WO2023132230A1 - 二軸延伸ポリアミドフィルムロール - Google Patents
二軸延伸ポリアミドフィルムロール Download PDFInfo
- Publication number
- WO2023132230A1 WO2023132230A1 PCT/JP2022/046839 JP2022046839W WO2023132230A1 WO 2023132230 A1 WO2023132230 A1 WO 2023132230A1 JP 2022046839 W JP2022046839 W JP 2022046839W WO 2023132230 A1 WO2023132230 A1 WO 2023132230A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyamide
- resin
- film roll
- biaxially stretched
- biomass
- Prior art date
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 71
- 229920002647 polyamide Polymers 0.000 title claims abstract description 71
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 62
- 239000002028 Biomass Substances 0.000 claims abstract description 57
- 239000002994 raw material Substances 0.000 claims abstract description 45
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 34
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 21
- 230000002285 radioactive effect Effects 0.000 claims abstract description 6
- 239000002344 surface layer Substances 0.000 claims abstract description 5
- 238000009998 heat setting Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 229920006233 biaxially oriented polyamide Polymers 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 229920000571 Nylon 11 Polymers 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 229920006152 PA1010 Polymers 0.000 claims description 8
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 7
- 229920006394 polyamide 410 Polymers 0.000 claims description 7
- OKTJSMMVPCPJKN-NJFSPNSNSA-N Carbon-14 Chemical compound [14C] OKTJSMMVPCPJKN-NJFSPNSNSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 239000000565 sealant Substances 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 238000004804 winding Methods 0.000 abstract description 7
- 238000005259 measurement Methods 0.000 abstract description 4
- 238000005452 bending Methods 0.000 abstract description 3
- 238000003853 Pinholing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 23
- 239000000853 adhesive Substances 0.000 description 21
- 230000001070 adhesive effect Effects 0.000 description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000011342 resin composition Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- -1 for example Polymers 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000004359 castor oil Substances 0.000 description 5
- 235000019438 castor oil Nutrition 0.000 description 5
- 229920006026 co-polymeric resin Polymers 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 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 5
- 239000010410 layer Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 229920002302 Nylon 6,6 Polymers 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DVPHDWQFZRBFND-DMHDVGBCSA-N 1-o-[2-[(3ar,5r,6s,6ar)-2,2-dimethyl-6-prop-2-enoyloxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-2-[4-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chlorophenyl)-4-oxoazetidin-3-yl]oxy-4-oxobutanoyl]oxyethyl] 4-o-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chloropheny Chemical group C1([C@H]2[C@H](C(N2SC(C)CC)=O)OC(=O)CCC(=O)OC(COC(=O)CCC(=O)O[C@@H]2[C@@H](N(C2=O)SC(C)CC)C=2C(=CC=CC=2)Cl)[C@@H]2[C@@H]([C@H]3OC(C)(C)O[C@H]3O2)OC(=O)C=C)=CC=CC=C1Cl DVPHDWQFZRBFND-DMHDVGBCSA-N 0.000 description 2
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QFNNDGVVMCZKEY-UHFFFAOYSA-N azacyclododecan-2-one Chemical compound O=C1CCCCCCCCCCN1 QFNNDGVVMCZKEY-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- YLBZIDMEEPTYHS-UHFFFAOYSA-N NCCCCCCCCCCN.NCCCCCCCCCCN Chemical compound NCCCCCCCCCCN.NCCCCCCCCCCN YLBZIDMEEPTYHS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000004959 Rilsan Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- VJJBJJBTUXPNEO-UHFFFAOYSA-N docosanamide;ethene Chemical compound C=C.CCCCCCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCCCCCC(N)=O VJJBJJBTUXPNEO-UHFFFAOYSA-N 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- SWSBIGKFUOXRNJ-CVBJKYQLSA-N ethene;(z)-octadec-9-enamide Chemical compound C=C.CCCCCCCC\C=C/CCCCCCCC(N)=O.CCCCCCCC\C=C/CCCCCCCC(N)=O SWSBIGKFUOXRNJ-CVBJKYQLSA-N 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
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- 150000002739 metals Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
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- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 230000002040 relaxant effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- 238000005019 vapor deposition process Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000010920 waste tyre Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/24—Component parts, details or accessories; Auxiliary operations for feeding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/24—Component parts, details or accessories; Auxiliary operations for feeding
- B29B7/242—Component parts, details or accessories; Auxiliary operations for feeding in measured doses
- B29B7/244—Component parts, details or accessories; Auxiliary operations for feeding in measured doses of several materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C31/00—Handling, e.g. feeding of the material to be shaped, storage of plastics material before moulding; Automation, i.e. automated handling lines in plastics processing plants, e.g. using manipulators or robots
- B29C31/04—Feeding of the material to be moulded, e.g. into a mould cavity
- B29C31/10—Feeding of the material to be moulded, e.g. into a mould cavity of several materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/28—Storing of extruded material, e.g. by winding up or stacking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/297—Feeding the extrusion material to the extruder at several locations, e.g. using several hoppers or using a separate additive feeding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
Definitions
- the present invention relates to a carbon-neutral biaxially stretched polyamide film roll that is suitably used for packaging films and the like and that uses biomass-derived raw materials, and a method for producing the same.
- a biaxially stretched film made of an aliphatic polyamide represented by polyamide 6 is excellent in impact resistance and bending pinhole resistance, and is widely used as various packaging materials.
- Biomass is an organic compound that is photosynthesised from carbon dioxide and water, and is a so-called carbon-neutral raw material that regenerates carbon dioxide and water by utilizing it. Carbon neutrality means reducing emissions of carbon dioxide, a greenhouse gas, to virtually zero by balancing the amount of carbon dioxide emitted and absorbed in the environment. Biomass plastics made from these biomass materials have been rapidly put to practical use, and a biaxially oriented polyamide film containing a polyamide 6 resin and a polyamide resin at least part of which is derived from biomass has been proposed (Patent Document 1). ).
- Polyamide 6 resin and polyamide resin, at least part of which is derived from biomass, may differ in specific gravity and shape of resin chips, so the segregation of these raw resin chips causes variation in the ratio of raw materials in the mixing and extrusion processes.
- the difference in biomass degree occurs in the MD (Machine Direction) direction of the film.
- the object of the present invention is to provide a biaxially oriented polyamide film using a raw material derived from biomass, and a film roll of a biaxially oriented polyamide film that has little variation in the degree of biomass in the MD direction even if it is a long film roll with a long winding length. and to provide a method for producing the same.
- the present invention consists of the following configurations.
- (Section 1) Made of a biaxially stretched polyamide film containing 99 to 70% by mass of polyamide 6 resin and 1 to 30% by mass of polyamide resin at least part of which is derived from biomass, Samples are taken every 1000 m from the surface layer of the film roll to the core in the MD direction, and the maximum value of biomass degree when measuring radioactive carbon 14 C is Xmax, the minimum value is Xmin, and the average value is Xave.
- the variation in biomass degree represented by (1) is 15% or less,
- a biaxially stretched polyamide film roll having a roll length of 1,000 to 60,000 m and a width of 400 to 3,000 mm.
- (Section 5) A laminated film roll obtained by laminating a sealant film on the biaxially oriented polyamide film roll according to any one of Items 1 to 4.
- (Section 6) A step of supplying and mixing a raw material resin to an extruder, extruding the raw material resin into a sheet form from the extruder, cooling it on a casting drum to form an unstretched sheet, and subjecting the molded unstretched sheet to MD
- a method for producing a biaxially stretched polyamide film roll characterized by melt extruding a raw material resin from an extruder.
- the raw resin chips of the second hopper are supplied through a pipe having an outlet in the first hopper and directly above the extruder, and the raw resin chips of the first hopper and the raw resin of the second hopper Item 7.
- FIG. 2 is a schematic diagram showing an example of a method of mixing two or more resins in a film roll manufacturing process.
- the biaxially stretched polyamide film of the present invention contains 70 to 99% by mass of polyamide 6 resin and 1 to 30% by mass of polyamide whose raw material is at least partly derived from biomass.
- the polyamide 6 resin is contained in an amount of 70% by mass or more, the excellent mechanical strength such as impact strength and the gas barrier property against oxygen, which are inherent to the biaxially stretched polyamide film made of polyamide 6, can be obtained.
- 1 to 30% by mass of polyamide at least part of which is derived from biomass, not only the effect of reducing the impact on carbon dioxide emissions in the environment, but also bending pinhole resistance and abrasion resistance Improves pinpoint performance.
- Polyamide 6 used in the present invention is usually produced by ring-opening polymerization of ⁇ -caprolactam.
- Polyamide 6 obtained by ring-opening polymerization is usually melt-extruded by an extruder after removing the lactam monomer with hot water and then drying.
- the relative viscosity of polyamide 6 is preferably 1.8-4.5, more preferably 2.6-3.2. If the relative viscosity is less than 1.8, the impact strength of the film will be insufficient. If it is more than 4.5, the load on the extruder is increased, making it difficult to obtain an unstretched film before stretching.
- polyamide 6 in addition to those polymerized from commonly used fossil fuel-derived monomers, polyamide 6 chemically recycled from waste polyamide 6 products such as waste plastic products, waste tire rubber, fibers, and fishing nets can also be used.
- waste polyamide 6 products such as waste plastic products, waste tire rubber, fibers, and fishing nets
- depolymerization is performed to obtain ⁇ -caprolactam, which is purified and then polyamide 6 is obtained.
- a method of polymerization can be used.
- polyamide 6 obtained by mechanically recycling waste material from the production process of the polyamide film can be used together.
- Mechanically recycled polyamide 6 is, for example, a non-standard film that cannot be shipped when manufacturing a biaxially stretched polyamide film, and waste materials generated as cut ends (edge trim) are collected and melted extrusion or compression molding. It is a raw material pelletized by
- Polyamide at least part of which is derived from biomass examples include polyamide 11, polyamide 410, polyamide 610, polyamide 1010, polyamide MXD10, and polyamide 11/6T copolymer resin.
- Polyamide 11 is a polyamide resin having a structure in which monomers having 11 carbon atoms are bonded via amide bonds.
- Polyamide 11 is usually obtained using aminoundecanoic acid or undecanelactam as a monomer.
- aminoundecanoic acid is desirable from the viewpoint of carbon neutrality because it is a monomer obtained from castor oil.
- These structural units derived from monomers having 11 carbon atoms account for preferably 50 mol% or more, more preferably 80% mol or more, more preferably 80% mol or more, and 100 mol% of all structural units in polyamide 11. good too.
- Polyamide 11 is usually produced by the ring-opening polymerization of undecanelactam described above.
- Polyamide 11 obtained by ring-opening polymerization is usually melt-extruded by an extruder after removing the lactam monomer with hot water and then drying.
- the relative viscosity of polyamide 11 is preferably 1.8 to 4.5, more preferably 2.4 to 3.2.
- Polyamide 410 is a polyamide resin having a structure in which a monomer having 4 carbon atoms and a diamine having 10 carbon atoms are copolymerized. Polyamide 410 typically utilizes sebacic acid and tetramethylene diamine. Sebacic acid is preferably made from castor oil, which is a vegetable oil, from an environmental point of view. Sebacic acid used here is preferably obtained from castor oil from the viewpoint of environmental protection, particularly from the viewpoint of carbon neutrality.
- Polyamide 610 is a polyamide resin having a structure in which a diamine having 6 carbon atoms and a dicarboxylic acid having 10 carbon atoms are polymerized. Hexamethylenediamine and sebacic acid are commonly used. Of these, sebacic acid is a monomer obtained from castor oil, and is desirable from the viewpoint of carbon neutrality. Structural units derived from these monomers having 6 carbon atoms and structural units derived from monomers having 10 carbon atoms, the total in PA610 is 50 mol of all structural units % or more, more preferably 80 mol % or more, and may be 100 mol %.
- Polyamide 1010 is a polyamide resin having a structure in which a diamine having 10 carbon atoms and a dicarboxylic acid having 10 carbon atoms are polymerized.
- Polyamide 1010 typically utilizes 1,10-decanediamine (decamethylenediamine) and sebacic acid. Decamethylenediamine and sebacic acid are monomers obtained from castor oil, and thus are desirable from the carbon neutral point of view.
- These structural units derived from a diamine having 10 carbon atoms and structural units derived from a dicarboxylic acid having 10 carbon atoms account for 50 mol% or more of all structural units in PA1010. It is preferably 80 mol % or more, more preferably 100 mol %.
- the lower limit of the content of the polyamide, at least part of which is derived from biomass is not particularly limited, but is preferably 1% by mass, more preferably 3% by mass or more.
- the upper limit of the content is 30% by mass, more preferably 20% by mass. If the content of the polyamide, at least part of which is derived from biomass, exceeds 30% by mass, the melt film may become unstable during casting, making it difficult to obtain a homogeneous unstretched film.
- the biaxially stretched polyamide film of the present invention requires various additives such as other thermoplastic resins, lubricants, heat stabilizers, antioxidants, antistatic agents, antifogging agents, ultraviolet absorbers, dyes, pigments, etc. can be included depending on
- the biaxially stretched polyamide film of the present invention can contain a thermoplastic resin in addition to the polyamide 6 and the polyamide resin at least part of which is derived from biomass as long as the object of the present invention is not impaired.
- a thermoplastic resin such as polyamide 12 resin, polyamide 66 resin, polyamide 6/12 copolymer resin, polyamide 6/66 copolymer resin, and polyamide MXD6 resin.
- Thermoplastic resins other than polyamides for example, polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate, and polyolefin polymers such as polyethylene and polypropylene, may be added as necessary. good. It is preferable that the raw materials for these thermoplastic resins are biomass-derived, since they do not affect the increase or decrease of carbon dioxide on the ground, thereby reducing the burden on the environment.
- the biaxially stretched polyamide film of the present invention preferably contains fine particles or an organic lubricant such as a fatty acid amide as a lubricant in order to improve slipperiness and facilitate handling.
- an organic lubricant such as a fatty acid amide
- the fine particles inorganic fine particles such as silica, kaolin, and zeolite, and polymer-based organic fine particles such as acryl-based and polystyrene-based organic fine particles can be appropriately selected and used. From the viewpoint of transparency and slipperiness, it is preferable to use fine silica particles.
- the fine particles preferably have an average particle size of 0.5 to 5.0 ⁇ m, more preferably 1.0 to 3.0 ⁇ m.
- the biaxially stretched polyamide film of the present invention may contain a fatty acid amide and/or a fatty acid bisamide for the purpose of improving slipperiness.
- Fatty acid amides and/or fatty acid bisamides include erucic acid amide, stearic acid amide, ethylene bis stearic acid amide, ethylene bis behenic acid amide, ethylene bis oleic acid amide and the like.
- the content of fatty acid amide and/or fatty acid bisamide is preferably 0.01 to 0.40% by mass, more preferably 0.05 to 0.30% by mass.
- the biaxially stretched polyamide film of the present invention contains a polyamide resin such as polyamide MXD6 resin, polyamide 12 resin, polyamide 66 resin, polyamide 6/12 copolymer resin, polyamide 6/66 copolymer resin for the purpose of improving slipperiness. can be added.
- a polyamide resin such as polyamide MXD6 resin, polyamide 12 resin, polyamide 66 resin, polyamide 6/12 copolymer resin, polyamide 6/66 copolymer resin for the purpose of improving slipperiness. can be added.
- the biaxially stretched polyamide film of the present invention can contain an antioxidant.
- Phenolic antioxidants are preferred as antioxidants.
- the phenolic antioxidant is preferably a fully hindered phenolic compound or a partially hindered phenolic compound.
- the thickness of the biaxially stretched polyamide film in the present invention is not particularly limited. 30 ⁇ m is used.
- the biaxially stretched polyamide film in the present invention preferably has a heat shrinkage rate of 0.6 to 3.0% in both the MD and TD directions at 160° C. for 10 minutes, more preferably 0.6. ⁇ 2.5%.
- a heat shrinkage rate of 3.0% or less, it is possible to suppress the occurrence of curling and shrinkage when heat is applied in subsequent processes such as lamination and printing.
- the impact strength of the biaxially stretched polyamide film in the present invention is preferably 0.7 J/15 ⁇ m or more.
- a more preferable impact strength is 0.9 J/15 ⁇ m or more.
- the upper limit of the impact strength is not particularly limited, it may be 2.0 J/15 ⁇ m or less, or 1.5 J/15 ⁇ m or less.
- the haze value of the biaxially stretched polyamide film in the invention is preferably 10% or less. More preferably 7% or less, still more preferably 5% or less. If the haze value is small, the transparency and gloss are good, so when used for packaging bags, clear printing can be performed and the product value is increased.
- the dynamic friction coefficient of the biaxially stretched polyamide film in the invention is preferably 1.0 or less. It is more preferably 0.7 or less, still more preferably 0.5 or less. If the coefficient of dynamic friction of the film is small, the slipperiness is improved and the handling of the film is facilitated. If the coefficient of dynamic friction of the film is too small, the film will be too slippery and difficult to handle.
- the content of biomass-derived carbon measured by radioactive carbon 14 C of ASTM D6866-18 that is, the degree of biomass is 1 to 30% with respect to the total carbon in the polyamide film. is preferred. Since carbon dioxide in the atmosphere contains 14 C at a certain rate (105.5 pMC), the 14 C content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. is known to be It is also known that fossil fuels contain almost no 14 C. Therefore, by measuring the ratio of 14 C contained in the total carbon atoms in the film, the ratio of biomass-derived carbon can be calculated.
- the film roll of the present invention is sampled every 1000 m from the surface layer of the film roll to the winding core in the MD direction, and the maximum value of biomass degree when measuring radiocarbon 14 C is Xmax, the minimum value is Xmin, and the average
- the variation in the degree of biomass represented by the following formula (1) is preferably 15% or less, more preferably 13% or less, and most preferably 10% or less.
- Formula (1) Vertical variation of biomass degree (%) ⁇ (Xmax-Xmin) / Xave ⁇ ⁇ 100
- the upper limit of the thickness accuracy of the film roll in the MD direction and the TD direction in the present invention is preferably 30% or less, more preferably 25% or less, and most preferably 20% or less.
- the thickness accuracy of the film is 30% or less, it is possible to suppress appearance defects of the film roll to be obtained, and to prevent the occurrence of wrinkles and winding misalignment due to meandering.
- polyamide 6 resin chips and polyamide resin chips at least part of which is derived from biomass are supplied to and mixed with an extruder equipped with a hopper, and the extruder A process of melt extruding a polyamide raw material resin from a sheet and cooling it on a casting drum to form an unstretched sheet, an MD stretching process of stretching the molded unstretched sheet in the MD direction, and a TD after the MD stretching
- raw material resin chips of polyamide 6 are supplied to a first hopper, and at least one of the raw materials is fed to a second hopper.
- the raw material resin chips of polyamide whose part is derived from biomass are supplied, and the raw resin chips supplied from the first hopper and the raw resin chips supplied from the second hopper are mixed right above the extruder, and then the extruder It is preferable to melt-extrude the raw material resin from.
- the raw material resin chips of the second hopper are supplied through a pipe (hereinafter sometimes referred to as an inner pipe) having an outlet directly above the extruder in the first hopper.
- the raw resin chips of the first hopper and the raw resin chips of the second hopper can be mixed.
- FIG. 1 is a schematic diagram showing an example of the relationship between an extruder 2 having a hopper 1 and an inner pipe 3.
- resins other than the polyamide 6 resin chips which are the main raw material of the polyamide film of the present invention, are supplied through the inner pipe 3, and the polyamide 6 resin chips are supplied from the upper part of the hopper 1.
- the inner pipe outlet 4 of the inner pipe 3 is directly above the raw material resin supply port 5 of the extruder 2, the mixing ratio of the raw materials can be kept constant.
- the raw material resin is melt extruded using an extruder, extruded into a film form from a T-die, cast on a cooling roll and cooled to obtain an unstretched film.
- the melting temperature of the resin is preferably 220-350°C. If it is less than the above range, unmelted materials may occur, resulting in appearance defects such as defects.
- the die temperature is preferably 250-350°C.
- the cooling roll temperature is preferably -30 to 80°C, more preferably 0 to 50°C.
- a method using an air knife or an electrostatic contact method in which static charge is applied is preferably applied. can. Especially the latter is preferably used.
- the stretching method may be a simultaneous biaxial stretching method or a sequential biaxial stretching method.
- single-stage stretching or multi-stage stretching such as two-stage stretching can be used as the stretching method in the MD direction.
- multi-stage stretching in the MD direction such as two-stage stretching is preferable in terms of physical properties and uniformity of physical properties in the MD and TD directions, that is, isotropy, rather than single-stage stretching.
- Stretching in the MD direction in the sequential biaxial stretching method is preferably roll stretching.
- the lower limit of the stretching temperature in the MD direction is preferably 50°C, more preferably 55°C, and still more preferably 60°C.
- the upper limit of the stretching temperature in the MD direction is preferably 120°C, more preferably 115°C, still more preferably 110°C.
- the lower limit of the draw ratio in the MD direction is preferably 2.2 times, more preferably 2.5 times, and still more preferably 2.8 times.
- the upper limit of the draw ratio in the MD direction is preferably 5.0 times, more preferably 4.5 times, and most preferably 4.0 times.
- the stretching ratio in the MD direction is the total stretching ratio obtained by multiplying the respective stretching ratios.
- the above-mentioned stretching is possible in each stretching. is preferably adjusted.
- the first stage stretching is preferably 1.5 to 2.1 times
- the second stage stretching is preferably 1.5 to 1.8 times.
- a film stretched in the MD direction is stretched in the TD direction with a tenter, heat-set, and then subjected to relaxation treatment (also called relaxation treatment).
- the lower limit of the stretching temperature in the TD direction is preferably 50°C, more preferably 55°C, still more preferably 60°C.
- the upper limit of the stretching temperature in the TD direction is preferably 190°C, more preferably 185°C, still more preferably 180°C.
- the lower limit of the draw ratio in the TD direction is preferably 2.8, more preferably 3.2, still more preferably 3.5, and particularly preferably 3.8.
- the upper limit of the draw ratio in the TD direction is preferably 5.5 times, more preferably 5.0 times, still more preferably 4.7 times, particularly preferably 4.5 times, and most preferably 4.5 times. Three times.
- the above draw ratio in the TD direction is the total draw ratio obtained by multiplying each ratio.
- the lower limit of the heat setting temperature is preferably 210°C, more preferably 212°C.
- the upper limit of the heat setting temperature is preferably 220°C, more preferably 218°C.
- the heat setting time is preferably 0.5 to 20 seconds. More preferably, it is 1 to 15 seconds.
- the heat setting time can be set to an appropriate time in consideration of the heat setting temperature and the wind speed in the heat setting zone.
- the temperature for the relaxation treatment can be selected in the range from the heat setting temperature to the glass transition temperature Tg of the resin, but the temperature within the range of [heat setting temperature -10°C] to [Tg + 10°C] is preferable.
- the lower limit of the relaxation rate of relaxation processing is preferably 0.5%, more preferably 1%.
- the upper limit of the relaxation rate is preferably 20%, more preferably 15%, still more preferably 10%.
- a vapor deposition film formed by the vapor deposition process a vapor deposition film of aluminum, a vapor deposition film of a single substance or a mixture of silicon oxide or aluminum oxide is preferably used. Furthermore, by coating a protective layer or the like on these vapor-deposited films, the oxygen barrier properties and the like can be improved.
- Heat-sealable laminated film roll When the polyamide film roll of the present invention is used as a packaging material, it is preferable to laminate a heat-sealable film called a sealant film.
- a laminated film roll can also be constructed by interposing an adhesive layer, a printed layer, a metal layer, or the like between the biaxially stretched polyamide film and the sealant film.
- a lamination method known methods such as a dry lamination method and an extrusion lamination method can be used, but any method may be used. Specific examples are shown below.
- Example of layer structure of the laminated film roll of the present invention ONY/adhesive/CPP, ONY/adhesive/Al/adhesive/CPP, PET/adhesive/ONY/adhesive/CPP, PET/adhesive/ONY/ Adhesive/Al/Adhesive/CPP, PET/Adhesive/Al/Adhesive/ONY/Adhesive/CPP, ONY/Adhesive/PET/Adhesive/CPP, ONY/PE/CPP, ONY/Adhesive/ EVOH/adhesive/CPP, ONY/adhesive/aluminum-deposited PET/adhesive/CPP, CPP/adhesive/ONY/adhesive/LLDPE, ONY/adhesive/aluminum-deposited CPP.
- Film evaluation was performed by the following measurement methods. Unless otherwise specified, measurements were carried out in a measurement room at 23° C. and a relative humidity of 65%.
- Film thickness accuracy in the MD direction A film test piece with a width of 5 cm and a length of 100 cm was cut out in the MD direction from the center of the film roll in the width direction, and the thickness was measured at 20 points at a pitch of 5 cm using a dial gauge (thickness gauge manufactured by Tester Sangyo Co., Ltd.). . Taking the maximum thickness as Tmax, the minimum thickness as Tmin, and the average thickness as Tave, the thickness precision (Tv) was obtained from the following equation (2).
- MD direction Tv (%) ⁇ (Tmax-Tmin)/Tave ⁇ x 100 [Thickness accuracy of film in TD direction]
- a film test piece having a width of 5 cm was cut out in the TD direction of the film roll, and measured at a pitch of 5 cm using a dial gauge (thickness measuring instrument manufactured by Tester Sangyo Co., Ltd.). With Tmax being the maximum thickness, Tmin being the minimum thickness, and Tave being the average thickness, the thickness precision (Tv) was obtained from the following equation (3).
- Formula (3) TD direction Tv (%) ⁇ (Tmax-Tmin)/Tave ⁇ x 100
- Thermal shrinkage rate (%) [(length before treatment - length after treatment) / length before treatment] ⁇ 100
- Example 1 A device consisting of an extruder and a co-extrusion T-die with a width of 380 mm is used, and the molten resin is extruded from the T-die into a film, cast on a cooling roll temperature-controlled at 20° C., and electrostatically adhered to form an unstretched film with a thickness of 200 ⁇ m. got The resin composition B was introduced using an inner pipe as shown in FIG. 1 so as to be mixed with the resin composition A directly above the extruder.
- Resin composition A Polyamide 6 (manufactured by Toyobo Co., Ltd., relative viscosity 2.8, melting point 220 ° C.) 97 parts by mass, porous silica fine particles (manufactured by Fuji Silysia Chemical Co., Ltd., average particle diameter 2.0 ⁇ m, pore volume 1 .6 ml/g) and 0.15 parts by mass of fatty acid bisamide (ethienbisstearic acid amide manufactured by Kyoeisha Chemical Co., Ltd.).
- Resin composition B Polyamide resin containing raw materials derived from biomass-polyamide 11 (manufactured by Arkema, relative viscosity 2.5, melting point 186 ° C.) 3.0 parts by mass
- the obtained unstretched film was guided to a roll type stretching machine, and after being stretched 1.73 times in the MD direction at 80°C by utilizing the peripheral speed difference of the rolls, it was further stretched 1.85 times at 70°C. Subsequently, this uniaxially stretched film was continuously guided to a tenter type stretching machine, preheated at 110°C, and stretched in the TD direction at 120°C for 1.2 times, 130°C for 1.7 times, and 160°C for 2.0 times. After stretching and heat setting treatment at 218 ° C., 7% relaxation treatment is performed at 218 ° C., and then the surface of the side to be dry laminated with the linear low density polyethylene film is corona discharge treated to form a jumbo biaxially oriented polyamide film.
- the obtained jumbo roll was slit to obtain a biaxially oriented polyamide film roll having a width of 1,000 mm and a winding length of 4,000 m.
- Table 1 shows the evaluation results of the obtained biaxially stretched polyamide film roll.
- Example 2 to Example 9 A biaxially oriented polyamide film roll was obtained in the same manner as in Example 1, except that the film forming conditions such as the raw material resin composition and the heat setting temperature were changed as shown in Table 1. Table 1 shows the evaluation results of the obtained biaxially stretched polyamide film roll.
- Example 1 A device consisting of an extruder and a co-extrusion T-die with a width of 380 mm is used, and the molten resin is extruded from the T-die into a film, cast on a cooling roll temperature-controlled at 20° C., and electrostatically adhered to form an unstretched film with a thickness of 200 ⁇ m. got The same resin composition A and resin composition B as in Example 1 were used, but the resin composition B was mixed at the top of the hopper without using an inner pipe. , fed the resin composition to the extruder.
- a biaxially oriented polyamide film roll was obtained under the same film-forming conditions as in Example 1, except that the mixing method of the resin composition was changed. Table 2 shows the evaluation results of the obtained biaxially stretched polyamide film roll.
- polyamide 410, polyamide 610, and polyamide 1010 which are polyamide resins containing raw materials derived from biomass, were as follows.
- the biaxially stretched polyamide film rolls of the examples were able to reduce the variation in biomass content when measuring radiocarbon 14 C in the MD direction by using an inner pipe for supplying raw materials.
- the comparative example does not use an inner pipe to supply raw materials, and the raw material segregation causes large fluctuations in the raw material ratio in the MD direction. There was a lot of variation in the biomass degree when measured.
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Abstract
Description
(項1)
ポリアミド6樹脂99~70質量%と少なくとも原料の一部がバイオマス由来であるポリアミド樹脂1~30質量%を含む二軸延伸ポリアミドフィルムからなり、
MD方向にフィルムロールの表層から巻き芯まで1000m毎にサンプリングし、放射性炭素14Cを測定したときのバイオマス度の最大値をXmax、最小値をXmin、平均値をXaveとしたときの、下記式(1)で表されるバイオマス度のばらつきが15%以下であり、
巻長1,000~60,000m、幅400~3,000mmである、二軸延伸ポリアミドフィルムロール。
式(1) バイオマス度のばらつき(%)={(Xmax-Xmin)/Xave}×100
(項2)
前記バイオマス度が1~30%である、項1に記載の二軸延伸ポリアミドフィルムロール。
(項3)
前記二軸延伸ポリアミドフィルムにおける原料の少なくとも一部がバイオマス由来であるポリアミド樹脂が、ポリアミド11、ポリアミド410、ポリアミド610、及びポリアミド1010からなる群から選ばれる少なくとも1種のポリアミド樹脂である、項1又は項2に記載のフィルムロール。
(項4)
前記フィルムロールのMD方向及びTD(Transverse Direction)方向の厚み精度がいずれも30%以下である、項1~3のいずれか一項に記載の二軸延伸ポリアミドフィルムロール。
(項5)
項1~4のいずれか一項に記載の二軸延伸ポリアミドフィルムロールにシーラントフィルムを積層した、積層フィルムロール。
(項6)
原料樹脂を押出機に供給及び混合し、該押出機から前記原料樹脂をシート状に溶融押出し、キャスティングドラム上で冷却して未延伸シートを成形する工程と、成形された前記未延伸シートをMD方向及びTD方向に延伸する工程と、熱固定工程とを含む、二軸延伸ポリアミドフィルムロールの製造方法において、第1のホッパーにポリアミド6の原料樹脂チップを供給し、第2のホッパーに少なくとも原料の一部がバイオマス由来であるポリアミドの原料樹脂チップを供給し、第1のホッパーから供給された原料樹脂チップと第2のホッパーから供給された原料樹脂チップを押出機の直上で混合した後、押出機から原料樹脂を溶融押出することを特徴とする、二軸延伸ポリアミドフィルムロールの製造方法。
(項7)
前記第2のホッパーの原料樹脂チップを、前記第1のホッパー内であって押出機直上に出口を有する配管を通じて供給し、前記第1のホッパーの原料樹脂チップと前記第2のホッパーの原料樹脂チップを混合する工程を含む、項6に記載の二軸延伸ポリアミドフィルムロールの製造方法。
本発明に使用するポリアミド6は、通常、ε-カプロラクタムの開環重合によって製造される。開環重合で得られたポリアミド6は、通常、熱水でラクタムモノマーを除去した後、乾燥してから押出し機で溶融押出しされる。
本発明に使用する、原料の少なくとも一部がバイオマス由来であるポリアミドとしては、例えば、ポリアミド11、ポリアミド410、ポリアミド610、ポリアミド1010、ポリアミドMXD10、及びポリアミド11・6T共重合樹脂などが挙げられる。
本発明の二軸延伸ポリアミドフィルムには、他の熱可塑性樹脂、滑剤、熱安定剤、酸化防止剤、帯電防止剤や防曇剤、紫外線吸収剤、染料、顔料等の各種の添加剤を必要に応じて含有させることができる。
本発明の二軸延伸ポリアミドフィルムには、本発明の目的を損なわない範囲で、上記のポリアミド6及び原料の少なくとも一部がバイオマス由来であるポリアミド樹脂の他に熱可塑性樹脂を含むことができる。例えば、ポリアミド12樹脂、ポリアミド66樹脂、ポリアミド6・12共重合樹脂、ポリアミド6・66共重合樹脂、ポリアミドMXD6樹脂、などのポリアミド系樹脂が挙げられる。必要に応じてポリアミド系以外の熱可塑性樹脂、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレン-2,6-ナフタレート等のポリエステル系重合体、ポリエチレン、ポリプロピレン等のポリオレフィン系重合体等を含有させてもよい。これらの熱可塑性樹脂の原料はバイオマス由来であると、地上の二酸化炭素の増減に影響を与えないので、環境負荷を低減できるので好ましい。
本発明の二軸延伸ポリアミドフィルムには、滑り性を良くして取扱い易くするために、滑剤として微粒子や脂肪酸アミドなどの有機滑剤を含有させることが好ましい。前記微粒子としては、シリカ、カオリン、ゼオライト等の無機微粒子、アクリル系、ポリスチレン系等の高分子系有機微粒子等の中から適宜選択して使用することができる。なお、透明性と滑り性の面から、シリカ微粒子を用いることが好ましい。前記微粒子の好ましい平均粒子径は0.5~5.0μmであり、より好ましくは1.0~3.0μmである。
本発明の二軸延伸ポリアミドフィルムには、酸化防止剤を含有させることができる。酸化防止剤としては、フェノール系酸化防止剤が好ましい。フェノール系酸化防止剤は、完全ヒンダードフェノール系化合物又は部分ヒンダードフェノール系化合物が好ましい。例えば、テトラキス-〔メチレン-3-(3′,5′-ジ-t-ブチル-4′-ヒドロキシフェニル)プロピオネート〕メタン、ステアリル-β-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、3,9-ビス〔1,1-ジメチル-2-〔β-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ〕エチル〕2,4,8,10-テトラオキサスピロ〔5,5〕ウンデカン等が挙げられる。フェノール系酸化防止剤を含有させることにより、二軸延伸ポリアミドフィルムの製膜操業性が向上する。
式(1) バイオマス度の縦方向ばらつき(%)={(Xmax-Xmin)/Xave}×100
フィルムの厚み精度が30%以下であることにより、得られるフィルムロールの外観不良を抑制することができるとともに、シワの発生や、蛇行による巻きズレなどを防止することができる。
本発明のポリアミドフィルムロールを得るため製造方法は、ポリアミド6樹脂チップと、少なくとも原料の一部がバイオマス由来であるポリアミド樹脂チップとを、ホッパーを備えた押出機に供給及び混合し、該押出機からポリアミド原料樹脂をシート状に溶融押出し、キャスティングドラム上で冷却して未延伸シートを成形する工程と、成形された前記未延伸シートをMD方向に延伸するMD延伸工程と、前記MD延伸後にTD延伸可能な温度に予熱する予熱工程、前記MD方向と直交するTD方向に延伸するTD延伸工程、前記MD延伸及び前記TD延伸を行なった後の前記ポリアミドフィルムを加熱し結晶化させて熱固定する熱固定工程、前記熱固定されたポリアミドフィルムを幅方向に緊張を緩和してフィルムの残留歪みを除去する熱緩和工程、並びに、熱緩和後のポリアミドフィルムを冷却する冷却工程を含む。
本発明のポリアミドフィルムロールを包装材料として用いる場合には、シーラントフィルムと呼ばれるヒートシール性のフィルムを積層することが好ましい。二軸延伸ポリアミドフィルムとシーラントフィルムの間に、接着剤層、印刷層、金属層などを介して積層フィルムロールを構成することもできる。積層の方法はドライラミネート方式、押し出しラミネート方式など公知の方法が使用できるが、いずれの方式であっても良い。以下に具体的な例を示す。
なお上記層構成に用いた各略称は以下の通りである。
/ :層の境界を表わす
ONY:二軸延伸ポリアミドフィルム
PET:延伸ポリエチレンテレフタレートフィルム
LLDPE:未延伸線状低密度ポリエチレンフィルム
CPP:未延伸ポリプロピレンフィルム
PE:押出しラミネート又は未延伸の低密度ポリエチレンフィルム
Al:アルミニウム箔
EVOH:エチレン-ビニルアルコール共重合樹脂
接着剤:フィルム同士を接着させる接着剤層
アルミ蒸着:アルミニウムが蒸着されていることを表わす
[フィルムのMD方向の厚み精度]
フィルムロールの幅方向に対する中央部から、MD方向に幅5cm、長さ100cmのフィルム試験片を切り出し、5cmピッチで、20箇所をダイアルゲージ(テスター産業社製厚さ測定器)を用いて測定した。最大厚みをTmax,最小厚みをTmin、平均厚みをTave とし、下記の式(2)より厚み精度(Tv)を求めた。
式(2) MD方向Tv(%)={(Tmax-Tmin)/Tave}×100
[フィルムのTD方向の厚み精度]
フィルムロールのTD方向に幅5cmのフィルム試験片を切り出し、5cmピッチで、ダイアルゲージ(テスター産業社製厚さ測定器)を用いて測定した。最大厚みをTmax,最小厚みをTmin、平均厚みをTave とし、下記の式(3)より厚み精度(Tv)を求めた。
式(3) TD方向Tv(%)={(Tmax-Tmin)/Tave}×100
フィルムのバイオマス度(%)は、ASTM D6866-18 Method B (AMS)に示された放射性炭素14C測定により行った。
フィルムの熱収縮率(%)は、MD方向及びTD方向それぞれについて、試験温度160℃、加熱時間10分間とした以外は、JIS C2318に記載の寸法変化試験法に準じて下記式(4)によって測定した。
式(4) 熱収縮率(%)=[(処理前の長さ-処理後の長さ)/処理前の長さ]×100
ポリアミドフィルムロールについて、MD方向にフィルムロールの表層から巻き芯まで1000m毎にサンプリングした。サンプリングした各フィルムについて、放射性炭素14Cを測定したときのバイオマス度を測定した。
得られたバイオマス度の最大値をXmax(%)、最小値をXmin(%)、平均値をXave(%)とし、下記式(1)で表されるバイオマス度のばらつきを求めた。
式(1) バイオマス度のばらつき(%)=100×(Xmax-Xmin)/Xave
<実施例1>
押出機と380mm巾の共押出Tダイよりなる装置を使用し、Tダイから溶融樹脂をフィルム状に押出し、20℃に温調した冷却ロールにキャストし静電密着させて厚み200μmの未延伸フィルムを得た。なお、樹脂組成物Bは、押出機の直上で樹脂組成物Aと混合するように、図1に示すようなインナーパイプを用いて投入した。
樹脂組成物A:ポリアミド6(東洋紡株式会社製、相対粘度2.8、融点220℃)97質量部、多孔質シリカ微粒子(富士シリシア化学株式会社製、平均粒子径2.0μm、細孔容積1.6ml/g)0.45質量部及び脂肪酸ビスアマイド(共栄社化学株式会社製エチエンビスステアリン酸アミド)0.15質量部からなる樹脂組成物。
樹脂組成物B:バイオマス由来の原料を含むポリアミド樹脂-ポリアミド11(アルケマ社製、相対粘度2.5、融点186℃)3.0質量部
原料樹脂組成物、熱固定温度などの製膜条件を表1のように変更した以外は、実施例1と同様の方法で二軸延伸ポリアミドフィルムロールを得た。得られた二軸延伸ポリアミドフィルムロールの評価結果を表1に示す。
押出機と380mm巾の共押出Tダイよりなる装置を使用し、Tダイから溶融樹脂をフィルム状に押出し、20℃に温調した冷却ロールにキャストし静電密着させて厚み200μmの未延伸フィルムを得た。実施例1と同じ樹脂組成物Aと樹脂組成物Bを用いたが、上記樹脂組成物Bの混合にはインナーパイプを用いず、樹脂組成物Aと樹脂組成物Bをホッパー上部で混合して、押出機に樹脂組成物を供給した。樹脂組成物の混合方法を変更した以外は、実施例1と同様の製膜条件で二軸延伸ポリアミドフィルムロールを得た。得られた二軸延伸ポリアミドフィルムロールの評価結果を表2に示す。
原料樹脂組成物、熱固定温度などの製膜条件を表2のように変更した以外は、比較例1と同様の方法で二軸延伸ポリアミドフィルムロールを得た。得られた二軸延伸ポリアミドフィルムロールの評価結果を表2に示す。
ポリアミド410:(DSM社製、ECOPaXX Q150-E、融点250℃)
ポリアミド610:(アルケマ社製、RilsanS SMNO、融点222℃)
ポリアミド1010:(アルケマ社製、RilsanT TMNO、融点202℃)
2 押出し機
3 インナーパイプ
4 インナーパイプ出口
5 原料樹脂供給口
Claims (7)
- ポリアミド6樹脂99~70質量%と少なくとも原料の一部がバイオマス由来であるポリアミド樹脂1~30質量%を含む二軸延伸ポリアミドフィルムからなり、
MD方向にフィルムロールの表層から巻き芯まで1000m毎にサンプリングし、放射性炭素14Cを測定したときのバイオマス度の最大値をXmax、最小値をXmin、平均値をXaveとしたときの、下記式(1)で表されるバイオマス度のばらつきが15%以下であり、
巻長1,000~60,000m、幅400~3,000mmである、二軸延伸ポリアミドフィルムロール。
式(1) バイオマス度のばらつき(%)={(Xmax-Xmin)/Xave}×100 - 前記バイオマス度が1~30%である、請求項1に記載の二軸延伸ポリアミドフィルムロール。
- 前記二軸延伸ポリアミドフィルムにおける原料の少なくとも一部がバイオマス由来であるポリアミド樹脂が、ポリアミド11、ポリアミド410、ポリアミド610、及びポリアミド1010からなる群から選ばれる少なくとも1種のポリアミド樹脂である、請求項1又は2に記載のフィルムロール。
- 前記フィルムロールのMD方向及びTD方向の厚み精度がいずれも30%以下である、請求項1~3のいずれか一項に記載の二軸延伸ポリアミドフィルムロール。
- 請求項1~4のいずれか一項に記載の二軸延伸ポリアミドフィルムロールにシーラントフィルムを積層した、積層フィルムロール。
- 原料樹脂を押出機に供給及び混合し、該押出機から前記原料樹脂をシート状に溶融押出し、キャスティングドラム上で冷却して未延伸シートを成形する工程と、成形された前記未延伸シートをMD方向及びTD方向に延伸する工程と、熱固定工程とを含む、二軸延伸ポリアミドフィルムロールの製造方法において、第1のホッパーにポリアミド6の原料樹脂チップを供給し、第2のホッパーに少なくとも原料の一部がバイオマス由来であるポリアミドの原料樹脂チップを供給し、第1のホッパーから供給された原料樹脂チップと第2のホッパーから供給された原料樹脂チップを押出機の直上で混合した後、押出機から原料樹脂を溶融押出することを特徴とする、二軸延伸ポリアミドフィルムロールの製造方法。
- 前記第2のホッパーの原料樹脂チップを、前記第1のホッパー内であって押出機直上に出口を有する配管を通じて供給し、前記第1のホッパーの原料樹脂チップと前記第2のホッパーの原料樹脂チップを混合する工程を含む、請求項6に記載の二軸延伸ポリアミドフィルムロールの製造方法。
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JP2016120721A (ja) * | 2011-03-01 | 2016-07-07 | 東洋紡株式会社 | 延伸ポリアミドフィルム |
WO2018062145A1 (ja) * | 2016-09-28 | 2018-04-05 | 東洋紡株式会社 | 白色熱収縮性ポリエステル系フィルムロール |
WO2020170714A1 (ja) | 2019-02-18 | 2020-08-27 | 東洋紡株式会社 | 二軸延伸ポリアミドフィルム及び積層フィルム |
WO2020203106A1 (ja) * | 2019-03-29 | 2020-10-08 | 東洋紡株式会社 | ポリエステルフィルム及びその製造方法 |
Cited By (1)
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CN118307777A (zh) * | 2024-06-05 | 2024-07-09 | 陕西爱弗特智能装备科技有限公司 | 一种芳香族聚噁二唑薄膜的涂布设备 |
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