EP4244414A1 - Antistatic spandex and garments thereof - Google Patents
Antistatic spandex and garments thereofInfo
- Publication number
- EP4244414A1 EP4244414A1 EP21840720.3A EP21840720A EP4244414A1 EP 4244414 A1 EP4244414 A1 EP 4244414A1 EP 21840720 A EP21840720 A EP 21840720A EP 4244414 A1 EP4244414 A1 EP 4244414A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- spandex
- ionic liquid
- antistatic
- sulfate
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002334 Spandex Polymers 0.000 title claims abstract description 135
- 239000004759 spandex Substances 0.000 title claims abstract description 135
- 239000002608 ionic liquid Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000000980 acid dye Substances 0.000 claims abstract description 6
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims description 52
- 230000000996 additive effect Effects 0.000 claims description 33
- 239000004744 fabric Substances 0.000 claims description 21
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 17
- 239000007795 chemical reaction product Substances 0.000 claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 17
- 239000000194 fatty acid Substances 0.000 claims description 17
- 229930195729 fatty acid Natural products 0.000 claims description 17
- 150000004665 fatty acids Chemical class 0.000 claims description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 16
- -1 imidazolinium alkyl sulfate Chemical class 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 claims description 8
- 229940008406 diethyl sulfate Drugs 0.000 claims description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 25
- 229920000642 polymer Polymers 0.000 description 17
- 235000004879 dioscorea Nutrition 0.000 description 16
- 239000000835 fiber Substances 0.000 description 13
- 238000004043 dyeing Methods 0.000 description 12
- 239000000975 dye Substances 0.000 description 11
- 229920002635 polyurethane Polymers 0.000 description 11
- 238000009991 scouring Methods 0.000 description 11
- 239000004952 Polyamide Substances 0.000 description 10
- 239000002216 antistatic agent Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229920002647 polyamide Polymers 0.000 description 10
- 230000003068 static effect Effects 0.000 description 10
- 239000004814 polyurethane Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 6
- 238000007730 finishing process Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000007786 electrostatic charging Methods 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 238000009940 knitting Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 210000004177 elastic tissue Anatomy 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000010016 exhaust dyeing Methods 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920003226 polyurethane urea Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- ASLICXGLMBICCD-UHFFFAOYSA-N 1-ethyl-4,5-dihydroimidazole Chemical compound CCN1CCN=C1 ASLICXGLMBICCD-UHFFFAOYSA-N 0.000 description 1
- ZLIUGCVPPWCSGV-UHFFFAOYSA-M 2-[1-ethyl-2-(15-methylhexadecyl)-4,5-dihydroimidazol-1-ium-1-yl]ethanol;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.OCC[N+]1(CC)CCN=C1CCCCCCCCCCCCCCC(C)C ZLIUGCVPPWCSGV-UHFFFAOYSA-M 0.000 description 1
- KBWINQAOGFKEEX-UHFFFAOYSA-M 2-[1-ethyl-2-(16-methylheptadecyl)-4,5-dihydroimidazol-1-ium-1-yl]ethanol;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.OCC[N+]1(CC)CCN=C1CCCCCCCCCCCCCCCC(C)C KBWINQAOGFKEEX-UHFFFAOYSA-M 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 210000003423 ankle Anatomy 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CXUJOBCFZQGUGO-UHFFFAOYSA-F calcium trimagnesium tetracarbonate Chemical compound [Mg++].[Mg++].[Mg++].[Ca++].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O CXUJOBCFZQGUGO-UHFFFAOYSA-F 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical group CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BXUQCHJUJZSORJ-UHFFFAOYSA-N ethyl hydrogen sulfate;5-ethyl-2-methyl-1h-imidazole Chemical compound CCOS(O)(=O)=O.CCC1=CN=C(C)N1 BXUQCHJUJZSORJ-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229910000515 huntite Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 210000002414 leg Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- DXJLCRNXYNRGRA-UHFFFAOYSA-M tributyl(methyl)azanium;iodide Chemical compound [I-].CCCC[N+](C)(CCCC)CCCC DXJLCRNXYNRGRA-UHFFFAOYSA-M 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
- D04B1/18—Other fabrics or articles characterised primarily by the use of particular thread materials elastic threads
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/16—Physical properties antistatic; conductive
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2501/00—Wearing apparel
Definitions
- This disclosure relates to spandex fiber comprising ionic liquids and fabrics and garments made from the spandex fiber.
- the spandex fiber exhibits antistatic properties and reduces garment cling.
- Electrostatic charge buildup is responsible for a variety of problems in the processing and the use of many industrial products and materials. Electrostatic charging can cause materials to stick together or to repel one another. In addition, static charge buildup can cause objects to attract dirt and dust that can lead to fabrication or soiling problems and can impair product performance. Sudden electrostatic discharges from insulating objects can also be a serious problem. When flammable materials are present, a static electric discharge can serve as an ignition source, resulting in fires and/or explosions.
- Electrostatic charge is a particular problem in the electronics industry, because modern electronic devices are extremely susceptible to permanent damage by electrostatic discharges.
- the buildup of electrostatic charge on insulating objects is especially common and problematic under conditions of low humidity and when liquids or solids move in contact with one another (tribocharging).
- Static charge build-up can be controlled by increasing the electrical conductivity of a material. This can be accomplished by increasing ionic or electronic conductivity.
- the most common means of controlling static accumulation today is by increasing electrical conductivity through moisture adsorption. This is commonly achieved by adding moisture to the surrounding air (humidification) or by the use of hygroscopic antistatic agents, which are generally referred to as humectants because they rely on the adsorption of atmospheric moisture for their effectiveness.
- Most antistatic agents operate by dissipating static charge as it builds up; thus, static decay rate and surface conductivity are common measures of the effectiveness of antistatic agents.
- Antistatic agents can be applied to the surface (external antistatic agent) or incorporated into the bulk (internal antistatic agent) of the otherwise insulating material.
- Internal antistatic agents are commonly employed in polymers such as plastics. [0005] Generally, internal antistatic agents fall into one of the following classes: (I) ones that are mixed directly into a molten polymer during melt processing; (2) ones that are mixed into a polymer solution, coated, and dried, or (3) ones that dissolve into a monomer (with or without a solvent) that is subsequently polymerized.
- Yams prepared from elastic polyurethane (PU) fibers comprising long chain synthetic polymers, a large portion of which are synthesized from PUs based on polyethers, polyesters and and/or polycarbonates are used in the production of sheet goods and woven textiles or substances which are suitable for garments, hosiery and sports clothing such as, but in no way limited to swimwear and bathing trunks. Knitting and weaving are forms of processing PU fibers.
- U.S. Patent 6,329,452 discloses adding dialkyl sulphosuccinate to elastic PU compositions and or by depositing this substance in a suitable form as an external preparation on elastic fibers for antistatic effect.
- U.S. Patent 6,849,676 discloses application of salts of sulfonates having Cs-3o hydrocarbon chain, sulfates having Cs-3o hydrocarbon chain and phosphates having Cs-3o hydrocarbon chain as antistatic agents in production of antistatic PU elastic fiber.
- U.S. Patent 8,715,799 discloses antistatic, thermoplastic PU comprising ethylmethylimidazole ethyl sulfate for shoe sector applications, elastomer rollers, manufacturing of electronically sensitive components and in pneumatic conveying of solids.
- U.S. Patent 8,993,660 discloses use of an antistatic composition comprising a polar thermoplastic polymer and an ionic liquid as an antistatic additive for non-polar thermo-plastic or elastomeric polymers.
- U.S. Patent 9,012,590 discloses electrostatic dissipative thermoplastic PU compositions made by reacting at least one polyester polyol intermediate with at least one diisocyanate and at least one chain extender.
- Published U.S. Patent Application No. 2015/0057388 discloses an antistatic PU with an ionic liquid as the antistatic additive.
- Published U.S. Patent Application No. 2017/0355805 discloses an ionic diol represented by formula wherein R 1 represents an alkyl group having from 6 to 18 carbon atoms; R 2 and R 3 independently represent alkyl groups having from 1 to 4 carbon atoms; R 4 represents an alkylene group having from 2 to 8 carbon atoms; and R 5 represents an alkylene group having from 1 to 8 carbon atoms in production of antistatic PUs.
- ionic diol see e.g. Published U.S. Patent Application No, 2017/0355805A1
- dialkyl sulphosuccinate see e.g. U.S. Patent 6,329,452B1
- sulfonates/sulfate/phosphate of C8-30 chain see e.g. U.S. Patent 6,849,676B1
- tri-n-butylmethylammonium bis- (trifluoromethanesulfonyl)imide see e.g. U.S. Patent 9,012,590
- antistatic additives is based primarily on cation/anion small organic compounds which are water soluble and have poor interaction with PUs.
- these antistatic additives are gradually wiped off from surfaces by moisture and/or water after long term usage.
- the small organic molecules are generally used as additives to a polyurethane matrix which is molded into parts such as shoes, belts, and rollers. In general, molded articles are not exposed to textile scouring and dyeing processes which can extract the small molecule additives. Therefore, durability of antistatic fiber is not a main concern in these applications.
- U.S. Patent 6,403,682 discloses spandex having improved heat-set efficiency, obtained by incorporating certain quaternary amine additives into the spinning solution. No anti-static properties of the quaternary amine additives are di closed.
- An aspect of the present invention relates to an antistatic spandex comprising spandex and an ionic liquid.
- the ionic liquid of the antistatic spandex comprises an imidazolinium alkyl sulfate having formula I wherein R1 represents alkyl or alkenyl groups with 6 to 22 carbons,
- R2 represents -CHs or -CH2CH3 groups
- R3 represents -CH2CH2OH or -CH2CH2NH2 groups
- R4 represents -CH3 or -CH2CH3 groups.
- the ionic liquid of the antistatic spandex comprises IH-Imidazolium, l-ethyl-2-(2-heptadecen-l-yl)-4,5-dihydro-3-(2-hydroxyethyl)-, ethyl sulfate (1 : 1).
- the ionic liquid of the antistatic spandex comprises a fatty acids reaction product with 2-((2-aminoethyl)amino)ethanol, or diethylenetriamine, dimethyl or diethyl sulfate quaternized.
- the ionic liquid of the antistatic spandex comprises a fatty acids, tail-oil, reaction product with 2-((2-aminoethyl)amino)ethanol, di-Et sulfate-quatemized.
- spandex comprising the ionic liquid in accordance with this disclosure may exhibit enhanced coloration as compared to spandex without the ionic liquid and/or reduced cling as compared to spandex without the ionic liquid.
- Another aspect of the present invention relates to an article of manufacture, at least a portion of which comprises this antistatic spandex.
- Nonlimiting examples of such articles include fabric or garments.
- Another aspect of the present invention relates to a spandex additive comprising an imidazolinium alkyl sulfate having formula I
- R1 represents alkyl or alkenyl groups with 6 to 22 carbons
- R2 represents -CHs or -CH2CH3 groups
- R3 represents -CH2CH2OH or -CH2CH2NH2 groups
- R4 represents -CH3 or -CH2CH3 groups
- Yet another aspect of the present invention relates to a method for producing antistatic spandex.
- the method comprises adding to spandex an ionic liquid.
- the ionic liquid comprises an imidazolinium alkyl sulfate having formula I formula II
- R1 represents alkyl or alkenyl groups with 6 to 22 carbons
- R2 represents -CPF, or -CH2CH3 groups
- R3 represents -CH2CH2OH or -CH2CH2NH2 groups
- R4 represents -CH3 or -CH2CH3 groups.
- the ionic liquid of the antistatic spandex comprises IH-Imidazolium, l-ethyl-2-(2-heptadecen-l-yl)-4,5-dihydro-3-(2-hydroxyethyl)-, ethyl sulfate (1 : 1).
- the ionic liquid comprises a fatty acids reaction product with 2-((2-aminoethyl)amino)ethanol, or di ethylenetri amine, dimethyl or diethyl sulfate quatemized.
- the ionic liquid comprises a fatty acids, tail-oil, reaction product with 2-((2-aminoethyl)amino)ethanol, di-Et sulfate-quaternized.
- Spandex produced in accordance with this method may also exhibit enhanced coloration as compared to spandex without the ionic liquid and/or reduced cling as compared to spandex without the ionic liquid.
- FIGs. 1 A through ID show two traditional choices for incorporating spandex into garments such as hosiery including every course style (ECPH) as depicted in FIG. 1 A and 1C and alternate course style (ACPH) as depicted in FIG. IB and ID.
- ECPH course style
- ACPH alternate course style
- the present invention relates to antistatic spandex as well as spandex additives, methods of production of the antistatic spandex and articles of manufacture, at least a portion of which comprise the antistatic spandex.
- the antistatic spandex of the present invention comprises segmented polyether-based polyurethaneurea, also routinely referred to as spandex.
- the antistatic spandex of the present invention further comprises an ionic liquid added to the spandex.
- the ionic liquid comprises an imidazolinium alkyl sulfate having formula I
- R1 represents alkyl or alkenyl groups with 6 to 22 carbons
- R2 represents -CH or -CH2CH3 groups
- R3 represents -CH2CH2OH or -CH2CH2NH2 groups
- R4 represents -CH3 or -CH2CH3 groups.
- the ionic liquid of the antistatic spandex comprises IH-Imidazolium, l-ethyl-2-(2-heptadecen-l-yl)-4,5-dihydro-3-(2-hydroxyethyl)-, ethyl sulfate (1 : 1).
- the ionic liquid comprises a fatty acids reaction product with 2-((2-aminoethyl)amino)ethanol, or di ethylenetri amine, dimethyl or diethyl sulfate quatemized.
- the ionic liquid comprises a fatty acids, tailoil, reaction product with 2-((2-aminoethyl)amino)ethanol, di-Et sulfate-quatemized, also referred to herein as INC.
- the ionic liquid is added at 0.3-10% by weight of the spandex. In one nonlimiting embodiment, the ionic liquid is added at 0.3-3% by weight of the spandex.
- weight of spandex it is meant the final weight of spandex including all additives.
- Nonlimiting examples of ionic liquids useful in the antistatic spandex of the present invention include a mixture of amide and imidazoline, quaternized by di-Et sulfate, also referred to as INC 2470 (hereinafter referred to as INC), COLA® SOLV IES: Isostearyl Ethylimidazolinium Ethosulfate, CAS # 67633-57-2 and COLA® SOLV OES: Oleyl Ethylimidazolinium Ethosulfate (hereinafter referred to as OES), CAS # 68039-12-3 available from Colonial Chemical Company.
- Ionic liquids can be simply mixed into the spandex solution at room temperature.
- the ionic liquid is blended with other typical spandex additive such as, but not limited to, antioxidants, antacids, delusterants or/or lubricants.
- the ionic liquid is added at 0.3-3% by weight of the spandex.
- the imidazolinium moiety in this ionic liquid additive contributes to good antistatic property with the long aliphatic chain helping it migrate to the fiber surface, thus providing for good durability during aqueous textile process.
- the antistatic property of spandex fiber of the present invention containing an ionic liquid such as INC eliminates the building up of static charges during the fabric/garment process.
- the antistatic spandex produced in accordance with the present invention exhibits excellent antistatic property, durability and commercial adaptability. Additional benefits, as demonstrated herein include enhanced coloration as compared to spandex without the ionic liquid and reduced cling as compared to spandex without the ionic liquid.
- spandex additive comprising an imidazolinium alkyl sulfate having formula I
- R1 represents alkyl or alkenyl groups with 6 to 22 carbons
- R2 represents -CHa or -CH2CH3 groups
- R3 represents -CH2CH2OH or -CH2CH2NH2 groups
- R4 represents -CH3 or -CH2CH3 groups
- Antistatic spandex of the present invention can be used in any application or article of manufacture in which spandex is routinely used.
- the antistatic spandex is used in a fabric.
- Fabrics comprising the antistatic spandex may have a spandex content of about 0.5 weight percent (wt. %) to about 40 wt. %, based on weight of the fabric.
- spandex content of about 0.5 weight percent (wt. %) to about 40 wt. %, based on weight of the fabric.
- circular knits comprising spandex may contain from about 2 wt. % to about 25 wt. % spandex
- legwear comprising spandex may contain from about 1 wt. % to about 40 wt. % spandex.
- the spandex or the fabric comprising it may be dyed and printed by customary dyeing and printing procedures, such as from an aqueous dye liquor by the exhaust method at temperatures between 60° C. and 100° C. Conventional methods may be followed when using an acid dye.
- the fabric in an exhaust dyeing method, the fabric can be introduced into an aqueous dye bath kept in agitation having a pH of between 3.5 and 6 which is then heated steadily from a temperature of approximately 20° C. to a temperature about 98° C. for 40 minutes. The dye bath and fabric are then held at temperature for another 40 minutes before cooling. Unfixed dye is then rinsed from the fabric.
- Additional examples of articles of manufacture, at least a portion of which comprise the antistatic spandex include, but are in no way limited to, sheet goods and knitted and woven textiles or substances which are suitable for garments, hosiery and sports clothing such as, but in no way limited to swimwear and bathing trunks.
- the antistatic spandex is particularly useful in knitting and weaving processes where electrostatic charge can be problematic.
- the antistatic spandex of the present invention is particularly useful in hosiery.
- Two traditional choices for incorporating spandex of the present invention into garments such as hosiery include every course style (ECPH) as depicted in FIG. 1 A and 1C and alternate course style (ACPH) as depicted in FIG. IB and ID.
- the spandex fiber may be covered with, for example, polyamide, or may be bare, and is knitted in every course as depicted in FIG. 1 A and 1C or alternate courses as depicted in FIG. IB and ID.
- Garments such as every course panty hose (ECPH) comprise balanced stitches and normally provide for a higher quality garment.
- Articles of manufacture in accordance with the present invention may be comprised of at least a portion of the knit structures described herein.
- Nonlimiting examples of these articles include clothing such as, but not limited to, pantyhose, stockings, knee highs, ankle highs, stay ups, leggings and socks. All standard garment processing steps are understood to be applicable to the fabric of this invention, (e.g. scour, dyeing, heat setting or boarding, application of softeners).
- a solution of segmented polyether-based polyurethaneurea elastomer was prepared by thoroughly mixing diphenylmethane diisocyanate (“MDI”) polytetramethylene glycol having a molecular weight of about 1800 in a molar (“capping”) ratio of 1.63. The mixture was maintained at a temperature of about 80-90° C. for about 90-100 minutes. The resulting “capped glycol”, comprising a mixture of isocyanate-terminated polyether glycol and unreacted diisocyanate, was cooled to 50° C. and mixed with DMAc to provide a solution containing about 45% solids.
- MDI diphenylmethane diisocyanate
- capping molar
- the capped glycol was reacted for 2-3 minutes at a temperature of about 75° C. with a DMAc solution containing a mixture of di ethylamine chain-terminator and 90/10 blend of ethylene diamine/2-methyl-l,5- diaminopentane chain-extender.
- the resulting polymer solution contained approximately 35% solids and had a viscosity of about 3,200 poises at 40° C.
- a film was casted from the spandex solution with drying in N2 chamber for 24 hours.
- Spandex polymer solution was spun to form 22 dtex yam without INC or OES additive.
- Example 5 and 6 with antistatic additives exhibited lower surface resistivity (better antistatic properties) than Example 4 without antistatic additives.
- Example 8 and 9 with antistatic additives exhibited lower surface resistivity (better antistatic properties) than Example 7 without antistatic additives after black dyed.
- Examples 5 and 6 without a dye exhibited better anti-static properties as compared to Examples 8 and 9 which were dyed black.
- Polyamide was 44 dtex. This format was selected to evaluate the dye pick up from polyamide and spandex separately (first and second sections respectively) and together in a more commercial construction (third section). The final composition of the tube was approximately 80% polyamide and 20% spandex. The tube was then scoured at 80° C.
- Example 10 with no antistatic additive showed limited shade depth compared to polyamide “L*” value while Example 11 with 1% INC additive provides a low “L*” value (18.4) like polyamide.
- “AE*” value calculated with CIE74 formula is a metric to measure the color difference. The lower “AE*” value the higher is the color match between two substrates.
- Example 10 with no antistatic additive shows poor color match between spandex and polyamide with “AE*” of 22.2 while Example 11 with 1% INC additive provides a better color match with lower “AE*” value of 5.1. The better color match between the two fibers contributes to providing better invisibility of the spandex in the knit structure, a desirable property of spandex containing fabrics.
- Each pantyhose was then dyed using standard industry protocols for nylon hosiery using acid dyes in black and beige/tan colors.
- the hosiery was boarded using a commercial Cortese boarding machine which accepts hosiery legs in clam-shell compression compartment and applies steam pressure for a selected dwell period.
- the black garments were further washed 5X in a normal residential laundering process to test efficacy after normal use.
- Garments were tested with synthetic light outerwear (polyester and acetate) and insulating footwear (rubber soles). Wearer noted the presence and degree of static cling between the knitted hosiery and synthetic outerwear (skirt or dress).
- an elastified knitted garment was prepared using ACPH wherein feed 1 and 3 were 22 dtex spandex of Example 4, 5, or 6 supra knitted bare with flat PA6,6 22f7 and feed 2 and 4 were PA only. Garment was dyed in medium skin tone shade for testing by a hosiery consumer panel.
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Abstract
Spandex containing an ionic liquid which exhibits antistatic properties and enhanced colorability and dyeability with acid dyes is provided as well as methods for its production and use in articles of manufacture.
Description
ANTISTATIC SPANDEX AND GARMENTS THEREOF
FIELD OF THE INVENTION
[0001] This disclosure relates to spandex fiber comprising ionic liquids and fabrics and garments made from the spandex fiber. The spandex fiber exhibits antistatic properties and reduces garment cling.
BACKGROUND OF THE INVENTION
[0002] Antistatic agents are used to dissipate electrostatic or static charge. Electrostatic charge buildup is responsible for a variety of problems in the processing and the use of many industrial products and materials. Electrostatic charging can cause materials to stick together or to repel one another. In addition, static charge buildup can cause objects to attract dirt and dust that can lead to fabrication or soiling problems and can impair product performance. Sudden electrostatic discharges from insulating objects can also be a serious problem. When flammable materials are present, a static electric discharge can serve as an ignition source, resulting in fires and/or explosions.
[0003] Electrostatic charge is a particular problem in the electronics industry, because modern electronic devices are extremely susceptible to permanent damage by electrostatic discharges. The buildup of electrostatic charge on insulating objects is especially common and problematic under conditions of low humidity and when liquids or solids move in contact with one another (tribocharging).
[0004] Static charge build-up can be controlled by increasing the electrical conductivity of a material. This can be accomplished by increasing ionic or electronic conductivity. The most common means of controlling static accumulation today is by increasing electrical conductivity through moisture adsorption. This is commonly achieved by adding moisture to the surrounding air (humidification) or by the use of hygroscopic antistatic agents, which are generally referred to as humectants because they rely on the adsorption of atmospheric moisture for their effectiveness. Most antistatic agents operate by dissipating static charge as it builds up; thus, static decay rate and surface conductivity are common measures of the effectiveness of antistatic agents. Antistatic agents can be applied to the surface (external antistatic agent) or incorporated into the bulk (internal antistatic agent) of the otherwise insulating material. Internal antistatic agents are commonly employed in polymers such as plastics.
[0005] Generally, internal antistatic agents fall into one of the following classes: (I) ones that are mixed directly into a molten polymer during melt processing; (2) ones that are mixed into a polymer solution, coated, and dried, or (3) ones that dissolve into a monomer (with or without a solvent) that is subsequently polymerized.
[0006] Yams prepared from elastic polyurethane (PU) fibers comprising long chain synthetic polymers, a large portion of which are synthesized from PUs based on polyethers, polyesters and and/or polycarbonates are used in the production of sheet goods and woven textiles or substances which are suitable for garments, hosiery and sports clothing such as, but in no way limited to swimwear and bathing trunks. Knitting and weaving are forms of processing PU fibers.
[0007] One problem that can occur during processing of knitted and woven fabrics is the electrostatic charging of the fiber materials. In some cases, this can result in sparks flying due to intense electric charge phenomena. Thus, electrostatic charging can cause unwanted reduction in processing speed and costly installation of spray bars in the processing machines to dissipate.
[0008] There is a need for other means to render elastic PU fibers antistatic.
[0009] U.S. Patent 6,329,452 discloses adding dialkyl sulphosuccinate to elastic PU compositions and or by depositing this substance in a suitable form as an external preparation on elastic fibers for antistatic effect.
[00010] U.S. Patent 6,849,676 discloses application of salts of sulfonates having Cs-3o hydrocarbon chain, sulfates having Cs-3o hydrocarbon chain and phosphates having Cs-3o hydrocarbon chain as antistatic agents in production of antistatic PU elastic fiber.
[00011] U.S. Patent 8,715,799 discloses antistatic, thermoplastic PU comprising ethylmethylimidazole ethyl sulfate for shoe sector applications, elastomer rollers, manufacturing of electronically sensitive components and in pneumatic conveying of solids. [00012] U.S. Patent 8,993,660 discloses use of an antistatic composition comprising a polar thermoplastic polymer and an ionic liquid as an antistatic additive for non-polar thermo-plastic or elastomeric polymers.
[00013] U.S. Patent 9,012,590 discloses electrostatic dissipative thermoplastic PU compositions made by reacting at least one polyester polyol intermediate with at least one diisocyanate and at least one chain extender.
[00014] Published U.S. Patent Application No. 2015/0057388 discloses an antistatic PU with an ionic liquid as the antistatic additive.
[00015] Published U.S. Patent Application No. 2017/0355805 discloses an ionic diol represented by formula
wherein R1 represents an alkyl group having from 6 to 18 carbon atoms; R2 and R3 independently represent alkyl groups having from 1 to 4 carbon atoms; R4 represents an alkylene group having from 2 to 8 carbon atoms; and R5 represents an alkylene group having from 1 to 8 carbon atoms in production of antistatic PUs.
[00016] However, use of small organic molecules like ionic liquids (see e.g. U.S. Patent 8,715,799, U.S. Patent 8,993,660, and published U.S. Patent Application No.
2015/0057388), ionic diol (see e.g. Published U.S. Patent Application No, 2017/0355805A1), dialkyl sulphosuccinate (see e.g. U.S. Patent 6,329,452B1), sulfonates/sulfate/phosphate of C8-30 chain (see e.g. U.S. Patent 6,849,676B1), and tri-n-butylmethylammonium bis- (trifluoromethanesulfonyl)imide (see e.g. U.S. Patent 9,012,590) as antistatic additives is based primarily on cation/anion small organic compounds which are water soluble and have poor interaction with PUs. Thus, these antistatic additives are gradually wiped off from surfaces by moisture and/or water after long term usage. Further, the small organic molecules are generally used as additives to a polyurethane matrix which is molded into parts such as shoes, belts, and rollers. In general, molded articles are not exposed to textile scouring and dyeing processes which can extract the small molecule additives. Therefore, durability of antistatic fiber is not a main concern in these applications.
[00017] U.S. Patent 6,403,682 discloses spandex having improved heat-set efficiency, obtained by incorporating certain quaternary amine additives into the spinning solution. No anti-static properties of the quaternary amine additives are di closed.
[00018] There is a need for functional antistatic additives for spandex fibers which resist removal by aqueous high-temperature scouring, dyeing, and finishing steps.
SUMMARY OF THE INVENTION
[00019] An aspect of the present invention relates to an antistatic spandex comprising spandex and an ionic liquid.
[00020] In one nonlimiting embodiment, the ionic liquid of the antistatic spandex comprises an imidazolinium alkyl sulfate having formula I
wherein R1 represents alkyl or alkenyl groups with 6 to 22 carbons,
R2 represents -CHs or -CH2CH3 groups,
R3 represents -CH2CH2OH or -CH2CH2NH2 groups, and
R4 represents -CH3 or -CH2CH3 groups.
[00021] In one nonlimiting embodiment, the ionic liquid of the antistatic spandex comprises IH-Imidazolium, l-ethyl-2-(2-heptadecen-l-yl)-4,5-dihydro-3-(2-hydroxyethyl)-, ethyl sulfate (1 : 1).
[00022] In one nonlimiting embodiment, the ionic liquid of the antistatic spandex comprises a fatty acids reaction product with 2-((2-aminoethyl)amino)ethanol, or diethylenetriamine, dimethyl or diethyl sulfate quaternized.
[00023] In one nonlimiting embodiment, the ionic liquid of the antistatic spandex comprises a fatty acids, tail-oil, reaction product with 2-((2-aminoethyl)amino)ethanol, di-Et sulfate-quatemized.
[00024] In addition to its antistatic characteristics, spandex comprising the ionic liquid in accordance with this disclosure may exhibit enhanced coloration as compared to spandex without the ionic liquid and/or reduced cling as compared to spandex without the ionic liquid. [00025] Another aspect of the present invention relates to an article of manufacture, at least a portion of which comprises this antistatic spandex. Nonlimiting examples of such articles include fabric or garments.
[00026] Another aspect of the present invention relates to a spandex additive comprising an imidazolinium alkyl sulfate having formula I
[00027] wherein R1 represents alkyl or alkenyl groups with 6 to 22 carbons,
R2 represents -CHs or -CH2CH3 groups,
R3 represents -CH2CH2OH or -CH2CH2NH2 groups, and
R4 represents -CH3 or -CH2CH3 groups;
IH-Imidazolium, l-ethyl-2-(2-heptadecen-l-yl)-4,5-dihydro-3-(2 -hydroxyethyl)-, ethyl sulfate (1 : 1); or a fatty acids reaction product with 2-((2-aminoethyl)amino)ethanol, or diethylenetriamine, dimethyl or diethyl sulfate quaternized; or a fatty acids, tail-oil, reaction product with 2-((2-aminoethyl)amino)ethanol, di-Et sulfate-quatemized. Addition of this additive to spandex increases dyeability of the spandex with acid dyes.
[00028] Yet another aspect of the present invention relates to a method for producing antistatic spandex. The method comprises adding to spandex an ionic liquid.
[00029] In one nonlimiting embodiment, the ionic liquid comprises an imidazolinium alkyl sulfate having formula I
formula II
[00030] wherein R1 represents alkyl or alkenyl groups with 6 to 22 carbons,
R2 represents -CPF, or -CH2CH3 groups,
R3 represents -CH2CH2OH or -CH2CH2NH2 groups, and
R4 represents -CH3 or -CH2CH3 groups.
[00031] In one nonlimiting embodiment, the ionic liquid of the antistatic spandex comprises IH-Imidazolium, l-ethyl-2-(2-heptadecen-l-yl)-4,5-dihydro-3-(2-hydroxyethyl)-, ethyl sulfate (1 : 1).
[00032] In another nonlimiting embodiment, the ionic liquid comprises a fatty acids reaction product with 2-((2-aminoethyl)amino)ethanol, or di ethylenetri amine, dimethyl or diethyl sulfate quatemized.
[00033] In another nonlimiting embodiment, the ionic liquid comprises a fatty acids, tail-oil, reaction product with 2-((2-aminoethyl)amino)ethanol, di-Et sulfate-quaternized.
[00034] Spandex produced in accordance with this method may also exhibit enhanced coloration as compared to spandex without the ionic liquid and/or reduced cling as compared to spandex without the ionic liquid.
BRIEF DESCRIPTION OF THE FIGURES
[00035] FIGs. 1 A through ID show two traditional choices for incorporating spandex into garments such as hosiery including every course style (ECPH) as depicted in FIG. 1 A and 1C and alternate course style (ACPH) as depicted in FIG. IB and ID.
DETAILED DESCRIPTION OF THE INVENTION
[00036] The present invention relates to antistatic spandex as well as spandex additives, methods of production of the antistatic spandex and articles of manufacture, at least a portion of which comprise the antistatic spandex.
[00037] The antistatic spandex of the present invention comprises segmented polyether-based polyurethaneurea, also routinely referred to as spandex.
[00038] The antistatic spandex of the present invention further comprises an ionic liquid added to the spandex.
[00039] In one nonlimiting embodiment, the ionic liquid comprises an imidazolinium alkyl sulfate having formula I
[00040] wherein R1 represents alkyl or alkenyl groups with 6 to 22 carbons,
R2 represents -CH or -CH2CH3 groups,
R3 represents -CH2CH2OH or -CH2CH2NH2 groups, and
R4 represents -CH3 or -CH2CH3 groups.
[00041] In one nonlimiting embodiment, the ionic liquid of the antistatic spandex comprises IH-Imidazolium, l-ethyl-2-(2-heptadecen-l-yl)-4,5-dihydro-3-(2-hydroxyethyl)-, ethyl sulfate (1 : 1).
[00042] In one nonlimiting embodiment, the ionic liquid comprises a fatty acids reaction product with 2-((2-aminoethyl)amino)ethanol, or di ethylenetri amine, dimethyl or diethyl sulfate quatemized.
[00043] In one nonlimiting embodiment, the ionic liquid comprises a fatty acids, tailoil, reaction product with 2-((2-aminoethyl)amino)ethanol, di-Et sulfate-quatemized, also referred to herein as INC.
[00044] In one nonlimiting embodiment, the ionic liquid is added at 0.3-10% by weight of the spandex. In one nonlimiting embodiment, the ionic liquid is added at 0.3-3% by weight of the spandex.
[00045] By the phrase “weight of spandex”, it is meant the final weight of spandex including all additives.
[00046] Nonlimiting examples of ionic liquids useful in the antistatic spandex of the present invention include a mixture of amide and imidazoline, quaternized by di-Et sulfate, also referred to as INC 2470 (hereinafter referred to as INC), COLA® SOLV IES: Isostearyl
Ethylimidazolinium Ethosulfate, CAS # 67633-57-2 and COLA® SOLV OES: Oleyl Ethylimidazolinium Ethosulfate (hereinafter referred to as OES), CAS # 68039-12-3 available from Colonial Chemical Company.
[00047] Also provided by the present invention are methods for producing antistatic spandex by adding one or more of these ionic liquids to the spandex. Ionic liquids can be simply mixed into the spandex solution at room temperature. In some nonlimiting embodiment, the ionic liquid is blended with other typical spandex additive such as, but not limited to, antioxidants, antacids, delusterants or/or lubricants. In one nonlimiting embodiment, the ionic liquid is added at 0.3-3% by weight of the spandex.
[00048] Without being bound to any particular theory, it is believed that the imidazolinium moiety in this ionic liquid additive contributes to good antistatic property with the long aliphatic chain helping it migrate to the fiber surface, thus providing for good durability during aqueous textile process. Further, the antistatic property of spandex fiber of the present invention containing an ionic liquid such as INC eliminates the building up of static charges during the fabric/garment process.
[00049] The antistatic spandex produced in accordance with the present invention exhibits excellent antistatic property, durability and commercial adaptability. Additional benefits, as demonstrated herein include enhanced coloration as compared to spandex without the ionic liquid and reduced cling as compared to spandex without the ionic liquid.
[00050] Also provided by the present invention is a spandex additive comprising an imidazolinium alkyl sulfate having formula I
[00051] wherein R1 represents alkyl or alkenyl groups with 6 to 22 carbons,
R2 represents -CHa or -CH2CH3 groups,
R3 represents -CH2CH2OH or -CH2CH2NH2 groups, and
R4 represents -CH3 or -CH2CH3 groups;
IH-Imidazolium, 1 -ethyl -2-(2-heptadecen-l-yl)-4, 5 -dihydro-3 -(2-hydroxy ethyl)-, ethyl sulfate (1 : 1); or a fatty acids reaction product with 2-((2-aminoethyl)amino)ethanol, or diethylenetriamine, dimethyl or diethyl sulfate quaternized; or a fatty acids, tail-oil, reaction product with 2-((2-aminoethyl)amino)ethanol, di-Et sulfate-quatemized.
[00052] The inventors herein have found that addition of said spandex additive to spandex increases dyeability of spandex with acid dyes.
[00053] Antistatic spandex of the present invention can be used in any application or article of manufacture in which spandex is routinely used.
[00054] In one nonlimiting embodiment, the antistatic spandex is used in a fabric.
Fabrics comprising the antistatic spandex may have a spandex content of about 0.5 weight percent (wt. %) to about 40 wt. %, based on weight of the fabric. For example, circular knits comprising spandex may contain from about 2 wt. % to about 25 wt. % spandex, legwear comprising spandex may contain from about 1 wt. % to about 40 wt. % spandex.
[00055] The spandex or the fabric comprising it may be dyed and printed by customary dyeing and printing procedures, such as from an aqueous dye liquor by the exhaust method at temperatures between 60° C. and 100° C. Conventional methods may be followed when using an acid dye. For example, in an exhaust dyeing method, the fabric can be introduced into an aqueous dye bath kept in agitation having a pH of between 3.5 and 6 which is then heated steadily from a temperature of approximately 20° C. to a temperature about 98° C. for 40 minutes. The dye bath and fabric are then held at temperature for another 40 minutes before cooling. Unfixed dye is then rinsed from the fabric.
[00056] Additional examples of articles of manufacture, at least a portion of which comprise the antistatic spandex include, but are in no way limited to, sheet goods and knitted and woven textiles or substances which are suitable for garments, hosiery and sports clothing such as, but in no way limited to swimwear and bathing trunks. The antistatic spandex is particularly useful in knitting and weaving processes where electrostatic charge can be problematic.
[00057] The antistatic spandex of the present invention is particularly useful in hosiery. Two traditional choices for incorporating spandex of the present invention into garments such as hosiery include every course style (ECPH) as depicted in FIG. 1 A and 1C and alternate
course style (ACPH) as depicted in FIG. IB and ID. The spandex fiber may be covered with, for example, polyamide, or may be bare, and is knitted in every course as depicted in FIG. 1 A and 1C or alternate courses as depicted in FIG. IB and ID. Garments such as every course panty hose (ECPH) comprise balanced stitches and normally provide for a higher quality garment.
[00058] Articles of manufacture in accordance with the present invention may be comprised of at least a portion of the knit structures described herein. Nonlimiting examples of these articles include clothing such as, but not limited to, pantyhose, stockings, knee highs, ankle highs, stay ups, leggings and socks. All standard garment processing steps are understood to be applicable to the fabric of this invention, (e.g. scour, dyeing, heat setting or boarding, application of softeners).
[00059] All patents, patent applications, test procedures, priority documents, articles, publications, manuals, and other documents cited herein are fully incorporated by reference to the extent such disclosure is not inconsistent with this invention and for all jurisdictions in which such incorporation is permitted.
[00060] The following Examples demonstrate the present invention and its capability for use. The invention is capable of other and different embodiments, and its several details are capable of modifications and/or substitution in various apparent respects, without departing from the spirit and scope of the present invention. Accordingly, the Examples are to be regarded as illustrative in nature and non-limiting.
EXAMPLES
Preparation of Spandex
[00061] A solution of segmented polyether-based polyurethaneurea elastomer was prepared by thoroughly mixing diphenylmethane diisocyanate (“MDI”) polytetramethylene glycol having a molecular weight of about 1800 in a molar (“capping”) ratio of 1.63. The mixture was maintained at a temperature of about 80-90° C. for about 90-100 minutes. The resulting “capped glycol”, comprising a mixture of isocyanate-terminated polyether glycol and unreacted diisocyanate, was cooled to 50° C. and mixed with DMAc to provide a solution containing about 45% solids. Then, with vigorous mixing, the capped glycol was reacted for 2-3 minutes at a temperature of about 75° C. with a DMAc solution containing a mixture of di ethylamine chain-terminator and 90/10 blend of ethylene diamine/2-methyl-l,5- diaminopentane chain-extender. The resulting polymer solution contained approximately 35% solids and had a viscosity of about 3,200 poises at 40° C.
Surface resistivities of spandex film
[00062] The resistivities of the spandex/additives were measured on the following nonlimiting examples of spandex film by ASTM D-257. Results are depicted in Table 1.
Example 1
[00063] A film was casted from the spandex solution with drying in N2 chamber for 24 hours.
Example 2
[00064] The INC additive and spandex polymer was mixed in DMAC at room temperature with 1.0 wt% antistatic additive. A film was casted from the solution with drying in N2 chamber for 24 hours.
Example 3
[00065] The INC additive and spandex polymer was mixed in DMAC at room temperature with 2.0 wt% antistatic additive. A film was casted from the solution with drying in N2 chamber for 24 hours.
Table 1: Surface resistivity of spandex films at 56% RH
Surface resistivities of spandex yarn
[00066] The resistivities of the spandex/additives were measured on the following nonlimiting examples of spandex yarn. Results are depicted in Table 2.
[00067] For spinning, the following ingredients were thoroughly mixed and added to the polymer solution to provide the listed amounts of additive (expressed as weight percent based on the final weight of spandex):
(a) 1.2% of Irganox 245, a hindered phenolic antioxidant;
(b) 1.5% of natural blend of huntite and hydromagnesite;
(c) 0.4% of a silicone oil;
(d) 0.17% titanium dioxide as delusterant; and
(e) and where applicable, the amount of fatty acids, tail-oil, reaction products with 2- ((2-aminoethyl)amino)ethanol, di-Et sulfate-quaternized (INC), or IH-Imidazolium, 1 -ethyl - 2-(2-heptadecen-l-yl)-4, 5 -dihydro-3 -(2-hydroxy ethyl)-, ethyl sulfate (1 : 1) (OES).
[00068] The spinning solutions were then conventionally dry-spun to form 22 decitex yarn without finish oil treatments. A thin layer of yam was peeled off the tube and the surface resistivity was measured by ASTM D-257.
Example 4
[00069] Spandex polymer solution was spun to form 22 dtex yam without INC or OES additive.
Example 5
[00070] The INC additive, spandex polymer, and other additives were mixed in DMAC at room temperature with 1.0 wt% antistatic additive. The polymer solution was spun to form 22 dtex yam with 1.0 wt% antistatic additive.
Example 6
[00071] The INC additive, spandex polymer, and other additives were mixed in DMAC at room temperature with 2.2 wt% antistatic additive. The polymer solution was spun to form 22 dtex yam with 2.2 wt% antistatic additive.
[00072] The spandex yams of Examples 4 through 7 were treated by scouring, dyeing and finishing aqueous textile process.
Scouring Process
[00073] In the scouring process, 8.0 grams of spandex yarn was pulled and placed into laundry bag. In a 1000 mL beaker, the yam was then added into -1000 mL solution of scouring agent Domoscour LFE-810 (Archroma U.S., Inc.) (0.5 g/L) and soda ash (0.5 g/L) with magnetic stirring. The temperature was raised to 80°C @3°C/min (~20min raised to 80°C) and held for 30 minutes. The yam was then rinsed with deionized DI water until clear.
Dyeing Process
[00074] In 1000 mL beaker, a 5% acetic acid stock solution was used to adjust pH to 4.5-5.0. 0.5g Dorolan Black (commercial from M. Dohmen GmbH) was then added to the solution and stirred until dissolved. Spandex yam in a laundry bag was then into the dye solution. The temperature was raise to 98 °C (close to boiling) at a rate of 2°C/min (increase to 98°C in about 35 min) and held at 98 °C for 30 min. The solution with spandex was then cooled to 70 °C and the dye solution was drained.
Finishing Process
[00075] Deionized water was added to a beaker and adjusted to a pH to 4.5-5.0 at room temp. 0.5g Domofix FN6(M. Dohmen USA, Inc.) fixing agent was added to the solution. The temperature was then raised to 75 °C with rate 2°C/min and held at 75 °C for 20 min
followed by cooling to 50°C and draining of the solution. The spandex was then rinsed with deionized water until clear and air-dried.
Example 7
[00076] The spandex yam in example 4 was treated by scouring, dyeing and finishing process.
Example 8
[00077] The spandex yam in example 5 was treated by scouring, dyeing and finishing process.
Example 9
[00078] The spandex yam in example 6 was treated by scouring, dyeing and finishing process.
Table 2: Surface resistivity of spandex yarns at 33% RH
[00079] Example 5 and 6 with antistatic additives exhibited lower surface resistivity (better antistatic properties) than Example 4 without antistatic additives. Example 8 and 9 with antistatic additives exhibited lower surface resistivity (better antistatic properties) than Example 7 without antistatic additives after black dyed. Examples 5 and 6 without a dye exhibited better anti-static properties as compared to Examples 8 and 9 which were dyed black.
Example 10
[00080] The INC additive, spandex polymer, and other additives were mixed in DMAC at room temperature with 1.5 wt% antistatic additive. The polymer solution was spun to form 22 dtex yam with 1.5 wt% antistatic additive.
Example 11
[00081] The OES additive, spandex polymer, and other additives were mixed in DMAC at room temperature with 1.5 wt% antistatic additive. The polymer solution was spun to form 22 dtex yam with 1.5 wt% antistatic additive.
Example 12
[00082] The spandex yam in example 10 was treated by scouring, dyeing and finishing process.
Example 13
[00083] The spandex yam in example 11 was treated by scouring, dyeing and finishing process.
Table 3: Surface resistivity of spandex yarns at 33% RH
Enhanced coloration of spandex fiber
[00084] Spandex (235 dtex), with and without the INC additive as disclosed in Examples 4 and 5 supra, herein referred to Examples 10 and 11 respectively, were knit in a tubular format with an alternating 100% polyamide section (to evaluate the color of polyamide only) with 100% spandex section (to evaluate the dye pick up of spandex only) and a spandex and polyimide knit together section representative of a commercial hosiery waist band. Polyamide was 44 dtex. This format was selected to evaluate the dye pick up from polyamide and spandex separately (first and second sections respectively) and together in a more commercial construction (third section). The final composition of the tube was approximately 80% polyamide and 20% spandex. The tube was then scoured at 80° C. with Ig/L of soda ash and detergent. The fabric was rinsed and then dyed through an exhaust dyeing method in a solution with 1.5g/L of acid donor and 3% black metal complex dye (CI 194) for 40 min. After dyeing, the fabric samples were fixed with 4% Sunlife TNF under acidic conditions. After drying, the fabric samples were analyzed by colorimeter for dye uptake under the competitive dye situation. Dyeability performance was determined from color shade lightness
“L*” values with a colorimeter spectral analyzer. Results are reported in CIELAB units under D65 illuminant. Color depth, “L*” values, on the dyed spandex sections were compared to polyamide sections from the same dyebath and listed in Table 4.
Table 4: Lab color results for finished fabrics
[00085] Example 10 with no antistatic additive showed limited shade depth compared to polyamide “L*” value while Example 11 with 1% INC additive provides a low “L*” value (18.4) like polyamide. “AE*” value calculated with CIE74 formula is a metric to measure the color difference. The lower “AE*” value the higher is the color match between two substrates. Example 10 with no antistatic additive shows poor color match between spandex and polyamide with “AE*” of 22.2 while Example 11 with 1% INC additive provides a better color match with lower “AE*” value of 5.1. The better color match between the two fibers contributes to providing better invisibility of the spandex in the knit structure, a desirable property of spandex containing fabrics.
Consumer testing and garment cling
[00086] Fabrics were knit using a Lonati 400 needles, 4 inches diameter hosiery knitting machine to make the constructions using the standard four feed system. An elastified knitted garment was prepared by typical ECPH wherein all 4 feeds were 22 dtex monofil spandex of either Example 4, 5, or 6 supra knitted bare with flat PA6,6 33f20. Each fabric sample was knit at 450 rpm. The fabrics indicated as every course single jersey included a plain stitch. The fabrics were sewed into garments in the form of traditional pantyhose.
[00087] Each pantyhose was then dyed using standard industry protocols for nylon hosiery using acid dyes in black and beige/tan colors. The hosiery was boarded using a commercial Cortese boarding machine which accepts hosiery legs in clam-shell compression compartment and applies steam pressure for a selected dwell period. The black garments were further washed 5X in a normal residential laundering process to test efficacy after normal use. Garments were tested with synthetic light outerwear (polyester and acetate) and
insulating footwear (rubber soles). Wearer noted the presence and degree of static cling between the knitted hosiery and synthetic outerwear (skirt or dress).
[00088] Similarly, an elastified knitted garment was prepared using ACPH wherein feed 1 and 3 were 22 dtex spandex of Example 4, 5, or 6 supra knitted bare with flat PA6,6 22f7 and feed 2 and 4 were PA only. Garment was dyed in medium skin tone shade for testing by a hosiery consumer panel.
[00089] Results of cling testing for these elastified knitted hosiery are depicted in Table 5.
Table 5: Garment wear tests for static control
Ranking
Noticeable and uncomfortable cling
* Minor cling with motion
+ No cling with motion
Claims
1. Antistatic spandex comprising spandex and an ionic liquid.
2. The antistatic spandex of claim 1 wherein the ionic liquid comprises an imidazolinium alkyl sulfate having formula I
wherein R1 represents alkyl or alkenyl groups with 6 to 22 carbons,
R2 represents -CEE or -CH2CH3 groups,
R3 represents -CH2CH2OH or -CH2CH2NH2 groups, and
R4 represents -CH3 or -CH2CH3 groups.
3. The antistatic spandex of claim 1 wherein the ionic liquid comprises 1H- Imidazolium, l-ethyl-2-(2-heptadecen-l-yl)-4,5-dihydro-3-(2-hydroxyethyl)-, ethyl sulfate
(1 :1).
4. The antistatic spandex of claim 1 wherein the ionic liquid comprises a fatty acids reaction product with 2-((2-aminoethyl)amino)ethanol, or diethylenetriamine, dimethyl or diethyl sulfate quaternized.
5. The antistatic spandex of claim 1 wherein the ionic liquid comprises a fatty acids, tail-oil, reaction product with 2-((2-aminoethyl)amino)ethanol, di-Et sulfate- quaternized.
6. The antistatic spandex of any of claims 1 through 5 wherein the ionic liquid is added at 0.3-10% by weight.
7. The antistatic spandex of any of claims 1 through 6 which exhibits enhanced coloration as compared to spandex without the ionic liquid.
8. The antistatic spandex of any of claims 1 through 7 which exhibits reduced cling as compared to spandex without the ionic liquid.
9. An article of manufacture, at least a portion of which comprises the antistatic spandex of any of claims 1 through 8.
10. The article of manufacture of claim 9 which is a fabric or garment.
11. A spandex additive comprising an imidazolinium alkyl sulfate having formula I
wherein R1 represents alkyl or alkenyl groups with 6 to 22 carbons,
R2 represents -CHs or -CH2CH3 groups,
R3 represents -CH2CH2OH or -CH2CH2NH2 groups, and
R4 represents -CH3 or -CH2CH3 groups;
IH-Imidazolium, l-ethyl-2-(2-heptadecen-l-yl)-4,5-dihydro-3-(2 -hydroxyethyl)-, ethyl sulfate (1 : 1); a fatty acids reaction product with 2-((2-aminoethyl)amino)ethanol, or diethylenetriamine, dimethyl or diethyl sulfate quaternized; or a fatty acids, tail-oil, reaction product with 2-((2-aminoethyl)amino)ethanol, di-Et sulfate-quatemized,
wherein addition of said spandex additive to spandex increases dyeability of spandex with acid dyes.
12. A method for producing antistatic spandex, said method comprising adding to spandex an ionic liquid.
13. The method of claim 12 wherein the ionic liquid comprises an imidazolinium alkyl sulfate having formula I
wherein R1 represents alkyl or alkenyl groups with 6 to 22 carbons,
R2 represents -CEE or -CH2CH3 groups,
R3 represents -CH2CH2OH or -CH2CH2NH2 groups, and
R4 represents -CH3 or -CH2CH3 groups.
14. The method of claim 12 wherein the ionic liquid comprises IH-Imidazolium, 1 -ethyl -2-(2-heptadecen-l-yl)-4,5-dihydro-3-(2-hydroxyethyl)-, ethyl sulfate (1 : 1).
15. The method of claim 12 wherein the ionic liquid comprises a fatty acids reaction product with 2-((2-aminoethyl)amino)ethanol, or di ethylenetri amine, dimethyl or diethyl sulfate quatemized.
16. The method of claim 12 wherein the ionic liquid comprises a fatty acids, tailoil, reaction product with 2-((2-aminoethyl)amino)ethanol, di-Et sulfate-quatemized.
17. The method of any of claims 12 through 16 wherein the ionic liquid is added at 0.3-10% by weight of the spandex.
18. The method of any of claims 12 through 17 wherein the produced spandex exhibits enhanced coloration as compared to spandex without the ionic liquid.
19. The method of any of claims 12 through 17 wherein the produced spandex exhibits reduced cling as compared to spandex without the ionic liquid.
20
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| US202063112371P | 2020-11-11 | 2020-11-11 | |
| US202163246028P | 2021-09-20 | 2021-09-20 | |
| PCT/US2021/058535 WO2022103715A1 (en) | 2020-11-11 | 2021-11-09 | Antistatic spandex and garments thereof |
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| EP (1) | EP4244414A1 (en) |
| KR (1) | KR20230113761A (en) |
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| JP3902405B2 (en) | 1998-01-09 | 2007-04-04 | 松本油脂製薬株式会社 | Antistatic polyurethane elastic fiber and raw material for its production |
| DE19805130A1 (en) | 1998-02-09 | 1999-08-12 | Bayer Ag | Antistatic polyurethane and elastane fibers |
| US6403682B1 (en) | 2001-06-28 | 2002-06-11 | E. I. Du Pont De Nemours And Company | Spandex containing quaternary amine additives |
| WO2007090755A1 (en) | 2006-02-07 | 2007-08-16 | Basf Aktiengesellschaft | Antistatic polyurethane |
| ATE506386T1 (en) | 2007-07-17 | 2011-05-15 | Basf Se | THERMOPLASTIC POLYURETHANE WITH ANTISTATIC PROPERTIES |
| KR101762327B1 (en) | 2009-10-15 | 2017-07-27 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | Electrostatic dissipative tpu and compositions thereof |
| EP2509459A1 (en) | 2009-12-10 | 2012-10-17 | Basf Se | Antistatic thermoplastic compositions |
| US10982381B2 (en) * | 2014-10-06 | 2021-04-20 | Natural Fiber Welding, Inc. | Methods, processes, and apparatuses for producing welded substrates |
| WO2016099995A1 (en) | 2014-12-16 | 2016-06-23 | 3M Innovative Properties Company | Ionic diol, antistatic polyurethane, and method of making the same |
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