JP7428022B2 - adhesive resin composition - Google Patents
adhesive resin composition Download PDFInfo
- Publication number
- JP7428022B2 JP7428022B2 JP2020041073A JP2020041073A JP7428022B2 JP 7428022 B2 JP7428022 B2 JP 7428022B2 JP 2020041073 A JP2020041073 A JP 2020041073A JP 2020041073 A JP2020041073 A JP 2020041073A JP 7428022 B2 JP7428022 B2 JP 7428022B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- resin composition
- adhesive resin
- propylene
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 85
- 239000004840 adhesive resin Substances 0.000 title claims description 75
- 229920006223 adhesive resin Polymers 0.000 title claims description 75
- -1 Polypropylene Polymers 0.000 claims description 56
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 51
- 229920005989 resin Polymers 0.000 claims description 50
- 239000011347 resin Substances 0.000 claims description 50
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 44
- 150000002484 inorganic compounds Chemical class 0.000 claims description 39
- 229910010272 inorganic material Inorganic materials 0.000 claims description 39
- 239000004743 Polypropylene Substances 0.000 claims description 36
- 229920001155 polypropylene Polymers 0.000 claims description 36
- 239000004711 α-olefin Substances 0.000 claims description 31
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 24
- 229920005672 polyolefin resin Polymers 0.000 claims description 22
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 15
- 239000010457 zeolite Substances 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- 239000003607 modifier Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 229910000859 α-Fe Inorganic materials 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000010410 layer Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 31
- 235000019645 odor Nutrition 0.000 description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 20
- 239000005977 Ethylene Substances 0.000 description 20
- 238000000465 moulding Methods 0.000 description 18
- 238000004898 kneading Methods 0.000 description 17
- 230000004048 modification Effects 0.000 description 15
- 238000012986 modification Methods 0.000 description 15
- 229920005604 random copolymer Polymers 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000012790 adhesive layer Substances 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 7
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 229920001384 propylene homopolymer Polymers 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920005629 polypropylene homopolymer Polymers 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 238000006011 modification reaction Methods 0.000 description 3
- 239000012766 organic filler Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 229920000007 Nylon MXD6 Polymers 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-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
- NLBJAOHLJABDAU-UHFFFAOYSA-N (3-methylbenzoyl) 3-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C=C(C)C=CC=2)=C1 NLBJAOHLJABDAU-UHFFFAOYSA-N 0.000 description 1
- QQYNRBAAQFZCLF-FBXFSONDSA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-epoxyisobenzofuran-1,3-dione Chemical compound O1[C@@H]2[C@@H]3C(=O)OC(=O)[C@@H]3[C@H]1C=C2 QQYNRBAAQFZCLF-FBXFSONDSA-N 0.000 description 1
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical compound CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- TZUHRPKXUADVEM-UHFFFAOYSA-N 2,5-dimethyl-2,5-bis[(2-methylpropan-2-yl)oxy]hexane Chemical compound CC(C)(C)OC(C)(C)CCC(C)(C)OC(C)(C)C TZUHRPKXUADVEM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- AGULWIQIYWWFBJ-UHFFFAOYSA-N 3,4-dichlorofuran-2,5-dione Chemical compound ClC1=C(Cl)C(=O)OC1=O AGULWIQIYWWFBJ-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-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
- YPRMWCKXOZFJGF-UHFFFAOYSA-N 3-bromofuran-2,5-dione Chemical compound BrC1=CC(=O)OC1=O YPRMWCKXOZFJGF-UHFFFAOYSA-N 0.000 description 1
- QRCRYGXAOIFJGN-UHFFFAOYSA-N 3-ethenyloxolane-2,5-dione Chemical compound C=CC1CC(=O)OC1=O QRCRYGXAOIFJGN-UHFFFAOYSA-N 0.000 description 1
- PXKKFBJFONPUED-UHFFFAOYSA-N 3-methyl-4-pent-2-enyloxolane-2,5-dione Chemical compound CCC=CCC1C(C)C(=O)OC1=O PXKKFBJFONPUED-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- HMMBJOWWRLZEMI-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CCCC2=C1C(=O)OC2=O HMMBJOWWRLZEMI-UHFFFAOYSA-N 0.000 description 1
- GBBPFLCLIBNHQO-UHFFFAOYSA-N 5,6-dihydro-4h-cyclopenta[c]furan-1,3-dione Chemical compound C1CCC2=C1C(=O)OC2=O GBBPFLCLIBNHQO-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
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- 229910052582 BN Inorganic materials 0.000 description 1
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
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- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 description 1
- 229920009382 Polyoxymethylene Homopolymer Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
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- 239000003463 adsorbent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229940047889 isobutyramide Drugs 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- KNRCVAANTQNTPT-UHFFFAOYSA-N methyl-5-norbornene-2,3-dicarboxylic anhydride Chemical compound O=C1OC(=O)C2C1C1(C)C=CC2C1 KNRCVAANTQNTPT-UHFFFAOYSA-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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 229920005675 propylene-butene random copolymer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、接着性樹脂組成物に係り、特に、加熱成形下でも作業環境中に不快な臭気の発生が少なく、且つポリオレフィン樹脂の分散性を高める機能を有する接着性樹脂組成物と、この接着性樹脂組成物よりなるポリオレフィン系樹脂用改質剤に関する。 The present invention relates to an adhesive resin composition, and in particular, an adhesive resin composition that generates little unpleasant odor in a working environment even under heat molding and has the function of improving the dispersibility of polyolefin resin, and this adhesive resin composition. The present invention relates to a modifier for polyolefin resins comprising a polyolefin resin composition.
ポリオレフィン系樹脂は、成形性、耐薬品性等は優れるため、各種分野で幅広く利用されている。
ポリオレフィン系樹脂を極性の高い材料と混合したり、組み合わせたりして使用する際には、極性の高い化合物で変性されたポリオレフィン系樹脂を使用することが知られている。
Polyolefin resins have excellent moldability, chemical resistance, etc., and are therefore widely used in various fields.
When mixing or combining a polyolefin resin with a highly polar material, it is known to use a polyolefin resin modified with a highly polar compound.
ポリオレフィン系樹脂の変性には不飽和カルボン酸がよく用いられる。変性されたポリオレフィン系樹脂は単独でも使用できるが、その他、変性されていないポリプロピレンやポリエチレン、プロピレン・α－オレフィン共重合体、エチレン・α－オレフィン共重合体と混合して接着性樹脂組成物として使用することもできる。 Unsaturated carboxylic acids are often used to modify polyolefin resins. The modified polyolefin resin can be used alone, but it can also be mixed with unmodified polypropylene, polyethylene, propylene/α-olefin copolymer, or ethylene/α-olefin copolymer to form an adhesive resin composition. You can also use
通常、これらの樹脂組成物は各種成形機を用いてフィルム状、シート状、もしくは板状等に加工される。その際、樹脂組成物を溶融させるため、通常２００℃前後で加熱することが行われる。この時、樹脂組成物中に含まれるポリオレフィン系樹脂や変性されたポリオレフィン系樹脂から、ポリオレフィンの分解物、および変性後に残存した未反応の不飽和カルボン酸や有機過酸化物の残渣による不快な臭気が発生することがある。 Usually, these resin compositions are processed into films, sheets, plates, etc. using various molding machines. At that time, in order to melt the resin composition, heating is usually performed at around 200°C. At this time, unpleasant odors are emitted from polyolefin resins and modified polyolefin resins contained in the resin composition, as well as decomposition products of polyolefins and residues of unreacted unsaturated carboxylic acids and organic peroxides that remain after modification. may occur.
この問題を解決する方法として、例えば、特許文献１には、食品包装容器用途のポリオレフィン樹脂組成物として、吸着性無機化合物としてゼオライトやフライポンタイトーシリカ複合体、ハイドロタルサイトをポリプロプレンやポリエチレン樹脂に添加する方法が開示されている。
特許文献２には、ポリプロピレンやポリエチレンなどのプラスチック容器中の臭気／味覚発生物質を除去する方法として、無機化合物としてケイ酸アルミニウムを原料に配合する方法が開示されている。
特許文献３には、不飽和カルボン酸又はその誘導体によって変性されたポリプロピレンと未変性のポリプロピレンにゼオライトを配合して接着強度を向上させることが開示されている。
As a method to solve this problem, for example, Patent Document 1 describes a polyolefin resin composition for food packaging containers in which adsorbent inorganic compounds such as zeolite, flypontite silica composite, and hydrotalcite are combined with polypropylene or polyethylene resin. Disclosed is a method for adding
Patent Document 2 discloses a method of blending aluminum silicate as an inorganic compound into raw materials as a method for removing odor/taste generating substances in plastic containers such as polypropylene and polyethylene.
Patent Document 3 discloses that zeolite is blended into polypropylene modified with an unsaturated carboxylic acid or a derivative thereof and unmodified polypropylene to improve adhesive strength.
近年、変性ポリオレフィンは、接着剤としての用途以外にも、ポリオレフィン系樹脂中に含まれる無機化合物やフィラー等の分散性を高める改質剤としても使用されており、改質剤として使用する際には、上述されている従来の臭気の改善以外にも、流動性や分散性の向上も必要とされる。 In recent years, modified polyolefins have been used not only as adhesives but also as modifiers to improve the dispersibility of inorganic compounds and fillers contained in polyolefin resins. In addition to the conventional odor improvement described above, improvements in fluidity and dispersibility are also required.
特許文献１および特許文献２では、ポリプロピレン又はポリエチレンにおける分解物や酸化防止剤から発生する臭気の低減のために無機化合物を添加しているが、不飽和カルボン酸により変性された変性ポリオレフィンなどからの臭気を低減するには不十分であった。
特許文献３では、不飽和カルボン酸又はその誘導体によって変性されたポリプロピレンと未変性のポリプロピレンに配合されるゼオライトによって、ある程度は臭気の改善ができるが、臭気の残存があることや、分散性が低いため、ゼオライトなどが一部で凝集してしまい、成形体にした際の外観が悪化するという問題があった。
In Patent Document 1 and Patent Document 2, inorganic compounds are added to reduce odors generated from decomposition products and antioxidants in polypropylene or polyethylene, but inorganic compounds are added to reduce odors generated from decomposition products and antioxidants in polypropylene or polyethylene. This was insufficient to reduce odor.
In Patent Document 3, odor can be improved to some extent by using zeolite blended with polypropylene modified with an unsaturated carboxylic acid or its derivative and unmodified polypropylene, but the odor remains and the dispersibility is low. Therefore, there was a problem in that the zeolite etc. agglomerated in some parts and the appearance of the molded product deteriorated.
本発明は、かかる状況に鑑み、加熱成形時に作業環境に放出される臭気が少ない上に、高い流動性を有し、ポリオレフィン系樹脂中に含まれる無機化合物やフィラー等の分散性を高める機能をも有する接着性樹脂組成物と、この接着性樹脂組成物よりなるポリオレフィン系樹脂用改質剤を提供することを目的とする。 In view of these circumstances, the present invention has been developed to provide a polyolefin resin that emits less odor into the working environment during heat molding, has high fluidity, and has the ability to enhance the dispersibility of inorganic compounds and fillers contained in polyolefin resins. An object of the present invention is to provide an adhesive resin composition having the following properties, and a modifier for polyolefin resins comprising this adhesive resin composition.
本発明者は、上記の課題を解決するために鋭意検討を行った結果、特定量の無機化合物と、不飽和カルボン酸でグラフト変性されたポリプロピレン系樹脂と共に不飽和カルボン酸でグラフト変性されたプロピレン・α－オレフィン共重合体を特定量配合した組成物が、メルトフローレート（ＭＦＲ）を特定の範囲とすることができ、流動性も上がり、且つ加熱成形時にも作業環境に放出される臭気が少なく、またポリオレフィン系樹脂の改質剤としても好適に用いることができる接着性樹脂組成物であることを見出し、本発明を完成するに至った。
即ち、本発明は以下を要旨とする。
As a result of intensive studies to solve the above problems, the present inventor has discovered that a specific amount of an inorganic compound, a polypropylene resin graft-modified with an unsaturated carboxylic acid, and propylene graft-modified with an unsaturated carboxylic acid.・A composition containing a specific amount of α-olefin copolymer can have a melt flow rate (MFR) within a specific range, improve fluidity, and reduce the odor released into the work environment during hot molding. The present inventors have discovered that this is an adhesive resin composition that can be used suitably as a modifier for polyolefin resins, and have completed the present invention.
That is, the gist of the present invention is as follows.
［１］ 下記成分（Ａ）～（Ｃ）を含み、該（Ａ）成分および（Ｃ）成分がα，β－エチレン性不飽和カルボン酸及び／又はその誘導体によりグラフト変性されており、該成分（Ａ）～（Ｃ）の合計量１００質量％に対して、成分（Ａ）の含有量が１０～３０質量％、成分（Ｂ）の含有量が２～５質量％、成分（Ｃ）の含有量が６５～８８質量％であり、メルトフローレート（１８０℃、荷重２．１６ｋｇ、ＪＩＳ Ｋ７２１０準拠）が２０～１３０ｇ／１０分である、接着性樹脂組成物
成分（Ａ）：プロピレン・α－オレフィン共重合体
成分（Ｂ）：無機化合物
成分（Ｃ）：成分（Ａ）以外のポリプロピレン系樹脂
[1] Contains the following components (A) to (C), in which the (A) component and (C) component are graft-modified with an α,β-ethylenically unsaturated carboxylic acid and/or a derivative thereof, and the component With respect to the total amount of (A) to (C) 100% by mass, the content of component (A) is 10 to 30% by mass, the content of component (B) is 2 to 5% by mass, and the content of component (C) is 10 to 30% by mass. Adhesive resin composition having a content of 65 to 88% by mass and a melt flow rate (180°C, load 2.16kg, JIS K7210 compliant) of 20 to 130 g/10 minutes Component (A): Propylene α -Olefin copolymer Component (B): Inorganic compound Component (C): Polypropylene resin other than component (A)
［２］ 前記樹脂組成物のグラフト率が０．３～１０質量％である、［１］に記載の接着性樹脂組成物。 [2] The adhesive resin composition according to [1], wherein the resin composition has a graft ratio of 0.3 to 10% by mass.
［３］ 前記成分（Ａ）のメルトフローレート（２３０℃、荷重２．１６ｋｇ、ＪＩＳ Ｋ７２１０準拠）が５～１０ｇ／１０分であり、前記成分（Ｃ）のメルトフローレート（２３０℃、荷重２．１６ｋｇ、ＪＩＳ Ｋ７２１０準拠）が０．５～１５ｇ／１０分である、［１］又は［２］に記載の接着性樹脂組成物。 [3] The melt flow rate of the component (A) (230°C, load 2.16kg, according to JIS K7210) is 5 to 10 g/10 minutes, and the melt flow rate of the component (C) (230°C, load 2 .16 kg, according to JIS K7210) is 0.5 to 15 g/10 minutes, the adhesive resin composition according to [1] or [2].
［４］ 前記成分（Ｂ）の無機化合物が酸性物質および塩基性物質に対して吸着機能を有し、平均粒子径が１～１０μｍである、［１］～［３］のいずれかに記載の接着性樹脂組成物。 [4] The inorganic compound according to any one of [1] to [3], wherein the inorganic compound of component (B) has an adsorption function for acidic substances and basic substances, and has an average particle size of 1 to 10 μm. Adhesive resin composition.
［５］ 前記成分（Ｂ）の無機化合物を複数種組み合わせてなる、［１］～［４］のいずれかに記載の接着性樹脂組成物。 [5] The adhesive resin composition according to any one of [1] to [4], which is formed by combining a plurality of inorganic compounds as component (B).
［６］前記成分（Ｂ）の無機化合物がゼオライトとジルコニウムフェライトである、［５］に記載の接着性樹脂組成物。 [6] The adhesive resin composition according to [5], wherein the inorganic compound of component (B) is zeolite and zirconium ferrite.
［７］ ［１］～［６］のいずれかに記載の接着性樹脂組成物よりなるポリオレフィン系樹脂用改質剤。 [7] A modifier for polyolefin resins comprising the adhesive resin composition according to any one of [1] to [6].
本発明の接着性樹脂組成物は、加熱成形時に作業環境に放出される臭気が少ない上に高い流動性を有し、無機化合物、或いはグラスファイバーなどの各種フィラーや充填剤を含む様々なポリオレフィン系樹脂材料に対して良好な分散性を付与することができる改質剤としても使用できることが期待される。また、流動性も高いため加工しやすい上に、この加工成形時の臭気も低減される。 The adhesive resin composition of the present invention emits less odor into the working environment during heat molding, has high fluidity, and is compatible with various polyolefins containing inorganic compounds or various fillers such as glass fiber. It is expected that it can also be used as a modifier that can impart good dispersibility to resin materials. Furthermore, since it has high fluidity, it is easy to process, and the odor during processing and molding is also reduced.
以下に本発明について詳細に説明するが、以下の説明は、本発明の実施の形態の一例であり、本発明はその要旨を超えない限り、以下の記載内容に限定されるものではなく、本発明の要旨を逸脱しない範囲において、任意に変形して実施することができる。
なお、本発明において、「～」を用いてその前後に数値又は物性値を挟んで表現する場合、その前後の値を含むものとして用いることとする。
The present invention will be described in detail below, but the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description unless it exceeds the gist of the invention. Any modifications may be made without departing from the spirit of the invention.
In the present invention, when expressed using "~" with numerical values or physical property values placed before and after it, it is assumed that the values before and after it are included.
以下において、共重合体（共重合樹脂）に含まれる単量体単位を単に「単位」と称す場合がある。例えば、プロピレンに基づく単量体単位を「プロピレン単位」と称し、エチレンに基づく単量体単位、α－オレフィンに基づく単量体単位をそれぞれ「エチレン単位」、「α－オレフィン単位」と称す場合がある。 In the following, the monomer units contained in the copolymer (copolymer resin) may be simply referred to as "units." For example, when a monomer unit based on propylene is referred to as a "propylene unit," and a monomer unit based on ethylene and a monomer unit based on α-olefin are referred to as "ethylene unit" and "α-olefin unit," respectively. There is.
本発明において、樹脂のメルトフローレート（ＭＦＲ）、密度、樹脂組成物のグラフト率は、以下のようにして測定された値である。 In the present invention, the melt flow rate (MFR) of the resin, the density, and the grafting rate of the resin composition are values measured as follows.
＜ＭＦＲ＞
ＪＩＳ Ｋ７２１０に従い、１８０℃又は２３０℃、荷重２．１６ｋｇの条件で測定される。
<MFR>
Measured according to JIS K7210 at 180°C or 230°C and a load of 2.16kg.
＜密度＞
ＪＩＳ Ｋ７１１２に従い、水中置換法で測定される。
<Density>
Measured by the underwater displacement method according to JIS K7112.
＜グラフト率＞
本発明の接着性樹脂組成物のグラフト率（変性量、グラフト量とも称される。）は、赤外分光測定装置で測定した際の、後述の原料成分（Ａ）のプロピレン・α－オレフィン共重合体及び成分（Ｃ）のポリプロピレン系樹脂にグラフトしたα，β－エチレン性不飽和カルボン酸及び／又はその誘導体（以下、「不飽和カルボン酸成分」と称す場合がある。）の含有率を意味する。例えば、樹脂組成物を厚さ１００μｍ程度のシート状にプレス成形したサンプル中の不飽和カルボン酸成分特有の吸収、具体的には１，９００～１，６００ｃｍ－１（Ｃ＝Ｏ伸縮振動帯）のカルボニル特性吸収を測定することにより求めることができる。グラフト率は、上記の方法で、予め作成した検量線から求めることもできる。
<Graft rate>
The grafting rate (also referred to as modification amount or grafting amount) of the adhesive resin composition of the present invention is the proportion of propylene/α-olefin of the raw material component (A) described below when measured with an infrared spectrometer. The content of α, β-ethylenically unsaturated carboxylic acid and/or its derivatives (hereinafter sometimes referred to as “unsaturated carboxylic acid component”) grafted onto the polymer and the polypropylene resin of component (C). means. For example, absorption specific to the unsaturated carboxylic acid component in a sample of a resin composition press-molded into a sheet with a thickness of about 100 μm, specifically 1,900 to 1,600 cm −1 (C=O stretching vibration band) It can be determined by measuring the carbonyl characteristic absorption of The grafting rate can also be determined from a calibration curve prepared in advance using the method described above.
［接着性樹脂組成物］
本発明の接着性樹脂組成物は、下記成分（Ａ）～（Ｃ）を含み、該（Ａ）成分および（Ｃ）成分がα，β－エチレン性不飽和カルボン酸及び／又はその誘導体によりグラフト変性されており、該成分（Ａ）～（Ｃ）の合計量１００質量％に対して、成分（Ａ）の含有量が１０～３０質量％、成分（Ｂ）の含有量が２～５質量％、成分（Ｃ）の含有量が６５～８８質量％であり、メルトフローレート（１８０℃、荷重２．１６ｋｇ、ＪＩＳ Ｋ７２１０準拠）が２０～１３０ｇ／１０分であることを特徴とする。
成分（Ａ）：プロピレン・α－オレフィン共重合体
成分（Ｂ）：無機化合物
成分（Ｃ）：成分（Ａ）以外のポリプロピレン系樹脂
[Adhesive resin composition]
The adhesive resin composition of the present invention contains the following components (A) to (C), and the (A) component and (C) component are grafted with an α,β-ethylenically unsaturated carboxylic acid and/or a derivative thereof. It has been modified, and the content of component (A) is 10 to 30% by mass and the content of component (B) is 2 to 5% by mass, based on the total amount of 100% by mass of components (A) to (C). %, the content of component (C) is 65 to 88% by mass, and the melt flow rate (180° C., load 2.16 kg, according to JIS K7210) is 20 to 130 g/10 minutes.
Component (A): Propylene/α-olefin copolymer Component (B): Inorganic compound Component (C): Polypropylene resin other than component (A)
＜成分（Ａ）＞
成分（Ａ）のプロピレン・α－オレフィン共重合体は、不飽和カルボン酸成分によりグラフト変性されることで、本発明の接着性樹脂組成物に接着性、機械的強度を付与するための成分である。成分（Ａ）は結晶性が低いことが特徴であり、不飽和カルボン酸成分によるグラフト変性の際、接着性樹脂組成物が固化するまでの時間が長くなる。そのため、接着性樹脂組成物中の臭気成分を系外に放出できる。成分（Ａ）のプロピレン・α－オレフィン共重合体のプロピレン単位の含有量は、通常３質量％以上であり、好ましくは、５～２０質量％であり、プロピレン以外のα－オレフィン単位を必須として含むものである。
<Component (A)>
The propylene/α-olefin copolymer of component (A) is a component for imparting adhesiveness and mechanical strength to the adhesive resin composition of the present invention by being graft-modified with an unsaturated carboxylic acid component. be. Component (A) is characterized by low crystallinity, and it takes a long time for the adhesive resin composition to solidify during graft modification with an unsaturated carboxylic acid component. Therefore, odor components in the adhesive resin composition can be released to the outside of the system. The content of propylene units in the propylene/α-olefin copolymer of component (A) is usually 3% by mass or more, preferably 5 to 20% by mass, and α-olefin units other than propylene are essential. It includes.
このプロピレン・α－オレフィン共重合体のプロピレン単位の含有量が上記下限以上であると力学特性が良好となる。一方、プロピレン単位の含有量が上記上限以下であれば、α－オレフィン単位を含有することによる接着性付与および低結晶化の効果を有効に得ることができる。
なお、本発明において、α－オレフィンはエチレンを含む広義のα－オレフィンであり、プロピレン・α－オレフィン共重合体におけるα－オレフィンとは、プロピレン以外のエチレンを含むα－オレフィンをさす。
If the content of propylene units in this propylene/α-olefin copolymer is at least the above-mentioned lower limit, the mechanical properties will be good. On the other hand, if the content of propylene units is below the above upper limit, the effects of imparting adhesion and reducing crystallization due to the inclusion of α-olefin units can be effectively obtained.
In the present invention, α-olefin is a broadly defined α-olefin that includes ethylene, and α-olefin in a propylene/α-olefin copolymer refers to an α-olefin that includes ethylene other than propylene.
成分（Ａ）のプロピレン・α－オレフィン共重合体を構成するα－オレフィンはプロピレン以外であれば、特に限定されないが、具体的には、例えば、エチレン、１－ブテン、３－メチル－１－ブテン、１－ペンテン、４－メチル－１－ペンテン、１－ヘキセン、１－オクテン、１－デセン等の１種又は２種以上が挙げられる。これらの中でも、α－オレフィンとしては炭素数が２、又は４～８であるものが好ましく、中でも、エチレン、１－ブテンが好ましい。 The α-olefin constituting the propylene/α-olefin copolymer of component (A) is not particularly limited as long as it is other than propylene, but specifically, for example, ethylene, 1-butene, 3-methyl-1- Examples include one or more of butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and the like. Among these, α-olefins having 2 or 4 to 8 carbon atoms are preferred, and ethylene and 1-butene are particularly preferred.
成分（Ａ）のプロピレン・α－オレフィン共重合体のＭＦＲ（２３０℃、荷重２．１６ｋｇ）は特に限定されないが、１．０～２０ｇ／１０分であることが好ましく、５～１０ｇ／１０分であることがより好ましい。ＭＦＲが上記下限以上であるとその他の樹脂との溶融混練の際、混練不足による異物の発生がなく、成形した際に良好な外観となる接着性樹脂組成物を得易く、また、上記上限以下であると、成分（Ａ）が配向することなく微分散性が保たれるために好ましい。 The MFR (230°C, load 2.16 kg) of the propylene/α-olefin copolymer of component (A) is not particularly limited, but is preferably 1.0 to 20 g/10 minutes, and 5 to 10 g/10 minutes. It is more preferable that When the MFR is at least the above lower limit, there will be no generation of foreign matter due to insufficient kneading when melt-kneading with other resins, and it will be easy to obtain an adhesive resin composition that has a good appearance when molded. This is preferable because component (A) maintains fine dispersibility without being oriented.
また、成分（Ａ）のプロピレン・α－オレフィン共重合体の密度は、特に限定されないが、好ましくは０．８９５ｇ／ｃｍ３以下、より好ましくは０．８８０ｇ／ｃｍ３以下である。プロピレン・α－オレフィン共重合体の密度が低くなるほど、成形時の歪緩和効果が十分となり層間接着強度が向上する傾向がある。プロピレン・α－オレフィン共重合体の密度の下限は限定されないが、通常０．８５０ｇ／ｃｍ３以上である。 Further, the density of the propylene/α-olefin copolymer of component (A) is not particularly limited, but is preferably 0.895 g/cm 3 or less, more preferably 0.880 g/cm 3 or less. As the density of the propylene/α-olefin copolymer decreases, the strain relaxation effect during molding tends to be sufficient and the interlayer adhesive strength tends to improve. The lower limit of the density of the propylene/α-olefin copolymer is not limited, but is usually 0.850 g/cm 3 or more.
本発明に好適なプロピレン・α－オレフィン共重合体としては市販品を用いることもでき、例えば、三井化学社製「タフマー（登録商標）」シリーズ、ＤＯＷ社製「エンゲージ（登録商標）」シリーズ等の中から前記の特性に該当するものを適宜選択することができる。 Commercially available propylene/α-olefin copolymers suitable for the present invention can also be used, such as the "Tafmer (registered trademark)" series manufactured by Mitsui Chemicals, the "Engage (registered trademark)" series manufactured by DOW, etc. Those that meet the above characteristics can be appropriately selected from among the above.
これらの成分（Ａ）は、１種のみを用いてもよく、プロピレン単位の含有量や物性等の異なるものを２種以上混合して用いてもよい。 These components (A) may be used alone or in combination of two or more different components having different propylene unit content, physical properties, etc.
本発明の接着性樹脂組成物において、成分（Ａ）のプロピレン・α－オレフィン共重合体の含有量は、成分（Ａ）、成分（Ｂ）および成分（Ｃ）の合計１００質量％に対して１０～３０質量％である。成分（Ａ）の含有量が上記上限よりも多いと耐熱性が低下し、上記下限よりも少ないと剥離時の伸びが損なわれて、接着強度が低下するため、好ましくは、成分（Ａ）の含有量は、成分（Ａ）、成分（Ｂ）および成分（Ｃ）の合計１００質量％に対して１５～２５質量％である。 In the adhesive resin composition of the present invention, the content of the propylene/α-olefin copolymer as component (A) is based on the total of 100% by mass of component (A), component (B), and component (C). It is 10 to 30% by mass. If the content of component (A) is more than the above upper limit, the heat resistance will decrease, and if it is less than the above lower limit, the elongation at the time of peeling will be impaired and the adhesive strength will decrease. The content is 15 to 25% by mass based on the total of 100% by mass of component (A), component (B) and component (C).
＜成分Ｂ＞
成分（Ｂ）の無機化合物は、本発明の接着性樹脂組成物に接着性を付与すると共に臭気を低減する機能を奏する成分である。
成分（Ｂ）の無機化合物は、酸性物質および塩基性物質に対して吸着機能を有することが好ましい。酸性物質と塩基性物質の双方に吸着機能を有する無機化合物であれば、原料の分解による低分子量体の酸性もしくは塩基性物質や反応残渣を取り除くことができ、好ましい。ここで、吸着性能を有するとは、固体表面からの引力で上記のような低分子量体を捕捉することを指し、多孔質の無機化合物であれば表面積が大きいため、より吸着性能が高く、臭気をより低減できるため好ましい。
<Component B>
The inorganic compound as component (B) is a component that provides adhesive properties to the adhesive resin composition of the present invention and also functions to reduce odor.
The inorganic compound of component (B) preferably has an adsorption function for acidic substances and basic substances. An inorganic compound having an adsorption function for both acidic substances and basic substances is preferable because it can remove low molecular weight acidic or basic substances and reaction residues resulting from decomposition of raw materials. Here, having adsorption performance refers to the ability to capture the above-mentioned low-molecular-weight substances by the attractive force from the solid surface. Porous inorganic compounds have a large surface area, so they have higher adsorption performance and odor. This is preferable because it can further reduce
酸性物質および塩基性物質に対して吸着機能を有する無機化合物は限定されないが、例えば、ケイ酸アルミニウム化合物であるゼオライト、ジルコニウムフェライトが挙げられる。
ゼオライトは（ＭＩ，ＭII
１／２）ｍ（ＡｌｍＳｉｎＯ２（ｍ＋ｎ））・Ｘ Ｈ２Ｏ（ｎ≧ｍ）で表され、ＭＩとしてはＬｉ＋やＮａ＋、Ｋ＋が挙げられる。ＭIIとしてはＣａ２＋やＭａ２＋、Ｂａ２＋が挙げられる。
ジルコニウムフェライトは表面水酸基に由来する大きなイオン交換機能を有しており、酸性物質および塩基性物質に対して吸着機能を有する。
The inorganic compound having an adsorption function for acidic substances and basic substances is not limited, and examples thereof include zeolite and zirconium ferrite, which are aluminum silicate compounds.
Zeolite is represented by (M I , M II 1/2 ) m (Al m Si n O 2 ( m+n )) x H 2 O (n≧m), and M I can be Li + , Na + , K + can be mentioned. Examples of M II include Ca 2+ , Ma 2+ , and Ba 2+ .
Zirconium ferrite has a large ion exchange function derived from surface hydroxyl groups, and has an adsorption function for acidic and basic substances.
成分（Ｂ）の無機化合物の平均粒子径は１～１０μｍであることが好ましい。無機化合物の平均粒子径が１０μｍ以下であれば本接着性樹脂組成物の使用の際に外観不良が生じない。また、無機化合物の平均粒子径が１μｍ以上であれば無機化合物同士の凝集が生じないため好適である。
ここで、無機化合物の平均粒子径は粒度分散測定のｄ５０の値である。
The average particle diameter of the inorganic compound of component (B) is preferably 1 to 10 μm. If the average particle diameter of the inorganic compound is 10 μm or less, no appearance defects will occur when the present adhesive resin composition is used. Further, it is preferable that the average particle diameter of the inorganic compound is 1 μm or more, since aggregation of the inorganic compounds does not occur.
Here, the average particle diameter of the inorganic compound is the d50 value of particle size dispersion measurement.
成分（Ｂ）の無機化合物は１種のみを用いてもよいが、２種（複数種）以上組み合わせて用いるのが好ましい。特にゼオライトとジルコニウムフェライトを併用するのが好ましい。２種以上の無機化合物、例えば、ゼオライトとジルコニウムフェライトとを併用することで、そのメカニズムの詳細は明らかではないが、臭気を低減することができる。 Although only one type of inorganic compound as component (B) may be used, it is preferable to use two or more types (plural types) or more in combination. In particular, it is preferable to use zeolite and zirconium ferrite together. By using two or more types of inorganic compounds, for example, zeolite and zirconium ferrite, odor can be reduced, although the details of the mechanism are not clear.
成分（Ｂ）の無機化合物は市販のものを使うことができる。成分（Ｂ）の無機化合物の市販品としては、例えば、ジルコニウムフェライトとしては、大阪ガスケミカル（株）製のセブントールが挙げられ、ゼオライトとしては、水澤化学（株）製のミズカライザーが挙げられる。 Commercially available inorganic compounds can be used as component (B). Commercially available inorganic compounds of component (B) include, for example, zirconium ferrite such as Seventol manufactured by Osaka Gas Chemical Co., Ltd., and zeolite such as Mizucalizer manufactured by Mizusawa Chemical Co., Ltd. .
本発明の接着性樹脂組成物において、成分（Ｂ）の無機化合物の含有量は、成分（Ａ）、成分（Ｂ）および成分（Ｃ）の合計１００質量％に対して、２～５質量％である。成分（Ｂ）の含有量が２重量％未満の場合は臭気を低減する効果が非常に小さく、また接着性も十分ではない。また、成分（Ｂ）の含有量が５質量％より多い場合は、無機化合物が吸水し、成形加工時の加熱により外観不良となる可能性がある上に、分散性も悪くなる。更に接着性樹脂組成物が硬くなるため接着性の低下を引き起こす。 In the adhesive resin composition of the present invention, the content of the inorganic compound as component (B) is 2 to 5% by mass based on the total of 100% by mass of component (A), component (B), and component (C). It is. If the content of component (B) is less than 2% by weight, the effect of reducing odor will be very small and the adhesiveness will not be sufficient. Moreover, when the content of component (B) is more than 5% by mass, the inorganic compound absorbs water, which may result in poor appearance due to heating during molding, and the dispersibility may also deteriorate. Furthermore, the adhesive resin composition becomes hard, resulting in a decrease in adhesive properties.
成分（Ｂ）として２種以上の無機化合物を組み合わせて用いる場合、その混合割合には特に制限はない。例えば、ゼオライトとジルコニウムフェライトを併用する場合、上記成分（Ｂ）の無機化合物の含有量の範囲においてゼオライトを１～４質量％、ジルコニウムフェライトを１～４質量％の範囲で混合して用いることが、併用による上記効果を得る上で好ましい。 When using a combination of two or more types of inorganic compounds as component (B), there is no particular restriction on the mixing ratio. For example, when using zeolite and zirconium ferrite together, it is possible to use a mixture of 1 to 4% by mass of zeolite and 1 to 4% by mass of zirconium ferrite within the content range of the inorganic compound of component (B). , is preferable for obtaining the above-mentioned effects when used in combination.
＜成分（Ｃ）＞
成分（Ｃ）のポリプロピレン系樹脂としては、例えばホモポリプロピレン（プロピレンの単独重合体）、プロピレンランダム共重合体が挙げられるが、本発明の接着性樹脂組成物を後述のポリオレフィン系樹脂用改質剤として用いる場合は、成分（Ｃ）としては、結晶性、力学特性の観点からホモポリプロピレンが好ましい。
<Component (C)>
Examples of the polypropylene resin of component (C) include homopolypropylene (propylene homopolymer) and propylene random copolymer. When used as component (C), homopolypropylene is preferable from the viewpoint of crystallinity and mechanical properties.
成分（Ｃ）のポリプロピレン系樹脂はプロピレン単位を５０質量％以上、好ましくは７０～１００質量％含むものであり、成分（Ａ）のプロピレン・α－オレフィン共重合体とは異なるものである。 The polypropylene resin of component (C) contains propylene units in an amount of 50% by mass or more, preferably 70 to 100% by mass, and is different from the propylene/α-olefin copolymer of component (A).
この成分（Ｃ）は本発明の接着性樹脂組成物に力学特性を付与するための成分であり、接着性樹脂組成物の力学特性の観点から、成分（Ｃ）のポリプロピレン系樹脂のプロピレン単位の含有量は上記下限以上であることが好ましい。 This component (C) is a component for imparting mechanical properties to the adhesive resin composition of the present invention, and from the viewpoint of the mechanical properties of the adhesive resin composition, the propylene unit of the polypropylene resin of component (C) is It is preferable that the content is at least the above lower limit.
成分（Ｃ）のポリプロピレン系樹脂は公知の方法によって製造される。例えば、チーグラーナッタ触媒、メタロセン触媒等の触媒を用い、バッチ法、気相法、スラリー法など公知の手段で製造される。 The polypropylene resin of component (C) is produced by a known method. For example, it is produced using a catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst by a known method such as a batch method, a gas phase method, or a slurry method.
成分（Ｃ）のポリプロピレン系樹脂のＭＦＲ（２３０℃、荷重２．１６ｋｇ）は特に制限はないが、０．５～３０ｇ／１０分であることが好ましく、０．５～１５ｇ／１０分であることが好ましく、３～１５ｇ／１０分であることが更に好ましい。成分（Ｃ）のポリプロピレン系樹脂のＭＦＲが上記上限以下であると、耐熱性、機械的強度等が良好なものとなる傾向があり、上記下限以上であると、成形性、延伸性等が良好なものとなる傾向がある。 The MFR (230°C, load 2.16 kg) of the polypropylene resin of component (C) is not particularly limited, but is preferably 0.5 to 30 g/10 minutes, and preferably 0.5 to 15 g/10 minutes. The rate is preferably 3 to 15 g/10 minutes, and more preferably 3 to 15 g/10 minutes. When the MFR of the polypropylene resin of component (C) is below the above upper limit, heat resistance, mechanical strength, etc. tend to be good, and when it is above the above lower limit, moldability, stretchability, etc. are good. It tends to become something.
成分（Ｃ）のポリプロピレン系樹脂は、１種のみを用いてもよく、単量体単位の組成や物性等の異なるものを２種以上混合して用いてもよい。 The polypropylene resin of component (C) may be used alone or in combination of two or more types having different monomer unit compositions, physical properties, etc.
本発明の接着性樹脂組成物において、成分（Ｃ）の含有量は、成分（Ａ）、成分（Ｂ）および成分（Ｃ）の合計１００質量％に対して６５～８８質量％である。成分（Ｃ）の含有量が６５質量％未満では力学特性が低くなり、８８質量％を超えると接着性樹脂組成物の接着性が低下する。 In the adhesive resin composition of the present invention, the content of component (C) is 65 to 88% by mass based on the total of 100% by mass of component (A), component (B) and component (C). If the content of component (C) is less than 65% by mass, the mechanical properties will decrease, and if it exceeds 88% by mass, the adhesiveness of the adhesive resin composition will decrease.
＜グラフト変性＞
成分（Ａ）及び成分（Ｃ）をグラフト変性するα，β－エチレン性不飽和カルボン酸としては、例えば、アクリル酸、マレイン酸、フマル酸、テトラヒドロフマル酸、イタコン酸、シトラコン酸、クロトン酸、イソクロトン酸等の不飽和カルボン酸が挙げられる。α，β－エチレン性不飽和カルボン酸の誘導体としては、コハク酸２－オクテン－１－イル無水物、コハク酸２－ドデセン－１－イル無水物、コハク酸２－オクタデセン－１－イル無水物、マレイン酸無水物、２，３－ジメチルマレイン酸無水物、ブロモマレイン酸無水物、ジクロロマレイン酸無水物、シトラコン酸無水物、イタコン酸無水物、１－ブテン－３，４－ジカルボン酸無水物、１－シクロペンテン－１，２－ジカルボン酸無水物、１，２，３，６－テトラヒドロフタル酸無水物、３，４，５，６－テトラヒドロフタル酸無水物、ｅｘｏ－３，６－エポキシ－１，２，３，６－テトラヒドロフタル酸無水物、５－ノルボルネン－２，３－ジカルボン酸無水物、メチル－５－ノルボルネン－２，３－ジカルボン酸無水物、ｅｎｄｏ－ビシクロ［２．２．２］オクト－５－エン－２，３－ジカルボン酸無水物、ビシクロ［２．２．２］オクト－７－エン－２，３，５，６－テトラカルボン酸無水物等の不飽和カルボン酸無水物が挙げられる。
<Graft modification>
Examples of the α,β-ethylenically unsaturated carboxylic acid for graft-modifying component (A) and component (C) include acrylic acid, maleic acid, fumaric acid, tetrahydrofumaric acid, itaconic acid, citraconic acid, crotonic acid, Examples include unsaturated carboxylic acids such as isocrotonic acid. Derivatives of α,β-ethylenically unsaturated carboxylic acids include 2-octen-1-yl succinate anhydride, 2-dodecen-1-yl succinate anhydride, and 2-octadecen-1-yl succinate anhydride. , maleic anhydride, 2,3-dimethylmaleic anhydride, bromomaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, 1-butene-3,4-dicarboxylic anhydride , 1-cyclopentene-1,2-dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, exo-3,6-epoxy- 1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, endo-bicyclo[2.2. 2] Unsaturated carboxylic acids such as oct-5-ene-2,3-dicarboxylic anhydride and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic anhydride Examples include anhydrides.
これらの不飽和カルボン酸成分は、変性すべき成分（Ａ）及び／又は成分（Ｃ）や変性条件に応じて適宜選択することができ、１種を単独で用いる場合に限らず、２種以上を併用しても良い。
これらの不飽和カルボン酸成分は、有機溶剤などに溶解して使用することもできる。
These unsaturated carboxylic acid components can be appropriately selected depending on the component (A) and/or component (C) to be modified and the modification conditions, and are not limited to the case where one type is used alone, but two or more types. may be used together.
These unsaturated carboxylic acid components can also be used after being dissolved in an organic solvent.
成分（Ａ）及び成分（Ｃ）のグラフト変性は、不飽和カルボン酸成分を添加して、好ましくはラジカル発生剤の存在下に不飽和カルボン酸成分を成分（Ａ）及び／又は成分（Ｃ）にグラフト重合させることで行うことができる。
ここで、グラフト変性は、混合前の成分（Ａ）と成分（Ｃ）の各々に対して行うこともできるが、成分（Ａ）と成分（Ｃ）の混合物に対して行うのが効率的である。特に、本発明の接着性樹脂組成物に必要な成分をすべて混合してなる混合物に不飽和カルボン酸成分とラジカル発生剤を添加して溶融混練することで行うことが好ましい。
Graft modification of component (A) and component (C) is carried out by adding an unsaturated carboxylic acid component to component (A) and/or component (C), preferably in the presence of a radical generator. This can be done by graft polymerization.
Here, graft modification can be performed on each of component (A) and component (C) before mixing, but it is more efficient to perform it on a mixture of component (A) and component (C). be. In particular, it is preferable to add an unsaturated carboxylic acid component and a radical generator to a mixture obtained by mixing all the components necessary for the adhesive resin composition of the present invention, and then melt-knead the mixture.
ここで使用されるラジカル発生剤としては、例えば、ｔ－ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、２，５－ジメチルヘキサン－２，５－ジハイドロパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルオキシ）ヘキサン、３，５，５－トリメチルヘキサノイルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、ベンゾイルパーオキサイド、ｍ－トルオイルパーオキサイド、ジクミルパーオキサイド、１，３－ビス（ｔ－ブチルパーオキシイソプロピル）ベンゼン、ジブチルパーオキサイド、メチルエチルケトンパーオキサイド、過酸化カリウム、過酸化水素等の有機及び無機の過酸化物；２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（イソブチルアミド）ジハライド、２，２’－アゾビス［２－メチル－Ｎ－（２－ヒドロキシエチル）プロピオンアミド］、アゾジ－ｔ－ブタン等のアゾ化合物；ジクミル等の炭素ラジカル発生剤が挙げられる。 Examples of the radical generator used here include t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5 -bis(t-butyloxy)hexane, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxybenzoate, benzoyl peroxide, m-toluoyl peroxide, dicumyl peroxide, 1,3-bis( Organic and inorganic peroxides such as t-butylperoxyisopropyl) benzene, dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide; 2,2'-azobisisobutyronitrile, 2,2' -Azo compounds such as azobis(isobutyramide) dihalide, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], azodi-t-butane; carbon radical generators such as dicumyl; It will be done.
上記のラジカル発生剤は、変性反応に供する成分（Ａ）及び／又は成分（Ｃ）の種類、変性剤としての不飽和カルボン酸成分の種類及び変性条件に応じて適宜選択することができ、１種を単独で用いても良く、２種以上を併用しても良い。
ラジカル発生剤は有機溶剤などに溶解して使用することもできる。
The above radical generator can be appropriately selected depending on the type of component (A) and/or component (C) to be subjected to the modification reaction, the type of unsaturated carboxylic acid component as a modifying agent, and the modification conditions. A species may be used alone or two or more species may be used in combination.
The radical generator can also be used after being dissolved in an organic solvent.
本発明の接着性樹脂組成物を得る際に行う変性反応としては、溶融混練反応法、溶液反応法、懸濁分散反応法など公知の種々の反応方法を使用することができるが、通常は溶融混練反応法が好ましい。 Various known reaction methods such as a melt-kneading reaction method, a solution reaction method, and a suspension dispersion reaction method can be used for the modification reaction to be carried out when obtaining the adhesive resin composition of the present invention. A kneading reaction method is preferred.
溶融混練反応法よる場合は、前記の各成分を所定の配合比にて均一に混合した後に溶融混練すれば良い。混合には、ヘンシェルミキサー、リボンブレンダー、Ｖ型ブレンダー等が使用され、溶融混練には、バンバリーミキサー、ニーダー、ロール、一軸又は二軸などの多軸混練押出機などが使用される。 When using the melt-kneading reaction method, the above-mentioned components may be uniformly mixed at a predetermined mixing ratio and then melt-kneaded. For mixing, a Henschel mixer, a ribbon blender, a V-type blender, etc. are used, and for melt kneading, a Banbury mixer, kneader, roll, multi-screw kneading extruder such as a single-screw or twin-screw extruder, etc. are used.
溶融混練は、樹脂が熱劣化しないように、通常１００℃以上、好ましくは１２０℃以上、より好ましくは１５０℃以上で、通常３００℃以下、好ましくは２８０℃以下、より好ましくは２５０℃以下の範囲で行う。 Melt kneading is usually carried out at a temperature of 100°C or higher, preferably 120°C or higher, more preferably 150°C or higher, and usually 300°C or lower, preferably 280°C or lower, more preferably 250°C or lower, in order to prevent thermal deterioration of the resin. Do it with
変性剤としての不飽和カルボン酸成分の配合量は、成分（Ａ）と成分（Ｃ）の合計１００質量部に対し、通常０．０１質量部以上、好ましくは０．０５質量部以上、より好ましくは０．１質量部以上で、通常３０質量部以下、好ましくは５質量部以下、より好ましくは４質量部以下である。不飽和カルボン酸成分の配合量が少な過ぎる場合は、十分な変性が行えず、多過ぎる場合は、配合量に応じたグラフト率が得られず不経済である。 The amount of the unsaturated carboxylic acid component as a modifier is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably is 0.1 parts by mass or more and usually 30 parts by mass or less, preferably 5 parts by mass or less, more preferably 4 parts by mass or less. If the amount of the unsaturated carboxylic acid component is too small, sufficient modification cannot be carried out, and if it is too large, a grafting ratio corresponding to the amount of the unsaturated carboxylic acid component cannot be obtained, which is uneconomical.
また、ラジカル発生剤の配合量は、成分（Ａ）と成分（Ｃ）の合計１００質量部に対し、通常０．００１質量部以上、好ましくは０．００５質量部以上、より好ましくは０．０１質量部以上で、通常３質量部以下、好ましくは１．５質量部以下、より好ましくは１．０質量部以下、更に好ましくは０．５質量部以下である。ラジカル発生剤の配合量が少な過ぎる場合は、変性が十分に起こらず、多過ぎる場合は、成分（Ａ）及び／又は成分（Ｃ）の変性時の低分子量化（粘度低下）が大きく、材料強度が著しく低下してしまう。即ち、この変性反応においては、成分（Ａ）及び／又は成分（Ｃ）に不飽和カルボン酸成分が付加するグラフト重合反応が主として起こるが、分解反応も起こり、分解により、得られる変性物は分子量が低下して溶融粘度が低くなる。ラジカル発生剤の使用量が多過ぎると、グラフト重合反応も起こり易いが、同時にこのような溶融粘度低下につながる分解反応も起こり易くなるため、好ましくない。 The amount of the radical generator to be added is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass, based on the total of 100 parts by mass of components (A) and (C). The amount is usually 3 parts by weight or less, preferably 1.5 parts by weight or less, more preferably 1.0 parts by weight or less, and still more preferably 0.5 parts by weight. If the amount of the radical generator is too small, modification will not occur sufficiently, and if it is too large, the molecular weight will be lowered (viscosity lowered) significantly during modification of component (A) and/or component (C), and the material will deteriorate. The strength will drop significantly. That is, in this modification reaction, a graft polymerization reaction in which an unsaturated carboxylic acid component is added to component (A) and/or component (C) mainly occurs, but a decomposition reaction also occurs, and the resulting modified product has a molecular weight of decreases and the melt viscosity decreases. If the amount of the radical generator used is too large, the graft polymerization reaction is likely to occur, but at the same time, the decomposition reaction that leads to such a decrease in melt viscosity is also likely to occur, which is not preferable.
この反応生成物は、接着性樹脂組成物として、後述の如く、そのまま接着性樹脂層の成形に供することができる。 This reaction product can be directly used as an adhesive resin composition to form an adhesive resin layer as described below.
なお、本発明の接着性樹脂組成物は、上記の通り、成分（Ａ）と成分（Ｃ）の混合物を不飽和カルボン酸成分でグラフト変性処理する他、グラフト変性処理された成分（Ａ）とグラフト変性処理された成分（Ｃ）を混合することにより製造することもできる。製造が容易であり、また、均一に変性処理された接着性樹脂組成物を得ることができることから、成分（Ａ）と成分（Ｃ）の混合物に対して上記の通りグラフト変性処理することが好ましい。 As mentioned above, the adhesive resin composition of the present invention can be prepared by graft-modifying a mixture of component (A) and component (C) with an unsaturated carboxylic acid component, and also by graft-modifying the mixture of component (A) and component (C) with the graft-modified component (A). It can also be produced by mixing component (C) that has been subjected to graft modification treatment. It is preferable to carry out the graft modification treatment on the mixture of component (A) and component (C) as described above because it is easy to manufacture and it is possible to obtain an adhesive resin composition that has been uniformly modified. .
＜その他の成分＞
本発明の接着性樹脂組成物には、上記の各成分に加え、本発明の効果を著しく損なわない範囲で各種目的に応じ他の任意の添加剤や樹脂等（以下、これらを「その他の成分」と称す。）を配合することができる。その他の成分は、１種類のみを用いても、２種類以上を任意の組合せと比率で併用してもよい。
<Other ingredients>
In addition to the above-mentioned components, the adhesive resin composition of the present invention may contain other arbitrary additives, resins, etc. (hereinafter referred to as "other components") according to various purposes within the range that does not significantly impair the effects of the present invention. ) can be blended. As for the other components, only one type may be used, or two or more types may be used in combination in any combination and ratio.
添加剤としては、一般的にポリオレフィン系樹脂に用いられる補助添加成分、具体的には、プロセス油、中和剤、加工助剤、可塑剤、結晶核剤、衝撃改良剤、難燃剤、難燃助剤、架橋剤、架橋助剤、帯電防止剤、滑剤、充填材、相溶化剤、耐熱安定剤、耐候安定剤（酸化防止剤、光安定剤、紫外線吸収剤等）、防曇剤、スリップ剤、アンチブロッキング剤、抗菌剤、カーボンブラック、着色剤（顔料、染料等）が挙げられる。 Additives include auxiliary additive components generally used in polyolefin resins, specifically process oils, neutralizing agents, processing aids, plasticizers, crystal nucleating agents, impact modifiers, flame retardants, and flame retardants. Auxiliary agents, crosslinking agents, crosslinking aids, antistatic agents, lubricants, fillers, compatibilizers, heat stabilizers, weather stabilizers (antioxidants, light stabilizers, ultraviolet absorbers, etc.), antifogging agents, slip agents, anti-blocking agents, antibacterial agents, carbon black, and colorants (pigments, dyes, etc.).
このうち、難燃剤は、ハロゲン系難燃剤と非ハロゲン系難燃剤に大別されるが、非ハロゲン系難燃剤が好ましく、具体的には、金属水酸化物、リン系難燃剤、窒素含有化合物（メラミン系、グアニジン系）難燃剤及び無機系化合物（硼酸塩、モリブデン化合物）難燃剤が挙げられる。 Among these, flame retardants are broadly classified into halogen flame retardants and non-halogen flame retardants, but non-halogen flame retardants are preferred, specifically metal hydroxides, phosphorus flame retardants, and nitrogen-containing compounds. (melamine-based, guanidine-based) flame retardants and inorganic compound (borates, molybdenum compounds) flame retardants.
熱安定剤及び酸化防止剤としては、例えば、ヒンダードフェノール類、リン化合物、ヒンダードアミン、イオウ化合物、銅化合物、アルカリ金属のハロゲン化物が挙げられる。 Examples of the heat stabilizer and antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, and alkali metal halides.
充填材は、有機充填材と無機充填材に大別される。有機充填材としては、澱粉、セルロース微粒子、木粉、おから、モミ殻、フスマ等の天然由来のポリマーやこれらの変性品等が挙げられる。また、無機充填材としては、タルク、炭酸カルシウム、炭酸亜鉛、ワラストナイト、シリカ、アルミナ、酸化マグネシウム、ケイ酸カルシウム、アルミン酸ナトリウム、珪酸マグネシウム、ガラスバルーン、カーボンブラック、酸化亜鉛、三酸化アンチモン、金属繊維、金属ウイスカー、セラミックウイスカー、チタン酸カリウム、窒化ホウ素、グラファイト、グラスファイバー（ＧＦ）、炭素繊維等が挙げられる。 Fillers are broadly classified into organic fillers and inorganic fillers. Examples of the organic filler include naturally occurring polymers such as starch, cellulose particles, wood flour, okara, rice husks, and bran, and modified products thereof. Inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, magnesium silicate, glass balloon, carbon black, zinc oxide, antimony trioxide. , metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, glass fiber (GF), carbon fiber, and the like.
これらの添加剤を用いる場合、その含有量は限定されないが、本発明の接着性樹脂組成物中の含有量として、通常０．０１質量％以上、好ましくは０．１質量％以上であり、また、通常５質量％以下、好ましくは２質量％以下であることが望ましい。なおこれらの添加剤は、本発明の接着性樹脂組成物をマスターバッチとして用いる場合には、前記した含有量の２～５０倍、好ましくは３～３０倍の濃度で含有させることもできる。 When using these additives, the content thereof is not limited, but the content in the adhesive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.1% by mass or more, and , usually 5% by mass or less, preferably 2% by mass or less. Note that when the adhesive resin composition of the present invention is used as a masterbatch, these additives may be contained at a concentration of 2 to 50 times, preferably 3 to 30 times, the above-mentioned content.
その他の成分として用いる樹脂としては、例えば、ポリフェニレンエーテル系樹脂；ポリカーボネート樹脂；ナイロン６６、ナイロン１１等のポリアミド系樹脂；ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル系樹脂；ポリスチレン等のスチレン系樹脂；及びポリメチルメタクリレート系樹脂等のアクリル／メタクリル系樹脂を挙げることができる。 Examples of resins used as other components include polyphenylene ether resins; polycarbonate resins; polyamide resins such as nylon 66 and nylon 11; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; styrene resins such as polystyrene; Acrylic/methacrylic resins such as polymethyl methacrylate resins can be mentioned.
本発明の接着性樹脂組成物がこれらのその他の樹脂を含有する場合、その含有量は、成分（Ａ）、成分（Ｂ）及び成分（Ｃ）の合計１００質量部に対して３０質量部以下であることが好ましい。 When the adhesive resin composition of the present invention contains these other resins, the content thereof is 30 parts by mass or less based on the total of 100 parts by mass of component (A), component (B), and component (C). It is preferable that
＜製造方法＞
成分（Ａ）～（Ｃ）と必要に応じて添加されるその他の成分を用いて、本発明の接着性樹脂組成物を製造するための混合・変性方法は、実用的には溶融混練法が好ましい。
<Manufacturing method>
Practical mixing and modification methods for producing the adhesive resin composition of the present invention using components (A) to (C) and other components added as necessary include the melt-kneading method. preferable.
溶融混練のための具体的な方法としては、成分（Ａ）～（Ｃ）、並びに必要に応じて添加されるその他の成分を、所定の配合割合にて、ヘンシェルミキサー、リボンブレンダー、Ｖ型ブレンダー等を用いて均一に混合した後、多軸混練押出機、例えば日本製鋼所の２軸混練押出機であるＴＥＸ２５を用いて混練する方法が例示できる。 As a specific method for melt-kneading, components (A) to (C) and other components added as necessary are mixed in a predetermined mixing ratio using a Henschel mixer, a ribbon blender, or a V-type blender. An example of a method is to uniformly mix the ingredients using a multi-screw kneading extruder, such as a twin-screw kneading extruder TEX25 manufactured by Japan Steel Works.
各成分の溶融混練の温度は、前述のグラフト変性の項に記載したように、通常１００～３００℃、好ましくは１２０～２８０℃、より好ましくは１５０～２５０℃である。更に、各成分の混練順序及び方法は、特に限定されるものではなく、成分（Ａ）～（Ｃ）と必要に応じて用いられるその他の成分とを一括して混練する方法、又は成分（Ａ）～（Ｃ）と必要に応じて用いられるその他の成分の一部を予め混練しておき、その後残りの成分を混練する方法でもよい。 The temperature for melt-kneading each component is generally 100 to 300°C, preferably 120 to 280°C, more preferably 150 to 250°C, as described in the above section on graft modification. Furthermore, the order and method of kneading each component are not particularly limited, and may include a method of kneading components (A) to (C) and other components used as necessary, or a method of kneading components (A) to (C) together with other components used as necessary. ) to (C) and some of the other components used as necessary may be kneaded in advance, and then the remaining components may be kneaded.
＜ＭＦＲ＞
本発明の接着性樹脂組成物のＭＦＲ（１８０℃、荷重２．１６ｋｇ）は２０～１３０ｇ／１０分であり、好ましくは２５～１００ｇ／１０分である。接着性樹脂組成物のＭＦＲが上記範囲であると良好な成形性、特に良好な共押出成形性が得られるため好ましい。
<MFR>
The MFR (180° C., load 2.16 kg) of the adhesive resin composition of the present invention is 20 to 130 g/10 minutes, preferably 25 to 100 g/10 minutes. It is preferable that the MFR of the adhesive resin composition is within the above range because good moldability, especially good coextrusion moldability can be obtained.
＜グラフト率＞
本発明の接着性樹脂組成物のグラフト率は０．３～１０質量％、特に０．５～３質量％であることが好ましい。グラフト率が上記下限以上であると、良好な接着性を得ることができる。ただし、グラフト率が高過ぎると焼け等が多くなり、その結果、製品の外観等に悪影響を及ぼすため、接着性樹脂組成物のグラフト率は上記上限以下であることが好ましい。
<Graft rate>
The graft ratio of the adhesive resin composition of the present invention is preferably 0.3 to 10% by weight, particularly 0.5 to 3% by weight. When the graft ratio is at least the above lower limit, good adhesiveness can be obtained. However, if the grafting rate is too high, burns and the like will increase, which will have a negative effect on the appearance of the product, so the grafting rate of the adhesive resin composition is preferably at most the above upper limit.
＜接着性樹脂組成物よりなる接着層＞
本発明の接着性樹脂組成物は、例えば積層体の接着層として用いることができる。より具体的には本発明の接着性樹脂組成物よりなる層を含むポリプロピレン系樹脂層とガスバリア層とを積層してなる積層体において、ガスバリア層に接して設けられる接着層として有用である。
<Adhesive layer made of adhesive resin composition>
The adhesive resin composition of the present invention can be used, for example, as an adhesive layer of a laminate. More specifically, it is useful as an adhesive layer provided in contact with a gas barrier layer in a laminate formed by laminating a gas barrier layer and a polypropylene resin layer including a layer made of the adhesive resin composition of the present invention.
この場合、本発明の接着性樹脂組成物からなる接着層の厚みは限定されるものではなく、用途や被接着層の種類等に応じて適宜決定されるが、通常１～１００μｍであることが好ましく、２～５０μｍであることがより好ましく、３～２０μｍであることが更に好ましい。 In this case, the thickness of the adhesive layer made of the adhesive resin composition of the present invention is not limited and is appropriately determined depending on the application and the type of layer to be adhered, but it is usually 1 to 100 μm. The thickness is preferably 2 to 50 μm, more preferably 3 to 20 μm.
また、一方の被接着層となるガスバリア層に用いられる樹脂としては、例えば、ポリアミド系樹脂、エチレン・ビニルアルコール共重合体（ＥＶＯＨ）が挙げられる。 Further, examples of the resin used for the gas barrier layer, which is one of the adhered layers, include polyamide resin and ethylene-vinyl alcohol copolymer (EVOH).
エチレン・ビニルアルコール共重合体は、通常エチレン・酢酸ビニル共重合体を鹸化して得られるものであり、本発明においては、そのエチレン単位の含有量が２０～５０モル％で、鹸化度が９５％以上のものが好ましい。なお、鹸化度の上限は１００％である。エチレン・ビニルアルコール共重合体のエチレン単位の含有量が少な過ぎると熱分解し易く、溶融成形が困難で、また延伸性にも劣り、かつ吸水し膨潤し易く耐水性が劣るものとなる。一方、エチレン・ビニルアルコール共重合体のエチレン単位の含有量が多過ぎると、耐ガス透過性が低下する傾向がある。また、鹸化度が低過ぎる場合には、耐ガス透過性が低下する傾向がある。 Ethylene/vinyl alcohol copolymer is usually obtained by saponifying ethylene/vinyl acetate copolymer, and in the present invention, the content of ethylene units is 20 to 50 mol% and the degree of saponification is 95. % or more is preferable. Note that the upper limit of the degree of saponification is 100%. If the content of ethylene units in the ethylene/vinyl alcohol copolymer is too low, it will be easily thermally decomposed, difficult to melt mold, and will have poor stretchability, and will easily absorb water and swell, resulting in poor water resistance. On the other hand, if the content of ethylene units in the ethylene/vinyl alcohol copolymer is too large, gas permeability resistance tends to decrease. Furthermore, if the degree of saponification is too low, gas permeability resistance tends to decrease.
ポリアミド樹脂としては、ε－カプロラクタム、ω－ラウロラクタム等のラクタムの重合体、６－アミノカプロン酸、１１－アミノウンデカン酸、１２－アミノドデカン酸等のアミノカルボン酸の重合体、ヘキサメチレンジアミン、デカメチレンジアミン、ドデカメチレンジアミン、２，２，４－又は２，４，４－トリメチルヘキサメチレンジアミン等の脂肪族ジアミン、１，３－又は１，４－ビス（アミノメチル）シクロヘキサン、ビス（ｐ－アミノシクロヘキシルメタン）等の脂環式ジアミン、ｍ－又はｐ－キシリレンジアミン等の芳香族ジアミン等のジアミンと、アジピン酸、スペリン酸、セバシン酸等の脂肪族ジカルボン酸、シクロヘキサンジカルボン酸等の脂環式ジカルボン酸、テレフタル酸、イソフタル酸等の芳香族ジカルボン酸等のジカルボン酸との重縮合体、及びこれらの共重合体であって、具体的には、ナイロン６、ナイロン９、ナイロン１１、ナイロン１２、ナイロン６６、ナイロン６１０、ナイロン６１１、ナイロン６１２、ナイロン６Ｔ、ナイロン６Ｉ、ナイロンＭＸＤ６があり、中でもナイロン６、ナイロンＭＸＤ６が好ましい。 Examples of the polyamide resin include lactam polymers such as ε-caprolactam and ω-laurolactam, aminocarboxylic acid polymers such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, hexamethylene diamine, and decaprolactam. Aliphatic diamines such as methylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis(p- Diamines such as alicyclic diamines such as aminocyclohexylmethane), aromatic diamines such as m- or p-xylylene diamine, aliphatic dicarboxylic acids such as adipic acid, superric acid, and sebacic acid, and fatty acids such as cyclohexanedicarboxylic acid. Polycondensates with dicarboxylic acids such as cyclic dicarboxylic acids, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and copolymers thereof, specifically nylon 6, nylon 9, nylon 11, There are nylon 12, nylon 66, nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, and nylon MXD6, of which nylon 6 and nylon MXD6 are preferred.
ガスバリア層の厚みとしては特に限定されるものではなく、用途や樹脂種、要求特性等によって適宜決定されるが、通常２～２００μｍ、好ましくは３～１００μｍである。 The thickness of the gas barrier layer is not particularly limited, and is appropriately determined depending on the use, resin type, required characteristics, etc., but is usually 2 to 200 μm, preferably 3 to 100 μm.
他方の被接着層となるポリプロピレン系樹脂層は、本発明の接着性樹脂組成物からなる接着層のみからなるものであってもよく、その他のポリプロピレン系樹脂層との積層構造であってもよい。 The polypropylene resin layer serving as the other adhered layer may consist only of an adhesive layer made of the adhesive resin composition of the present invention, or may have a laminated structure with other polypropylene resin layers. .
その他のポリプロピレン系樹脂層を構成するプロピレン系樹脂とは、プロピレン含量が５０モル％以上のプロピレン系樹脂である。具体的には、プロピレン単独重合体（プロピレンホモポリマー）、プロピレン・エチレンランダム共重合体、プロピレン・ブテンランダム共重合体、プロピレン・エチレン・ヘキセンランダム共重合体、プロピレン・エチレン・オクテンランダム共重合体、プロピレン・ブテン・ヘキセンランダム共重合体、プロピレン・ブテン・オクテンランダム共重合体、プロピレン・ヘキセン・オクテンランダム共重合体、プロピレン・エチレンブロック共重合体等のプロピレン系重合体を挙げることができ、中でもＭＦＲ（２３０℃，２．１６ｋｇ）０．１～３０ｇ／１０分の、プロピレン単独重合体（プロピレンホモポリマー）、プロピレン・エチレンランダム共重合体、プロピレン・ブテンランダム共重合体、プロピレン・エチレン・ヘキセンランダム共重合体、プロピレン・エチレン・オクテンランダム共重合体、プロピレン・ブテン・ヘキセンランダム共重合体、プロピレン・ブテン・オクテンランダム共重合体、特にプロピレン単独重合体（プロピレンホモポリマー）、プロピレン・エチレンランダム共重合体、プロピレン・ブテンランダム共重合体が好ましく用いられる。 The propylene resin constituting the other polypropylene resin layer is a propylene resin having a propylene content of 50 mol% or more. Specifically, propylene homopolymer (propylene homopolymer), propylene/ethylene random copolymer, propylene/butene random copolymer, propylene/ethylene/hexene random copolymer, propylene/ethylene/octene random copolymer , propylene-based polymers such as propylene/butene/hexene random copolymer, propylene/butene/octene random copolymer, propylene/hexene/octene random copolymer, propylene/ethylene block copolymer, etc. Among them, propylene homopolymer (propylene homopolymer), propylene/ethylene random copolymer, propylene/butene random copolymer, propylene/ethylene/ Hexene random copolymer, propylene/ethylene/octene random copolymer, propylene/butene/hexene random copolymer, propylene/butene/octene random copolymer, especially propylene homopolymer (propylene homopolymer), propylene/ethylene Random copolymers and propylene-butene random copolymers are preferably used.
その他のポリプロピレン系樹脂層の厚みとしては特に限定されるものではなく、用途や樹脂種、要求特性等によって適宜決定されるが、通常２０～５，０００μｍ、好ましくは３０～４，０００μｍである。 The thickness of the other polypropylene resin layer is not particularly limited, and is appropriately determined depending on the use, resin type, required characteristics, etc., but is usually 20 to 5,000 μm, preferably 30 to 4,000 μm.
なお、上記のポリプロピレン系樹脂層、及び前述のガスバリア層には、その目的を損なわない範囲において、本発明の接着性樹脂組成物或いはその成分を含んでいてもよく、また、前述の本発明の接着性樹脂組成物が含有していてもよいその他の成分や添加剤を含有していてもよい。 The above-mentioned polypropylene resin layer and the above-mentioned gas barrier layer may contain the adhesive resin composition of the present invention or its components as long as the purpose thereof is not impaired. It may contain other components and additives that may be contained in the adhesive resin composition.
上記の積層体は、更にその他の層が積層されていてもよい。
その他の層としては特に制限されることはない。例えば、ポリカーボネート樹脂；ポリスチレン（ＧＰＰＳ）、ハイインパクトポリスチレン（ＨＩＰＳ）、スチレン－アクリロニトリルグラフト共重合体（ＡＢＳ樹脂）等のスチレン系樹脂等からなる樹脂層や、プロピレン系樹脂以外のオレフィン系重合体、ポリフェニレンエーテル系樹脂、ポリオキシメチレンホモポリマー、ポリオキシメチレンコポリマー等のポリオキシメチレン系樹脂、ポリメチルメタクリレート系樹脂等のアクリル／メタクリル系樹脂等のその他の熱可塑性樹脂層が挙げられる。
The above-mentioned laminate may further have other layers laminated thereon.
Other layers are not particularly limited. For example, polycarbonate resin; a resin layer made of styrene resin such as polystyrene (GPPS), high impact polystyrene (HIPS), styrene-acrylonitrile graft copolymer (ABS resin), olefin polymer other than propylene resin, Examples of other thermoplastic resin layers include polyoxymethylene resins such as polyphenylene ether resins, polyoxymethylene homopolymers and polyoxymethylene copolymers, and acrylic/methacrylic resins such as polymethyl methacrylate resins.
本発明の接着性樹脂組成物を用いた積層体が多層シートである場合、その総厚みは２００～５，０００μｍであることが好ましい。また、本発明の接着性樹脂組成物を用いた積層体が多層フィルムである場合、その総厚みは３０～２００μｍであることが好ましい。 When the laminate using the adhesive resin composition of the present invention is a multilayer sheet, the total thickness thereof is preferably 200 to 5,000 μm. Further, when the laminate using the adhesive resin composition of the present invention is a multilayer film, the total thickness thereof is preferably 30 to 200 μm.
上記の積層体を製造する方法としては、従来より公知の種々の手法を採用することができる。例えば、押出機で溶融させた個々の溶融樹脂を多層ダイスに供給し、ダイスの中で積層する共押出法によるインフレーション成形、Ｔ－ダイ成形によるフィルム成形もしくはシート成形を行う方法が挙げられる。更に、単体又は他樹脂との共押出しにより得られた本発明の接着性樹脂組成物フィルムと被着材フィルムとの熱ラミネート、ヒートシール等による積層法を用いることもできる。 As a method for manufacturing the above-mentioned laminate, various conventionally known methods can be employed. Examples include inflation molding by a coextrusion method in which individual molten resins melted in an extruder are supplied to a multilayer die and laminated in the die, and film molding or sheet molding by T-die molding. Furthermore, it is also possible to use a lamination method such as thermal lamination, heat sealing, etc. of the adhesive resin composition film of the present invention obtained by coextrusion alone or with other resins and an adherend film.
以下、共押出法について詳細に説明する。
上記の各層を構成する組成物の原料を予め溶融混練若しくはドライブレンドによって調製し、単軸、２軸などの押出成形法により押出し、フィードブロック、マルチマニフォールドダイなどで合流し積層構造にし、所定の形状のダイから押出して、冷却後、フィルム形状の場合は巻き取り機で巻き取る。共押出成形法における押出し温度は、ガスバリア層の樹脂の特性によって適時選択されるが、一般的に３００℃以下に抑制するのが好ましい。フィルムの引き取り速度（ｍ／ｈ）は所望の厚みに応じて適時設定し、押出機の基材原料の吐出量（ｇ／ｈ）は、用いる原料の種類、目的とするフィルムの各層厚み等により適宜選択することが好ましい。冷却方法は公知の方法を採用することができるが、例として、ロール上へのキャスト冷却、ないしはエアナイフによる冷却、丸ダイスから押出してブローアップによる冷却の方法により冷却して、積層体を得る。
The coextrusion method will be explained in detail below.
The raw materials for the compositions constituting each of the above layers are prepared in advance by melt-kneading or dry blending, extruded using a single-screw or twin-screw extrusion method, and then combined in a feed block, multi-manifold die, etc. to form a laminated structure. It is extruded from a shaped die, and after cooling, it is wound up with a winding machine if it is in a film shape. The extrusion temperature in the coextrusion molding method is appropriately selected depending on the characteristics of the resin of the gas barrier layer, but it is generally preferable to suppress it to 300°C or less. The film take-up speed (m/h) is set appropriately according to the desired thickness, and the discharge rate (g/h) of the base material of the extruder is determined depending on the type of raw material used, the intended thickness of each layer of the film, etc. It is preferable to select it appropriately. As the cooling method, a known method can be used, but for example, a laminate is obtained by cooling by casting onto a roll, cooling with an air knife, extruding from a round die and cooling by blow-up.
上記のようにして製造された積層体に対して延伸や、熱成形等の二次成形を施すこともできる。 The laminate produced as described above can also be subjected to stretching or secondary forming such as thermoforming.
本発明の接着性樹脂組成物は、ガスバリア性の樹脂に対して優れた接着強度特性を示す。このため、このような本発明の接着性樹脂組成物を接着層とする本発明の積層体は、優れた接着強度特性を示し、更に強度、耐熱性及びガスバリア性等にも優れたものとすることができる。従って、この積層体は、ハム等の畜肉包装フィルム、ゼリーカップや米飯トレーなどの一般食品包装用材料に好適に使用することができる。 The adhesive resin composition of the present invention exhibits excellent adhesive strength characteristics with respect to gas barrier resins. Therefore, the laminate of the present invention having such an adhesive resin composition of the present invention as an adhesive layer exhibits excellent adhesive strength characteristics, and further has excellent strength, heat resistance, gas barrier properties, etc. be able to. Therefore, this laminate can be suitably used for packaging films for meat such as ham, and general food packaging materials such as jelly cups and rice trays.
［ポリオレフィン系樹脂用改質剤］
本発明の接着性樹脂組成物は、ポリオレフィン系樹脂の改質剤として好適に使用できる。中でもポリオレフィン系樹脂、特にポリプロピレン系樹脂の分散性を高める分散剤として好適に使用できる。特に、ポリオレフィン系樹脂中に充填剤、例えば、本発明の成分（Ｂ）のような無機化合物やタルクやマイカなどの天然鉱物やグラスファイバー等の無機充填材や、ウッドチップ等の有機充填材、ＥＶＯＨやナイロンのような高極性ポリマーが含まれている場合に、これらの分散性を高める改質剤として有用である。
この場合、本発明の接着性樹脂組成物に含まれる成分（Ｃ）としては、ホモポリプロピレンが好適である。
[Modifier for polyolefin resin]
The adhesive resin composition of the present invention can be suitably used as a modifier for polyolefin resins. Among them, it can be suitably used as a dispersant to improve the dispersibility of polyolefin resins, especially polypropylene resins. In particular, fillers such as inorganic compounds such as component (B) of the present invention, natural minerals such as talc and mica, inorganic fillers such as glass fiber, organic fillers such as wood chips, etc. When highly polar polymers such as EVOH and nylon are contained, it is useful as a modifier to improve their dispersibility.
In this case, homopolypropylene is suitable as component (C) contained in the adhesive resin composition of the present invention.
以下、実施例及び比較例を挙げて本発明の内容を更に具体的に説明するが、本発明はこれらの実施例により何ら限定されるものではない。なお、以下の実施例における各種の製造条件や評価結果の値は、本発明の実施態様における上限又は下限の好ましい値としての意味をもつものであり、好ましい範囲は前記した上限又は下限の値と、下記実施例の値又は実施例同士の値との組み合わせで規定される範囲であってもよい。 EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples in any way. In addition, the values of various manufacturing conditions and evaluation results in the following examples have the meaning as preferable upper or lower limits in the embodiments of the present invention, and the preferable ranges are different from the above-mentioned upper or lower limits. , it may be a range defined by the values of the following examples or a combination of values of the examples.
［原材料］
以下の諸例では次の原材料を使用した。
[raw materials]
The following raw materials were used in the examples below.
＜成分（Ａ）：プロピレン・α－オレフィン共重合体＞
・Ａ－１：三井化学社製 タフマー（登録商標）ＸＭ－７０７０（プロピレン・１－ブテン共重合体、ＭＦＲ（２３０℃、荷重２．１６ｋｇ）：７ｇ／１０分、密度：０．８６０ｇ／ｃｍ３）
・Ａ－２：三井化学社製 タフマー（登録商標）Ｐ０２８０（エチレン・プロピレン共重合体、ＭＦＲ（２３０℃、荷重２．１６ｋｇ）：５．４ｇ／１０分、密度：０．８７０ｇ／ｃｍ３）
<Component (A): Propylene/α-olefin copolymer>
・A-1: Mitsui Chemicals Tafmer (registered trademark) 3 )
・A-2: Mitsui Chemicals Tafmer (registered trademark) P0280 (ethylene-propylene copolymer, MFR (230°C, load 2.16 kg): 5.4 g/10 minutes, density: 0.870 g/cm 3 )
＜成分（Ｂ）：無機化合物＞
・Ｂ－１：ジルコニウムフェライト 大阪ガスケミカル（株）製 セブントールＮ－ＰＣ５０（平均粒子径：３μｍ）
・Ｂ－２：ジルコニウムフェライト 大阪ガスケミカル（株）製 セブントールＯＭ－１（平均粒子径：２μｍ）
・Ｂ－３：ゼオライト 水澤化学（株）製 ミズカライザーＤＳ（Ａ型ナトリウムゼオライト、平均粒子径：２μｍ）
<Component (B): Inorganic compound>
・B-1: Zirconium ferrite Seventall N-PC50 manufactured by Osaka Gas Chemical Co., Ltd. (average particle size: 3 μm)
・B-2: Zirconium ferrite Seventor OM-1 manufactured by Osaka Gas Chemical Co., Ltd. (average particle diameter: 2 μm)
・B-3: Zeolite Mizusawa Chemical Co., Ltd. Mizukalyzer DS (A-type sodium zeolite, average particle size: 2 μm)
＜成分（Ｃ）：成分（Ａ）以外のポリプロピレン系樹脂＞
・Ｃ－１：ホモポリプロピレン 市販品（ＭＦＲ（２３０℃、荷重２．１６ｋｇ）：２ｇ／１０分）
・Ｃ－２：ホモポリプロピレン 市販品（ＭＦＲ（２３０℃、荷重２．１６ｋｇ）：０．５ｇ／１０分）
・Ｃ－３：ホモポリプロピレン 市販品（ＭＦＲ（２３０℃、荷重２．１６ｋｇ）：１１ｇ／１０分）
<Component (C): Polypropylene resin other than component (A)>
・C-1: Homopolypropylene commercially available product (MFR (230°C, load 2.16kg): 2g/10 minutes)
・C-2: Homopolypropylene commercially available product (MFR (230°C, load 2.16kg): 0.5g/10 minutes)
・C-3: Homopolypropylene commercially available product (MFR (230°C, load 2.16kg): 11g/10 minutes)
＜成分（Ｄ）：ラジカル発生剤＞
有機過酸化物 日本油脂（株）製 パーヘキサ２５Ｂ
<Component (D): Radical generator>
Organic peroxide Perhexa 25B manufactured by Nippon Oil & Fats Co., Ltd.
＜成分（Ｅ）：不飽和カルボン酸成分＞
無水マレイン酸 市販品
<Component (E): Unsaturated carboxylic acid component>
Maleic anhydride commercially available product
［接着性樹脂組成物の作製］
上記に記載した原材料を、それぞれ表－１及び表－２に記載の配合量にてドライブレンドして混合し、２軸押出機（日本製鋼所社製、ＴＥＸ２５αIII、Ｄ＝２５ｍｍφ、Ｌ／Ｄ＝５２．５）を用い、設定温度２３０℃、スクリュー回転数４００ｒｐｍ、押出量２０ｋｇ／ｈで溶融混練し、ストランドカットによりペレット状の接着性樹脂組成物を得た。
[Preparation of adhesive resin composition]
The raw materials listed above were dry blended and mixed in the amounts listed in Tables 1 and 2, respectively, using a twin-screw extruder (manufactured by Japan Steel Works, TEX25αIII, D=25mmφ, L/D= 52.5) at a set temperature of 230° C., a screw rotation speed of 400 rpm, and an extrusion rate of 20 kg/h, followed by strand cutting to obtain a pellet-shaped adhesive resin composition.
［評価方法］
得られた接着性樹脂組成物について、以下の方法で評価を行った。
[Evaluation method]
The obtained adhesive resin composition was evaluated by the following method.
＜フィラー分散性＞
上記で得られた接着性樹脂組成物のうち、成分（Ｂ）を用いたものについて、厚み０．１ｍｍの単層フィルムを以下の製造方法により作製した。
（株）ＧＳＩクレオス社製単層Ｔダイフィルム成形機（押出機：５０ｍｍφ、リップ開度：０．３ｍｍ）を用いて上記接着性樹脂組成物の厚み０．１ｍｍ単層フィルムを得た。成形温度は２３０℃、成形速度は５ｍ／ｍｉｎとした。
上記で得られた単層フィルムについて、目視により外観を観察し、凝集物が無く平滑なものは◎、ほぼ平滑なものは○、凝集物があり平滑でないものは×とした。
<Filler dispersibility>
Among the adhesive resin compositions obtained above, a single layer film having a thickness of 0.1 mm was produced using the component (B) by the following manufacturing method.
A 0.1 mm thick single layer film of the adhesive resin composition was obtained using a single layer T-die film molding machine (extruder: 50 mmφ, lip opening: 0.3 mm) manufactured by GSI Creos Co., Ltd. The molding temperature was 230°C, and the molding speed was 5 m/min.
The appearance of the single-layer film obtained above was visually observed, and those that were smooth without aggregates were rated ◎, those that were almost smooth were rated ○, and those that were not smooth and had aggregates were rated ×.
＜接着性＞
上記で得られた接着性樹脂組成物を接着層とし、以下の製造方法により多層フィルムを得た。
プラ技研社製多層押出フィルム成形機（各層の押出機：４０ｍｍφ，４５０ｍｍ幅マルチマニフォールドダイス、リップ開度：０．５ｍｍ）を用いて、３種５層多層フィルムを得た。層構成は、ポリプロピレン層／接着層／ＥＶＯＨ層／接着層／ポリプロピレン層とし、各層厚みを３５μｍ／１０μｍ／１０μｍ／１０μｍ／３５μｍとし、多層フィルムの全厚みを１００μｍとした。成形温度は２８０℃、成形速度は２０ｍ／分とし、冷却は、冷却ロール（温度３０℃）を用いた後、エアナイフ冷却を行うことにより実施した。なお、上記のポリプロピレン層、ＥＶＯＨ層には以下のものを用いた。
ポリプロピレン層：日本ポリプロ社製 ポリプロピレン系樹脂
ノバテック（登録商標）ＰＰ ＦＷ４Ｂ
ＥＶＯＨ：クラレ社製 クラレエバール Ｆ１０１Ａ
上記で得られた多層フィルムを押出方向（ＭＤ方向）に幅１５ｍｍの短冊状に切り出して試験片とし、２３℃雰囲気下、速度３００ｍｍ／ｍｉｎにて１８０°ピール剥離試験を行い、接着強度を測定し、下記基準で評価した。ここで、接着強度は、ＥＶＯＨ層と接着層との界面における接着強度である。
○：５Ｎ／１５ｍｍ以上
×：５Ｎ／１５ｍｍ未満
<Adhesiveness>
Using the adhesive resin composition obtained above as an adhesive layer, a multilayer film was obtained by the following manufacturing method.
Three types of 5-layer multilayer films were obtained using a multilayer extrusion film forming machine manufactured by Plagiken Co., Ltd. (extruder for each layer: 40 mmφ, 450 mm width multi-manifold die, lip opening: 0.5 mm). The layer structure was polypropylene layer/adhesive layer/EVOH layer/adhesive layer/polypropylene layer, and the thickness of each layer was 35 μm/10 μm/10 μm/10 μm/35 μm, and the total thickness of the multilayer film was 100 μm. The molding temperature was 280° C., the molding speed was 20 m/min, and cooling was performed by using a cooling roll (temperature 30° C.) followed by air knife cooling. The following materials were used for the above polypropylene layer and EVOH layer.
Polypropylene layer: Polypropylene resin manufactured by Nippon Polypro Co., Ltd.
Novatec (registered trademark) PP FW4B
EVOH: Kuraray Eval F101A manufactured by Kuraray Co., Ltd.
The multilayer film obtained above was cut into test pieces with a width of 15 mm in the extrusion direction (MD direction), and a 180° peel test was performed at a speed of 300 mm/min in an atmosphere of 23°C to measure the adhesive strength. and evaluated based on the following criteria. Here, the adhesive strength is the adhesive strength at the interface between the EVOH layer and the adhesive layer.
○: 5N/15mm or more ×: Less than 5N/15mm
＜臭気＞
接着性樹脂組成物のペレットの臭気を以下の方法にて評価した。
各ペレット８０ｇを５００ｍＬの共栓付き三角フラスコに入れ、栓をして８０℃にコントロールされたギアオーブンに入れて２時間加熱した。加熱後、三角フラスコを取り出し、１０分以内に臭いを嗅ぎ、臭気の強度を０～５の７段階（０：無臭、０．５：ほぼ無臭、１：やっと感じる、２：感じられる、３：かなり臭う、４：強く臭う、５：激しく臭う）で評価した。評価は５人で行い、評価結果を平均してサンプルの臭気とした。
<Odor>
The odor of the adhesive resin composition pellets was evaluated by the following method.
80 g of each pellet was placed in a 500 mL Erlenmeyer flask with a stopper, and the flask was sealed and heated in a gear oven controlled at 80° C. for 2 hours. After heating, take out the Erlenmeyer flask, smell it within 10 minutes, and rate the odor intensity on a scale of 7 from 0 to 5 (0: no odor, 0.5: almost no odor, 1: barely felt, 2: can be felt, 3: Evaluation was made on a scale of ``smells quite a bit,'' 4: ``smells strongly,'' and 5: ``smells strongly.'' The evaluation was performed by five people, and the evaluation results were averaged to determine the odor of the sample.
表－１及び表－２に各実施例及び比較例の結果を示す。
なお、表－１及び表－２には、前述の方法で測定した接着性樹脂組成物のＭＦＲ（１８０℃，荷重２．１６ｋｇ、ＪＩＳ Ｋ ７２１０準拠）と、グラフト率を併記した。
Tables 1 and 2 show the results of each example and comparative example.
Note that Tables 1 and 2 also list the MFR (180° C., load 2.16 kg, according to JIS K 7210) of the adhesive resin composition measured by the method described above, and the graft ratio.
表１及び表－２から明らかなように、本発明の接着性樹脂組成物を用いた実施例１～９は、成分（Ｂ）の無機化合物の分散性が良好であり、臭気テストでも良い結果を示した。特に無機化合物を２種類併用した実施例８，９は、臭気が十分に低減されている。
これに対して、表－２に示されるように、変性された成分（Ｃ）のみを用いた比較例１は、臭気が強い結果であった。
成分（Ｂ）を含まない樹脂組成物の比較例２および比較例３も、臭気が強い結果であった。
成分（Ａ）を含まない樹脂組成物の比較例４および比較例５もまた臭気が強かった。
比較例６では、成分（Ｂ）が過剰に存在することで、異物が発生し、外観の悪いものとなった。
比較例７では、未変性の樹脂を使用したため、臭気の問題はないが極性材料への密着性に乏しい結果となった。
As is clear from Table 1 and Table 2, Examples 1 to 9 using the adhesive resin composition of the present invention had good dispersibility of the inorganic compound of component (B) and good results in the odor test. showed that. In particular, in Examples 8 and 9 in which two types of inorganic compounds were used in combination, odor was sufficiently reduced.
On the other hand, as shown in Table 2, Comparative Example 1 using only the modified component (C) had a strong odor.
Comparative Examples 2 and 3, which were resin compositions that did not contain component (B), also had strong odor.
Comparative Examples 4 and 5, which were resin compositions that did not contain component (A), also had a strong odor.
In Comparative Example 6, the excessive presence of component (B) resulted in the generation of foreign matter, resulting in a poor appearance.
In Comparative Example 7, since an unmodified resin was used, there was no odor problem, but the result was poor adhesion to polar materials.
Claims (5)
成分（Ａ）：プロピレン・α－オレフィン共重合体
成分（Ｂ）：ゼオライト及び／又はジルコニウムフェライトである無機化合物
成分（Ｃ）：成分（Ａ）以外のポリプロピレン系樹脂 Contains the following components (A) to (C), the component (A) and the component (C) are graft-modified with an α,β-ethylenically unsaturated carboxylic acid and/or a derivative thereof, and the component (A) The content of component (A) is 10 to 30 mass %, the content of component (B) is 2 to 5 mass %, and the content of component (C) is An adhesive resin composition having a melt flow rate (180° C., load 2.16 kg, JIS K7210 compliant) of 20 to 130 g/10 minutes. Component (A): propylene/α-olefin. Polymer Component (B): Inorganic compound that is zeolite and/or zirconium ferrite Component (C): Polypropylene resin other than component (A)
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