US20160273140A1 - Flexible non-woven mat - Google Patents
Flexible non-woven mat Download PDFInfo
- Publication number
- US20160273140A1 US20160273140A1 US15/029,665 US201415029665A US2016273140A1 US 20160273140 A1 US20160273140 A1 US 20160273140A1 US 201415029665 A US201415029665 A US 201415029665A US 2016273140 A1 US2016273140 A1 US 2016273140A1
- Authority
- US
- United States
- Prior art keywords
- woven mat
- weight percent
- fibers
- woven
- mat according
- 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.)
- Abandoned
Links
- 239000011230 binding agent Substances 0.000 claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 67
- 239000000835 fiber Substances 0.000 claims abstract description 59
- 239000003365 glass fiber Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 18
- 239000012209 synthetic fiber Substances 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 36
- 239000010440 gypsum Substances 0.000 claims description 26
- 229910052602 gypsum Inorganic materials 0.000 claims description 26
- 229920001187 thermosetting polymer Polymers 0.000 claims description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 19
- 239000012815 thermoplastic material Substances 0.000 claims description 19
- 239000007822 coupling agent Substances 0.000 claims description 16
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 16
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 9
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
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- 239000002216 antistatic agent Substances 0.000 claims description 2
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- 239000003921 oil Substances 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 18
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- 229920002125 Sokalan® Polymers 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004584 polyacrylic acid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920005594 polymer fiber Polymers 0.000 description 6
- 230000002787 reinforcement Effects 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 4
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- 239000011159 matrix material Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
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- 230000003389 potentiating effect Effects 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- 241001599832 Agave fourcroydes Species 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 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
- 239000004593 Epoxy Substances 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GSFXLBMRGCVEMO-UHFFFAOYSA-N [SiH4].[S] Chemical class [SiH4].[S] GSFXLBMRGCVEMO-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical class [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- WIJVUKXVPNVPAQ-UHFFFAOYSA-N silyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)O[SiH3] WIJVUKXVPNVPAQ-UHFFFAOYSA-N 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical class NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
- D04H1/42—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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4218—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B13/00—Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material
- B32B13/14—Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
-
- 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
- D04H1/42—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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
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- 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
- D04H1/54—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 welding together the fibres, e.g. by partially melting or dissolving
- D04H1/542—Adhesive fibres
- D04H1/544—Olefin series
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- 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
- D04H1/54—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 welding together the fibres, e.g. by partially melting or dissolving
- D04H1/542—Adhesive fibres
- D04H1/546—Polyvinyl acetate
-
- 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
- D04H1/54—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 welding together the fibres, e.g. by partially melting or dissolving
- D04H1/542—Adhesive fibres
- D04H1/55—Polyesters
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- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/14—Polyalkenes, e.g. polystyrene polyethylene
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/24—Polyesters
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- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/38—Inorganic fibres or flakes siliceous
- D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
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- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/13—Silicon-containing compounds
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- 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
-
- 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
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Definitions
- the present invention relates to non-woven fiber mats with improved flexibility, and methods of manufacturing a non-woven fiber mat with improved flexibility, for the preparation of reinforced articles.
- Non-woven mats include a fibrous web bound together by a suitable resinous binder.
- Reinforcement fibers such as glass fibers, are useful in a variety of technologies, and may be used in the form of continuous or chopped filaments, strands, rovings, woven fabrics, nonwoven fabrics, meshes, and scrims, such as to reinforce polymers.
- Reinforced polymeric composites can be formed in a variety of ways from a polymeric matrix material, reinforcing material, and any other components. Such composites are formed using reinforcement fibers which provide dimensional stability and excellent mechanical properties to the resulting composites.
- glass fibers provide dimensional stability as they generally do not shrink or stretch in response to changes in atmospheric conditions. Further, glass fibers have high tensile strength, heat resistance, moisture resistance, and high thermal conductivity.
- Non-woven fiber mats are commonly used in pultrusion processes to form pultruded parts.
- pultrusion involves impregnating fiber mats with a suitable resin material and passing the impregnated mat through a heated die. By passing the impregnated and consolidated mat through the heated die, the mat may be formed into a desired shaped and resin is cured to hold the mat together. The composite part exiting the heated die is then cut to a desired length.
- the continuous nature of the pultrusion process advantageously enables composites of any desired length to be produced.
- problems associated with the pultrusion process One problem lies within the resin bath.
- Thermoset resins are often used, which generally require the use of volatile unsaturated monomers such as styrene and/or methyl methacrylate.
- Styrene is a potent solvent, and can easily swell and degrade a binder applied to the reinforcement mat. Such degradation of the binder can cause the fiber mat to weaken and be unable to withstand the strong pulling forces encountered in the pultrusion process.
- continuous filament mats are flexible, conformable, and have an excellent resistance to styrene, they possess several drawbacks. For instance, continuous filament mats are expensive to manufacture because fabrication of the continuous filament mats occurs at a slow rate, such as, 50-75 feet per minute (fpm). Additionally, the utilization of continuous filament mats yields laminates that have a poor surface finish due to the long strands of glass that form the mats. Further, continuous filament mats are dense and add increased weight to the final part, which may be an undesirable feature.
- chopped strand mats are less expensive to manufacture than continuous filament mats because fabrication occurs at a faster rate (that is, 500-1500 fpm). Additionally, chopped strand mats are essentially fully dispersed fibers, which give the pultruded part a smoother appearance than continuous filament mats. In addition, chopped strand mats are advantageously “space filling” without adding a lot of weight to the laminate. Despite these positive attributes, chopped strand mats can be very stiff with thermoset binders and therefore difficult to form into complex shapes. Additionally, the stiffness of the chopped strand mats causes a feel that may be undesirable to customers.
- the physical properties of a non-woven chopped strand mat are improved by formulating a binder composition with excellent tensile strength coupled with good flexibility for use in combination with proper fiber design.
- a flexible non-woven chopped strand mat that includes a mixture of about 10 to about 100 weight percent glass fibers and about 0 to about 90 weight percent synthetic fibers.
- the non-woven chopped strand mat further includes a binder composition comprising a binder resin and a silane coupling agent.
- the synthetic fibers include at least one of polypropylene, polyester, and a combination thereof.
- the binder resin includes at least one of a thermoset material, a thermoplastic material, or a combination thereof.
- a thermoset material for example, a mixture of one or more of an acrylic material, a urea formaldehyde material, or a combination thereof, with ethylene vinyl acetate.
- Some exemplary embodiments of the present invention include a binder resin having about 50 to 100 weight percent thermoplastic material and 0 to about 50 weight percent thermoset material.
- the binder composition used in the flexible non-woven mats is resistant to styrene monomers.
- the flexible non-woven chopped strand mat has an average machine direction tensile strength of at least 30 lb in the machine direction and at least 20 lb in the cross direction.
- machine direction it is meant the direction that coincides with the direction the mat moves during manufacture.
- the mat may further have a MD (machine direction) Gurley stiffness of about 2000 to about 7000 milligrams of force (mgf), measured by a Gurley Stiffness tester.
- a pultruded composite product in various exemplary embodiments of the present invention, includes a plurality of rovings impregnated with a thermosetting resin and a flexible non-woven chopped strand mat.
- Various exemplary aspects of the flexible non-woven mat include a mixture of about 10 to about 95 weight percent glass fibers and about 5 to about 90 weight percent synthetic fibers.
- the non-woven chopped strand mat further includes a binder composition that includes a binder resin and a silane coupling agent.
- the binder resin may include at least one of a thermoset material, a thermoplastic material, or a combination thereof.
- a thermoset material for example, a mixture of one or more of an acrylic material, a urea formaldehyde material, or a combination thereof, along with a ethylene vinyl acetate.
- Some exemplary embodiments of the binder resin include about 50 to 100 weight percent thermoplastic material and 0 to about 50 weight percent thermoset material.
- a gypsum wall board in yet other exemplary embodiments of the present invention, includes a gypsum core and at least one flexible non-woven mat.
- Some exemplary embodiments of the flexible non-woven chopped strand mat include a mixture of about 10 to about 95 weight percent glass fibers and about 5 to about 90 weight percent synthetic fibers.
- the non-woven mat further includes a binder composition that includes a binder resin and a silane coupling agent.
- the general inventive concepts relate to a flexible non-woven chopped strand mat (generally, the non-woven mat) with improved properties.
- the flexible non-woven mat demonstrates improved mechanical strength, such as high machine direction tensile strength and cross-direction tensile strength, while also showing improved flexibility.
- the softness and flexibility of the inventive non-woven mats improves downstream processes, for example, the formation of pultruded products having complex shapes and/or the production of gypsum wall boards.
- the inventive flexible non-woven mats are resistant to styrene and polyester that may be present in resin formulations utilized in pultrusion processes.
- Some exemplary embodiments of the present invention relate to a flexible non-woven mat which may be utilized in various downstream processes, for example, in pultrusion processes and in gypsum wallboard formation.
- the non-woven mat is characterized by a number of attributes including very good flexibility, For instance, in some exemplary embodiments, the non-woven mats demonstrate a reduced stiffness of less than 6000 mgf, or less than 5000 mgf. This stiffness level is greatly reduced from conventional non-woven mats with stiffnesses around 7000 mgf.
- the flexible non-woven mats of the present invention may comprise a plurality of fibers, including any of glass fibers, synthetic fibers, or a blend thereof.
- the glass fibers can be made from any type of glass. Examples of glass fibers include A-type glass fibers, C-type glass fibers, E-type glass fibers, S-type glass fibers, ECR-type glass fibers (e.g., Advantex® glass fibers commercially available from Owens Corning), Hiper-texTM, wool glass fibers, and combinations thereof.
- Advantex® glass fibers commercially available from Owens Corning
- Hiper-texTM wool glass fibers
- the use of other reinforcing fibers such as mineral fibers, carbon fibers, ceramic fibers, natural fibers, and/or synthetic fibers in the non-woven mat is also considered to be within the purview of the general inventive concepts.
- natural fiber refers to plant fibers extracted from any part of a plant, including, but not limited to, the stem, seeds, leaves, roots, or phloem.
- natural fibers which may be suitable for use as the reinforcing fiber material include basalt, cotton, jute, bamboo, ramie, bagasse, hemp, coir, linen, kenaf, sisal, flax, henequen, and combinations thereof.
- synthetic fibers as used herein is meant to indicate any man-made fiber having suitable reinforcing characteristics, such as polyester, polyethylene, polyethylene terephthalate, polypropylene, polyamide, aramid, and polyaramid fibers, and combinations thereof.
- the fibers used to form the non-woven mats according to the present invention include a blend of glass fibers and synthetic resin fibers, such as polymer fibers.
- the polymer fibers include those made from polypropylene, polyester, or a combination thereof.
- the polymer fibers are formed from polyethylene terephthalate (PET).
- the fibers used to form the non-woven mats according to the present invention include a blend of about 10 to about 100 percent by weight glass fibers and about 0 to about 90 percent by weight polymer fibers. In other exemplary embodiments, the fibers include a blend of about 50 to about 90 percent by weight glass fibers and about 10 to about 50 percent by weight polymer fibers, or from about 75 to about 90 percent by weight glass fibers and about 10 to 25 percent by weight polymer fibers.
- the glass fibers may be formed by conventional methods known to those skilled in the art.
- the glass fibers may be formed by a continuous manufacturing process in which molten glass passes through the holes of a “bushing,” the streams of molten glass thereby formed are solidified into filaments, and the filaments are combined together to form a fiber, “roving,” “strand,” or the like.
- an aqueous sizing composition (also referred to as a size) may optionally be applied to the fibers.
- the sizing composition is not limited, and may be any sizing known to those of skill in the art.
- sizing compositions contain a lubricant to protect the fibers from damage by abrasion, a film-forming resin to help bond the fibers to the polymer forming the body or matrix of the composite in which the fibers will be used, and a coupling agent to improve the adhesion of the film-forming resin to the surfaces of the glass fibers.
- the sizing composition may be applied by conventional methods such as by an application roller or by spraying the size directly onto the fibers.
- the size protects the glass fibers from breakage during subsequent processing, helps to retard interfilament abrasion, ensures the integrity of the strands of glass fibers, promotes the interconnection of the glass filaments that form the strand, etc.
- the glass fibers may be chopped and packaged as chopped strand glass for subsequent processing into a wet-laid, non-woven mat as described below.
- the chopped fibers may have a length from about 0.5 to about 2.0 inches, or from about 1.0 to about 1.5 inches.
- the chopped fibers may have varying lengths from each other within the non-woven mat.
- the fibers may have a diameter from about 5 microns to about 20 microns, or from about 10 microns to about 16 microns.
- the chopped fibers may have varying lengths from each other within the non-woven mat.
- the fibers may be of uniform length and/or diameter, or the fibers may have a variety of lengths and diameters, such as desired for a particular application.
- the flexible non-woven mat may be framed by a variety of processes, including dry-laid and wet-laid processes.
- the non-woven mat is formed by a wet-laid process, which involves forming an aqueous dispersion or slurry of discrete fibers in a mix tank filled with various components (sometimes referred to as white water), such as water, surfactants, viscosity modifiers, defoaming agents, lubricants, biocides, and/or other chemical agents, along with agitation, to form a chopped glass fiber slurry. It is desirable that the slurry is agitated sufficiently to provide a uniform or nearly uniform dispersion of fibers.
- the aqueous fiber dispersion or slurry may then be processed into a wet-laid mat according to any number of conventional methods known in the art.
- the aqueous fiber slurry is deposited onto a moving screen or conveyor, on which the majority of the water drains through, leaving a randomly oriented fiber web.
- the fiber web may be further dried by a vacuum slot or other drying means.
- a binder composition may then be applied to the fiber web in a conventional manner, such as by curtain coating, spraying, a twin wire dip bath, a two roll padder, and the like. Water, excess binder, and excess coupling agent may then be removed by a vacuum or other water removal means. Finally, the binder-coated fiber product may be dried and cured in one or more ovens. An exemplary temperature range for drying is from about 350° F. (218° C.) to about 600° F. (304° C.). The dried and cured product is the finished non-woven flexible mat.
- the binder composition is formulated such that once the binder is cured, it is able to impart very good mechanical strength (total tensile strength of at least 80 lbs), flexibility (Gurley stiffness of less than 5000 mgf), and solvent resistance (styrene retention of at least 60%).
- the binder composition comprises a binder resin material, a coupling agent, and one or more optional additives.
- the binder resin may be a thermoset material, a thermoplastic material, or a mixture of thermoset and thermoplastic materials.
- the thermoset material may comprise, for example, an acrylic material, a urea formaldehyde material, or a combination of the two materials.
- the acrylic material is polyacrylic acid, such as low molecular weight polyacrylic acid with a molecular weight at or below 10,000. The thermoset material, once cross-linked under proper curing conditions, provides good tensile performance and solvent resistance, helping maintain mat integrity in different applications.
- the thermoplastic material may include any thermoplastic material having a low Tg (i.e., below ⁇ 15° C.), for example, ethylene vinyl acetate (“EVA”).
- EVA ethylene vinyl acetate
- the EVA comprises Dur-O-Set® E-646.
- the thermoplastic material is self cross-linking and can provide the softness needed for flexible mats.
- binder compositions that incorporates resins with differing functionalities (e.g., thermoset and thermoplastic) may impart improved properties to a fiber reinforced mat.
- the combination of such properties may allow the non-woven mats to be used in challenging applications, such as in pultrusion applications, as a replacement for continuous filament mats.
- Some exemplary binder compositions include about 0 to about 50 percent by weight thermoset material, such as polyacrylic acid and about 50 to about 100 percent by weight thermoplastic material, such as EVA.
- the binder composition comprises about 15 to about 30 percent by weight polyacrylic acid and about 70 to about 85 percent by weight EVA.
- the binder resin may be present in the binder composition in an amount from about 90 percent to about 99 percent by weight of the total binder composition, and in exemplary embodiments, from about 97 percent to about 99 percent by weight.
- percent by weight and “percent by weight of the composition” are meant to denote percent by weight of the total components of the composition.
- the binder composition may further include a coupling agent.
- a coupling agent may be present in the binder composition in an amount from about 0.05 percent to about 10.0 percent by weight of the total binder composition, and in other exemplary embodiments, in an amount from about 0.1 percent to about 3.0 percent by weight.
- Various exemplary embodiments include about 0.2 percent by weight of a coupling agent.
- coupling agents also function to reduce the level of fuzz, or broken fiber filaments, during subsequent processing.
- At least one of the coupling agents is a silane coupling agent.
- Suitable silane coupling agents may include silanes containing one or more nitrogen atoms that have one or more functional groups such as amine (primary, secondary, tertiary, and quaternary), amino, imino, amido, imido, ureido, or isocyanato.
- Suitable silane coupling agents may also include, but are not limited to, aminosilanes, silane esters, vinyl silanes, methacryloxy silanes, epoxy silanes, sulfur silanes, ureido silanes, and isocyanato silanes.
- the binder composition may optionally include additional components, for example, dyes, oils, fillers, colorants, aqueous dispersions, UV stabilizers, lubricants, wetting agents, surfactants, viscosity modifiers, and/or antistatic agents.
- the aqueous dispersions may include antioxidant dispersions, which counter the effects of oxidation by the binder composition due to aging.
- One exemplary antioxidant dispersion includes Bostex 537, from Akron Dispersions, Inc.
- the antioxidant dispersion may be included in amounts from 0 to about 5 percent by weight, or from about 0.5 to about 3 percent by weight. Some exemplary embodiments include about 1.8 percent by weight of an antioxidant dispersion.
- Additives may be included in the binder composition in an amount of about 0.0 percent to about 10 percent by weight of the binder composition.
- the binder composition further includes water to dissolve or disperse the components for application onto the reinforcement fibers.
- Water may be added in an amount sufficient to dilute the aqueous binder composition to a viscosity that is suitable for its application to the reinforcement fibers.
- the binder composition may contain from about 50 percent to about 75 percent by weight of the binder composition of water.
- the bonded mats of the present invention may have an average thickness of between about 25 and 75 millimeters, or from about 30 to about 60 millimeters.
- the binder Once the binder is cured, it imparts additional features, such as improved mechanical strength (e.g., in both the machine and cross-direction tensile strengths), flexibility, and solvent resistance.
- the flexible non-woven mats have an average tensile strength of at least 30 lb in the machine direction and at least 20 lb in the cross direction. In some exemplary embodiments, the flexible non-woven mats have a machine direction tensile strength of at least 50 lb and a cross-direction tensile strength of at least 30 lb. The flexible non-woven mats may further have a total tensile strength (machine direction+cross-direction) of at least 50 lb, or at least 80 lb.
- the non-woven mats have improved flexibility, which may be measured using a Gurley stiffness tester.
- the non-woven mat has a Gurley stiffness of about 2000 to about 7000 mgf, or from about 2500 to about 6000 mgf, and in other exemplary embodiments, less than 5000 mgf.
- the flexible non-woven mats may be used in a variety of downstream processes to form a variety of end products.
- the flexible non-woven mat is used to form a composite product through a pultrusion process.
- the pultrusion process includes feeding rovings and at least one non-woven mat into a thermosetting resin bath where the rovings are moved over spreader bars which aid in impregnating the resin into the fibers.
- the rovings may be made from glass, graphite, boron, polyaramid fibers, or other similar fibers.
- the roving is made from glass fibers.
- the rovings and the non-woven mat exit the resin bath and are pre-formed by a pre-former into a shape or profile prior to entering a heated molding die.
- the rovings and non-woven mat, which have the pre-formed shape, are then cured into the desired form of the composite by heating continuously as the part passes through the heated molding die.
- a pair of caterpillar rollers may be used to pull the rovings and mat through the bath, pre-former, and /or heated die.
- the composite part exiting the heated die is then cut to a desired length by a cutting apparatus.
- the fibers of the continuous roving are impregnated with a polymer resin, the mat is coated with the polymer resin, and the fibers and mat are shaped into the form of the composite and cut to form a pultruded part.
- the rovings impart a longitudinal tensile strength and the non-woven mat imparts a transverse tensile strength to the pultruded part.
- the binder composition provides improved resistance to styrene monomers commonly found in thermosetting resins used in pultrusion processes. This enhanced resistance to styrene makes the inventive flexible mats more suitable for pultrusion processes.
- styrene monomers are a potent solvent and can act to swell and degrade the binder, thereby weakening the continuity of the mat.
- the flexible non-woven mats may also be used in other processes, such as, for example, the production of gypsum wall boards and/or gypsum panels frequently used in building construction.
- Wall boards formed of a gypsum core sandwiched between facing layers are commonly used in the construction industry as internal walls and ceilings for both residential and commercial buildings.
- the gypsum core typically contains gypsum, optionally some wet chopped glass fibers, water resistant chemicals, binders, accelerants, and low-density fillers. It is known in the art to form gypsum boards by providing a continuous layer of a facing material, such as a fibrous veil, and depositing a gypsum slurry onto one surface of the facing material.
- a second continuous layer of facing material is then applied to the opposite surface of the gypsum slurry.
- the gypsum slurry is sandwiched between opposing layers of facing material.
- the sandwiched gypsum slurry is then adjusted to a desired thickness and dried to harden the gypsum core and form a gypsum board.
- the gypsum board may be cut to predetermined dimensions (e.g., length) for end use. Glass fibers are commonly used in the production of gypsum wall boards to improve the tensile and tear strength of the products.
- the flexible non-woven mats may be used as the facings in a gypsum wall board to provide increased dimensional stability in the presence of moisture, increased biological resistance, increased air permeability, and greater physical and mechanical properties, such as better strength and durability, than conventional gypsum boards faced with paper or other cellulosic facing materials.
- Three non-woven mats were made by a conventional wet laid coating process in which chopped glass fibers, after being deposited onto a moving screen in the form of an aqueous slurry, were coated with an aqueous dispersion of a binder composition and then dried and cured.
- Each mat was made with 1.25′′ M fiber (16 micrometer diameter) with the same loss on ignition (LOI) and base weight.
- the binder composition applied to each mat included a varied ratio of thermoplastic/thermoset components.
- the binder of the first mat include 100 percent polyacrylic acid
- the binder of the second mat included 75 percent polyacrylic acid and 25 percent ethylene vinyl acetate
- the binder of the third mat included 50 percent polyacrylic acid and 50 percent ethylene vinyl acetate.
- Each composition was cured at 485° F.
- the fiberglass mats so obtained were then tested for max bending strength and Gurley stiffness, to determine the bending resistance/stiffness of the mat.
- the flexibility of a non-woven mat improves with an increase in the amount of EVA in the binder composition.
- flexible mats may be made with Gurley stiffnesses less than 7000 mgf, and 50 weight parent EVA in the binder composition, non-woven mats may be produced with Gurley stiffnesses of less than 5000 mgf.
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Abstract
Description
- The present application claims the benefit of provisional patent application No. 61/891,564, filed Oct. 16, 2013, titled “Flexible Non-Woven Mat” which is incorporated herein by reference.
- The present invention relates to non-woven fiber mats with improved flexibility, and methods of manufacturing a non-woven fiber mat with improved flexibility, for the preparation of reinforced articles.
- Conventional non-woven mats include a fibrous web bound together by a suitable resinous binder. Reinforcement fibers, such as glass fibers, are useful in a variety of technologies, and may be used in the form of continuous or chopped filaments, strands, rovings, woven fabrics, nonwoven fabrics, meshes, and scrims, such as to reinforce polymers. Reinforced polymeric composites can be formed in a variety of ways from a polymeric matrix material, reinforcing material, and any other components. Such composites are formed using reinforcement fibers which provide dimensional stability and excellent mechanical properties to the resulting composites.
- For example, glass fibers provide dimensional stability as they generally do not shrink or stretch in response to changes in atmospheric conditions. Further, glass fibers have high tensile strength, heat resistance, moisture resistance, and high thermal conductivity.
- Non-woven fiber mats are commonly used in pultrusion processes to form pultruded parts. Generally, pultrusion involves impregnating fiber mats with a suitable resin material and passing the impregnated mat through a heated die. By passing the impregnated and consolidated mat through the heated die, the mat may be formed into a desired shaped and resin is cured to hold the mat together. The composite part exiting the heated die is then cut to a desired length.
- The continuous nature of the pultrusion process advantageously enables composites of any desired length to be produced. However, there are numerous problems associated with the pultrusion process. One problem lies within the resin bath. Thermoset resins are often used, which generally require the use of volatile unsaturated monomers such as styrene and/or methyl methacrylate. Styrene is a potent solvent, and can easily swell and degrade a binder applied to the reinforcement mat. Such degradation of the binder can cause the fiber mat to weaken and be unable to withstand the strong pulling forces encountered in the pultrusion process.
- Both continuous filament mats and chopped strand mats coated with a binder may be used in the pultrusion process. Although continuous filament mats are flexible, conformable, and have an excellent resistance to styrene, they possess several drawbacks. For instance, continuous filament mats are expensive to manufacture because fabrication of the continuous filament mats occurs at a slow rate, such as, 50-75 feet per minute (fpm). Additionally, the utilization of continuous filament mats yields laminates that have a poor surface finish due to the long strands of glass that form the mats. Further, continuous filament mats are dense and add increased weight to the final part, which may be an undesirable feature.
- In contrast, chopped strand mats are less expensive to manufacture than continuous filament mats because fabrication occurs at a faster rate (that is, 500-1500 fpm). Additionally, chopped strand mats are essentially fully dispersed fibers, which give the pultruded part a smoother appearance than continuous filament mats. In addition, chopped strand mats are advantageously “space filling” without adding a lot of weight to the laminate. Despite these positive attributes, chopped strand mats can be very stiff with thermoset binders and therefore difficult to form into complex shapes. Additionally, the stiffness of the chopped strand mats causes a feel that may be undesirable to customers.
- Therefore, a need exists for a non-woven mat that is flexible enough to be formed into complex shapes, is compatible with the matrix resin, and is lightweight yet has sufficient strength properties such that it can be used satisfactorily in downstream processing, such as pultrusion and the formation of gypsum wall boards.
- In some exemplary embodiments of the present invention, the physical properties of a non-woven chopped strand mat are improved by formulating a binder composition with excellent tensile strength coupled with good flexibility for use in combination with proper fiber design.
- In various exemplary embodiments of the present invention, a flexible non-woven chopped strand mat is provided that includes a mixture of about 10 to about 100 weight percent glass fibers and about 0 to about 90 weight percent synthetic fibers. The non-woven chopped strand mat further includes a binder composition comprising a binder resin and a silane coupling agent.
- In accordance with further exemplary embodiments of the present invention, it has been found that the synthetic fibers include at least one of polypropylene, polyester, and a combination thereof.
- In accordance with various exemplary embodiments of the present invention, the binder resin includes at least one of a thermoset material, a thermoplastic material, or a combination thereof. Some exemplary embodiments include a mixture of thermoset and thermoplastic materials, for example, a mixture of one or more of an acrylic material, a urea formaldehyde material, or a combination thereof, with ethylene vinyl acetate. Some exemplary embodiments of the present invention include a binder resin having about 50 to 100 weight percent thermoplastic material and 0 to about 50 weight percent thermoset material.
- In accordance with various exemplary embodiments of the present invention, the binder composition used in the flexible non-woven mats is resistant to styrene monomers.
- In some exemplary embodiments, the flexible non-woven chopped strand mat has an average machine direction tensile strength of at least 30 lb in the machine direction and at least 20 lb in the cross direction. By ‘machine direction” it is meant the direction that coincides with the direction the mat moves during manufacture. The mat may further have a MD (machine direction) Gurley stiffness of about 2000 to about 7000 milligrams of force (mgf), measured by a Gurley Stiffness tester.
- In various exemplary embodiments of the present invention, a pultruded composite product is provided. The pultruded composite product includes a plurality of rovings impregnated with a thermosetting resin and a flexible non-woven chopped strand mat. Various exemplary aspects of the flexible non-woven mat include a mixture of about 10 to about 95 weight percent glass fibers and about 5 to about 90 weight percent synthetic fibers. The non-woven chopped strand mat further includes a binder composition that includes a binder resin and a silane coupling agent.
- Moreover, in accordance with further exemplary embodiments of the present invention, the binder resin may include at least one of a thermoset material, a thermoplastic material, or a combination thereof. Some exemplary embodiments of the binder resin include a mixture of thermoset and thermoplastic materials, for example, a mixture of one or more of an acrylic material, a urea formaldehyde material, or a combination thereof, along with a ethylene vinyl acetate. Some exemplary embodiments of the binder resin include about 50 to 100 weight percent thermoplastic material and 0 to about 50 weight percent thermoset material.
- In yet other exemplary embodiments of the present invention, a gypsum wall board is provided. The gypsum wall board includes a gypsum core and at least one flexible non-woven mat. Some exemplary embodiments of the flexible non-woven chopped strand mat include a mixture of about 10 to about 95 weight percent glass fibers and about 5 to about 90 weight percent synthetic fibers. The non-woven mat further includes a binder composition that includes a binder resin and a silane coupling agent.
- While various exemplary embodiments are described or suggested herein, other exemplary embodiments utilizing a variety of methods and materials similar or equivalent to those described or suggested herein are encompassed by the general inventive concepts.
- Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. In this connection, unless otherwise indicated, concentrations of ingredients given in this document refer to the concentrations of these ingredients in the master batch or concentrate, in keeping with customary practice.
- The general inventive concepts relate to a flexible non-woven chopped strand mat (generally, the non-woven mat) with improved properties. In some exemplary embodiments, the flexible non-woven mat demonstrates improved mechanical strength, such as high machine direction tensile strength and cross-direction tensile strength, while also showing improved flexibility. The softness and flexibility of the inventive non-woven mats improves downstream processes, for example, the formation of pultruded products having complex shapes and/or the production of gypsum wall boards. Additionally, in accordance with various exemplary embodiments, the inventive flexible non-woven mats are resistant to styrene and polyester that may be present in resin formulations utilized in pultrusion processes.
- Some exemplary embodiments of the present invention relate to a flexible non-woven mat which may be utilized in various downstream processes, for example, in pultrusion processes and in gypsum wallboard formation. The non-woven mat is characterized by a number of attributes including very good flexibility, For instance, in some exemplary embodiments, the non-woven mats demonstrate a reduced stiffness of less than 6000 mgf, or less than 5000 mgf. This stiffness level is greatly reduced from conventional non-woven mats with stiffnesses around 7000 mgf.
- The flexible non-woven mats of the present invention may comprise a plurality of fibers, including any of glass fibers, synthetic fibers, or a blend thereof. The glass fibers can be made from any type of glass. Examples of glass fibers include A-type glass fibers, C-type glass fibers, E-type glass fibers, S-type glass fibers, ECR-type glass fibers (e.g., Advantex® glass fibers commercially available from Owens Corning), Hiper-tex™, wool glass fibers, and combinations thereof. The use of other reinforcing fibers such as mineral fibers, carbon fibers, ceramic fibers, natural fibers, and/or synthetic fibers in the non-woven mat is also considered to be within the purview of the general inventive concepts. The term “natural fiber” as used in conjunction with the present invention refers to plant fibers extracted from any part of a plant, including, but not limited to, the stem, seeds, leaves, roots, or phloem. Examples of natural fibers which may be suitable for use as the reinforcing fiber material include basalt, cotton, jute, bamboo, ramie, bagasse, hemp, coir, linen, kenaf, sisal, flax, henequen, and combinations thereof. The term “synthetic fibers” as used herein is meant to indicate any man-made fiber having suitable reinforcing characteristics, such as polyester, polyethylene, polyethylene terephthalate, polypropylene, polyamide, aramid, and polyaramid fibers, and combinations thereof.
- In some exemplary embodiments, the fibers used to form the non-woven mats according to the present invention include a blend of glass fibers and synthetic resin fibers, such as polymer fibers. In accordance with various exemplary embodiments, the polymer fibers include those made from polypropylene, polyester, or a combination thereof. In some exemplary embodiments, the polymer fibers are formed from polyethylene terephthalate (PET).
- In some exemplary embodiments, the fibers used to form the non-woven mats according to the present invention include a blend of about 10 to about 100 percent by weight glass fibers and about 0 to about 90 percent by weight polymer fibers. In other exemplary embodiments, the fibers include a blend of about 50 to about 90 percent by weight glass fibers and about 10 to about 50 percent by weight polymer fibers, or from about 75 to about 90 percent by weight glass fibers and about 10 to 25 percent by weight polymer fibers.
- The glass fibers may be formed by conventional methods known to those skilled in the art. For example, the glass fibers may be formed by a continuous manufacturing process in which molten glass passes through the holes of a “bushing,” the streams of molten glass thereby formed are solidified into filaments, and the filaments are combined together to form a fiber, “roving,” “strand,” or the like.
- After the glass fibers are drawn from the bushing, an aqueous sizing composition (also referred to as a size) may optionally be applied to the fibers. The sizing composition is not limited, and may be any sizing known to those of skill in the art. Generally sizing compositions contain a lubricant to protect the fibers from damage by abrasion, a film-forming resin to help bond the fibers to the polymer forming the body or matrix of the composite in which the fibers will be used, and a coupling agent to improve the adhesion of the film-forming resin to the surfaces of the glass fibers. The sizing composition may be applied by conventional methods such as by an application roller or by spraying the size directly onto the fibers. The size protects the glass fibers from breakage during subsequent processing, helps to retard interfilament abrasion, ensures the integrity of the strands of glass fibers, promotes the interconnection of the glass filaments that form the strand, etc.
- After the glass fibers are treated with the sizing composition, they may be chopped and packaged as chopped strand glass for subsequent processing into a wet-laid, non-woven mat as described below. In some exemplary embodiments, the chopped fibers may have a length from about 0.5 to about 2.0 inches, or from about 1.0 to about 1.5 inches. The chopped fibers may have varying lengths from each other within the non-woven mat.
- In addition, the fibers may have a diameter from about 5 microns to about 20 microns, or from about 10 microns to about 16 microns. The chopped fibers may have varying lengths from each other within the non-woven mat.
- It has been discovered that decreasing the length and/or diameter of the fibers may improve the toughness of a non-woven mat formed therefrom. The improvement in toughness may result from increased interfacial bonding that occurs with finer and shorter fibers, under the same basic weight construction. Interfacial bonding helps deflect stress concentration and crack propagation, which leads to enhanced toughness. However, although fine fibers can create more closed mats with better tensile strengths, finer fibers tend to cause a loss of air permeation and reduced resin penetration. Therefore, since pultrusion applications require mats to be open enough to allow the resin to penetrate through, a balance must be achieved between achieving toughness and air permeation when forming the fibers for use herein. The fibers may be of uniform length and/or diameter, or the fibers may have a variety of lengths and diameters, such as desired for a particular application.
- The flexible non-woven mat may be framed by a variety of processes, including dry-laid and wet-laid processes. In some exemplary embodiments, the non-woven mat is formed by a wet-laid process, which involves forming an aqueous dispersion or slurry of discrete fibers in a mix tank filled with various components (sometimes referred to as white water), such as water, surfactants, viscosity modifiers, defoaming agents, lubricants, biocides, and/or other chemical agents, along with agitation, to form a chopped glass fiber slurry. It is desirable that the slurry is agitated sufficiently to provide a uniform or nearly uniform dispersion of fibers.
- The aqueous fiber dispersion or slurry may then be processed into a wet-laid mat according to any number of conventional methods known in the art. For example, the aqueous fiber slurry is deposited onto a moving screen or conveyor, on which the majority of the water drains through, leaving a randomly oriented fiber web. The fiber web may be further dried by a vacuum slot or other drying means.
- A binder composition may then be applied to the fiber web in a conventional manner, such as by curtain coating, spraying, a twin wire dip bath, a two roll padder, and the like. Water, excess binder, and excess coupling agent may then be removed by a vacuum or other water removal means. Finally, the binder-coated fiber product may be dried and cured in one or more ovens. An exemplary temperature range for drying is from about 350° F. (218° C.) to about 600° F. (304° C.). The dried and cured product is the finished non-woven flexible mat.
- In accordance with various aspects of the present invention, the binder composition is formulated such that once the binder is cured, it is able to impart very good mechanical strength (total tensile strength of at least 80 lbs), flexibility (Gurley stiffness of less than 5000 mgf), and solvent resistance (styrene retention of at least 60%).
- In some exemplary embodiments, the binder composition comprises a binder resin material, a coupling agent, and one or more optional additives. The binder resin may be a thermoset material, a thermoplastic material, or a mixture of thermoset and thermoplastic materials. The thermoset material may comprise, for example, an acrylic material, a urea formaldehyde material, or a combination of the two materials. In some exemplary embodiments, the acrylic material is polyacrylic acid, such as low molecular weight polyacrylic acid with a molecular weight at or below 10,000. The thermoset material, once cross-linked under proper curing conditions, provides good tensile performance and solvent resistance, helping maintain mat integrity in different applications. In some exemplary embodiments, the thermoplastic material may include any thermoplastic material having a low Tg (i.e., below −15° C.), for example, ethylene vinyl acetate (“EVA”). In some exemplary embodiments, the EVA comprises Dur-O-Set® E-646. The thermoplastic material is self cross-linking and can provide the softness needed for flexible mats.
- It has been discovered that formulating a binder composition that incorporates resins with differing functionalities (e.g., thermoset and thermoplastic) may impart improved properties to a fiber reinforced mat. In particular, the combination of such properties may allow the non-woven mats to be used in challenging applications, such as in pultrusion applications, as a replacement for continuous filament mats. Some exemplary binder compositions include about 0 to about 50 percent by weight thermoset material, such as polyacrylic acid and about 50 to about 100 percent by weight thermoplastic material, such as EVA. In other exemplary embodiments, the binder composition comprises about 15 to about 30 percent by weight polyacrylic acid and about 70 to about 85 percent by weight EVA.
- In some exemplary embodiments, the binder resin may be present in the binder composition in an amount from about 90 percent to about 99 percent by weight of the total binder composition, and in exemplary embodiments, from about 97 percent to about 99 percent by weight. As used herein, the phrases “percent by weight” and “percent by weight of the composition” are meant to denote percent by weight of the total components of the composition.
- The binder composition may further include a coupling agent. It is to be appreciated that the coupling agents described herein are exemplary in nature, and any suitable coupling agent known to those of ordinary skill in the art may be utilized in any of the exemplary embodiments described or otherwise suggested herein. In some exemplary embodiments, the coupling agent, or coupling agents, may be present in the binder composition in an amount from about 0.05 percent to about 10.0 percent by weight of the total binder composition, and in other exemplary embodiments, in an amount from about 0.1 percent to about 3.0 percent by weight. Various exemplary embodiments include about 0.2 percent by weight of a coupling agent. Besides their role of coupling the surface of the reinforcement fibers and the surrounding matrix, coupling agents also function to reduce the level of fuzz, or broken fiber filaments, during subsequent processing.
- In some exemplary embodiments, at least one of the coupling agents is a silane coupling agent. Suitable silane coupling agents may include silanes containing one or more nitrogen atoms that have one or more functional groups such as amine (primary, secondary, tertiary, and quaternary), amino, imino, amido, imido, ureido, or isocyanato. Suitable silane coupling agents may also include, but are not limited to, aminosilanes, silane esters, vinyl silanes, methacryloxy silanes, epoxy silanes, sulfur silanes, ureido silanes, and isocyanato silanes. Specific, non-limiting examples of silane coupling agents for use in the instant invention include γ-methacryloxypropyl-trimethoxysilane(A-174), γ-aminopropyltriethoxysilane(A-1100), n-phenyl-γ-aminopropyltrimethoxysilane(Y-9669), n-trimethoxy-silyl-propyl-ethylene-diamine(A-1120), methyl-trichlorosilane(A-154), γ-chloropropyl-trimethoxy-silane(A-143), vinyl-triacetoxysilane(A-188), and methyltrimethoxysilane(A-1630).
- The binder composition may optionally include additional components, for example, dyes, oils, fillers, colorants, aqueous dispersions, UV stabilizers, lubricants, wetting agents, surfactants, viscosity modifiers, and/or antistatic agents. The aqueous dispersions may include antioxidant dispersions, which counter the effects of oxidation by the binder composition due to aging. One exemplary antioxidant dispersion includes Bostex 537, from Akron Dispersions, Inc. The antioxidant dispersion may be included in amounts from 0 to about 5 percent by weight, or from about 0.5 to about 3 percent by weight. Some exemplary embodiments include about 1.8 percent by weight of an antioxidant dispersion. Additives may be included in the binder composition in an amount of about 0.0 percent to about 10 percent by weight of the binder composition.
- In accordance with some exemplary embodiments, the binder composition further includes water to dissolve or disperse the components for application onto the reinforcement fibers. Water may be added in an amount sufficient to dilute the aqueous binder composition to a viscosity that is suitable for its application to the reinforcement fibers. For example, the binder composition may contain from about 50 percent to about 75 percent by weight of the binder composition of water.
- The bonded mats of the present invention may have an average thickness of between about 25 and 75 millimeters, or from about 30 to about 60 millimeters.
- Incorporating a soft, but strong binder composition, in combination with the proper blend of glass and/or synthetic fibers, produces a flexible non-woven mat with improved processing capabilities, which facilitate use in pultrusion processes, the formation of smooth gypsum mats, and other related applications for which non-woven mats have here before been ill suited. Once the binder is cured, it imparts additional features, such as improved mechanical strength (e.g., in both the machine and cross-direction tensile strengths), flexibility, and solvent resistance.
- In some exemplary embodiments, the flexible non-woven mats have an average tensile strength of at least 30 lb in the machine direction and at least 20 lb in the cross direction. In some exemplary embodiments, the flexible non-woven mats have a machine direction tensile strength of at least 50 lb and a cross-direction tensile strength of at least 30 lb. The flexible non-woven mats may further have a total tensile strength (machine direction+cross-direction) of at least 50 lb, or at least 80 lb.
- As mentioned above, the non-woven mats have improved flexibility, which may be measured using a Gurley stiffness tester. In some exemplary embodiments, the non-woven mat has a Gurley stiffness of about 2000 to about 7000 mgf, or from about 2500 to about 6000 mgf, and in other exemplary embodiments, less than 5000 mgf.
- The flexible non-woven mats may be used in a variety of downstream processes to form a variety of end products. In some exemplary embodiments, the flexible non-woven mat is used to form a composite product through a pultrusion process. In some exemplary embodiments, the pultrusion process includes feeding rovings and at least one non-woven mat into a thermosetting resin bath where the rovings are moved over spreader bars which aid in impregnating the resin into the fibers. The rovings may be made from glass, graphite, boron, polyaramid fibers, or other similar fibers. Preferably, the roving is made from glass fibers.
- Once the rovings are sufficiently impregnated with the resin, the rovings and the non-woven mat exit the resin bath and are pre-formed by a pre-former into a shape or profile prior to entering a heated molding die. The rovings and non-woven mat, which have the pre-formed shape, are then cured into the desired form of the composite by heating continuously as the part passes through the heated molding die. A pair of caterpillar rollers may be used to pull the rovings and mat through the bath, pre-former, and /or heated die. The composite part exiting the heated die is then cut to a desired length by a cutting apparatus. In this manner, the fibers of the continuous roving are impregnated with a polymer resin, the mat is coated with the polymer resin, and the fibers and mat are shaped into the form of the composite and cut to form a pultruded part. The rovings impart a longitudinal tensile strength and the non-woven mat imparts a transverse tensile strength to the pultruded part.
- As discussed herein, the binder composition provides improved resistance to styrene monomers commonly found in thermosetting resins used in pultrusion processes. This enhanced resistance to styrene makes the inventive flexible mats more suitable for pultrusion processes. As discussed herein, styrene monomers are a potent solvent and can act to swell and degrade the binder, thereby weakening the continuity of the mat. By providing a flexible non-woven mat resistant to styrene monomers, the flexible non-woven mat, and thus the resulting pultruded part incorporating the same, maintain tensile strength in the longitudinal direction as well as in the transverse direction.
- The flexible non-woven mats may also be used in other processes, such as, for example, the production of gypsum wall boards and/or gypsum panels frequently used in building construction. Wall boards formed of a gypsum core sandwiched between facing layers are commonly used in the construction industry as internal walls and ceilings for both residential and commercial buildings. The gypsum core typically contains gypsum, optionally some wet chopped glass fibers, water resistant chemicals, binders, accelerants, and low-density fillers. It is known in the art to form gypsum boards by providing a continuous layer of a facing material, such as a fibrous veil, and depositing a gypsum slurry onto one surface of the facing material. A second continuous layer of facing material is then applied to the opposite surface of the gypsum slurry. In this manner, the gypsum slurry is sandwiched between opposing layers of facing material. The sandwiched gypsum slurry is then adjusted to a desired thickness and dried to harden the gypsum core and form a gypsum board. Next, the gypsum board may be cut to predetermined dimensions (e.g., length) for end use. Glass fibers are commonly used in the production of gypsum wall boards to improve the tensile and tear strength of the products.
- In accordance with various exemplary embodiments, the flexible non-woven mats may be used as the facings in a gypsum wall board to provide increased dimensional stability in the presence of moisture, increased biological resistance, increased air permeability, and greater physical and mechanical properties, such as better strength and durability, than conventional gypsum boards faced with paper or other cellulosic facing materials.
- Having generally introduced the general inventive concepts by disclosing various exemplary embodiments thereof, a further understanding can be obtained by reference to certain specific examples illustrated below which are provided for purposes of illustration only and are not intended to be all inclusive or otherwise limiting of the general inventive concepts.
- In order to more thoroughly describe this invention, the following working example is provided.
- Three non-woven mats were made by a conventional wet laid coating process in which chopped glass fibers, after being deposited onto a moving screen in the form of an aqueous slurry, were coated with an aqueous dispersion of a binder composition and then dried and cured. Each mat was made with 1.25″ M fiber (16 micrometer diameter) with the same loss on ignition (LOI) and base weight. The binder composition applied to each mat included a varied ratio of thermoplastic/thermoset components. The binder of the first mat include 100 percent polyacrylic acid, the binder of the second mat included 75 percent polyacrylic acid and 25 percent ethylene vinyl acetate, and the binder of the third mat included 50 percent polyacrylic acid and 50 percent ethylene vinyl acetate. Each composition was cured at 485° F.
- The fiberglass mats so obtained were then tested for max bending strength and Gurley stiffness, to determine the bending resistance/stiffness of the mat.
- The results obtained are set forth in Table 1.
-
TABLE 1 Mat Flexibility vs. Binder Component Ratio Max Load (3 pts bending Gurley Stiffness Binder formulation test, Machine Direction) (Machine Direction) 100% PAA 111.8 gram force (gf) 7758 mgf 75% PAA/25% EVA 100.8 gram force (gf) 6768 mgf 50% PAA/50% EVA 54.9 gram force (gf) 4516 mgf - As shown in Table 1, the flexibility of a non-woven mat improves with an increase in the amount of EVA in the binder composition. For instance, by including 25 weight percent EVA in a binder formulation, flexible mats may be made with Gurley stiffnesses less than 7000 mgf, and 50 weight parent EVA in the binder composition, non-woven mats may be produced with Gurley stiffnesses of less than 5000 mgf.
- Although several exemplary only a few embodiments of the present invention have been described herein, it should be appreciated that many modifications can be made without departing from the spirit and scope of the general inventive concepts. All such modifications are intended to be included within the scope of this invention and the related general inventive concepts, which are to be limited only by the following claims.
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Also Published As
Publication number | Publication date |
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KR20160070139A (en) | 2016-06-17 |
CN105723023B (en) | 2020-06-09 |
EP3058126B1 (en) | 2017-09-06 |
CN105723023A (en) | 2016-06-29 |
RU2675890C2 (en) | 2018-12-25 |
JP6550383B2 (en) | 2019-07-24 |
EP3058126A1 (en) | 2016-08-24 |
WO2015057763A1 (en) | 2015-04-23 |
KR102233322B1 (en) | 2021-03-26 |
CA2927534A1 (en) | 2015-04-23 |
MX355282B (en) | 2018-04-12 |
CA2927534C (en) | 2022-10-04 |
JP2016533438A (en) | 2016-10-27 |
MX2016004858A (en) | 2016-12-20 |
RU2016116848A3 (en) | 2018-05-30 |
ES2644034T3 (en) | 2017-11-27 |
RU2016116848A (en) | 2017-11-20 |
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