolls.
BNSDOCID: cWO_2010085664A1_I_>
These examples of lamination processes are not intended to be limiting.
Essentially any lamination process that is operative may be used.
The Examples below are provided to describe the invention in further detail.
These Examples, which set forth a preferred mode presently contemplated for carrying out the invention, are intended to illustrate and not to limit the invention.
EXAMPLES
Control Example CE1 A commercially available Butacite PVB sheet from DuPont, which comprises 72.97 wt% of poly(vinyl butyral), 26.7 wt% of triethyleneglycol di-2-ethyl-hexanoate, 0.1 wt% of TinuvinTM P Benzotriazole UV Absorber (Ciba), 0.003 wt% of TinuvinTM 123 hindered amine light stabilizer (HALS) (Ciba), and 0.22 wt% octylphenol, based on the total weight of the PVB
composition, was laminated to a silver coated glass sheet at the silver coated side. After 1000 hours of conditioning at 85% RH, 85 C and under a bias of 1000 V, the PVB
sheet changed color from near water white to dark brown.
In connection with Control Example CE1, TinuvinTMP is a 2-H substituted derivative of benzotriazole. Accordingly, it is not an unsaturated heterocyclic compound as the term is defined herein.
Control Examples CE2 to CE7 and Examples El to E5 Solutions of dried neat PVB resin (6.9 x 10-5 mol), silver nitrate (1.2 x 10-5 mol), and additive(s) were prepared by mixing a solution of silver nitrate and additives in methanol with a solution of PVB flake in methanol. The PVB resin had a residual OH level of 18.8 wt%, as determined by ASTM E222-00(2005)el (Standard Test Methods for Hydroxyl Groups Using Acetic Anhydride Acetylation, Test B, Reflux Method), and a molecular weight of greater than 125,000 Da, as determined by size exclusion chromatography.
Two control solutions (CE2 and CE3), one with PVB in methanol without additives and one with PVB and silver nitrate in methanol without additives, were also prepared. The solutions were then heated at 60 C for two to eight hours. Their color change was monitored by measurement with a HunterLab Ultrascan Colorimeter (Hunter Labs, Reston, VA).
Yellowness index (YI) was calculated by ASTM E313-05, using a 2 observer and Illuminant C (2 /C), and normalized to a 1.0 cm pathlength. The results are summarized in Table 1.
BNSDOCID: <WO_2010005664A1_1_>
TABLE I
Sample Unsaturated UV Absorber Other Additives Yl Heterocyclic Compound CE2* --- --- -- 6*
CE3 -- -- -- 290.1 Tinuvin P
CE4 --- Benzotriazole UV --- 139.7 Absorber**
2.6 x 10-5 mol**
Tinuvin 326 CE5 Benzotriazole UV --- 175.8 Absorber"*
6.1 x 10-6 mol CE6 - _- Octylphenol*** 197.6 2.88 x 10 mol N,N-CE7 -- --- Diethylcyclohexylamine*** 151.2 1.3 x 10-3 cool E1 Benzotriazole'** -- 22.9 1.64 x 10" mol Tinuvin P
Benzotriazole*** Benzotriazole UV
E2 Absorber** -- 7.8 1.64 x 10-3 mol 8.9 x 10-6 mol Tinuvin 770 Low Benzotriazole*** Molecular Weight Hindered Amine Light E3 1.64 x 10-3 mol Stabilizer (HALS)** 11.1 5.7 x 10-6 mol Tinuvin P Tinuvin 770 Low Benzotriazole UV Molecular Weight Benzotriazole*** Hindered Amine Light E4 Absorber** Stabilizer (HALS)** 10.2 1.1 x 10-3 mol 8.9 x 10-6 mol s 5.7x10- mol Imidazole***
E5 8.6 x 10'4 mol -- -- 9.6 Notes: *A solution of PVB in methanol without silver nitrate;
**Ciba, Tarrytown, NY;
***Sigma Aldrich, St. Louis, MO.
BNSDOCID: <WO_2010085664A1_I_>
The data in Table 1 show that, as a result of the addition of silver nitrate to the PVB/methanol solution, the yellowness index (Yl) was changed from 6 (in Control Example CE2) to 290.1 (in Control Example CE3). Upon addition of an unsaturated heterocyclic compound (benzotriazole in Examples El to E4 and imidazole in Example E5), the Yl was reduced significantly compared to the PVB/silver nitrate/methanol control solutions (Control Examples CE3 to CE7). Addition of optional UV absorbers (e.g., TinuvinTMP, as in Example E2), hindered amines (e.g., TinuvinTM 770, as in Example E3), or both (as in Example E4) can provide a further reduction of YI.
Control Example CE8 and Example E6 In Example E6, 72.46 wt% of the dried neat PVB resin used in Examples El to E5 was blended with a solution of 0.5 wt% 1 H-benzotriazole, 0.12 wt% TinuvinTM P, and 0.22 wt%
octylphenol in 26.7 wt% triethylene glycol di-2-ethylhexanoate. This blend was fed into a single screw extruder and melted at a temperature of 200 C, nominally. The resulting melt was pressed into a 30 mil thick sheet, and the sheet was laminated between a first float glass sheet and a second float glass sheet. The second float glass sheet had a silver coating (200 nm thick) on the side that was laminated in contact with the PVB sheet. The laminate of Control Example CE8 had the same structure, except that the PVB sheet was comprised of 72.96 wt%
PVB resin, 26.7 wt% triethylene glycol di-2-ethylhexanoate, 0.12 wt% TinuvinTM
P, and 0.22 wt% octylphenol.
The laminates of Control Example CE8 and Example E6 were placed into a chamber held at 85 C and 85% relative humidity (RH) for 1000 hours and subjected to a bias of 1000 V.
After this exposure, the PVB sheet in the laminate of Control Example CE8 was dark brown, while the PVB sheet in the laminate of Example E6 was only lightly yellowed.
This result demonstrates that the addition of the 0.5 wt% of 1 H-benzotriazole mitigates the yellowing of a PVB sheet that is in contact with silver.
While certain of the preferred embodiments of the present invention have been described and specifically exemplified above, it is not intended that the invention be limited to such embodiments. Various modifications may be made without departing from the scope and spirit of the present invention, as set forth in the following claims.
Bt SDOCID: <WO_2010085664A1_I_>
Claims (15)
1. A solar cell module comprising a solar cell assembly comprising one or more solar cells and a poly(vinyl butyral) encapsulant, wherein (i) the solar cell assembly further comprises a silver component; (ii) the silver component comprises elemental silver; (iii) the silver component is in contact with the poly(vinyl butyral) encapsulant; (iv) the poly(vinyl butyral) encapsulant comprises a poly(vinyl butyral) polymer, about 15 to about 45 wt%
of one or more plasticizers and about 0.1 to about 2 wt% of one or more unsaturated heterocyclic compounds, based on the total weight of the poly(vinyl butyral) encapsulant.
of one or more plasticizers and about 0.1 to about 2 wt% of one or more unsaturated heterocyclic compounds, based on the total weight of the poly(vinyl butyral) encapsulant.
2. The solar cell module of Claim 1, wherein the unsaturated heterocyclic compound is 1H-benzotriazole or a non-2-H substituted benzotriazole derivative having a formula of:
or imidazole or an imidazole derivative having a formula of:
wherein R represents a hydrogen atom or a substituent; wherein, when the unsaturated heterocyclic compound comprises more than one substituent R, the substituents R are identical or different; and wherein the substituents R are selected from the group consisting of alkyl groups that are branched or unbranched, linear or cyclic; singly or multiply unsaturated hydrocarbon groups that are unbranched or branched, linear or cyclic, aromatic or non-aromatic; amino groups; hydroxyl groups; alkoxy groups; and halogen atoms; and further wherein one or more of the substituents R may optionally be substituted with one or more halogen atoms that may be the same or different or with one or more branched or unbranched alkyl groups comprising from 1 to 4 carbon atoms that may be the same or different.
or imidazole or an imidazole derivative having a formula of:
wherein R represents a hydrogen atom or a substituent; wherein, when the unsaturated heterocyclic compound comprises more than one substituent R, the substituents R are identical or different; and wherein the substituents R are selected from the group consisting of alkyl groups that are branched or unbranched, linear or cyclic; singly or multiply unsaturated hydrocarbon groups that are unbranched or branched, linear or cyclic, aromatic or non-aromatic; amino groups; hydroxyl groups; alkoxy groups; and halogen atoms; and further wherein one or more of the substituents R may optionally be substituted with one or more halogen atoms that may be the same or different or with one or more branched or unbranched alkyl groups comprising from 1 to 4 carbon atoms that may be the same or different.
3. The solar cell module of claim 2, wherein R represents hydrogen or a substituent selected from the group consisting of branched and linear alkyl groups having from 1 to 4 carbon atoms.
4. The solar cell module of Claim 1, wherein the unsaturated heterocyclic compound is selected from the group consisting of 1H-benzotriazole; 5-methyl-1H-benzotriazole;
imidazole; 2-methyl imidazole; and 1H-1,2,3-triazole.
imidazole; 2-methyl imidazole; and 1H-1,2,3-triazole.
5. The solar cell module of Claim 1, wherein the poly(vinyl butyral) encapsulant comprises about 0.2 to about 0.5 wt% of the unsaturated heterocyclic compound(s).
6. The solar cell module of Claim 1, wherein the poly(vinyl butyral) encapsulant is in the form of a poly(vinyl butyral) sheet; and wherein the poly(vinyl butyral) sheet has a yellowness index of about 60 or less when measured in accordance with ASTM
after 1000 hours under a bias of 1,000 V and at 85°C and 85% relative humidity (RH).
after 1000 hours under a bias of 1,000 V and at 85°C and 85% relative humidity (RH).
7. The solar cell module of Claim 1, wherein the poly(vinyl butyral) encapsulant further comprises one or more additives selected from the group consisting of about 0.01 to about 1 wt% of at least one UV absorber; about 0.01 to about 1 wt% of at least one thermal stabilizer; about 0.01 to about 1 wt% of at least one hindered amine;
and about 0.01 to about 1 wt% of at least one chelating agent, based on the total weight of the poly(vinyl butyral).
and about 0.01 to about 1 wt% of at least one chelating agent, based on the total weight of the poly(vinyl butyral).
8. The solar cell module of Claim 7, wherein the UV absorber(s) are 2H-substituted benzotriazole derivatives; or wherein the thermal stabilizer(s) comprise octylphenol or butylated hydroxytoluene; or wherein the wherein the hindered amine(s) are selected from the group consisting of 2,2,6,6-tetramethylpiperadine, 2,2,6,6-tetramethylpiper-adinol, 2-(dimethylamino) pyridine, 4-(dimethylamino) pyridine, N-butyl piperidine, N,N-diethyl cyclohexylamine, and hindered amine light stabilizers; or wherein the chelating agent(s) are selected from the group consisting of ethylenediaminetetraacetic acid, ethylenediamine monoacetic acid, ethylenediamine diacetic acid, ethylenediamine triacetic acid, ethylene diamine, tris(2-aminoethyl)amine and diethylenetriamine-pentacetic acid.
9. The solar cell module of Claim 1, wherein the silver component consists of substantially pure silver, or wherein the silver component comprises at least about 2 wt% of elemental silver, or wherein the silver component comprises a silver alloy, said alloy comprising at least about 2 wt% of elemental silver.
10. The solar cell module of Claim 1, wherein the silver component is selected from the group consisting of conductive pastes, connecting wires, conductive coatings, and reflector films.
11. The solar cell module of Claim 1, wherein the solar cells comprise wafer-based solar cells selected from the group consisting of monocrystalline silicon (c-Si) and multi-crystalline silicon (mc-Si) based solar cells, or wherein the solar cells comprise thin film solar cells and the thin film solar cells comprise one or more materials selected from the group consisting of amorphous silicon (a-Si), microcrystalline silicon (µc-Si), cadmium telluride (CdTe), copper indium selenide (CIS), copper indium/gallium diselenide (CIGS), light absorbing dyes, and organic semiconductors.
12. A pre-lamination assembly for preparing a solar cell module, said pre-lamination assembly comprising:
a solar cell assembly, said solar cell assembly comprising at least one solar cell and a silver component; a poly(vinyl butyral) sheet having a thickness of about 0.25 mm to about 1.2 mm and comprising a poly(vinyl butyral) encapsulant, said poly(vinyl butyral) encapsulant comprising a poly(vinyl butyral) resin, about 15 to about 45 wt%
of a plasticizer and about 0.1 to about 2 wt% of an unsaturated heterocyclic compound, based on the total weight of the poly(vinyl butyral) encapsulant; and optionally wherein the poly(vinyl butyral) sheet has a yellowness index of about 60 or less, as measured in accordance with ASTM E313-05 after 1000 hours at 85% relative humidity (RH) and at 85°C with a bias of 1,000 V; wherein said poly(vinyl butyral) sheet is in contact with the silver component.
a solar cell assembly, said solar cell assembly comprising at least one solar cell and a silver component; a poly(vinyl butyral) sheet having a thickness of about 0.25 mm to about 1.2 mm and comprising a poly(vinyl butyral) encapsulant, said poly(vinyl butyral) encapsulant comprising a poly(vinyl butyral) resin, about 15 to about 45 wt%
of a plasticizer and about 0.1 to about 2 wt% of an unsaturated heterocyclic compound, based on the total weight of the poly(vinyl butyral) encapsulant; and optionally wherein the poly(vinyl butyral) sheet has a yellowness index of about 60 or less, as measured in accordance with ASTM E313-05 after 1000 hours at 85% relative humidity (RH) and at 85°C with a bias of 1,000 V; wherein said poly(vinyl butyral) sheet is in contact with the silver component.
13. The pre-lamination assembly of claim 12, further comprising one or more additional layers selected from the group consisting of:
a second poly(vinyl butyral) sheet that may be the same as or different from the poly(vinyl butyral) sheet, said second poly(vinyl butyral) sheet being in contact with the solar cell assembly; a protective outer layer that is in contact with the poly(vinyl butyral) sheet; a second protective outer layer that may be the same as or different from the protective outer layer, said second protective outer layer in contact with the second poly(vinyl butyral) sheet; and a substrate or a superstrate that is in contact with the solar cell assembly and with the poly(vinyl butyral) sheet.
a second poly(vinyl butyral) sheet that may be the same as or different from the poly(vinyl butyral) sheet, said second poly(vinyl butyral) sheet being in contact with the solar cell assembly; a protective outer layer that is in contact with the poly(vinyl butyral) sheet; a second protective outer layer that may be the same as or different from the protective outer layer, said second protective outer layer in contact with the second poly(vinyl butyral) sheet; and a substrate or a superstrate that is in contact with the solar cell assembly and with the poly(vinyl butyral) sheet.
14. A process for reducing or preventing discoloration of poly(vinyl butyral) encapsulant in a solar cell module, said process comprising the steps of:
providing a poly(vinyl butyral) sheet comprising a poly(vinyl butyral) encapsulant, said poly(vinyl butyral) encapsulant comprising a poly(vinyl butyral) resin, about
providing a poly(vinyl butyral) sheet comprising a poly(vinyl butyral) encapsulant, said poly(vinyl butyral) encapsulant comprising a poly(vinyl butyral) resin, about
15 to about 45 wt% of a plasticizer and about 0.1 to about 2 wt% of an unsaturated heterocyclic compound, based on the total weight of the poly(vinyl butyral) encapsulant, and optionally wherein the poly(vinyl butyral) sheet has a yellowness index of about 60 or less in accordance with ASTM
E313-05 after 1000 hours at 85% relative humidity (RH) and at 85°C with a bias of 1,000 V;
forming a solar cell module by encapsulating a solar cell assembly in the poly(vinyl butyral) sheet, said solar cell assembly comprising a silver component that is in contact with the poly(vinyl butyral) sheet; and operating the solar cell module under a set of conditions for a period of time;
wherein the yellowness index of the poly(vinyl butyral) encapsulant will be unchanged after the period of operation; or wherein the change in the yellowness index of the poly(vinyl butyral) encapsulant after the period of operation is smaller than the change in the yellowness index of a second poly(vinyl butyral) encapsulant after the same period of operation under the same set of conditions in a second solar cell module that is substantially identical to the solar cell module; wherein said second poly(vinyl butyral) encapsulant does not comprise an unsaturated heterocyclic compound.
E313-05 after 1000 hours at 85% relative humidity (RH) and at 85°C with a bias of 1,000 V;
forming a solar cell module by encapsulating a solar cell assembly in the poly(vinyl butyral) sheet, said solar cell assembly comprising a silver component that is in contact with the poly(vinyl butyral) sheet; and operating the solar cell module under a set of conditions for a period of time;
wherein the yellowness index of the poly(vinyl butyral) encapsulant will be unchanged after the period of operation; or wherein the change in the yellowness index of the poly(vinyl butyral) encapsulant after the period of operation is smaller than the change in the yellowness index of a second poly(vinyl butyral) encapsulant after the same period of operation under the same set of conditions in a second solar cell module that is substantially identical to the solar cell module; wherein said second poly(vinyl butyral) encapsulant does not comprise an unsaturated heterocyclic compound.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2010/027976 WO2011115628A1 (en) | 2010-03-19 | 2010-03-19 | Photovoltaic module with stabilized polymer |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2791015A1 true CA2791015A1 (en) | 2011-09-22 |
Family
ID=42470691
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2791015A Abandoned CA2791015A1 (en) | 2010-03-19 | 2010-03-19 | Photovoltaic module with stabilized polymer |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP2547516A1 (en) |
JP (1) | JP2013522904A (en) |
KR (1) | KR20130010889A (en) |
CN (1) | CN102811854A (en) |
AU (1) | AU2010348376A1 (en) |
BR (1) | BR112012022911A2 (en) |
CA (1) | CA2791015A1 (en) |
MX (1) | MX2012010354A (en) |
RU (1) | RU2528397C2 (en) |
SG (1) | SG183430A1 (en) |
WO (1) | WO2011115628A1 (en) |
ZA (1) | ZA201206288B (en) |
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JP2012516061A (en) | 2009-01-22 | 2012-07-12 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Poly (vinyl butyral) encapsulant containing a chelating agent for solar cell modules |
WO2016007889A1 (en) * | 2014-07-10 | 2016-01-14 | Georgia Tech Research Corporation | Carbon nanotube compositions |
US9822236B2 (en) * | 2014-08-21 | 2017-11-21 | Solutia Inc. | Polymer interlayers comprising special effect metal pigments |
WO2016032837A1 (en) * | 2014-08-25 | 2016-03-03 | Solutia Inc. | Thin film photovoltaic module with stabilized polymer |
EP3185309A1 (en) * | 2015-12-23 | 2017-06-28 | Amcor Flexibles Transpac | Heat reflective solar module |
RU168774U1 (en) * | 2016-03-04 | 2017-02-17 | Валентин Петрович Пивнов | REFLECTIVE FILM |
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-
2010
- 2010-03-19 EP EP10712833A patent/EP2547516A1/en not_active Withdrawn
- 2010-03-19 BR BR112012022911A patent/BR112012022911A2/en not_active IP Right Cessation
- 2010-03-19 AU AU2010348376A patent/AU2010348376A1/en not_active Abandoned
- 2010-03-19 WO PCT/US2010/027976 patent/WO2011115628A1/en active Application Filing
- 2010-03-19 MX MX2012010354A patent/MX2012010354A/en unknown
- 2010-03-19 RU RU2012144439/04A patent/RU2528397C2/en not_active IP Right Cessation
- 2010-03-19 KR KR1020127023885A patent/KR20130010889A/en not_active Application Discontinuation
- 2010-03-19 JP JP2013500034A patent/JP2013522904A/en active Pending
- 2010-03-19 CN CN2010800655874A patent/CN102811854A/en active Pending
- 2010-03-19 SG SG2012061925A patent/SG183430A1/en unknown
- 2010-03-19 CA CA2791015A patent/CA2791015A1/en not_active Abandoned
-
2012
- 2012-08-21 ZA ZA2012/06288A patent/ZA201206288B/en unknown
Also Published As
Publication number | Publication date |
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ZA201206288B (en) | 2013-05-29 |
RU2012144439A (en) | 2014-04-27 |
KR20130010889A (en) | 2013-01-29 |
JP2013522904A (en) | 2013-06-13 |
RU2528397C2 (en) | 2014-09-20 |
MX2012010354A (en) | 2012-11-16 |
EP2547516A1 (en) | 2013-01-23 |
WO2011115628A1 (en) | 2011-09-22 |
CN102811854A (en) | 2012-12-05 |
BR112012022911A2 (en) | 2019-09-24 |
AU2010348376A1 (en) | 2012-09-27 |
SG183430A1 (en) | 2012-09-27 |
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