TW201720988A - 萊賽爾(lyocell)纖維之用途 - Google Patents
萊賽爾(lyocell)纖維之用途 Download PDFInfo
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- TW201720988A TW201720988A TW105125185A TW105125185A TW201720988A TW 201720988 A TW201720988 A TW 201720988A TW 105125185 A TW105125185 A TW 105125185A TW 105125185 A TW105125185 A TW 105125185A TW 201720988 A TW201720988 A TW 201720988A
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- 239000000835 fiber Substances 0.000 title claims abstract description 59
- 229920000433 Lyocell Polymers 0.000 title claims abstract description 49
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- -1 alkali metal salts Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 2
- 239000000243 solution Substances 0.000 description 16
- 239000006210 lotion Substances 0.000 description 12
- 229920002678 cellulose Polymers 0.000 description 10
- 239000001913 cellulose Substances 0.000 description 10
- 238000009987 spinning Methods 0.000 description 10
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000004448 titration Methods 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 229920003043 Cellulose fiber Polymers 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- JMHWNJGXUIJPKG-UHFFFAOYSA-N CC(=O)O[SiH](CC=C)OC(C)=O Chemical compound CC(=O)O[SiH](CC=C)OC(C)=O JMHWNJGXUIJPKG-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 229960001950 benzethonium chloride Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004750 melt-blown nonwoven Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/049—Cleaning or scouring pads; Wipes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0208—Tissues; Wipes; Patches
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/027—Fibers; Fibrils
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/416—Quaternary ammonium compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/731—Cellulose; Quaternized cellulose derivatives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/005—Antimicrobial preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/1233—Carbonates, e.g. calcite or dolomite
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
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- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Dermatology (AREA)
- Biomedical Technology (AREA)
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- Emergency Medicine (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
本發明關於萊賽爾纖維在包含非織基材及含有具四級銨鹽之化合物的液體之產品中的用途,其中該萊賽爾纖維係包含在該非織基材中,且其中該萊賽爾纖維含有併入該纖維之基本上不溶於水的鹽。
Description
本發明關於萊賽爾纖維在包含非織基材及含有具四級銨鹽之化合物的液體之產品中的用途。此等產品在下文中亦稱為「濕巾(wet/moist wipe)」。
尤其是,本發明關於萊賽爾纖維在衛生產品之濕巾(尤其是家用、餐飲、醫療及其他市場區域用的消毒及殺菌擦拭巾)中的用途。
為了衛生之目的,常使用分別含有四級銨鹽作為活性物質之濕巾。擦拭巾(wipe)主要由浸漬液體(諸如含有所述四級銨鹽的溶液或分散液)之非織基材組成。該液體在下文中亦稱為「洗劑(lotion)」。該等四級銨鹽展現抗微生物活性。
在美國,存在於抗微生物擦拭巾(antimicrobial wipe)溶液中之活性成分的化合物及量係於下列EPA案號:EPA-HQ-OPP-2006-0339和EPA-HQ-OPP-2006-0338以及21美國聯邦法規§178.1010(b)及(c)中指明。
FDA法規適用於「食品處理設備及所指明之其他食品接觸物件」,而EPA法規涵蓋大部分其他用途,主要是用於硬表面(hard surface)的殺菌擦拭巾(sanitation wipe)。§178.1010(b)規定可使用之化合物,而§178.1010(c)規定溶液中之活性成分量的最少量及不超過的量,而EPA法規規定最大四級銨鹽濃度。
滿足現今引用之法規的濕巾之組成主要為聚酯(PES)纖維、聚丙烯(PP)纖維或其混合物,以及該等纖維與僅有非常少百分比之少量纖維素纖維的混合物。
濕巾通常係以一般為10至超過100單張之堆疊而包在包裝袋中。在貯存期間,因重力及非纖維素纖維之間的不良交互作用之故,洗劑易於從頂部滲至底部。此造成洗劑之不均勻分布,其影響來自該包裝之單一擦拭巾的有效性。因PES及PP纖維之疏水性質緣故,若使用水性配方,則此作用會更強。
為了減輕此作用,可使用纖維素纖維(cellulosic fibre),因為該等纖維為親水性且能改善洗劑的分布。然而,各纖維素纖維含有陰離子性的羧基。洗劑中之陰離子性的羧基與陽離子性的物質(活性物質)之間的交互作用會降低此等產品的有效性。
為了克服此問題,可增加四級銨鹽在擦拭巾上之負載量以補償(compensate)此化學連結(chemical tie-up)。然而,此超負載(over-loading)有時會使產品超出FDA專論(FDA monograph)。
根據US 2011/0220311,將溶解之金屬鹽添加至洗劑以防止四級銨鹽被纖維素纖維吸附。相較於洗劑中之活性物質,該等鹽具有少得多之陽離子。因此,該等陽離子可更快速結合至纖維素的表面並遮蔽陰離子電荷。因此,活性物質不會結合至纖維素,且能自由地發揮消毒劑作用。
根據US 2006/0193990,係添加包含聚合物及界面活性劑之黏合劑,其補償(compensate)在網狀產品的纖維上之表面電荷,陽離子性官能劑因而在洗劑中保持游離(free),且可以達到所希望之消毒效果的充足量遞送至表面。
US 2005/0245151關於藉由在織品被洗劑所飽和之前將化學阻隔材料(chemical blocking material)(聚醯胺-環氧氯丙烷樹脂、聚醯胺樹脂、三聚氰胺樹脂、高分子量陽離子型化學材料)添加至非織品(non-woven fabric)來增強洗劑之陽離子組分從非織濕巾材料脫離的方法。
在WO 2007/016579中,揭示包含陽離子型纖維化合物(諸如具有陽離子最後加工(cationic finish)之聚葡萄胺糖纖維(chitosan fibre))之陽離子型纖維殺菌基材。
US 7 637 271(The Clorox Company)揭示添加0.1至20%之聚合鋁化合物(polyaluminium compound)(氯化物、氯化羥鹽(chlorohydrate)、硫酸鹽)至清潔組成物。
根據先前技術,必須有額外化學品及後處理步驟以影響濕巾產品中所使用的纖維素纖維之表面電荷。此造成額
外成本及化學負載。
需要具有充足脫離性質及消除在包裝中之流體遷移的濕巾。
本發明下之問題係藉由在包含非織基材及含有具四級銨鹽之化合物的液體之產品中使用萊賽爾纖維而解決,其中該萊賽爾纖維係包含在該非織基材中,且其中該萊賽爾纖維含有併入該纖維之基本上不溶於水的鹽。
本發明之較佳實施態樣係於依附之申請專利範圍中提出。
使用含有併入纖維之基本上不溶於水的鹽(essentially water-insoluble salt)之萊賽爾纖維令人訝異地解決了前文所論述之濕巾的問題。
尤其是,藉由將基本上不溶於水的鹽併入萊賽爾纖維,已發現在製造濕巾階段中毋需進一步處理或添加其他材料來避免前文論述的問題。
用語「萊賽爾(lyocell)」為BISFA(國際人造纖維標準局(The International Bureau for the Standardization of man made fibres))對藉由將纖維素溶於有機溶劑而不形成衍生物且利用乾-濕紡絲法(dry-wet spinning process)或熔噴法(melt-blown process)從所述溶液擠
出纖維所製造之纖維素纖維所指派的通稱。在這方面,應暸解有機溶劑為有機化學物及水的混合物。目前,使用N-甲基-味啉-N-氧化物(NMMO)作為商業規模生產的有機溶劑。
在該方法中,纖維素之溶液經常利用成形工具(forming tool)擠製,而藉此被模製。經模製溶液經過空氣隙(air gap)進入沉澱浴(precipitation bath),於該處藉由沉澱該溶液而獲得經模製體(moulded body)。清洗該經模製體並在其他處理步驟之後視需要乾燥。製造萊賽爾纖維之方法係描述於例如US A 4,246,221。萊賽爾纖維以高抗張強度(tensile strength)、高濕模數(wet-modulus)及高環圈強度(loop strength)著稱。
在用語「併入所述纖維」之下,熟練的技術人士暸解基本上不溶於水的鹽分布在纖維(fibre)的纖維基質(cellulosic matrix)內,基本上遍布其整個截面(cross-section)。
已熟知經由併入各種添加劑使纖維素纖維以及萊賽爾纖維改質。
如熟練的技術人士本身已知,將改質化合物併入萊賽爾纖維可藉由在紡絲程序(spinning process)之前將該化合物摻入紡絲溶液及/或藉由將該化合物摻入該溶液之前驅物(precursor)而達成。
作為紡絲溶液之「前驅物」,應暸解製造紡絲溶液之起始及中間材料,尤其是:
- 所使用之起始纖維素材料,例如紙漿(pulp)
- 所使用之溶劑(水性三級胺氧化物(aqueous tertiary amine oxide),在下文中使用用語「NMMO」作為所有適用之胺氧化物的縮寫)
- 起始纖維素材料與溶劑NMMO之混合物,尤其是纖維素於水性NMMO中之懸浮液,由彼可製成該溶液。
WO 2009/036481揭示含有選自珍珠粉、經研磨珍珠層(ground nacre)及其混合物所組成之群組的材料併入其中之萊賽爾纖維。
下文中,如本發明所使用之含有併入其中之基本上不溶於水的鹽的萊賽爾纖維係稱為「經改質萊賽爾纖維」。
在「基本上不溶於水的」鹽之下,熟練的技術人士暸解鹽係具有非常低之水中溶解度以致其在製造萊賽爾纖維(包括其之後處理)的水性環境中不會被洗出,或僅洗出達商業生產之生態及經濟要求方面可接受的程度。
較佳地,本發明中所使用之鹽在15℃至25℃的水中之溶解度為5g/l或更低,諸如3g/l或更低、1g/l或更低,尤佳為低於0.1g/l。
較佳地,鹽在酸性條件下為可溶。
通常,應用至非織基材以製造濕巾的含有具有四級銨鹽之化合物的洗劑的pH值為約小於7,尤其是3至6,諸如4.0至5.5。
若在此等酸性條件下,纖維中所含之鹽為可溶,其會解離至一定程度。然後該鹽中之陽離子結合至纖維素,因
此遮蔽該纖維素之陰離子電荷而不需要添加其他添加劑。
作為替代方案,經改質之萊賽爾纖維或含有該經改質之萊賽爾纖維的非織基材可在以含有四級銨鹽之洗劑處理之前以酸性介質處理。同樣的,藉由此種處理,會遮蔽纖維素纖維之陰離子電荷。該替代方案將使得能在濕巾之製造階段中使用無酸性pH值的洗劑。再者,可在該替代方案下應用更嚴格的處理條件(諸如使用更強酸)。
萊賽爾纖維通常每克纖維含有約20μmol至50μmol、尤其是25μmol至40μmol之量的羧基(carboxylic)(即,陰離子性基團)。因此,一般而言,目的係提供經改質纖維,其中於纖維之酸性處理時,來自纖維中所含之鹽的足量陽離子會被釋放以儘可能完全遮蔽此等陰離子電荷。
很明顯的,本目的可基於熟練的技術人士之知識,藉由適當選擇下列參數而解決:- 鹽之性質,因此包括其價數(valence)及其溶解度(solubility)兩者- 包含在纖維中之鹽的量,及- 用以處理纖維及/或非織基材之酸性液體的性質及量。
在本發明之較佳實施態樣中,所使用之基本上不溶於水的鹽可選自由下列所組成之群組的鹽:鹼金屬、鹼土金屬、過渡金屬、鋁及其混合物。
更佳地,該鹽為無機鹽。
尤佳地,該鹽係選自由下列所組成之群組:碳酸鈣、氧化鋅、磷酸鈣、氫氧化鎂、氫氧化鋁、草酸鈣、碳酸鋇、有機草酸鹽及其混合物。
根據本發明所使用之萊賽爾纖維較佳含有以乾燥纖維之重量計為0.1重量%至50重量%、較佳為1重量%至10重量%、尤佳為2重量%至7重量%之量的該無機鹽。
為製造濕巾所使用之四級銨鹽(quaternary ammonium salt)較佳為四級銨氯化物(quaternary ammonium chloride)。
尤其是,所述四級銨鹽可選自由下列所組成之群組:氯化正烷基苄基二甲銨(n-alkylbenzyldimethylammoniumchloride)(BAC或ABDAC)、氯化二正烷基二甲銨(di-n-alkyldimethyl ammoniumchloride)(DDAC)、氯化正烷基二甲基乙基苄銨(n-alkyldimethylethylbenzylammonium chloride)(ADEBAC)、氯化正烷基三甲銨(n-alkyltrimethylammonium chloride)、氯化辛基癸基二甲銨(octyldecyldimethylammonium chloride)、氯化二癸基二甲銨(didecyldimethylammonium chloride)、氯化二辛基二甲銨(dioctyldimethylammonium chloride)、氯化本索寧(benzethonium chloride)及其混合物。
含有經改質之萊賽爾纖維的非織基材可藉由熟練的技術人士已知之方法製造。在本發明較佳實施態樣中,含有經改質之萊賽爾纖維的非織基材為熔噴產物(melt-blown product)。從纖維素於NMMO中之溶液製造熔噴產物尤其
是從例如WO 98/26122、WO 99/47733、WO 98/07911、US 6,197,230、WO 99/64649、WO 05/106085、EP 1 358 369及WO 2007/124521已知。
較佳地,非織基材含有經改質萊賽爾纖維之量以乾燥基材之重量計為5重量%至100重量%、較佳為10重量%至50重量%、尤佳為20重量%至30重量%。
在非織基材含有「100重量%」之量的經改質萊賽爾纖維之下,熟練的技術人士暸解基材基本上由所述經改質萊賽爾纖維所組成,諸如從纖維素於NMMO中之溶液所製造的熔噴非織產物(melt-blown non-woven product)。因而不排除存在少量添加劑,諸如用於纖維及/或非織基材之表面處理。
如本身已知,非織基材可含有經改質萊賽爾纖維與疏水性纖維(諸如PP纖維、PES纖維及其混合物)之混合物。
本發明亦關於包含非織基材及含有具四級銨鹽之化合物的溶液之產品,其中,萊賽爾纖維係包含在該非織基材中,且其中,該萊賽爾纖維含有併入該纖維之基本上不溶於水的鹽。
至於本發明產品(即,濕巾)中所使用之纖維、鹽之性質、及其他較佳實施態樣的細節,可參考上述段落。
根據先前技術製造其中分別併入1.1重量%;2.9重量%;4.1重量%;4.8重量%及6.2重量%(以絕對乾燥(bone-dry)纖維計)之CaCO3的萊賽爾纖維。如此,製備含有上述濃度之CaCO3的纖維素於水性NMMO中之13重量%的紡絲原液(spinning dope)。隨後使用萊賽爾法(lyocell process)之紡絲原液的紡絲形成最終纖維(1.7dtex,38mm)。
該等空氣乾燥之纖維係混(mingle)以400重量%(以空氣乾燥之纖維計)之BAC水溶液(氯化烷基二甲基苄銨(alkyldimethylbenzylammonium chloride),1000ppm),及使用下文於實施例4中解釋的滴定法測定脫離性質(release property)。將該BAC水溶液調整至酸性pH。
明顯看出,可用之活性物質(accessible active substance)的濃度隨著併入CaCO3之增加而提高。在表1中,彙總不同CaCO3纖維類型的滴定結果。
根據先前技術製造其中分別併入1.5重量%;2重量%;2.5重量%及3.0重量%(以絕對乾燥纖維計)之ZnO的萊賽爾纖維。如此,製備含有上述濃度之ZnO的纖維素於水性NMMO中之13重量%的紡絲原液。隨後使用萊賽爾法之紡絲原液的紡絲形成最終纖維(1.7dtex,38mm)。
該等空氣乾燥之纖維係混(mingle)以400重量%(以空氣乾燥之纖維計)之BAC水溶液(氯化烷基二甲基苄銨,1000ppm),及使用下文於實施例4中解釋的滴定法測定脫離性質。將該BAC水溶液調整至酸性pH。
在表2中,彙總不同ZnO纖維類型的滴定結果。
比較實施例1及2中提及的纖維類型與不含不溶於水的鹽之標準萊賽爾纖維的BAC脫離性質。
明顯看出,相較於標準萊賽爾纖維,根據本發明所使用之纖維類型顯示出至少兩倍BAC脫離。
四級脫離(quaternary release)係使用實施例4中所
述的滴定法測定。在表3中,彙總不同纖維類型的滴定結果。
待測定之陽離子性物質(BAC或其他QAC)係使用十二烷基硫酸鈉(sodium dodecylsulfate)於含有水及氯化溶劑(chlorinated solvent)(二氯甲烷、氯仿、、、等)之兩相系統(two-phase system)中利用溴酚藍(bromophenol blue)作為指示劑來滴定。
陽離子性物質(cationic substance)與可溶於氯化溶劑之溴酚藍形成錯合物。以陰離子性界面活性劑(anionic surfactant)滴定該錯合物導致置換指示劑陰離子,以及新形成的錯合物通過至該水相。在滴定結束時,所釋放之指示劑使氯化相(chlorinated phase)染成藍色/藍紫色(blue/violet),而水相重回淡黃色/無色(yellowish/colorless)。
測定實施例1及2中所述之纖維類型的纖維資料(fibre data)。表4顯示纖維資料不會隨著併入所提及之鹽而改變。
FFk:經調節之韌度(Tenacity conditioned)
FDk:經調節之伸長率(Elongation conditioned)(FDk)。
Claims (16)
- 一種萊賽爾纖維在包含非織基材及含有具四級銨鹽之化合物的液體之產品中的用途,其中,該萊賽爾纖維係包含在該非織基材中,且其中,該萊賽爾纖維含有併入該纖維之基本上不溶於水的鹽。
- 如申請專利範圍第1項之用途,其中,該鹽於15℃至25℃的水中溶解度為5g/l或更低,諸如3g/l或更低、1g/l或更低、較佳係低於0.1g/l。
- 如申請專利範圍第2項之用途,其中,該鹽係選自由下列所組成之群組:鹼金屬鹽、鹼土金屬鹽、過渡金屬鹽、鋁鹽、及其混合物。
- 如前述申請專利範圍中任一項之用途,其中,該鹽為無機鹽。
- 如申請專利範圍第1或2項之用途,其中,該鹽係選自由下列所組成之群組:碳酸鈣、氧化鋅、磷酸鈣、氫氧化鎂、氫氧化鋁、草酸鈣、碳酸鋇、有機草酸鹽(organic oxalate)、及其混合物。
- 如前述申請專利範圍中任一項之用途,其中,該萊賽爾纖維含有以乾燥纖維之重量計為0.1重量%至50重量%、較佳為1重量%至10重量%、尤佳為2重量%至7重量%之量的該無機鹽。
- 如前述申請專利範圍中任一項之用途,其中,含有該萊賽爾纖維之該非織基材為熔噴產物(melt-blown product)。
- 如前述申請專利範圍中任一項之用途,其中,該非織基材含有以乾燥基材之重量計為5重量%至100重量%,諸如10重量%至80重量%、20重量%至60重量%、尤佳為20重量%至30重量%之量的該萊賽爾纖維。
- 一種產品,其包含非織基材及含有具四級銨鹽之化合物的溶液,其中,萊賽爾纖維係包含在該非織基材中,且其中,該萊賽爾纖維含有併入該纖維之基本上不溶於水的鹽。
- 如申請專利範圍第9項之產品,其中,該鹽於15℃至25℃的水中溶解度為5g/l或更低,諸如3g/l或更低、1g/l或更低、較佳係低於0.1g/l。
- 如申請專利範圍第10項之產品,其中,該鹽係選自由下列所組成之群組:鹼金屬鹽、鹼土金屬鹽、過渡金屬鹽、鋁鹽、及其混合物。
- 如申請專利範圍第9至11項中任一項之產品,其中,該鹽為無機鹽。
- 如申請專利範圍第9或10項之產品,其中,該鹽係選自由下列所組成之群組:碳酸鈣、氧化鋅、磷酸鈣、氫氧化鎂、氫氧化鋁、草酸鈣、碳酸鋇、有機草酸鹽、及其混合物。
- 如申請專利範圍第10至13項中任一項之產品,其中,該萊賽爾纖維含有以乾燥纖維之重量計為0.1重量%至50重量%、較佳為1重量%至10重量%、尤佳為2重量%至7重量%之量的該鹽。
- 如申請專利範圍第10至14項中任一項之產品,其中,含有該萊賽爾纖維之該非織基材為熔噴產物。
- 如申請專利範圍第10至15項中任一項之產品,其中,該非織基材含有以乾燥基材之重量計為5重量%至100重量%,諸如10重量%至80重量%、20重量%至60重量%、尤佳為20重量%至30重量%之量的該萊賽爾纖維。
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TW105125185A TWI705171B (zh) | 2015-09-16 | 2016-08-08 | 萊賽爾(lyocell)纖維之用途 |
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US (1) | US20180258375A1 (zh) |
EP (2) | EP3144376A1 (zh) |
JP (1) | JP2018527480A (zh) |
KR (1) | KR20180069787A (zh) |
CN (1) | CN107949630B (zh) |
AU (1) | AU2016321846B2 (zh) |
CA (1) | CA2997403A1 (zh) |
ES (1) | ES2871018T3 (zh) |
MX (1) | MX2018003253A (zh) |
PL (1) | PL3350308T3 (zh) |
RU (1) | RU2720084C2 (zh) |
TW (1) | TWI705171B (zh) |
WO (1) | WO2017046044A1 (zh) |
Families Citing this family (1)
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WO2023086213A1 (en) * | 2021-11-13 | 2023-05-19 | Ascend Performance Materials Operations Llc | Wet wipes with zinc loading |
Family Cites Families (27)
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US4246221A (en) | 1979-03-02 | 1981-01-20 | Akzona Incorporated | Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent |
GB9407496D0 (en) * | 1994-04-15 | 1994-06-08 | Courtaulds Fibres Holdings Ltd | Fibre treatment |
FR2735794B1 (fr) | 1995-06-26 | 1997-09-19 | Elysees Balzac Financiere | Procede de preparation d'un melange de fibres et de microfibres cellulosiques |
US6210801B1 (en) | 1996-08-23 | 2001-04-03 | Weyerhaeuser Company | Lyocell fibers, and compositions for making same |
ATE225418T1 (de) | 1996-08-23 | 2002-10-15 | Weyerhaeuser Co | Lyocellfasern und verfahren zu ihrer herstellung |
GB9625634D0 (en) | 1996-12-10 | 1997-01-29 | Courtaulds Fibres Holdings Ltd | Method of manufacture of nonwoven fabric |
GB2337957A (en) | 1998-06-05 | 1999-12-08 | Courtaulds Fibres | Method of manufacture of a nonwoven fabric |
US7101612B2 (en) * | 2000-05-04 | 2006-09-05 | Kimberly Clark Worldwide, Inc. | Pre-moistened wipe product |
CA2346626A1 (en) * | 2000-05-11 | 2001-11-11 | Unilever Plc | Antimicrobial cleansing composition and wipe |
JP2004512877A (ja) * | 2000-11-01 | 2004-04-30 | ザ、プロクター、エンド、ギャンブル、カンパニー | 制御された液体放出が可能なあらかじめ湿ったワイプ用の多層基材 |
DE10065859B4 (de) | 2000-12-22 | 2006-08-24 | Gerking, Lüder, Dr.-Ing. | Verfahren und Vorrichtung zur Herstellung von im Wesentlichen endlosen feinen Fäden |
US7838447B2 (en) * | 2001-12-20 | 2010-11-23 | Kimberly-Clark Worldwide, Inc. | Antimicrobial pre-moistened wipers |
US20030157856A1 (en) | 2002-01-14 | 2003-08-21 | Schroeder Gary L. | Moist wipe and method of making same |
US20030144640A1 (en) * | 2002-01-24 | 2003-07-31 | Nguyen Hien Vu | High absorbency lyocell fibers and method for producing same |
US20050245151A1 (en) | 2002-06-21 | 2005-11-03 | Ahistrom Windsor Locks Llc | Nonwoven wiping material with improved quaternary salt release properties |
ES2381047T3 (es) * | 2003-01-15 | 2012-05-22 | Sca Hygiene Products Ab | Toallita limpiadora atrapabacterias |
WO2005106085A1 (en) | 2004-04-26 | 2005-11-10 | Biax Fiberfilm Corporation | Apparatus , product and process forming micro-fiber cellulosic nonwoven webs |
GB0417477D0 (en) * | 2004-08-05 | 2004-09-08 | Tencel Ltd | Anti-microbial fibres |
US7485589B2 (en) | 2005-08-02 | 2009-02-03 | Pgi Polymer, Inc. | Cationic fibrous sanitizing substrate |
AT503625B1 (de) | 2006-04-28 | 2013-10-15 | Chemiefaser Lenzing Ag | Wasserstrahlverfestigtes produkt enthaltend cellulosische fasern |
DE502007006156D1 (de) * | 2006-07-21 | 2011-02-17 | Smart Fiber Ag | Reinigungstuch |
US20090004474A1 (en) * | 2007-06-29 | 2009-01-01 | Weyerhaeuser Co. | Lyocell fibers with anti-microbial activity |
AT505787B1 (de) | 2007-09-18 | 2009-06-15 | Chemiefaser Lenzing Ag | Lyocellfaser |
US7637271B1 (en) | 2008-10-30 | 2009-12-29 | The Clorox Company | Polyaluminum compositions |
US8328988B2 (en) | 2010-03-15 | 2012-12-11 | Weyerhaeuser Nr Company | Reduction of the adsorption of quaternary ammonium salts onto cellulosic fibers |
AT512601B1 (de) * | 2012-03-05 | 2014-06-15 | Chemiefaser Lenzing Ag | Verfahren zur Herstellung einer Cellulosesuspension |
JP2014218443A (ja) * | 2013-05-01 | 2014-11-20 | 有限会社岡田技研 | 抗菌剤組成物およびこれを用いた清拭シート |
-
2015
- 2015-09-16 EP EP15185393.4A patent/EP3144376A1/en not_active Withdrawn
-
2016
- 2016-08-08 TW TW105125185A patent/TWI705171B/zh not_active IP Right Cessation
- 2016-09-13 CA CA2997403A patent/CA2997403A1/en active Pending
- 2016-09-13 KR KR1020187007742A patent/KR20180069787A/ko not_active Application Discontinuation
- 2016-09-13 CN CN201680053220.8A patent/CN107949630B/zh active Active
- 2016-09-13 AU AU2016321846A patent/AU2016321846B2/en not_active Ceased
- 2016-09-13 MX MX2018003253A patent/MX2018003253A/es unknown
- 2016-09-13 RU RU2018113462A patent/RU2720084C2/ru active
- 2016-09-13 EP EP16763834.5A patent/EP3350308B1/en active Active
- 2016-09-13 ES ES16763834T patent/ES2871018T3/es active Active
- 2016-09-13 PL PL16763834T patent/PL3350308T3/pl unknown
- 2016-09-13 US US15/760,369 patent/US20180258375A1/en not_active Abandoned
- 2016-09-13 WO PCT/EP2016/071486 patent/WO2017046044A1/en active Application Filing
- 2016-09-13 JP JP2018513788A patent/JP2018527480A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
JP2018527480A (ja) | 2018-09-20 |
EP3350308A1 (en) | 2018-07-25 |
TWI705171B (zh) | 2020-09-21 |
WO2017046044A1 (en) | 2017-03-23 |
EP3350308B1 (en) | 2021-02-17 |
RU2720084C2 (ru) | 2020-04-24 |
AU2016321846B2 (en) | 2020-07-09 |
EP3144376A1 (en) | 2017-03-22 |
AU2016321846A1 (en) | 2018-03-15 |
RU2018113462A3 (zh) | 2019-10-17 |
PL3350308T3 (pl) | 2021-08-23 |
CA2997403A1 (en) | 2017-03-23 |
RU2018113462A (ru) | 2019-10-17 |
CN107949630B (zh) | 2021-03-23 |
KR20180069787A (ko) | 2018-06-25 |
ES2871018T3 (es) | 2021-10-28 |
MX2018003253A (es) | 2018-05-17 |
CN107949630A (zh) | 2018-04-20 |
US20180258375A1 (en) | 2018-09-13 |
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