JP7412112B2 - Modified polyolefin resin and its uses - Google Patents
Modified polyolefin resin and its uses Download PDFInfo
- Publication number
- JP7412112B2 JP7412112B2 JP2019157193A JP2019157193A JP7412112B2 JP 7412112 B2 JP7412112 B2 JP 7412112B2 JP 2019157193 A JP2019157193 A JP 2019157193A JP 2019157193 A JP2019157193 A JP 2019157193A JP 7412112 B2 JP7412112 B2 JP 7412112B2
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- JP
- Japan
- Prior art keywords
- polyolefin resin
- modified polyolefin
- component
- resin
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005672 polyolefin resin Polymers 0.000 title claims description 114
- 229920005989 resin Polymers 0.000 claims description 50
- 239000011347 resin Substances 0.000 claims description 50
- 239000000853 adhesive Substances 0.000 claims description 37
- 230000001070 adhesive effect Effects 0.000 claims description 37
- 150000001414 amino alcohols Chemical class 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 17
- -1 polypropylene, ethylene-propylene copolymer Polymers 0.000 claims description 16
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 15
- 238000005227 gel permeation chromatography Methods 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 238000004566 IR spectroscopy Methods 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 3
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 56
- 239000002243 precursor Substances 0.000 description 37
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 10
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 10
- 238000010559 graft polymerization reaction Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 238000013112 stability test Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920005675 propylene-butene random copolymer Polymers 0.000 description 6
- 230000009435 amidation Effects 0.000 description 5
- 238000007112 amidation reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000003849 aromatic solvent Substances 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002987 primer (paints) Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010421 standard material Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- AYAUWVRAUCDBFR-ONEGZZNKSA-N (e)-4-oxo-4-propoxybut-2-enoic acid Chemical compound CCCOC(=O)\C=C\C(O)=O AYAUWVRAUCDBFR-ONEGZZNKSA-N 0.000 description 1
- AYAUWVRAUCDBFR-ARJAWSKDSA-N (z)-4-oxo-4-propoxybut-2-enoic acid Chemical compound CCCOC(=O)\C=C/C(O)=O AYAUWVRAUCDBFR-ARJAWSKDSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- LHYBRZAQMRWQOJ-UHFFFAOYSA-N 2-methyl-2-(methylamino)propan-1-ol Chemical compound CNC(C)(C)CO LHYBRZAQMRWQOJ-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- GQZXRLWUYONVCP-UHFFFAOYSA-N 3-[1-(dimethylamino)ethyl]phenol Chemical compound CN(C)C(C)C1=CC=CC(O)=C1 GQZXRLWUYONVCP-UHFFFAOYSA-N 0.000 description 1
- LQGKDMHENBFVRC-UHFFFAOYSA-N 5-aminopentan-1-ol Chemical compound NCCCCCO LQGKDMHENBFVRC-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- DSTWFRCNXMNXTR-AATRIKPKSA-N dipropyl (e)-but-2-enedioate Chemical compound CCCOC(=O)\C=C\C(=O)OCCC DSTWFRCNXMNXTR-AATRIKPKSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 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
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 229940074369 monoethyl fumarate Drugs 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000768 polyamine Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Description
本発明は、変性ポリオレフィン樹脂及びその用途に関する。 The present invention relates to modified polyolefin resins and uses thereof.
変性ポリオレフィン樹脂は、ＬｉＢソフトパックラミネート用接着剤用途等、様々な用途に用いられている。変性ポリオレフィン樹脂は、高温状況下で使用される場合もあり、耐熱性が高いことが求められている。 Modified polyolefin resins are used in various applications, such as adhesive applications for LiB soft pack laminates. Modified polyolefin resins are sometimes used under high temperature conditions and are required to have high heat resistance.
変性ポリオレフィン樹脂の耐熱性を向上するために、高融点樹脂を併用する方法が開示されている（例えば、特許文献１参照）。しかしながら、高融点樹脂を併用する場合、高融点樹脂の併用比率を大きくすると、溶液安定性が低下することが知られている。そのため、接着剤やプライマー、塗料等の用途に用いる場合、改善の余地がある。 In order to improve the heat resistance of a modified polyolefin resin, a method of using a high melting point resin in combination has been disclosed (for example, see Patent Document 1). However, when a high melting point resin is used in combination, it is known that when the proportion of the high melting point resin is increased, the solution stability decreases. Therefore, there is room for improvement when used in applications such as adhesives, primers, and paints.
変性ポリオレフィン樹脂の耐熱性（８０℃や１２０℃雰囲気下における剥離強度）と溶液安定性のバランスを図ることを目的として、高融点樹脂の併用比率を最適化する技術が提案されている（例えば、特許文献２参照）。 With the aim of achieving a balance between the heat resistance (peel strength in an atmosphere of 80°C or 120°C) and solution stability of modified polyolefin resins, techniques have been proposed to optimize the ratio of high melting point resins (for example, (See Patent Document 2).
変性ポリオレフィン樹脂を車載用ＬｉＢ用途に用いる場合、さらなる耐熱性が求められている。耐熱性と溶液安定性のバランスを図ることを目的とした、高融点樹脂の併用比率を最適化する手段では、要求される性能を十分満足できないのが現状である。 When a modified polyolefin resin is used for automotive LiB applications, higher heat resistance is required. At present, the required performance cannot be fully satisfied by means of optimizing the ratio of high melting point resins used in combination for the purpose of achieving a balance between heat resistance and solution stability.
本発明の課題は、耐熱性と溶液安定性のバランスに優れる変性ポリオレフィン樹脂を提供することである。 An object of the present invention is to provide a modified polyolefin resin that has an excellent balance between heat resistance and solution stability.
本発明者らは、上記課題について鋭意検討した結果、ポリオレフィン樹脂をα，β－不飽和カルボン酸又はその誘導体とアミノアルコールでグラフト変性し、赤外分光スペクトル測定における、所定のピークの高さ比の範囲を特定することにより、上記の課題を解決できることを見出し、本発明を完成するに至った。
即ち、本発明者らは、下記の〔１〕～〔９〕を提供する。
〔１〕α，β－不飽和カルボン酸又はその誘導体（ＩＩ）（以下、「成分（ＩＩ）」ともいう）と、一級又は二級のアミノ基を有するアミノアルコール（ＩＩＩ）（以下、「成分（ＩＩＩ）」ともいう）による、ポリオレフィン樹脂（Ｉ）のグラフト変性物であり、赤外分光スペクトル測定において観察される、アミド結合由来のピーク高さをＡとし、メチレン結合由来のピーク高さをＢとしたときに、ピーク高さ比（Ａ／Ｂ×１００）（以下、「ピーク高さ比（Ａ／Ｂ×１００）」ともいう）が０．１～６．０％の範囲である、変性ポリオレフィン樹脂。
〔２〕前記ポリオレフィン樹脂（Ｉ）が、ポリプロピレン、エチレン－プロピレン共重合体、プロピレン－１－ブテン共重合体、及びエチレン－プロピレン－１－ブテン共重合体からなる群より選ばれる少なくとも１種である、上記〔１〕に記載の変性ポリオレフィン樹脂。
〔３〕前記α，β－不飽和カルボン酸又はその誘導体（ＩＩ）が、無水マレイン酸、無水イタコン酸、及びマレイン酸からなる群より選ばれる少なくとも１種である、上記〔１〕又は〔２〕に記載の変性ポリオレフィン樹脂。
〔４〕前記グラフト変性物が、下記一般式（１）で表される（メタ）アクリル酸エステル（ＩＶ）（以下、「成分（ＩＶ）」ともいう）による変性物である上記〔１〕～〔３〕のいずれかに記載の変性ポリオレフィン樹脂。
〔５〕ポリスチレン標準によるゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって測定した重量平均分子量が、１０，０００～２００，０００である、上記〔１〕～〔４〕のいずれかに記載の変性ポリオレフィン樹脂。
〔６〕上記〔１〕～〔５〕のいずれかに記載の変性ポリオレフィン樹脂を含む接着剤。
〔７〕上記〔１〕～〔５〕のいずれかに記載の変性ポリオレフィン樹脂を含むプライマー。
〔８〕上記〔１〕～〔５〕のいずれかに記載の変性ポリオレフィン樹脂を含む塗料。
〔９〕上記〔１〕～〔５〕のいずれかに記載の変性ポリオレフィン樹脂を含むインキ。
As a result of intensive study on the above-mentioned problem, the present inventors graft-modified polyolefin resin with α,β-unsaturated carboxylic acid or its derivative and amino alcohol, and determined the height ratio of a predetermined peak in infrared spectroscopy. The inventors have discovered that the above problems can be solved by specifying the range of , and have completed the present invention.
That is, the present inventors provide the following [1] to [9].
[1] α,β-unsaturated carboxylic acid or its derivative (II) (hereinafter also referred to as “component (II)”) and an amino alcohol (III) having a primary or secondary amino group (hereinafter referred to as “component (II)”) (III)) is a graft modified product of polyolefin resin (I), which is observed in infrared spectroscopy. The peak height derived from amide bond is A, and the peak height derived from methylene bond is defined as A. When B, the peak height ratio (A / B × 100) (hereinafter also referred to as "peak height ratio (A / B × 100)") is in the range of 0.1 to 6.0%, Modified polyolefin resin.
[2] The polyolefin resin (I) is at least one selected from the group consisting of polypropylene, ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer. A certain modified polyolefin resin according to [1] above.
[3] The above [1] or [2], wherein the α,β-unsaturated carboxylic acid or its derivative (II) is at least one selected from the group consisting of maleic anhydride, itaconic anhydride, and maleic acid. ] The modified polyolefin resin described in ].
[4] The above [1]~, wherein the graft modified product is a modified product using a (meth)acrylic acid ester (IV) represented by the following general formula (1) (hereinafter also referred to as "component (IV)") The modified polyolefin resin according to any one of [3].
[5] The modified polyolefin resin according to any one of [1] to [4] above, which has a weight average molecular weight of 10,000 to 200,000 as measured by gel permeation chromatography (GPC) using a polystyrene standard.
[6] An adhesive comprising the modified polyolefin resin according to any one of [1] to [5] above.
[7] A primer comprising the modified polyolefin resin according to any one of [1] to [5] above.
[8] A paint containing the modified polyolefin resin according to any one of [1] to [5] above.
[9] An ink containing the modified polyolefin resin according to any one of [1] to [5] above.
本発明によれば、耐熱性と溶液安定性のバランスに優れる変性ポリオレフィン樹脂を提供することができる。 According to the present invention, a modified polyolefin resin having an excellent balance between heat resistance and solution stability can be provided.
以下、本発明をその好適な実施形態に即して詳細に説明する。なお、本明細書中、「ＡＡ～ＢＢ」とは、ＡＡ以上ＢＢ以下を意味する。 Hereinafter, the present invention will be explained in detail based on its preferred embodiments. In this specification, "AA to BB" means AA or more and BB or less.
［１．変性ポリオレフィン樹脂］
本発明の変性ポリオレフィン樹脂は、成分（ＩＩ）と、成分（ＩＩＩ）による、ポリオレフィン樹脂（Ｉ）のグラフト変性物である。また、本発明の変性ポリオレフィン樹脂において、グラフト変性物は成分（ＩＶ）による変性物であることが好ましい。さらに、本発明の変性ポリオレフィン樹脂は、赤外分光スペクトル測定において観察される、アミド結合由来のピーク高さをＡとし、メチレン結合由来のピーク高さをＢとしたときに、ピーク高さ比（Ａ／Ｂ×１００）が０．１～６．０％の範囲である。
[1. Modified polyolefin resin]
The modified polyolefin resin of the present invention is a graft modified product of polyolefin resin (I) with component (II) and component (III). Further, in the modified polyolefin resin of the present invention, the graft modified product is preferably a modified product using component (IV). Furthermore, the modified polyolefin resin of the present invention has a peak height ratio ( A/B×100) is in the range of 0.1 to 6.0%.
本発明の変性ポリオレフィン樹脂が、高融点樹脂の併用比率の最適化という従来手段とは異なる手段で、耐熱性が優れる理由を次のように推察し得る。ポリオレフィン樹脂に水酸基を導入することにより、他の樹脂に存在する架橋成分との反応性を高め得る。その結果、硬化物の架橋密度が向上し得る。従って、硬化物の耐熱性を向上し得る。 The reason why the modified polyolefin resin of the present invention has excellent heat resistance by optimizing the combination ratio of high melting point resin, which is different from the conventional method, can be inferred as follows. By introducing a hydroxyl group into a polyolefin resin, reactivity with crosslinking components present in other resins can be increased. As a result, the crosslinking density of the cured product can be improved. Therefore, the heat resistance of the cured product can be improved.
本発明の変性ポリオレフィン樹脂は、以下の構造を有すると推察される。まず、成分（ＩＩ）及び必要に応じて成分（ＩＶ）が、ポリオレフィン樹脂（Ｉ）にグラフト重合している。また、グラフト重合により導入された成分（ＩＩ）に由来するカルボニル基の少なくとも一部と、成分（ＩＩＩ）に由来する窒素原子により、アミド結合が形成されている。従って、本発明の変性ポリオレフィン樹脂は、ポリオレフィン樹脂（Ｉ）に、成分（ＩＩ）がグラフト重合し、成分（ＩＩ）の少なくとも一部と、成分（ＩＩＩ）によるアミド結合を有するとともに、成分（ＩＩＩ）に由来する水酸基を有すると推察される。 The modified polyolefin resin of the present invention is presumed to have the following structure. First, component (II) and optionally component (IV) are graft-polymerized onto polyolefin resin (I). Furthermore, an amide bond is formed by at least a portion of the carbonyl group derived from component (II) introduced by graft polymerization and the nitrogen atom derived from component (III). Therefore, the modified polyolefin resin of the present invention is obtained by graft polymerization of component (II) to polyolefin resin (I), and has an amide bond formed by at least a part of component (II) and component (III), and has an amide bond formed by component (III). ) is presumed to have a hydroxyl group derived from
本発明の変性ポリオレフィン樹脂は、赤外分光スペクトルにおいて観察される、アミド結合由来のピーク高さをＡとし、メチレン結合由来のピーク高さをＢとしたとき、ピーク高さ比（Ａ／Ｂ×１００）が０．１～６．０％の範囲である。ピーク高さ比は、ポリオレフィン樹脂（Ｉ）に対する成分（ＩＩＩ）の付加量を評価し得る。
ピーク高さ比（Ａ／Ｂ×１００）の下限は、０．１％以上であり、好ましくは０．３％以上であり、より好ましくは０．５％以上である。０．１％以上であると、成分（ＩＩＩ）由来の水酸基を有し、硬化剤成分等との架橋反応が進行して架橋密度を高くし得る。従って、硬化物の耐熱性に優れる変性ポリオレフィン樹脂とし得る。また、その上限は、６．０％以下であり、好ましくは５．０％以下であり、より好ましくは３．０％以下である。６．０％以下であると、成分（ＩＩＩ）由来の水酸基量が適切となるため、成分（ＩＩＩ）とポリオレフィン樹脂骨格にグラフトした成分（ＩＩ）が反応することによる溶液の増粘を抑え、溶液安定性に優れる変性ポリオレフィン樹脂とし得る。
The modified polyolefin resin of the present invention has a peak height ratio (A/B× 100) is in the range of 0.1 to 6.0%. The peak height ratio can evaluate the amount of component (III) added to polyolefin resin (I).
The lower limit of the peak height ratio (A/B×100) is 0.1% or more, preferably 0.3% or more, and more preferably 0.5% or more. When it is 0.1% or more, it has a hydroxyl group derived from component (III), and a crosslinking reaction with a curing agent component etc. proceeds, thereby increasing the crosslinking density. Therefore, the cured product can be a modified polyolefin resin with excellent heat resistance. Further, its upper limit is 6.0% or less, preferably 5.0% or less, and more preferably 3.0% or less. If it is 6.0% or less, the amount of hydroxyl groups derived from component (III) will be appropriate, suppressing the thickening of the solution due to reaction between component (III) and component (II) grafted to the polyolefin resin skeleton, It can be a modified polyolefin resin with excellent solution stability.
赤外分光スペクトルにおいて、アミド結合由来のピークを観測し得ることから、変性ポリオレフィン樹脂が、成分（ＩＩＩ）に由来する水酸基を有することを推察し得る。ここで、アミド結合由来のピークは、波数１６１０～１６８０ｃｍ－１に現れるピークであり、Ｃ＝Ｏ伸縮振動に帰属される。
また、赤外分光スペクトルにおいて、ポリオレフィン樹脂（Ｉ）骨格のメチレン結合由来のピークも確認し得る。ここで、メチレン結合由来のピークは、波数１４２０～１５００ｃｍ－１に現れるピークであり、Ｃ－Ｈ変角振動に帰属される。
Since a peak derived from an amide bond can be observed in the infrared spectrum, it can be inferred that the modified polyolefin resin has a hydroxyl group derived from component (III). Here, the peak derived from the amide bond is a peak appearing at a wave number of 1610 to 1680 cm −1 and is attributed to C=O stretching vibration.
Moreover, in the infrared spectroscopic spectrum, a peak derived from the methylene bond of the polyolefin resin (I) skeleton can also be confirmed. Here, the peak derived from the methylene bond is a peak appearing at a wave number of 1420 to 1500 cm −1 and is attributed to C—H bending vibration.
本発明の変性ポリオレフィン樹脂において、ポリスチレン標準によるゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって測定した重量平均分子量は、１０，０００～２００，０００の範囲が好ましく、３０，０００～２００，０００、３０，０００～１８０，０００の範囲がより好ましく、３０，０００～１７０，０００、３０，０００～１３０，０００の範囲がさらに好ましく、５０，０００～１７０，０００の範囲がさらにより好ましい。
なお、ＧＰＣの測定条件は、以下の条件であり、後段の実施例における重量平均分子量は、この条件で測定した値である。
測定機器：ＨＬＣ－８３２０ＧＰＣ（東ソー社製）
溶離液：テトラヒドロフラン
カラム：ＴＳＫｇｅｌ（東ソー社製）
標準物質；ポリスチレン（東ソー製、ＧＬサイエンス製）
検出器；示差屈折計（東ソー製）
In the modified polyolefin resin of the present invention, the weight average molecular weight measured by gel permeation chromatography (GPC) using a polystyrene standard is preferably in the range of 10,000 to 200,000, preferably 30,000 to 200,000, 30,000 to 30,000. The range of 180,000 to 180,000 is more preferred, the range of 30,000 to 170,000, the range of 30,000 to 130,000 is even more preferred, and the range of 50,000 to 170,000 is even more preferred.
The measurement conditions for GPC are as follows, and the weight average molecular weights in the later examples are values measured under these conditions.
Measuring equipment: HLC-8320GPC (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Column: TSKgel (manufactured by Tosoh Corporation)
Standard material: Polystyrene (manufactured by Tosoh, GL Science)
Detector: Differential refractometer (manufactured by Tosoh)
［１－１．ポリオレフィン樹脂（Ｉ）］
ポリオレフィン樹脂（Ｉ）は、特に限定されず、１種単独のオレフィン重合体であっても、２種以上のオレフィン重合体の共重合体であってもよい。また、共重合体である場合、ランダム共重合体であってもよく、ブロック共重合体であってもよい。オレフィンとしては、α－オレフィンが好適に用いられる。α－オレフィンとしては、例えば、エチレン、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、１－ヘプテン、１－オクテンが挙げられる。
[1-1. Polyolefin resin (I)]
The polyolefin resin (I) is not particularly limited, and may be a single type of olefin polymer or a copolymer of two or more types of olefin polymers. Further, when it is a copolymer, it may be a random copolymer or a block copolymer. As the olefin, α-olefin is preferably used. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.
ポリオレフィン樹脂（Ｉ）としては、ポリプロピレン基材等の非極性樹脂基材への十分な付着性を発現させるという観点から、ポリプロピレン（プロピレン単独重合体）、エチレン－プロピレン共重合体、プロピレン－１－ブテン共重合体、エチレン－プロピレン－１－ブテン共重合体がより好適に用いられる。
本明細書において、「ポリプロピレン」とは、基本単位がプロピレン由来の構成単位である重合体を表す。「エチレン－プロピレン共重合体」とは、基本単位がエチレン及びプロピレン由来の構成単位である共重合体を表す。「プロピレン－ブテン共重合体」とは、基本単位がプロピレン及びブテン由来の構成単位である共重合体を表す。これらの（共）重合体は、基本単位以外の他のオレフィン由来の構成単位を少量含有していてもよい。この含有量は、樹脂本来の性能を著しく損なわない量であればよい。このような他のオレフィン由来の構成単位は、例えば、変性ポリオレフィン樹脂の製造までの工程で混入することがある。
As the polyolefin resin (I), polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1- Butene copolymers and ethylene-propylene-1-butene copolymers are more preferably used.
As used herein, "polypropylene" refers to a polymer whose basic unit is a constitutional unit derived from propylene. "Ethylene-propylene copolymer" refers to a copolymer whose basic units are structural units derived from ethylene and propylene. "Propylene-butene copolymer" refers to a copolymer whose basic units are constitutional units derived from propylene and butene. These (co)polymers may contain a small amount of other olefin-derived structural units other than the basic units. This content may be any amount that does not significantly impair the inherent performance of the resin. Such structural units derived from other olefins may be mixed, for example, in the process up to the production of modified polyolefin resin.
ポリオレフィン樹脂（Ｉ）は、構成単位１００モル％中、プロピレン由来の構成単位を５０モル％以上含むことが好ましい。プロピレン由来の構成単位を上記範囲で含むと、プロピレン樹脂等の非極性樹脂基材に対する接着性を保持できる。 It is preferable that the polyolefin resin (I) contains 50 mol% or more of propylene-derived structural units in 100 mol% of the structural units. When the structural unit derived from propylene is contained in the above range, adhesiveness to a non-polar resin base material such as propylene resin can be maintained.
ポリオレフィン樹脂（Ｉ）は、重合触媒としてメタロセン触媒を用いて得られるものが好ましい。
メタロセン触媒としては、公知のものを使用できる。メタロセン触媒は、下記成分（１）及び成分（２）と、さらに必要に応じて成分（３）とを組み合わせて得られるものが好ましい。
・成分（１）；共役五員環配位子を少なくとも一個有する周期律表４～６族の遷移金属化合物であるメタロセン錯体；
・成分（２）；イオン交換性層状ケイ酸塩；
・成分（３）；有機アルミニウム化合物。
The polyolefin resin (I) is preferably one obtained using a metallocene catalyst as a polymerization catalyst.
As the metallocene catalyst, known ones can be used. The metallocene catalyst is preferably one obtained by combining the following components (1) and (2), and further, if necessary, component (3).
・Component (1); metallocene complex which is a transition metal compound of Groups 4 to 6 of the periodic table and having at least one conjugated five-membered ring ligand;
・Component (2); Ion exchange layered silicate;
- Component (3); organoaluminum compound.
メタロセン触媒を用いると、次の特徴を有する。ポリオレフィン樹脂（Ｉ）の分子量分布が狭くなる。また、ポリオレフィン樹脂（Ｉ）が共重合体の場合は、ランダム共重合性に優れ、組成分布が狭く、さらに、共重合し得るコモノマーの範囲が広くなる。このような特徴を有するポリオレフィン樹脂（Ｉ）は、本発明の変性ポリオレフィン樹脂に好適に用いられる。 The use of metallocene catalysts has the following characteristics. The molecular weight distribution of the polyolefin resin (I) becomes narrow. Furthermore, when the polyolefin resin (I) is a copolymer, it has excellent random copolymerizability, has a narrow composition distribution, and has a wide range of comonomers that can be copolymerized. Polyolefin resin (I) having such characteristics is suitably used for the modified polyolefin resin of the present invention.
エチレン－プロピレン共重合体及びプロピレン－ブテン共重合体がランダム共重合体である場合、構成単位１００モル％中、エチレン由来の構成単位又はブテン由来の構成単位を５～５０モル％の量で含み、プロピレン由来の構成単位を５０～９５モル％の量で含むことが好ましい。 When the ethylene-propylene copolymer and propylene-butene copolymer are random copolymers, they contain ethylene-derived structural units or butene-derived structural units in an amount of 5 to 50 mol% in 100 mol% of the structural units. , it is preferable that the structural unit derived from propylene be contained in an amount of 50 to 95 mol%.
ポリオレフィン樹脂（Ｉ）の重量平均分子量は、特に限定されない。しかしながら、変性ポリオレフィン樹脂の重量平均分子量が、好ましくは１０，０００～２００，０００であり、より好ましくは３０，０００～２００，０００、３０，０００～１８０,０００であり、さらに好ましくは３０，０００～１７０，０００、３０，０００～１３０，０００であり、さらにより好ましくは５０，０００～１７０，０００である。このため、ポリオレフィン樹脂（Ｉ）の重量平均分子量が２００，０００超である場合、得られる変性ポリオレフィン樹脂の重量平均分子量が上記範囲となるように、調整することが好ましい。具体的には、熱やラジカルの存在下で減成して、分子量を適当な範囲、例えば２００，０００以下となるように調整する。なお、ポリオレフィン樹脂（Ｉ）の重量平均分子量は、上記と同様に、ゲルパーミエーションクロマトグラフィー（ＧＰＣ、標準物質：ポリスチレン）によって測定した値である。また、測定条件は、上記と同じである。 The weight average molecular weight of the polyolefin resin (I) is not particularly limited. However, the weight average molecular weight of the modified polyolefin resin is preferably 10,000 to 200,000, more preferably 30,000 to 200,000, 30,000 to 180,000, and even more preferably 30,000. 170,000, 30,000 to 130,000, and even more preferably 50,000 to 170,000. Therefore, when the weight average molecular weight of the polyolefin resin (I) is more than 200,000, it is preferable to adjust the weight average molecular weight of the resulting modified polyolefin resin to fall within the above range. Specifically, the molecular weight is adjusted to an appropriate range, for example, 200,000 or less, by degrading it in the presence of heat or radicals. The weight average molecular weight of the polyolefin resin (I) is a value measured by gel permeation chromatography (GPC, standard material: polystyrene) in the same manner as above. Moreover, the measurement conditions are the same as above.
ポリオレフィン樹脂（Ｉ）は、１種単独で用いても、２種以上を組み合わせて用いてもよい。２種以上を組み合わせて用いるときは、その割合は特に限定されない。 The polyolefin resin (I) may be used alone or in combination of two or more. When two or more types are used in combination, the ratio is not particularly limited.
［１－２．α，β－不飽和カルボン酸又はその誘導体（ＩＩ）（成分（ＩＩ））］
成分（ＩＩ）のうち、α，β－不飽和カルボン酸としては、例えば、フマル酸、マレイン酸、イタコン酸、メサコン酸、シトラコン酸、アコニット酸、ナジック酸が挙げられる。これらの中でも、不飽和ジカルボン酸が好ましい。また、成分（ＩＩ）のうち、α，β－不飽和カルボン酸の誘導体としては、例えば、α，β－不飽和カルボン酸の酸無水物、及びフマル酸モノメチル、フマル酸モノエチル、フマル酸モノプロピル、フマル酸モノブチル、フマル酸ジメチル、フマル酸ジエチル、フマル酸ジプロピル、フマル酸ジブチル、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノプロピル、マレイン酸モノブチル、マレイン酸ジメチル、マレイン酸ジエチル、マレイン酸ジプロピル、マレイン酸ジブチル、マレイミド、Ｎ－フェニルマレイミドが挙げられる。これらの中でも、α，β－不飽和カルボン酸の酸無水物が好ましい。
[1-2. α,β-unsaturated carboxylic acid or its derivative (II) (component (II))]
Among component (II), examples of the α,β-unsaturated carboxylic acid include fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, aconitic acid, and nadic acid. Among these, unsaturated dicarboxylic acids are preferred. Among component (II), derivatives of α,β-unsaturated carboxylic acids include, for example, acid anhydrides of α,β-unsaturated carboxylic acids, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate. , monobutyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, Examples include dibutyl maleate, maleimide, and N-phenylmaleimide. Among these, acid anhydrides of α,β-unsaturated carboxylic acids are preferred.
成分（ＩＩ）としては、変性ポリオレフィン樹脂の水酸基量を適切にする観点から、無水マレイン酸、無水イタコン酸、マレイン酸が好ましく、無水マレイン酸がより好ましい。
なお、成分（ＩＩ）は、１種単独で用いてもよく、２種以上の組合せを用いてもよい。すなわち、成分（ＩＩ）は、α，β－不飽和カルボン酸及びその誘導体からなる群より選ばれる少なくとも１種である。α，β－不飽和カルボン酸を２種以上組み合わせて用いてもよく、上記誘導体を２種以上組み合わせて用いてもよい。また、α，β－不飽和カルボン酸１種以上とその誘導体１種以上とを組み合わせて用いてもよい。なお、２種以上を組み合わせて用いる場合、その割合は特に限定されない。
As component (II), from the viewpoint of optimizing the amount of hydroxyl groups in the modified polyolefin resin, maleic anhydride, itaconic anhydride, and maleic acid are preferable, and maleic anhydride is more preferable.
In addition, component (II) may be used alone or in combination of two or more. That is, component (II) is at least one selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof. Two or more types of α,β-unsaturated carboxylic acids may be used in combination, and two or more types of the above derivatives may be used in combination. Furthermore, one or more α,β-unsaturated carboxylic acids and one or more derivatives thereof may be used in combination. Note that when two or more types are used in combination, the ratio is not particularly limited.
［１－３．アミノアルコール（ＩＩＩ）（成分（ＩＩＩ））］
成分（ＩＩＩ）は、水酸基とともに、一級又は二級のアミノ基を有する。成分（ＩＩＩ）は、一級のアミノ基を有することが好ましい。
[1-3. Amino alcohol (III) (component (III))]
Component (III) has a hydroxyl group and a primary or secondary amino group. Component (III) preferably has a primary amino group.
成分（ＩＩＩ）としては、例えば、２－アミノエタノール、３－アミノ－１－プロパノール、４－アミノ－１－ブタノール、５－アミノ－１－ペンタノール、２－アミノ－１－ブタノール、２－アミノ－２－メチル－１－プロパノール、２－アミノ－２－メチル－１，３－プロパンジオール、２－メチルアミノ－２－メチル－１－プロパノール、Ｎ－アミノエチルエタノールアミン、２－（２－アミノエトキシ）エタノールが挙げられる。これらの中でも、２－アミノエタノール、２－（２－アミノエトキシ）エタノール、３－アミノ－１－プロパノール、４－アミノ－１－ブタノール、２－アミノ－２－メチル－１－プロパノールが好ましい。
成分（ＩＩＩ）は、１種単独で用いてもよく、２種以上の組合せを用いてもよい。なお、２種以上を組み合わせて用いる場合、その割合は特に限定されない。
As component (III), for example, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 2-amino-1-butanol, 2-amino -2-Methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-methylamino-2-methyl-1-propanol, N-aminoethylethanolamine, 2-(2-amino (ethoxy) ethanol. Among these, 2-aminoethanol, 2-(2-aminoethoxy)ethanol, 3-amino-1-propanol, 4-amino-1-butanol, and 2-amino-2-methyl-1-propanol are preferred.
Component (III) may be used alone or in combination of two or more. Note that when two or more types are used in combination, the ratio is not particularly limited.
［１－４．（（メタ）アクリル酸エステル）（ＩＶ）（成分（ＩＶ））］
（メタ）アクリル酸エステルは、一般式（１）で表される化合物である。成分（ＩＶ）を用いて変性すると、変性ポリオレフィン樹脂の分子量分布を狭くすることができ、溶液の低温安定性、他樹脂との相溶性、接着性を向上させることができる。一般式（１）で表される（メタ）アクリル酸エステルは、１種単独で用いてもよく、複数種を任意の割合で混合して用いてもよい。
[1-4. ((meth)acrylic acid ester) (IV) (component (IV))]
(Meth)acrylic acid ester is a compound represented by general formula (1). When modified using component (IV), the molecular weight distribution of the modified polyolefin resin can be narrowed, and the low-temperature stability of the solution, compatibility with other resins, and adhesiveness can be improved. The (meth)acrylic acid esters represented by the general formula (1) may be used alone or in a mixture of multiple types in any proportion.
一般式（１）中、Ｒ１は、Ｈ又はＣＨ３を表し、ＣＨ３が好ましい。Ｒ２は、ＣｎＨ２ｎ＋１を表す。ｎは、８～１８の整数を表し、８～１５が好ましく、８～１４がより好ましく、８～１３がさらに好ましい。式（１）で表される化合物としては、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、オクチル（メタ）アクリレートが好ましく、ラウリルメタクリレート、オクチルメタクリレート、トリデシルメタクリレートがより好ましい。 In general formula (1), R 1 represents H or CH 3 , preferably CH 3 . R 2 represents C n H 2n+1 . n represents an integer of 8 to 18, preferably 8 to 15, more preferably 8 to 14, and even more preferably 8 to 13. As the compound represented by formula (1), lauryl (meth)acrylate, tridecyl (meth)acrylate, and octyl (meth)acrylate are preferable, and lauryl methacrylate, octyl methacrylate, and tridecyl methacrylate are more preferable.
［２．変性ポリオレフィン樹脂の製造方法］
変性ポリオレフィン樹脂は、ポリオレフィン樹脂（Ｉ）を、成分（ＩＩ）と、成分（ＩＩＩ）と、必要に応じて成分（ＩＶ）とにより変性して得られる。より詳細には、ポリオレフィン樹脂（Ｉ）を、成分（ＩＩ）及び必要に応じて成分（ＩＶ）で変性して、前駆体樹脂を得る工程（Ａ）（以下、「工程（Ａ）」ともいう）と、得られた前駆体樹脂を成分（ＩＩＩ）で変性して、変性ポリオレフィン樹脂を得る工程（Ｂ））（以下、「工程（Ｂ）」ともいう）と、から構成されていてもよい。このような製造方法について、以下に詳しく説明する。
[2. Manufacturing method of modified polyolefin resin]
The modified polyolefin resin is obtained by modifying polyolefin resin (I) with component (II), component (III), and optionally component (IV). More specifically, a step (A) of obtaining a precursor resin by modifying the polyolefin resin (I) with component (II) and optionally component (IV) (hereinafter also referred to as "step (A)") ), and step (B)) of obtaining a modified polyolefin resin by modifying the obtained precursor resin with component (III) (hereinafter also referred to as "step (B)"). . Such a manufacturing method will be explained in detail below.
［２－１．工程（Ａ）］
工程（Ａ）では、成分（ＩＩ）及び必要に応じて成分（ＩＶ）がポリオレフィン樹脂（Ｉ）に導入されればよく、成分（ＩＩ）及び必要に応じて成分（ＩＶ）がポリオレフィン樹脂（Ｉ）にグラフト重合により導入されることが好ましい。グラフト重合反応の際には、ラジカル発生剤を用いてもよい。工程（Ａ）としては、例えば、トルエン等の溶剤に成分（Ｉ）、成分（ＩＩ）、及び必要に応じて成分（ＩＶ）を加熱溶解し、ラジカル発生剤を添加する溶液法；バンバリーミキサー、ニーダー、押出機等の機器に、成分（Ｉ）、成分（ＩＩ）、必要に応じて成分（ＩＶ）及びラジカル発生剤を添加し混練する溶融混練法等が挙げられる。ここで、成分（ＩＩ）及び必要に応じて成分（ＩＶ）を２種以上用いる場合、これらは一括添加しても、逐次添加してもよい。逐次添加の場合、成分（ＩＩ）及び必要に応じて成分（ＩＶ）をグラフト重合させるか順序は、特に限定されない。また、成分（ＩＩ）及び必要に応じて成分（ＩＶ）を２種以上用いる場合、その割合は特に限定されない。
[2-1. Process (A)]
In step (A), component (II) and optionally component (IV) may be introduced into polyolefin resin (I), and component (II) and optionally component (IV) may be introduced into polyolefin resin (I). ) is preferably introduced by graft polymerization. A radical generator may be used during the graft polymerization reaction. Step (A) includes, for example, a solution method in which component (I), component (II), and optionally component (IV) are heated and dissolved in a solvent such as toluene, and a radical generator is added; a Banbury mixer; Examples include a melt-kneading method in which component (I), component (II), optionally component (IV), and a radical generator are added to equipment such as a kneader or an extruder and kneaded. Here, when two or more types of component (II) and optionally component (IV) are used, they may be added all at once or sequentially. In the case of sequential addition, the order in which component (II) and optionally component (IV) are graft-polymerized is not particularly limited. Furthermore, when two or more types of component (II) and optionally component (IV) are used, the proportion thereof is not particularly limited.
グラフト重合反応の際には、成分（ＩＩ）の使用量は、ポリオレフィン樹脂（Ｉ）１００質量部に対して、０．５～２０質量部が好ましく、０．５～１０質量部がより好ましい。 In the graft polymerization reaction, the amount of component (II) used is preferably 0.5 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of polyolefin resin (I).
グラフト重合反応の際には、必要に応じて使用する成分（ＩＶ）の使用量は、変性ポリオレフィン樹脂（Ｉ）を１００重量部とした場合に、０．１～１０重量部が好ましく、０．４～４重量部がより好ましい。成分（ＩＶ）の使用量が０．１重量部以上であることにより、変性ポリオレフィン樹脂の分子量分布を十分狭い範囲に保ち得る。すなわち、高分子量部分の悪影響を防止して、溶剤溶解性、溶液の低温安定性及び他樹脂との相溶性を良好に保持し得る。また、低分子量部分の悪影響を防止して、接着力を向上し得る。成分（ＩＶ）の使用量が１０重量部以下であることにより、グラフト未反応物の発生を防止し、樹脂被着体に対する接着性を良好に保持し得る。 In the graft polymerization reaction, the amount of component (IV) used as necessary is preferably 0.1 to 10 parts by weight, and 0.1 to 10 parts by weight, based on 100 parts by weight of the modified polyolefin resin (I). More preferably 4 to 4 parts by weight. When the amount of component (IV) used is 0.1 parts by weight or more, the molecular weight distribution of the modified polyolefin resin can be kept within a sufficiently narrow range. That is, it is possible to prevent the adverse effects of the high molecular weight portion and maintain good solvent solubility, low-temperature stability of the solution, and compatibility with other resins. In addition, it is possible to prevent the adverse effects of low molecular weight moieties and improve adhesive strength. When the amount of component (IV) used is 10 parts by weight or less, generation of graft unreacted substances can be prevented and adhesion to the resin adherend can be maintained well.
ラジカル発生剤は、公知のものより適宜選択できる。公知のラジカル発生剤の中でも、有機過酸化物系化合物が好ましい。有機過酸化物系化合物としては、例えば、ジ－ｔ－ブチルパーオキサイド、ジクミルパーオキサイド、ｔ－ブチルクミルパーオキサイド、ベンゾイルパーオキサイド、ジラウリルパーオキサイド、クメンハイドロパーオキサイド、ｔ－ブチルハイドロパーオキサイド、１，１－ビス（ｔ－ブチルパーオキシ）－３，５，５－トリメチルシクロヘキサン、１，１－ビス（ｔ－ブチルパーオキシ）－シクロヘキサン、シクロヘキサノンパーオキサイド、ｔ－ブチルパーオキシベンゾエート、ｔ－ブチルパーオキシイソブチレート、ｔ－ブチルパーオキシ－３，５，５－トリメチルヘキサノエート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔ－ブチルパーオキシイソプロピルカーボネート、クミルパーオキシオクトエート、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキサンが挙げられる。これらの中でも、ジ－ｔ－ブチルパーオキサイド、ジラウリルパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキサンが好ましい。 The radical generator can be appropriately selected from known radical generators. Among known radical generators, organic peroxide compounds are preferred. Examples of organic peroxide compounds include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide. oxide, 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t-Butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate, cumylperoxy Examples include octoate and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane. Among these, di-t-butyl peroxide, dilauryl peroxide, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane are preferred.
ラジカル発生剤の添加量の下限は、成分（ＩＩ）及び必要により使用する成分（ＩＶ）の合計１００質量部に対し、好ましくは１質量部以上であり、より好ましくは３質量部以上である。１質量部以上であると、成分（ＩＩ）及び必要により使用する成分（ＩＶ）をグラフト重合で導入し得る。また、添加量の上限は、好ましくは１００質量部以下であり、より好ましくは５０質量部以下である。１００質量部以下であると、経済的である。 The lower limit of the amount of the radical generator added is preferably 1 part by mass or more, more preferably 3 parts by mass or more, based on a total of 100 parts by mass of component (II) and optionally used component (IV). When the amount is 1 part by mass or more, component (II) and optionally used component (IV) can be introduced by graft polymerization. Further, the upper limit of the amount added is preferably 100 parts by mass or less, more preferably 50 parts by mass or less. It is economical if the amount is 100 parts by mass or less.
工程（Ａ）において、ポリオレフィン樹脂（Ｉ）にグラフト重合しない、成分（ＩＩ）及び必要により使用する成分（ＩＶ）、即ち、未反応物は、例えば、貧溶媒で抽出して除去してもよい。 In step (A), component (II) that does not graft polymerize to polyolefin resin (I) and optionally used component (IV), that is, unreacted materials, may be removed by, for example, extraction with a poor solvent. .
このようにして、工程（Ａ）により、前駆体樹脂が得られる。成分（ＩＩ）及び必要により使用する成分（ＩＶ）のそれぞれのグラフト量は、特に制限されないが、前駆体樹脂１００質量％に対し、０質量％超２０質量％以下が好ましく、０質量％超１０質量％以下がより好ましく、０質量％超４質量％以下がさらに好ましく、０質量％超４質量％以下がさらにより好ましい。グラフト量が上記範囲にあると、変性ポリオレフィン樹脂の水酸基量を調整し得る。
α，β－不飽和カルボン酸又はその誘導体（ＩＩ）の導入量（グラフト重量）は、アルカリ滴定法により求め得る。また、（メタ）アクリル酸エステルの導入量（グラフト重量）は、１Ｈ－ＮＭＲにより求め得る。
In this way, a precursor resin is obtained in step (A). The amount of grafting of component (II) and optionally used component (IV) is not particularly limited, but is preferably more than 0% by mass and 20% by mass or less, and more than 10% by mass based on 100% by mass of the precursor resin. It is more preferably less than 0% by mass, even more preferably more than 0% by mass and less than 4% by mass, even more preferably more than 0% by mass and not more than 4% by mass. When the amount of grafting is within the above range, the amount of hydroxyl groups in the modified polyolefin resin can be adjusted.
The amount of α,β-unsaturated carboxylic acid or its derivative (II) introduced (graft weight) can be determined by an alkaline titration method. Further, the amount of (meth)acrylic acid ester introduced (graft weight) can be determined by 1 H-NMR.
工程（Ａ）で得られた前駆体樹脂は、変性ポリオレフィン樹脂の重量平均分子量が上述した好適な範囲となるよう、ポリスチレン標準によるゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって測定した重量平均分子量が、１０，０００～２００，０００であることが好ましい。
また、前駆体樹脂は、示差走査型熱量計（ＤＳＣ）によって測定した融点が、５０～１５０℃が好ましく、５０～１２５℃がより好ましい。
さらに、前駆体樹脂は、アルカリ滴定法によって測定した酸価が５～５０ｍｇＫＯＨ／ｇであることが好ましい。酸価が上記範囲にあると、最終的に得られる変性ポリオレフィン樹脂に対して、水酸基量が適切となる。
The precursor resin obtained in step (A) has a weight average molecular weight of 10 as measured by gel permeation chromatography (GPC) using a polystyrene standard so that the weight average molecular weight of the modified polyolefin resin falls within the above-mentioned preferred range. ,000 to 200,000.
Further, the precursor resin preferably has a melting point of 50 to 150°C, more preferably 50 to 125°C, as measured by a differential scanning calorimeter (DSC).
Further, it is preferable that the precursor resin has an acid value of 5 to 50 mgKOH/g as measured by an alkaline titration method. When the acid value is within the above range, the amount of hydroxyl groups will be appropriate for the modified polyolefin resin finally obtained.
［２－２．工程（Ｂ）］
工程（Ｂ）では、まず、有機溶剤の沸点以下の温度、通常、５０～１１０℃（好ましくは５０～１１０℃）で、工程（Ａ）で得られた前駆体樹脂を所定時間加熱攪拌して有機溶剤に溶解する。有機溶剤としては、例えば、トルエン、キシレン等の芳香族溶剤；酢酸エチル、酢酸ブチル等のエステル溶剤；メチルエチルケトン、メチルブチルケトン、エチルシクロヘキサン等のケトン溶剤；シクロヘキサン、メチルシクロヘキサン、ノナン、デカン等の脂肪族又は脂環式炭化水素溶剤が挙げられる。これら有機溶剤は１種単独で用いてもよく、２種以上の混合溶剤でもよい。環境問題の観点から、有機溶剤として、芳香族溶剤以外の溶剤を使用することが好ましく、脂環式炭化水素溶剤とエステル溶剤又はケトン溶剤との混合溶剤を使用することがより好ましい。次に、成分（ＩＩＩ）を添加する。これにより、変性ポリオレフィン樹脂が得られる。すなわち、グラフト重合によりポリオレフィン樹脂（Ｉ）に導入された成分（ＩＩ）に由来するカルボニル基と、成分（ＩＩＩ）に由来するアミノ基とによりアミド結合を形成すると考えられる。このように、変性ポリオレフィン樹脂は、グラフト重合によりポリオレフィン樹脂（Ｉ）に導入された成分（ＩＩ）を介して、成分（ＩＩＩ）に由来する水酸基が導入されると考えられる。
[2-2. Process (B)]
In step (B), first, the precursor resin obtained in step (A) is heated and stirred at a temperature below the boiling point of the organic solvent, usually 50 to 110 °C (preferably 50 to 110 °C) for a predetermined time. Soluble in organic solvents. Examples of organic solvents include aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl butyl ketone, and ethyl cyclohexane; and fats such as cyclohexane, methyl cyclohexane, nonane, and decane. or alicyclic hydrocarbon solvents. These organic solvents may be used alone or in a mixture of two or more. From the viewpoint of environmental issues, it is preferable to use a solvent other than an aromatic solvent as the organic solvent, and it is more preferable to use a mixed solvent of an alicyclic hydrocarbon solvent and an ester solvent or a ketone solvent. Next, component (III) is added. Thereby, a modified polyolefin resin is obtained. That is, it is considered that an amide bond is formed by a carbonyl group derived from component (II) introduced into polyolefin resin (I) by graft polymerization and an amino group derived from component (III). Thus, it is thought that the modified polyolefin resin has a hydroxyl group derived from the component (III) introduced through the component (II) introduced into the polyolefin resin (I) by graft polymerization.
［３．被膜形成用組成物］
変性ポリオレフィン樹脂を含む被膜形成用組成物は、本発明の変性ポリオレフィン樹脂と、必要に応じて他の成分として、溶液、硬化剤、及び接着成分からなる群より選択される少なくとも１種の成分をさらに含むものが好ましい。被膜形成用組成物は、具体的には、プライマー用組成物、塗料用組成物、インキ組成物、接着剤用組成物として好適に用いられる。
[3. Film-forming composition]
A film-forming composition containing a modified polyolefin resin contains the modified polyolefin resin of the present invention and, if necessary, at least one component selected from the group consisting of a solution, a curing agent, and an adhesive component as other components. Preferably, it further includes. Specifically, the film-forming composition is suitably used as a primer composition, a paint composition, an ink composition, or an adhesive composition.
（溶液）
被膜形成用組成物の一実施態様は、上記の変性ポリオレフィン樹脂と溶液を含む樹脂組成物である。溶液としては、有機溶剤が挙げられる。有機溶剤としては、例えば、トルエン、キシレン等の芳香族溶剤；酢酸エチル、酢酸ブチル等のエステル溶剤；メチルエチルケトン、メチルブチルケトン、エチルシクロヘキサン等のケトン溶剤；シクロヘキサン、メチルシクロヘキサン、ノナン、デカン等の脂肪族又は脂環式炭化水素溶剤が挙げられる。これら有機溶剤は、１種単独で用いてもよく、２種以上の混合溶剤として樹脂組成物に含まれていてよい。環境問題の観点から、有機溶剤として、芳香族溶剤以外の溶剤を使用することが好ましく、脂環式炭化水素溶剤とエステル溶剤又はケトン溶剤との混合溶剤を使用することがより好ましい。
(solution)
One embodiment of the film-forming composition is a resin composition containing the above-mentioned modified polyolefin resin and a solution. Examples of the solution include organic solvents. Examples of organic solvents include aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl butyl ketone, and ethyl cyclohexane; and fats such as cyclohexane, methyl cyclohexane, nonane, and decane. or alicyclic hydrocarbon solvents. These organic solvents may be used alone, or may be included in the resin composition as a mixed solvent of two or more. From the viewpoint of environmental issues, it is preferable to use a solvent other than an aromatic solvent as the organic solvent, and it is more preferable to use a mixed solvent of an alicyclic hydrocarbon solvent and an ester solvent or a ketone solvent.
（硬化剤）
被膜形成用組成物の他の実施態様は、上記の変性ポリオレフィン樹脂と硬化剤を含む硬化用組成物である。硬化剤としては、多官能イソシアネート化合物、エポキシ化合物、ポリアミン化合物、或いはそれらの官能基が保護基でブロックされた架橋剤が例示される。本発明の変性ポリオレフィン樹脂を含む被膜形成用組成物では、水酸基との反応性に富むイソシアネート基を含有する化合物を使用することが好ましく、多官能イソシアネート化合物がより好ましい。硬化剤は、１種単独であってもよいし、複数種の組み合わせであってもよい。
(hardening agent)
Another embodiment of the film-forming composition is a curing composition containing the above-mentioned modified polyolefin resin and a curing agent. Examples of the curing agent include polyfunctional isocyanate compounds, epoxy compounds, polyamine compounds, and crosslinking agents whose functional groups are blocked with protective groups. In the film-forming composition containing the modified polyolefin resin of the present invention, it is preferable to use a compound containing an isocyanate group that is highly reactive with hydroxyl groups, and polyfunctional isocyanate compounds are more preferable. The curing agent may be used alone or in combination.
硬化剤の配合量は、本発明の変性ポリオレフィン樹脂中の成分（ＩＩＩ）の含有量により適宜選択できる。また、硬化剤を配合する場合は、目的に応じて有機スズ化合物、第三級アミン化合物等の触媒を併用することができる。 The blending amount of the curing agent can be appropriately selected depending on the content of component (III) in the modified polyolefin resin of the present invention. Further, when a curing agent is added, a catalyst such as an organic tin compound or a tertiary amine compound can be used in combination depending on the purpose.
（接着成分）
被膜形成用組成物のさらに他の実施態様は、上記の変性ポリオレフィン樹脂と接着成分を含む接着剤組成物である。接着成分としては、所望の効果を阻害しない範囲でポリエステル系接着剤、ポリウレタン系接着剤、アクリル系接着剤等の公知の接着成分を用いることができる。
(adhesive component)
Yet another embodiment of the film-forming composition is an adhesive composition containing the above-mentioned modified polyolefin resin and an adhesive component. As the adhesive component, known adhesive components such as polyester adhesives, polyurethane adhesives, acrylic adhesives, etc. can be used within a range that does not impede the desired effect.
被膜形成用組成物は、例えば、分散媒中に変性ポリオレフィン樹脂が分散した分散体組成物であってもよい。分散媒は、非水系であってもよく、水系（水分散体組成物）であってもよい。非水系溶媒としては、キシレン、トルエン、ベンゼン等の有機溶媒が挙げられる。また、水分散体組成物を調製する場合、その固形分は１５～５０質量％程度である。 The film-forming composition may be, for example, a dispersion composition in which a modified polyolefin resin is dispersed in a dispersion medium. The dispersion medium may be non-aqueous or aqueous (aqueous dispersion composition). Examples of non-aqueous solvents include organic solvents such as xylene, toluene, and benzene. Further, when preparing an aqueous dispersion composition, the solid content thereof is about 15 to 50% by mass.
本発明の変性ポリオレフィン樹脂は、耐熱性、溶液安定性に優れるので、金属及び／又は樹脂用の接着剤組成物、プライマー用組成物として用いることが好ましい。例えば、アルミラミネートフィルム等のラミネートフィルムにおける接着剤として有用である。 Since the modified polyolefin resin of the present invention has excellent heat resistance and solution stability, it is preferably used as an adhesive composition for metals and/or resins, and a composition for primers. For example, it is useful as an adhesive in laminate films such as aluminum laminate films.
本発明の変性ポリオレフィン樹脂は、積層体を構成する層の１つの材料であってもよい。積層体は、変性ポリオレフィン樹脂を含む層、金属層及び樹脂層を有する。積層体における層の配置は特に限定されないが、金属層及び樹脂層が変性ポリオレフィン樹脂を含む層を挟んで位置する態様、金属層を挟んで第１の樹脂層と第２の樹脂層が存在し、金属層と各樹脂層の間に変性ポリオレフィン樹脂を含む層が挟持されている態様が例示される。積層体は、リチウムイオン二次電池、コンデンサー、電気二重層キャパシター等の外装材として用いられるものであってもよく、用いられることが好ましい。 The modified polyolefin resin of the present invention may be a material for one of the layers constituting the laminate. The laminate has a layer containing a modified polyolefin resin, a metal layer, and a resin layer. The arrangement of the layers in the laminate is not particularly limited, but there are embodiments in which the metal layer and the resin layer are located with a layer containing a modified polyolefin resin in between, and in which the first resin layer and the second resin layer are located with the metal layer in between. An example is an embodiment in which a layer containing a modified polyolefin resin is sandwiched between a metal layer and each resin layer. The laminate may be used as an exterior material for lithium ion secondary batteries, capacitors, electric double layer capacitors, etc., and is preferably used.
以下、本発明を実施例により詳細に説明する。以下の実施例は、本発明を好適に説明するためのものであって、本発明を限定するものではない。なお、変性ポリオレフィン樹脂の物性値並びに変性ポリオレフィン樹脂の評価は、下記に記載した方法で行った。また、「部」は別途記載がない限り質量部を示す。 Hereinafter, the present invention will be explained in detail with reference to Examples. The following examples are provided to suitably illustrate the present invention, but are not intended to limit the present invention. In addition, the physical property values of the modified polyolefin resin and the evaluation of the modified polyolefin resin were performed by the method described below. Moreover, "parts" indicate parts by mass unless otherwise specified.
［重量平均分子量］：ＧＰＣ（東ソー社製、標準物質：ポリスチレン樹脂）にて、下記条件により測定した。
測定機器：ＨＬＣ－８３２０ＧＰＣ（東ソー社製）
溶離液：テトラヒドロフラン
カラム：ＴＳＫｇｅｌ（東ソー社製）
検出器；示差屈折計（東ソー製）
[Weight average molecular weight]: Measured by GPC (manufactured by Tosoh Corporation, standard material: polystyrene resin) under the following conditions.
Measuring equipment: HLC-8320GPC (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Column: TSKgel (manufactured by Tosoh Corporation)
Detector: Differential refractometer (manufactured by Tosoh)
［融点］：ＪＩＳ Ｋ７１２１－１９８７に準拠し、ＤＳＣ測定装置（ティー・エイ・インスツルメント・ジャパン社製 ＤＩＳＣＯＶＥＲＹ ＤＳＣ２５００）を用いて以下の手法により測定した。約５ｍｇの試料を１５０℃で１０分間加熱融解状態を保持した。１０℃／分の速度で降温して－５０℃で安定保持した。そして、１０℃／分で１５０℃まで昇温して融解した時の融解ピーク温度を測定し、該温度をＴｍとして評価した。 [Melting point]: Measured according to JIS K7121-1987 using a DSC measuring device (DISCOVERY DSC2500 manufactured by TA Instruments Japan) according to the following method. Approximately 5 mg of the sample was heated and kept in a molten state at 150° C. for 10 minutes. The temperature was lowered at a rate of 10°C/min and stably maintained at -50°C. Then, the temperature was raised to 150°C at a rate of 10°C/min to measure the melting peak temperature, and this temperature was evaluated as Tm.
［α，β－不飽和カルボン酸又はその誘導体のグラフト量（質量％）］：アルカリ滴定法により測定した。 [Amount of grafted α,β-unsaturated carboxylic acid or its derivative (% by mass)]: Measured by alkaline titration method.
［（メタ）アクリル酸エステルのグラフト重量（重量％）］：１Ｈ－ＮＭＲにより測定した。 [Graft weight (% by weight) of (meth)acrylic acid ester]: Measured by 1 H-NMR.
［赤外分光スペクトル］：変性ポリオレフィン樹脂水分散体組成物を４０℃、２４時間乾燥して乾燥物を得た。得られた乾燥物を有機溶剤に溶解して溶液を得た。ＫＢｒ板に溶液を塗布、乾燥して薄膜を形成し、ＦＴ－ＩＲ（日本分光社製 ＦＴ／ＩＲ－４１００）にて、４００～４０００ｃｍ－１の赤外吸光スペクトルを観測した。なお、解析は、付属ソフトウェア（Ｓｐｅｃｔｒｏ Ｍａｎａｇｅｒ、日本分光社）によって行った。
波数１６１０～１６８０ｃｍ－１に現れるピークを、アミド結合由来のピークに帰属し、波数１４２０～１５００ｃｍ－１に現れるピークを、メチレン結合由来のピークに帰属した。そして、アミド結合由来のピーク高さをＡとし、メチレン結合由来のピーク高さをＢとし、ピーク高さ比（Ａ／Ｂ×１００）を算出した。
[Infrared spectroscopy spectrum]: The modified polyolefin resin aqueous dispersion composition was dried at 40° C. for 24 hours to obtain a dried product. The obtained dried product was dissolved in an organic solvent to obtain a solution. The solution was applied to a KBr plate and dried to form a thin film, and an infrared absorption spectrum of 400 to 4000 cm -1 was observed using FT-IR (FT/IR-4100 manufactured by JASCO Corporation). The analysis was performed using the attached software (Spectro Manager, JASCO Corporation).
A peak appearing at a wave number of 1610 to 1680 cm -1 was assigned to a peak derived from an amide bond, and a peak appearing at a wave number of 1420 to 1500 cm -1 was assigned to a peak derived from a methylene bond. Then, the peak height derived from the amide bond was defined as A, the peak height derived from the methylene bond was defined as B, and the peak height ratio (A/B x 100) was calculated.
［溶液安定性試験］：透明なガラスビーカー内で、実施例及び比較例で得られる変性ポリオレフィン樹脂を、メチルシクロヘキサン／メチルエチルケトン溶液（混合比８０／２０）に溶解して、１５質量％の濃度の変性ポリオレフィン樹脂の塗料組成物（組成物溶液）を調製した。溶剤が揮発しないようにしっかりと封をし、室温（２３℃）にて１週間静置した後に溶解安定性を目視し、下記評価基準で評価した。
Ａ：組成物溶液は透明なままであり、流動性が保たれている。
Ｂ：組成物溶液の流動性が若干低下するが、実用上問題はない。
Ｃ：組成物溶液は濁っており、流動性が低下している。
[Solution stability test]: In a transparent glass beaker, the modified polyolefin resins obtained in Examples and Comparative Examples were dissolved in methylcyclohexane/methyl ethyl ketone solution (mixing ratio 80/20) to give a concentration of 15% by mass. A coating composition (composition solution) of a modified polyolefin resin was prepared. The solution was tightly sealed to prevent the solvent from volatilizing and allowed to stand at room temperature (23° C.) for one week, and then the dissolution stability was visually observed and evaluated using the following evaluation criteria.
A: The composition solution remains clear and fluid.
B: The fluidity of the composition solution is slightly reduced, but there is no practical problem.
C: The composition solution is cloudy and has decreased fluidity.
［耐熱性（熱間付着強度）試験］：アルミ箔上に樹脂乾燥膜厚が２μｍとなるように＃１６のマイヤーバーで接着剤組成物を塗布し、８０℃で６０秒間乾燥した。塗布済みのアルミ箔を無延伸ポリプロピレン（ＣＰＰ）シートと貼合した。これを、２００℃×１秒間、１００ｋＰａの条件で熱圧着を行った後、１５ｍｍ幅に切り出した試験片を作製した。試験片を４０℃で７２時間養生することにより、接着剤組成物の架橋反応を促進した。２３℃、相対湿度５０％の恒温恒湿条件下で２４時間保管した後、島津製作所製オートグラフシステム（ＡＧ－５００ＮＸ型）を用いて、２３℃、８０℃又は１２０℃の各温度下で、１８０度方向剥離、剥離速度１００ｍｍ／ｍｉｎの条件でラミネート接着強度を測定した。３回試験を行って、その平均値を結果とした。
なお、接着剤組成物の詳細は、後述する。
[Heat resistance (hot adhesion strength) test]: The adhesive composition was applied onto aluminum foil using a #16 Meyer bar so that the resin dry film thickness was 2 μm, and dried at 80° C. for 60 seconds. The coated aluminum foil was bonded to a non-stretched polypropylene (CPP) sheet. This was subjected to thermocompression bonding at 200° C. for 1 second at 100 kPa, and then a test piece was cut out to a width of 15 mm. The crosslinking reaction of the adhesive composition was promoted by curing the test piece at 40° C. for 72 hours. After being stored for 24 hours under constant temperature and humidity conditions of 23°C and 50% relative humidity, the samples were stored at 23°C, 80°C, or 120°C using a Shimadzu Autograph System (Model AG-500NX). The laminate adhesive strength was measured under the conditions of 180 degree peeling and a peeling rate of 100 mm/min. The test was conducted three times and the average value was taken as the result.
Note that details of the adhesive composition will be described later.
［ゲル含量（％）］：上記と同じ組成の接着剤組成物をテフロン（登録商標）製シャーレに適量流し入れ、８０℃で１８０秒間乾燥してフィルムを作製した。４０℃で７２時間養生を行ったフィルム０．２グラムを正確に秤量した後、１００ｃｃのトルエンに入れ、５０℃雰囲気下で２４時間放置溶解した。濾過した後、濾物を乾燥して、トルエン不溶分（ゲル）を測定し、下記式（２）に基づいて含量を算出した。
（トルエン不溶分重量／フィルム重量）×１００ （２）
[Gel content (%)]: An appropriate amount of the adhesive composition having the same composition as above was poured into a Teflon (registered trademark) petri dish and dried at 80° C. for 180 seconds to prepare a film. After accurately weighing 0.2 g of the film that had been cured at 40°C for 72 hours, it was placed in 100 cc of toluene and left to dissolve in an atmosphere of 50°C for 24 hours. After filtration, the filtrate was dried, the toluene insoluble content (gel) was measured, and the content was calculated based on the following formula (2).
(Toluene insoluble content weight/film weight) x 100 (2)
［合成例１：前駆体樹脂（１）の製造］
攪拌機、冷却管、及び滴下漏斗を取り付けた四つ口フラスコ中で、プロピレン－ブテンランダム共重合体〔Ｐ－Ｂ〕（プロピレン成分８０モル％、ブテン成分２０モル％、Ｔｍ＝８５℃）１００部をトルエン４００ｇ中に加熱溶解した。系内の温度を１１０℃に保持して撹拌しながら、無水マレイン酸４．０部、ラウリルメタクリレート４．０部、ジ－ｔ－ブチルパーオキサイド１．０部をそれぞれ３時間かけて滴下し、さらに１時間反応を行った。
反応終了後、室温まで冷却し、重量平均分子量が６６，０００の前駆体樹脂（１）を得た。反応物を大過剰のアセトン中に投入することで精製して、無水マレイン酸及びラウリルメタクリレートのグラフト重量を測定したところ、各々３．３重量％、３．０重量％であった。得られた前駆体樹脂（１）１５ｇに、メチルシクロヘキサン６８ｇ及びメチルエチルケトン１７ｇを加えて加熱溶解し、前駆体樹脂（１）を含む溶液（前駆体溶液（１））を得た。物性値等を含めて表１に示す。
[Synthesis Example 1: Production of precursor resin (1)]
In a four-necked flask equipped with a stirrer, a cooling tube, and a dropping funnel, 100 parts of propylene-butene random copolymer [PB] (propylene component 80 mol%, butene component 20 mol%, Tm = 85 ° C.) was heated and dissolved in 400 g of toluene. While maintaining the temperature in the system at 110°C and stirring, 4.0 parts of maleic anhydride, 4.0 parts of lauryl methacrylate, and 1.0 parts of di-t-butyl peroxide were each added dropwise over 3 hours. The reaction was further carried out for 1 hour.
After the reaction was completed, the mixture was cooled to room temperature to obtain a precursor resin (1) having a weight average molecular weight of 66,000. The reaction product was purified by pouring it into a large excess of acetone, and the graft weights of maleic anhydride and lauryl methacrylate were measured to be 3.3% by weight and 3.0% by weight, respectively. 68 g of methylcyclohexane and 17 g of methyl ethyl ketone were added to 15 g of the obtained precursor resin (1) and dissolved by heating to obtain a solution containing the precursor resin (1) (precursor solution (1)). Table 1 shows the physical property values, etc.
［合成例２：前駆体樹脂（２）の製造］
合成例１のプロピレン－ブテンランダム共重合体〔Ｐ－Ｂ〕をプロピレン成分９５モル％、ブテン成分５モル％、Ｔｍ＝１２０℃のプロピレン－ブテンランダム共重合体〔Ｐ－Ｂ〕に変更した以外は、合成例１と同様に合成し、重量平均分子量が１５０，０００の前駆体樹脂（２）を得た。反応物を大過剰のアセトン中に投入することで精製して、無水マレイン酸及びラウリルメタクリレートのグラフト重量を測定したところ、各々３．５重量％、３．１重量％であった。得られた前駆体樹脂（２）１５ｇに、メチルシクロヘキサン６８ｇ及びメチルエチルケトン１７ｇを加えて加熱溶解し、前駆体樹脂（２）を含む溶液（前駆体溶液（２））を得た。物性値等を含めて表１に示す。
[Synthesis Example 2: Production of precursor resin (2)]
Except that the propylene-butene random copolymer [PB] of Synthesis Example 1 was changed to a propylene-butene random copolymer [PB] with a propylene component of 95 mol%, a butene component of 5 mol%, and Tm = 120 ° C. was synthesized in the same manner as in Synthesis Example 1 to obtain a precursor resin (2) having a weight average molecular weight of 150,000. The reaction product was purified by pouring it into a large excess of acetone, and the graft weights of maleic anhydride and lauryl methacrylate were measured to be 3.5% by weight and 3.1% by weight, respectively. 68 g of methylcyclohexane and 17 g of methyl ethyl ketone were added to 15 g of the obtained precursor resin (2) and dissolved by heating to obtain a solution containing the precursor resin (2) (precursor solution (2)). Table 1 shows the physical property values, etc.
［合成例３：前駆体樹脂（３）の製造］
合成例１で無水マレイン酸を５．０部とした以外は合成例１と同様に合成し、重量平均分子量が１６０，０００の前駆体樹脂（３）を得た。反応物を大過剰のアセトン中に投入することで精製して、無水マレイン酸及びラウリルメタクリレートのグラフト重量を測定したところ、各々４．２重量％、３．１重量％であった。得られた前駆体樹脂（３）１５ｇに、メチルシクロヘキサン６８ｇ及びメチルエチルケトン１７ｇを加えて加熱溶解し、前駆体樹脂（３）を含む溶液（前駆体溶液（３））を得た。物性値等を含めて表１に示す。
[Synthesis Example 3: Production of precursor resin (3)]
Synthesis was carried out in the same manner as in Synthesis Example 1 except that maleic anhydride was changed to 5.0 parts to obtain a precursor resin (3) having a weight average molecular weight of 160,000. The reaction product was purified by pouring it into a large excess of acetone, and the graft weights of maleic anhydride and lauryl methacrylate were measured to be 4.2% by weight and 3.1% by weight, respectively. 68 g of methylcyclohexane and 17 g of methyl ethyl ketone were added to 15 g of the obtained precursor resin (3) and dissolved by heating to obtain a solution containing the precursor resin (3) (precursor solution (3)). Table 1 shows the physical property values, etc.
［実施例１：前駆体樹脂（１）のアミド化］
合成例１で得られた前駆体樹脂（１）（固形）１００部を、攪拌機、冷却管、及び滴下漏斗を取り付けた四つ口フラスコ中で、メチルシクロヘキサン２８０ｇ中に加熱溶解した。系内の温度を９０℃に保持して撹拌しながら、２－アミノ－２－メチル－１－プロパノール〔ＡＭＰ〕３．３部を添加し、１２０分攪拌した。その後、室温まで冷却し、メチルエチルケトン７０ｇを添加して固形分１５．０％となるよう調整した。これより、変性ポリオレフィン樹脂（１）を含む溶液を得た。物性値等を含めて表２に示す。
[Example 1: Amidation of precursor resin (1)]
100 parts of the precursor resin (1) (solid) obtained in Synthesis Example 1 was heated and dissolved in 280 g of methylcyclohexane in a four-necked flask equipped with a stirrer, a cooling tube, and a dropping funnel. While stirring and maintaining the temperature in the system at 90° C., 3.3 parts of 2-amino-2-methyl-1-propanol [AMP] was added, and the mixture was stirred for 120 minutes. Thereafter, the mixture was cooled to room temperature, and 70 g of methyl ethyl ketone was added to adjust the solid content to 15.0%. From this, a solution containing the modified polyolefin resin (1) was obtained. Table 2 shows the physical property values, etc.
［実施例２：前駆体樹脂（１）のアミド化］
合成例１で得られた前駆体樹脂（１）（固形）１００部を、攪拌機、冷却管、及び滴下漏斗を取り付けた四つ口フラスコ中で、メチルシクロヘキサン２７６ｇ中に加熱溶解した。系内の温度を９０℃に保持して撹拌しながら、２－アミノ－２－メチル－１－プロパノール〔ＡＭＰ〕１．７部を添加し、１２０分攪拌した。その後、室温まで冷却し、メチルエチルケトン６９ｇを添加して固形分１５．０％となるよう調整した。これより、変性ポリオレフィン樹脂（２）を含む溶液を得た。物性値等を含めて表２に示す。
[Example 2: Amidation of precursor resin (1)]
100 parts of the precursor resin (1) (solid) obtained in Synthesis Example 1 was heated and dissolved in 276 g of methylcyclohexane in a four-necked flask equipped with a stirrer, a cooling tube, and a dropping funnel. While stirring and maintaining the temperature in the system at 90° C., 1.7 parts of 2-amino-2-methyl-1-propanol [AMP] was added, and the mixture was stirred for 120 minutes. Thereafter, the mixture was cooled to room temperature, and 69 g of methyl ethyl ketone was added to adjust the solid content to 15.0%. From this, a solution containing the modified polyolefin resin (2) was obtained. Table 2 shows the physical property values, etc.
［実施例３：前駆体樹脂（３）のアミド化］
合成例３で得られた前駆体樹脂（３）（固形）１００部を、攪拌機、冷却管、及び滴下漏斗を取り付けた四つ口フラスコ中で、メチルシクロヘキサン２７３ｇに加熱溶解した。系内の温度を９０℃に保持して撹拌しながら、２－アミノ－２－メチル－１－プロパノール〔ＡＭＰ〕０．９部を添加し、１２０分攪拌した。その後、室温まで冷却し、メチルエチルケトン６８ｇを添加して固形分１５．０％となるよう調整した。これより、変性ポリオレフィン樹脂（３）を含む溶液を得た。物性値等を含めて表２に示す。
[Example 3: Amidation of precursor resin (3)]
100 parts of the precursor resin (3) (solid) obtained in Synthesis Example 3 was heated and dissolved in 273 g of methylcyclohexane in a four-necked flask equipped with a stirrer, a cooling tube, and a dropping funnel. While stirring and maintaining the temperature in the system at 90° C., 0.9 part of 2-amino-2-methyl-1-propanol [AMP] was added, and the mixture was stirred for 120 minutes. Thereafter, the mixture was cooled to room temperature, and 68 g of methyl ethyl ketone was added to adjust the solid content to 15.0%. From this, a solution containing the modified polyolefin resin (3) was obtained. Table 2 shows the physical property values, etc.
［比較例１：前駆体樹脂（１）のアミド化］
合成例１で得られた前駆体樹脂（１）（固形）１００部を、攪拌機、冷却管、及び滴下漏斗を取り付けた四つ口フラスコ中で、メチルシクロヘキサン９６５ｇ中に加熱溶解した。系内の温度を９０℃に保持して撹拌しながら、２－アミノ－２－メチル－１－プロパノール〔ＡＭＰ〕６．７部を添加し、１２０分攪拌した。その後、室温まで冷却し、メチルエチルケトン２４１ｇを添加して固形分１５．０％となるよう調整した。これより、変性ポリオレフィン樹脂（３）を含む溶液を得た。
[Comparative Example 1: Amidation of precursor resin (1)]
100 parts of the precursor resin (1) (solid) obtained in Synthesis Example 1 was heated and dissolved in 965 g of methylcyclohexane in a four-necked flask equipped with a stirrer, a cooling tube, and a dropping funnel. While stirring and maintaining the temperature in the system at 90° C., 6.7 parts of 2-amino-2-methyl-1-propanol [AMP] was added, and the mixture was stirred for 120 minutes. Thereafter, the mixture was cooled to room temperature, and 241 g of methyl ethyl ketone was added to adjust the solid content to 15.0%. From this, a solution containing the modified polyolefin resin (3) was obtained.
［接着剤組成物の製造及び評価］
（実施例４）
実施例１で得た変性ポリオレフィン樹脂（１）を含む溶液２０ｇに、反応触媒としてジブチルスズジラウレート（以下、〔ＤＢＴＬ〕という）３．０ｍｇを添加して混合し、これに多官能イソシアネート化合物（三井化学社製、商品名「タケネート１７７Ｎ」）を、１．１ｇ（ＮＣＯ／ＯＨ＝２．１）配合して混合し、接着剤組成物（１）を得た。この接着剤組成物（１）を用いて耐熱性試験、ゲル含量測定及び溶液安定性試験を実施した。結果を表３に示す。
[Manufacture and evaluation of adhesive composition]
(Example 4)
To 20 g of the solution containing the modified polyolefin resin (1) obtained in Example 1, 3.0 mg of dibutyltin dilaurate (hereinafter referred to as [DBTL]) was added as a reaction catalyst and mixed, and to this was added a polyfunctional isocyanate compound (Mitsui Chemicals). Adhesive composition (1) was obtained by blending and mixing 1.1 g (NCO/OH=2.1) of ``Takenate 177N'' (manufactured by Co., Ltd., trade name: "Takenate 177N"). A heat resistance test, gel content measurement, and solution stability test were conducted using this adhesive composition (1). The results are shown in Table 3.
（実施例５）
実施例２で得た変性ポリオレフィン樹脂（２）を含む溶液を用いた以外は、実施例４と同様にして接着剤組成物（２）を得た。この接着剤組成物（２）を用いて耐熱性試験、ゲル含量測定及び溶液安定性試験を実施した。結果を表３に示す。
(Example 5)
An adhesive composition (2) was obtained in the same manner as in Example 4, except that the solution containing the modified polyolefin resin (2) obtained in Example 2 was used. A heat resistance test, gel content measurement, and solution stability test were conducted using this adhesive composition (2). The results are shown in Table 3.
（実施例６）
実施例３で得た変性ポリオレフィン樹脂（３）を含む溶液を用いた以外は、実施例４と同様にして接着剤組成物（３）を得た。この接着剤組成物（３）を用いて耐熱性試験、ゲル含量測定及び溶液安定性試験を実施した。結果を表３に示す。
(Example 6)
An adhesive composition (3) was obtained in the same manner as in Example 4, except that the solution containing the modified polyolefin resin (3) obtained in Example 3 was used. A heat resistance test, gel content measurement, and solution stability test were conducted using this adhesive composition (3). The results are shown in Table 3.
（比較例２）
合成例１で得た前駆体溶液（１）２０ｇに、反応触媒としてジブチルスズジラウレート（以下〔ＤＢＴＬ〕という）３．０ｍｇを添加して混合し、接着剤組成物（４）を得た。この接着剤組成物（４）を用いて耐熱性試験、ゲル含量測定及び溶液安定性試験を実施した。結果を表３に示す。
(Comparative example 2)
3.0 mg of dibutyltin dilaurate (hereinafter referred to as [DBTL]) as a reaction catalyst was added to 20 g of the precursor solution (1) obtained in Synthesis Example 1 and mixed to obtain an adhesive composition (4). A heat resistance test, gel content measurement, and solution stability test were conducted using this adhesive composition (4). The results are shown in Table 3.
（比較例３）
合成例１で得た前駆体溶液（１）を用いた以外は、実施例４と同様にして接着剤組成物（５）を得た。この接着剤組成物（５）を用いて耐熱性試験、ゲル含量測定及び溶液安定性試験を実施した。結果を表３に示す。
(Comparative example 3)
An adhesive composition (5) was obtained in the same manner as in Example 4, except that the precursor solution (1) obtained in Synthesis Example 1 was used. A heat resistance test, gel content measurement, and solution stability test were conducted using this adhesive composition (5). The results are shown in Table 3.
（比較例４）
比較例１で得た変性ポリオレフィン樹脂（４）を含む溶液を用いた以外は、実施例４と同様にして接着剤組成物（６）を得た。この接着剤組成物（６）を用いて耐熱性試験、ゲル含量測定及び溶液安定性試験を実施した。結果を表３に示す。
(Comparative example 4)
An adhesive composition (6) was obtained in the same manner as in Example 4, except that the solution containing the modified polyolefin resin (4) obtained in Comparative Example 1 was used. A heat resistance test, gel content measurement, and solution stability test were conducted using this adhesive composition (6). The results are shown in Table 3.
（比較例５）
合成例２で得た前駆体溶液（２）を用いた以外は、実施例４と同様にして接着剤組成物（７）を得た。この接着剤組成物（７）を用いて耐熱性試験、ゲル含量測定及び溶液安定性試験を実施した。結果を表３に示す。
(Comparative example 5)
An adhesive composition (7) was obtained in the same manner as in Example 4, except that the precursor solution (2) obtained in Synthesis Example 2 was used. A heat resistance test, gel content measurement, and solution stability test were conducted using this adhesive composition (7). The results are shown in Table 3.
表３から明らかな通り、本発明の変性ポリオレフィン樹脂は、ゲル含量が高く、１２０℃の高温での耐熱性（熱間強度）及び溶液安定性が優れている（実施例４～６）。
これに対し、アミド化を行っていない前駆体溶液（１）は、実施例４～６と比較してゲル含量が低く、１２０℃の高温で耐熱性が急激に劣り（比較例３）、ピーク高さ比が本願の範囲から外れる変性ポリオレフィン樹脂（４）は、実施例４～６と比較してゲル含量が低く、耐熱性及び溶液安定性も劣っていた（比較例４）。また、高融点樹脂を原料としアミド化を行っていない前駆体溶液（２）は、耐熱性は優れるが、溶液安定性が劣っていた（比較例５）。なお、アミド化を行っていない前駆体溶液に多官能イソシアネート化合物を添加せずに評価を行った場合、ゲル含量は０％であり１２０℃の高温での熱間強度も発現しなかった（比較例２）。
As is clear from Table 3, the modified polyolefin resin of the present invention has a high gel content and is excellent in heat resistance (hot strength) and solution stability at a high temperature of 120° C. (Examples 4 to 6).
On the other hand, the precursor solution (1) that was not amidated had a lower gel content compared to Examples 4 to 6, and its heat resistance was sharply inferior at a high temperature of 120°C (Comparative Example 3), and the peak Modified polyolefin resin (4) with a height ratio outside the range of the present application had a lower gel content and poorer heat resistance and solution stability than Examples 4 to 6 (Comparative Example 4). Further, the precursor solution (2), which was made from a high melting point resin and was not subjected to amidation, had excellent heat resistance but poor solution stability (Comparative Example 5). In addition, when evaluation was performed without adding a polyfunctional isocyanate compound to a precursor solution that was not amidated, the gel content was 0% and no hot strength was developed at a high temperature of 120°C (comparison). Example 2).
Claims (9)
一級又は二級のアミノ基を有するアミノアルコール（ＩＩＩ）と、
下記一般式（１）で表される（メタ）アクリル酸エステル（ＩＶ）とによる、ポリオレフィン樹脂（Ｉ）のグラフト変性物であり、
赤外分光スペクトル測定において観察される、アミド結合由来のピーク高さをＡとし、メチレン結合由来のピーク高さをＢとしたときに、
ピーク高さ比（Ａ／Ｂ×１００）が２．５７３～６．０％の範囲である、
変性ポリオレフィン樹脂。
ＣＨ ２ ＝Ｃ（Ｒ １ ）ＣＯＯＲ ２ ・・・（１）
（前記一般式（１）中、Ｒ １ は、水素原子又はメチル基を示し、Ｒ ２ は、Ｃ ｎ Ｈ ２ｎ＋１ で表される炭化水素基を示す。但し、ｎは、８～１８の整数である。） α,β-unsaturated carboxylic acid or its derivative (II),
An amino alcohol (III) having a primary or secondary amino group ,
A graft modified product of a polyolefin resin ( I) with a (meth)acrylic acid ester (IV) represented by the following general formula (1) ,
When the peak height derived from the amide bond observed in infrared spectrometry is A, and the peak height derived from the methylene bond is B,
The peak height ratio (A/B x 100) is in the range of 2.573 to 6.0%,
Modified polyolefin resin.
CH2 = C(R1 ) COOR2 ... (1)
(In the general formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrocarbon group represented by C n H 2n+1 . However, n is an integer of 8 to 18. be.)
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| JP2003327761A (en) | 2002-03-05 | 2003-11-19 | Nippon Paper Industries Co Ltd | Aqueous dispersion, its manufacturing method and use |
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