EP2686476A2 - Processes to make water and oil repellent bcf yarn - Google Patents
Processes to make water and oil repellent bcf yarnInfo
- Publication number
- EP2686476A2 EP2686476A2 EP12757287.3A EP12757287A EP2686476A2 EP 2686476 A2 EP2686476 A2 EP 2686476A2 EP 12757287 A EP12757287 A EP 12757287A EP 2686476 A2 EP2686476 A2 EP 2686476A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- yarn
- bcf yarn
- soil
- nylon
- fluorochemical
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 95
- 230000008569 process Effects 0.000 title claims abstract description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 24
- 230000002940 repellent Effects 0.000 title description 2
- 239000005871 repellent Substances 0.000 title description 2
- 239000002689 soil Substances 0.000 claims abstract description 103
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 238000009732 tufting Methods 0.000 claims abstract description 9
- 238000009941 weaving Methods 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 38
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000004952 Polyamide Substances 0.000 claims description 13
- 229920002647 polyamide Polymers 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 11
- -1 softeners Substances 0.000 claims description 11
- 238000004804 winding Methods 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 10
- 239000004677 Nylon Substances 0.000 claims description 9
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 9
- 229920001778 nylon Polymers 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 238000009998 heat setting Methods 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000299 Nylon 12 Polymers 0.000 claims description 4
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 4
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 3
- 150000001718 carbodiimides Chemical class 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 150000003673 urethanes Chemical class 0.000 claims description 3
- 239000012963 UV stabilizer Substances 0.000 claims description 2
- 239000003429 antifungal agent Substances 0.000 claims description 2
- 229940121375 antifungal agent Drugs 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 2
- 239000007844 bleaching agent Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 1
- 239000003352 sequestering agent Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 19
- 238000004043 dyeing Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 5
- 238000009940 knitting Methods 0.000 abstract description 2
- 239000000306 component Substances 0.000 description 29
- 239000004744 fabric Substances 0.000 description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 239000011737 fluorine Substances 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000699 topical effect Effects 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000000980 acid dye Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 241000506680 Haemulon melanurum Species 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- CEZCCHQBSQPRMU-UHFFFAOYSA-L chembl174821 Chemical compound [Na+].[Na+].COC1=CC(S([O-])(=O)=O)=C(C)C=C1N=NC1=C(O)C=CC2=CC(S([O-])(=O)=O)=CC=C12 CEZCCHQBSQPRMU-UHFFFAOYSA-L 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000012192 staining solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 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 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G27/00—Floor fabrics; Fastenings therefor
- A47G27/02—Carpets; Stair runners; Bedside rugs; Foot mats
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
- D06B3/04—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of yarns, threads or filaments
- D06B3/06—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of yarns, threads or filaments individually handled
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/34—Yarns or threads having slubs, knops, spirals, loops, tufts, or other irregular or decorative effects, i.e. effect yarns
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
- D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/01—Stain or soil resistance
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23907—Pile or nap type surface or component
- Y10T428/23957—Particular shape or structure of pile
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
- Y10T428/2925—Helical or coiled
Definitions
- the invention relates to anti-soil application processes for bulk continuous filament (BCF) carpet and related textile fabrics, and specifically, to processes for applying anti-soil compositions on BCF yarns during cable or air twisting processes prior to weaving, knitting or tufting.
- the process foregoes the need to treat carpets and other textiles made from the BCF yarn, thus eliminating costly and environmentally unfavorable dyeing and low pH chemical treatment processes.
- Also disclosed herein are systems used to apply the anti-soil formulations to the BCF yarn, and soil repellant yarns, and carpets with improved anti-soil properties made from the BCF yarn of the disclosed process.
- Topical application at the carpet mill can be in the form of exhaust application and spray application.
- Exhaust application i.e. flex-nip process at high (300 - 400 wt.%) wet pick-up
- Exhaust applications typically use higher amounts of water and energy to dry and cure the carpet than do spray applications.
- Spray-on fluorochemical products are designed to use less water and energy than exhaust applications, but they do not impart anti-soil properties that are as good as those provided by the exhaust applications owing to limited depth of penetration into the fabric, especially deep pile fabrics and those incorporating the tightly twisted yarns that are now becoming more popular.
- the carpet is also steamed and dyed first, steamed again, rinsed and extracted; and then a blend of SB and FC is applied together at high wet pick up, after which the carpet and chemicals are exposed once again to steam to fix the treatment, followed by drying.
- a blend of SB and FC is applied together at high wet pick up, after which the carpet and chemicals are exposed once again to steam to fix the treatment, followed by drying.
- low pH solutions, excess water, and energy are required for the SB and FC to penetrate the carpet and achieve uniform coverage.
- the typical prior art process is as follows: BCF yarn ⁇ Twist ⁇ heat set ⁇ tufting ⁇ carpet ⁇ dye ⁇ stain block / anti-soil.
- Carpets have also long been constructed of dyed or pigmented yarns, which constructions are treated in numerous possible ways, including the options of further dyeing, and the application of stain and/or soil resistant compositions with the concomitant use of steam and rinse water, as in the processes described above.
- the invention disclosed herein provides a process to make textile fabrics, especially tufted articles, without the requirement for subsequent stain and soil resistant chemistry application, thus avoiding the cost and waste of steam fixing and rinsing attendant with such large-scale fabric applications.
- the process involves application of topical chemistries to dyed or pigmented yarns immediately after twisting or cabling one or more such yarns together. The chemistries are then heat-set onto the twisted yarn under dry conditions, and the twisted yarn subsequently weaved or tufted into a finished fabric or carpet.
- Novel systems that enable the efficient application of topical chemistries to yarn subsequent to twisting and prior to winding and heat-setting are also disclosed.
- the disclosed process uses an atopical chemistry composition applicator positioned within a mechanical twisting process downstream of the twisted yarn take-up reel and upstream of the yarn winder.
- the disclosed process moves the backend, large scale and wasteful anti-soil application step, and if necessary, stain block application step, up front during yarn twisting.
- the carpet manufacturing process now becomes: BCF yarn ⁇ twist ⁇ FC (and optional SB) ⁇ heat set (optionally dry heat set) ⁇ tufting ⁇ carpet.
- the disclosed process is as effective, or even more effective, than processes of the prior art in terms of fabric soil resistance.
- the process of the disclosed invention is counter intuitive since treating the carpet yarn prior to heat setting and tufting is known to affect the quality of the finished carpet, particularly during dyeing. Further, the inventive process is also counter intuitive because soil resistant compositions tend to be very difficult to apply uniformly to twisted yarn bundles at the usual line speed without substantial waste. Moreover, the disclosed process is counter intuitive because the prior art yarn twisting apparatuses have not previously accepted topical chemistry applications to twisted yarn prior to winding. However, as shown below, Nylon carpets manufactured with the treated BCF yarn show superior anti-soil properties over the same carpets without such treatment.
- the anti-soil composition can be comprised of a high specific surface energy chemical or other material, for example a fluorochemical that imparts high specific surface energy properties such as high contact angles for water and oil, or even a non-fluorochemical particulate material having similar properties.
- the anti-soil composition can further comprise an anti-stain component.
- an untufted, twisted BCF yarn comprising an anti-soil component
- said anti-soil component is present on said twisted BCF yarn prior to tufting the BCF yarn.
- the anti-soil component is present at an on weight of fiber from about 100 ppm to about 1000 ppm.
- the yarn can comprise polyamide fiber and/or have polymer components selected from polyester and polypropylene.
- the yarn can be tufted and manufactured into carpet or fabrics.
- a process for manufacturing carpet comprising providing an untufted, twisted BCF yarn comprising an anti-soil component, tufting said BCF yarn, and weaving into said carpet. Because of the anti-soil component present on the BCF yarn prior to tufting and weaving, there is no need to treat the finished carpet with an anti-soil composition.
- a system for applying an anti-soil composition to twisted BCF fiber is disclosed.
- the system comprises: (a) a first yarn take-up device that receives at least two individual yarn members and transmits a single yarn member; (b) an anti-soil composition applicator disposed downstream of said yarn take-up device that applies said anti-soil composition to said single yarn member; and (c) a second yarn take-up device that receives said single yarn member.
- the anti-soil composition can be comprised of a high specific surface energy chemical or other material, for example a fluorochemical that imparts high specific surface energy properties such as high contact angles for water and oil, or even a non-fluorochemical particulate material having similar properties.
- the anti-soil composition can further comprise an anti-stain component.
- Figure 1 shows the current cable twisting process.
- Figure 2 shows one aspect of the disclosed process.
- QWF On weight of fiber
- WPU Weight pick-up
- a process for treating twisted BCF yarn comprising contacting the BCF yam with an anti-soil composition while said yarn is in motion and prior to contacting and winding the yarn onto a take-up reel or winder to create a yarn package or cake.
- the anti-soil composition comprises an anti-soil component and is adapted to be applied onto twisted BCF yarn at a wet pick-up of between about 5 wt.% and about 50 wt.%., including between about 10 wt.% and about 30 wt%, about 20 wt.% to about 30 wt.%, and about 10 wt.% to about 20 wt.%.
- the twisted BCF yam can be optionally heat set after contacting the yarn with the anti-soil composition.
- Heat setting temperatures can range from about 125°C to about 200°C, including from about 160°C to about 195°C.
- Heat setting dwell times can range from about 0.5 to about 4 minutes, including from about 0.5 to about 3 minute and from about 0.5 to about 1 minute.
- Anti-soil components for use in the disclosed anti-soil compositions impart high specific surface energy properties such as high contact angles for water and oil (e.g. water and oil "beads up” on surfaces treated by it).
- the anti-soil component can comprise a fluorochemical dispersion, which dispersion may be predominantly either cationic or anionic, including those selected from the group consisting of fluorochemical allophanates, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides, fluorochemical quanidines, and fluorochemicals incorporating C-2 to C-8 chemistries.
- the fluorochemical can have less than or equal to eight fluorinated carbons, including less than or equal to six fluorinated carbons.
- Example fluorochemical anti-soil components include: DuPont TLF 10816 and 10894; Daikin TG 251 1 , and DuPont Capstone RCP.
- Non-fluorinated anti-soil components can include: silicones, silsesquioxanes and fluorosilanated and fluoroalkylated particulates, anionic non-fluorinated surfactants and anionic hydrotrope non-fluorinated surfactants, including sulfonates, sulfates, phosphates and carboxylates. (See U.S. Patent No. 6,824,854, herein incorporated by reference).
- the anti-soil compositions can also have an optional stain blocker component comprising an acidic moiety which associates with polymer amine end groups and protects them from staining by acidic dye stains.
- the general category of chemicals suitable to the process of the instant invention can comprise any chemical that blocks positively charged dye sites.
- Stain blockers are available in various forms such as syntans, sulfonated novolacs, or sulfonated aromatic aldehyde condensation products (SACs), and/or reaction products of formaldehyde, phenol, polymethacrylic acid, maleic anyhydride, and sulfonic acid.
- the stain blocker is typically water soluble and generally penetrates the fiber while the anti-soil, usually a fluorochemical, is a non- water soluble dispersion that coats the surface of fiber.
- stain blockers include, but are not limited to: phenol formaldehyde polymers or copolymers such as CEASESTAIN and STAINAWAY (from American Emulsions Company, Inc., Dalton, Ga.), MESITOL (from Bayer Corporation, Rock Hill, N.C.), ERIONAL (from Ciba Corporation, Greensboro, N.C.), INTRATEX (from Crompton & Knowles Colors, Inc., Charlotte, N.C.), STAINKLEER (from Dyetech, Inc., Dalton, Ga.), LANOSTAIN (from Lenmar Chemical Corporation, Dalton, Ga.), and SR-300, SR-400, and SR-500 (from E. I.
- polymers of methacrylic acid such as the SCOTCHGARD FX series carpet protectors (from 3M Company, St. Paul Minn.); sulfonated fatty acids from Rockland React-Rite, Inc., Rockmart, Ga); and stain resist chemistries from ArrowStar LLC, Dalton and Tri-Tex, Canada.
- the anti-soil composition is adapted to contact the twisted BCF yarn while it is in motion and prior to contacting the take-up reel or winder. Further, the anti-soil composition can be at a neutral pH (e.g. 6 to 8) because the yarn can be optionally heat set after application of the composition. The process foregoes the need for harsh low pH chemicals.
- any suitable device that applies wet ingredients to a dry substrate can perform the contacting.
- Such devices include, but are not limited to: applicator pad, ceramic tip, ceramic ring, nip rollers, wet-wick, dip-tank, sprayer, and mister.
- the contacting can be done by one or more devices, where each device can be the same or different.
- two, three, or more application devices can be used to apply the anti-soil composition at different points in the process.
- one or more application devices can apply an anti-soil component and one or more separate devices an anti-stain component. Multiple application devices and locations can provide better application uniformity when using certain BCF yarns.
- the wet pick-up of anti-soil composition is between about 5 wt.% and about 50 wt.%., including between about 10 wt.% and about 30 wt%, about 20 wt.% to about 30 wt.%, and about 10 wt.% to about 20 wt.%.
- the resulting twisted BCF yarn if a fluorine based anti-soil component is used, can have an on weight of fiber from about 100 ppm to about 1000 ppm fluorine, including from about 100 to about 500 ppm fluorine, from about 200 to about 400 ppm, and from about 100 ppm to about 300 ppm fluorine.
- the anti-soil composition further comprises a stain blocker, it is present on weight of fiber from about 500 ppm to about 4%, including from about 1000 ppm to about 3%, from about 0.5% to about 2%, and from about 0.5% to about 1 %.
- Common stain blockers use sulfonated moieties as part of the chemistry, which results in the presence of sulfur on the treated fiber.
- the sulfur content can range from about 50 ppm with 5% stain blocker to about 1 ppm with 0.1% stain blocker on weight of fiber.
- the sulfur content on weight of fiber will range from about 0.5 ppm to about 40 ppm, including from about 1 ppm to about 30 ppm, from about 5 ppm to about 20 ppm, and from about 5 ppm to about 10 ppm.
- Sulfur content can be determined by x-ray diffraction or other methods.
- the anti-soil composition can further comprise a component selected from the group consisting of: odor control agents, anti-microbial agents, anti-fungal agents, fragrance agents, bleach resist agents, softeners, and UV stabilizers.
- the twisted BCF yarn can be made from polyamide fibers, such as those made from nylon 6,6, nylon 6, nylon 4,6, nylon 6,10, nylon 10,10, nylon 12, its copolymers, and blends thereof. Further, the twisted BCF yarn can also have additional polymer components, such as polyester and/or polyolefin components.
- the polyolefin component can be polypropylene.
- the additional polymer components can be incorporated with the polyamide (by melt-blend or co-polymerization) prior to making a polyamide fiber (e.g. a polyamide/polyester fiber), or can be stand-alone fibers that are twisted with the polyamide fibers to make the twisted BCF yarn.
- the BCF yarn can be manufactured with olefin, polyamide, and / or polyester polymer components.
- An unexpected benefit of the disclosed process has been discovered in that, whereas a small amount of anti-soil composition is applied compared to known exhaust processes, a high anti-soil component content, such as fluorine, is achieved on the surface of the yarn.
- the anti-soil composition applied in the process of the disclosed invention can be either fluorochemical or non-fluorochemical based, or a mixture of fluorochemical or fluoropolymer material with non-fluorinated soil resistant materials.
- the disclosed process may be applied to yarns that do not require subsequent dyeing, having either a pigment or pigment included in their composition prior to twisting.
- the pigmented yarns can be made by solution dyed as well as cationic and anionic dyed fibers.
- Yarns suitable for use in the process may further comprise inherent stain resistance, whether by base composition as in the case of polypropylene or polyester, or by the inclusion of strong acid functionality in the polymer composition of the yarn, as in the case of nylon.
- Use of dyed or pigmented yarns (i.e. colored yarns) with the disclosed process eliminates the need for subsequent dyeing and enables the creation of colored carpets that are soil resistant, without the need for subsequent dyeing and soil resistant chemical application.
- the twisted BCF yarn made with the various aspects of the disclosed process, by itself or blended with non-treated fibers and yarns, can be tufted and manufactured into carpets or fabrics.
- Carpets made with the twisted BCF yarn exhibit an oil repellency rating of 5 or higher and a water repellency rating of 5 or higher.
- the disclosed process can also be advantageously applied in certain processes where a styling advantage might be derived from differential dyeing and finishing after carpet formation.
- a soil resistant or stain resistant twisted yarn of the disclosed invention could optionally be tufted into a carpet among untreated yarns prior to dyeing, thus creating an aesthetic alternative.
- the system includes: (a) a first yarn take-up device that receives at least two individual yarn members and transmits a single yarn member; (b) an anti-soil composition applicator disposed downstream of the first yam take-up device that applies the anti-soil composition to the single yarn member; and (c) a second yarn take- up device that receives the single yarn member.
- the first yarn take-up device can be a take-up roll or reel that can twist the at least two individual yarn members into a single yarn member.
- the individual yarn members can be single filaments or fibers, or yarns made from a plurality of filaments or fibers.
- the applicator can be any suitable device that applies wet ingredients to a dry substrate, including, but not limited to: applicator pad, nip rollers, wet-wick, dip-tank, sprayer, and mister.
- the wet pick-up of composition is between about 5 wt.% and about 50 wt.%., including between about 10 wt.% and about 30 wt%, about 20 wt.% to about 30 wt.%, and about 10 wt.% to about 20 wt.%.
- the resulting twisted BCF yarn if a fluorine based anti-soil component is used, can have an on weight of fiber from about 100 ppm to about 1000 ppm fluorine, including from about 100 to about 500 ppm fluorine, from about 200 to about 400 ppm, and from about 100 ppm to about 300 ppm fluorine. If the anti-soil composition further comprises a stain blocker, it is present on weight of fiber from about 500 ppm to about 4%, including from about 1000 ppm to about 3%, from about 0.5% to about 2%, and from about 0.5% to about 1 %.
- the second yarn take-up device can be a winder.
- Figure 1 shows the current cable twisting process.
- creel yarn 10 and bucket yarn 15 which is fed at a spindle speed of 7000 rpm, pass through an anti- balloon device 20 and onto a take-up roll 25. From here, the twisted yarn 30 is wound up on a winder 35.
- Figure 2 shows one aspect of the disclosed process.
- creel yarn 1 10 and bucket yarn 115 which is fed at a spindle speed of 7000 rpm, pass through anti-balloon device 120 and onto a take-up roll 125.
- An anti-soil composition applicator 140 is disposed downstream of take-up roll 125, which applies an anti-soil component to the twisted yarn 30. From here, the twisted and treated yarn is wound up on a winder 135.
- nylon 6,6 carpets made from two 922 denier beige color solution dyed BCF fibers that have been treated various aspects of the process disclosed above and similar fibers with no treatment. Selection of alternative anti-soil components and stain blocker components, fibers and textiles having different surface chemistries will necessitate minor adjustments to the variables herein described.
- Acid dye stain resistance is evaluated using a procedure modified from the American Association of Textile Chemists and Colorists (AATCC) Method 175-2003, "Stain Resistance: Pile Floor Coverings.”
- 9 wt % of aqueous staining solution is prepared, according to the manufacturer's directions, by mixing cherry-flavored KOOL- AID ® powder (Kraft/General Foods, White Plains, N.Y., a powdered drink mix containing, inter alia, FD&C Red No. 40).
- a carpet sample (4x6-inch) is placed on a flat non-absorbent surface.
- a hollow plastic 2-inch (5.1cm) diameter cup is placed tightly over the carpet sample.
- KOOL-AID® staining solution Twenty ml of the KOOL-AID® staining solution is poured into the cup and the solution is allowed to absorb completely into the carpet sample. The cup is removed and the stained carpet sample is allowed to sit undisturbed for 24 hours. Following incubation, the stained sample is rinsed thoroughly under cold tap water, excess water is removed by centrifugation, and the sample is dried in air. The carpet sample was visually inspected and rated for staining according to the FD&C Red No. 40 Stain Scale described in AATCC Method 175-2003. Stain resistance is measured using a 1-10 scale. An undetectable test staining is accorded a value of 10.
- the repellency rating of the sample is the highest rating number liquid used to pass the repellency test. Carpets with a rating of 4 or higher have good anti-soiling properties. Without anti-soil treatment, most nylon carpets have a rating of 1 for both oil and water repellency.
- Two 922 denier beige color solution dyed Nylon 66 BCF made from cationic dyeable polymer were cable twisted on a Volkman at 7000 rpm to form a 6.0 tpi two ply yarn using the process described in figure 1.
- the winding speed was about 50 ypm.
- the cable twisted yarn was subsequently heat-set on a Suessen with 200°C dry air.
- the holdup time in the channel was about 60 seconds.
- the heat treated yarn was converted into a 35 oz per square yard, 1/12 gauge, 3/8" pile height cut pile carpet.
- Two 922 denier beige color solution dyed Nylon 66 BCF made from cationic dyeable polymer were cable twisted on a Volkman at 7000 rpm to form a 6.0 tpi two ply yarn using the process described in figure 2.
- the winding speed was about 50 ypm.
- a chemical applicator was inserted between the take up roll and winder as described in figure 3 option A.
- a 1 ⁇ 2 inch wide cotton wick (Wet Wick by Perperell MA) was used to apply 50% A-201 anti-soil chemical onto the cable twisted yarn at a wet-pickup of about 20 wt%.
- the cable twisted yarn went through the wet wick at about 50 ypm.
- the cable twisted yarn was subsequently heat-set on a Suessen with 200°C dry air.
- the holdup time in the channel was about 60 seconds.
- the heatset yarn was analyzed to have 925 ppm Fluorine.
- the heat treated yarn was converted into a 35 oz per square yard, 1/12 gauge, 3/8" pile height cut pile carpet.
- Two 922 denier beige color solution dyed Nylon 66 BCF made from cationic dyeable polymer were cable twisted on a Volkman at 7000 rpm to form a 6.0 tpi two ply yarn using the process described in figure 2.
- the winding speed was about 50 ypm.
- a chemical applicator was inserted between the take up roll and winder as described in figure 2.
- a 1 ⁇ 2 inch wide cotton wick (Wet Wick by Perperell MA) was used to apply 25% A-201 anti-soil chemical onto the cable twisted yarn.
- the cable twisted yarn went through the wet wick at about 50 ypm.
- the cable twisted yarn was subsequently heat- set on a Suessen with 200°C dry air.
- the holdup time in the channel was about 60 seconds.
- the heatset yarn was analyzed to have 445 ppm Fluorine.
- the heat treated yarn was converted into a 35 oz per square yard, 1/12 gauge, 3/8" pile height cut pile carpet.
- Two 922 denier beige color solution dyed Nylon 66 BCF made from cationic dyeable polymer were cable twisted on a Volkman at 7000 rpm to form a 6.0 tpi two ply yarn using the process described in figure 2.
- the winding speed was about 50 ypm.
- a chemical applicator was inserted between the take up roll and winder as described in figure 2.
- a 1 ⁇ 2 inch wide cotton wick (Wet Wick by Perperell MA) was used to apply 12.5% A-201 anti-soil chemical onto the cable twisted yarn.
- the cable twisted yarn went through the wet wick at about 50 ypm.
- the cable twisted yarn was subsequently heat-set on a Suessen with 200°C dry air.
- the holdup time in the channel was about 60 seconds.
- the heatset yarn was analyzed to have 270 ppm Fluorine.
- the heat treated yarn was converted into a 35 oz per square yard, 1/12 gauge, 3/8" pile height cut pile carpet.
- Table 1 below reports the repellency and stain tests of the four examples.
- carpets made from the treated BCF yarn show excellent and good oil and water repellency ratings. This indicates that the disclosed inventive process is an acceptable replacement to existing exhaust type applications for applying anti-soil compositions to carpets and fabrics.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Carpets (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161453326P | 2011-03-16 | 2011-03-16 | |
| PCT/US2012/029151 WO2012125777A2 (en) | 2011-03-16 | 2012-03-15 | Processes to make water and oil repellent bcf yarn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2686476A2 true EP2686476A2 (en) | 2014-01-22 |
| EP2686476A4 EP2686476A4 (en) | 2015-08-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP12757287.3A Withdrawn EP2686476A4 (en) | 2011-03-16 | 2012-03-15 | METHODS OF MANUFACTURING HYDROFUGE AND OIL FLOATING BLEEDING (BCF) CONTINUOUS FILAMENT YARN |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20140065346A1 (en) |
| EP (1) | EP2686476A4 (en) |
| JP (1) | JP2014512459A (en) |
| CN (1) | CN103415661A (en) |
| AU (1) | AU2012229932A1 (en) |
| CA (1) | CA2829977A1 (en) |
| WO (1) | WO2012125777A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2012316378A1 (en) * | 2011-09-26 | 2014-03-13 | Invista Technologies S.A R.L. | Processes to dye and treat BCF yarn |
| WO2014047136A1 (en) * | 2012-09-19 | 2014-03-27 | Invista Technologies S.A.R.L. | Processes to make water and oil repellent bcf yarn |
| WO2014047138A1 (en) * | 2012-09-19 | 2014-03-27 | Invista Technologies S.À R.L. | Processes to dye and treat bcf yarn |
| EP2898137A1 (en) * | 2012-09-19 | 2015-07-29 | Invista Technologies S.à.r.l. | Processes to dye and treat single bcf yarn |
| US20170016160A1 (en) * | 2014-04-10 | 2017-01-19 | Invista North America S.Ar.L. | Multicolor carpet and method of making same |
| CA2987755A1 (en) * | 2015-06-12 | 2016-12-15 | Leon Dyers, Jr. | Curable compositions containing benzoxazine epoxy blend and use thereof |
| CN106702520A (en) * | 2015-08-06 | 2017-05-24 | 江苏开利地毯股份有限公司 | Method for producing water-repellent anti-fouling type polypropylene BCF filament |
| CN106917170A (en) * | 2017-04-20 | 2017-07-04 | 湖北名仁纺织科技有限公司 | A kind of mould carbon fiber polyester thread of anti-soil and its production method |
| CN110685046B (en) * | 2019-08-19 | 2022-04-22 | 浙江海洋大学 | Anti-fouling and anti-fatigue multi-strand monofilament mixed-twisted net wire and preparation method thereof |
| CN110923883A (en) * | 2019-12-11 | 2020-03-27 | 江苏羽鸣科技有限公司 | Method for making feather yarn |
| CN116791257A (en) * | 2023-06-27 | 2023-09-22 | 烟台鑫泰汽车配件有限公司 | Stain resistant yarn and carpet made of same |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4565717A (en) * | 1983-10-20 | 1986-01-21 | E. I. Dupont De Nemours And Company | Antisoiling treatment of synthetic filaments |
| US5153046A (en) * | 1990-05-24 | 1992-10-06 | E. I. Du Pont De Nemours And Company | Fluorochemical composition for imparting antisoiling protection and lubricity to textile fibers |
| US5908663A (en) * | 1996-02-01 | 1999-06-01 | Minnesota Mining And Manufacturing Company | Topical carpet treatment |
| US5674437A (en) * | 1996-02-28 | 1997-10-07 | Glotex Corporation | Method of providing luminescence to fibrous materials |
| US5948480A (en) * | 1997-03-31 | 1999-09-07 | E.I. Du Pont De Nemours And Company | Tandem application of soil and stain resists to carpeting |
| DE29810240U1 (en) * | 1998-06-09 | 1998-09-24 | Scheibler Peltzer GmbH & Co, 47803 Krefeld | Cleaning cloth |
| AU2002228999A1 (en) * | 2000-11-28 | 2002-06-11 | E.I. Du Pont De Nemours And Company | Application of a fluorochemical solution to a finished fiber |
| US7078454B2 (en) * | 2002-04-17 | 2006-07-18 | 3M Innovative Properties Company | Repellent fluorochemical compositions |
| US20060236466A1 (en) * | 2003-02-06 | 2006-10-26 | Lin Perry H | Effectively printable polymide yarn, process for making the same, and fabric produced therefrom |
| AU2010256456B2 (en) * | 2009-06-05 | 2016-07-07 | Invista Technologies S.A.R.L. | Systems and methods for intermittently colored yarn |
-
2012
- 2012-03-15 US US14/005,142 patent/US20140065346A1/en not_active Abandoned
- 2012-03-15 EP EP12757287.3A patent/EP2686476A4/en not_active Withdrawn
- 2012-03-15 CA CA2829977A patent/CA2829977A1/en not_active Abandoned
- 2012-03-15 JP JP2013558156A patent/JP2014512459A/en not_active Withdrawn
- 2012-03-15 CN CN2012800134679A patent/CN103415661A/en active Pending
- 2012-03-15 AU AU2012229932A patent/AU2012229932A1/en not_active Abandoned
- 2012-03-15 WO PCT/US2012/029151 patent/WO2012125777A2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014512459A (en) | 2014-05-22 |
| AU2012229932A1 (en) | 2013-09-26 |
| CN103415661A (en) | 2013-11-27 |
| WO2012125777A3 (en) | 2012-12-20 |
| NZ615126A (en) | 2015-06-26 |
| EP2686476A4 (en) | 2015-08-12 |
| CA2829977A1 (en) | 2012-09-20 |
| WO2012125777A2 (en) | 2012-09-20 |
| US20140065346A1 (en) | 2014-03-06 |
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