CN115477801A - Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure comprising same - Google Patents
Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure comprising same Download PDFInfo
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- CN115477801A CN115477801A CN202110668496.XA CN202110668496A CN115477801A CN 115477801 A CN115477801 A CN 115477801A CN 202110668496 A CN202110668496 A CN 202110668496A CN 115477801 A CN115477801 A CN 115477801A
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- China
- Prior art keywords
- evoh
- ethylene
- resin composition
- vinyl alcohol
- alcohol copolymer
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- 229920000219 Ethylene vinyl alcohol Polymers 0.000 title claims abstract description 346
- 239000011342 resin composition Substances 0.000 title claims abstract description 104
- 239000008188 pellet Substances 0.000 claims description 118
- 239000002245 particle Substances 0.000 claims description 64
- 239000012748 slip agent Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000005977 Ethylene Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 239000012790 adhesive layer Substances 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 230000005484 gravity Effects 0.000 claims description 5
- 238000007127 saponification reaction Methods 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 abstract description 310
- 238000012545 processing Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 307
- 239000010408 film Substances 0.000 description 51
- 239000000314 lubricant Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 43
- 238000000034 method Methods 0.000 description 33
- 239000008187 granular material Substances 0.000 description 29
- 238000001035 drying Methods 0.000 description 25
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 17
- 239000004327 boric acid Substances 0.000 description 17
- 239000012467 final product Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 14
- 239000001632 sodium acetate Substances 0.000 description 14
- 235000017281 sodium acetate Nutrition 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 230000003746 surface roughness Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000004291 polyenes Chemical class 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229940037312 stearamide Drugs 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XLLZUKPXODPNPP-UHFFFAOYSA-N [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] XLLZUKPXODPNPP-UHFFFAOYSA-N 0.000 description 1
- BUWURQPWRDROFU-UHFFFAOYSA-N [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] BUWURQPWRDROFU-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910001730 borate mineral Inorganic materials 0.000 description 1
- 239000010429 borate mineral Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- BMQVDVJKPMGHDO-UHFFFAOYSA-K magnesium;potassium;chloride;sulfate;trihydrate Chemical compound O.O.O.[Mg+2].[Cl-].[K+].[O-]S([O-])(=O)=O BMQVDVJKPMGHDO-UHFFFAOYSA-K 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229960001855 mannitol Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- VPOLVWCUBVJURT-UHFFFAOYSA-N pentadecasodium;pentaborate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] VPOLVWCUBVJURT-UHFFFAOYSA-N 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DPUZPWAFXJXHBN-UHFFFAOYSA-N tetrasodium dioxidoboranyloxy(dioxido)borane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]B([O-])OB([O-])[O-] DPUZPWAFXJXHBN-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
- C08L23/0861—Saponified vinylacetate
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- 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
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to an ethylene-vinyl alcohol copolymer (EVOH) resin composition, an ethylene-vinyl alcohol copolymer film formed therefrom, and a multilayer structure comprising the same. The EVOH resin composition has a surface core height difference (Sk) of 0.6-2.0 [ mu ] m and an overall standard deviation of the Sk of 0.05-0.55. The invention can reduce the torque output during processing, achieve the energy-saving effect, and also improve the stability during output so as to obtain better film appearance.
Description
Technical Field
The present invention relates to an ethylene-vinyl alcohol (EVOH) resin composition. The EVOH resin composition has a surface roughness in a specific range, and particularly has a core height difference (Sk) of 0.6 to 2.0 μm and an overall standard deviation of Sk of 0.05 to 0.55. Also disclosed are a film formed from the EVOH resin composition and a multilayer structure comprising the EVOH resin composition.
Background
EVOH resins are widely used in multilayer bodies for preserving perishable goods. For example, EVOH resins and multilayer bodies are commonly used in the food packaging industry, medical equipment and consumable industry, pharmaceutical industry, electronic industry, and agricultural chemical industry. EVOH resins are commonly used for incorporation into multilayer bodies as a distinct layer to serve as an oxygen barrier.
In the past, EVOH pellets often had problems of screw piling or blocking during extrusion, which resulted in an increase in the screw torque value, and these problems may possibly lower the visual appearance and mechanical strength of films formed from EVOH. Furthermore, these problems have not been adequately addressed or solved by known techniques.
Disclosure of Invention
In view of the continuous demand for providing an EVOH resin film-formed appearance with reduced torque output at the time of processing.
The present invention relates to an ethylene-vinyl alcohol copolymer (EVOH) resin composition having a specific range of surface roughness, wherein the ethylene-vinyl alcohol copolymer resin composition comprises an ethylene-vinyl alcohol copolymer resin, for example, having a surface core height difference (Sk) of 0.6-2.0 μm and an overall standard deviation of the Sk of 0.05-0.55. In a preferred embodiment, the EVOH resin composition has a surface core height difference (Sk) of 0.6-2.0 μm and an overall standard deviation of Sk of 0.10-0.45. The EVOH resin composition may be in the form of pellets, films, fibers, and the like. The EVOH resin composition is useful for preparing films or multilayer structures. The inventors found that by controlling the roughness parameter Sk of the surface of the EVOH resin composition to a specific range, the torque value of EVOH pellets during screw processing can be reduced to achieve energy saving effect, thereby realizing cost-effective preparation of EVOH resin composition, and also improving the stability during output to obtain a better film appearance.
In other aspects of the present invention, there is provided an EVOH resin composition (or pellets thereof) having a slip agent amount of 50 to 200ppm. For example, the EVOH resin composition of the present invention has a surface core height difference (Sk) of 0.6 to 2.0 μm, and an overall standard deviation of the Sk of 0.05 to 0.55, and has a slip agent amount of 50 to 200ppm. In some cases, the EVOH resin composition may have a boron content of between 10-450ppm. For example, the EVOH resin composition of the present invention has a surface core height difference (Sk) of 0.6 to 2.0 μm and an overall standard deviation of the Sk of 0.05 to 0.55, and has a boron content of 10 to 450ppm.
In addition/or alternatively, the ethylene-vinyl alcohol copolymer resin in the EVOH resin composition may have a saponification degree of 99.5mole% or more. The ethylene-vinyl alcohol copolymer resin in the EVOH resin composition may have an ethylene content of about 20to about 48 mole%. For example, the ethylene vinyl alcohol copolymer can have an ethylene content of about 25to about 45mole%. The EVOH resin composition may be formed of two or more EVOH having different ethylene contents.
In a non-limiting example, the EVOH resin composition has a bulk specific gravity of between 73 and 76g/cm 3 . In some cases, the EVOH resin composition may have a repose angle of 12.0 to 21.0 degrees.
In a non-limiting example, the ethylene-vinyl alcohol copolymer resin composition has a water content of less than 1.1 weight percent.
The EVOH resin composition may be in the form of pellets, films, fibers, and the like. In some embodiments, the EVOH resin composition is in the form of pellets, and the weight of 100 pellets is between 1.4 and 2.3g.
According to at least one embodiment, the multilayer structure comprises: (a) at least one layer is formed of an EVOH resin as described previously; (b) at least one polymer layer; and (c) at least one adhesive layer. The polymer layer may be, for example: selected from the group consisting of a low density polyethylene layer, a polyethylene-grafted maleic anhydride (pe-maleic anhydride) layer, a polypropylene layer, and a nylon layer. The adhesive layer is a tie layer.
Drawings
An implementation of the present technology will now be described, by way of example only, with reference to the accompanying drawings, in which:
FIG. 1 is a three-dimensional illustration of core height differences as applied in accordance with the present invention;
fig. 2 is a two-dimensional illustrative view of core height differences as applied in accordance with the present invention.
It should be understood that aspects of the present invention are not limited to the configurations, instrumentality and characteristics shown in the drawings.
Detailed Description
The present invention relates to an ethylene-vinyl alcohol copolymer (EVOH) resin composition. The EVOH resin composition has a specific surface roughness range, and particularly has a surface having a core height difference (Sk) of 0.6 to 2.0 μm and an overall standard deviation of the Sk of 0.05 to 0.55. The control of the surface roughness Sk of the EVOH resin composition can ensure that the EVOH resin composition and a film thereof have good efficacy by controlling different addition methods and addition amounts of slip agents in the preparation of EVOH. The EVOH resin composition is useful for preparing films or multilayer structures. The inventors have found that by controlling the roughness parameter Sk of the surface of the EVOH resin composition to a specific range, the torque value of the EVOH pellets at the screw output can be reduced to achieve the effect of saving energy, and the stability at the output can be improved to obtain a better film appearance.
The height difference (Sk) of the core part can be comprehensively evaluated according to the parameter. Sk refers to a value obtained by subtracting the minimum height from the maximum height of the core unit, and is calculated from a height difference between 0% and 100% of the equivalent linear load area ratio. As shown in fig. 1 and 2, sk represents the height of the core portion, i.e., the distance between the upper and lower levels of the core surface; smr1 represents a load area ratio (expressed in percentage) that distinguishes the core portion from the projecting wave crest portion; smr2 represents a load area ratio (expressed in percentage) that distinguishes the core portion from the projecting wave trough portion; spk represents the height of the removed peak, i.e., the average height of the peak above the surface of the core; svk denotes the depth of the valley removed, i.e. the average height of the valley below the surface of the core. This parameter extends the load length rate curve parameter of the profile parameter into three dimensions. The Sk may be, for example, 0.6-2.0 μm, 0.6-1.9 μm, 0.6-1.8 μm, 0.6-1.7 μm, 0.6-1.6 μm, 0.6-1.5 μm, 0.6-1.4 μm, 0.6-1.3 μm, 0.6-1.2 μm, 0.6-1.1 μm, 0.6-1.0 μm, 0.6-0.9 μm, 0.8-2.0 μm, 0.8-1.9 μm, 0.8-1.8 μm, 0.8-1.7 μm, 0.8-1.6 μm, 0.8-1.5 μm, 0.8-1.4 μm, 0.8-1.3 μm, 0.8-1.2 μm, 0.8-1.1.6 μm, 0.8-1.5 μm, 0.8-1.4 μm, 0.8-1.3 μm, 1.8-1.2 μm, 1.1.6 μm, 1.1.1.1.1.1.1.1.5 μm, 1.6-1.1.1.1.1.1.1.1.1.1.1.1.1.6 μm, 0.1.1.1.1.1.1.1.1.1.1.1.1.1.1.1.1.1.6 μm, 0.1.1.1.1.1.1.1.1.1.1.1.1.1.1.1.6 μm, 0.1.1.1.1.2 μm, 0.1.1.1.1.1.6-1.1.1.1.1.1.1.1.1.1.1.2 μm, 0.8-1.1.6 μm, 0.1.1.1.1.1.1.1.1.1.1.1.1.1.1.6 μm, 0.1.1.1.6 μm, 0.6 μm, 0.1.8-1.1.1.1.1.1.1.1.1.1.1.1.1.1.1.1.1.1.1.1.1.1.2 μm, 0.6 μm, 0.2 μm, 0.8-1.2 μm, 0.2 μm, 0.6 μm, 0.1.1.8-1.2.2.2.2.2.2 μm, 0.2 μm, 0.8-1.8-1.2 μm, 0.2.2 μm, 0.6 μm, 0.2.2.2.8-1.2.2.2.2.2.2.2.2.2 μm, 0.2.8-1.2.8-1.2 μm, 0.2 μm, 0.8-1.2 μm, 0.2.2.2.2.2.2 μm, 0.2.2.2.2.2.8-1.2.2.8-1.2.8-1.2 μm, 0.2 μm, 0.2.2.2.2.2.2.2.2.2.2.2 μm, 0.2 μm, 0.2.2.8-1.2.8-1.2.2.2.2.2.2.2.8-1.2.2.8-1.2 μm, 0.8-1.2.2.2 μm, 0.2.2.8-1.2.2.2.2.2.8-1.2 μm, 0.2 μm, 0.8-1.2.2 μm, 0.8-1.2.2.2.2.8-1.8-1. In some cases, the overall standard deviation of Sk may be, for example, between 0.05-0.55, 0.05-0.50, 0.05-0.45, 0.05-0.40, 0.05-0.35, 0.05-0.30, 0.05-0.25, 0.05-0.20, 0.05-0.15, 0.10-0.55, 0.10-0.50, 0.10-0.45, 0.10-0.40, 0.10-0.35, 0.10-0.30, 0.10-0.25, 0.10-0.20, 0.20-0.55, 0.20-0.50, 0.20-0.45, 0.20-0.40, 0.20-0.35, 0.20-0.30, 0.30-0.55, 0.30-0.50, 0.30-0.45, 0.30-0.40, 0.40-0.55, 0.50, 0.30-0.45, 0.40-0.40, 0.55, 0.50, 0.20-0.40-0.35, or 0.55. In some embodiments, the difference in core height (Sk) of the surface of the EVOH resin composition is between 0.6 and 2.0 μm, and the overall standard deviation of Sk is between 0.05 and 0.55. In a preferred embodiment, the difference in height (Sk) of the core portion of the surface of the EVOH resin composition is in the range of 0.6-2.0 μm and the overall standard deviation of Sk is in the range of 0.10-0.45, and excessively high values of Sk tend to cause friction during transportation of pellets in the screw, which leads to an increase in the torque value at the time of screw output; the excessively low Sk value shows that the height difference of the surface core part is small, so that when the screw is heated and conducted in the middle of a screw, the contact area is small, the phenomenon of uneven heating is easy to occur, and the final film thickness uniformity is reduced; on the other hand, when the total standard deviation of Sk is high, the surface properties are not uniform, stability at the screw output is easily affected, and the film thickness is easily uneven.
In one aspect, the present invention provides an EVOH resin composition. The EVOH resin composition may be in the form of pellets, films, fibers, and the like. The EVOH pellets as used herein refers to the form and/or shape of one or more pellets formed from an EVOH resin composition by pelletization. Although the EVOH resin composition is described throughout the present invention as being pelletized to form one or more EVOH pellets, the EVOH resin composition may be processed into beads, cubes, chips, shavings, and the like. In some embodiments, the EVOH resin composition is in the form of pellets, which may be cylindrical, spherical, or flat, cylindrical, elliptical, or angular, spherical, elliptical, or chess. In other embodiments, the EVOH resin composition is in the form of pellets, and the weight of 100 pellets is 1.4-2.3g. The weight of the aforementioned 100 particles may be for example, between 1.4-2.3g, 1.4-2.2g, 1.4-2.1g, 1.4-2.0g, 1.4-1.9g, 1.4-1.8g, 1.4-1.7g, 1.5-2.3g, 1.5-2.2g, 1.5-2.1g, 1.5-2.0g, 1.5-1.9g, 1.5-1.8g, 1.5-1.7g, 1.6-2.3g, 1.6-2.2g 1.6-2.1g, 1.6-2.0g, 1.6-1.9g, 1.6-1.8g, 1.6-1.7g, 1.7-2.3g, 1.7-2.2g, 1.7-2.1g, 1.7-2.0g, 1.7-1.9g, 1.7-1.8g, 1.8-2.3g, 1.8-2.2g, 1.8-2.1g, 1.8-2.0g or 1.8-1.9 g.
The EVOH pellets are formed from an EVOH having an ethylene content. For example, the ethylene content of the EVOH can be about 20to about 48mole%, about 20to about 45mole%, about 25to about 45mole%, about 28 to about 42mole%, or about 30 to about 40mole%. The EVOH resin composition may be formed of two or more EVOH having different ethylene contents. For example, the ethylene content of one of the EVOH may be in a range of about 20to about 35mole%, such as about 24 to about 35mole%, about 28 to about 35mole%, about 20to about 32mole%, about 24 to about 32mole%, about 28 to about 32mole%, about 20to about 30mole%, or about 24 to about 30mole%. Additionally or alternatively, one of the EVOH may have an ethylene content in a range of about 36 to about 48mole%, such as about 40 to about 48mole%, about 44 to about 48mole%, about 36 to about 45mole%, or about 40 to about 45mole%. However, in some preferred embodiments, the EVOH resin composition is formed from a single EVOH having an ethylene content of about 20to about 48 mole%.
Additionally or alternatively, the EVOH in the EVOH resin composition 100 may have a saponification degree of 90mole% or more, preferably 95mole% or more, preferably 97mole% or more, preferably 99.5mole% or more.
The EVOH resin composition may contain a boron compound and/or boric acid and/or cinnamic acid and/or an alkali metal and/or a conjugated polyene and/or a lubricant and/or an alkaline earth metal in some cases. The above-mentioned materials can impart better properties to the EVOH resin composition.
Additionally, or alternatively, according to other aspects of the present invention, the EVOH resin composition may have a boron content of 10 to 450ppm. For example, the EVOH resin composition of the present invention has a surface core height difference (Sk) of 0.6 to 2.0 μm and an overall standard deviation of the Sk of 0.05 to 0.55, and has a boron content of 10 to 450ppm. Without being bound to any particular theory, it is believed that the addition of the boron compound to the EVOH resin composition, resulting in a boron content of the EVOH composition of 10 to 450ppm, reduces or eliminates the adhesion of the EVOH resin composition during extrusion through a screw extruder, and further improves the uniformity of film thickness and flexibility. In some cases, such EVOH resin compositions may clean the screw extruder during extrusion by removing or at least partially removing EVOH resin that previously adhered to the inner surfaces of the screw extruder.
Typical EVOH resin compositions may comprise an ethylene vinyl alcohol copolymer; and a boron compound, wherein the ethylene-vinyl alcohol copolymer resin composition has a boron content of 10 to 450ppm. In some cases, it is possible to use, the EVOH resin composition may have a boron content of 10 to 450ppm, 10 to about 400ppm, 10 to about 350ppm, 10 to about 300ppm, 10 to about 275ppm, 10 to about 250ppm, 10 to about 225ppm, 10 to about 200ppm, 10 to about 175ppm, about 20to 450ppm, about 20to about 400ppm, about 20to about 350ppm, about 20to about 300ppm, about 20to about 275ppm, about 20to about 250ppm, about 20to about 225ppm, about 20to about 200ppm, about 20to about 175ppm, about 60 to 450ppm, about 60 to about 400ppm, about 60 to about 350ppm, about 60 to about 300ppm, about 60 to about 275ppm, about 60 to about 250ppm, about 60 to about 225ppm, about 60 to about 200ppm, about 60 to about 175ppm, about 100 to 450ppm, about 100 to about 450ppm, about about 100 to about 400ppm, about 100 to about 350ppm, about 100 to about 300ppm, about 100 to about 275ppm, about 100 to about 250ppm, about 100 to about 225ppm, about 100 to about 200ppm, about 100 to about 175ppm, about 140 to 450ppm, about 140 to about 400ppm, about 140 to about 350ppm, about 140 to about 300ppm, about 140 to about 275ppm, about 140 to about 250ppm, about 140 to about 225ppm, about 140 to about 200ppm, about 180 to about 450ppm, about 180 to about 400ppm, about 180 to about 350ppm, about 180 to about 300ppm, about 180 to about 275ppm, about 180 to about 250ppm, about 180 to about 225ppm, about 220 to 450ppm, about 220 to about 400ppm, about 220 to about 350ppm, about 220 to about 300ppm, about 220 to about 275ppm. When the boron content of the EVOH resin composition is in a certain range, the viscosity of the EVOH resin composition can be increased, the chance of adhesion of the EVOH resin composition to a screw is reduced, or EVOH on the screw is removed, so that the material has a self-cleaning function, and the uniformity of the film thickness can be further improved. In some cases, the EVOH resin composition may further include cinnamic acid, an alkali metal, a conjugated polyene, an alkaline earth metal, a salt thereof and/or a mixture thereof, in addition to a boron content of 10 to 450ppm. These are common materials usually present in EVOH resin compositions, making them more advantageous. When the content of the compound having a conjugated polyene structure is 1 to 30000ppm per unit weight of the EVOH resin composition, the coloration after heating can be further suppressed, and the thermal stability is further improved. On the other hand, if the content of the alkali metal compound or the alkaline earth metal compound is 1 to 1000ppm in terms of metal per unit weight of the EVOH resin composition, the long run moldability is further improved.
In some cases, the boron compound may include boric acid or a metal salt thereof. <xnotran> , , ( , ), , ( , , , ), ( , ), ( , , , , ), ( , ), ( (II), , ), ( , , , , , ), ( , ), ( , , , ), ( , , , ), , ( , , , , ), ( (I), , ), ( , , ), . </xnotran> Borate minerals such as borax, kainite, boronite, periclase/ganglite (suanite), and szaibelyite may be included. Among them, borax, boric acid and sodium borate (e.g., sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate and sodium octaborate) are preferably used.
The EVOH resin composition may further contain a lubricant, and when the content of the lubricant per unit weight of the EVOH resin composition is 1 to 300ppm, the EVOH resin composition can be more excellent in processability. In some embodiments, the EVOH resin composition (or pellets thereof) having a slip agent amount of between 50-200ppm, for example, between 50-200ppm, 50-180ppm, 50-160ppm, 50-140ppm, 50-120ppm, 50-100ppm, 50-90ppm, 50-80ppm, 50-70ppm, 60-200ppm, 60-180ppm, 60-160ppm, 60-140ppm, 60-120ppm, 60-100ppm, 60-90ppm, 60-80ppm, 60-70ppm, 70-200ppm, 70-180ppm, 70-160ppm, 70-140ppm, 70-120ppm, 70-100ppm, 70-90ppm, 70-80ppm, 90-200ppm, 90-180ppm, 90-160ppm, 90-120ppm, 90-100ppm, 100-200ppm, 100-180ppm, 100-160ppm, 100-140ppm, 100-120ppm, 110-200ppm, 110-180ppm, 110-160ppm, 110-140ppm, 130-200ppm, 130-180ppm, 130-150 ppm, 150-150 ppm, 180-180 ppm or 180 ppm. For example, the EVOH resin composition of the present invention has a surface core height difference (Sk) of 0.6 to 2.0 μm, and an overall standard deviation of the Sk of 0.05 to 0.55, and has a slip agent amount of 50 to 200ppm. In some instances, such as saturated fatty acid amides (e.g., behenamide, stearamide, and the like), unsaturated fatty acid amides (e.g., oleamide, erucamide, and the like), butyl stearate, stearyl alcohol, glyceryl monostearate, calcium stearate, zinc stearate, ethylene bis-stearamide (stearamide), sorbitan monopalmitate, sorbitan monostearate, mannitol, stearic acid, hardened castor oil, ethylene bis-stearamide, and the like. The lubricant can be used alone in 1 or in combination of 2 or more.
In a non-limiting example, the EVOH resin composition has a bulk specific gravity of between 73 and 76g/cm 3 . For example, between 73 and 76g/cm 3 、73-75.8g/cm 3 、73-75.6g/cm 3 、73-75.4g/cm 3 、73-75.2g/cm 3 、73-75g/cm 3 、73-74.8g/cm 3 、73-74.6g/cm 3 、73-74.4g/cm 3 、73-74.2g/cm 3 、73-74g/cm 3 、73.5-76g/cm 3 、73.5-75.8g/cm 3 、73.5-75.6g/cm 3 、73.5-75.4g/cm 3 、73.5-75.2g/cm 3 、73.5-75g/cm 3 、73.5-74.8g/cm 3 、73.5-74.6g/cm 3 、73.5-74.4g/cm 3 、73.5-74.2g/cm 3 、73.5-74g/cm 3 、74-76g/cm 3 、74-75.8g/cm 3 、74-75.6g/cm 3 、74-75.4g/cm 3 、74-75.2g/cm 3 、74-75g/cm 3 、74-74.8g/cm 3 、74-74.6g/cm 3 、74.5-76g/cm 3 、74.5-75.8g/cm 3 、74.5-75.6g/cm 3 、74.5-75.4g/cm 3 、74.5-75.2g/cm 3 、74.5-75g/cm 3 、75-76g/cm 3 、75-75.8g/cm 3 Or 75-75.6g/cm 3 In the meantime.
In some cases, the EVOH resin composition may have a repose angle of 12.0 to 21.0 degrees. <xnotran> , 12.0-21.0 , 12.0-20.5 , 12.0-20.0 , 12.0-19.5 , 12.0-19.0 , 12.0-18.5 , 12.0-18.0 , 12.0-17.5 , 12.0-17.0 , 12.0-16.5 , 12.0-16.0 , 12.0-15.5 , 12.0-15.0 , 12.0-14.5 , 12.0-14.0 , 12.0-13.5 , 12.0-13.0 , 13.0-21.0 , 13.0-20.5 , 13.0-20.0 , 13.0-19.5 , 13.0-19.0 , 13.0-18.5 , 13.0-18.0 , 13.0-17.5 , 13.0-17.0 , 13.0-16.5 , 13.0-16.0 , 13.0-15.5 , 13.0-15.0 , 13.0-14.5 , 13.0-14.0 , 14.0-21.0 , 14.0-20.5 , 14.0-20.0 , 14.0-19.5 , 14.0-19.0 , 14.0-18.5 , 14.0-18.0 , 14.0-17.5 , 14.0-17.0 , 14.0-16.5 , 14.0-16.0 , 14.0-15.5 , 14.0-15.0 , 15.0-21.0 , 15.0-20.5 , 15.0-20.0 , 15.0-19.5 , 15.0-19.0 , 15.0-18.5 , 15.0-18.0 , 15.0-17.5 , 15.0-17.0 , 15.0-16.5 , 15.0-16.0 , 16.0-21.0 , 16.0-20.5 , 16.0-20.0 , 16.0-19.5 , 16.0-19.0 , 16.0-18.5 , 16.0-18.0 , 16.0-17.5 , 16.0-17.0 , 17.0-21.0 , 17.0-20.5 , 17.0-20.0 , 17.0-19.5 , 17.0-19.0 , 17.0-18.5 17.0-18.0 . </xnotran>
The EVOH resin composition of the present invention typically has a water content within a specific range, for example, the water content of the EVOH resin composition may be less than 1.1 weight percent (wt%), less than 1.02%, less than 1.0%, less than 0.9%, less than 0.8%, less than 0.7%, less than 0.6%, less than 0.5%, less than 0.4%, less than 0.3%, less than 0.2%, or less than 0.1% as evaluated as the water content of the EVOH resin composition in volatile parts. Or between 0.01 and 1.1wt%, between 0.08 and 1.1wt%, or between 0.05 and 1.1wt%. It has been unexpectedly found that the water content of the EVOH resin composition must be controlled within a certain range, and that if the water content is too high, the subsequent processing problems occur, such as the formation of bubbles, uneven film thickness, and increased flow marks in the film or multilayer structure formed from the EVOH resin composition. The EVOH pellets finally obtained were analyzed for volatiles using the ISO 14663-2Annex A method.
The EVOH resin composition is advantageous for more efficiently producing an EVOH film formed therefrom. Suitable methods and equipment for preparing EVOH films may include those readily understood by one of ordinary skill in the art. The inventors believe that by controlling the surface roughness of the EVOH resin composition, the EVOH resin composition can reduce the torque in the extruder and also improve the appearance of a film or multilayer structure formed from the EVOH resin composition.
In still another aspect, the present invention provides a multilayer structure having at least one layer formed of the EVOH resin composition of the present invention; at least one polymer layer; and at least one adhesive layer. The polymeric layer may be selected from the group consisting of a low density polyethylene layer, a polyethylene grafted maleic anhydride layer, a polypropylene layer, a nylon layer, and combinations thereof. The adhesive layer may be a tie layer, such as ARKEMA OREVAC 18729 from ARKEMA.
Examples
The following non-limiting examples of various aspects of the present invention are provided primarily to illustrate various aspects of the present invention and the effects achieved thereby.
Example 1
The following provides a non-limiting method for producing EVOH pellets formed from an EVOH resin composition. 10 non-limiting example EVOH resin compositions (examples EVOH 1-10) and 7 comparative example EVOH resin compositions (comparative examples EVOH 1-7) were prepared according to a method similar to that disclosed below. However, the specific methods of preparing the example EVOH's 1-10 and the comparative example EVOH's 1-7 generally differ from the methods disclosed below in one or more respects.
The scheme controls different addition modes of the lubricant solution to enable the lubricant to be uniformly attached to the surface, and further controls whether nitrogen is introduced into the lubricant solution or not and the mass ratio of the lubricant solution to particles to achieve ideal lubricant attachment amount and attachment uniformity.
EXAMPLES EVOH
1 granule
An ethylene-vinyl acetate copolymer (hereinafter referred to as "EVAC") having an ethylene content of 32mole% was saponified to a degree of saponification of 99.5% to prepare an EVOH polymer. Subsequently, EVOH was dissolved in a solution containing methanol and water (ratio 70. Thereafter, the EVOH solid content of the solution was 41wt.%, and the solution was left at 60 ℃.
The EVOH/methanol/water solution was pumped by a pump into a feed pipe having a flow rate of 120L/min and then into an inlet pipe having a diameter of 2.8 mm. And extruded into water at 1.5 ℃ in the form of strands, solidified by staying in water for 100 seconds, and cut at 1500rpm using a rotary knife to form EVOH pellets, thereby forming EVOH pellets by strand dicing. The EVOH pellets were centrifuged to separate EVOH pellets. The separated EVOH particles were washed with water. The EVOH pellets were cylindrical pellets having a height of about 3mm and a cross-sectional area of about 2.4mm in the major axis.
Next, ethylene Bisstearamide (EBS), a lubricant, was added to the EVOH pellets in such an amount that the final product contained 50ppm of the lubricant and was added uniformly in the solution. That is, particles immersed in a boric acid/sodium acetate solution are first uniformly dispersed by adding a specified amount of slip agent to the solution, and then immersed in the solution in a ratio of 1. And finally, mixing the particles and the solution at 80 ℃ for 24 hours, introducing nitrogen gas at the flow rate of 10L/min to uniformly mix the particles and the solution, evaporating the solvent to dryness, and finally drying the finished product to obtain the EVOH particles added with the lubricant.
EXAMPLES EVOH
2 particles of
EVOH pellets used in example EVOH 2 were prepared using a similar method to the example EVOH 1 pellets. However, in the preparation of EVOH pellets of example EVOH 2, a slip agent was added to the EVOH pellets in such an amount that the final product contained 60ppm of slip agent and was added so as to be homogeneous in the solution.
That is, the particles soaked in the boric acid/sodium acetate solution are added with a certain amount of lubricant according to the weight of the solution to uniformly disperse the lubricant, and then the particles are soaked in the solution, wherein the weight ratio of the solution to the particles is 0.8. And finally, mixing the particles and the solution at 80 ℃ for 24 hours, introducing nitrogen gas at the flow rate of 10L/min to uniformly mix the particles and the solution, evaporating the solvent to dryness, and finally drying the finished product to obtain the EVOH particles added with the lubricant.
EXAMPLES EVOH
3 granules
EVOH pellets used in example EVOH 3 were prepared using a similar method to the example EVOH 1 pellets. However, in the preparation of EVOH pellets of example EVOH 3, a slip agent was added to the EVOH pellets in such an amount that the final product contained 90ppm of slip agent, and the addition was carried out by spraying before drying.
That is, the particles soaked in boric acid/sodium acetate are taken out, and a solution dispersed in 1000ml of water at a specific lubricant amount is sprayed at room temperature, wherein the ratio of the sprayed solution to the particle amount is 1. And finally, drying the granules to obtain finished EVOH granules added with the lubricant.
EXAMPLES EVOH
4 granules
EVOH pellets for example EVOH 4 were prepared using a similar method to the example EVOH 1 pellets. However, when EVOH pellets of example EVOH 4 were prepared, a slip agent was added to the EVOH pellets so that the amount of the slip agent added was adjusted to 150ppm in the final product, and the addition was carried out by spraying before drying.
That is, the particles soaked in boric acid/sodium acetate are taken out, and a solution dispersed in 1000ml of water at a specific lubricant amount is sprayed at room temperature, wherein the ratio of the sprayed solution to the particle amount is 1. And finally, drying the granules to obtain the finished product, namely the EVOH granules added with the slip agent.
EXAMPLES EVOH
5 particles
EVOH pellets for example EVOH 5 were prepared using a similar method to the example EVOH 1 pellets. However, when EVOH pellets of example EVOH 5 were prepared, a slip agent was added to the EVOH pellets so that the amount of the slip agent added was adjusted to 175ppm in the final product, and the resulting mixture was sprayed before drying.
That is, the particles soaked in boric acid/sodium acetate were taken out, and a solution dispersed in 1000ml of water at a specified lubricant amount was sprayed at room temperature, the ratio of the sprayed solution to the amount of the particles being 0.9. And finally, drying the granules to obtain the finished product, namely the EVOH granules added with the slip agent.
EXAMPLES EVOH
6 granules
EVOH pellets for example EVOH 6 were prepared using a similar method to that for example EVOH 1 pellets, however, the EVOH pellets for example EVOH 6 were saponified with an ethylene-vinyl acetate copolymer having an ethylene content of 29 mole%.
In addition, when EVOH pellets of example EVOH 6 were prepared, a lubricant was added to the EVOH pellets so that the amount of the lubricant added was adjusted to 75ppm in the final product, and the lubricant was added so as to be uniform in the solution. That is, the particles soaked in the boric acid/sodium acetate solution are added with a certain amount of lubricant according to the weight of the solution to uniformly disperse the lubricant, and then the particles are soaked in the solution, wherein the weight ratio of the solution to the particles is 0.9. And finally, mixing the particles and the solution at 80 ℃ for 24 hours, introducing nitrogen gas at the flow rate of 10L/min to uniformly mix the particles and the solution, evaporating the solvent to dryness, and finally drying the finished product to obtain the EVOH particles added with the lubricant.
EXAMPLES EVOH
7 granules
EVOH pellets for example EVOH 7 were prepared using a similar method to the example EVOH 6 pellets. However, in the preparation of EVOH pellets of example EVOH 7, a slip agent was added to the EVOH pellets in such an amount that the final product contained 90ppm, and the addition was carried out by spraying before drying.
That is, the particles soaked in boric acid/sodium acetate were taken out, and a solution dispersed in 1000ml of water at a specified lubricant amount was sprayed at room temperature, the ratio of the sprayed solution to the amount of the particles being 0.9. And finally, drying the granules to obtain the finished product, namely the EVOH granules added with the slip agent.
EXAMPLES EVOH
8 granules
EVOH pellets used in example EVOH 8 were prepared using a similar method to the example EVOH 6 pellets. However, when EVOH pellets of example EVOH 8 were prepared, a slip agent was added to the EVOH pellets in such an amount that the final product contained 150ppm, and the resulting mixture was sprayed before drying.
That is, the particles soaked in boric acid/sodium acetate were taken out, and a solution dispersed in 1000ml of water at a specified lubricant amount was sprayed at room temperature, the ratio of the sprayed solution to the amount of the particles being 0.8. And finally, drying the granules to obtain the finished product, namely the EVOH granules added with the slip agent.
EXAMPLES EVOH
9 granules
EVOH pellets used in example EVOH 9 were prepared using a similar method to the example EVOH 6 pellets. However, when EVOH pellets of example EVOH 9 were prepared, a slip agent was added to the EVOH pellets in such an amount that the final product contained 175ppm, and the addition was carried out by spraying before drying.
That is, the particles soaked in boric acid/sodium acetate are taken out, and a solution dispersed in 1000ml of water at a specific lubricant amount is sprayed at room temperature, wherein the ratio of the sprayed solution to the particle amount is 1. And finally, drying the granules to obtain the finished product, namely the EVOH granules added with the slip agent.
EXAMPLES EVOH
10 particles
EVOH pellets for example EVOH 10 were prepared using a similar method to the example EVOH 6 pellets. However, when EVOH pellets of example EVOH 10 were prepared, a slip agent was added to the EVOH pellets so that the amount of the slip agent added was 60ppm in the final product, and the resulting mixture was sprayed before drying.
That is, the particles soaked in boric acid/sodium acetate were taken out, and a solution dispersed in 1000ml of water at a specified lubricant amount was sprayed at room temperature, the ratio of the sprayed solution to the amount of the particles being 0.8. And finally, drying the granules to obtain the finished product, namely the EVOH granules added with the slip agent.
Comparative example EVOH
1 granule
EVOH pellets for comparative example EVOH 1 were prepared using a similar procedure to that of example EVOH 1 pellets. However, when EVOH pellets of comparative example EVOH 1 were prepared, no slip agent was added to the EVOH pellets.
Comparative example EVOH
2 granules
EVOH pellets for comparative example EVOH 2 were prepared using a similar method to that for example EVOH 1 pellets. However, when EVOH pellets of comparative example EVOH 2 were prepared, a slip agent was added to the EVOH pellets so that the amount of the slip agent added was adjusted to 30ppm in the final product, and the resulting mixture was sprayed before drying.
That is, the particles soaked in boric acid/sodium acetate were taken out, and a solution dispersed in 1000ml of water at a specified lubricant amount was sprayed at room temperature, the ratio of the sprayed solution to the amount of the particles being 0.8. And finally, drying the granules to obtain finished EVOH granules added with the lubricant.
Comparative example EVOH
3 granules
EVOH pellets for comparative example EVOH 3 were prepared using a similar method to that of example EVOH 1 pellets. However, when EVOH pellets of comparative example EVOH 3 were prepared, a slip agent was added to the EVOH pellets so that the amount of the added slip agent was adjusted to 250ppm in the final product and was added so as to be uniform in the solution.
That is, the particles soaked in the boric acid/sodium acetate solution are added with a certain amount of lubricant according to the weight of the solution to uniformly disperse the lubricant, and then the particles are soaked in the solution, wherein the weight ratio of the solution to the particles is 0.8. And finally, uniformly mixing the particles and the solution at 80 ℃ for 24 hours, uniformly mixing the particles and the solution, evaporating the solvent to dryness, and finally drying a finished product to obtain the EVOH particles added with the lubricant.
Comparative example EVOH
4 particles
EVOH pellets for comparative example EVOH 4 were prepared using a similar method to that of example EVOH 1 pellets. However, when EVOH pellets of comparative example EVOH 4 were prepared, a lubricant was added to the EVOH pellets so that the amount of the lubricant added was adjusted to 90ppm in the final product, and the addition was made in the form of an EVOH solution.
That is, an ethylene-vinyl acetate copolymer having an ethylene content of 32mole% was saponified to have a saponification degree of 99.5% to prepare an EVOH polymer. Subsequently, EVOH was dissolved in a solution containing methanol and water (ratio 70. A slip agent was added in a specific amount relative to the weight of the solution, after which the EVOH solid content of the solution was 41wt.%, and the solution was left at 60 ℃.
The above-mentioned solution of methanol, water and EVOH was then pelletized by underwater pelletizing. Specifically, the solution of methanol, water and EVOH was pumped into a feed tube at a flow rate of 120L/min using a pump, then fed into an inlet tube having a diameter of 2.8mm, and cut at 1500rpm using a rotary knife. Water at 5 ℃ was added to cool the EVOH pellets. Subsequently, the EVOH pellets were centrifuged to separate out EVOH particles. The separated EVOH pellets were washed with water and then dried to obtain EVOH pellets to which a slip agent was added.
Comparative example EVOH
5 particles
EVOH pellets for comparative example EVOH 5 were prepared using a similar procedure to that of example EVOH 1 pellets. However, when EVOH pellets of comparative example EVOH 5 were prepared, a slip agent was added to the EVOH pellets so that the amount of the additive was adjusted to 250ppm in the final product, and the resulting mixture was sprayed before drying.
That is, the particles soaked in boric acid/sodium acetate are taken out, and a solution dispersed in 1000ml of water at a specific lubricant amount is sprayed at room temperature, wherein the ratio of the sprayed solution to the particle amount is 0.9. And finally, drying the granules to obtain the finished product, namely the EVOH granules added with the slip agent.
Comparative example EVOH
6 particles
EVOH pellets for comparative example EVOH 6 were prepared using a similar method to that of example EVOH 1 pellets. However, when EVOH pellets of comparative example EVOH 6 were prepared, a slip agent was added to the EVOH pellets so that the amount of the added slip agent was adjusted to 60ppm in the final product, and the added slip agent was added in a dry-blended form after drying the pellets. That is, dry blending of the EVOH pellets after drying and the lubricant is carried out by a dry blender.
Comparative example EVOH
7 granules
EVOH pellets for comparative example EVOH 7 were prepared using a similar method to that of example EVOH 1 pellets. However, when EVOH pellets of comparative example EVOH 7 were prepared, a lubricant was added to the EVOH pellets in such an amount that the final product contained 75ppm and the lubricant was added so as to be uniform in the solution.
That is, the particles soaked in the boric acid/sodium acetate solution are added with a certain amount of lubricant according to the weight of the solution to uniformly disperse the lubricant, and then the particles are soaked in the solution, wherein the weight ratio of the solution to the particles is 0.9. And finally, uniformly mixing the particles and the solution at 80 ℃ for 24 hours without introducing nitrogen, simultaneously evaporating the solvent to dryness, and finally drying the finished product to obtain the EVOH particles added with the lubricant.
Example 2
Films were formed using the example EVOH particles 1-10, respectively, according to the method described below. The EVOH pellets of examples 1 to 10 and the EVOH pellets of comparative examples 1 to 7 were fed into a single-layer T-die casting film extruder (optical control system MEV 4) to prepare films. The films formed from the EVOH pellets of examples 1-10 and the EVOH pellets of comparative examples 1-7 each had a thickness of 20 μm. The temperature of the extruder was set at 220 deg.C and the temperature of the die (i.e., T-die) was set at 230 deg.C. The rotational frequency of the screw was 7rpm (rotations/minutes).
Example 3
The EVOH pellets of examples 1-10 and the EVOH pellets of comparative examples 1-7 were evaluated to judge the properties of these EVOH pellets and films formed therefrom. Example EVOH pellets 1-10 were prepared according to a method similar to that described in example 1 above, as described above. However, the method for producing EVOH pellets 1-10 differs for the EVOH pellets produced in the following respects: different ethylene contents, addition method of lubricant, amount of lubricant, nitrogen introduction or not, proportion of blending solution and particles, operation temperature and operation time. Comparative example EVOH pellets 1-7 were also prepared according to a method similar to that described in example 1.
The extruder mean torque values were further evaluated. Films were formed from example EVOH 1-10 and comparative example EVOH 1-7 individually in a similar manner as described in example 2, and the films were evaluated for film thickness uniformity.
Table 1 below provides a summary of some of the properties of the example EVOH pellets 1-10 and the comparative example EVOH pellets 1-7, namely, the amount of added slip, the bulk specific gravity, the angle of repose, the 100 pellet weight, the overall standard deviation of Sk, the extruder average torque, and the film thickness uniformity of the films formed from the example EVOH 1-10 and the comparative example EVOH 1-7.
The surface roughness characteristic of the EVOH resin composition may also be described by the line maximum height (Rz) of the surface, which is defined by the standard reference JIS B0601 (2001 version), as the sum of the height of the highest peak and the depth of the deepest valley in a profile curve over a reference length.
TABLE 1
Remarking: rz is the line maximum height roughness.
TABLE 1 (continuation)
Remarking: rz is the line maximum height roughness.
In order to evaluate the particle surface roughness Sk of the EVOH examples 1 to 10 and the EVOH comparative examples 1 to 7, EVOH particles were placed on a plate, the particle surface roughness was measured (excluding a part of data with a tilt of more than 0.5 tenths when measuring to ensure a relatively horizontal state of the scanning plane (tilt = 129 μm on the side of the maximum height Sz of the plane/analysis range). LEXT OLS5000-SAF manufactured by Olympus, and an image was made at an air temperature of 24 ± 3 ℃ and a relative humidity of 63 ± 3%. The filter was set to be unfiltered.the light source was a light source of wavelength of 405 nm. The objective lens was 100 × magnified (MPLAPON-100 × LEXT). The optical zoom was set to 1.0 × 129 μm when measuring rz.the image area was set to be a centerline of the image area. The resolution was set to be 2012 pixel × 1024 pixels.the values of 100 particles were measured and the average and the standard deviation thereof were measured by ISO 25178 JIS method; rz 0601 (2001) method.
The repose angle of the EVOH of examples 1-10 and the EVOH of comparative examples 1-7 was evaluated by laying an A4 blank sheet on a bench top, filling a glass funnel with EVOH resin of a fixed height, slowly lifting the glass funnel, lifting the glass funnel at a rate of 2cm/s, and measuring the angle between the side of the particle swarm and the table top by a protractor.
The bulk specific gravities of the EVOH's of examples 1-10 and comparative examples EVOH's 1-7 were evaluated and analyzed by the method of JIS K-7365.
Examples 1-10 and comparative examples 1-7 extruder torque values during processing were data for a screw extruder using an OCS, model ME25, and the samples were poured into the machine at 50rpm for 5 minutes to clean and measure the samples: the average torque value of the film was measured at 7rpm and screw temperatures of Zone1, zone2, zone3, zone4, zone5 at 195 ℃, zone2, zone3, zone4, zone 230 ℃ for 15 to 20 minutes per minute.
Further, film appearance evaluations were conducted for the films formed from the examples EVOH 1-10 and the comparative examples EVOH 1-7. In the evaluation, the state of a normally extruded film was controlled to an average thickness of 25 μm; the condition of uneven film thickness is that a film surface of 10 × 10cm is selected, the average mark 9 positions are marked, the thickness is more than +/-10 μm of the original theory, and the film thickness is uneven when the mark exceeds 5 points. If the film thickness is normal, represented by O; if the film thickness is not uniform, the film thickness is expressed by delta; if the membrane is broken, X is used.
The amount of lubricant adhering to the surfaces of pellets was measured by the following method for the examples EVOH 1-10 and comparative examples EVOH 1-7: 20g of dioctyl phthalate (DOP) were placed in a 50ml beaker, then 10g of EVOH pellets were placed and stirred well. Then, the lubricant on the particle surface was eluted into DOP by heating and stirring on a thermal stirrer heated to 100 ℃ for 60 minutes or more. 20to 30mg of the DOP solution containing the lubricant was added to a trace nitrogen analyzer (manufactured by Mitsubishi chemical corporation, TN-2100H) to quantitatively analyze the nitrogen concentration.
The results show that the example EVOH 1-10 has a low torsional output (19 to 25 Torr), and the film formed from the example EVOH 1-10 does not have broken film or uneven film thickness, indicating that the example EVOH 1-10 exhibits better processing torsional output and film appearance.
As a result of the tests of the present invention, it was found that by controlling the surface roughness parameter Sk and the standard deviation thereof of the EVOH resin composition within a specific range, the torque value of EVOH pellets during screw processing can be reduced, or the stability during screw processing can be improved to obtain a good film appearance. As shown in table 1, comparative examples EVOH 1 to 5 had Sk outside the desired range described herein, comparative examples EVOH 2, 6 and 7 had Sk total standard deviation outside the desired range described herein, and test results showed that comparative examples EVOH 1 and 4 had high output Torque values (140 and 120 torr), while comparative examples EVOH 1, 2, 4, 6 and 7 had uneven film thickness, and comparative examples EVOH 3 and 5 had broken films, and thus the films formed from comparative examples EVOH 1 to 7 all had poor film appearance.
In summary, the EVOH resin composition of the present invention has the surface roughness parameters Sk and the total standard deviation of Sk in a specific range, can reduce the torsion value of EVOH pellets when processed in screw output, so as to achieve the effect of energy saving, realize a cost-effective preparation method of EVOH resin composition, and also can improve the stability in output to obtain a better film appearance. The inventors have found that the EVOH resin composition and its film have excellent efficacy by controlling the surface roughness Sk of the EVOH resin composition by controlling the method and amount of different additives in the EVOH process.
All ranges provided herein are intended to include each specific range within the given range as well as combinations of sub-ranges between the given ranges. Moreover, unless otherwise indicated, all ranges provided herein are inclusive of the endpoints of the ranges. Thus, ranges 1-5 specifically include 1, 2, 3, 4, and 5, as well as sub-ranges such as 2-5, 3-5, 2-3, 2-4, 1-4, and the like.
All publications and patent applications cited in this specification are herein incorporated by reference, and for any and all purposes, each individual publication or patent application is specifically and individually indicated to be incorporated by reference. In the event of a discrepancy between this document and any publication or patent application incorporated by reference herein, this document controls.
The terms including, having, and comprising as used herein have an open, non-limiting meaning. The terms a and an should be understood to cover the plural as well as the singular. The term one or more refers to at least one and may therefore include a single feature or a mixture/combination of features.
Except in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are to be understood as being modified in all instances by the term about, meaning within ± 5% of the number indicated. As used herein, the term substantially free or substantially free means less than about 2% of a particular feature. All elements or features positively set forth herein are negatively excluded from the claimed scope.
Claims (15)
1. An ethylene-vinyl alcohol copolymer resin composition comprising an ethylene-vinyl alcohol copolymer resin; characterized in that the ethylene-vinyl alcohol copolymer resin composition has a surface having a difference in height of a core portion of 0.6 to 2.0 μm and an overall standard deviation of the difference in height of the core portion of 0.05 to 0.55.
2. The ethylene-vinyl alcohol copolymer resin composition according to claim 1, wherein the total standard deviation of the difference in height of the core portion is from 0.10 to 0.45.
3. The ethylene-vinyl alcohol copolymer resin composition according to claim 1, wherein the ethylene-vinyl alcohol copolymer resin composition is in the form of particles.
4. The ethylene-vinyl alcohol copolymer resin composition according to claim 1, wherein the ethylene content of the ethylene-vinyl alcohol copolymer resin is from 20to 48mole percent.
5. The ethylene-vinyl alcohol copolymer resin composition according to any one of claims 1 to 4, wherein the saponification degree of the ethylene-vinyl alcohol copolymer resin is more than 99.5 mol%.
6. The ethylene-vinyl alcohol copolymer resin composition according to any one of claims 1 to 4, which has a slip agent amount of 50 to 200ppm.
7. The ethylene-vinyl alcohol copolymer resin composition according to any one of claims 1 to 4, whereinIn that it has a bulk specific gravity of from 73 to 76g/cm 3 。
8. The ethylene-vinyl alcohol copolymer resin composition according to any one of claims 1 to 4, wherein the ethylene-vinyl alcohol copolymer resin composition is in the form of pellets, and the weight of 100 pellets is from 1.4 to 2.3g.
9. The ethylene-vinyl alcohol copolymer resin composition according to any one of claims 1 to 4, wherein the angle of repose is from 12.0 to 21.0 degrees.
10. The ethylene-vinyl alcohol copolymer resin composition according to any one of claims 1 to 4, wherein the boron content is from 10 to 450ppm.
11. The ethylene-vinyl alcohol copolymer resin composition according to any one of claims 1 to 4, wherein the maximum height of the surface line is 1.0 to 9.9 μm.
12. The ethylene-vinyl alcohol copolymer resin composition according to any one of claims 1 to 4, having a water content of less than 1.1% by weight.
13. An ethylene-vinyl alcohol copolymer film formed from the ethylene-vinyl alcohol copolymer resin composition according to any one of claims 1 to 12.
14. A multilayer structure, comprising:
(a) At least one layer formed from the ethylene-vinyl alcohol copolymer resin of any one of claims 1-12;
(b) At least one polymer layer; and
(c) At least one adhesive layer.
15. The multi-layer structure of claim 14, wherein the polymer layer is selected from the group consisting of a low density polyethylene layer, a polyethylene grafted maleic anhydride layer, a polypropylene layer, and a nylon layer, and the adhesive layer is an adhesive layer.
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| CN202110668496.XA CN115477801B (en) | 2021-06-16 | 2021-06-16 | Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure comprising the same |
| JP2021181403A JP7326404B2 (en) | 2021-06-16 | 2021-11-05 | Ethylene-vinyl alcohol copolymer resin composition |
| EP22162237.6A EP4105024A1 (en) | 2021-06-16 | 2022-03-15 | Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure containing the same |
| KR1020220032541A KR102467557B1 (en) | 2021-06-16 | 2022-03-16 | Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure containing the same |
| US17/700,999 US11566091B2 (en) | 2021-06-16 | 2022-03-22 | Ethylene vinyl alcohol copolymer resin composition, ethylene vinyl alcohol copolymer film formed therefrom, and multilayer structure containing the same |
| EP22824279.8A EP4357408A1 (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure |
| PCT/CN2022/099144 WO2022262806A1 (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure |
| PCT/CN2022/099166 WO2022262811A1 (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure |
| TW111122427A TWI803356B (en) | 2021-06-16 | 2022-06-16 | Ethylene vinyl alcohol copolymer resin particle composition, ethylene vinyl alcohol copolymer film and multilayer structure formed therefrom |
| KR1020237043513A KR20240009479A (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film and multilayer structure consisting thereof |
| EP22824284.8A EP4357409A1 (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure |
| KR1020237043517A KR20240009480A (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film and multilayer structure consisting thereof |
| PCT/CN2022/099172 WO2022262813A1 (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure |
| TW111122430A TWI803358B (en) | 2021-06-16 | 2022-06-16 | Ethylene vinyl alcohol copolymer resin particle composition, ethylene vinyl alcohol copolymer film and multilayer structure formed therefrom |
| BR112023026465A BR112023026465A2 (en) | 2021-06-16 | 2022-06-16 | COMPOSITION OF ETHYLENE-VINYL ALCOHOL COPOLYMER RESIN PARTICLES, ETHYLENE-VINYL ALCOHOL COPOLYMER FILM AND MULTILAYER STRUCTURE |
| TW111122432A TWI799293B (en) | 2021-06-16 | 2022-06-16 | Ethylene vinyl alcohol copolymer resin particle composition, ethylene vinyl alcohol copolymer film and multilayer structure formed therefrom |
| BR112023026464A BR112023026464A2 (en) | 2021-06-16 | 2022-06-16 | COMPOSITION OF ETHYLENE-VINYL ALCOHOL COPOLYMER RESIN PARTICLES, ETHYLENE-VINYL ALCOHOL COPOLYMER FILM AND MULTILAYER STRUCTURE |
| KR1020237043504A KR20240009477A (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film and multilayer structure consisting thereof |
| EP22824286.3A EP4357410A1 (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure |
| BR112023026466A BR112023026466A2 (en) | 2021-06-16 | 2022-06-16 | COMPOSITION OF ETHYLENE-VINYL ALCOHOL COPOLYMER RESIN PARTICLES, ETHYLENE-VINYL ALCOHOL COPOLYMER FILM AND MULTILAYER STRUCTURE |
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