US3853608A - Manufacture of a reinforced, non-woven textile fiber sheet material - Google Patents
Manufacture of a reinforced, non-woven textile fiber sheet material Download PDFInfo
- Publication number
- US3853608A US3853608A US00291323A US29132372A US3853608A US 3853608 A US3853608 A US 3853608A US 00291323 A US00291323 A US 00291323A US 29132372 A US29132372 A US 29132372A US 3853608 A US3853608 A US 3853608A
- Authority
- US
- United States
- Prior art keywords
- weight
- fleece
- elastomer
- liquid
- binder
- 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.)
- Expired - Lifetime
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000004753 textile Substances 0.000 title claims description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 39
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims description 71
- 239000006185 dispersion Substances 0.000 claims description 45
- 229920001971 elastomer Polymers 0.000 claims description 45
- 239000000806 elastomer Substances 0.000 claims description 45
- 229920001577 copolymer Polymers 0.000 claims description 28
- 229920002545 silicone oil Polymers 0.000 claims description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 17
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- WXVTYVAWKFXHBD-UHFFFAOYSA-N 4-hydroxy-3-(hydroxymethyl)-2-methylbut-2-enamide Chemical compound NC(=O)C(C)=C(CO)CO WXVTYVAWKFXHBD-UHFFFAOYSA-N 0.000 claims description 3
- YXFVVABEGXRONW-CNRUNOGKSA-N tritiomethylbenzene Chemical compound [3H]CC1=CC=CC=C1 YXFVVABEGXRONW-CNRUNOGKSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 15
- 230000015271 coagulation Effects 0.000 description 11
- 238000005345 coagulation Methods 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- KNIUHBNRWZGIQQ-UHFFFAOYSA-N 7-diethoxyphosphinothioyloxy-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 KNIUHBNRWZGIQQ-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- -1 ethylene ureas Chemical class 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 239000000701 coagulant Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000002649 leather substitute Substances 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920013648 Perbunan Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 244000309466 calf Species 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- VAMFXQBUQXONLZ-UHFFFAOYSA-N icos-1-ene Chemical group CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 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
- D04H1/58—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
- D04H1/42—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
- D04H1/4334—Polyamides
-
- 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
-
- 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
- D04H1/645—Impregnation followed by a solidification process
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—Polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/12—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with filaments or yarns secured together by chemical or thermo-activatable bonding agents, e.g. adhesives, applied or incorporated in liquid or solid form
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2033—Coating or impregnation formed in situ [e.g., by interfacial condensation, coagulation, precipitation, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2041—Two or more non-extruded coatings or impregnations
- Y10T442/2098—At least two coatings or impregnations of different chemical composition
Definitions
- ABSTRACT This invention relates to a random fiber sheet material having regions in which fiber cross-over points are bonded by synthetic elastomer binder, the regions being separated within the material by regions in which there is no bonding of fiber cross-over points.
- the invention also relates to a process for the preparation of the material.
- the fleeces are impregnated with solutions or dispersions of suitable elastomers and the polymer is then deposited in the fleece by coagulation.
- the elastomer is preferentially absorded at the cross-over points of the fibers and deposits in compact layers on the walls of the cavities of the fleece.
- the known processes for bonding fleeces have the disadvantage that it is not possible reliably to avoid excessive bonding" or inadequate bonding" in the whole of the fleece or parts thereof.
- the known processes therefore give only fiber fleeces which are not entirely satisfactory as regards their mechanical properties.
- the stress-strain curve of the fleeces bonded in accordance with the known processes shows a positive curvature. It immediately rises rapidly, and a low initial modulus of such fleeces is not achievable by known processes. This fact is of particular disadvantage if these fleeces are further converted into leather-like material, from which, for example, shoe uppers are manufactured.
- the present invention provides a process for the manufacture of a chemically bonded non-woven textile fiber sheet material, wherein a. a non-woven textile fiber sheet material is treated with a binder liquid composed of an aqueous dispersion of a synthetic elastomer containing chemically reactive groups and a solution of silicone oil in toluene,
- the resulting material is treated with a liquid containing a synthetic elastomer
- the elastomer is deposited by coagulation in the cavities in the material
- the resulting material is subjected to the action of heat for drying or drying and crosslinking of the deposited elastomer.
- the resulting bonded fleece does not display the disadvantages of the known fleeces so that it is neither excessively bonded nor inadequately bonded and pos- I sesses an S-shaped course of the stress-strain curve, with low initial modulus, high tensile strength and tear propagation strength and displays the leather-like properties which are closely associated with these physical properties.
- the bonded fiber fleece of the invention is such that the binder is spatially distributed therein at centers of bonding in the form of segregated regions and the parts of the fleece lying between these regions are unbonded.
- the invention accordingly, further provides a random fiber sheet material having regions in which fiber cross-over points are bonded by synthetic elastomer binder, the regions being separated within the material by regions in which there is no bonding of fiber crossover points.
- the fleece is bonded by subjecting it to the action of a binder liquid which is composed of an aqueous dispersion of a synthetic elastomer containing reactive groups and a solution of Silicone oil in toluene.
- the reactive groups of the elastomeric binder enable the latter to react, under the action of heat and, advantageously, with the conjoint use of crosslinking catalysts, with chemical compounds which possess reactive groups, so as to undergo crosslinking.
- the aqueous dispersion used for the manufacture of the binder liquid may have a polymeric solids content in the range of 5 to 30% by weight, preferably in the range of 10 to 20% by weight, relative to the total weight of the dispersion.
- the solution of silicone oil in toluene may contain 10 to 50% by weight of silicone oil relative to the total weight of this solution.
- the binder liquid is manufactured by mixing the two above-mentioned liquids with one another.
- the solution of silicone oil in toluene may be added to the clastomeric dispersion in an amount in the range of 8 to 60 g, preferably 20 to 40 g, per liter of dispersion.
- the dispersed phase of the aqueous dispersion is composed of a synthetic elastomer with reactive groups, especially COOH /orCON(CH OI-I) groups.
- Synthetic elastomers based on acrylic copolymers are preferred, especially acrylic copolymers which are composed of 3 or 4 chemically different acrylic compounds. At the same time it is essential that the copolymers should be composed to the extent of at least 5% and at most 25% of acrylic compounds with free reactive groups. Butyl acrylate is preferred as quantitatively the main constituent of the copolymers.
- Mixtures of copolymers of the specified type also can be used in the dispersed form.
- a particularly preferred aqueous copolymer dispersion consists of approximately 92% by weight of butyl acrylate, approximately 4% by weight of methacrylic acid and approximately 4% by weight of acrylamide.
- the dispersion has a solids content of 40% by weight relative to the total weight of the dispersion.
- Another preferred aqueous copolymer dispersion consists of approximately 86% by weight of butyl acrylate, approximately 4% by weight of itaconic acid, ap-
- polyurethanes or synthetic rubbers Apart from the synthetic elastomers based on polyacrylate which have been stated to be preferred and which function as fiber binders, it is possible to use polyurethanes or synthetic rubbers, provided that they still contain reactive groups, for example polyurethanes with free OH and/or COOH groups and/or polyurethanes which still possess reactive isocyanate groups.
- An example of an elastomer suitable for fiber bonding is a copolymer based on butadiene-acrylonitrilemethacrylic acid.
- the binder liquid is allowed to act on the fiber sheet, for example by impregnating the sheet in the liquid.
- the impregnated fleece is thereafter freed from excess binder liquid by squeezing out, for example .in the nip of a pair of rollers.
- the impregnating liquid which acts on the fleece in the fourth process step contains one or more synthetic coating agents.
- synthetic coating agents there are to be'understood chemical compounds which are capable of forming acoating on the fiber surface which after the action of sufficient heat on the fibers coated with the agent is firmly bonded to the'fiber surface as a result of the high adhesion between the fiber surface and coating caused by the action of heat.
- Suitable coating agents are: ethylene ureas of the general formula ll CH wherein R is an aliphatic chain with 14 to 22 carbon atoms, fatty'amines having a carbon chain of 16 to 18 carbon atoms, paraffins, etherified fat-modified synthetic resins with side chains of between l2 and 18 carbon atoms, cross-linkable an'd non-cross-linkable silicones, such as, for example, dimethyl-polysiloxane and hydrogenomethyl-polysiloxane or cross-linkable polymers suitable for'textile finishing, which possess perfluorinated aliphatic side chains (for example, Scotchgard" Registered Trade Mark of Minnesota Minning and Manufacturing Co., U.S.H.).
- Suitable crosslinkable polymers have a perfluorinated aliphatic side chain with 6 to 14, especially 8 to 12, carbon atoms.
- the perfluorinated cross-linkable aliphatic side chains can be bonded to the carboxyl group of the polymer by a sulfonamide group.
- the coating agent must possess the inherent properties that no, or virtually no, physical bonding forces act between adjacent surfaces of the coating and surfaces of the consolidating material, i.e., the adhesion between the surfaces is so slight that only sliding displacement of the surface relative to one another is possible under the action of external mechanical force on the fleece, for example on bending or stretching the fleece.
- the coating agent is introduced into the fleece in the form of a liquid solution or dispersion the impregnating liquid by, for example, impregnating the fleece with the liquid and then expelling the solvent or dispersing agent, for example by the action of sufficient heat on the fleece, A liquor ratio in the range of 1:10
- Suitable liquids for the manufacture of a solution which contains the coating agent are those which do not have a solvent action on the fibers of the fleece, for example water.
- Suitable dispersing agents for the manaufacture of a liquid dispersion of a coating agent are those which do not have a solvent action on the fibers of the fleece, for example water.
- the proportion of coating agent in the impregnating liquid may be in the range of 2 to 30% by weight relative to the total weight of the impregnating liquid, and especially in the range of 6 to 12% by weight.
- the coating agent is to be regarded as bonded in a wash-resistant manner to the fiber surface if the adhesion between the fiber surface and the coating agent is so great that on five mechanical washes at C. according to DIN 54,010 no detachment, or virtually no detachment, of the coating agent from the fiber surface occurs.
- a suitable wash liquid is: 5 g/l of soap and 2 g/l of anhydrous sodium carbonate, washing time 30 minutes, 60C., i250 liquor ratio.
- the elastomer liquid incorporated into the fleece in the seventh process step is composed of a solution of a synthetic elastomer in an organic solvent or of an aqueous dispersion of a synthetic elastomer.
- Aqueous elastomer dispersions are preferred.
- a suitable elastomer solution is, for example, polyurethane in dimethylformamide.
- An aqueous dispersion of a copolymer based on butadiene-acrylonitrile-methacrylic acid is preferred and copolymers containing approximately 64% by weight of butadiene approximately 32% by weight of acrylonitrile and approximately 4% by weight of methacrylic acid, in each case relative to the total weight of the copolymer, are very particularly preferred.
- the proportion of elastomer in the solution may be 20 to 40% by weight, relative to the total weight of the solution.
- the proportion of polymer in the elastomer dispersion may be 20 to 50% by weight, relative to the total weight of the dispersion.
- Suitable non-woven textile fiber sheets are those which consist wholly or predominantly of synthetic fibers; the snythetic fiber content of the fleece can consist either of fibers which are chemically of the same nature or of a mixture of fibers of different chemical composition; for example, a random fiber fleece can be made up of 50% of polyester and 50% of polyamide fibers.
- the fleece density may be in the range of 0.08 to 0.6 g/cm Mechanical pre-consolidation and densification of the raw fleece is possible by needle-punching or by needle-punching and shrinkage, if heat-shrinkable fibers are used in the fleece. Fleece densities of between 0.3 and 0.6 g/cm can only be brought about by subsequent calendering of the fleece at elevated temperatures.
- fleeces which are used as substrates for the manufacture of leather substitutes or for textile uses, it is advisable conjointly to use a proportion (up to 50 to 60%) of natural fibers (cellulose or wool) or hydrophilic fibers, such as reclaimed fibers or polyvinyl alcohol fibers, in order in this way to achieve favorable physiological properties.
- natural fibers cellulose or wool
- hydrophilic fibers such as reclaimed fibers or polyvinyl alcohol fibers
- the original fleeces have a very flat shape of the stress-strain curve, with a low initial modulus,
- the course of the curve namely initial modulus, middle section and destruction phase can be varied within wide limits in the original fleece through the nature of the fibers chosen, their titre, the fiber orientation, the length and surface characteristics of the fibers and the density of the fleece.
- the aqueous binder dispersion should contain a synthetic elastomer which can be coagulated by heat.
- the binder liquid contains a chemical compound which makes it possible for the elastomer to coagulate spontaneously under the action of sufficient heat.
- Suitable agents which influence the ease of coagulation of the elastomer by heat are, for example, polysiloxanes.
- the proportion of the fiber-bonding elastomer in the fleece according to the invention may be in the range of 5 to 30% by weight relative to the starting weight of the original fleece.
- the synthetic elastomer which binds the fibers is localized in the form of a plurality of segregated regions arranged spatially relatively remote from one another in the fleece, within which regions the fibers and fiber cross-over points enclosed by the elastomer are bonded by the chemical binder while the fiber regions and fiber cross-over points located between the segrated binder regions are not bonded.
- the fleece according to the invention is distinguished by segregated regions of binder; the overall structure of the binder in the fleece can be described as honeycomb-like.
- the result of the first series of process steps is that the desired distribution of the chemical binder in the fleece is achieved.
- the coagulation conditions of the elastomeric binder should be so chosen that spontaneous coagulation occurs only after the elastomer dispersion has spread horizontally in the fleece and before migration of the dispersion at right angles to the horizontal plane commences.
- the appropriate coagulation conditions can be determined by simple preliminary experiments in each individual case.
- the desired distribution of the chemical binder in the fleece is achieved.
- the fleece becomes reinforced only within the stated regions by relatively large binder particles.
- the chemical binder is very much more effective than in the case of diffuse distribution, with small binder particles distributed essentially at random over the cross-section of the fleece. The highest bonding strength is achieved when the adhesion of the binder to the fibers and the cohesion of the binder differ as little as possible from the fiber strength.
- the concentration and the amount of the silicone oil solution in aromatic solvents, and the coagulation conditions for precipitating the elastomeric binder from the binder liquid must be suited to the particular binder concentration in the binder liquid and to the binder type.
- the above-mentioned conditions must at the same time be so chosen that the particular binder concentration gives an optimum as regards mesh width," i.e., as regards the spacing of the individual regions containing binder. lt easily can be: seen that for an in,- creasing binder concentration (increasing binder content of the fleece) the mesh width" of the bonded fiber cross-over points in the fleece must decrease.
- the mechanical properties of the fleece as a result already can be determined after the preliminary bonding according to the process steps (a) to (c).
- the development of the honeycomb structure of the binder in the fleece can be intensified by increasing the concentration of the silicone oil solution in the aromatic solvent, which is added to the elastomer dispersion or elastomer solution.
- the proportion of the synthetic elastomer embedded in the fleece and not contributing to fiber bonding is 10 to 50% by weight relative to the bonded and impregnated fleece.
- a random fiber sheet based on synthetic fibers is impregnated with binder liquid and is thereafter freed from excess of binder liquid, for example by expressing the fleece web in the nip of a pair of rollers. Thereafter,
- the fleece is sufficiently heated at a temperature of 120 to 180 C for'a period in the range of 30 seconds to 30 minutes to initiate the coagulation and expel the liquid volatile constituent of the binder liquid, and to cross-link the elastomeric binder.
- the bonded fleece is subjected to the action of an impregnating liquid, for example by immersing the fleece in this liquid.
- the impregnated fleece is then freed from excess of impregnating liquid, for example by expressing in the nip of a pair of rollers.
- the impregnated fleece is then heated at a temperature in the range of 100 to 170 C for a period in the range of 30 seconds to minutes, as a result of which the fleece is dried and the impregnating agent is crosslinked to give a coating which adheres firmly to the surface of the fiber which are free from elastomeric binder and on the binder.
- synthetic elastomer is embedded in the cavities of the impregnated fleece, without adhering to the fibers, by treating the fleece with a polymer solution or polymer dispersion, for example by impregnating the fleece therewith, freeing the fleece from excess of polymer liquid, for example by expressing the fleece in the nip of a pair of rollers, and subjecting the fleece to sufficient heat to cause the precipitation of the clastomer in the form of globular particles in the cavities of the fleece.
- the coagulation temperature is roughly in the region of 40 C.
- the liquid still contained in the fleece is expelled, for example by drying the fleece in a tenter frame drier at a temperature which suffices to expel the volatile constituents, for example 100 to 120 C.
- the fleece is then subjected to a temperature in the range of 120 to 180 C i briefly indicated:
- the composition, orientation, length and titre of the fibers and the density of the .fleece can be varied. Furthermore, the type, amount and mesh width of the binder, the substance used as the finish and the amount applied, and also the amount and type of the filler, can be chosen as desired. In the case of the filler, prime factors are the plastic-elastic and the physiological-hygenie properties.
- the complicated structure of the material necessary to produce the required mechanical properties can be achieved by verys'imple process steps.
- the properties concerned are the following mechanical leather-like properties:
- the most important characteristic is an S-shaped course of the stress-strain curve, with a low initial modulus. This curve can be adjusted as desired. It is an important pre-requisite that the starting fleece should be isotropic over its surface. Such a characteristic shape of the curve cannot be achieved by any of the previous methods of bonding.
- the important property ofsuppleness depends on thi's course of the curve. A material can be described as supple if, when stressed mechanically it can easily. give to a slight stress- (flat initial course and low initial modulus) while it offers increasing resistance to a greater stress (steep middle part of the curve).
- the rolling and creasing behavior is very leatherlike since the reinforced fiber network and the filler can move independently of one another.
- the differences in density of the fleece are also completely compensated since the binder is drawn into the regions where there is a high density of fibers while the filler is repelled, by the finish, into the regions where there is a low fiber density.
- both a leather substitute and a textile material can be obtained, as desired, by simple measures, and that these materials have hitherto unattainable mechanical properties.
- EXAMPLE 1 A random fiber fleece of 50% of polyester fibers and 50% of polyamide fibers staple length 30 mm, titre 1.3 dtex which has a density of 0.15 g/cm, a tensile strength of0.4 kp/mm (DlN 53,328) and a tear propagation strength of 8.5 kp/mm (according to [UP 8) is impregnated with a binder liquid of the following composition:
- the fleece is than heated at 180 C for a period of 3 minutes, by radiation from an infra-red radiator;
- the bonded fleece is then impregnated in an impreg nating bath containing g of dimethylpolysiloxane (for example Primenit" SW of Farbwerke Hoechst AG) per liter of liquor.
- the fleece is impregnated with the impregnating liquor or a Foulard machine.
- the excess of impregnating liquid is expressed from the fleece in the nip of a pair of rollers and the fleece is then dried in a tenter frame drier at 100 to C and subsequently heated in this drier at C. for a period of 30 seconds.
- the impregnated fleece is then dipped in an aqueous dispersion of a copolymer consisting of 64% by weight of butadiene, 32% by weight of acrylonitrile and 4% by weight of methacrylic acid (for example Perbunan NT of Wegwood Bayer), withdrawn from the impregnating bath and then freed from excess of dispersion by expressing in the nip of a pair of rollers.
- the elastomer is then coagulated on the fleece by heat from an infra-red radiator.
- the coagulation temperature is 30 C.
- the fleece is dried in a tenter frame drier at 100 C and is then heated at a temperature of 160 C for 5 minutes. This heat treatment vulcanizes and cross-links the elastomer.
- the fleece is soft and supple and can be used as a substrate for the manufacture of a synthetic material having properties resembling box calf.
- the fleece has the following characteristics:
- EXAMPLE 3 A random fiber fleece according to Example 1, of density 0.18 g/cm, is treated with a binder liquid of the following composition:
- the impregnating step is carried out as described in Example 1, except that the impregnating liquid is an aqueous liquid which contains 80 g/l of cross-linkable silicone (for example Akophob" SN of Farbwerke Hoechst AG).
- the impregnating liquid is an aqueous liquid which contains 80 g/l of cross-linkable silicone (for example Akophob" SN of Farbwerke Hoechst AG).
- the impregnated fleece is further treated as indicated in Example 1 and there is incorporated an aqueous elastomer dispersion of the following composition:
- the fleece When the fleece has been impregnated in this liquid, it is withdrawn and the excess of liquid is expressed in the nip of a pair of rollers. The fleece is then subjected to the radiation of an infrared radiator and the elasto' mer in the fleece is thereby coagulated (coagulation temperature 38 C). Thereafter the fleece is dried in a tenter frame drier and is then heat-treated for 5 minutes at C, whereby the elastomer is cross-linked.
- the fleece produced can be used as a substrate for a synthetic leather substitute having properties resembling soft cowhide.
- the fleece has a total elastomer content of 48% by weight relative to the total weight of the fleece, a tensile strength of 1.6 kp/mm a tear propagation strength of 10 kp/mm and a force required for 5% elongation of 0.06 kp/mm". 5
- EXAMPLE 4 A random fiber fleece of the composition described in Example 1, having a density of 0.28 glcm, is bonded in the manner described in Example 1 except that the binder dispersion has the following composition:
- the impregnating step is carried out as in Example 2,
- melamine-formaldehyde precondensate for example Cassurit" MLP of Farbwerke Cassella, Frankfurt/M., Mainkur
- MgCl 12 g/l of a synthetic perfluorinated compound for example Oleophobol" FC 218 of Chemische Fabrik Pfersee.
- aqueous solution 50% by weight aqueous solution 2.4 g ofa 20% by weight solution of silicone oil in toluene (for example Silicone Oil AL of Wacker- Chemie), and g 2.4 g of polysiloxane (for example Coagulant WS of Wegriken Bayer).
- silicone oil in toluene for example Silicone Oil AL of Wacker- Chemie
- polysiloxane for example Coagulant WS of
- the fleece produced is suitable for use as a substrate for the manufacture of a synthetic material having leather-like properties of the type of soft cowhide.
- EXAMPLE 7 A polyester spun fleece of density 0.54 g/cm (filament titre 8 dtex) is bonded in the manner described in Example 1, with binder liquid of the following composition:
- the fleece is impregnated in the manner indicated in Example 1.
- Example 2 In contrast to Example 1, no elastomer is incorporated into the bonded and impregnated fleece.
- the fleece is split into individual layers parallel to the plane of the fleece.
- the layers have a weight per unit area of approximately g/m
- the tensile strength of such a layer is 1.4 kp/mm and the tear propagation strength is 9 kp/mm.
- a process for the manufacture of chemically bonded non-woven textile fiber sheet material which comprises a. treating a non-woven textile fiber sheet material with a binder liquid composed of an aqeous dispersion of a synthetic elastomer containing chemically reactive groups and a solution of silicone oil in toluene,
- step (a) contains as said aqueous dispersion an aqueous dispersionn of a copolymer of 92 by weight of butyl acrylate, 4% by weight of methacrylic acid and 4% by weight of acrylamide.
- step (21) contains said aqueous dispersion an aqueous dispersion of a copolymer of 8671 by weight of butyl acrylate. 4% by weight of itaconic acid. 871 by weight of dimethylolmethacrylic acid amide and 2% by weight of methacrylic acid.
- step (g) there is used a copolymer based on butadiene-acrylonitrile-methacrylic acid.
- step (g) there is used a copolymer of approximately 64% by weight of butadiene, approximately 32% by weight of acrylonitrile and approximately 4% by weight of methacryllic acid.
- step (g) polyurethane is used.
- step ((1) contains dimethylpolysiloxane.
- step ((1) contains a melamineformaldehyde precondensate and a synthetic perl'luorinated compound.
- a chemically bonded non-woven textile fiber sheet material when made by the process claimed in claim 1.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Nonwoven Fabrics (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US439739A US3922419A (en) | 1971-09-24 | 1974-02-05 | Manufacture of a reinforced, non-woven textile fiber sheet material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2147757A DE2147757C3 (de) | 1971-09-24 | 1971-09-24 | Verfahren zur Herstellung eines verfestigten, ungewebten textlien Faserflächengebildes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3853608A true US3853608A (en) | 1974-12-10 |
Family
ID=5820486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00291323A Expired - Lifetime US3853608A (en) | 1971-09-24 | 1972-09-22 | Manufacture of a reinforced, non-woven textile fiber sheet material |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US3853608A (cs) |
| JP (1) | JPS4842175A (cs) |
| CS (1) | CS161957B2 (cs) |
| DE (1) | DE2147757C3 (cs) |
| FR (1) | FR2153405B1 (cs) |
| GB (1) | GB1412642A (cs) |
| IT (1) | IT965463B (cs) |
| RO (1) | RO62456A (cs) |
| YU (1) | YU242372A (cs) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3973067A (en) * | 1971-05-18 | 1976-08-03 | The Kendall Company | Short-fibered nonwoven fabrics |
| US4324831A (en) * | 1974-11-14 | 1982-04-13 | Montedison S.P.A. | Formed structures based on synthetic fibers and having soundproofing properties |
| US5194484A (en) * | 1991-09-25 | 1993-03-16 | E. I. Du Pont De Nemours And Company | Process for making fluoropolymer composites |
| US6117489A (en) * | 1995-09-07 | 2000-09-12 | Teijin Limited | Microporous sheet, substrate for artificial leather using said sheet, and process for production of said sheet |
| ES2448740A1 (es) * | 2013-12-17 | 2014-03-14 | Tejidos Royo, S.L. | Procedimiento de obtención de un tejido con aspecto de piel, símil al cuero, y correspondiente tejido obtenido |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4882114A (en) | 1984-01-06 | 1989-11-21 | The Wiggins Teape Group Limited | Molding of fiber reinforced plastic articles |
| GB8618729D0 (en) | 1986-07-31 | 1986-09-10 | Wiggins Teape Group Ltd | Fibrous structure |
| GB8618726D0 (en) | 1986-07-31 | 1986-09-10 | Wiggins Teape Group Ltd | Thermoplastics material |
| GB8618727D0 (en) | 1986-07-31 | 1986-09-10 | Wiggins Teape Group Ltd | Thermoplastic sheets |
| US5215627A (en) | 1986-07-31 | 1993-06-01 | The Wiggins Teape Group Limited | Method of making a water laid fibrous web containing one or more fine powders |
| US5242749A (en) | 1987-03-13 | 1993-09-07 | The Wiggins Teape Group Limited | Fibre reinforced plastics structures |
| GB8818425D0 (en) | 1988-08-03 | 1988-09-07 | Wiggins Teape Group Ltd | Plastics material |
| JP2852440B2 (ja) * | 1989-10-30 | 1999-02-03 | コニカ株式会社 | ハロゲン化銀写真感光材料 |
| JP2805908B2 (ja) * | 1989-11-02 | 1998-09-30 | 東レ株式会社 | 人工皮革用繊維質シート状物 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3322606A (en) * | 1963-06-24 | 1967-05-30 | Du Pont | Double-faced pile article |
| US3369948A (en) * | 1964-11-12 | 1968-02-20 | Du Pont | Method of producing a pile fabric |
| US3401078A (en) * | 1962-10-19 | 1968-09-10 | Battelle Institut E V | Paper and process for making same of synthetic fibers bonded at their intercrossing points by a thermoplastic polyamide resin |
| US3501368A (en) * | 1963-08-06 | 1970-03-17 | Freudenberg Carl Kg | Interlining |
| US3770562A (en) * | 1971-09-09 | 1973-11-06 | Kendall & Co | Composite nonwoven fabrics |
-
1971
- 1971-09-24 DE DE2147757A patent/DE2147757C3/de not_active Expired
-
1972
- 1972-09-21 RO RO7272294A patent/RO62456A/ro unknown
- 1972-09-22 US US00291323A patent/US3853608A/en not_active Expired - Lifetime
- 1972-09-22 CS CS6491A patent/CS161957B2/cs unknown
- 1972-09-22 FR FR7233622A patent/FR2153405B1/fr not_active Expired
- 1972-09-22 GB GB4398072A patent/GB1412642A/en not_active Expired
- 1972-09-22 IT IT52899/72A patent/IT965463B/it active
- 1972-09-25 YU YU02423/72A patent/YU242372A/xx unknown
- 1972-09-25 JP JP47096040A patent/JPS4842175A/ja active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3401078A (en) * | 1962-10-19 | 1968-09-10 | Battelle Institut E V | Paper and process for making same of synthetic fibers bonded at their intercrossing points by a thermoplastic polyamide resin |
| US3322606A (en) * | 1963-06-24 | 1967-05-30 | Du Pont | Double-faced pile article |
| US3501368A (en) * | 1963-08-06 | 1970-03-17 | Freudenberg Carl Kg | Interlining |
| US3369948A (en) * | 1964-11-12 | 1968-02-20 | Du Pont | Method of producing a pile fabric |
| US3770562A (en) * | 1971-09-09 | 1973-11-06 | Kendall & Co | Composite nonwoven fabrics |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3973067A (en) * | 1971-05-18 | 1976-08-03 | The Kendall Company | Short-fibered nonwoven fabrics |
| US4324831A (en) * | 1974-11-14 | 1982-04-13 | Montedison S.P.A. | Formed structures based on synthetic fibers and having soundproofing properties |
| US5194484A (en) * | 1991-09-25 | 1993-03-16 | E. I. Du Pont De Nemours And Company | Process for making fluoropolymer composites |
| US6117489A (en) * | 1995-09-07 | 2000-09-12 | Teijin Limited | Microporous sheet, substrate for artificial leather using said sheet, and process for production of said sheet |
| ES2448740A1 (es) * | 2013-12-17 | 2014-03-14 | Tejidos Royo, S.L. | Procedimiento de obtención de un tejido con aspecto de piel, símil al cuero, y correspondiente tejido obtenido |
| WO2015092091A1 (es) * | 2013-12-17 | 2015-06-25 | Tejidos Royo, S.L. | Procedimiento de obtención de un tejido con aspecto de piel, símil al cuero, y correspondiente tejido obtenido |
| EP2905375A4 (en) * | 2013-12-17 | 2015-12-09 | Tejidos Royo S L | METHOD FOR THE PRODUCTION OF A TISSUE COMPRISING LEATHER, ARTIFICIAL LEATHER AND TISSUE MANUFACTURED IN THIS PROCESS |
| US10287729B2 (en) * | 2013-12-17 | 2019-05-14 | Tejidos Royo, S.L. | Process for obtaining a fabric with the appearance of leather, imitation leather, and the fabric obtained |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2147757C3 (de) | 1980-10-09 |
| FR2153405A1 (cs) | 1973-05-04 |
| FR2153405B1 (cs) | 1976-08-13 |
| YU242372A (en) | 1979-10-31 |
| DE2147757B2 (de) | 1980-02-21 |
| RO62456A (fr) | 1979-02-15 |
| GB1412642A (en) | 1975-11-05 |
| JPS4842175A (cs) | 1973-06-19 |
| CS161957B2 (cs) | 1975-06-10 |
| IT965463B (it) | 1974-01-31 |
| DE2147757A1 (de) | 1973-04-12 |
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