US20020028858A1 - Latex binder for nonwoven fibers and article made therewith - Google Patents
Latex binder for nonwoven fibers and article made therewith Download PDFInfo
- Publication number
- US20020028858A1 US20020028858A1 US09/921,241 US92124101A US2002028858A1 US 20020028858 A1 US20020028858 A1 US 20020028858A1 US 92124101 A US92124101 A US 92124101A US 2002028858 A1 US2002028858 A1 US 2002028858A1
- Authority
- US
- United States
- Prior art keywords
- latex
- fibers
- styrene
- monomer mixture
- butadiene
- 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.)
- Granted
Links
- 229920000126 latex Polymers 0.000 title claims abstract description 52
- 239000004816 latex Substances 0.000 title claims abstract description 52
- 239000011230 binding agent Substances 0.000 title claims abstract description 29
- 239000000835 fiber Substances 0.000 title claims description 59
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims abstract description 9
- PLOYJEGLPVCRAJ-UHFFFAOYSA-N buta-1,3-diene;prop-2-enoic acid;styrene Chemical compound C=CC=C.OC(=O)C=C.C=CC1=CC=CC=C1 PLOYJEGLPVCRAJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 6
- 150000003254 radicals Chemical class 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 8
- 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
- 238000009960 carding Methods 0.000 claims description 6
- 239000004753 textile Substances 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920001059 synthetic polymer Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920002972 Acrylic fiber Polymers 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229920006397 acrylic thermoplastic Polymers 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 2
- 230000009286 beneficial effect Effects 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000004744 fabric Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical class C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
-
- 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
-
- 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
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
-
- 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
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/902—Core-shell
Definitions
- the present invention relates to a latex binder for treating nonwoven fibers and a method of manufacture of a personal hygiene article including the latex binder. More particularly, the present invention relates to a latex binder for treating nonwoven fibers to make a nonwoven fabric that is particularly suitable for use as a permeable sublayer of a personal hygiene article.
- a nonwoven fabric is a web or continuous sheet of fibers laid down mechanically.
- the fibers may be deposited in a random manner or oriented in one direction.
- Most widely used fibers include cellulosics, polyamides, polyesters, polypropylene and polyethylene.
- the spun fibers, which may be drawn, are laid down directly onto a belt by carding, airlaying or wet-laying.
- the sheet is then bonded together with a latex binder and subsequently treated in an oven or a calendar to complete the bonding process.
- lattices for nonwoven fabrics are those prepared from polymers of butadiene-styrene, butadiene-acrylonitrile, vinyl acetate, acrylic monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate and the like. It will be appreciated that to be useful as a nonwoven fabric in many applications, such as a permeable sublayer of a personal hygiene article, the latex binder should possess several desired physical properties. The desired physical properties include adequate tensile strength, a high modulus or stiffness under certain conditions, and good textile qualities such as tenacity, handle and the like.
- the present invention relates to a latex that is particularly suitable for utilization as a binder for nonwoven applications.
- the latex is prepared by a process including the steps of:
- the latex is particularly suitable to treat nonwoven fibers to form a permeable sublayer of a personal hygiene article.
- the permeable sublayer is typically interposed between a topsheet layer and a backsheet layer typically used to form the personal hygiene article.
- the permeable sublayer of the personal hygiene article is a web or mat comprised of randomly arranged nonwoven fibers having an open structure and high loft.
- the web may be formed by carding when the fibers are of such a character, by virtue of their length and flexibility, as to be capable of carding.
- the crimped fibers are placed on a moving support and then treated with a latex binder as described herein.
- the fibers may be of one composition or mixtures of fibers in a given web.
- the preferred fibers include polyolefins, especially polyesters, poly(ethylene terephthalate), and acrylics, polyamides, polypropylene.
- the polyolefin fibers include polypropylene, polyethylene, polybutene and their copolymers.
- the polyester fibers include any long chain synthetic polymer composed of at least 85% by weight of an ester of a dihydric alcohol and terephthalic acid such as polyethylene terephthalate, and, in addition liquid crystal polyesters, thermotropic polyesters and the like.
- the acrylic fibers include any fiber forming substance containing a long chain synthetic polymer composed of at least 85% by weight acrylonitrile units —CH 2 CH(CN)—. It will be appreciated that other types of fibers may also be employed in accordance with the teachings of the present invention. For example, high modulus fibers more commonly known as graphite fibers made from rayon, polyacrylonitrile or petroleum pitch may also be used.
- the fibers may be of most any suitable size and randomly arranged to most any suitable thickness depending upon the desired end use of the nonwoven fabric.
- the fibers are typically of a length of about 0.25 to 2 inches and typically about 1.2-15 denier.
- the fibers may be laid in an overlapping, intersecting random arrangement to a thickness of about 0.25 inches or less to form a mat of fibers.
- the fibers may be arranged by most any convenient known manner such as by wet laying, air-laying or carding.
- the fabric of the present invention is made by forming a mat of randomly arranged fibers. After the fibers are randomly arranged as desired, a latex binder is applied to the fibers.
- the latex binder is applied in an effective amount which will result in the fabric having sufficient strength and cohesiveness for the intended end use application.
- the latex binder may be applied to the layer of randomly arranged fibers in a spaced, intermittent pattern of binder sites, or uniformly applied throughout the layer of fibers. It will be further appreciated that the exact amount of the latex binder employed depends, in part, upon factors such as the type of fiber, weight of fibrous layer, nature of latex binder and the like. For example, end uses which require a stronger fabric may utilize more binder.
- a typical content of latex binder applied on a fiber mat is about 15-40 wt %. It is preferred that the minimum amount of latex binder be applied to obtain the desired required physical properties of the nonwoven fabric such as tensile, hand and the like as well known in the art.
- a plurality of webs may also be superimposed upon one another to achieve a sufficient thickness.
- the webs may be superimposed by alternating layers of carded webs disposed with their fiber orientation directions disposed at angles such as 60 degrees or 90 degrees with respect to intervening layers.
- the latex binder utilized in accordance with the present invention may be prepared by well-known conventional emulsion polymerization techniques using one or more ethylenically unsaturated monomers and a polymeric surfactant as herein disclosed and additional conventional additives such as free-radical initiators, optional chain transfer agents, chelating agents and the like can be utilized as set forth in U.S. Pat. No. 5,166,259 to Schmeing and White.
- the monomer mixture also includes about 0.5-2.5 wt % itaconic acid, preferably 2 wt % itaconic acid of the total composition, about 20-55 wt % butadiene and acrylic acid in an amount of about 6-10 wt %, preferably 8 wt %.
- a surfactant is added to the monomer mixture in an amount of about 0.05-2.0 wt %.
- the surfactant may be most any suitable emulsifier, soap, or the like well known in the art and suitable at the pH of the latex in accordance with the present invention.
- suitable emulsifiers and surfactants include alkyl sulfates, alkyl sulfosuccinates, alkyl aryl sulfonates, alpha-olefin sulfonates, fatty or rosin acid salts, only or octyl phenol reaction products of ethylene oxide and the like.
- Other surfactants that may be used include those identified in Surface Active Agents, Schwartz and Berry, Vol.
- the copolymer is then neutralized to a pH of about 4.5 to 7.0 to form the latex.
- the pH of the latex is neutralized by addition of a base.
- a suitable base include potassium hydroxide, sodium bicarbonate, ammonium hydroxide, sodium hydroxide and the like.
- the amount of base added to the latex is adjusted to obtain the desired pH range as is well known in the art.
- Polymerization is typically carried out from about 150 degrees Fahrenheit to 170 degrees Fahrenheit. Polymerization is generally conducted for about 4 to 24 hours, however polymerization conditions may vary as desired to provide different conversion levels of monomer to copolymer. The monomer mixture is allowed to react until substantially constant solids at which time at least 99% of the monomers have been converted.
- a charge comprising styrene, butadiene and acrylic acid was then charged to the reactor sequentially.
- the first increment was added to the reactor approximately 5 minutes after the ammonium persulfate was added. Additional increments were then added to the reactor at staged intervals of about 15 or 20 minutes. The increments may be added over most any suitable number of staged intervals depending upon the amount of latex binder to be polymerized. For example, the increments may be added from 6 stages up to 12 or more stages. After the last increment was added to the reactor the reaction was monitored until the solid level of the latex in the reactor indicated an acceptable conversion level.
- the resulting latex binder was then applied to polyester fibers. After applying the latex binder to the nonwoven fibers the latex binder was oven dried at 212 degrees Fahrenheit to bond the fibers and then cured at 300 degrees Fahrenheit for 1 minute to form a dimensionally stable nonwoven fabric.
- styrene-butadiene latex binder Representative physical properties of the styrene-butadiene latex binder are shown in Table 1. As shown in Table 1, the fibers had a higher hand value and higher dry tensile properties as compared to polyester fibers treated with GenFlo 3060.
- GenFlo 3060 is a styrene butadiene rubber latex commercially available from GenCorp Inc. TABLE 1 GenFlo 3060 Latex Latex content (%) 39.5 39.9 Yellow Index ⁇ 7.6 ⁇ 7.7 Hand Value 44.3 68.8 Cross Direction, dry Tensile (grams) 323 503 Elongation (%) 27 17 TEA 199 206 Cross Direction, wet Tensile (grams) 162 141 Elongation (%) 39 4 TEA 79 10
- the wet tensile measurements were determined in substantially the same manner as the dry tensile measurements except the fabric strip was soaked in water solution for about 30 seconds prior to testing on the Instron.
- the Hand Values are a quantitative measure of the fabric as well known in the textile industry.
- the Hand Values reported are an average value of the readings determined on a Thwing Albert Handle-O-Meter by using a 5 inch square piece of the fabric. The fabric was tested on the Handle-O-Meter in both the Machine and Cross machine directions.
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Abstract
Description
- The present invention relates to a latex binder for treating nonwoven fibers and a method of manufacture of a personal hygiene article including the latex binder. More particularly, the present invention relates to a latex binder for treating nonwoven fibers to make a nonwoven fabric that is particularly suitable for use as a permeable sublayer of a personal hygiene article.
- A nonwoven fabric is a web or continuous sheet of fibers laid down mechanically. The fibers may be deposited in a random manner or oriented in one direction. Most widely used fibers include cellulosics, polyamides, polyesters, polypropylene and polyethylene. The spun fibers, which may be drawn, are laid down directly onto a belt by carding, airlaying or wet-laying. The sheet is then bonded together with a latex binder and subsequently treated in an oven or a calendar to complete the bonding process.
- Commonly used lattices for nonwoven fabrics are those prepared from polymers of butadiene-styrene, butadiene-acrylonitrile, vinyl acetate, acrylic monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate and the like. It will be appreciated that to be useful as a nonwoven fabric in many applications, such as a permeable sublayer of a personal hygiene article, the latex binder should possess several desired physical properties. The desired physical properties include adequate tensile strength, a high modulus or stiffness under certain conditions, and good textile qualities such as tenacity, handle and the like.
- It is an object of the present invention to provide a nonwoven fabric having a high modulus. It is another object of the present invention to provide a nonwoven fabric having desired physical properties. Yet another object of the present invention is to provide a nonwoven fabric of chemically bonded fibers that is simple and economical to manufacture.
- Briefly, the present invention relates to a latex that is particularly suitable for utilization as a binder for nonwoven applications. The latex is prepared by a process including the steps of:
- (1) polymerizing a monomer mixture comprising styrene, itaconic acid, surfactant and water soluble free radical initiator to form a seed;
- (2) sequentially adding equal increments of a monomer mixture of styrene, butadiene and acrylic acid to the seed under emulsion polymerization conditions to form a styrene-butadiene-acrylic acid copolymer; and then
- (3) neutralizing the styrene-butadiene-acrylic acid copolymer to a pH of about 4.5 to 7 to form the latex.
- The latex is particularly suitable to treat nonwoven fibers to form a permeable sublayer of a personal hygiene article. The permeable sublayer is typically interposed between a topsheet layer and a backsheet layer typically used to form the personal hygiene article.
- The present invention relates to a latex suitable for utilization as a binder to chemically bond fibers and form a nonwoven fabric. The nonwoven fabric is particularly suitable for use as a permeable sublayer of a personal hygiene article of a type well known in the art. Examples of personal hygiene articles include diapers, feminine hygiene articles and the like.
- The permeable sublayer of the personal hygiene article is a web or mat comprised of randomly arranged nonwoven fibers having an open structure and high loft. The web may be formed by carding when the fibers are of such a character, by virtue of their length and flexibility, as to be capable of carding. During carding the crimped fibers are placed on a moving support and then treated with a latex binder as described herein.
- The fibers may include natural textile fibers such as jute, sisal, ramie, hemp, and cotton as well as many artificial organic textile fibers or filaments including rayon, those of cellulose esters such as cellulose acetate, vinyl resin fibers such as those of polyvinyl chloride, copolymers of vinyl chloride with vinyl acetate, vinylidene chloride or acrylonitrile, copolymers of acrylonitrile with vinyl chloride, vinyl acetate, methacrylonitrile, vinyl pyridine, polymers and copolymers of olefins such as ethylene and propylene, also condensation polymers such as polyamides or nylon types, polyesters such as ethylene glycol terephthalate polymers and the like.
- The fibers may be of one composition or mixtures of fibers in a given web. The preferred fibers include polyolefins, especially polyesters, poly(ethylene terephthalate), and acrylics, polyamides, polypropylene. The polyolefin fibers include polypropylene, polyethylene, polybutene and their copolymers. The polyester fibers include any long chain synthetic polymer composed of at least 85% by weight of an ester of a dihydric alcohol and terephthalic acid such as polyethylene terephthalate, and, in addition liquid crystal polyesters, thermotropic polyesters and the like. The acrylic fibers include any fiber forming substance containing a long chain synthetic polymer composed of at least 85% by weight acrylonitrile units —CH2CH(CN)—. It will be appreciated that other types of fibers may also be employed in accordance with the teachings of the present invention. For example, high modulus fibers more commonly known as graphite fibers made from rayon, polyacrylonitrile or petroleum pitch may also be used.
- The fibers may be of most any suitable size and randomly arranged to most any suitable thickness depending upon the desired end use of the nonwoven fabric. The fibers are typically of a length of about 0.25 to 2 inches and typically about 1.2-15 denier. The fibers may be laid in an overlapping, intersecting random arrangement to a thickness of about 0.25 inches or less to form a mat of fibers. The fibers may be arranged by most any convenient known manner such as by wet laying, air-laying or carding.
- The fabric of the present invention is made by forming a mat of randomly arranged fibers. After the fibers are randomly arranged as desired, a latex binder is applied to the fibers. The latex binder is applied in an effective amount which will result in the fabric having sufficient strength and cohesiveness for the intended end use application. As well known in the art, the latex binder may be applied to the layer of randomly arranged fibers in a spaced, intermittent pattern of binder sites, or uniformly applied throughout the layer of fibers. It will be further appreciated that the exact amount of the latex binder employed depends, in part, upon factors such as the type of fiber, weight of fibrous layer, nature of latex binder and the like. For example, end uses which require a stronger fabric may utilize more binder. A typical content of latex binder applied on a fiber mat is about 15-40 wt %. It is preferred that the minimum amount of latex binder be applied to obtain the desired required physical properties of the nonwoven fabric such as tensile, hand and the like as well known in the art.
- The latex is then cured using methods well known in the art such as by application of heat or radiation. The term “cured” refers to the latex being cross-linked to increase the tensile strength properties. The curing of the treated fibers is affected at a temperature above the glass transition temperature of the binder.
- To obtain a sufficient thickness for the end use intended a plurality of webs may also be superimposed upon one another to achieve a sufficient thickness. The webs may be superimposed by alternating layers of carded webs disposed with their fiber orientation directions disposed at angles such as 60 degrees or 90 degrees with respect to intervening layers.
- The latex binder utilized in accordance with the present invention may be prepared by well-known conventional emulsion polymerization techniques using one or more ethylenically unsaturated monomers and a polymeric surfactant as herein disclosed and additional conventional additives such as free-radical initiators, optional chain transfer agents, chelating agents and the like can be utilized as set forth in U.S. Pat. No. 5,166,259 to Schmeing and White.
- In accordance with a preferred embodiment of the present invention, the latex is prepared by polymerizing a monomer mixture comprising styrene, itaconic acid, surfactant and a water soluble free radical initiator to form a seed. A monomer mixture is then added incrementally to the seed under emulsion polymerization conditions. The monomer mixture includes styrene, butadiene, and acrylic acid. The monomer mixture is preferably added incrementally to the seed to form a styrene-butadiene-acrylic acid copolymer. In the preferred embodiment, the monomer mixture includes about 34-70 wt % styrene of the total composition. The monomer mixture also includes about 0.5-2.5 wt % itaconic acid, preferably 2 wt % itaconic acid of the total composition, about 20-55 wt % butadiene and acrylic acid in an amount of about 6-10 wt %, preferably 8 wt %.
- A surfactant is added to the monomer mixture in an amount of about 0.05-2.0 wt %. The surfactant may be most any suitable emulsifier, soap, or the like well known in the art and suitable at the pH of the latex in accordance with the present invention. Examples of suitable emulsifiers and surfactants include alkyl sulfates, alkyl sulfosuccinates, alkyl aryl sulfonates, alpha-olefin sulfonates, fatty or rosin acid salts, only or octyl phenol reaction products of ethylene oxide and the like. Other surfactants that may be used include those identified in Surface Active Agents, Schwartz and Berry, Vol. 1, Interscience Publishers, Inc., New York, 1958; Surface Activity, Moilet, Collie and Black, D. Van Nostrand Company, Inc., New York, 1961; Organic Chemistry, Feiser and Feiser, D.C. Heath and Company, Boston, 1944; and The Merck Index, Seventh Edition, Merck & Co., Inc., Rahway, N.J., 1960, all of which are hereby incorporated by reference.
- The copolymer is then neutralized to a pH of about 4.5 to 7.0 to form the latex. The pH of the latex is neutralized by addition of a base. Examples of a suitable base include potassium hydroxide, sodium bicarbonate, ammonium hydroxide, sodium hydroxide and the like. The amount of base added to the latex is adjusted to obtain the desired pH range as is well known in the art.
- Polymerization is typically carried out from about 150 degrees Fahrenheit to 170 degrees Fahrenheit. Polymerization is generally conducted for about 4 to 24 hours, however polymerization conditions may vary as desired to provide different conversion levels of monomer to copolymer. The monomer mixture is allowed to react until substantially constant solids at which time at least 99% of the monomers have been converted.
- The invention will be further clarified by a consideration of the following example, which is intended to be purely exemplary of the invention.
- Initially, a charge of deionized water, styrene and itaconic acid, and water soluble free radical initiator were added to a reactor having a volume of about 20 gallons and having a capacity to hold about 140 lb. of latex. The reactor was then evacuated with a vacuum (about 20 inches of mercury), purged with nitrogen and heated to a desired temperature. Ammonium persulfate was then added to the reactor as about a 10% solution in deionized water.
- A charge comprising styrene, butadiene and acrylic acid was then charged to the reactor sequentially.
- The first increment was added to the reactor approximately 5 minutes after the ammonium persulfate was added. Additional increments were then added to the reactor at staged intervals of about 15 or 20 minutes. The increments may be added over most any suitable number of staged intervals depending upon the amount of latex binder to be polymerized. For example, the increments may be added from 6 stages up to 12 or more stages. After the last increment was added to the reactor the reaction was monitored until the solid level of the latex in the reactor indicated an acceptable conversion level.
- The resulting latex binder was then applied to polyester fibers. After applying the latex binder to the nonwoven fibers the latex binder was oven dried at 212 degrees Fahrenheit to bond the fibers and then cured at 300 degrees Fahrenheit for 1 minute to form a dimensionally stable nonwoven fabric.
- Representative physical properties of the styrene-butadiene latex binder are shown in Table 1. As shown in Table 1, the fibers had a higher hand value and higher dry tensile properties as compared to polyester fibers treated with GenFlo 3060. GenFlo 3060 is a styrene butadiene rubber latex commercially available from GenCorp Inc.
TABLE 1 GenFlo 3060 Latex Latex content (%) 39.5 39.9 Yellow Index −7.6 −7.7 Hand Value 44.3 68.8 Cross Direction, dry Tensile (grams) 323 503 Elongation (%) 27 17 TEA 199 206 Cross Direction, wet Tensile (grams) 162 141 Elongation (%) 39 4 TEA 79 10 - All of the reported performance properties were determined after conditioning the fibers for about 24 hours at TAPPI (Technical Association of the Pulp and Paper Industry) Standard Conditions of approximately 72 degrees Fahrenheit and about 50% relative humidity. The tensile values, both dry and wet, were determined in accordance with ASTM D 1117-80 entitled “Standard Methods of Testing Nonwoven Fabrics” published in the 1980 Annual Book of ASTM Standards. Following the ASTM standard test method, dry tensile measurements were determined by using 1 inch wide and 4 inch long strips of fabric pulled at a rate of 5 inches per minute at an initial jaw separation of about 3 inches on an Instron. The wet tensile measurements were determined in substantially the same manner as the dry tensile measurements except the fabric strip was soaked in water solution for about 30 seconds prior to testing on the Instron. The Hand Values are a quantitative measure of the fabric as well known in the textile industry. The Hand Values reported are an average value of the readings determined on a Thwing Albert Handle-O-Meter by using a 5 inch square piece of the fabric. The fabric was tested on the Handle-O-Meter in both the Machine and Cross machine directions.
- The patents and documents referred to herein are hereby incorporated by reference.
- Having described presently preferred embodiments of the present invention, it is to be understood that it may be otherwise embodied within the scope of the appended claims.
Claims (18)
Priority Applications (3)
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US10/854,690 US6987153B2 (en) | 1999-08-05 | 2004-05-26 | Latex binder for nonwoven fibers and article made therewith |
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US20030105190A1 (en) | 1999-08-05 | 2003-06-05 | Diehl David F. | Latex binder for nonwoven fibers and article made therewith |
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US6337359B1 (en) | 2002-01-08 |
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