JPWO2020040281A1 - Resin composition and multi-layer structure using it - Google Patents
Resin composition and multi-layer structure using it Download PDFInfo
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- JPWO2020040281A1 JPWO2020040281A1 JP2020538480A JP2020538480A JPWO2020040281A1 JP WO2020040281 A1 JPWO2020040281 A1 JP WO2020040281A1 JP 2020538480 A JP2020538480 A JP 2020538480A JP 2020538480 A JP2020538480 A JP 2020538480A JP WO2020040281 A1 JPWO2020040281 A1 JP WO2020040281A1
- Authority
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- Prior art keywords
- resin composition
- acid
- ethylene
- multilayer structure
- modified polypropylene
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 121
- -1 polypropylene Polymers 0.000 claims abstract description 108
- 239000004743 Polypropylene Substances 0.000 claims abstract description 107
- 229920001155 polypropylene Polymers 0.000 claims abstract description 106
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 83
- 239000002253 acid Substances 0.000 claims abstract description 27
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 230000004888 barrier function Effects 0.000 claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005977 Ethylene Substances 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 238000007127 saponification reaction Methods 0.000 claims abstract description 12
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 29
- 238000011084 recovery Methods 0.000 claims description 22
- 238000000465 moulding Methods 0.000 claims description 18
- 150000002989 phenols Chemical class 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 230000035699 permeability Effects 0.000 claims description 9
- 239000005022 packaging material Substances 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 73
- 239000010410 layer Substances 0.000 description 73
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 70
- 239000008188 pellet Substances 0.000 description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 238000004898 kneading Methods 0.000 description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- 239000004840 adhesive resin Substances 0.000 description 10
- 229920006223 adhesive resin Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001879 gelation Methods 0.000 description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 7
- 239000011654 magnesium acetate Substances 0.000 description 7
- 229940069446 magnesium acetate Drugs 0.000 description 7
- 235000011285 magnesium acetate Nutrition 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010421 standard material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
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- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
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- 229920005673 polypropylene based resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000552 rheumatic effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Abstract
エチレン−ビニルアルコール共重合体（Ａ）、酸変性ポリプロピレン（Ｂ）及び多価金属イオン（Ｃ）を含有する樹脂組成物であって、（Ａ）のエチレン単位含有量が１５〜６０モル％、けん化度が８５モル％以上であり、（Ｂ）の酸価が２〜７０ｍｇＫＯＨ／ｇ、ＭＦＲ（１９０℃、２．１６ｋｇ荷重下）が４〜１０００ｇ/１０ｍｉｎ、融点が１３０℃以上であり、（Ｃ）がマグネシウムイオン、カルシウムイオン及び亜鉛イオンからなる群から選択される少なくとも１種であり、（Ａ）に対する（Ｂ）の質量比［（Ｂ）／（Ａ）］が０．８／９９．２〜１０／９０であり、全樹脂成分に対する（Ａ）及び（Ｂ）の合計含有量が９０質量％以上であり、かつ（Ｃ）の含有量が６０〜３００ｐｐｍである、樹脂組成物とする。このような樹脂組成物をガスバリア層として有する多層構造体はガスバリア性及び外観に優れるとともに、当該樹脂組成物は長期間の連続溶融成形を行うことが可能であり、なおかつ再利用しやすい。
A resin composition containing an ethylene-vinyl alcohol copolymer (A), an acid-modified polypropylene (B) and a polyvalent metal ion (C), wherein the ethylene unit content of (A) is 15 to 60 mol%. The degree of saponification is 85 mol% or more, the acid value of (B) is 2 to 70 mgKOH / g, the MFR (190 ° C., under a 2.16 kg load) is 4 to 1000 g / 10 min, and the melting point is 130 ° C. or higher. C) is at least one selected from the group consisting of magnesium ion, calcium ion and zinc ion, and the mass ratio of (B) to (A) [(B) / (A)] is 0.8 / 99. The resin composition is 2 to 10/90, the total content of (A) and (B) with respect to the total resin components is 90% by mass or more, and the content of (C) is 60 to 300 ppm. .. A multilayer structure having such a resin composition as a gas barrier layer is excellent in gas barrier properties and appearance, and the resin composition can be continuously melt-molded for a long period of time and is easily reused.
Description
本発明は、エチレン−ビニルアルコール共重合体を含有する樹脂組成物及びそれを用いた多層構造体、また、該多層構造体の回収方法及び該多層構造体の回収物を含む回収組成物に関する。 The present invention relates to a resin composition containing an ethylene-vinyl alcohol copolymer, a multilayer structure using the same, a method for recovering the multilayer structure, and a recovery composition containing the recovered product of the multilayer structure.
従来、ポリオレフィンに代表される熱可塑性樹脂からなる層と、バリア性に優れるエチレン−ビニルアルコール共重合体（以下、ＥＶＯＨと略称することがある）からなる層とを含む多層構造体は、そのバリア性を活かして食品包装容器や燃料容器などの各種用途に用いられている。このような多層構造体はフィルム、シート、カップ、トレイ、ボトル、タンクなどの各種成形品として用いられる。このとき、上記各種成形品を得る際に発生する端部や不良品等を回収し、溶融成形して熱可塑性樹脂層とＥＶＯＨ層を含む多層構造体の少なくとも１層として再使用する場合がある。このような回収技術は、廃棄物削減や経済性の点で有用であり、広く採用されている。 Conventionally, a multilayer structure including a layer made of a thermoplastic resin typified by polyolefin and a layer made of an ethylene-vinyl alcohol copolymer having excellent barrier properties (hereinafter, may be abbreviated as EVOH) is a barrier thereof. It is used in various applications such as food packaging containers and fuel containers by taking advantage of its properties. Such a multilayer structure is used as various molded products such as films, sheets, cups, trays, bottles, and tanks. At this time, there are cases where the end portions, defective products, etc. generated when the various molded products are obtained are recovered, melt-molded, and reused as at least one layer of a multilayer structure including a thermoplastic resin layer and an EVOH layer. .. Such recovery techniques are useful in terms of waste reduction and economy, and are widely adopted.
しかしながら、熱可塑性樹脂層とＥＶＯＨ層を含む多層構造体の回収物を再使用する際には、溶融成形時の熱劣化によりゲル化を起こしたり、劣化物が押出機内のスクリュー等に付着したりして、長期間の連続溶融成形を行うことが困難な場合があった。さらに、このような劣化物が成形品中に混入することにより、得られる成形品においてフィッシュアイが発生するという問題もあった。また、熱可塑性樹脂とＥＶＯＨとの相溶性が悪いため、成形品の外観に濁りやムラが生じたり、機械物性が低下したりする問題もあった。また、回収された樹脂が成形品の最外層に再使用される場合には、溶融成形時にダイに目ヤニと称される相分離異物が付着したり、成形品の表面にストリーク（縞模様）が発生したりする場合もあった。 However, when the recovered product of the multilayer structure including the thermoplastic resin layer and the EVOH layer is reused, gelation may occur due to thermal deterioration during melt molding, or the deteriorated product may adhere to screws or the like in the extruder. Therefore, it may be difficult to perform continuous melt molding for a long period of time. Further, there is also a problem that fish eyes are generated in the obtained molded product when such a deteriorated product is mixed in the molded product. Further, since the compatibility between the thermoplastic resin and EVOH is poor, there is a problem that the appearance of the molded product becomes turbid or uneven, and the mechanical properties are deteriorated. In addition, when the recovered resin is reused for the outermost layer of the molded product, phase-separated foreign matter called rheumatism adheres to the die during melt molding, or streaks (striped patterns) appear on the surface of the molded product. In some cases.
このようなゲル化や相溶性を改善させる方法として、回収物に対して樹脂組成物等からなる回収助剤を添加する方法が知られている。特許文献１には、ＥＶＯＨを含む粉砕物に、オレフィン−カルボン酸ビニルエステル共重合体及び／又はそのケン化物、脂肪酸金属塩、及び／又は金属化合物を含有する樹脂組成物を添加する方法が記載されている。また、特許文献２には、ＥＶＯＨを含む粉砕物に配合する樹脂組成物として、酸グラフト変性ポリオレフィン系樹脂、脂肪酸金属塩及び／又は金属化合物を含有する樹脂組成物が記載されている。 As a method for improving such gelation and compatibility, a method of adding a recovery aid made of a resin composition or the like to the recovered product is known. Patent Document 1 describes a method of adding a resin composition containing an olefin-carboxylic acid vinyl ester copolymer and / or a saponified product thereof, a fatty acid metal salt, and / or a metal compound to a ground product containing EVOH. Has been done. Further, Patent Document 2 describes a resin composition containing an acid graft-modified polyolefin resin, a fatty acid metal salt and / or a metal compound as a resin composition to be blended in a pulverized product containing EVOH.
しかしながら、回収物に回収助剤を添加するためには、工程数を増やしたり、設備を追加したりする必要があるためコスト高となる場合があり、その改善が求められていた。 However, in order to add the recovery aid to the recovered product, it is necessary to increase the number of steps or add equipment, which may increase the cost, and improvement thereof has been required.
本発明は上記課題を解決するためになされたものであり、ガスバリア性及び外観に優れる多層構造体が得られるとともに長期間の連続溶融成形を行うことが可能であり、なおかつ再使用しやすい樹脂組成物を提供する。 The present invention has been made to solve the above problems, and a resin composition capable of obtaining a multilayer structure having excellent gas barrier properties and appearance, being capable of continuous melt molding for a long period of time, and being easy to reuse. Provide things.
上記課題は、ＥＶＯＨ（Ａ）、酸変性ポリプロピレン（Ｂ）及び多価金属イオン（Ｃ）を含有する樹脂組成物であって、ＥＶＯＨ（Ａ）のエチレン単位含有量が１５〜６０モル％、けん化度が８５モル％以上であり、酸変性ポリプロピレン（Ｂ）の酸価が２〜７０ｍｇＫＯＨ／ｇ、ＭＦＲ（１９０℃、２．１６ｋｇ荷重下）が４〜１０００ｇ/１０ｍｉｎ、融点が１３０℃以上であり、多価金属イオン（Ｃ）がマグネシウムイオン、カルシウムイオン及び亜鉛イオンからなる群から選択される少なくとも１種であり、ＥＶＯＨ（Ａ）に対する酸変性ポリプロピレン（Ｂ）の質量比［（Ｂ）／（Ａ）］が０．８／９９．２〜１０／９０であり、全樹脂成分に対するＥＶＯＨ（Ａ）及び酸変性ポリプロピレン（Ｂ）の合計含有量が９０質量％以上であり、かつ多価金属イオン（Ｃ）の含有量が６０〜３００ｐｐｍである、樹脂組成物を提供することによって解決される。 The above-mentioned problem is a resin composition containing EVOH (A), acid-modified polypropylene (B) and polyvalent metal ion (C), in which the ethylene unit content of EVOH (A) is 15 to 60 mol% and saponification. The degree is 85 mol% or more, the acid value of the acid-modified polypropylene (B) is 2 to 70 mgKOH / g, the MFR (190 ° C., under a 2.16 kg load) is 4 to 1000 g / 10 min, and the melting point is 130 ° C. or higher. , Polyvalent metal ion (C) is at least one selected from the group consisting of magnesium ion, calcium ion and zinc ion, and the mass ratio of acid-modified polypropylene (B) to EVOH (A) [(B) / ( A)] is 0.8 / 99.2 to 10/90, the total content of EVOH (A) and acid-modified polypropylene (B) with respect to all resin components is 90% by mass or more, and polyvalent metal ions. It is solved by providing a resin composition having a content of (C) of 60 to 300 ppm.
このとき、酸変性ポリプロピレン（Ｂ）の酸価が４〜３０ｍｇＫＯＨ／ｇ、ＭＦＲ（１９０℃、２．１６ｋｇ荷重下）が５０〜６００ｇ/１０ｍｉｎであることが好ましい。ＥＶＯＨ（Ａ）に対する酸変性ポリプロピレン系樹脂（Ｂ）の重量平均分子量比［（Ｂ）／（Ａ）］が０．９〜５であることも好ましい。本発明の樹脂組成物が多価金属イオン（Ｃ）を炭素数１〜３のカルボン酸塩として含有することも好ましい。本発明の樹脂組成物が、ＥＶＯＨ（Ａ）と酸変性ポリプロピレン（Ｂ）の合計１００質量部に対して、エステル結合又はアミド結合を有するヒンダードフェノール系化合物（Ｄ）を０．０５〜１０質量部さらに含有することも好ましい。ＥＶＯＨ（Ａ）に対する本発明の樹脂組成物のＭＦＲ（１９０℃、２．１６ｋｇ荷重下）の比［樹脂組成物／ＥＶＯＨ（Ａ）］が０．６以上であることも好ましい。ＥＶＯＨ（Ａ）に対する本発明の樹脂組成物の酸素透過度（２０℃、６５％ＲＨ条件下）の比［樹脂組成物／ＥＶＯＨ（Ａ）］が２以下であることも好ましい。本発明の樹脂組成物を溶融成形して得られる厚み２０μｍのフィルムのヘイズが５％以下であることも好ましい。 At this time, it is preferable that the acid value of the acid-modified polypropylene (B) is 4 to 30 mgKOH / g and the MFR (190 ° C., under a load of 2.16 kg) is 50 to 600 g / 10 min. It is also preferable that the weight average molecular weight ratio [(B) / (A)] of the acid-modified polypropylene-based resin (B) to EVOH (A) is 0.9 to 5. It is also preferable that the resin composition of the present invention contains a polyvalent metal ion (C) as a carboxylate having 1 to 3 carbon atoms. The resin composition of the present invention contains 0.05 to 10 parts by mass of a hindered phenolic compound (D) having an ester bond or an amide bond with respect to a total of 100 parts by mass of EVOH (A) and acid-modified polypropylene (B). It is also preferable to further contain the part. It is also preferable that the ratio of the MFR (190 ° C., under a load of 2.16 kg) of the resin composition of the present invention to EVOH (A) [resin composition / EVOH (A)] is 0.6 or more. It is also preferable that the ratio of the oxygen permeability (under 20 ° C. and 65% RH conditions) of the resin composition of the present invention to EVOH (A) [resin composition / EVOH (A)] is 2 or less. It is also preferable that the haze of the film having a thickness of 20 μm obtained by melt-molding the resin composition of the present invention is 5% or less.
本発明の樹脂組成物からなるバリア層を有する多層構造体が本発明の好適な実施態様である。本発明の多層構造体がポリプロピレンからなる最外層及び最内層をさらに有することが好ましい。また、本発明の多層構造体の回収物を含む回収層を有する多層構造体も本発明の好適な実施態様である。そして、これらの多層構造体を有する包装材料が本発明のより好適な実施態様である。 A multilayer structure having a barrier layer made of the resin composition of the present invention is a preferred embodiment of the present invention. It is preferred that the multilayer structure of the present invention further has an outermost layer and an innermost layer made of polypropylene. A multilayer structure having a recovery layer containing a recovered product of the multilayer structure of the present invention is also a preferred embodiment of the present invention. A packaging material having these multilayer structures is a more preferred embodiment of the present invention.
上記課題は、本発明の多層構造体の回収物を含む、回収組成物を提供することによっても解決される。また、上記課題は、本発明の多層構造体を粉砕した後に溶融成形する、多層構造体の回収方法を提供することによっても解決される。 The above problems are also solved by providing a recovered composition containing a recovered product of the multilayer structure of the present invention. Further, the above problem is also solved by providing a method for recovering a multilayer structure in which the multilayer structure of the present invention is crushed and then melt-molded.
本発明の樹脂組成物をガスバリア層として有する多層構造体は、ガスバリア性及び外観に優れる。また、本発明の樹脂組成物は粘度安定性が高いため、長期間の連続溶融成形を行うことが可能である。さらに、本発明の多層構造体の回収物を溶融成形する際に、樹脂の劣化（ゲル化）や相溶性不良による諸問題の発生が抑制される。したがって、回収助剤を用いることなく、前記回収物を多層構造体の少なくとも１層として再使用できるため、多層構造体の製造工程が簡略化され、製造コストも低減する。 The multilayer structure having the resin composition of the present invention as a gas barrier layer is excellent in gas barrier property and appearance. Further, since the resin composition of the present invention has high viscosity stability, it is possible to carry out continuous melt molding for a long period of time. Further, when the recovered product of the multilayer structure of the present invention is melt-molded, various problems due to deterioration (gelation) of the resin and poor compatibility are suppressed. Therefore, since the recovered product can be reused as at least one layer of the multilayer structure without using a recovery aid, the manufacturing process of the multilayer structure is simplified and the manufacturing cost is also reduced.
本発明の樹脂組成物は、ＥＶＯＨ（Ａ）、酸変性ポリプロピレン（Ｂ）及び多価金属イオン（Ｃ）を含有するものであって、ＥＶＯＨ（Ａ）のエチレン単位含有量が１５〜６０モル％、けん化度が８５モル％以上であり、酸変性ポリプロピレン（Ｂ）の酸価が２〜７０ｍｇＫＯＨ／ｇ、ＭＦＲ（１９０℃、２．１６ｋｇ荷重下）が４〜１０００ｇ/１０ｍｉｎ、融点が１３０℃以上であり、多価金属イオン（Ｃ）がマグネシウムイオン、カルシウムイオン及び亜鉛イオンからなる群から選択される少なくとも１種であり、ＥＶＯＨ（Ａ）に対する酸変性ポリプロピレン（Ｂ）の質量比［（Ｂ）／（Ａ）］が０．８／９９．２〜１０／９０であり、全樹脂成分に対するＥＶＯＨ（Ａ）及び酸変性ポリプロピレン（Ｂ）の合計含有量が９０質量％以上であり、かつ多価金属イオン（Ｃ）の含有量が６０〜３００ｐｐｍであるものである。 The resin composition of the present invention contains EVOH (A), acid-modified polypropylene (B) and polyvalent metal ion (C), and the ethylene unit content of EVOH (A) is 15 to 60 mol%. The degree of saponification is 85 mol% or more, the acid value of acid-modified polypropylene (B) is 2 to 70 mgKOH / g, MFR (190 ° C., under a 2.16 kg load) is 4 to 1000 g / 10 min, and the melting point is 130 ° C. or higher. The polyvalent metal ion (C) is at least one selected from the group consisting of magnesium ion, calcium ion and zinc ion, and the mass ratio of acid-modified polypropylene (B) to EVOH (A) [(B). / (A)] is 0.8 / 99.2 to 10/90, and the total content of EVOH (A) and acid-modified polypropylene (B) with respect to all resin components is 90% by mass or more, and is multivalent. The content of the metal ion (C) is 60 to 300 ppm.
当該樹脂組成物は、ガスバリア性や外観に優れるうえに、粘度安定性が高いため、長期間の連続溶融成形を行うことが可能である。したがって、本発明の樹脂組成物は多層構造体のバリア層として好適に用いられる。さらに、本発明の樹脂組成物からなる層を有する多層構造体の回収物を溶融成形する際に、樹脂の劣化（ゲル化）や、ＥＶＯＨ（Ａ）とポリプロピレンの相溶性不良による外観や機械物性の低下が抑制される。したがって、回収助剤を用いることなく、前記回収物を多層構造体の少なくとも１層として再使用することができる。 The resin composition is excellent in gas barrier property and appearance, and has high viscosity stability, so that it can be continuously melt-molded for a long period of time. Therefore, the resin composition of the present invention is suitably used as a barrier layer of a multilayer structure. Further, when the recovered product of the multilayer structure having a layer made of the resin composition of the present invention is melt-molded, the appearance and mechanical properties due to deterioration (gelation) of the resin and poor compatibility between EVOH (A) and polypropylene The decrease is suppressed. Therefore, the recovered product can be reused as at least one layer of the multilayer structure without using a recovery aid.
本発明の樹脂組成物に含有されるＥＶＯＨ（Ａ）は、通常、エチレンとビニルエステルとを重合して得られるエチレン−ビニルエステル共重合体をけん化することにより得られる。ＥＶＯＨ（Ａ）のエチレン単位含有量は１５〜６０モル％である。当該含有量が１５モル％以上であることにより、本発明の樹脂組成物の溶融成形性が向上する。エチレン単位含有量は、２０モル％以上が好ましく、２５モル以上がより好ましい。一方、エチレン単位含有量が６０モル％以下であることにより、本発明の樹脂組成物のガスバリア性が向上する。エチレン単位含有量は、５０モル％以下が好ましく、４０モル以下がより好ましい。ＥＶＯＨ（Ａ）のエチレン単位含有量及びけん化度は、１Ｈ−ＮＭＲ測定により求められる。EVOH (A) contained in the resin composition of the present invention is usually obtained by saponifying an ethylene-vinyl ester copolymer obtained by polymerizing ethylene and vinyl ester. The ethylene unit content of EVOH (A) is 15-60 mol%. When the content is 15 mol% or more, the melt moldability of the resin composition of the present invention is improved. The ethylene unit content is preferably 20 mol% or more, more preferably 25 mol% or more. On the other hand, when the ethylene unit content is 60 mol% or less, the gas barrier property of the resin composition of the present invention is improved. The ethylene unit content is preferably 50 mol% or less, more preferably 40 mol or less. The ethylene unit content and saponification degree of EVOH (A) can be determined by 1 1 H-NMR measurement.
ＥＶＯＨ（Ａ）のけん化度は８５モル％以上である。けん化度とは、ＥＶＯＨ（Ａ）中のビニルアルコール単位及びビニルエステル単位の総数に対するビニルアルコール単位の数の割合を意味する。けん化度が８５モル％以上であることにより、本発明の樹脂組成物のガスバリア性が向上する。けん化度は９５モル％以上が好ましく、９９モル％以上がより好ましい。 The saponification degree of EVOH (A) is 85 mol% or more. The saponification degree means the ratio of the number of vinyl alcohol units to the total number of vinyl alcohol units and vinyl ester units in EVOH (A). When the saponification degree is 85 mol% or more, the gas barrier property of the resin composition of the present invention is improved. The degree of saponification is preferably 95 mol% or more, more preferably 99 mol% or more.
ＥＶＯＨ（Ａ）は、本発明の効果を阻害しない範囲であれば、エチレン、ビニルエステル及びビニルアルコール以外の他の単量体単位を含有していてもよい。他の単量体単位の含有量は５質量％以下が好ましく、３質量％以下がより好ましく、１質量％以下がさらに好ましく、実質的に含有されていないことが特に好ましい。他の単量体単位としては、プロピレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテンなどのα−オレフィン；（メタ）アクリル酸エステル；マレイン酸、フマル酸、イタコン酸などの不飽和カルボン酸；アルキルビニルエーテル；Ｎ−（２−ジメチルアミノエチル）メタクリルアミド又はその４級化物、Ｎ−ビニルイミダゾール又はその４級化物、Ｎ−ビニルピロリドン、Ｎ，Ｎ−ブトキシメチルアクリルアミド、ビニルトリメトキシシラン、ビニルメチルジメトキシシラン、ビニルジメチルメトキシシランなどが挙げられる。 EVOH (A) may contain monomer units other than ethylene, vinyl ester and vinyl alcohol as long as the effects of the present invention are not impaired. The content of the other monomer unit is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 1% by mass or less, and particularly preferably not substantially contained. Other monomeric units include α-olefins such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene; (meth) acrylic acid esters; non-maleic acid, fumaric acid, itaconic acid and the like. Saturated carboxylic acid; alkyl vinyl ether; N- (2-dimethylaminoethyl) methacrylicamide or its quaternary product, N-vinylimidazole or its quaternary product, N-vinylpyrrolidone, N, N-butoxymethylacrylamide, vinyltrimethoxy Examples thereof include silane, vinylmethyldimethoxysilane, and vinyldimethylmethoxysilane.
ＥＶＯＨ（Ａ）のＭＦＲ（メルトフローレート、１９０℃、２．１６ｋｇ荷重下）は０．１〜５０ｇ/１０ｍｉｎが好ましい。ＥＶＯＨ（Ａ）のＭＦＲは０．５ｇ/１０ｍｉｎ以上がより好ましく、１ｇ/１０ｍｉｎ以上がさらに好ましい。一方、ＥＶＯＨ（Ａ）のＭＦＲは３０ｇ/１０ｍｉｎ以下がより好ましく、１５ｇ/１０ｍｉｎ以下がさらに好ましい。本発明において、樹脂のＭＦＲは、ＪＩＳ Ｋ ７２１０：２０１４に準拠して測定される。 The MFR (melt flow rate, 190 ° C., under a load of 2.16 kg) of EVOH (A) is preferably 0.1 to 50 g / 10 min. The MFR of EVOH (A) is more preferably 0.5 g / 10 min or more, further preferably 1 g / 10 min or more. On the other hand, the MFR of EVOH (A) is more preferably 30 g / 10 min or less, and further preferably 15 g / 10 min or less. In the present invention, the MFR of the resin is measured according to JIS K 7210: 2014.
ＥＶＯＨ（Ａ）の重量平均分子量が３００００〜１０００００であることが好ましい。重量平均分子量がこのような範囲であることにより、本発明の樹脂組成物の成形加工性と機械物性が向上する。重量平均分子量は３５０００以上がより好ましく、４００００以上がさらに好ましい。一方、重量平均分子量は９００００以下がより好ましく、８００００以下がさらに好ましい。樹脂の重量平均分子量はゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定により求められる。 The weight average molecular weight of EVOH (A) is preferably 30,000 to 100,000. When the weight average molecular weight is in such a range, the molding processability and mechanical properties of the resin composition of the present invention are improved. The weight average molecular weight is more preferably 35,000 or more, and even more preferably 40,000 or more. On the other hand, the weight average molecular weight is more preferably 90,000 or less, and even more preferably 80,000 or less. The weight average molecular weight of the resin is determined by gel permeation chromatography (GPC) measurement.
ＥＶＯＨ（Ａ）の酸素透過度（２０℃、６５％ＲＨ条件下）は０．０５〜５ｃｃ・２０μｍ／（ｍ２・ｄａｙ・ａｔｍ）が好ましい。酸素透過度がこのような範囲であることにより、本発明の樹脂組成物のガスバリア性が向上する。前記酸素透過度は、２ｃｃ・２０μｍ／（ｍ２・ｄａｙ・ａｔｍ）以下がより好ましく、１ｃｃ・２０μｍ／（ｍ２・ｄａｙ・ａｔｍ）以下がさらに好ましい。本発明において、樹脂の酸素透過度は実施例に記載された方法により測定される。The oxygen permeability of EVOH (A) (under 20 ° C. and 65% RH conditions) is preferably 0.05 to 5 cc · 20 μm / (m 2 · day · atm). When the oxygen permeability is in such a range, the gas barrier property of the resin composition of the present invention is improved. The oxygen permeability is more preferably 2cc · 20μm / (m 2 · day · atm) or less, more preferably 1cc · 20μm / (m 2 · day · atm) or less. In the present invention, the oxygen permeability of the resin is measured by the method described in Examples.
本発明の樹脂組成物に含有される酸変性ポリプロピレン（Ｂ）としては、例えばポリプロピレンを酸でグラフト変性させて得られるグラフト変性ポリプロピレンや、プロピレンと酸を共重合させて得られるプロピレン系共重合体が挙げられる。酸変性ポリプロピレン（Ｂ）中のプロピレン単位含有量は５０モル％以上であることが好ましく、７０モル％以上がより好ましく、９０モル％以上がさらに好ましく、９５モル％以上が特に好ましい。 Examples of the acid-modified polypropylene (B) contained in the resin composition of the present invention include graft-modified polypropylene obtained by graft-modifying polypropylene with an acid, and a propylene-based copolymer obtained by copolymerizing propylene and an acid. Can be mentioned. The propylene unit content in the acid-modified polypropylene (B) is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably 95 mol% or more.
酸変性ポリプロピレン（Ｂ）として用いられるグラフト変性ポリプロピレンとしては、ポリプロピレン又はプロピレン系共重合体を酸でグラフト変性させたものが挙げられる。グラフト変性に供されるプロピレン系共重合体としては、プロピレンと、エチレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテンなどのα−オレフィンとを共重合したものが挙げられる。これらにグラフト変性させる酸としては、不飽和カルボン酸又はその誘導体を用いることができ、例えば、アクリル酸、メタクリル酸、フマル酸、イタコン酸、マレイン酸；無水マレイン酸、無水イタコン酸などが挙げられる。中でも無水マレイン酸グラフト変性ポリプロピレンが最も好適である。 Examples of the graft-modified polypropylene used as the acid-modified polypropylene (B) include those obtained by graft-modifying polypropylene or a propylene-based copolymer with an acid. Examples of the propylene-based copolymer used for graft modification include those obtained by copolymerizing propylene with α-olefins such as ethylene, 1-butene, 1-hexene and 4-methyl-1-pentene. As the acid to be graft-modified to these, an unsaturated carboxylic acid or a derivative thereof can be used, and examples thereof include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid; maleic anhydride, itaconic anhydride and the like. .. Of these, maleic anhydride graft-modified polypropylene is most suitable.
酸変性ポリプロピレン（Ｂ）として用いられるプロピレン系共重合体としては、グラフト変性に供されるものとして上述したポリプロピレンやプロピレン系共重合体に対して、さらに酸をランダム共重合させたものが挙げられる。このとき用いられる酸としては、ポリプロピレンをグラフト変性させる酸として上述したものが挙げられる。 Examples of the propylene-based copolymer used as the acid-modified polypropylene (B) include those obtained by randomly copolymerizing the above-mentioned polypropylene or propylene-based copolymer with an acid as the one to be subjected to graft modification. .. Examples of the acid used at this time include those described above as the acid for graft-modifying polypropylene.
酸変性ポリプロピレン（Ｂ）の酸価は２〜７０ｍｇＫＯＨ／ｇである。酸価が２ｍｇＫＯＨ／ｇ以上であることにより、ＥＶＯＨ（Ａ）とポリプロピレンとの相溶性が向上する。酸価は４ｍｇＫＯＨ／ｇ以上が好ましく、６ｍｇＫＯＨ／ｇ以上がより好ましい。一方、酸価が７０ｍｇＫＯＨ／ｇ以下であることにより、本発明の樹脂組成物の粘度安定性が良好となる。さらに、本発明の樹脂組成物からなる層とポリプロピレン層を積層させた多層構造体を回収して再使用する際に、ＥＶＯＨ（Ａ）とポリプロピレンとの相溶性が向上するうえに、樹脂のゲル化が抑制される。酸価は３０ｍｇＫＯＨ／ｇ以下が好ましく、２０ｍｇＫＯＨ／ｇ以下がより好ましい。本発明において、樹脂の酸価は実施例に記載された方法により測定される。 The acid value of the acid-modified polypropylene (B) is 2 to 70 mgKOH / g. When the acid value is 2 mgKOH / g or more, the compatibility between EVOH (A) and polypropylene is improved. The acid value is preferably 4 mgKOH / g or more, and more preferably 6 mgKOH / g or more. On the other hand, when the acid value is 70 mgKOH / g or less, the viscosity stability of the resin composition of the present invention becomes good. Further, when the multilayer structure in which the layer made of the resin composition of the present invention and the polypropylene layer are laminated is recovered and reused, the compatibility between EVOH (A) and polypropylene is improved, and the resin gel is used. The conversion is suppressed. The acid value is preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g or less. In the present invention, the acid value of the resin is measured by the method described in Examples.
酸変性ポリプロピレン（Ｂ）のＭＦＲ（１９０℃、２．１６ｋｇ荷重下）は４〜１０００ｇ/１０ｍｉｎである。ＭＦＲがこのような範囲であることにより、本発明の樹脂組成物からなる層とポリプロピレン層を積層させた多層構造体を回収して再使用する際に、ＥＶＯＨ（Ａ）とポリプロピレンとの相溶性が向上し、また樹脂組成物の粘度安定性が増すことで成形加工性も改善する。酸変性ポリプロピレン（Ｂ）のＭＦＲは５０ｇ/１０ｍｉｎ以上が好ましく、１００ｇ/１０ｍｉｎ以上がより好ましい。一方、酸変性ポリプロピレン（Ｂ）のＭＦＲは６００ｇ/１０ｍｉｎ以下がより好ましく、４００ｇ/１０ｍｉｎ以下がさらに好ましい。 The MFR (190 ° C., under a load of 2.16 kg) of the acid-modified polypropylene (B) is 4 to 1000 g / 10 min. When the MFR is in such a range, the compatibility between EVOH (A) and polypropylene when the multilayer structure in which the layer made of the resin composition of the present invention and the polypropylene layer are laminated is recovered and reused. And the viscosity stability of the resin composition is increased, so that the molding processability is also improved. The MFR of the acid-modified polypropylene (B) is preferably 50 g / 10 min or more, and more preferably 100 g / 10 min or more. On the other hand, the MFR of the acid-modified polypropylene (B) is more preferably 600 g / 10 min or less, and further preferably 400 g / 10 min or less.
酸変性ポリプロピレン（Ｂ）の重量平均分子量が５００００〜３５００００であることが好ましい。重量平均分子量がこのような範囲であることにより、本発明の樹脂組成物からなる層とポリプロピレン層を積層させた多層構造体を回収して再使用する際に、ＥＶＯＨ（Ａ）とポリプロピレンとの相溶性が向上し、また樹脂組成物の粘度安定性が増すことで成形加工性も改善する。酸変性ポリプロピレン（Ｂ）の重量平均分子量は６００００以上がより好ましく、７００００以上がさらに好ましい。一方、酸変性ポリプロピレン（Ｂ）の重量平均分子量は１５００００以下がより好ましく、１２００００以下がさらに好ましい。 The weight average molecular weight of the acid-modified polypropylene (B) is preferably 50,000 to 350,000. When the weight average molecular weight is in such a range, EVOH (A) and polypropylene are used when recovering and reusing a multilayer structure in which a layer made of the resin composition of the present invention and a polypropylene layer are laminated. The compatibility is improved, and the viscosity stability of the resin composition is increased, so that the molding processability is also improved. The weight average molecular weight of the acid-modified polypropylene (B) is more preferably 60,000 or more, further preferably 70,000 or more. On the other hand, the weight average molecular weight of the acid-modified polypropylene (B) is more preferably 150,000 or less, further preferably 120,000 or less.
酸変性ポリプロピレン（Ｂ）の密度は、０．８８〜０．９３ｇ／ｃｍ３が好ましい。当該密度がこのような範囲であることにより、本発明の樹脂組成物からなる層とポリプロピレン層を積層させた多層構造体を回収して再使用する際に、ＥＶＯＨ（Ａ）とポリプロピレンとの相溶性が向上する。酸変性ポリプロピレン（Ｂ）の密度は０．８９ｇ／ｃｍ３以上がより好ましい。一方、酸変性ポリプロピレン（Ｂ）の密度は０．９１ｇ／ｃｍ３以下がより好ましい。本発明において、樹脂の密度は実施例に記載された方法により測定される。The density of the acid-modified polypropylene (B) is preferably 0.88 to 0.93 g / cm 3. When the density is in such a range, the phase of EVOH (A) and polypropylene is used when the multilayer structure in which the layer made of the resin composition of the present invention and the polypropylene layer are laminated is recovered and reused. Increases solubility. The density of the acid-modified polypropylene (B) is more preferably 0.89 g / cm 3 or more. On the other hand, the density of the acid-modified polypropylene (B) is more preferably 0.91 g / cm 3 or less. In the present invention, the density of the resin is measured by the method described in Examples.
酸変性ポリプロピレン（Ｂ）の融点は１３０℃以上である。融点がこのような範囲であることにより、得られる樹脂組成物の耐熱性が向上し、また本発明の樹脂組成物からなる層とポリプロピレン層を積層させた多層構造体を回収して再使用する際に、ＥＶＯＨ（Ａ）とポリプロピレンとの相溶性も向上する。融点は１４０℃以上が好ましい。一方、融点は通常１６５℃以下である。本発明において、樹脂の融点は実施例に記載された方法により測定される。 The melting point of the acid-modified polypropylene (B) is 130 ° C. or higher. When the melting point is in such a range, the heat resistance of the obtained resin composition is improved, and the multilayer structure in which the layer made of the resin composition of the present invention and the polypropylene layer are laminated is recovered and reused. At the same time, the compatibility between EVOH (A) and polypropylene is also improved. The melting point is preferably 140 ° C. or higher. On the other hand, the melting point is usually 165 ° C. or lower. In the present invention, the melting point of the resin is measured by the method described in Examples.
本発明の樹脂組成物における、ＥＶＯＨ（Ａ）に対する酸変性ポリプロピレン（Ｂ）の質量比［（Ｂ）／（Ａ）］が０．８／９９．２〜１０／９０である必要がある。比［（Ｂ）／（Ａ）］が０．８／９９．２以上であることにより、本発明の樹脂組成物の粘度安定性が良好となる。また、本発明の樹脂組成物からなる層とポリプロピレン層を積層させた多層構造体を回収して再使用する際に、ＥＶＯＨ（Ａ）とポリプロピレンとの相溶性が向上する。さらに、本発明の樹脂組成物を含む多層構造体の回収物を溶融混練して得られる回収組成物の色相が良好となる。比［（Ｂ）／（Ａ）］は２／９８以上が好ましく、４／９６以上がより好ましい。一方、比［（Ｂ）／（Ａ）］が１０／９０以下であることにより、本発明の樹脂組成物の粘度安定性、ガスバリア性及び透明性が良好となる。また、樹脂のゲル化が抑制される。比［（Ｂ）／（Ａ）］は８／９２以下がより好ましく、６／９４以下がさらに好ましい。 In the resin composition of the present invention, the mass ratio [(B) / (A)] of the acid-modified polypropylene (B) to EVOH (A) needs to be 0.8 / 99.2 to 10/90. When the ratio [(B) / (A)] is 0.8 / 99.2 or more, the viscosity stability of the resin composition of the present invention is good. Further, when the multilayer structure in which the layer made of the resin composition of the present invention and the polypropylene layer are laminated is recovered and reused, the compatibility between EVOH (A) and polypropylene is improved. Further, the hue of the recovered composition obtained by melt-kneading the recovered product of the multilayer structure containing the resin composition of the present invention is improved. The ratio [(B) / (A)] is preferably 2/98 or more, and more preferably 4/96 or more. On the other hand, when the ratio [(B) / (A)] is 10/90 or less, the viscosity stability, gas barrier property and transparency of the resin composition of the present invention are improved. In addition, gelation of the resin is suppressed. The ratio [(B) / (A)] is more preferably 8/92 or less, and even more preferably 6/94 or less.
本発明の樹脂組成物中の全樹脂成分に対するＥＶＯＨ（Ａ）及び酸変性ポリプロピレン（Ｂ）の合計含有量が９０質量％以上である必要がある。合計含有量は９５質量％以上が好ましく、９８質量％以上がより好ましく、本発明の樹脂組成物中の樹脂成分が実質的にＥＶＯＨ（Ａ）及び酸変性ポリプロピレン（Ｂ）のみであることがさらに好ましい。 The total content of EVOH (A) and acid-modified polypropylene (B) with respect to all the resin components in the resin composition of the present invention needs to be 90% by mass or more. The total content is preferably 95% by mass or more, more preferably 98% by mass or more, and further, the resin components in the resin composition of the present invention are substantially only EVOH (A) and acid-modified polypropylene (B). preferable.
ＥＶＯＨ（Ａ）とポリプロピレンとの相溶性がさらに良好となる点から、ＥＶＯＨ（Ａ）に対する酸変性ポリプロピレン（Ｂ）の重量平均分子量比［（Ｂ）／（Ａ）］が０．９〜５であることが好ましい。重量平均分子量比［（Ｂ）／（Ａ）］は３以下がより好ましく、２以下がさらに好ましい。 The weight average molecular weight ratio [(B) / (A)] of the acid-modified polypropylene (B) to EVOH (A) is 0.9 to 5 from the viewpoint of further improving the compatibility between EVOH (A) and polypropylene. It is preferable to have. The weight average molecular weight ratio [(B) / (A)] is more preferably 3 or less, and even more preferably 2 or less.
本発明の樹脂組成物の成形加工性が改善される点から、ＥＶＯＨ（Ａ）に対する本発明の樹脂組成物のＭＦＲ（１９０℃、２．１６ｋｇ荷重下）の比［樹脂組成物／ＥＶＯＨ（Ａ）］が０．６以上であることが好ましく、０．７以上がより好ましく、０．８以上がさらに好ましい。一方、前記比［樹脂組成物／ＥＶＯＨ（Ａ）］は、通常、１未満である。 From the viewpoint of improving the molding processability of the resin composition of the present invention, the ratio of the MFR (190 ° C., under a load of 2.16 kg) of the resin composition of the present invention to EVOH (A) [resin composition / EVOH (A). )] Is preferably 0.6 or more, more preferably 0.7 or more, and even more preferably 0.8 or more. On the other hand, the ratio [resin composition / EVOH (A)] is usually less than 1.
本発明の樹脂組成物の酸素バリア性がさらに高くなる点から、ＥＶＯＨ（Ａ）に対する本発明の樹脂組成物の酸素透過度（２０℃、６５％ＲＨ条件下）の比［樹脂組成物／ＥＶＯＨ（Ａ）］が２以下であることが好ましい。比［樹脂組成物／ＥＶＯＨ（Ａ）］は１．５以下がより好ましく、１．２以下がさらに好ましい。 The ratio of the oxygen permeability of the resin composition of the present invention to EVOH (A) (under 20 ° C. and 65% RH conditions) [resin composition / EVOH] from the viewpoint of further increasing the oxygen barrier property of the resin composition of the present invention. (A)] is preferably 2 or less. The ratio [resin composition / EVOH (A)] is more preferably 1.5 or less, and even more preferably 1.2 or less.
本発明の樹脂組成物は、多価金属イオン（Ｃ）として、マグネシウムイオン、カルシウムイオン及び亜鉛イオンからなる群から選択される少なくとも１種を含有する。これにより、樹脂のゲル化や押出機内のスクリューへの付着が抑制される。中でも、本発明の樹脂組成物は、多価金属イオン（Ｃ）として、マグネシウムイオン又はカルシウムイオンを含有することが好ましく、マグネシウムイオンを含有することがより好ましい。 The resin composition of the present invention contains at least one selected from the group consisting of magnesium ion, calcium ion and zinc ion as the polyvalent metal ion (C). As a result, gelation of the resin and adhesion to the screw in the extruder are suppressed. Above all, the resin composition of the present invention preferably contains magnesium ion or calcium ion as the polyvalent metal ion (C), and more preferably contains magnesium ion.
本発明の樹脂組成物が、多価金属イオン（Ｃ）をカルボン酸塩として含有することが好ましい。このときのカルボン酸としては、脂肪族カルボン酸、芳香族カルボン酸のいずれであってもよいが、脂肪族カルボン酸が好ましい。脂肪族カルボン酸としては、ギ酸、酢酸、プロピオン酸、酪酸、ラウリン酸、ステアリン酸、ミリスチン酸、ベヘン酸、モンタン酸等が挙げられ、酢酸が好ましい。カルボン酸塩の炭素数は１〜１０が好ましく、５以下がより好ましく、３以下がさらに好ましく、２が特に好ましい。 The resin composition of the present invention preferably contains a polyvalent metal ion (C) as a carboxylate. The carboxylic acid at this time may be either an aliphatic carboxylic acid or an aromatic carboxylic acid, but an aliphatic carboxylic acid is preferable. Examples of the aliphatic carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, myristic acid, behenic acid, montanic acid and the like, and acetic acid is preferable. The carbon number of the carboxylate is preferably 1 to 10, more preferably 5 or less, further preferably 3 or less, and particularly preferably 2.
本発明の樹脂組成物中の多価金属イオン（Ｃ）の含有量が６０〜３００ｐｐｍである必要がある。当該含有量が６０ｐｐｍ以上であることにより、本発明の樹脂組成物の粘度安定性が良好となるとともに、樹脂のゲル化や押出機内のスクリューへの付着が抑制される。多価金属イオン（Ｃ）の前記含有量は８０ｐｐｍ以上が好ましい。一方、多価金属イオン（Ｃ）の含有量が３００ｐｐｍ以下であることにより、本発明の樹脂組成物の粘度安定性及び色相が良好となる。多価金属イオン（Ｃ）含有量は２００ｐｐｍ以下が好ましい。 The content of the multivalent metal ion (C) in the resin composition of the present invention needs to be 60 to 300 ppm. When the content is 60 ppm or more, the viscosity stability of the resin composition of the present invention is improved, and gelation of the resin and adhesion to the screw in the extruder are suppressed. The content of the polyvalent metal ion (C) is preferably 80 ppm or more. On the other hand, when the content of the polyvalent metal ion (C) is 300 ppm or less, the viscosity stability and hue of the resin composition of the present invention are improved. The polyvalent metal ion (C) content is preferably 200 ppm or less.
樹脂組成物の増粘及びゲル化や押出機内のスクリューへの付着がさらに抑制される点から、本発明の樹脂組成物が、エステル結合又はアミド結合を有するヒンダードフェノール系化合物（Ｄ）をさらに含有することが好ましい。ヒンダードフェノール系化合物（Ｄ）は、少なくとも１つのヒンダードフェノール基を有する。ヒンダードフェノール基とは、フェノールのヒドロキシル基が結合した炭素に隣接する炭素の少なくとも１つに嵩高い置換基が結合したものをいう。嵩高い置換基としては、炭素原子１〜１０のアルキル基が好ましく、ｔ−ブチル基がより好ましい。 The resin composition of the present invention further comprises a hindered phenolic compound (D) having an ester bond or an amide bond from the viewpoint of further suppressing thickening and gelation of the resin composition and adhesion to the screw in the extruder. It is preferable to contain it. The hindered phenolic compound (D) has at least one hindered phenolic group. The hindered phenol group refers to a group in which a bulky substituent is bonded to at least one of the carbons adjacent to the carbon to which the hydroxyl group of phenol is bonded. As the bulky substituent, an alkyl group having 1 to 10 carbon atoms is preferable, and a t-butyl group is more preferable.
ヒンダードフェノール系化合物（Ｄ）は室温付近において固体であることが好ましい。ブリードアウトを抑制する点から、ヒンダードフェノール系化合物（Ｄ）の融点又は軟化温度は、５０℃以上が好ましく、６０℃以上がより好ましく、７０℃以上がさらに好ましい。同様の点から、ヒンダードフェノール系化合物（Ｄ）の分子量は、２００以上が好ましく、４００以上がより好ましく、６００以上がさらに好ましい。一方、前記分子量は、通常、２０００以下である。また、ＥＶＯＨ（Ａ）との混合を容易にする点から、ヒンダードフェノール系化合物（Ｄ）の融点又は軟化温度は、２００℃以下が好ましく、１９０℃以下がより好ましく、１８０℃以下がさらに好ましい。 The hindered phenolic compound (D) is preferably solid at around room temperature. From the viewpoint of suppressing bleed-out, the melting point or softening temperature of the hindered phenolic compound (D) is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 70 ° C. or higher. From the same point of view, the molecular weight of the hindered phenolic compound (D) is preferably 200 or more, more preferably 400 or more, still more preferably 600 or more. On the other hand, the molecular weight is usually 2000 or less. Further, the melting point or softening temperature of the hindered phenolic compound (D) is preferably 200 ° C. or lower, more preferably 190 ° C. or lower, still more preferably 180 ° C. or lower, from the viewpoint of facilitating mixing with EVOH (A). ..
ヒンダードフェノール系化合物（Ｄ）はエステル結合又はアミド結合を有する必要がある。エステル結合を有するヒンダードフェノール系化合物（Ｄ）としては、ヒンダードフェノール基を有する脂肪族カルボン酸と脂肪族アルコールとのエステルが挙げられ、アミド結合を有するヒンダードフェノール系化合物（Ｄ）としては、ヒンダードフェノール基を有する脂肪族カルボン酸と脂肪族アミンとのアミドが挙げられる。中でも、ヒンダードフェノール系化合物（Ｄ）がアミド結合を有することが好ましい。 The hindered phenolic compound (D) must have an ester bond or an amide bond. Examples of the hindered phenolic compound (D) having an ester bond include an ester of an aliphatic carboxylic acid having a hindered phenol group and an aliphatic alcohol, and examples of the hindered phenolic compound (D) having an amide bond include an ester. , Amides of aliphatic carboxylic acids having a hindered phenol group and aliphatic amines. Above all, it is preferable that the hindered phenolic compound (D) has an amide bond.
ヒンダードフェノール系化合物（Ｄ）の具体的な構造としては、ＢＡＳＦ社からからイルガノックス１０１０として市販されているペンタエリトリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート]、イルガノックス１０７６として市販されている3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリル、イルガノックス１０３５として市販されている2,2'-チオジエチルビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート]、イルガノックス１１３５として市販されている3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロパン酸オクタデシル、イルガノックス２４５として市販されているビス(3-tert-ブチル-4-ヒドロキシ-5-メチルベンゼンプロパン酸)エチレンビス(オキシエチレン)、イルガノックス２５９として市販されている1,6-ヘキサンジオールビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート]、イルガノックス１０９８として市販されているN,N'-ヘキサメチレンビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロパンアミド]が挙げられる。これらの中でも、イルガノックス１０９８として市販されているN,N'-ヘキサメチレンビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロパンアミド]、及びイルガノックス１０１０として市販されているペンタエリトリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート]が好ましく、前者がより好ましい。 As a specific structure of the hindered phenolic compound (D), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl), which is commercially available as Irganox 1010 from BASF, Inc. Propionate], Stearyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate marketed as Irganox 1076, 2,2'-thiodiethylbis [commercially available as Irganox 1035 [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoate commercially available as Irganox 1135 , Bis (3-tert-butyl-4-hydroxy-5-methylbenzenepropanoic acid) commercially available as Irganox 245, ethylene bis (oxyethylene), 1,6-hexanediol bis commercially available as Irganox 259. [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propanamide]. Among these, N, N'-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide] commercially available as Irganox 1098 and Irganox 1010 are commercially available. Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is preferable, and the former is more preferable.
本発明の樹脂組成物がヒンダードフェノール系化合物（Ｄ）を含有する場合、その含有量は、ＥＶＯＨ（Ａ）及び酸変性ポリプロピレン（Ｂ）の合計１００質量部に対して、０．０５〜１０質量部が好ましい。ヒンダードフェノール系化合物（Ｄ）の含有量が上記範囲であると、樹脂組成物の着色やブツの発生や、ヒンダードフェノール系化合物（Ｄ）のブリードアウトが抑制される。前記含有量は、０．２質量部以上がより好ましく、０．５質量部以上がさらに好ましい。一方、前記含有量は、２質量部以下がより好ましく、１．５質量部以下がさらに好ましい。 When the resin composition of the present invention contains a hindered phenolic compound (D), the content thereof is 0.05 to 10 with respect to a total of 100 parts by mass of EVOH (A) and acid-modified polypropylene (B). Parts by mass are preferred. When the content of the hindered phenol-based compound (D) is within the above range, coloring of the resin composition, generation of lumps, and bleed-out of the hindered phenol-based compound (D) are suppressed. The content is more preferably 0.2 parts by mass or more, and further preferably 0.5 parts by mass or more. On the other hand, the content is more preferably 2 parts by mass or less, and further preferably 1.5 parts by mass or less.
本発明の樹脂組成物は、本発明の効果が阻害されない範囲であれば、ＥＶＯＨ（Ａ）及び酸変性ポリプロピレン（Ｂ）等の樹脂、多価金属イオン（Ｃ）及びヒンダードフェノール系化合物（Ｄ）以外の他の成分を含有してもよい。他の成分としては、アルカリ金属塩、リン酸化合物、ホウ素化合物、酸化促進剤、ヒンダードフェノール系化合物（Ｄ）以外の酸化防止剤、可塑剤、熱安定剤（溶融安定剤）、光開始剤、脱臭剤、紫外線吸収剤、帯電防止剤、滑剤、着色剤、フィラー、乾燥剤、充填剤、顔料、染料、加工助剤、難燃剤、防曇剤等が挙げられる。本発明の樹脂組成物中の、樹脂、多価金属イオン（Ｃ）及びヒンダードフェノール系化合物（Ｄ）以外の他の成分の含有量は１０質量％以下が好ましく、５質量％以下がより好ましく、２質量％以下がさらに好ましい。 The resin composition of the present invention includes resins such as EVOH (A) and acid-modified polypropylene (B), polyvalent metal ions (C), and hindered phenolic compounds (D) as long as the effects of the present invention are not impaired. ) May be contained. Other components include alkali metal salts, phosphoric acid compounds, boron compounds, oxidation accelerators, antioxidants other than hindered phenol compounds (D), plasticizers, heat stabilizers (melt stabilizers), and photoinitiators. , Deodorant, UV absorber, antistatic agent, lubricant, colorant, filler, desiccant, filler, pigment, dye, processing aid, flame retardant, antifogging agent and the like. The content of the components other than the resin, the polyvalent metal ion (C) and the hindered phenolic compound (D) in the resin composition of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less. 2, 2% by mass or less is more preferable.
本発明の樹脂組成物を溶融成形して得られる厚み２０μｍのフィルムのヘイズが５％以下であることが好ましい。ヘイズが５％以下である樹脂組成物は外観に優れ、包装材料等として好適に用いられる。ヘイズは３％以下がより好ましく、１％以下がさらに好ましい。本発明において、フィルムのヘイズは実施例に記載された方法により測定される。 The haze of a film having a thickness of 20 μm obtained by melt-molding the resin composition of the present invention is preferably 5% or less. A resin composition having a haze of 5% or less has an excellent appearance and is suitably used as a packaging material or the like. The haze is more preferably 3% or less, still more preferably 1% or less. In the present invention, the haze of the film is measured by the method described in the examples.
本発明の樹脂組成物の製造方法は特に限定されないが、ＥＶＯＨ（Ａ）、酸変性ポリプロピレン（Ｂ）、多価金属イオン（Ｃ）、必要に応じてその他の添加剤を溶融混練することにより製造できる。このとき、ＥＶＯＨ（Ａ）と酸変性ポリプロピレン（Ｂ）を溶融混練した後に、多価金属イオン（Ｃ）を加えてさらに溶融混練してもよい。多価金属イオン（Ｃ）は、粉末など固体状態のまま、又は溶融物として配合することもできるし、溶液に含まれる溶質又は分散液に含まれる分散質として配合することもできる。溶液、分散液としては、それぞれ水溶液、水分散液が好適である。溶融混練は、例えばニーダールーダー、押出機、ミキシングロール、バンバリーミキサーなどの既知の混合装置又は混練装置を使用して行うことができる。溶融混練時の温度は、使用するＥＶＯＨ（Ａ）や酸変性ポリプロピレン（Ｂ）の融点などに応じて適宜調節でき、通常、１５０℃以上３００℃以下の温度範囲内の温度を採用すればよい。 The method for producing the resin composition of the present invention is not particularly limited, but it is produced by melt-kneading EVOH (A), acid-modified polypropylene (B), polyvalent metal ion (C), and other additives if necessary. can. At this time, after melt-kneading EVOH (A) and acid-modified polypropylene (B), polyvalent metal ions (C) may be added and further melt-kneaded. The polyvalent metal ion (C) can be blended in a solid state such as powder or as a melt, or can be blended as a solute contained in a solution or a dispersoid contained in a dispersion liquid. As the solution and the dispersion liquid, an aqueous solution and an aqueous dispersion liquid are suitable, respectively. The melt kneading can be carried out using a known mixing device or kneading device such as a kneader ruder, an extruder, a mixing roll, and a Banbury mixer. The temperature at the time of melt-kneading can be appropriately adjusted according to the melting point of EVOH (A) or acid-modified polypropylene (B) to be used, and usually, a temperature within a temperature range of 150 ° C. or higher and 300 ° C. or lower may be adopted.
本発明の樹脂組成物からなるバリア層（以下、樹脂組成物層と略記することがある）を有する多層構造体が本発明の好適な実施態様である。本発明の樹脂組成物はガスバリア性に優れるとともに、色相及び透明性にも優れる。したがって、このような樹脂組成物をバリア層として用いた多層構造体はガスバリア性及び外観に優れる。 A multilayer structure having a barrier layer made of the resin composition of the present invention (hereinafter, may be abbreviated as a resin composition layer) is a preferred embodiment of the present invention. The resin composition of the present invention is excellent not only in gas barrier property but also in hue and transparency. Therefore, a multilayer structure using such a resin composition as a barrier layer is excellent in gas barrier property and appearance.
本発明の多層構造体がポリプロピレンからなる層をさらに有することが好ましい。そして、本発明の多層構造体がポリプロピレンからなる最外層及び最内層をさらに有することがより好ましい。ポリプロピレンは、耐熱性、機械物性、ヒートシール性に優れ、また経済的に入手できることから、ポリプロピレンからなる層を最外層及び最内層に有する多層構造体は、レトルト容器等の包装材料としても好ましく使用することができる。前記ポリプロピレンとしては、例えばポリプロピレン；プロピレンと、エチレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテンなどのα−オレフィンとを共重合したプロピレン系共重合体が挙げられる。プロピレン系共重合体中のプロピレン単位含有量は５０モル％以上であることが好ましく、７０モル％以上がより好ましく、９０モル％以上がさらに好ましく、９５モル％以上が特に好ましい。 It is preferred that the multilayer structure of the present invention further has a layer made of polypropylene. It is more preferable that the multilayer structure of the present invention further has an outermost layer and an innermost layer made of polypropylene. Since polypropylene has excellent heat resistance, mechanical properties, and heat sealability, and is economically available, a multilayer structure having a polypropylene layer as the outermost layer and the innermost layer is preferably used as a packaging material for retort containers and the like. can do. Examples of the polypropylene include polypropylene; a propylene-based copolymer obtained by copolymerizing propylene with α-olefins such as ethylene, 1-butene, 1-hexene and 4-methyl-1-pentene. The propylene unit content in the propylene-based copolymer is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably 95 mol% or more.
本発明の多層構造体に用いられるポリプロピレンのＭＦＲ（１９０℃、２．１６ｋｇ荷重下）は、通常０．１〜５０ｇ/１０ｍｉｎである。また、当該ポリプロピレンの密度は、通常０．８８〜０．９３ｇ／ｃｍ３である。The polypropylene MFR (190 ° C., under a 2.16 kg load) used in the multilayer structure of the present invention is usually 0.1 to 50 g / 10 min. The density of the polypropylene is usually 0.88 to 0.93 g / cm 3 .
本発明の多層構造体において、本発明の樹脂組成物層と他の層の間に接着性樹脂からなる層（以下、接着性樹脂層と略記することがある）が配置されていることが好ましい。接着性樹脂としては、酸価が０．５ｍｇＫＯＨ／ｇ以上２ｍｇＫＯＨ／ｇ未満、重量平均分子量が４０００００以上、ＭＦＲ（１９０℃、２．１６ｋｇ荷重下）が０．５〜３ｇ/１０ｍｉｎである酸変性ポリプロピレンが通常用いられる。接着性樹脂として使用される酸変性ポリプロピレンと上述した酸変性ポリプロピレン（Ｂ）とは、酸価、重合度及びＭＦＲ等の物性が互いに異なり、互いを置き換えて機能、品質要求を満たすことは一般に困難である。 In the multilayer structure of the present invention, it is preferable that a layer made of an adhesive resin (hereinafter, may be abbreviated as an adhesive resin layer) is arranged between the resin composition layer of the present invention and another layer. .. As the adhesive resin, acid modification having an acid value of 0.5 mgKOH / g or more and less than 2 mgKOH / g, a weight average molecular weight of 400,000 or more, and an MFR (190 ° C., under a 2.16 kg load) of 0.5 to 3 g / 10 min. Polypropylene is usually used. The acid-modified polypropylene used as an adhesive resin and the acid-modified polypropylene (B) described above have different physical properties such as acid value, degree of polymerization and MFR, and it is generally difficult to replace each other to meet the function and quality requirements. Is.
本発明の多層構造体中の各層の厚みは用途に応じて適宜調整すればよい。本発明の多層構造体の厚みに対する、本発明の樹脂組成物層の厚みの比［樹脂組成物層／多層構造体］は、通常、０．０１〜０．１５である。ここで、樹脂組成物層が複数含まれている場合はそれらの合計厚みを用いる。本発明の多層構造体における、接着性樹脂層の厚みに対する本発明の樹脂組成物層の厚みの比［樹脂組成物層／接着性樹脂層］は、通常、０．５〜５である。ここで、樹脂組成物層や接着性樹脂層が複数含まれている場合は合計厚みを用いる。 The thickness of each layer in the multilayer structure of the present invention may be appropriately adjusted according to the intended use. The ratio of the thickness of the resin composition layer of the present invention to the thickness of the multilayer structure of the present invention [resin composition layer / multilayer structure] is usually 0.01 to 0.15. Here, when a plurality of resin composition layers are contained, the total thickness thereof is used. In the multilayer structure of the present invention, the ratio of the thickness of the resin composition layer of the present invention to the thickness of the adhesive resin layer [resin composition layer / adhesive resin layer] is usually 0.5 to 5. Here, when a plurality of resin composition layers and adhesive resin layers are included, the total thickness is used.
本発明の多層構造体の製造方法としては、例えば共押出成形法、押出ラミネート法、ドライラミネート法、共射出成形法等が例示される。共押出成形法としては、共押出ラミネート法、共押出シート成形法、共押出インフレーション成形法、共押出ブロー成形法等が挙げられる。 Examples of the method for producing the multilayer structure of the present invention include a coextrusion molding method, an extrusion laminating method, a dry laminating method, and a co-injection molding method. Examples of the coextrusion molding method include a coextrusion laminating method, a coextrusion sheet molding method, a coextrusion inflation molding method, and a coextrusion blow molding method.
得られた多層構造体のシート、フィルム、パリソン等に対して、さらに絞り成形等の熱成形法、ロール延伸法、パンタグラフ式延伸法、インフレーション延伸法、ブロー成形法等の二次加工を施してもよい。 The obtained sheet, film, parison, etc. of the multilayer structure is further subjected to secondary processing such as a thermoforming method such as drawing molding, a roll stretching method, a pantograph stretching method, an inflation stretching method, and a blow molding method. May be good.
本発明の多層構造体を製造する際に発生する端部や不良品を回収した回収物（スクラップ）を再使用することが好ましい。本発明の多層構造体を粉砕した後に溶融成形する多層構造体の回収方法、及び本発明の多層構造体の回収物を含む回収組成物もまた本発明の好適な実施態様である。 It is preferable to reuse the recovered product (scrap) obtained by recovering the edges and defective products generated when the multilayer structure of the present invention is manufactured. A method for recovering a multilayer structure in which the multilayer structure of the present invention is crushed and then melt-molded, and a recovery composition containing a recovered product of the multilayer structure of the present invention are also preferred embodiments of the present invention.
本発明の多層構造体の回収に際して、まず、本発明の多層構造体の回収物を破砕する。粉砕された回収物を、そのまま溶融成形して回収組成物を得てもよいし、必要に応じてその他の成分とともに溶融成形して回収組成物を得てもよい。回収物に添加する成分としてはポリプロピレンが挙げられる。当該ポリプロピレンとしては、本発明の多層構造体に用いられるものとして上述したものが用いられる。本発明の多層構造体の回収物を溶融成形する際に、回収助剤を用いなくても、樹脂のゲル化や相溶性不足に起因する外観や機械物性の低下が抑制される。したがって、本発明の多層構造体の回収物に対して回収助剤を添加する必要はなく、工程の簡略化やコスト低減のためには、回収助剤を添加しないことが好ましい。粉砕された回収物を直接多層構造体等の成形品の製造に供してもよいし、粉砕された回収物を溶融成形して、回収組成物からなるペレットを得た後、当該ペレットを成形品の製造に供してもよい。 When recovering the multilayer structure of the present invention, first, the recovered product of the multilayer structure of the present invention is crushed. The crushed recovered product may be melt-molded as it is to obtain a recovered composition, or if necessary, melt-molded together with other components to obtain a recovered composition. Examples of the component added to the recovered product include polypropylene. As the polypropylene, the polypropylene described above is used as the polypropylene used for the multilayer structure of the present invention. When the recovered product of the multilayer structure of the present invention is melt-molded, deterioration of appearance and mechanical properties due to gelation of the resin and insufficient compatibility can be suppressed without using a recovery aid. Therefore, it is not necessary to add the recovery aid to the recovered product of the multilayer structure of the present invention, and it is preferable not to add the recovery aid in order to simplify the process and reduce the cost. The crushed recovered product may be directly used for manufacturing a molded product such as a multilayer structure, or the crushed recovered product is melt-molded to obtain pellets composed of the recovered composition, and then the pellet is used as a molded product. May be used for the production of.
こうして得られる回収組成物における、ポリプロピレンに対するＥＶＯＨ（Ａ）の質量比[ＥＶＯＨ（Ａ）／ポリプロピレン]は、２／９８〜３０／７０であることが好ましい。質量比[ＥＶＯＨ（Ａ）／ポリプロピレン]が２／９８未満の場合、回収物の使用比率が低下するおそれがある。一方、質量比[ＥＶＯＨ（Ａ）／ポリプロピレン]が３０／７０以下であることにより、回収組成物の溶融成形性と機械物性が向上する。 The mass ratio of EVOH (A) to polypropylene in the recovered composition thus obtained [EVOH (A) / polypropylene] is preferably 2/98 to 30/70. If the mass ratio [EVOH (A) / polypropylene] is less than 2/98, the usage ratio of the recovered material may decrease. On the other hand, when the mass ratio [EVOH (A) / polypropylene] is 30/70 or less, the melt moldability and mechanical properties of the recovered composition are improved.
本発明の回収組成物を、上述した多層構造体を構成する少なくとも１層として再使用することが好ましい。すなわち、回収物を溶融成形して得られた回収層を含有する多層構造体からなる成形品を製造し、その成形品の回収物を、再び同様の多層構造体における回収層の原料として用いることが好ましい。 It is preferable that the recovered composition of the present invention is reused as at least one layer constituting the above-mentioned multilayer structure. That is, a molded product composed of a multilayer structure containing a recovery layer obtained by melt molding the recovered product is produced, and the recovered product of the molded product is used again as a raw material for the recovery layer in the same multilayer structure. Is preferable.
回収層をさらに有する多層構造体の層構成として、下記のものが例示される。ここで、ポリプロピレン層をＰ、本発明の樹脂組成物層をＥ、接着性樹脂層をＡ、回収層をＲとする。
３層 Ｒ／Ａ／Ｅ
４層 Ｐ／Ｒ／Ａ／Ｅ
５層 Ｐ／Ａ／Ｅ／Ａ／Ｒ，Ｒ／Ａ／Ｅ／Ａ／Ｒ
６層 Ｐ／Ｒ／Ａ／Ｅ／Ａ／Ｐ、Ｐ／Ｒ／Ａ／Ｅ／Ａ／Ｒ
７層 Ｐ／Ｒ／Ａ／Ｅ／Ａ／Ｒ／ＰThe following is exemplified as a layer structure of a multilayer structure further having a recovery layer. Here, the polypropylene layer is P, the resin composition layer of the present invention is E, the adhesive resin layer is A, and the recovery layer is R.
3 layers R / A / E
4-layer P / R / A / E
5 layers P / A / E / A / R, R / A / E / A / R
6 layers P / R / A / E / A / P, P / R / A / E / A / R
7 layers P / R / A / E / A / R / P
本発明の多層構造体中の回収層の厚みは用途に応じて適宜調整すればよいが、本発明の多層構造体の合計厚みに対する、本発明の回収層の厚みの比［回収層／多層構造体］は、通常、０．１〜０．８である。ここで、回収層が複数含まれている場合は合計厚みを用いる。 The thickness of the recovery layer in the multilayer structure of the present invention may be appropriately adjusted according to the intended use, but the ratio of the thickness of the recovery layer of the present invention to the total thickness of the multilayer structure of the present invention [recovery layer / multilayer structure]. Body] is usually 0.1 to 0.8. Here, when a plurality of recovery layers are included, the total thickness is used.
本発明の樹脂組成物層をバリア層として有する多層構造体は、ガスバリア性及び外観に優れる。しかも、当該多層構造体の回収物を溶融成形する場合、回収助剤を用いなくても、樹脂の劣化（ゲル化）や相溶性不足に起因する問題の発生が抑制される。そのため、本発明の多層構造体の回収物は再使用しやすい。したがって、本発明の樹脂組成物からなる層を有する多層構造体は、食品包装容器の包装材料等として好適に用いられる。 The multilayer structure having the resin composition layer of the present invention as a barrier layer is excellent in gas barrier property and appearance. Moreover, when the recovered product of the multilayer structure is melt-molded, the occurrence of problems due to deterioration (gelation) of the resin and insufficient compatibility can be suppressed even if a recovery aid is not used. Therefore, the recovered product of the multilayer structure of the present invention is easy to reuse. Therefore, the multilayer structure having a layer made of the resin composition of the present invention is suitably used as a packaging material for food packaging containers and the like.
以下、実施例を用いて本発明を更に具体的に説明する。
（１）ＥＶＯＨのエチレン単位含有量及びけん化度
ＥＶＯＨのペレットを、内部標準物質としてテトラメチルシラン（ＴＭＳ）、添加剤としてトリフルオロ酢酸（ＴＦＡ）を含む重ジメチルスルホキシド（ＤＭＳＯ−ｄ６）に溶解した。得られた溶液を５００ＭＨｚの１Ｈ−ＮＭＲ（日本電子株式会社製「ＧＸ−５００」）を用いて８０℃で測定し、エチレン単位、ビニルアルコール単位、ビニルエステル単位のピーク強度比よりエチレン単位含有量及びけん化度を求めた。Hereinafter, the present invention will be described in more detail with reference to Examples.
(1) Ethylene unit content of EVOH and degree of saponification The EVOH pellets are dissolved in deuterated dimethyl sulfoxide (DMSO-d 6 ) containing tetramethylsilane (TMS) as an internal standard and trifluoroacetic acid (TFA) as an additive. bottom. The obtained solution was measured at 80 ° C. using 1 H-NMR (“GX-500” manufactured by JEOL Ltd.) at 500 MHz, and contained ethylene units based on the peak intensity ratio of ethylene units, vinyl alcohol units, and vinyl ester units. The amount and degree of saponification were determined.
（２）メルトフローレート
メルトフローレート（ＭＦＲ）は、ＪＩＳ Ｋ ７２１０：２０１４に準拠し、温度１９０℃、荷重２１６０ｇの条件で測定した。(2) Melt flow rate The melt flow rate (MFR) was measured in accordance with JIS K 7210: 2014 under the conditions of a temperature of 190 ° C. and a load of 2160 g.
（３）ＥＶＯＨの重量平均分子量
ＥＶＯＨの重量平均分子量（Ｍｗ）は、ヘキサフルオロイソプロパノールを移動相に用い、示差屈折率検出器を用いて、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定により、ポリメタクリル酸メチル換算値として求めた。具体的には、以下の方法を採用した。
装置：東ソー社製「ＨＬＣ−８３２０ＧＰＣ」
ＧＰＣカラム：東ソー株式会社製「ＧＭＨＨＲ（Ｓ）」２本を直列に連結
移動相：ヘキサフルオロイソプロパノール（２０ｍｍｏｌ／Ｌトリフルオロ酢酸ナトリウムを含む）
流速：０．２ｍＬ／分
試料濃度：１ｍｇ／ｍＬ
試料注入量：１０μＬ
カラム温度：４０℃
検出器：示差屈折率検出器
標準物質：ポリメタクリル酸メチル(3) Weight average molecular weight of EVOH The weight average molecular weight (Mw) of EVOH is polymethacrylic acid by gel permeation chromatography (GPC) measurement using hexafluoroisopropanol as the mobile phase and a differential refractometer. It was calculated as a methyl conversion value. Specifically, the following method was adopted.
Equipment: "HLC-8320GPC" manufactured by Tosoh Corporation
GPC column: Two "GMHHR (S)" manufactured by Tosoh Corporation are connected in series. Mobile phase: Hexafluoroisopropanol (including 20 mmol / L sodium trifluoroacetate)
Flow velocity: 0.2 mL / min Sample concentration: 1 mg / mL
Sample injection volume: 10 μL
Column temperature: 40 ° C
Detector: Differential Refractometer Detector Standard Material: Polymethylmethacrylate
（４）酸変性ポリプロピレンの酸価
変性ポリプロピレンペレット４００ｍｇをキシレン８０ｍｌに溶解させ、フェノールフタレインを指示薬として、水酸化カリウム−エタノール溶液で滴定することで酸価を求めた。水酸化カリウム−エタノール溶液の濃度は、酸価に応じて、０．００５〜０．５ｍｏｌ／Ｌの範囲で適宜調整した。(4) Acid Value of Acid-Modified Polypropylene The acid value was determined by dissolving 400 mg of modified polypropylene pellets in 80 ml of xylene and titrating with a potassium hydroxide-ethanol solution using phenolphthalein as an indicator. The concentration of the potassium hydroxide-ethanol solution was appropriately adjusted in the range of 0.005 to 0.5 mol / L according to the acid value.
（５）酸変性ポリプロピレンの重量平均分子量
酸変性ポリプロピレンの重量平均分子量（Ｍｗ）は、１，２−ジクロロベンゼンを移動相に用い、示差屈折率検出器を用いて、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定により、ポリスチレン換算値として求めた。具体的には、以下の方法を採用した。
装置：東ソー社製「８１２１ＨＴＧＰＣ」
ＧＰＣカラム：昭和電工株式会社製「ＨＴ−８０６Ｍ」２本を直列に連結
移動相：１，２−ジクロロベンゼン
流速：１．０ｍＬ／分
試料濃度：０．１１ｍｇ／ｍｌ
試料注入量：３００μＬ
カラム温度：１４０℃
検出器：示差屈折率検出器
標準物質：ポリスチレン(5) Weight average molecular weight of acid-modified polypropylene For the weight average molecular weight (Mw) of acid-modified polypropylene, 1,2-dichlorobenzene is used as the mobile phase, and gel permeation chromatography (GPC) is performed using a differential refractometer. ) It was determined as a polypropylene conversion value by measurement. Specifically, the following method was adopted.
Equipment: "8121HTGPC" manufactured by Tosoh Corporation
GPC column: Two "HT-806M" manufactured by Showa Denko KK are connected in series. Mobile phase: 1,2-dichlorobenzene Flow velocity: 1.0 mL / min Sample concentration: 0.11 mg / ml
Sample injection volume: 300 μL
Column temperature: 140 ° C
Detector: Differential Refractometer Detector Standard Material: Polystyrene
（６）酸変性ポリプロピレンの密度
酸変性ポリプロピレンペレットについて、乾式自動密度計（島津製作所製「アキュピックII １３４０」）を用いて密度を求めた。(6) Density of Acid-Modified Polypropylene The density of acid-modified polypropylene pellets was determined using a dry automatic densitometer (“Accupic II 1340” manufactured by Shimadzu Corporation).
（７）酸変性ポリプロピレンの融点
酸変性ポリプロピレンペレットについて、示差走査熱量計（ＴＡ Ｉｎｓｔｒｕｍｅｎｔ社製「Ｑ２０００」）を用いて、２０℃から２２０℃まで１０℃／分で昇温した後、−１０℃／分で２０℃まで冷却し、再度２０℃から２２０℃まで１０℃／分で昇温して測定を実施した。２回目の昇温過程における融解ピークから融点を求めた。(7) Melting Point of Acid-Modified Polypropylene Acid-modified polypropylene pellets were heated from 20 ° C. to 220 ° C. at 10 ° C./min using a differential scanning calorimeter (“Q2000” manufactured by TA Instrument), and then −10 ° C. The measurement was carried out by cooling to 20 ° C. at / min and raising the temperature again from 20 ° C. to 220 ° C. at 10 ° C./min. The melting point was determined from the melting peak in the second heating process.
（８）樹脂組成物の粘度安定性
各実施例及び比較例で得られた樹脂組成物ペレット６０ｇをラボプラストミル（二軸異方向）を用いて窒素雰囲気下、２３０℃、１００ｒｐｍの条件で混練したときのトルク変化を測定した。混練開始１０分後及び６０分後のトルク値（それぞれＴＩ及びＴＦ）を算出し、ＴＦ／ＴＩの比率によって、下記のＡ〜Ｃの基準で評価することでロングラン性の指標とした。なお、基準Ｃは実使用において使用困難である。
Ａ ：４０／１００以上１２０／１００未満
Ｂ ：２０／１００以上４０／１００未満、又は１２０／１００以上１４０／１００未満
Ｃ ：２０／１００未満、又は１４０／１００以上(8) Viscosity stability of resin composition 60 g of resin composition pellets obtained in each Example and Comparative Example are kneaded using a laboplast mill (biaxially different directions) under a nitrogen atmosphere at 230 ° C. and 100 rpm. The change in torque was measured. The torque values (TI and TF, respectively) 10 minutes and 60 minutes after the start of kneading were calculated and evaluated according to the criteria of A to C below according to the TF / TI ratio, which was used as an index of long-running property. Criterion C is difficult to use in actual use.
A: 40/100 or more and less than 120/100 B: 20/100 or more and less than 40/100, or 120/100 or more and less than 140/100 C: less than 20/100 or 140/100 or more
（９）樹脂組成物の色相
ＨｕｎｔｅｒＬａｂ社製分光測色計「ＬａｂＳｃａｎ ＸＥ Ｓｅｎｓｏｒ」を用い、各実施例及び比較例で得られた樹脂組成物のペレットのＹＩ（イエローインデックス）値を測定した。なお、ＹＩ値は対象物の黄色度（黄色み）を表す指標であり、ＹＩ値が高いほど黄色度が強く、一方、ＹＩ値が低いほど黄色度が弱く、着色が少ないことを表す。(9) Hue of Resin Composition Using a spectrophotometer "LabScan XE Sensor" manufactured by HunterLab, the YI (yellow index) value of the pellets of the resin composition obtained in each Example and Comparative Example was measured. The YI value is an index indicating the yellowness (yellowness) of the object, and the higher the YI value, the stronger the yellowness, while the lower the YI value, the weaker the yellowness and less coloring.
（１０）酸素透過度
各実施例及び比較例で使用したＥＶＯＨ又は得られた樹脂組成物ペレットを用いて下記に示す押出条件にて単層製膜を行うことにより厚み２０μｍの単層フィルムを得た。単層フィルムの厚みは、引取りロール速度を変えることによって調整した。
押出機：東洋精機製作所製１軸押出機
スクリュー径：２０ｍｍφ（Ｌ／Ｄ＝２０、圧縮比＝３．５、フルフライト型）
スクリュー回転数：４０ｒｐｍ
押出温度：Ｃ１／Ｃ２／Ｃ３／Ｄ＝１９０／２２０／２２０／２２０℃
引取りロール温度：８０℃
得られた単層フィルムについて、酸素透過量測定装置（モダンコントロール社製「ＭＯＣＯＮ ＯＸ−ＴＲＡＮ２／２０」）を用い、温度２０℃、酸素供給側及びキャリアガス側の湿度６５％ＲＨ、酸素圧力１気圧、キャリアガス圧力１気圧の条件下で酸素透過速度［単位：ｃｃ・２０μｍ／（ｍ２・ｄａｙ・ａｔｍ）］を測定した。キャリアガスとしては２体積％の水素ガスを含む窒素ガスを使用した。(10) Oxygen Permeability A single-layer film having a thickness of 20 μm was obtained by forming a single-layer film under the extrusion conditions shown below using EVOH or the obtained resin composition pellets used in each Example and Comparative Example. rice field. The thickness of the monolayer film was adjusted by changing the take-up roll speed.
Extruder: Single-screw extruder manufactured by Toyo Seiki Seisakusho Screw diameter: 20 mmφ (L / D = 20, compression ratio = 3.5, full flight type)
Screw rotation speed: 40 rpm
Extrusion temperature: C1 / C2 / C3 / D = 190/220/220/220 ° C.
Pick-up roll temperature: 80 ° C
For the obtained single layer film, an oxygen permeation measuring device (“MOCON OX-TRAN2 / 20” manufactured by Modern Control Co., Ltd.) was used, the temperature was 20 ° C., the humidity on the oxygen supply side and the carrier gas side was 65% RH, and the oxygen pressure was 1. The oxygen permeation rate [unit: cc · 20 μm / (m 2 · day · atm)] was measured under the conditions of atmospheric pressure and carrier gas pressure of 1 atm. As the carrier gas, nitrogen gas containing 2% by volume of hydrogen gas was used.
（１１）ヘイズ
上記（１０）で得られた単層フィルムについて、反射・透過率計（村上色彩技術研究所製「ＨＲ−１００」）を用いてヘイズ値を測定した。(11) Haze The haze value of the single-layer film obtained in (10) above was measured using a reflectance / transmittance meter (“HR-100” manufactured by Murakami Color Technology Laboratory).
（１２）回収性評価（ダイビルドアップ、スクリュービルドアップ、回収組成物の色相）
日本ポリプロ株式会社製ポリプロピレン「ノバテックＰＰ ＥＡ７ＡＤ」（密度０．９０ｇ／ｃｃ、ＭＦＲ（１９０℃、２．１６ｋｇ荷重下）０．７ｇ／１０分）３１５０ｇと、各実施例及び比較例で得られた樹脂組成物のペレット３５０ｇを混合し、下記に示す押出条件にて溶融混練した後、得られたペレットを再度溶融混練する操作を４回繰り返し、計５回溶融混練した。この間、各溶融混練の過程において、３０分間おきにダイ上に蓄積された付着樹脂を採取、秤量し、測定値の合計をダイビルドアップ（目ヤニ）量とした。次に、１ｋｇの高密度ポリエチレンでパージした後、スクリューを取り外してスクリュー上の付着樹脂を採取・秤量することでスクリュービルドアップ（ゲル化した樹脂）量を求めた。また、ＨｕｎｔｅｒＬａｂ社製分光測色計「ＬａｂＳｃａｎ ＸＥ Ｓｅｎｓｏｒ」を用い、計５回の溶融混練後に得られた回収組成物ペレットのＹＩ（イエローインデックス）値を測定した。なお、ダイビルドアップ量は樹脂組成物とポリプロピレンとの相溶性の指標となり、ダイビルドアップ量が少ない程、相溶性が優れ、相溶性不足に起因する問題が起こりにくくなる。
押出機：東洋精機製作所製２軸押出機
スクリュー径：２５ｍｍφ
スクリュー回転数：１００ｒｐｍ
シリンダー、ダイ温度設定：Ｃ１／Ｃ２／Ｃ３／Ｃ４／Ｃ５／Ｄ＝１８０／２００／２３０／２３０／２３０／２３０℃
吐出速度：６ｋｇ／時間(12) Recoverability evaluation (die build-up, screw build-up, hue of recovered composition)
Polypropylene "Novatec PP EA7AD" manufactured by Japan Polypropylene Corporation (density 0.90 g / cc, MFR (190 ° C., under 2.16 kg load) 0.7 g / 10 minutes) 3150 g, obtained in each Example and Comparative Example. 350 g of pellets of the resin composition were mixed and melt-kneaded under the extrusion conditions shown below, and then the operation of melt-kneading the obtained pellets again was repeated 4 times, and melt-kneaded a total of 5 times. During this period, in each melt-kneading process, the adhesive resin accumulated on the die was collected and weighed every 30 minutes, and the total of the measured values was taken as the die build-up (rheumatic) amount. Next, after purging with 1 kg of high-density polyethylene, the screw was removed, and the adhesive resin on the screw was collected and weighed to determine the amount of screw build-up (gelled resin). In addition, the YI (yellow index) value of the recovered composition pellets obtained after a total of 5 melt-kneading was measured using a spectrocolorimeter "LabScan XE Sensor" manufactured by HunterLab. The amount of die build-up is an index of compatibility between the resin composition and polypropylene, and the smaller the amount of die build-up, the better the compatibility and the less likely the problem is due to insufficient compatibility.
Extruder: Twin-screw extruder manufactured by Toyo Seiki Seisakusho Screw diameter: 25 mmφ
Screw rotation speed: 100 rpm
Cylinder, die temperature setting: C1 / C2 / C3 / C4 / C5 / D = 180/200/230/230/230/230 ° C
Discharge rate: 6 kg / hour
実施例１
エチレン含有量３２モル％、けん化度９９．９モル％、ＭＦＲ（１９０℃、２．１６ｋｇ荷重）１．６７ｇ／１０ｍｉｎ、重量平均分子量４８０００、酸素透過度（２０℃、６５％ＲＨ条件下）０．２９ｃｃ・２０μｍ／（ｍ２・ｄａｙ・ａｔｍ）であるＥＶＯＨ（Ａ−１）９５質量部と、酸価７．９ｍｇＫＯＨ／ｇ、ＭＦＲ（１９０℃、２．１６ｋｇ荷重）２８０ｇ／１０ｍｉｎ、重量平均分子量８７０００、密度０．９０ｇ／ｃｍ３、融点１５３℃である無水マレイン酸グラフト変性ポリプロピレン（Ｂ−１）５質量部と、酢酸マグネシウムを２軸押出機を用いて２２０℃で溶融混練した後、ペレタイザーを用いてペレット化することにより樹脂組成物ペレットを得た。このとき、樹脂組成物中の酢酸マグネシウムの含有量（金属イオン換算）が１００ｐｐｍとなるようにその添加量を調整した。ＥＶＯＨ（Ａ−１）及び酸変性ポリプロピレン（Ｂ−１）の分析は、上記（１）〜（７）の方法により行った。当該樹脂組成物ペレットを用いて上記（２）、（８）〜（１２）の評価を行った。結果を表３に示す。Example 1
Ethylene content 32 mol%, saponification degree 99.9 mol%, MFR (190 ° C, 2.16 kg load) 1.67 g / 10 min, weight average molecular weight 48000, oxygen permeability (20 ° C, 65% RH conditions) 0 .29 cc · 20 μm / (m 2 · day · atm) EVOH (A-1) 95 parts by mass, acid value 7.9 mgKOH / g, MFR (190 ° C, 2.16 kg load) 280 g / 10 min, weight average After melt-kneading 5 parts by mass of maleic anhydride graft-modified polypropylene (B-1) having a molecular weight of 87,000, a density of 0.90 g / cm 3 , and a melting point of 153 ° C. and magnesium acetate at 220 ° C. using a twin-screw extruder. Resin composition pellets were obtained by pelletizing with a pelletizer. At this time, the amount of magnesium acetate added was adjusted so that the content of magnesium acetate (in terms of metal ions) in the resin composition was 100 ppm. The analysis of EVOH (A-1) and acid-modified polypropylene (B-1) was carried out by the methods (1) to (7) above. The above (2), (8) to (12) were evaluated using the resin composition pellets. The results are shown in Table 3.
実施例２〜１１、比較例２〜６
酸変性ポリプロピレンとして表１又は表２に記載されたものを用いた以外は、実施例１と同様にして樹脂組成物ペレットの作製及び評価を行った。結果を表３に示す。Examples 2-11, Comparative Examples 2-6
Resin composition pellets were prepared and evaluated in the same manner as in Example 1 except that the acid-modified polypropylenes listed in Table 1 or Table 2 were used. The results are shown in Table 3.
実施例１２〜１５、比較例８
ＥＶＯＨ（Ａ−１）と無水マレイン酸グラフト変性ポリプロピレン（Ｂ−１）の混合比を表１又は表２に記載されたとおりに変更した以外は、実施例１と同様にして樹脂組成物ペレットの作製及び評価を行った。結果を表３に示す。Examples 12 to 15, Comparative Example 8
The resin composition pellets were prepared in the same manner as in Example 1 except that the mixing ratio of EVOH (A-1) and maleic anhydride graft-modified polypropylene (B-1) was changed as shown in Table 1 or Table 2. It was prepared and evaluated. The results are shown in Table 3.
実施例１６〜１８、比較例９、１０
酢酸マグネシウムの添加量を表１又は表２に記載されたとおりに変更した以外は、実施例１と同様にして樹脂組成物ペレットの作製及び評価を行った。結果を表３に示す。Examples 16-18, Comparative Examples 9, 10
Resin composition pellets were prepared and evaluated in the same manner as in Example 1 except that the amount of magnesium acetate added was changed as shown in Table 1 or Table 2. The results are shown in Table 3.
実施例１９、２０
酢酸マグネシウムを酢酸カルシウム（実施例１９）又は酢酸亜鉛（実施例２０）に変更した以外は、実施例１と同様にして樹脂組成物ペレットの作製及び評価を行った。結果を表３に示す。Examples 19, 20
Resin composition pellets were prepared and evaluated in the same manner as in Example 1 except that magnesium acetate was changed to calcium acetate (Example 19) or zinc acetate (Example 20). The results are shown in Table 3.
実施例２１〜２４
ＥＶＯＨ（Ａ−１）、無水マレイン酸グラフト変性ポリプロピレン（Ｂ−１）、酢酸マグネシウムとともに、表２に記載されたヒンダードフェノール系化合物（Ｄ）を溶融混練した以外は実施例１と同様にして樹脂組成物ペレットの作製及び評価を行った。結果を表３に示す。Examples 21-24
Same as in Example 1 except that the hindered phenolic compound (D) shown in Table 2 was melt-kneaded together with EVOH (A-1), maleic anhydride graft-modified polypropylene (B-1), and magnesium acetate. Resin composition pellets were prepared and evaluated. The results are shown in Table 3.
実施例２５、２６
ＥＶＯＨとして表２に記載されたものを用いた以外は、実施例１と同様にして樹脂組成物ペレットの作製及び評価を行った。結果を表３に示す。Examples 25, 26
Resin composition pellets were prepared and evaluated in the same manner as in Example 1 except that the EVOH shown in Table 2 was used. The results are shown in Table 3.
比較例１
無水マレイン酸グラフト変性ポリプロピレン（Ｂ−１）及び酢酸マグネシウムを添加しなかった以外は、実施例１と同様にして樹脂組成物ペレットの作製及び評価を行った。結果を表３に示す。Comparative Example 1
Resin composition pellets were prepared and evaluated in the same manner as in Example 1 except that maleic anhydride graft-modified polypropylene (B-1) and magnesium acetate were not added. The results are shown in Table 3.
比較例７
無水マレイン酸グラフト変性ポリプロピレン（Ｂ−１）を添加しなかった以外は、実施例１と同様にして樹脂組成物ペレットの作製及び評価を行った。結果を表３に示す。Comparative Example 7
Resin composition pellets were prepared and evaluated in the same manner as in Example 1 except that maleic anhydride graft-modified polypropylene (B-1) was not added. The results are shown in Table 3.
比較例１１、１２
無水マレイン酸グラフト変性ポリプロピレン（Ｂ−１）の代わりに表２に記載された無水マレイン酸グラフト変性ポリエチレン（Ｂ−１７又はＢ−１８）を用いた以外は、実施例１と同様にして樹脂組成物ペレットの作製及び評価を行った。結果を表３に示す。Comparative Examples 11 and 12
The resin composition was the same as in Example 1 except that the maleic anhydride graft-modified polyethylene (B-17 or B-18) shown in Table 2 was used instead of the maleic anhydride graft-modified polypropylene (B-1). Product pellets were prepared and evaluated. The results are shown in Table 3.
Claims (14)
エチレン−ビニルアルコール共重合体（Ａ）のエチレン単位含有量が１５〜６０モル％、けん化度が８５モル％以上であり、
酸変性ポリプロピレン（Ｂ）の酸価が２〜７０ｍｇＫＯＨ／ｇ、ＭＦＲ（１９０℃、２．１６ｋｇ荷重下）が４〜１０００ｇ/１０ｍｉｎ、融点が１３０℃以上であり、
多価金属イオン（Ｃ）がマグネシウムイオン、カルシウムイオン及び亜鉛イオンからなる群から選択される少なくとも１種であり、
エチレン−ビニルアルコール共重合体（Ａ）に対する酸変性ポリプロピレン（Ｂ）の質量比［（Ｂ）／（Ａ）］が０．８／９９．２〜１０／９０であり、
全樹脂成分に対するエチレン−ビニルアルコール共重合体（Ａ）及び酸変性ポリプロピレン（Ｂ）の合計含有量が９０質量％以上であり、かつ
多価金属イオン（Ｃ）の含有量が６０〜３００ｐｐｍである、樹脂組成物。A resin composition containing an ethylene-vinyl alcohol copolymer (A), an acid-modified polypropylene (B), and a polyvalent metal ion (C).
The ethylene-vinyl alcohol copolymer (A) has an ethylene unit content of 15 to 60 mol% and a saponification degree of 85 mol% or more.
The acid value of the acid-modified polypropylene (B) is 2 to 70 mgKOH / g, the MFR (190 ° C., under a load of 2.16 kg) is 4 to 1000 g / 10 min, and the melting point is 130 ° C. or higher.
The polyvalent metal ion (C) is at least one selected from the group consisting of magnesium ion, calcium ion and zinc ion.
The mass ratio [(B) / (A)] of the acid-modified polypropylene (B) to the ethylene-vinyl alcohol copolymer (A) was 0.8 / 99.2 to 10/90.
The total content of the ethylene-vinyl alcohol copolymer (A) and the acid-modified polypropylene (B) with respect to all the resin components is 90% by mass or more, and the content of the polyvalent metal ion (C) is 60 to 300 ppm. , Resin composition.
A method for recovering a multilayer structure, wherein the multilayer structure according to any one of claims 9 to 11 is crushed and then melt-molded.
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| PCT/JP2019/032990 WO2020040281A1 (en) | 2018-08-24 | 2019-08-23 | Resin composition and multilayer structure using same |
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| JP2020538480A Active JP7321163B2 (en) | 2018-08-24 | 2019-08-23 | Resin composition and multilayer structure using the same |
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| WO2022030465A1 (en) * | 2020-08-04 | 2022-02-10 | 株式会社クラレ | Multilayer structure, packaging material in which same is used, recovery composition, and method for producing recovery composition |
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| US5260371A (en) * | 1991-07-23 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Process for making melt stable ethylene vinyl alcohol polymer compositions |
| JP2002121342A (en) * | 2000-10-18 | 2002-04-23 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and method of using it |
| JP2006137957A (en) * | 2001-01-22 | 2006-06-01 | Kuraray Co Ltd | Method for producing ethylene-vinyl alcohol copolymer resin composition |
| JP2006307208A (en) * | 2005-03-31 | 2006-11-09 | Kuraray Co Ltd | Maleated thermoplastic resin and process for producing the same |
| WO2006118272A1 (en) * | 2005-04-28 | 2006-11-09 | Mitsubishi Chemical Corporation | Acid-modified polypropylene resin, method for producing same, and resin composition using same |
| WO2011040523A1 (en) * | 2009-10-02 | 2011-04-07 | 株式会社クラレ | Compatibilising agent and method for producing same |
| WO2011118648A1 (en) * | 2010-03-25 | 2011-09-29 | 株式会社クラレ | Resin composition, process for production thereof, and multilayer structure |
| JP2011202147A (en) * | 2010-03-02 | 2011-10-13 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition, and molded article and multilayered structure using the same |
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2019
- 2019-08-23 WO PCT/JP2019/032990 patent/WO2020040281A1/en active Application Filing
- 2019-08-23 JP JP2020538480A patent/JP7321163B2/en active Active
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| US5260371A (en) * | 1991-07-23 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Process for making melt stable ethylene vinyl alcohol polymer compositions |
| JP2002121342A (en) * | 2000-10-18 | 2002-04-23 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and method of using it |
| JP2006137957A (en) * | 2001-01-22 | 2006-06-01 | Kuraray Co Ltd | Method for producing ethylene-vinyl alcohol copolymer resin composition |
| JP2006307208A (en) * | 2005-03-31 | 2006-11-09 | Kuraray Co Ltd | Maleated thermoplastic resin and process for producing the same |
| WO2006118272A1 (en) * | 2005-04-28 | 2006-11-09 | Mitsubishi Chemical Corporation | Acid-modified polypropylene resin, method for producing same, and resin composition using same |
| WO2011040523A1 (en) * | 2009-10-02 | 2011-04-07 | 株式会社クラレ | Compatibilising agent and method for producing same |
| JP2011202147A (en) * | 2010-03-02 | 2011-10-13 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition, and molded article and multilayered structure using the same |
| WO2011118648A1 (en) * | 2010-03-25 | 2011-09-29 | 株式会社クラレ | Resin composition, process for production thereof, and multilayer structure |
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| WO2020040281A1 (en) | 2020-02-27 |
| JP7321163B2 (en) | 2023-08-04 |
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