US20150292144A1 - Composition for permanently hydrophilizing polyolefin fibers and use thereof - Google Patents
Composition for permanently hydrophilizing polyolefin fibers and use thereof Download PDFInfo
- Publication number
- US20150292144A1 US20150292144A1 US14/439,280 US201314439280A US2015292144A1 US 20150292144 A1 US20150292144 A1 US 20150292144A1 US 201314439280 A US201314439280 A US 201314439280A US 2015292144 A1 US2015292144 A1 US 2015292144A1
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- United States
- Prior art keywords
- composition according
- atoms
- alkoxylated
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- composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 239000000835 fiber Substances 0.000 title claims abstract description 45
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 32
- -1 cationic quaternary ammonium compound Chemical class 0.000 claims abstract description 27
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 17
- 239000004753 textile Substances 0.000 claims abstract description 16
- 239000004744 fabric Substances 0.000 claims abstract description 14
- 150000003014 phosphoric acid esters Chemical class 0.000 claims abstract description 10
- 239000004745 nonwoven fabric Substances 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
- 229930195729 fatty acid Natural products 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 18
- 150000004665 fatty acids Chemical class 0.000 claims description 15
- 125000003342 alkenyl group Chemical group 0.000 claims description 14
- 150000002191 fatty alcohols Chemical class 0.000 claims description 11
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 150000003254 radicals Chemical class 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 235000019198 oils Nutrition 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000003346 palm kernel oil Substances 0.000 claims description 2
- 235000019865 palm kernel oil Nutrition 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 230000000996 additive effect Effects 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000013508 migration Methods 0.000 abstract description 12
- 230000005012 migration Effects 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 239000012530 fluid Substances 0.000 abstract description 9
- 206010021639 Incontinence Diseases 0.000 abstract description 2
- 229940126601 medicinal product Drugs 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 17
- 230000002209 hydrophobic effect Effects 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 12
- 238000009736 wetting Methods 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 235000013162 Cocos nucifera Nutrition 0.000 description 6
- 244000060011 Cocos nucifera Species 0.000 description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 6
- 210000002700 urine Anatomy 0.000 description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZEMPKEQAKRGZGQ-VBJOUPRGSA-N triricinolein Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC)COC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-VBJOUPRGSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004708 Very-low-density polyethylene Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- 229920001866 very low density polyethylene Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920001054 Poly(ethylene‐co‐vinyl acetate) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- SFFFIHNOEGSAIH-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene;ethene Chemical group C=C.C1C2CCC1C=C2 SFFFIHNOEGSAIH-UHFFFAOYSA-N 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 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
- 230000035699 permeability Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000004711 α-olefin 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/007—Addition polymers
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
- D06M13/295—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing polyglycol moieties; containing neopentyl moieties
-
- 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
- D06M15/53—Polyethers
-
- 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
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
-
- 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
- D06M2200/11—Oleophobic properties
Definitions
- the present invention relates to compositions, preferably in the form of spin finishes, for polyolefin fibers or filaments imparting to these basically hydrophobic fibers permanently hydrophilic properties, as well as to fibers and filaments finished with these compositions, and to textile fabrics made thereof, in particular nonwoven fabrics.
- Hydrophilic nonwoven fabrics are used as covering fibrous webs, i.e. as the top layer or as an intermediate layer in multi-layer fibrous webs, for hygiene products such as baby diapers, sanitary napkins, incontinence products and similar products. It is the task of such nonwovens to quickly pass body fluids such as urine to the underlying absorption layer.
- a preparation for permanent hydrophilization is supposed to adhere to the polyolefin as long as possible and impart to the nonwoven fabric a consistent hydrophilicity over a long time.
- nonwoven fabrics are made of filaments and/or fibers, with random-laid fiber nonwovens bonded by either physical methods such as needling or by chemical means.
- a hydrophilizing fiber preparation must additionally meet further requirements.
- the preparation must permit fiber production and processing and also impart to the fibers and filaments optimum sliding properties and cohesion, and provide them with a sufficient antistatic finish.
- U.S. Pat. No. 4,988,449 describes hydrophilizing compositions that contain diethanol amides such as non-ionic surfactants, alkyl phosphates, quaternary ammonium salts and/or alkyl imidazolium salts and are used as agents imparting fluid permeability to polyolefin nonwovens.
- diethanol amides such as non-ionic surfactants, alkyl phosphates, quaternary ammonium salts and/or alkyl imidazolium salts and are used as agents imparting fluid permeability to polyolefin nonwovens.
- hydrophilizing compositions that contain polyoxyalkylene-modified polydimethylsiloxanes alone or in combination with non-ionic surfactants, alkyl phosphates, quaternary ammonium salts and/or alkyl imidazolium salts.
- EP 410 485 B1 discloses a method for hydrophilizing polyolefin fiber nonwovens by applying to the surface of the fibers an aqueous mixture of alkoxylated surfactants, wherein the composition consists either of at least 80% alkoxylated triglycerides of C 18 fatty acids, with these triglycerides containing a large proportion of alkoxylated ricinolein or alkoxylated and hydrogenated ricinolein, or of at least 80% of a mixture of alkoxylated or alkoxylated and hydrogenated ricinolein, a polyalkylene-modified water-soluble polydimethylsiloxane and an antistatic compound, the latter being for example a neutralized phosphoric acid ester, an alkoxylated phosphate, potassium salt, ammonium salt or an alkyoxylated ammonium salt.
- hydrophilizing compositions that contain non-ionic surfactants in combination with a polyoxyalkylene-modified polydimethylsiloxane and/or a quaternary ammonium compound.
- EP 1 600 532 B1 describes hydrophilizing compositions comprising an alkoxylated glycerol esterified with a fatty acid and an alkoxylated or alkoxylated and hydrogenated ricinolein esterified with a fatty acid.
- compositions hydrophilically finishing fibers and nonwoven fabrics that are resistant to migration of constituents in the preparation, whether dry and/or wet, to adjacent hydrophobic areas of the nonwoven.
- this object is solved by a composition for permanently hydrophilizing polyolefin fibers and filaments and textile fabrics made thereof such as nonwoven fabrics and other nonwoven textile products according to claim 1 .
- composition for permanently hydrophilizing polyolefin fibers and filaments and textile fabrics made thereof comprises:
- R 1 is an alkyl group having 1 to 22 C atoms or an alkenyl group having 2 to 22 C atoms,
- R 2 and R 3 independently represent an alkyl group having 1 to 22 C atoms, hydroxyethyl or a polyglycol radical,
- Y ⁇ is one of the anions CH 3 OSO 3 ⁇ , C 2 H S OSO 3 ⁇ , CH 3 COO ⁇ , Cl ⁇ , phosphate, lactate, citrate, and
- n and n independently represent an integer from 1 to 6;
- R 4 , R 5 and R 6 independently represent
- a neutralizing agent for the phosphoric acid ester all suitable bases such as LiOH, NaOH, KOH, NH 3 , mono-, di- or triethanolamine can be used.
- composition according to the present invention has excellent permanently hydrophilizing properties, an excellent transit capacity and a good resistance to migration of the constituents in the preparation to adjacent hydrophobic areas of the nonwoven fabric.
- these compositions can be used particularly well as fiber preparations for the permanent hydrophilic finishing of polyolefin fibers, polyolefin filaments and nonwoven textile products made thereof, in particular nonwoven fabrics.
- the non-ionic surfactant in component (A) of the composition according to the present invention is preferably selected from the group of fatty alcohol alkoxylates having 6 to 18 C atoms in the hydrocarbon chain. Particularly preferred are fatty alcohol alkoxylates having 8 to 16 C atoms in the hydrocarbon chain.
- the fatty alcohol alkoxylates can have a hydroxyl or an alkyl or alkenyl ether group as a terminal group. Particularly preferred are hydroxyl group-terminated fatty alcohol alkoxylates.
- the number of alkoxy groups in the non-ionic surfactant of component (A) is preferably 1 to 10, more preferably 2 to 8 and particularly preferably 2 to 6.
- the alkoxy groups are preferably ethyl(ene)oxy (EO) and/or propyl(ene)oxy (PO) groups, particularly preferably EO groups.
- the radicals R 1 to R 3 in formula (I) are preferably alkyl groups as derived from vegetable oils and oil blends. It is particularly preferred that the radicals R 1 , R 2 , and R 3 are derived from vegetable oils with a high proportion of saturated fatty acids, in particular palm oil or palm kernel oil.
- the quaternary ammonium compounds are present as a solid at room temperature.
- the quaternary ammonium compounds have a melting point of 25 to 80° C., particularly preferably a melting point of 30 to 50° C.
- At least one of the radicals R 4 , R 5 and R 6 in formula (II) of the neutralized phosphoric acid ester of component (C) is preferably an alkoxylated alkyl or alkenyl group having 6 to 18 C atoms in the hydrocarbon chain and 1 to 6 alkoxy groups, particularly preferably an alkoxylated alkyl or alkenyl group having 10 to 18 C atoms in the hydrocarbon chain and 1 to 4 alkoxy groups.
- the alkoxy groups are preferably ethyl(ene)oxy (EO) and/or propyl(ene)oxy (PO) groups, particularly preferably EO groups.
- At least one of the radicals R 4 , R 5 and R 6 in formula (II) is an alkyl group or an alkenyl group having 6 to 18 C atoms, particularly preferably having 10 to 18 C atoms.
- composition according to the present invention can optionally contain further additives from the group of cohesion agents, lubricants, corrosion inhibitors and emulsifiers as component (D).
- the composition according to the present invention consists of components (A), (B) and (C) as well as optionally one or more of the additives according to component (D).
- component (A) is present in a proportion of 20 to 35% by weight
- component (B) is present in a proportion of 20 to 35% by weight
- component (C) is present in a proportion of 35 to 45% by weight, each based on the total weight of components (A), (B) and (C).
- component (D) can be added to both the composition according to the present invention comprising components (A), (B) and (C) and the application liquor.
- a castor oil alkoxylate for example Emulsogen EL 360 from Clariant, or a castor oil alkoxylate having up to 10 ethoxy and up to 3 propoxy units is used as a cohesion agent.
- the proportion of the cohesion agent in the composition according to the present invention is preferably 1 to 10% by weight, based on the total weight of the composition.
- the cohesion agent is added subsequently to the application liquor.
- the lubricant is a fatty acid ethoxylate, particularly preferably a coconut fatty acid alkyoxylate such as Genagen C100 from Clariant, a coconut fatty acid having up to 10 ethoxy units or a coconut fatty acid having up to 10 ethoxy and 3 propoxy units.
- the proportion of the lubricant in the composition according to the present invention is preferably 1 to 10% by weight, based on the total weight of the composition.
- the lubricant is added subsequently to the application liquor.
- a fatty acid amine derivative is used as a corrosion inhibitor for the protection of the metal parts of the spinning machines and the other processing machines, e.g. of the card.
- the corrosion inhibitor is an oleyl sarkosinate.
- the proportion of the corrosion inhibitor in the composition according to the present invention is preferably 0 to 2% by weight, based on the total weight of the composition.
- the corrosion inhibitor is added subsequently to the application liquor.
- a fatty acid ethoxylate is again preferably used, particularly preferably a coconut fatty acid alkyoxylate such as Genagen C100 from Clariant, a coconut fatty acid having up to 10 ethoxy units or a coconut fatty acid having up to 10 ethoxy and 3 propoxy units.
- the proportion of the emulsifier in the composition according to the present invention is preferably 1 to 50% by weight, based on the total weight of the composition.
- the composition according to the present invention is present in the form of an aqueous dispersion or paste whose drying residue at 105° C. is between 5 and 95% by weight.
- composition according to the present invention is preferably used as a fiber preparation for permanently hydrophilizing polyolefin fibers or polyolefin filaments or as an agent for the permanent hydrophilic finishing of nonwoven textile products made of polyolefin fibers or polyolefin filaments.
- polystyrene resin ethylene- or propylene-based homo- or copolymers can be used.
- polystyrene resins examples include polyethylenes such as HDPE (high-density polyethylene), LDPE (low-density polyethylene), VLDPE (very low-density polyethylene), LLDPE (linear low-density polyethylene), MDPE (medium-density polyethylene), UHMPE (ultra-high molecular polyethylene), VPE (cross-linked polyethylene), HPPE (high-pressure polyethylene); polypropylenes such as isotactic polypropylene, syndiotactic polypropylene, metallocene-catalyzed polypropylene, impact strength-modified polypropylene; ethylene- and propylene-based random copolymers, ethylene- and propylene-based block copolymers; EPM (poly[ethylene-co-propylene]); EPDM (poly[ethylene-co-propylene-co-conjugated diene]).
- HDPE high-density polyethylene
- LDPE low-density
- polystyrene polystyrene
- examples of such polymers are poly(ethylene-co-ethyl acrylate), poly(ethylene-co-vinyl acetate), poly(ethylene-co-vinyl chloride) and poly(styrene-co-acrylonitrile).
- Graft copolymers such as polymer blends, i.e. mixtures of polymers which contain, inter alia, the above-mentioned polymers, for example polyethylene- and polypropylene-based polymer blends, are also suitable.
- bi-component fibers with a core/shell structure such as PE/PP and PP/PET biopolymers can be used.
- composition according to the present invention can be applied to the fibers, filaments or nonwoven textile products in the form of an aqueous emulsion or in the form of an aqueous dispersion, preferably in an amount of 0.1 to 2%, based on the dry weight of the respective product (fiber, filament, nonwoven fabric).
- the composition is applied by means of metering pins, kiss rollers, dip baths or by spraying. Any viscosity desired for the respective application form can be adjusted by diluting the composition with water.
- polyolefin fibers and filaments that are permanently hydrophilically finished or treated with the composition according to the present invention are also an object of the invention.
- the invention relates to a double finish and treatment of the polyolefin fibers/filaments and nonwoven textile products in which the composition according to the present invention initially provides the fibers or filaments and subsequently the entire nonwoven textile or fabric made thereof with a permanently hydrophilic finish.
- nonwoven fabrics finished according to the present invention are non-bonded random-laid fiber nonwovens or chemically or physically bonded, e.g. needled or heat-set nonwovens.
- dkpalmcarboxyethylyhydroxyethyl-methylammonium-methosulfate quaternary ammonium compound derived from palm fatty acid; melting point: 35° C.
- Components A, B and C were thoroughly mixed, homogenized and optionally neutralized.
- the composition obtained this way was diluted with distilled or demineralized water, forming a dispersion containing 5% by weight of the composition.
- Components A, B and C were thoroughly mixed, homogenized and optionally neutralized.
- the composition obtained this way was diluted with distilled or demineralized water, forming a dispersion containing 5% by weight of the composition.
- Components A, B and C were thoroughly mixed, homogenized and optionally neutralized.
- the composition obtained this way was diluted with distilled or demineralized water, forming a dispersion containing 5% by weight of the composition.
- di-(oleylcarboxyethyl)-hydroxyethyl-methylammonium-methosulfate (quaternary ammonium compound; melting point: ⁇ 20° C.)
- Components A, B and C were thoroughly mixed, homogenized and optionally neutralized.
- the composition obtained this way was diluted with distilled or demineralized water, forming a dispersion containing 5% by weight of the composition.
- Components A, B and C were thoroughly mixed, homogenized and optionally neutralized.
- the composition obtained this way was diluted with distilled or demineralized water, forming a dispersion containing 5% by weight of the composition.
- a fiber preparation according to the compositions described in U.S. Pat. No. 4,988,449 was made comprising an alkyl diethanolamide, a salt of an acidic alkyl phosphoric acid ester, a non-ionic surfactant and a quaternary modified polydimethylsiloxane.
- compositions according to Examples 1 and 2 and Comparative examples 1 to 6 were used as a fiber preparation for the permanent hydrophilic finishing of a polypropylene (PP) spunbond nonwoven with an area density of 15 g/m 2 .
- the time required for 5 ml of a synthetic urine solution to penetrate a prepared nonwoven fabric and enter the underlying absorption layer made of filter paper is measured.
- the hydrophilic finish provided is washed out or indeed imparts permanent hydrophilicity
- five successive measurements are made on the same fabric, with the absorbent filter paper renewed each time. The five measured values are given in seconds.
- the amount (in grams) of fluid flowing back into an overlying dry filter paper when a 4 kg load is placed on a soaked fabric is measured.
- a PP spunbond nonwoven is placed with an inclination of 45° on a filter paper serving as an absorption layer.
- the run length necessary to completely pass a defined amount of a synthetic urine solution through the fabric into the underlying absorption layer is determined.
- a maximum run length of 30 mm is allowed.
- test field counts as passed if the amount of fluid has been absorbed by the underlying absorption layer within two seconds. To obtain a statement on the permanence of a fiber preparation, the test is repeated each time after a waiting time of 3 minutes without exchanging the absorption layer. The test result indicates the number of test fields passed.
- hydrophilic and hydrophobic layers are alternately stacked and stored for 48 hours under pressure (bearing load of 10 kg) at an elevated temperature of 60° C.
- the hydrophobic layers of nonwoven fabric are placed in a solution of synthetic urine, and the wetting of the layers is assessed. Ideally, there is no wetting of the hydrophobic nonwoven fabric. Assessment is based on the following criteria:
- Grade 2 max. 5 wetting sites with a diameter of ⁇ 2 mm visible
- Grade 4 more than 15 wetting sites with a diameter of ⁇ 2 mm visible, or wetting sites with a diameter of >2 mm visible
- the detachment of a fiber preparation and its transfer from hydrophilic to hydrophobic areas in contact with a fluid are tested.
- a hydrophilic piece of nonwoven fabric finished with a fiber preparation is placed in a Petri dish containing synthetic urine, and a hydrophobic piece of nonwoven fabric is laid on top. After 30 seconds wetting of the hydrophobic piece of nonwoven fabric is assessed. Ideally, the hydrophobic nonwoven fabric is not hydrophilized. Assessment is made by specifying the wetted surface in percent.
- Examples 1 and 2 according to the present invention containing a non-ionic surfactant together with a quaternary ammonium compound and a neutralized phosphoric acid ester mixture meet the requirements for quickly and permanently hydrophilizing the polyolefin nonwoven fabric without migration.
- Comparative examples 1 to 3 and the commercially available comparative examples 4 to 6 fail to meet at least one of the desired requirements.
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Abstract
The invention relates to a composition for permanently hydrophilizing polyolefin fibers and polyolefin filaments as well as nonwoven textile fabrics made thereof for use as hygiene products such as baby diapers and sanitary napkins or medicinal products such as incontinence products, wound dressings and surgical covers.
The composition contains a combination of a non-ionic surfactant, a cationic quaternary ammonium compound and a neutralized phosphoric acid ester. The fiber products finished with the composition exhibit improved resistance to wet migration and dry migration and quick fluid absorption.
Description
- The present invention relates to compositions, preferably in the form of spin finishes, for polyolefin fibers or filaments imparting to these basically hydrophobic fibers permanently hydrophilic properties, as well as to fibers and filaments finished with these compositions, and to textile fabrics made thereof, in particular nonwoven fabrics.
- Hydrophilic nonwoven fabrics are used as covering fibrous webs, i.e. as the top layer or as an intermediate layer in multi-layer fibrous webs, for hygiene products such as baby diapers, sanitary napkins, incontinence products and similar products. It is the task of such nonwovens to quickly pass body fluids such as urine to the underlying absorption layer.
- Ordinary hydrophilizing preparations are wiped off the nonwoven fabric more or less quickly and distinctly during fluid transport within the diaper or other product, making the covering fibrous web gradually lose its hydrophilic properties and, due to the hydrophobic properties of polyolefins, become more and more hydrophobic. Upon subsequent further contact with body fluids, the passing of said fluids to the absorption layer will be increasingly complicated and finally impossible. As a result, the fluids leak from the nonwoven construct, and the nonwoven construct can no longer exert its original function of keeping a baby's or a patient's skin dry.
- In contrast to that, a preparation for permanent hydrophilization is supposed to adhere to the polyolefin as long as possible and impart to the nonwoven fabric a consistent hydrophilicity over a long time.
- Typically, nonwoven fabrics are made of filaments and/or fibers, with random-laid fiber nonwovens bonded by either physical methods such as needling or by chemical means. In the production of carded nonwovens that are subsequently heat-set a hydrophilizing fiber preparation must additionally meet further requirements. In this case, for nonwovens to be produced at an acceptable rate, the preparation must permit fiber production and processing and also impart to the fibers and filaments optimum sliding properties and cohesion, and provide them with a sufficient antistatic finish.
- U.S. Pat. No. 4,988,449 describes hydrophilizing compositions that contain diethanol amides such as non-ionic surfactants, alkyl phosphates, quaternary ammonium salts and/or alkyl imidazolium salts and are used as agents imparting fluid permeability to polyolefin nonwovens.
- From U.S. Pat. No. 5,258,129 hydrophilizing compositions are known that contain polyoxyalkylene-modified polydimethylsiloxanes alone or in combination with non-ionic surfactants, alkyl phosphates, quaternary ammonium salts and/or alkyl imidazolium salts.
- EP 410 485 B1 discloses a method for hydrophilizing polyolefin fiber nonwovens by applying to the surface of the fibers an aqueous mixture of alkoxylated surfactants, wherein the composition consists either of at least 80% alkoxylated triglycerides of C18 fatty acids, with these triglycerides containing a large proportion of alkoxylated ricinolein or alkoxylated and hydrogenated ricinolein, or of at least 80% of a mixture of alkoxylated or alkoxylated and hydrogenated ricinolein, a polyalkylene-modified water-soluble polydimethylsiloxane and an antistatic compound, the latter being for example a neutralized phosphoric acid ester, an alkoxylated phosphate, potassium salt, ammonium salt or an alkyoxylated ammonium salt.
- From EP 0 839 947 A2 hydrophilizing compositions are known that contain non-ionic surfactants in combination with a polyoxyalkylene-modified polydimethylsiloxane and/or a quaternary ammonium compound.
- EP 1 600 532 B1 describes hydrophilizing compositions comprising an alkoxylated glycerol esterified with a fatty acid and an alkoxylated or alkoxylated and hydrogenated ricinolein esterified with a fatty acid.
- Although these known compositions impart to the fibers and nonwoven fabrics treated or finished with them permanently hydrophilic properties, their production is expensive and they need to be improved with regard to the rate at which the fluid is passed through the nonwoven fabric into the absorption layer.
- Furthermore, there is a need for compositions hydrophilically finishing fibers and nonwoven fabrics that are resistant to migration of constituents in the preparation, whether dry and/or wet, to adjacent hydrophobic areas of the nonwoven.
- Thus, it is the object of the invention to provide a composition with good permanently hydrophilizing properties, a rapid transit capacity and a low tendency to migrate into adjacent hydrophobic areas of the nonwoven fabric.
- According to the present invention, this object is solved by a composition for permanently hydrophilizing polyolefin fibers and filaments and textile fabrics made thereof such as nonwoven fabrics and other nonwoven textile products according to claim 1.
- Further advantageous embodiments are stated in the sub-claims which can be optionally combined with each other.
- The composition for permanently hydrophilizing polyolefin fibers and filaments and textile fabrics made thereof comprises:
- (A) 15 to 50% by weight of at least one non-ionic surfactant, wherein the non-ionic surfactant is selected from the following group of compounds, each having one or more branched or straight-chain, saturated or unsaturated C6-C18 hydrocarbon chains in their molecule: alkoxylated C6-C18 fatty alcohols, alkoxylated C6-C18 amines, alkoxylated C6-C18 amides, alkoxylated C6-C18 fatty acids, alkoxylated C6-C18 fatty acid esters and alkoxylated C8-C18 alkylphenoles;
(B) 15 to 50% by weight of at least one quaternary ammonium compound of the general formula (I): -
[R1—C(═O)—X—(CH2)n—NR2R3—(CH2)m—X—C(═O)—R1]+Y− (I) - wherein
- R1 is an alkyl group having 1 to 22 C atoms or an alkenyl group having 2 to 22 C atoms,
- R2 and R3 independently represent an alkyl group having 1 to 22 C atoms, hydroxyethyl or a polyglycol radical,
- X is an oxygen atom, NH, N—CH3 or a (OC2H4)z group with z=1 to 10,
- Y− is one of the anions CH3OSO3 −, C2HSOSO3 −, CH3COO−, Cl−, phosphate, lactate, citrate, and
- m and n independently represent an integer from 1 to 6;
- wherein the quaternary ammonium compound is present as a solid at room temperature (20° C.);
- (C) 15 to 50% by weight of at least one neutralized phosphoric acid ester of the general formula (II):
-
P(═O)(OR4)(OR5)(OR6) (II) - wherein
- R4, R5 and R6 independently represent
-
- (i) an alkoxylated alkyl group having 3 to 22 C atoms in the hydrocarbon chain or an alkoxylated alkenyl group having 3 to 22 C atoms in the hydrocarbon chain, wherein the number of alkoxy groups per alkyl or alkylene group is between 1 and 10 and the alkyl groups or alkenyl groups in each case may be branched or straight-chain, saturated or unsaturated;
- (ii) an alkyl group having 3 to 22 C atoms or an alkenyl group having 3 to 22 C atoms that in each case may be branched or straight-chain, saturated or unsaturated, and/or
- (iii) hydrogen,
- with at least one of the radicals R4, R5 and R6 not being hydrogen.
- As a neutralizing agent for the phosphoric acid ester, all suitable bases such as LiOH, NaOH, KOH, NH3, mono-, di- or triethanolamine can be used.
- The composition according to the present invention has excellent permanently hydrophilizing properties, an excellent transit capacity and a good resistance to migration of the constituents in the preparation to adjacent hydrophobic areas of the nonwoven fabric.
- In aqueous dilutions, these compositions can be used particularly well as fiber preparations for the permanent hydrophilic finishing of polyolefin fibers, polyolefin filaments and nonwoven textile products made thereof, in particular nonwoven fabrics.
- The non-ionic surfactant in component (A) of the composition according to the present invention is preferably selected from the group of fatty alcohol alkoxylates having 6 to 18 C atoms in the hydrocarbon chain. Particularly preferred are fatty alcohol alkoxylates having 8 to 16 C atoms in the hydrocarbon chain.
- The fatty alcohol alkoxylates can have a hydroxyl or an alkyl or alkenyl ether group as a terminal group. Particularly preferred are hydroxyl group-terminated fatty alcohol alkoxylates.
- The number of alkoxy groups in the non-ionic surfactant of component (A) is preferably 1 to 10, more preferably 2 to 8 and particularly preferably 2 to 6. The alkoxy groups are preferably ethyl(ene)oxy (EO) and/or propyl(ene)oxy (PO) groups, particularly preferably EO groups.
- In the quaternary ammonium compound of component (B) the radicals R1 to R3 in formula (I) are preferably alkyl groups as derived from vegetable oils and oil blends. It is particularly preferred that the radicals R1, R2, and R3 are derived from vegetable oils with a high proportion of saturated fatty acids, in particular palm oil or palm kernel oil.
- According to the present invention, the quaternary ammonium compounds are present as a solid at room temperature.
- According to a particularly preferred embodiment of the composition according to the present invention the quaternary ammonium compounds have a melting point of 25 to 80° C., particularly preferably a melting point of 30 to 50° C.
- At least one of the radicals R4, R5 and R6 in formula (II) of the neutralized phosphoric acid ester of component (C) is preferably an alkoxylated alkyl or alkenyl group having 6 to 18 C atoms in the hydrocarbon chain and 1 to 6 alkoxy groups, particularly preferably an alkoxylated alkyl or alkenyl group having 10 to 18 C atoms in the hydrocarbon chain and 1 to 4 alkoxy groups. The alkoxy groups are preferably ethyl(ene)oxy (EO) and/or propyl(ene)oxy (PO) groups, particularly preferably EO groups.
- According to another preferred embodiment at least one of the radicals R4, R5 and R6 in formula (II) is an alkyl group or an alkenyl group having 6 to 18 C atoms, particularly preferably having 10 to 18 C atoms.
- In addition, the composition according to the present invention can optionally contain further additives from the group of cohesion agents, lubricants, corrosion inhibitors and emulsifiers as component (D).
- Preferably, the composition according to the present invention consists of components (A), (B) and (C) as well as optionally one or more of the additives according to component (D). Particularly preferably, component (A) is present in a proportion of 20 to 35% by weight, component (B) is present in a proportion of 20 to 35% by weight and component (C) is present in a proportion of 35 to 45% by weight, each based on the total weight of components (A), (B) and (C).
- The other additives of component (D) can be added to both the composition according to the present invention comprising components (A), (B) and (C) and the application liquor.
- Preferably, a castor oil alkoxylate, for example Emulsogen EL 360 from Clariant, or a castor oil alkoxylate having up to 10 ethoxy and up to 3 propoxy units is used as a cohesion agent. The proportion of the cohesion agent in the composition according to the present invention is preferably 1 to 10% by weight, based on the total weight of the composition.
- It is preferred that the cohesion agent is added subsequently to the application liquor.
- Preferably, the lubricant is a fatty acid ethoxylate, particularly preferably a coconut fatty acid alkyoxylate such as Genagen C100 from Clariant, a coconut fatty acid having up to 10 ethoxy units or a coconut fatty acid having up to 10 ethoxy and 3 propoxy units. The proportion of the lubricant in the composition according to the present invention is preferably 1 to 10% by weight, based on the total weight of the composition.
- It is preferred that the lubricant is added subsequently to the application liquor.
- Preferably, a fatty acid amine derivative is used as a corrosion inhibitor for the protection of the metal parts of the spinning machines and the other processing machines, e.g. of the card. Particularly preferably, the corrosion inhibitor is an oleyl sarkosinate. The proportion of the corrosion inhibitor in the composition according to the present invention is preferably 0 to 2% by weight, based on the total weight of the composition.
- It is preferred that the corrosion inhibitor is added subsequently to the application liquor.
- As the emulsifier, a fatty acid ethoxylate is again preferably used, particularly preferably a coconut fatty acid alkyoxylate such as Genagen C100 from Clariant, a coconut fatty acid having up to 10 ethoxy units or a coconut fatty acid having up to 10 ethoxy and 3 propoxy units. The proportion of the emulsifier in the composition according to the present invention is preferably 1 to 50% by weight, based on the total weight of the composition.
- Preferably, the composition according to the present invention is present in the form of an aqueous dispersion or paste whose drying residue at 105° C. is between 5 and 95% by weight.
- The composition according to the present invention is preferably used as a fiber preparation for permanently hydrophilizing polyolefin fibers or polyolefin filaments or as an agent for the permanent hydrophilic finishing of nonwoven textile products made of polyolefin fibers or polyolefin filaments.
- As the polyolefin, ethylene- or propylene-based homo- or copolymers can be used.
- Examples of such polyolefins are polyethylenes such as HDPE (high-density polyethylene), LDPE (low-density polyethylene), VLDPE (very low-density polyethylene), LLDPE (linear low-density polyethylene), MDPE (medium-density polyethylene), UHMPE (ultra-high molecular polyethylene), VPE (cross-linked polyethylene), HPPE (high-pressure polyethylene); polypropylenes such as isotactic polypropylene, syndiotactic polypropylene, metallocene-catalyzed polypropylene, impact strength-modified polypropylene; ethylene- and propylene-based random copolymers, ethylene- and propylene-based block copolymers; EPM (poly[ethylene-co-propylene]); EPDM (poly[ethylene-co-propylene-co-conjugated diene]).
- Further suitable polyolefins are, for example, polystyrene;
- poly(methylstyrene); poly(oxymethylene); metallocene-catalyzed alpha-olefin or cycloolefin copolymers such as norbornene-ethylene copolymers; copolymers containing at least 60% ethylene and/or styrene and less than 40% monomers such as vinyl acetate, acrylic acid ester, methacrylic acid ester, acrylic acid, acrylonitrile or vinyl chloride. Examples of such polymers are poly(ethylene-co-ethyl acrylate), poly(ethylene-co-vinyl acetate), poly(ethylene-co-vinyl chloride) and poly(styrene-co-acrylonitrile).
- Graft copolymers such as polymer blends, i.e. mixtures of polymers which contain, inter alia, the above-mentioned polymers, for example polyethylene- and polypropylene-based polymer blends, are also suitable. In addition, bi-component fibers with a core/shell structure such as PE/PP and PP/PET biopolymers can be used.
- The composition according to the present invention can be applied to the fibers, filaments or nonwoven textile products in the form of an aqueous emulsion or in the form of an aqueous dispersion, preferably in an amount of 0.1 to 2%, based on the dry weight of the respective product (fiber, filament, nonwoven fabric).
- As known to those skilled in the art, the composition is applied by means of metering pins, kiss rollers, dip baths or by spraying. Any viscosity desired for the respective application form can be adjusted by diluting the composition with water.
- Therefore, polyolefin fibers and filaments that are permanently hydrophilically finished or treated with the composition according to the present invention are also an object of the invention.
- In addition, the invention relates to a double finish and treatment of the polyolefin fibers/filaments and nonwoven textile products in which the composition according to the present invention initially provides the fibers or filaments and subsequently the entire nonwoven textile or fabric made thereof with a permanently hydrophilic finish.
- It is particularly preferred that the nonwoven fabrics finished according to the present invention are non-bonded random-laid fiber nonwovens or chemically or physically bonded, e.g. needled or heat-set nonwovens.
- Below, the invention is explained by means of several preferred embodiments, which, however, are not to be construed as limiting.
- Component A
- 34.2% by weight C10 fatty alcohol polyethylene glycol ether-4EO (non-ionic surfactant)
- Component B
- 28.2% by weight dkpalmcarboxyethylyhydroxyethyl-methylammonium-methosulfate (quaternary ammonium compound derived from palm fatty acid; melting point: 35° C.)
- Component C
- 37.6% by weight mono- and di-(C12-C18)-alkyl phosphoric acid ester, potassium salt
- Components A, B and C were thoroughly mixed, homogenized and optionally neutralized. The composition obtained this way was diluted with distilled or demineralized water, forming a dispersion containing 5% by weight of the composition.
- Component A
- 24.1% by weight C12-C14 fatty alcohol polyethylene glycol ether-(3EO)
- Component B
- 32.0% by weight dkpalmcarboxyethylyhydroxyethyl-methylammonium-methosulfate
- Component C
- 43.9% by weight mono- and di-(C12-C18)-alkyl phosphoric acid ester, potassium salt
- Components A, B and C were thoroughly mixed, homogenized and optionally neutralized. The composition obtained this way was diluted with distilled or demineralized water, forming a dispersion containing 5% by weight of the composition.
- Component A
- 34.2% by weight bis-isooctyl sodium sulfosuccinate (ionic surfactant)
- Component B
- 28.2% by weight dkpalmcarboxyethylyhydroxyethyl-methylammonium-methosulfate
- Component C
- 37.6% by weight mono- and di-(C12-C18)-alkyl phosphoric acid ester, potassium salt
- Components A, B and C were thoroughly mixed, homogenized and optionally neutralized. The composition obtained this way was diluted with distilled or demineralized water, forming a dispersion containing 5% by weight of the composition.
- Component A
- 24.0% by weight C12-C14 fatty alcohol polyethylene glycol ether-6EO (non-ionic-surfactant)
- Component B
- 32.5% by weight di-(oleylcarboxyethyl)-hydroxyethyl-methylammonium-methosulfate (quaternary ammonium compound; melting point: <20° C.)
- Component C
- 43.5% by weight mono- and di-(C12-C18)-alkyl phosphoric acid ester, potassium salt
- Components A, B and C were thoroughly mixed, homogenized and optionally neutralized. The composition obtained this way was diluted with distilled or demineralized water, forming a dispersion containing 5% by weight of the composition.
- Component A
- 34.2% by weight bis-isooctyl sodium sulfosuccinate (ionic surfactant)
- Component B
- 28.2% by weight di-(oleylcarboxyethyl)-hydroxyethyl-methylammonium-methosulfate
- Component C
- 37.6% by weight mono- and di-(C12-C18)-alkyl phosphoric acid ester, potassium salt
- Components A, B and C were thoroughly mixed, homogenized and optionally neutralized. The composition obtained this way was diluted with distilled or demineralized water, forming a dispersion containing 5% by weight of the composition.
- A permanently hydrophilizing fiber preparation from Schill+Seilacher GmbH, Boblingen, commercially available under the designation Silastol™ PHP 20 and essentially comprising a mixture of cationic antistatic agents, non-ionogenic emulsifiers and special wetting agents, was used as another specimen.
- A fiber preparation according to the compositions described in U.S. Pat. No. 4,988,449 was made comprising an alkyl diethanolamide, a salt of an acidic alkyl phosphoric acid ester, a non-ionic surfactant and a quaternary modified polydimethylsiloxane.
- A permanently hydrophilizing fiber preparation on the basis of fatty acid polyethylene glycol esters that is commercially available under the designation Stantex™ S 6327 (Pulcra Chemicals) was used as another specimen.
- Investigation of Hydrophilizing Properties
- All preparations described above were adjusted, by dilution with distilled or demineralized water, to a dispersion containing 5% by weight active components. The 5% by weight active dispersion of the compositions according to Examples 1 and 2 and Comparative examples 1 to 6 was used as a fiber preparation for the permanent hydrophilic finishing of a polypropylene (PP) spunbond nonwoven with an area density of 15 g/m2. The applied weight of the active substance (OPU or oil pick up), based on the dry weight of the PP nonwoven, was 0.45 to 0.65%.
- For the testing of the compositions in conjunction with the above-mentioned textile substrate the studies described below were performed.
- Strike-Through Time
- According to the EDANA method ERT 150.2-93, the time required for 5 ml of a synthetic urine solution to penetrate a prepared nonwoven fabric and enter the underlying absorption layer made of filter paper is measured. To find out whether the hydrophilic finish provided is washed out or indeed imparts permanent hydrophilicity, five successive measurements are made on the same fabric, with the absorbent filter paper renewed each time. The five measured values are given in seconds.
- Wetback
- According to the EDANA method ERT 151.0-93, the amount (in grams) of fluid flowing back into an overlying dry filter paper when a 4 kg load is placed on a soaked fabric is measured.
- Runoff Test
- Based on the EDANA method 152.0-99, a PP spunbond nonwoven is placed with an inclination of 45° on a filter paper serving as an absorption layer. The run length necessary to completely pass a defined amount of a synthetic urine solution through the fabric into the underlying absorption layer is determined. To pass the test, a maximum run length of 30 mm is allowed.
- Ten Drop Test
- In the ten drop test according to an in-house testing method, a 10-well metal mask is placed on a piece of nonwoven fabric as an absorption layer. Successively, one drop of a synthetic urine solution is pipetted into each well. A test field counts as passed if the amount of fluid has been absorbed by the underlying absorption layer within two seconds. To obtain a statement on the permanence of a fiber preparation, the test is repeated each time after a waiting time of 3 minutes without exchanging the absorption layer. The test result indicates the number of test fields passed.
- Dry Migration
- In the dry migration test according to an in-house testing method, migration of the constituents of the hydrophilic fiber preparation into the surrounding hydrophobic nonwoven material is simulated. To this end, hydrophilic and hydrophobic layers are alternately stacked and stored for 48 hours under pressure (bearing load of 10 kg) at an elevated temperature of 60° C. The hydrophobic layers of nonwoven fabric are placed in a solution of synthetic urine, and the wetting of the layers is assessed. Ideally, there is no wetting of the hydrophobic nonwoven fabric. Assessment is based on the following criteria:
- Grade 1: No Wetting Visible
- Grade 2: max. 5 wetting sites with a diameter of <2 mm visible
- Grade 3: 6 to 15 wetting sites with a diameter of <2 mm visible
- Grade 4: more than 15 wetting sites with a diameter of <2 mm visible, or wetting sites with a diameter of >2 mm visible
- Wet Migration
- In the wet migration test according to an in-house testing method, the detachment of a fiber preparation and its transfer from hydrophilic to hydrophobic areas in contact with a fluid are tested. To this end, a hydrophilic piece of nonwoven fabric finished with a fiber preparation is placed in a Petri dish containing synthetic urine, and a hydrophobic piece of nonwoven fabric is laid on top. After 30 seconds wetting of the hydrophobic piece of nonwoven fabric is assessed. Ideally, the hydrophobic nonwoven fabric is not hydrophilized. Assessment is made by specifying the wetted surface in percent.
- The results of the tests performed with regard to the compositions according to Examples 1 and 2 and Comparative examples 1 to 6 are shown in Table 1 below, with the target values compared to the measuring values obtained in each case. The test is considered as passed if all measuring values are within the range of the target values.
- Examples 1 and 2 according to the present invention containing a non-ionic surfactant together with a quaternary ammonium compound and a neutralized phosphoric acid ester mixture meet the requirements for quickly and permanently hydrophilizing the polyolefin nonwoven fabric without migration.
- Comparative examples 1 to 3 and the commercially available comparative examples 4 to 6 fail to meet at least one of the desired requirements.
-
TABLE 1 Test results for Examples 1 and 2 as well as Comparative examples 1 to 6 Multiple OPU Strike-Through Wetback Examples Component A [%] [s] [g] Target value — <2/<3/<3/<3/<3 max. 0.3 Example 1 non-ionic 0.45 1.35/2.21/2.29/2.29/ 0.23 2.23 Example 2 non-ionic 0.55 1.22/2.11/2.23/2.27/ 0.16 2.41 Comparative anionic 0.55 1.33/2.48/2.57/2.51/ 0.23 example 1 2.51 Comparative non-ionic 0.45 1.24/2.18/2.56/4.20/ 0.22 example 2 2.63 Comparative anionic 0.54 1.53/2.61/2.80/2.60/ 0.18 example 3 2.51 Comparative — 0.65 1.65/3.07/5.29/4.82/ 3.9 example 4 2.75 Comparative — 0.57 1.41/2.45/4.37/5.58/ n.d. example 5 4.66 Comparative — 0.51 1.86/4.70/5.68/8.75/ 0.12 example 6 8.41 45° runoff Ten hole Dry migration Wet migration Examples [mm] test Grade [%] Target value max. 30 10/10/10 1 max. 15 Example 1 23 10/10/10 1 8 Example 2 29 10/10/10 1 6 Comparative 27 10/10/10 1 45 example 1 Comparative 53 9/10/10 1 13 example 2 Comparative 25 10/10/10 1 30 example 3 Comparative 24 10/10/9 4 100 example 4 Comparative 31 7/10/10 1 64 example 5 Comparative 152 8/9/8 1 15 example 6
Claims (18)
1. A composition for permanently hydrophilizing polyolefin fibers and filaments as well as nonwoven textile products made thereof, comprising
(A) 15 to 50% by weight of at least one non-ionic surfactant, wherein the non-ionic surfactant is a compound selected from the group consisting of: alkoxylated C6-C18 fatty alcohols, alkoxylated C6-C18 amines, alkoxylated C6-C18 amides, alkoxylated C6-C18 fatty acids, alkoxylated C6-C18 fatty acid esters and alkoxylated C8-C18 alkylphenols, and wherein the non-ionic surfactant has one or more branched or straight-chain, saturated or unsaturated C6-C18 hydrocarbon chain;
(B) 15 to 50% by weight of at least one quaternary ammonium compound of the general formula (I):
[R1—C(═O)—X—(CH2)n—NR2R3—(CH2)m—X—C(═O)—R1]+Y− (I)
[R1—C(═O)—X—(CH2)n—NR2R3—(CH2)m—X—C(═O)—R1]+Y− (I)
wherein
R1 is an alkyl group having 1 to 22 C atoms or an alkenyl group having 2 to 22 C atoms,
R2 and R3 independently represent an alkyl group having 1 to 22 C atoms, hydroxyethyl or a polyglycol radical,
X is an oxygen atom, NH, N—CH3 or a (OC2H4)z group with z=1 to 10,
Y− is one of the anions CH3OSO3 −, C2HSOSO3 −, CH3COO−, Cl−, phosphate, lactate, citrate, and
m and n independently represent an integer from 1 to 6;
wherein the quaternary ammonium compound is present as a solid at room temperature of 20° C.;
(C) 15 to 50% by weight of at least one neutralized phosphoric acid ester of the general formula (II):
P(═O)(OR4)(OR5)(OR6) (II)
P(═O)(OR4)(OR5)(OR6) (II)
wherein
R4, R5 and R6 independently represent
(i) an alkoxylated alkyl group having a hydrocarbon chain comprising 3 to 22 C atoms or an alkoxylated alkenyl group having a hydrocarbon chain comprising 3 to 22 C atoms, wherein the number of alkoxy groups per alkyl or alkylene group is between 1 and 10 and the alkyl groups or alkenyl groups in each case may be branched or straight-chain, saturated or unsaturated;
(ii) an alkyl group having 3 to 22 C atoms or an alkenyl group having 3 to 22 C atoms that in each case may be branched or straight-chain, saturated or unsaturated, and/or
(iii) hydrogen,
with at least one of the radicals R4, R5 and R6 not being hydrogen.
2. The composition according to claim 1 , wherein the non-ionic surfactant of component (A) has 1 to 10 alkoxy groups in the molecule.
3. The composition according to claim 1 wherein the non-ionic surfactant of component (A) is selected from the group of fatty alcohol alkoxylates having 6 to 18 C atoms in the hydrocarbon chain.
4. The composition according to claim 3 , wherein the fatty alcohol alkoxylate has terminal hydroxyl groups.
5. The composition according to claim 1 , wherein at least one of the radicals R1, R2 and R3 in the quaternary ammonium salt of component (B) is derived from vegetable oils or oil blends.
6. The composition according to claim 5 , wherein at least one of the radicals R1, R2 and/or R3 in the quaternary ammonium salt of component (B) is derived from palm oil or palm kernel oil.
7. The composition according to claim 1 , wherein the quaternary ammonium salt of component (B) has a melting point of 25 to 80° C.
8. The composition according to claim 1 , wherein the phosphoric acid ester according to component (C) has alkoxylated alkyl groups and/or alkenyl groups having 6 to 18 C atoms in the hydrocarbon chain and 1 to 6 alkoxy groups.
9. The composition according to claim 1 , wherein the phosphoric acid ester according to component (C) has alkyl groups and/or alkenyl groups having 6 to 18 C atoms.
10. The composition according to claim 1 , wherein the phosphoric acid ester according to component (C) is neutralized with at least one base selected from the group consisting of LiOH, NaOH, KOH, NH3, mono-, di- and triethanolamine.
11. The composition according to claim 1 , wherein the composition is present in the form of an aqueous dispersion or paste having a content of active components of from 5 to 95% by weight.
12. The composition according to claim 1 , wherein the composition optionally contains at least one further additive selected from the group of cohesion agents, lubricants, corrosion inhibitors and emulsifiers as component (D).
13. The use of a composition according to claim 1 , adapted for use as a fiber preparation for permanently hydrophilizing polyolefin fibers or polyolefin filaments.
14. The composition according to one of claim 1 , adapted for use as an agent for the permanent hydrophilic finishing of textile fabrics made of polyolefin fibers or polyolefin filaments, including polyolefin fiber nonwovens.
15. A polyolefin fiber or filament permanently hydrophilically finished or treated with a composition according to claim 1 .
16. A nonwoven textile fabric made of polyolefin fibers or filaments permanently hydrophilically finished with a composition according to claim 1 .
17. The textile fabric according to claim 16 , wherein the fabric is a polyolefin random-laid fiber nonwoven.
18. The textile fabric according to claim 16 , wherein the fabric is a needled polyolefin fiber nonwoven.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102012021742.0A DE102012021742A1 (en) | 2012-11-06 | 2012-11-06 | Composition for the permanent hydrophilization of polyolefin fibers and their use |
| DE102012021742.0 | 2012-11-06 | ||
| PCT/EP2013/072678 WO2014072210A1 (en) | 2012-11-06 | 2013-10-30 | Composition for permanently hydrophilizing polyolefin fibers and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20150292144A1 true US20150292144A1 (en) | 2015-10-15 |
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ID=49518945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US14/439,280 Abandoned US20150292144A1 (en) | 2012-11-06 | 2013-10-30 | Composition for permanently hydrophilizing polyolefin fibers and use thereof |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20150292144A1 (en) |
| EP (1) | EP2917398B1 (en) |
| JP (1) | JP6241829B2 (en) |
| KR (1) | KR102106115B1 (en) |
| CN (1) | CN104903509B (en) |
| DE (1) | DE102012021742A1 (en) |
| DK (1) | DK2917398T3 (en) |
| ES (1) | ES2613880T3 (en) |
| IL (1) | IL238665B (en) |
| MY (1) | MY185896A (en) |
| SA (1) | SA515360388B1 (en) |
| WO (1) | WO2014072210A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170356126A1 (en) * | 2014-12-17 | 2017-12-14 | Kao Corporation | Liquid film cleavage agent |
| US10233589B2 (en) | 2014-12-22 | 2019-03-19 | Schill + Seilacher Gmbh | Composition for the permanent hydrophilic finishing of textile fibers and textile products |
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| DE102014111881A1 (en) | 2014-08-20 | 2016-02-25 | Klaus Schmitt Beteiligungsgesellschaft Mbh | Aqueous waterproofing agent for fabrics of hydrophobic thermoplastic materials and products made therefrom |
| CN105332278B (en) * | 2015-11-26 | 2017-12-05 | 常州市灵达化学品有限公司 | The environmentally friendly multiple hydrophilic finishing agent of polyolefm non-woven cloth |
| CN105316944B (en) * | 2015-11-26 | 2017-10-10 | 常州市灵达化学品有限公司 | The multiple hydrophilizing agent of polyolefm non-woven cloth longtitudinal dispersion type |
| CN105714555A (en) * | 2015-12-28 | 2016-06-29 | 福建恒安集团有限公司 | Polypropylene spunbonded nonwoven after going through surface hydrophilic treatment |
| CN105714561A (en) * | 2015-12-28 | 2016-06-29 | 福建恒安集团有限公司 | Finishing agent of emulsion composition for polypropylene spunbonded nonwoven |
| CN108611852A (en) * | 2018-05-08 | 2018-10-02 | 浙江理工大学 | A kind of ES fibers are without the multiple hydrophilic finish of silicon |
| CN108611697A (en) * | 2018-05-08 | 2018-10-02 | 浙江理工大学 | A kind of multiple hydrophilic finish of ES fibers |
| KR102106060B1 (en) | 2018-06-22 | 2020-04-29 | 한국에너지기술연구원 | Method of hydrophilic surface modification for hydrophobic polylefin and use thereof |
| CN108998889A (en) * | 2018-08-17 | 2018-12-14 | 绩溪袁稻农业产业科技有限公司 | A kind of preparation process of ES hydrophilic fibers non-woven fabrics |
| KR102420139B1 (en) | 2020-10-16 | 2022-07-12 | 도레이첨단소재 주식회사 | Highly absorbent composite fiber, highly absorbent non-woven fabric and article including the non-woven fabric |
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-
2012
- 2012-11-06 DE DE102012021742.0A patent/DE102012021742A1/en not_active Withdrawn
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- 2013-10-30 KR KR1020157013146A patent/KR102106115B1/en not_active Expired - Fee Related
- 2013-10-30 EP EP13786214.0A patent/EP2917398B1/en not_active Not-in-force
- 2013-10-30 WO PCT/EP2013/072678 patent/WO2014072210A1/en not_active Ceased
- 2013-10-30 DK DK13786214.0T patent/DK2917398T3/en active
- 2013-10-30 CN CN201380058160.5A patent/CN104903509B/en not_active Expired - Fee Related
- 2013-10-30 US US14/439,280 patent/US20150292144A1/en not_active Abandoned
- 2013-10-30 MY MYPI2015701324A patent/MY185896A/en unknown
- 2013-10-30 ES ES13786214.0T patent/ES2613880T3/en active Active
- 2013-10-30 JP JP2015540107A patent/JP6241829B2/en not_active Expired - Fee Related
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2015
- 2015-05-05 SA SA515360388A patent/SA515360388B1/en unknown
- 2015-05-06 IL IL238665A patent/IL238665B/en active IP Right Grant
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| US10233589B2 (en) | 2014-12-22 | 2019-03-19 | Schill + Seilacher Gmbh | Composition for the permanent hydrophilic finishing of textile fibers and textile products |
Also Published As
| Publication number | Publication date |
|---|---|
| SA515360388B1 (en) | 2016-02-25 |
| KR20150082329A (en) | 2015-07-15 |
| MY185896A (en) | 2021-06-14 |
| KR102106115B1 (en) | 2020-05-04 |
| IL238665A0 (en) | 2015-06-30 |
| EP2917398B1 (en) | 2016-12-07 |
| EP2917398A1 (en) | 2015-09-16 |
| JP6241829B2 (en) | 2017-12-06 |
| WO2014072210A1 (en) | 2014-05-15 |
| ES2613880T3 (en) | 2017-05-26 |
| CN104903509B (en) | 2018-07-03 |
| JP2015533391A (en) | 2015-11-24 |
| DK2917398T3 (en) | 2017-03-06 |
| DE102012021742A1 (en) | 2014-05-08 |
| CN104903509A (en) | 2015-09-09 |
| IL238665B (en) | 2019-02-28 |
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