TWI722223B - 聚烯烴系黏著劑組成物 - Google Patents
聚烯烴系黏著劑組成物 Download PDFInfo
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- TWI722223B TWI722223B TW106125388A TW106125388A TWI722223B TW I722223 B TWI722223 B TW I722223B TW 106125388 A TW106125388 A TW 106125388A TW 106125388 A TW106125388 A TW 106125388A TW I722223 B TWI722223 B TW I722223B
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- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
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- CRJPRKBQDOAWLN-ROUUACIJSA-N [(2S)-5-amino-2-(hexylamino)-5-oxopentanoyl] (2S)-5-amino-2-(hexylamino)-5-oxopentanoate Chemical compound C(CCCCC)N[C@@H](CCC(N)=O)C(=O)OC([C@@H](NCCCCCC)CCC(N)=O)=O CRJPRKBQDOAWLN-ROUUACIJSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
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- GPDWNEFHGANACG-UHFFFAOYSA-L [dibutyl(2-ethylhexanoyloxy)stannyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)O[Sn](CCCC)(CCCC)OC(=O)C(CC)CCCC GPDWNEFHGANACG-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FYPVXEILSNEKOO-UHFFFAOYSA-L calcium;butanoate Chemical compound [Ca+2].CCCC([O-])=O.CCCC([O-])=O FYPVXEILSNEKOO-UHFFFAOYSA-L 0.000 description 1
- KCVBJDWRXNEWRM-UHFFFAOYSA-L calcium;naphthalene-1-carboxylate Chemical compound [Ca+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 KCVBJDWRXNEWRM-UHFFFAOYSA-L 0.000 description 1
- NDWWLJQHOLSEHX-UHFFFAOYSA-L calcium;octanoate Chemical compound [Ca+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O NDWWLJQHOLSEHX-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
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- 150000001735 carboxylic acids Chemical class 0.000 description 1
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- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
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- HHZAIOOQYMFSFC-UHFFFAOYSA-L cobalt(2+);3-oxobutanoate Chemical compound [Co+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O HHZAIOOQYMFSFC-UHFFFAOYSA-L 0.000 description 1
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- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OZVCIJIOEZNZFL-UHFFFAOYSA-H dialuminum;phthalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C1=CC=CC=C1C([O-])=O.[O-]C(=O)C1=CC=CC=C1C([O-])=O.[O-]C(=O)C1=CC=CC=C1C([O-])=O OZVCIJIOEZNZFL-UHFFFAOYSA-H 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 1
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- WWRYOAYBSQIWNU-UHFFFAOYSA-L magnesium;decanoate Chemical compound [Mg+2].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O WWRYOAYBSQIWNU-UHFFFAOYSA-L 0.000 description 1
- OFUAIAKLWWIPTC-UHFFFAOYSA-L magnesium;naphthalene-2-carboxylate Chemical compound [Mg+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 OFUAIAKLWWIPTC-UHFFFAOYSA-L 0.000 description 1
- LUYZTDPLLWFWQU-UHFFFAOYSA-L magnesium;terephthalate Chemical compound [Mg+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 LUYZTDPLLWFWQU-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UICBCXONCUFSOI-UHFFFAOYSA-N n'-phenylacetohydrazide Chemical compound CC(=O)NNC1=CC=CC=C1 UICBCXONCUFSOI-UHFFFAOYSA-N 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RWMKSKOZLCXHOK-UHFFFAOYSA-M potassium;butanoate Chemical compound [K+].CCCC([O-])=O RWMKSKOZLCXHOK-UHFFFAOYSA-M 0.000 description 1
- QDIGBJJRWUZARS-UHFFFAOYSA-M potassium;decanoate Chemical compound [K+].CCCCCCCCCC([O-])=O QDIGBJJRWUZARS-UHFFFAOYSA-M 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 125000001042 pteridinyl group Chemical class N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000000561 purinyl group Chemical class N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 125000002294 quinazolinyl group Chemical class N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229960005480 sodium caprylate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 1
- CVYDEWKUJFCYJO-UHFFFAOYSA-M sodium;docosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O CVYDEWKUJFCYJO-UHFFFAOYSA-M 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ROEHNQZQCCPZCH-UHFFFAOYSA-N tert-butyl 2-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OC(C)(C)C ROEHNQZQCCPZCH-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- PWBHRVGYSMBMIO-UHFFFAOYSA-M tributylstannanylium;acetate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(C)=O PWBHRVGYSMBMIO-UHFFFAOYSA-M 0.000 description 1
- HFFZSMFXOBHQLV-UHFFFAOYSA-M tributylstannyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)CCCC HFFZSMFXOBHQLV-UHFFFAOYSA-M 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- WDHVIZKSFZNHJB-UHFFFAOYSA-L zinc;butanoate Chemical compound [Zn+2].CCCC([O-])=O.CCCC([O-])=O WDHVIZKSFZNHJB-UHFFFAOYSA-L 0.000 description 1
- NVKSAUAQUPYOPO-UHFFFAOYSA-L zinc;decanoate Chemical compound [Zn+2].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O NVKSAUAQUPYOPO-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
本發明之課題為提供一種黏著劑組成物,含有改性聚烯烴及環氧樹脂,其適用期特性良好,且與金屬基材及聚烯烴樹脂基材之黏著性良好。本發明為一種黏著劑組成物,含有酸價為5~50mgKOH/g-resin之結晶性酸改性聚烯烴(A)、環氧丙基胺型環氧樹脂(B1)、環氧丙基醚型環氧樹脂(B2)、及有機溶劑(E),更含有酸酐單體(C)及具有2個以上的氮之雜環式化合物(D)中之任一者。
Description
本發明關於用來將聚烯烴樹脂基材與金屬基材予以黏著之黏著劑組成物。更詳細而言關於含有結晶性酸改性聚烯烴、環氧樹脂及有機溶劑,更含有酸酐單體及具有2個以上的氮之雜環式化合物中之任一者之黏著劑組成物。
自以往,在家電之外板、家具用材料、建築內裝用構件等之金屬基材會使用疊層體,該疊層體係於其表面塗佈氯乙烯樹脂(以下亦簡稱「聚氯乙烯」)後層合而成,但近來環境問題受到放大檢視,有人提出以聚烯烴樹脂代替聚氯乙烯。聚烯烴樹脂無毒性且對酸、鹼、有機溶劑等展現強耐久性,其機械性強度、耐磨耗性亦優異且價格低廉,因此廣泛地使用在各種領域。
但是,由於聚烯烴樹脂為非極性,故與金屬基材之黏著係為困難。以往為了該聚烯烴樹脂與金屬基材之黏著,已有人提出各種黏著劑。具代表性者為在將苯酚樹脂、三聚氰胺樹脂、環氧樹脂等之熱硬化性樹脂或熱塑性樹脂溶解於有機溶劑而成的基礎黏著劑中,混合溶劑分散型改性聚烯烴樹脂而成者。但是,該等黏著劑難說是具有充分的黏著性。又,也有人提出在結晶性酸改性聚烯烴與環氧樹脂中摻合鄰苯二酚等之黏著劑組成物(專利文獻1)、或摻合馬來酸改性氯化聚丙烯與螯合環氧樹脂與溶劑之黏著劑組成物(專利文獻2)。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開2003-261847號公報 [專利文獻2]日本特開2009-292853號公報
[發明所欲解決之課題] 但是,上述方法有時會有摻合酸改性聚烯烴溶液後之適用期特性不良的情況,又即使適用期特性不是太大的問題,但最重要的和金屬基材之黏著性及耐藥品性仍為不足。亦即,上述方法並非為滿足適用期特性、黏著性及耐藥品性者。尤其是使用聚丙烯(以下亦稱為PP)基材時,亦非為能在熱收縮等之影響小的諸如80℃以下之低溫進行貼合與熟成(aging)之黏著劑。在此,適用期特性係指在酸改性聚烯烴中摻合交聯劑或硬化劑,並在其剛進行摻合或經過一定時間後之該溶液的安定性。
就聚烯烴樹脂基材與金屬基材之疊層體而言,近年,將聚丙烯薄膜與鋁箔利用黏著劑貼合而成的疊層體使用作為鋰離子電池用外裝體之探討正盛,就黏著劑以及疊層體而言,尋求對於內容物即電解液之耐藥品性(以下亦稱為耐電解液性)。
又,鋰離子電池之電解液例如可使作為電解質之LiPF6
及LiBF4
等之鋰鹽溶解於碳酸酯類等之非水溶劑中而得。作為電解質使用的鋰鹽會因水分而水解並產生氟化氫。因此,在產生氟化氫的情況會發生構成電池之金屬製的構件被腐蝕、或作為外裝體使用之疊層薄膜型包裝材之層間的黏著性降低等的困擾。
本發明係鑑於上述以往的問題而成,本發明人們針對聚烯烴樹脂基材和金屬基材之黏著劑進行深入探討後之結果發現:含有結晶性酸改性聚烯烴(以下亦簡稱為酸改性聚烯烴)、環氧樹脂及有機溶劑,更含有酸酐單體及具有2個以上的氮之雜環式化合物中之任一者之黏著劑組成物,兼具適用期特性、在80℃以下之貼合或熟成時的黏著性及耐藥品性,尤其兼具混入了水分後的耐電解液性,乃至完成本發明。
亦即,本發明目的係提供一種黏著劑組成物,在摻合結晶性酸改性聚烯烴、硬化劑及硬化促進劑後之適用期特性良好,且具有在低溫之貼合、熟成時對於聚烯烴樹脂基材和金屬基材雙方之良好的黏著性及耐藥品性。 [解決課題之手段]
為了達成上述課題,本發明人們深入探討乃至於提出以下發明。
一種黏著劑組成物,含有酸價為5~50mgKOH/g-resin之結晶性酸改性聚烯烴(A)、環氧丙基胺型環氧樹脂(B1)、環氧丙基醚型環氧樹脂(B2)、及有機溶劑(E),更含有酸酐單體(C)及具有2個以上的氮之雜環式化合物(D)中之任一者。
前述環氧丙基胺型環氧樹脂(B1)宜為1分子中具有2個以上的環氧丙基之環氧樹脂。
前述環氧丙基胺型環氧樹脂(B1)宜為通式(1)表示之化合物。 [化1]通式(1) 通式(1)中,R為也可具有取代基之芳基,X1及X2各別獨立地為也可具有取代基之碳數1~5的伸烷基,m為1或2,n為1或2。
前述環氧丙基醚型環氧樹脂(B2)宜為1分子中具有2個以上的環氧丙基且不含氮原子之環氧樹脂。
前述酸酐單體(C)宜為1分子中具有1個以上的酸酐環,且酸價為100mgKOH/g以上之化合物。
具有2個以上的氮之雜環式化合物(D)宜為具有2個以上的氮之5員環芳香族雜環式化合物。
相對於100質量份之結晶性酸改性聚烯烴(A),宜含有0.01~20質量份之環氧丙基胺型環氧樹脂(B1),1~50質量份之環氧丙基醚型環氧樹脂(B2),1~50質量份之酸酐單體(C),0.01~5質量份之具有2個以上的氮之雜環式化合物(D),80~1000質量份之有機溶劑(E)。
有機溶劑(E)宜為溶劑(E1)與溶劑(E2)之混合液,溶劑(E1)宜選自於由芳香烴、脂肪族烴、脂環族烴及鹵化烴構成之群組中之1種以上的溶劑,溶劑(E2)宜選自於由醇系溶劑、酮系溶劑、酯系溶劑及二醇醚系溶劑構成之群組中之1種以上的溶劑,且溶劑(E1)/溶劑(E2)=50~97/50~3(質量比)較理想。
如前述任一項所記載之黏著劑組成物,係用於聚烯烴樹脂基材與金屬基材之黏著。
一種聚烯烴樹脂基材與金屬基材之疊層體,係利用如前述任一項所記載之黏著劑組成物予以黏著而成。一種鋰離子電池用包裝材料,含有前述疊層體作為構成構件。 [發明之效果]
本發明相關之黏著劑組成物含有結晶性酸改性聚烯烴、2種環氧樹脂、及有機溶劑,更含有酸酐單體及具有2個以上的氮之雜環式化合物中之任一者,即使長時間保存仍不會發生增黏、凝膠化,且可維持良好的適用期特性。此外,即使在聚烯烴基材之熱收縮影響小的諸如80℃以下之低溫貼合並實施熟成,仍可兼具與聚烯烴樹脂基材及金屬基材之良好的黏著性及耐藥品性。
以下,針對本發明之實施形態進行詳細說明。
<結晶性酸改性聚烯烴(A)> 本發明所使用的結晶性酸改性聚烯烴(A)並無特別限制,但宜為藉由將α,β-不飽和羧酸及其酸酐中之至少1種接枝於聚乙烯、聚丙烯及丙烯-α-烯烴共聚物中之至少1種而得者。
丙烯-α-烯烴共聚物係以丙烯為主體,並於其上共聚合α-烯烴而成者。作為α-烯烴可使用例如:乙烯、1-丁烯、1-庚烯、1-辛烯、4-甲基-1-戊烯、乙酸乙烯酯等中之1種或數種。該等α-烯烴之中宜為乙烯、1-丁烯。丙烯-α-烯烴共聚物中之丙烯成分與α-烯烴成分之比率並無限制,但丙烯成分宜為50莫耳%以上,為70莫耳%以上更佳。
作為α,β-不飽和羧酸及其酸酐中之至少1種可列舉例如:馬來酸、伊康酸、檸康酸及它們的酸酐。該等之中宜為酸酐,為馬來酸酐更佳。具體而言,可列舉:馬來酸酐改性聚丙烯、馬來酸酐改性丙烯-乙烯共聚物、馬來酸酐改性丙烯-丁烯共聚物、馬來酸酐改性丙烯-乙烯-丁烯共聚物等,該等結晶性酸改性聚烯烴可使用1種之或將2種以上組合使用。其中宜為馬來酸酐改性丙烯-丁烯共聚物。就馬來酸酐改性丙烯-丁烯共聚物中之丙烯成分/1-丁烯成分(莫耳比)而言,宜為90~50/10~50,為85~60/15~40更佳,為80~55/20~45再更佳,為75~60/25~40特佳。藉由設定在上述範圍,尤其可展現優良的適用期特性、黏著性及耐藥品性。
考慮適用期特性及與聚烯烴樹脂基材及金屬基材之黏著性的觀點,結晶性酸改性聚烯烴(A)之酸價的下限必須為5mgKOH/g-resin以上,宜為10mgKOH/g-resin以上,為14mgKOH/g-resin以上更佳,為16mgKOH/g-resin以上再更佳,為18mgKOH/g-resin以上特佳,為20mgKOH/g-resin以上最佳。未達前述之值的話,有時會有和環氧樹脂之相容性低,且不會展現黏著強度之情況,而且會有交聯密度低,且欠缺耐藥品性的情況。上限必須為50mgKOH/g-resin以下,宜為48mgKOH/g-resin以下,為46mgKOH/g-resin以下更佳,為44mgKOH/g-resin以下再更佳,為42mgKOH/g-resin以下特佳,為40mgKOH/g-resin以下最佳。超過前述之值的話,有時會有溶液之黏度、安定性降低,且適用期特性降低的情況。此外,製造效率也會降低,故較不理想。酸價可利用α,β-不飽和羧酸及其酸酐中之至少1種的接枝量(添加量)來控制。
結晶性酸改性聚烯烴(A)之重量平均分子量(Mw)宜為40,000~180,000之範圍。為50,000~160,000之範圍更佳,為60,000~150,000之範圍再更佳,為70,000~140,000之範圍特佳,為80,000~130,000之範圍最佳。未達前述之值的話,會有凝聚力變弱且黏著性差的情況。另一方面,超過前述之值的話,會有流動性低且在黏著時的操作性上發生問題之情況。若為前述範圍內,則會促進和環氧樹脂之硬化反應,故較理想。
結晶性酸改性聚烯烴(A)中的結晶性係指:使用差示掃描型熱量計(DSC),以20℃/分鐘條件從-100℃昇溫到250℃,並在該昇溫過程中顯示明確的熔解峰部者。
藉由將酸改性聚烯烴設定為具有結晶性,與非晶性相比,前者凝聚力強,且黏著性、耐藥品性優良,故為有利。
結晶性酸改性聚烯烴(A)之熔點(Tm)宜為50℃~120℃之範圍。為60℃~100℃之範圍更佳,為70℃~90℃之範圍最佳。未達前述之值的話,會有源自結晶之凝聚力變弱,且黏著性、耐藥品性差的情況。另一方面,超過前述之值的話,會有溶液安定性、流動性低且在黏著時的操作性上發生問題之情況。
結晶性酸改性聚烯烴(A)之熔解熱(ΔH)宜為5J/g~60J/g之範圍。為10J/g~50J/g之範圍更佳,為20J/g~40J/g之範圍最佳。未達前述之值的話,會有源自結晶之凝聚力變弱,且黏著性、耐藥品性差的情況。另一方面,超過前述之值的話,會有溶液安定性、流動性低且在黏著時的操作性上發生問題的情況。
就結晶性酸改性聚烯烴(A)之製造方法而言並無特別限制,例如可舉自由基接枝反應(亦即對成為主鏈之聚合物生成自由基物種(radical species),並將該自由基物種作為聚合起始點,使不飽和羧酸及酸酐接枝聚合之反應)等。
就自由基產生劑而言並無特別限制,宜使用有機過氧化物。就有機過氧化物而言並無特別限制,可列舉:過氧化苯二甲酸二(三級丁酯)、三級丁基過氧化氫、過氧化二異丙苯、過氧化苯甲醯、過氧化苯甲酸三級丁酯、過氧化-2-乙基己酸三級丁酯、過氧化三甲基乙醯酸三級丁酯、過氧化甲乙酮、二(三級丁基)過氧化物、過氧化月桂醯等之過氧化物;偶氮雙異丁腈、偶氮雙異丙腈等之偶氮腈類等。
<環氧丙基胺型環氧樹脂(B1)> 本發明所使用之環氧丙基胺型環氧樹脂(B1)若為1分子中具有1個以上之環氧丙基之環氧樹脂則無特別限制。環氧樹脂1分子中宜具有2個以上之環氧丙基,環氧樹脂1分子中具有3個以上之環氧丙基更佳,環氧樹脂1分子中具有4個以上之環氧丙基再更佳。
又,環氧丙基胺型環氧樹脂(B1)藉由使用下述通式(1)表示之化合物,會更提昇耐藥品性,較為理想。 [化1]通式(1) 通式(1)中,R為也可具有取代基之芳基,宜為也可具有取代基之苯基。就前述芳基之取代基而言並無特別限制,可列舉:碳數1以上5以下之烷基、碳數1以上5以下之烷氧基、羥基、胺基、環氧丙基、環氧丙基胺基、或環氧丙基醚基。X1及X2各別獨立為碳數1以上5以下之也可具有取代基之直鏈伸烷基,理想碳數為4以下,為3以下更佳,為2以下再更佳。就前述伸烷基之取代基而言並無特別限制,可列舉:碳數1以上5以下之烷基、碳數1以上5以下之烷氧基、或胺基。m為1或2,n為1或2。理想為m或n之任一者為2,更理想為m、n皆為2。
就環氧丙基胺型環氧樹脂(B1)之具體例而言並無特別限制,可列舉:四環氧丙基二胺基二苯甲烷、三環氧丙基對胺基苯酚、四環氧丙基雙胺甲基環己酮、N,N,N’,N’-四環氧丙基間二甲苯二胺等之環氧丙基胺系等。其中宜為N,N,N’,N’-四環氧丙基間二甲苯二胺。該等環氧丙基胺型環氧樹脂(B1)可單獨使用或將2種以上併用。
環氧丙基胺型環氧樹脂(B1)之摻合量,相對於100質量份之結晶性酸改性聚烯烴(A),宜為0.01質量份以上,為0.05質量份以上更佳,為0.1質量份以上再更佳,為1質量份以上特佳,為2質量份以上最佳。未達前述範圍的話,會有不展現觸媒作用,且於80℃以下之貼合、熟成中的黏著性及耐藥品性低的情況。又,宜為20質量份以下,為18質量份以下更佳,為16質量份以下再更佳,為14質量份以下特佳,為12質量份以下最佳。若超過前述範圍,會有交聯反應過度進行而剛性變高,且黏著性降低之傾向。而且會有在黏著劑組成物之溶液保存時,交聯反應容易進行而適用期降低之傾向。
<環氧丙基醚型環氧樹脂(B2)> 本發明所使用的環氧丙基醚型環氧樹脂(B2)若為分子內具有環氧丙基醚基之環氧樹脂則無特別限制。宜為環氧樹脂1分子中具有2個以上之環氧丙基之環氧樹脂,為環氧樹脂1分子中具有2個以上之環氧丙基,且不含氮原子之環氧樹脂再更佳。
環氧丙基醚型環氧樹脂(B2)之摻合量,相對於100質量份之結晶性酸改性聚烯烴(A),宜為1質量份以上,為2質量份以上更佳,為3質量份以上再更佳,為4質量份以上特佳,為5質量份以上最佳。又,宜為50質量份以下,為40質量份以下更佳,為30質量份以下再更佳,為25質量份以下特佳,為20質量份以下最佳。藉由設定在前述範圍內,可展現優良的黏著性及耐藥品性。
就環氧丙基醚型環氧樹脂(B2)之具體例而言並無特別限制,可列舉:苯酚酚醛清漆樹脂型環氧樹脂、甲酚酚醛清漆樹脂型環氧樹脂,考慮和金屬基材之黏著性及耐藥品性的觀點,它們較為理想。該等環氧丙基醚型環氧樹脂(B2)可單獨使用或將2種以上併用。
在本發明中係併用前述環氧丙基胺型環氧樹脂(B1)與前述環氧丙基醚型環氧樹脂(B2)之2種環氧樹脂作為必要成分。藉由併用環氧丙基胺型環氧樹脂(B1)與環氧丙基醚型環氧樹脂(B2),可展現優良的黏著性、耐藥品性。亦即,環氧丙基胺型環氧樹脂(B1)在結晶性酸改性聚烯烴(A)與環氧丙基醚型環氧樹脂(B2)反應時具有觸媒作用。此外,環氧丙基胺型環氧樹脂(B1)在結晶性酸改性聚烯烴(A)與環氧丙基胺型環氧樹脂(B1)、環氧丙基胺型環氧樹脂(B1)彼此、及環氧丙基醚型環氧樹脂(B2)彼此、環氧丙基胺型環氧樹脂(B1)與環氧丙基醚型環氧樹脂(B2)反應時具有硬化觸媒作用,故藉由摻合可提昇在80℃以下之貼合、熟成中與金屬基材之黏著性及耐藥品性。
環氧丙基胺型環氧樹脂(B1)與環氧丙基醚型環氧樹脂(B2)之合計摻合量,相對於100質量份之結晶性酸改性聚烯烴(A),宜為2~70質量份,為5~50質量份更佳,為10~30質量份最佳。未達前述範圍,則會有無法獲得充分的硬化效果,而黏著性及耐藥品性低的情況,若超過前述範圍,則適用期特性與和烯烴基材之黏著性降低,考慮成本面的觀點較不理想。
環氧丙基胺型環氧樹脂(B1)之摻合量宜為環氧樹脂整體之1~50質量%,為2~30質量%更佳,為3~10質量%最佳。摻合量未達前述範圍的話,會有無法展現觸媒作用,而在低溫貼合、熟成中的黏著性及耐藥品性低的情況,超過前述範圍的話,會有交聯反應過度地進行而剛性變高,黏著性降低的傾向。而且會有黏著劑組成物在溶液保存中,交聯反應容易進行而適用期降低的傾向。
也可併用其他的環氧樹脂作為本發明所使用的環氧樹脂。例如可列舉:六氫苯二甲酸環氧丙酯、二聚酸環氧丙酯等之環氧丙酯型;異氰尿酸三環氧丙酯、或甲酸-3,4-環氧環己酯(3,4-epoxycyclohexyl methyl carboxylate)、環氧化聚丁二烯、環氧化大豆油等之脂環族或脂肪族環氧化物等,可單獨使用一種,將二種以上併用也無妨。
<酸酐單體(C)> 本發明所使用的酸酐單體(C),若為1分子中具有1個以上之酸酐環之化合物則無特別限制,可列舉:苯二甲酸酐、偏苯三甲酸酐、四氫苯二甲酸酐、甲基四氫苯二甲酸酐、甲基五氫苯二甲酸酐、甲基三氫苯二甲酸酐、三烷基四氫苯二甲酸酐、甲基環己烯二羧酸酐、氯橋酸酐、四溴苯二甲酸酐等之具有脂環結構、或芳香環結構者;或琥珀酸酐、馬來酸酐、戊二酸酐、丁基琥珀酸酐、己基琥珀酸酐、辛基琥珀酸酐、十二烷基琥珀酸酐、十二烯基琥珀酸酐、四丙烯基琥珀酸酐、丁基馬來酸酐、戊基馬來酸酐、己基馬來酸酐、辛基馬來酸酐、癸基馬來酸酐、十二烷基馬來酸酐、丁基麩胺酸酐、己基麩胺酸酐、庚基麩胺酸酐、辛基麩胺酸酐、癸基麩胺酸酐、十二烷基麩胺酸酐等之具有烷基鏈與酸酐者,可僅單獨使用一種,也可將多數併用。具體而言,已有新日本理化(股)製之RIKACID(註冊商標)等上市且可使用。
藉由將和環氧丙基胺型環氧樹脂(B1)及/或環氧丙基醚型環氧樹脂(B2)具有反應性之酸酐單體(C)與結晶性酸改性聚烯烴(A)併用,交聯密度會變高,例如,即使在電解液混入水分的情況,黏著劑組成物之耐藥品性(耐電解液性)仍不會降低,可維持良好的狀態。
酸酐單體之酸價宜為100mgKOH/g以上,為150mgKOH/g以上更佳,為200mgKOH/g以上再更佳。未達前述值的話,有時會有不展現硬化促進作用,而黏著劑組成物之耐藥品性降低的情況。又,酸價宜為1000mgKOH/g以下,為900mgKOH/g以下更佳,為800mgKOH/g以下再更佳。超過前述值的話,有時會有適用期特性降低的情況。
本發明所使用的酸酐單體(C)之摻合量,相對於100質量份之結晶性酸改性聚烯烴(A),宜為1質量份以上,為2質量份以上更佳,為3質量份以上再更佳,為4質量份以上特佳,為5質量份以上最佳。又,宜為50質量份以下,為48質量份以下更佳,為45質量份以下再更佳,為40質量份以下特佳,為35質量份以下最佳。藉由設定在前述範圍,可展現優良的黏著性及耐藥品性。
<具有2個以上的氮之雜環式化合物(D)> 本發明所使用的具有2個以上的氮之雜環式化合物(D),係1分子中具有2個以上之氮原子之雜環式化合物,就雜環之環結構成分而言,宜具有2個以上之氮原子。具有2個以上的氮之雜環式化合物(D),具有和結晶性聚烯烴(A)、和環氧丙基胺型環氧樹脂(B1)及/或環氧丙基醚型環氧樹脂(B2)之優良的硬化促進作用(觸媒作用)。因此,藉由含有具有2個以上的氮之雜環式化合物(D),例如,即使在電解液混入水分的情況,黏著劑組成物之耐藥品性(耐電解液性)仍不會降低,可維持良好的狀態。此外,藉由和前述酸酐單體(C)併用,可有效提高交聯密度,且可展現極優良的黏著性及耐藥品性。例如,即使在電解液混入水分的情況,黏著劑組成物之耐藥品性(耐電解液性)仍不會降低,可維持極良好的狀態。
就具有2個以上的氮之雜環式化合物(D)而言並無特別限制,可列舉:哌化合物等之脂肪族雜環式化合物;咪唑化合物、吡唑化合物等之5員環芳香族雜環式化合物;嘧啶化合物、嗒化合物、吡化合物、三化合物等之6員環芳香族雜環式化合物;喹唑啉化合物、呔化合物、喋啶化合物、苯并咪唑化合物、嘌呤化合物等之多環芳香族雜環式化合物,考慮觸媒效果、耐藥品性之觀點,咪唑化合物特佳。具體而言,可列舉:1,2-二甲基咪唑、1-甲基-2-乙基咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-苄基-2-苯基咪唑偏苯三甲酸鹽、1-苄基-2-乙基咪唑、1-苄基-2-乙基-5-甲基咪唑、2-乙基咪唑、2-異丙基咪唑、2-苯基-4-苄基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-十一烷基咪唑、1-氰乙基-2-異丙基咪唑、1-氰乙基-2-苯基咪唑、1-氰乙基-2-甲基咪唑偏苯三甲酸鹽、1-氰乙基-2-苯基咪唑偏苯三甲酸鹽、1-氰乙基-2-苯基-4,5-二(氰乙氧基甲基)咪唑、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三、2,4-二胺基-6-[2’-乙基-4-甲基咪唑基-(1’)]-乙基-s-三、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三、2-甲基咪唑異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三-異三聚氰酸加成物、2-苯基-4,5-二羥甲基咪唑、2-苯基-4-苄基-5-羥甲基咪唑、4,4’-亞甲基-雙(2-乙基-5-甲基咪唑)、1-胺基乙基-2-甲基咪唑、1-十二烷基-2-甲基-3-苄基咪唑氯化物、2-甲基咪唑・苯并三唑加成物、1-胺基乙基-2-乙基咪唑、1-(氰乙基胺基乙基)-2-甲基咪唑、N,N’-[2-甲基咪唑基-(1)-乙基]-己二醯基二醯胺、N,N’-雙-[2-甲基咪唑基-(1)-乙基]脲、N-[2-甲基咪唑基-1-乙基]脲、N,N’-[2-甲基咪唑基-(1)-乙基]十二烷二醯基二醯胺、N,N’-[2-甲基咪唑基-(1)-乙基]二十烷二醯基二醯胺、1-苄基-2-苯基咪唑・鹽酸鹽等。
具有2個以上的氮之雜環式化合物(D)之摻合量,相對於100質量份之結晶性酸改性聚烯烴(A),宜為0.01質量份以上,為0.02質量份以上更佳,為0.05質量份以上再更佳,為0.1質量份以上特佳,為0.2質量份以上最佳。未達前述範圍的話,有時會有不展現硬化促進(觸媒)作用的情況,會有在80℃以下貼合變得困難的情形。若在例如PP基材不受收縮等之影響的40℃左右實施熟成時,會有黏著性、耐藥品性降低、或發生熟成時間需要設定較長的情形。又,宜為5質量份以下,為4質量份以下更佳,為3質量份以下再更佳,為2質量份以下特佳,為1質量份以下最佳。若超過前述範圍,會有交聯反應過度地進行而剛性變高、黏著性降低的傾向。而且會有黏著劑組成物在溶液保存中,交聯反應容易進行、適用期降低的傾向。又,考慮製造成本之觀點也較不理想。
具有2個以上的氮之雜環式化合物(D)之摻合量,相對於環氧丙基胺型環氧樹脂(B1)與環氧丙基醚型環氧樹脂(B2)之合計摻合量,宜為1~100質量%,為2~70質量%更佳,為3~50質量%最佳。摻合量未達前述範圍的話,會有不展現觸媒作用,在低溫之貼合、熟成中的黏著性及耐藥品性低的情形。超過前述範圍的話,會有交聯反應過度地進行而剛性變高、黏著性降低的傾向、或黏著劑組成物在溶液保存中,有交聯反應容易進行、適用期降低的傾向。又,考慮製造成本的觀點也較不理想。
具有2個以上的氮之雜環式化合物(D)可單獨摻合,也可將多種化合物併用,亦可併用其他的硬化促進劑。作為其他的硬化促進劑可列舉:羧酸金屬鹽、3級胺類、4級銨鹽、有機過氧化物、肼化合物、金屬螯合物化合物、硫脲類、含磷化合物、鹼性硫化劑類等。作為前述羧酸金屬鹽可例舉:碳數1~30之羧酸的金屬鹽。作為構成該羧酸金屬鹽之羧酸可列舉例如:乙酸、丁酸、辛酸、癸酸、月桂酸、肉荳蔻酸、棕櫚酸、硬脂酸、油酸、二十二酸、辛烯酸、芥酸、反油酸、己二酸、丙二酸、琥珀酸、戊二酸、檸檬酸、酒石酸、蘋果酸、二乙醇酸等之脂肪族羧酸;苯甲酸、氯苯甲酸、大茴香酸、胺基苯甲酸、苯二甲酸、對苯二甲酸、萘甲酸、萘二羧酸、苯三羧酸等之芳香族羧酸;環烷酸;丙酮酸等。又,作為構成該羧酸金屬鹽之金屬可列舉例如:Li、Na、K、Mg、Ca、Zn、Al、Cu、Pb、Co、Fe、Mn、Sn、Ti等。作為該羧酸金屬鹽,具體而言可列舉:乙酸鋰、乙酸鈉、乙酸鎂、乙酸鋁、丁酸鉀、丁酸鈣、丁酸鋅、辛酸鈉、辛酸鈣、癸酸鉀、癸酸鎂、癸酸鋅、月桂酸鋰、月桂酸鈉、月桂酸鈣、月桂酸鋁、肉荳蔻酸鉀、肉荳蔻酸鈉、肉荳蔻酸鋁、棕櫚酸鈉、棕櫚酸鋅、棕櫚酸鎂、硬脂酸鈉、硬脂酸鉀、硬脂酸鈣、硬脂酸鋅、油酸鈉、二十二酸鈉,苯甲酸鈉、苯甲酸鋅、苯二甲酸鈉、苯二甲酸鋁、對苯二甲酸鎂、萘二羧酸鈣、月桂酸二丁基錫、月桂酸三丁基錫、月桂酸二辛基錫、乙酸三丁基錫、二乙酸二丁基錫、二乙酸二辛基錫、2-乙基己酸二丁基錫、鈦酸四丁酯、鈦酸四異丁酯、鈦酸四-2-乙基己酯、環烷酸鈷、環烷酸銅、環烷酸鎂、乙醯乙酸鈷等。它們之中,宜列舉月桂酸鋰、月桂酸鈉、月桂酸鈣、月桂酸鋁、肉荳蔻酸鉀、肉荳蔻酸鈉、肉荳蔻酸鋁、棕櫚酸鈉、棕櫚酸鋅、棕櫚酸鎂、硬脂酸鈉、硬脂酸鉀、硬脂酸鈣、硬脂酸鋅、油酸鈉。又,也可使用具有羧酸之金屬鹽結構之聚合物作為羧酸之金屬鹽。作為如此的聚合物可列舉:具有乙烯與自由基聚合性羧酸之IA族、IIA族、IIB族、IIIB族之金屬(例如Li、Na、K、Mg、Ca、Zn、Al等)鹽經共聚合而成的結構者;具有乙烯與自由基聚合性羧酸之金屬鹽與其他自由基聚合性羧酸及/或其衍生物經多元共聚合而成的結構者等。又,作為前述3級胺類可列舉例如:二甲基苯基胺、三乙醇胺、二甲基對甲基苯基胺等。又,作為前述肼化合物可舉例如:1-乙醯基-2-苯基肼等。又,作為前述金屬螯合物化合物可舉例如:乙醯丙酮釩等。又,作為前述含磷化合物可列舉例如:二甲基膦、三苯基膦等。又,作為前述鹼性硫化劑類可列舉例如:六亞甲基四胺、正丁基醛-苯胺縮合物等。
<有機溶劑(E)> 本發明所使用的有機溶劑(E)若為使結晶性酸改性聚烯烴(A)、環氧丙基胺型環氧樹脂(B1)、環氧丙基醚型環氧樹脂(B2)、酸酐單體(C)、及具有2個以上的氮之雜環式化合物(D)溶解者,則無特別限制。具體而言,例如可使用:苯、甲苯、二甲苯等之芳香烴;己烷、庚烷、辛烷、癸烷等之脂肪族系烴;環己烷、環己烯、甲基環己烷、乙基環己烷等之脂環族烴;三氯乙烯、二氯乙烯、氯苯、氯仿等之鹵化烴;甲醇、乙醇、異丙醇、丁醇、戊醇、己醇、丙二醇、苯酚等之醇系溶劑;丙酮、甲基異丁酮、甲乙酮、戊酮、己酮、環己酮、異佛爾酮、苯乙酮等之酮系溶劑;甲基賽璐蘇、乙基賽璐蘇等之賽璐蘇類;乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酸甲酯、甲酸丁酯等之酯系溶劑;乙二醇單正丁醚、乙二醇單異丁醚、乙二醇單三級丁醚、二乙二醇單正丁醚、二乙二醇單異丁醚、三乙二醇單正丁醚、四乙二醇單正丁醚等之二醇醚系溶劑等,可使用它們中之1種或將2種以上併用。
有機溶劑(E)相對於100質量份之結晶性酸改性聚烯烴(A),宜為80質量份以上,為90質量份以上更佳,為100質量份以上再更佳,為110質量份以上特佳。未達前述範圍的話,有時會有溶液狀態及適用期特性降低的情況。又,宜為1000質量份以下,為900質量份以下更佳,為800質量份以下再更佳,為700質量份以下特佳。超過前述範圍的話,會有就製造成本、運送成本方面而言不利的情況。
考慮黏著劑組成物之溶液狀態及適用期特性的觀點,有機溶劑(E)宜為選自於由芳香族烴、脂肪族烴、脂環族烴及鹵化烴構成之群組中之1種以上之溶劑(E1)以及選自於由醇系溶劑、酮系溶劑、酯系溶劑及二醇醚系溶劑構成之群組中之1種以上之溶劑(E2)的混合液較理想。就混合比而言,宜為溶劑(E1)/溶劑(E2)=50~97/50~3(質量比),為55~95/45~5(質量比)更佳,為60~90/40~10(質量比)再更佳,為70~80/30~20(質量比)特佳。在上述範圍之外的話,有時會有黏著劑組成物之溶液狀態及適用期特性降低的情況。又,溶劑(E1)為芳香族烴或脂環族烴,溶劑(E2)為酮系溶劑特佳。
<黏著劑組成物> 本發明相關之黏著劑組成物係含有前述結晶性酸改性聚烯烴(A)、環氧丙基胺型環氧樹脂(B1)、環氧丙基醚型環氧樹脂(B2)、及有機溶劑(E),且更含有酸酐單體(C)及具有2個以上的氮之雜環式化合物(D)中之任一者的組成物。較佳為含有結晶性酸改性聚烯烴(A)、環氧丙基胺型環氧樹脂(B1)、環氧丙基醚型環氧樹脂(B2)、及有機溶劑(E)、酸酐單體(C)及具有2個以上的氮之雜環式化合物(D)之組成物。結晶性酸改性聚烯烴(A)、環氧丙基胺型環氧樹脂(B1)、環氧丙基醚型環氧樹脂(B2)、酸酐單體(C)、及具有2個以上的氮之雜環式化合物(D)可溶解於有機溶劑(E),亦可分散於有機溶劑(E)。考慮適用期特性的觀點,宜溶解於有機溶劑(E)。
本發明相關之黏著劑組成物在不損及本發明之性能的範圍內,可摻合前述改性聚烯烴(A)、環氧丙基胺型環氧樹脂(B1)、環氧丙基醚型環氧樹脂(B2)、酸酐單體(C)、具有2個以上的氮之雜環式化合物(D)及有機溶劑(E)之外的各種添加劑而使用。就添加劑而言並無特別限制,宜使用阻燃劑、顏料、抗結塊劑等。
<疊層體> 本發明之疊層體,係以本發明相關之黏著劑組成物將聚烯烴樹脂基材與金屬基材予以疊層而成者。
就疊層方法而言,可利用習知的層合製造技術。並非特別限制,但例如可使用輥塗佈機、塗佈棒等適當的塗佈方法將黏著劑組成物塗佈於金屬基材之表面,並使其乾燥。乾燥後,在已形成於金屬基材表面之黏著劑層仍為熔融狀態時,將聚烯烴樹脂基材疊層黏著於該塗佈面而獲得層合結構體。 前述利用黏著劑組成物所形成的黏著劑層之厚度並無特別限制,宜設定為0.5~10μm,設定為0.8~9.5μm更佳,設定為1~9μm再更佳。
<聚烯烴樹脂基材> 就聚烯烴樹脂基材而言,從以往公知的聚烯烴樹脂之中適當選擇即可。並非特別限制,但例如可使用聚乙烯、聚丙烯、乙烯-丙烯共聚物等。其中,宜使用聚丙烯之無延伸薄膜(以下亦稱CPP)。其厚度並無特別限制,宜為20~100μm,為25~95μm更佳,為30~90μm再更佳。另外,聚烯烴樹脂基材中,因應需要也可摻合顏料、各種添加物。
<金屬基材> 就金屬基材而言並無特別限制,例如可使用鋁、銅、鋼鐵、鋅、杜拉鋁(duralumin)、壓鑄金屬(die cast)等之各種金屬及其合金。又,就其形狀而言,可取得金屬箔、壓延鋼板、平板、管材、罐、蓋等任意形狀。一般而言,考慮加工性等之觀點,鋁箔較理想。又,雖然依使用目的而有所不同,但一般而言,係以0.01~10mm之厚度的片材之形式來使用,宜以0.02~5mm之厚度的片材之形式使用。 又,針對該等金屬基材,考慮耐腐蝕性、黏著性之觀點,宜使用表面預先施予表面處理者,具體而言可例舉鉻酸鹽處理等。
以下,舉實施例更詳細地說明本發明。但本發明不限於實施例。在實施例及比較例中簡稱份係代表質量份。
<結晶性酸改性聚烯烴(A)之製造例> [製造例1] 將丙烯-丁烯共聚物(三井化學公司製「TAFMER(註冊商標)XM7080」)100質量份、甲苯150質量份及馬來酸酐25質量份、二(三級丁基)過氧化物6質量份添加入1L高溫高壓釜(autoclave)中,昇溫至140℃後,再攪拌3小時。其後,將得到的反應液冷卻後,將其注入到已放入大量甲乙酮之容器中,使樹脂析出。其後,藉由將含有該樹脂之液體進行離心分離,將經馬來酸酐接枝聚合而成的酸改性丙烯-丁烯共聚物與(聚)馬來酸酐及低分子量物質分離並予以純化。其後,藉由於減壓下在70℃使其乾燥5小時,獲得馬來酸酐改性丙烯-丁烯共聚物(PO-1,酸價48mgKOH/g-resin,重量平均分子量50,000,Tm75℃,△H25J/g)。
[製造例2] 藉由將馬來酸酐之進料量變更為20質量份,除此之外,與製造例1同樣地進行,獲得馬來酸酐改性丙烯-丁烯共聚物(PO-2,酸價25mgKOH/g-resin,重量平均分子量80,000,Tm75℃,△H30J/g)。
[製造例3] 藉由將馬來酸酐之進料量變更為3質量份,且將二(三級丁基)過氧化物變更為0.5質量份,除此之外,與製造例1同樣地進行,獲得馬來酸酐改性丙烯-丁烯共聚物(PO-3,酸價5mgKOH/g-resin,重量平均分子量180,000,Tm80℃,△H25J/g)。
[製造例4] 藉由將馬來酸酐之進料量變更為30質量份,除此之外,與製造例1同樣地進行,獲得馬來酸酐改性丙烯-丁烯共聚物(PO-4,酸價55mgKOH/g-resin,重量平均分子量40,000,Tm70℃,△H25J/g)。
[製造例5] 藉由將馬來酸酐之進料量變更為2質量份,且將二(三級丁基)過氧化物變更為0.5質量份,除此之外,與製造例1同樣地進行,獲得馬來酸酐改性丙烯-丁烯共聚物(PO-5,酸價3mgKOH/g-resin,重量平均分子量200,000,Tm80℃,△H25J/g)。
(主劑1之製作) 藉由將製造例1所得到的馬來酸酐改性丙烯-丁烯共聚物(PO-1)100質量份、甲基環己烷280質量份及甲乙酮120質量份進料於具備水冷回流冷凝器與攪拌機之500ml之四口燒瓶中,邊攪拌邊昇溫至80℃,再持續攪拌1小時,獲得主劑1。溶液狀態如表1所示。
(主劑2~12之製作) 將結晶性酸改性聚烯烴及有機溶劑按照表1所示進行變更,並以和主劑1同樣的方法製得主劑2~12。摻合量、溶液狀態如表1所示。
[表1][實施例1] 摻合500質量份之主劑1、20質量份之作為硬化劑之係環氧丙基醚型環氧樹脂(B2)之jER(註冊商標)152、2質量份之係環氧丙基胺型環氧樹脂(B1)之TETRAD(註冊商標)-X、20質量份之作為添加劑之係酸酐單體(C)之RIKACID(註冊商標)DDSA,獲得黏著劑組成物。其適用期特性、黏著性及耐藥品性之評價結果如表2所示。
[實施例2~69、比較例1~7] 將主劑1~12及各硬化劑按照表2~5所示進行變更,並以和實施例1同樣的方法進行實施例2~69、比較例1~7。其摻合量、適用期特性、黏著性及耐藥品性如表2~5所示。
表2~5所使用的硬化劑如下所示。 <環氧丙基胺型環氧樹脂(B1)> N,N,N’,N’-四環氧丙基間二甲苯二胺:TETRAD(註冊商標)-X(三菱瓦斯化學公司製) <環氧丙基醚型環氧樹脂(B2)> 苯酚酚醛清漆樹脂型環氧樹脂:jER(註冊商標)152(三菱化學公司製) 鄰甲酚酚醛清漆樹脂型環氧樹脂:YDCN-700-3(新日鐵住金化學公司製) <其他硬化劑> 聚異氰酸酯:DURANATE(註冊商標)TPA-100(旭化成公司製) 矽烷偶合劑:KBM-403(信越SILICONE公司製) <酸酐單體(C)> 四丙烯基琥珀酸酐:RIKACID(註冊商標)DDSA 四氫苯二甲酸酐:RIKACID(註冊商標)TH <具有2個以上的氮之雜環式化合物(D)> 1-苄基-2-甲基咪唑:CUREZOL(註冊商標)1B2MZ(四國化成公司製)
根據下述方法針對如上述進行而獲得的各改性聚烯烴、主劑及黏著劑組成物實施分析測定及評價。 [酸價之測定] <結晶性酸改性聚烯烴(A)> 本發明中的結晶性酸改性聚烯烴(A)之酸價(mgKOH/g-resin)係指中和1g的酸改性聚烯烴(A)所必須要的KOH量,依據JIS K0070(1992)之試驗方法進行測定。具體而言,係使酸改性聚烯烴1g溶解於已將溫度調整至100℃之二甲苯100g後,於同溫度以酚酞作為指示劑,並以0.1mol/L氫氧化鉀乙醇溶液[商品名「0.1mol/L乙醇性氫氧化鉀溶液」,和光純藥(股)製]實施滴定。此時,將滴定需要的氫氧化鉀量換算成mg而算出酸價(mgKOH/g-resin)。
<酸酐單體(C)> 本發明中的酸酐單體(C)之酸價(mgKOH/g)係使用酸酐單體之分子量(M)、琥珀酸酐基的數量(n),並利用下式計算而得的值。 酸價(mgKOH/g-resin)= [琥珀酸酐之分子量(M)×(n)×2×氫氧化鉀之分子量×1000(mg)/琥珀酸酐之分子量] 琥珀酸酐之分子量:100.07,氫氧化鉀之分子量:56.11
[重量平均分子量(Mw)之測定] 本發明中的重量平均分子量係利用日本WATERS公司製凝膠滲透層析儀Alliance e2695(以下稱GPC,標準物質:聚苯乙烯樹脂,移動相:四氫呋喃,管柱:Shodex KF-806+KF-803,管柱溫度:40℃,流速:1.0ml/分鐘,檢測器:光電二極體陣列檢測器(波長254nm=紫外線))測定而得的值。
[熔點、熔解熱之測定] 本發明中的熔點、熔解熱係使用差示掃描熱量計(以下稱DSC,TA Instruments Japan製,Q-2000),由以20℃/分鐘的速度昇溫熔解、冷卻樹脂化後,再度昇溫熔解時的熔解峰部之最高點溫度及面積測定而得的值。
[主劑溶液狀態之評價] 針對主劑1~12之溶液狀態,使用東機產業公司製之布氏黏度計(Brookfield viscometer)TVB-10M(以下亦稱B型黏度計),測定於25℃之溶液黏度來進行評價。 <評價基準> ○(於實用上為優良):未達500mPa・s △(可實用):500mPa・s以上未達1000mPa・s ×(不可實用):1000mPa・s以上或因凝膠化導致無法測定黏度
[適用期特性之評價] 適用期特性係指於結晶性酸改性聚烯烴摻合交聯劑或硬化劑,並在剛進行摻合或摻合後經過一定時間後之該溶液的安定性。適用期特性良好的情況係指溶液之黏度上昇少且可長時間保存,適用期特性不良的情況係指溶液之黏度上昇(增黏),嚴重時會造成凝膠化現象,且難以塗佈到基材,無法長時間保存。 實施例1~69及比較例1~7所得到的黏著劑組成物之適用期特性係儲藏於25℃及40℃之環境氣體24小時後,使用B型黏度計測定25℃之溶液黏度來進行評價。評價結果如表2~5所示。 <評價基準> ○(在實用上為優良):未達500mPa・s △(可實用):500mPa・s以上未達1000mPa・s ×(不可實用):1000mPa・s以上或因凝膠化導致無法測定黏度
[金屬基材與聚烯烴樹脂基材之疊層體之製作] 金屬基材使用經鉻酸鹽處理之鋁箔(住輕鋁箔公司製,8079-0,厚度40μm),聚烯烴樹脂基材使用無延伸聚丙烯薄膜(東洋紡公司製PYLEN(註冊商標)FILM CT,厚度40μm)(以下亦稱CPP)。 使用塗佈棒將實施例1~69及比較例1~7所得到的黏著劑組成物塗佈於金屬基材,並調整使其乾燥後之黏著劑層的膜厚成為3μm。使用溫風乾燥機使塗佈面於100℃環境氣體乾燥1分鐘,獲得膜厚3μm之黏著劑層。將聚烯烴樹脂基材疊合於前述黏著劑層表面,並使用TESTER SANGYO公司製之小型桌上測試層合機(SA-1010-S),以80℃、0.3MPa、1m/分鐘條件進行貼合,並以40℃、50%RH條件熟成120小時而獲得疊層體。
對於如上述般進行而得到的疊層體,以下述方法實施評價。
[黏著性之評價] 將前述疊層體裁切成100mm×15mm大小,利用T型剝離試驗實施黏著性之評價。評價結果如表2、3所示。
<T型剝離試驗> 依據ASTM-D1876-61之試驗法,使用ORIENTEC Corporation公司製之TENSILON RTM-100,於25℃環境下測定拉伸速度50mm/分鐘的剝離強度。金屬基材/聚烯烴樹脂基材間之剝離強度(N/cm)係5次試驗值之平均值。
<評價基準> ☆(在實用上特別優良):8.0N/cm以上或CPP之材料破損(以下亦簡稱「材料破損」)材料破損係指金屬基材/CPP之界面未發生剝離,而是金屬基材或CPP被破壞的情況。 ◎(在實用上為優良):7.5N/cm以上未達8.0N/cm ○(可實用):7.0N/cm以上未達7.5N/cm ×(不可實用):未達7.0N/cm
[耐藥品性之評價] 為了探討作為鋁箔與CPP之疊層體的使用形態之一的鋰離子電池之包裝材之利用性,實施了利用電解液試驗所為之耐藥品性(以下亦稱耐電解液性)之評價。將前述疊層體裁切成100mm×15mm大小,於已添加300ppm水之電解液[於碳酸伸乙酯/碳酸二乙酯/碳酸二甲酯=1/1/1(體積比)中添加六氟化磷酸鋰(LiPF6
)而成者],在85℃浸漬3天、或於已添加500ppm水之電解液,在85℃浸漬5天。其後,將疊層體取出並以離子交換水清洗,以擦拭紙(paper wiper)將水擦掉,使水分充分乾燥,裁切成100mm×15mm大小,並利用T型剝離試驗實施耐藥品性之評價。
<評價基準> ☆(在實用上特別優良):8.0N/cm以上或材料破損 ◎(在實用上為優良):7.5N/cm以上未達8.0N/cm ○(可實用):7.0N/cm以上未達7.5N/cm ×(不可實用):未達7.0N/cm [產業上利用性]
本發明相關之黏著劑組成物含有酸改性聚烯烴、環氧樹脂及有機溶劑以及酸酐單體及具有2個以上的氮之雜環式化合物中之任一者,即使長期保存仍不會發生增黏、凝膠化,可維持良好的適用期特性,且可兼具與金屬基材及聚烯烴樹脂基材之間良好的黏著性。因此,由本發明之黏著劑組成物形成的聚烯烴樹脂基材與金屬基材之疊層結構體不僅可利用於家電外板、家具用材料、建築內裝用構件等領域,亦可廣泛地利用於作為個人電腦、行動電話、攝影機等所使用的鋰電池之包裝材(袋形態)。
Claims (10)
- 一種黏著劑組成物,含有酸價為5~50mgKOH/g-resin之結晶性酸改性聚烯烴(A)、環氧丙基胺型環氧樹脂(B1)、環氧丙基醚型環氧樹脂(B2)、及有機溶劑(E),更含有酸酐單體(C)及具有2個以上的氮之雜環式化合物(D)中之任一者,該酸酐單體(C)係1分子中具有1個以上之酸酐環且酸價為100mgKOH/g以上且1000mgKOH/g以下之化合物,相對於100質量份之結晶性酸改性聚烯烴(A),含有0.01~20質量份之環氧丙基胺型環氧樹脂(B1),1~50質量份之環氧丙基醚型環氧樹脂(B2),80質量份以上之有機溶劑(E),含有酸酐單體(C)之情況下,相對於100質量份之結晶性酸改性聚烯烴(A),含有1~50質量份之酸酐單體(C),含有具有2個以上的氮之雜環式化合物(D)之情況下,相對於100質量份之結晶性酸改性聚烯烴(A),含有0.01~5質量份之具有2個以上的氮之雜環式化合物(D)。
- 如申請專利範圍第1項之黏著劑組成物,其中,該環氧丙基胺型環氧樹脂(B1)為1分子中具有2個以上的環氧丙基之環氧樹脂。
- 如申請專利範圍第1或2項之黏著劑組成物,其中,該環氧丙基醚型環氧樹脂(B2)為1分子中具有2個以上的環氧丙基且不含氮原子之環氧樹脂。
- 如申請專利範圍第1或2項之黏著劑組成物,其中,該具有2個以上的氮之雜環式化合物(D)為具有2個以上的氮之5員環芳香族雜環式化合物。
- 如申請專利範圍第1或2項之黏著劑組成物,含有結晶性酸改性聚烯烴(A)、環氧丙基胺型環氧樹脂(B1)、環氧丙基醚型環氧樹脂(B2)、酸酐單體(C)、具有2個以上的氮之雜環式化合物(D)及有機溶劑(E),且相對於100質量份之結晶性酸改性聚烯烴(A),含有0.01~20質量份之環氧丙基胺型環氧樹脂(B1),1~50質量份之環氧丙基醚型環氧樹脂(B2),1~50質量份之酸酐單體(C),0.01~5質量份之具有2個以上的氮之雜環式化合物(D),80~1000質量份之有機溶劑(E)。
- 如申請專利範圍第1或2項之黏著劑組成物,其中,該有機溶劑(E)為溶劑(E1)與溶劑(E2)之混合液,溶劑(E1)係選自於由芳香烴、脂肪族烴、脂環族烴及鹵化 烴構成之群組中之1種以上的溶劑,溶劑(E2)係選自於由醇系溶劑、酮系溶劑、酯系溶劑及二醇醚系溶劑構成之群組中之1種以上的溶劑,且溶劑(E1)/溶劑(E2)=50~97/50~3(質量比)。
- 如申請專利範圍第1或2項之黏著劑組成物,係用於聚烯烴樹脂基材與金屬基材之黏著。
- 一種聚烯烴樹脂基材與金屬基材之疊層體,係利用如申請專利範圍第1至8項中任一項之黏著劑組成物予以黏著而成。
- 一種鋰離子電池用包裝材料,含有如申請專利範圍第9項之聚烯烴樹脂基材與金屬基材之疊層體作為構成構件。
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TW201610048A (zh) * | 2014-06-11 | 2016-03-16 | Toyo Boseki | 聚烯烴系接著劑組成物 |
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CN109476969B (zh) | 2021-11-02 |
JP6278167B1 (ja) | 2018-02-14 |
CN109476969A (zh) | 2019-03-15 |
TW201823406A (zh) | 2018-07-01 |
KR20190038844A (ko) | 2019-04-09 |
JPWO2018030050A1 (ja) | 2018-08-09 |
KR102301875B1 (ko) | 2021-09-15 |
WO2018030050A1 (ja) | 2018-02-15 |
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