US3752733A - Bonded nonwoven fibrous product - Google Patents
Bonded nonwoven fibrous product Download PDFInfo
- Publication number
- US3752733A US3752733A US00872412A US3752733DA US3752733A US 3752733 A US3752733 A US 3752733A US 00872412 A US00872412 A US 00872412A US 3752733D A US3752733D A US 3752733DA US 3752733 A US3752733 A US 3752733A
- Authority
- US
- United States
- Prior art keywords
- ethylene
- fibers
- vinyl chloride
- nonwoven fibrous
- percent
- 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 76
- 239000005977 Ethylene Substances 0.000 abstract description 74
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 73
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 41
- 239000000178 monomer Substances 0.000 abstract description 19
- 239000000203 mixture Substances 0.000 abstract description 13
- 239000000835 fiber Substances 0.000 description 78
- 239000000047 product Substances 0.000 description 61
- 239000007767 bonding agent Substances 0.000 description 42
- 239000002657 fibrous material Substances 0.000 description 37
- -1 for example Substances 0.000 description 23
- 239000002253 acid Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 15
- 150000007513 acids Chemical class 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 229920002994 synthetic fiber Polymers 0.000 description 12
- 239000012209 synthetic fiber Substances 0.000 description 12
- 229920002522 Wood fibre Polymers 0.000 description 10
- 239000002025 wood fiber Substances 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000004745 nonwoven fabric Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical class OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 5
- 235000011087 fumaric acid Nutrition 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Chemical class OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002238 fumaric acids Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical class OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 150000002689 maleic acids Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000001530 fumaric acid Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011976 maleic acid Chemical class 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Chemical class 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- FPPLCVCBDMUGNC-UHFFFAOYSA-N 2,3-dioctylbutanedioic acid Chemical compound C(CCCCCCC)C(C(=O)O)C(C(=O)O)CCCCCCCC FPPLCVCBDMUGNC-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical class FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- VRWOCLJWLOZDAI-UHFFFAOYSA-N 2-methyl-n-propanoylprop-2-enamide Chemical compound CCC(=O)NC(=O)C(C)=C VRWOCLJWLOZDAI-UHFFFAOYSA-N 0.000 description 1
- GQVHDJDEKIOIGV-UHFFFAOYSA-N 4-methyl-2-methylidene-3-oxopent-4-enoic acid Chemical class CC(=C)C(=O)C(=C)C(O)=O GQVHDJDEKIOIGV-UHFFFAOYSA-N 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000282461 Canis lupus Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001481789 Rupicapra Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SINBSQXYGVEEHM-ONEGZZNKSA-N bis(3-hydroxypropyl) (e)-but-2-enedioate Chemical compound OCCCOC(=O)\C=C\C(=O)OCCCO SINBSQXYGVEEHM-ONEGZZNKSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 210000000085 cashmere Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical class OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- DSTWFRCNXMNXTR-AATRIKPKSA-N dipropyl (e)-but-2-enedioate Chemical compound CCCOC(=O)\C=C\C(=O)OCCC DSTWFRCNXMNXTR-AATRIKPKSA-N 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- ZFRKEVMBGBIBGT-UHFFFAOYSA-N ethenyl benzenesulfonate Chemical compound C=COS(=O)(=O)C1=CC=CC=C1 ZFRKEVMBGBIBGT-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 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 description 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- 210000000050 mohair Anatomy 0.000 description 1
- JWHMNITWPQGHPL-UHFFFAOYSA-N n-(2-hydroxypropanoyl)-2-methylprop-2-enamide Chemical class CC(O)C(=O)NC(=O)C(C)=C JWHMNITWPQGHPL-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical compound CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- JICVCSXXNQPZEZ-UHFFFAOYSA-N prop-2-enoyl 3-hydroxypropanoate Chemical compound OCCC(=O)OC(=O)C=C JICVCSXXNQPZEZ-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Chemical class OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- 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
- D21H17/35—Polyalkenes, e.g. polystyrene
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
-
- D—TEXTILES; PAPER
- 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
-
- 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
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
- D21H17/43—Carboxyl groups or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
Definitions
- This invention relates to bonded nonwoven fibrous products employing an ethylene/vinyl chloride interpolymer as the bonding agent.
- nonwoven fibrous material as used herein means a consolidated mass of fibers laid down by mechanical, chemical, pneumatic, electrical or vacuum means, or otherwise deposited, into the desired shape, either flat (webs, mats or sheets) or three-dimensional.
- Nonwoven fibrous material can be formed by both a wet process and a dry process.
- the fibers are slurried in water or similar inert liquid. The slurry is spread on a fiat surface, the inert liquid drained OE, and the Web dried under pressure to form the loosely consolidated mass of randomly-distributed fibers.
- the fibers in the dry state are laid on a solid, fiat surface, for example, a conveyer, by mechanical means or pneumatic means, for example, a carding machine or an air-lay machine.
- the dry process can be used to lay down the fibers in either a random distribution or an oriented distribution.
- a thorough discussion of the formation of nonwoven fabrics is presented in Non Woven Fabrics by F. N. Buresh Reinhold Publishing Company, New York, NY. (1962).
- the material is at this point only a flimsy structure having virtually no tensile strength and is unable to remain as a unitary piece without support.
- the nonwoven fibrous material possess the necessary tensile strength and cohesion required for practical applications, it is necessary that the fibers be bonded and interlocked in some fashion.
- the usual and most economical means of accomplishing the bonding and interlocking of the fibers is to impregnate or saturate the nonwoven fibrous material with a bonding agent followed by heating or other means of activation in order to coalesce and fuse the bonding agent, and bond and interlock the fibers.
- bonded nonwoven products exhibit good elongation, resistance to oils and solvents, good drape and hand characteristics, good flame resistance, and non-discoloration, as well as high tensile strength.
- bonded nonwoven fibrous products which exhibit the desirable combination of high tensile strength and elongation, as well as good hand and drape characteristics, are obtained by using an ethylene/vinyl chloride interpolymer as the bonding agent for the nonwoven fibrous material.
- the bonded nonwoven fibrous products of this invention can be formed of either natural or synthetic fibers or any combination thereof with the selection of the fiber merely depending upon the specific end use intended for the bonded nonwoven fibrous product.
- the fibers that can be used in accordance with this invention are natural fibers, for example, Wood, jute, sisal, hemp, cotton linters, silk, mohair, cashmere, asbestos and wool, and synthetic fibers, for example, glass, rayon cellulose esters such as cellulose acetate, polyvinyl chloride, polyvinyl acetate, polyacrylonitrile and copolymers thereof, polyethylene, polypropylene and the like, polyesters such as eth'ylene glycol-terephthalate polymers, and polyamides of the nylon type.
- the bonded nonwoven fibrous products of this invention are prepared from a plurality of natural fibers, or a plurality of synthetic fibers, or a combination of natural and synthetic fibers.
- Combinations of wood fiber and cotton fiber can be advantageously employed in end products such as shoe liners and the like.
- the wood fiber comprises the major amount of the fiber content of such bonded nonwoven fibrous products.
- Combinations of glass fiber and asbestos fiber are generally employed in insulating applications.
- Combinations of glass fiber and wood fiber are also useful in certain drapery applications.
- the weight ratio of glass fiber to cellulosic fiber in such bonded nonwoven fibrous products is usually from about 1:10 to about 10: 1.
- a combination of wood fibers and nylon fibers or a combination of wood fibers and rayon fibers can be advantageously employed.
- Combinations of wood fiber and nylon fiber as well as combinations of wood fiber and polyester fiber are also widely employed in various applications where reinforced sheeting is required.
- the weight ratio of natural fiber to synthetic fiber is generally from about 1:20 to about 20:1 and preferably from about 1:1 to about 3:1.
- nonwoven fibrous materials useful in the preparation of the bonded nonwoven fibrous products of this invention can be prepared by any method known to the art.
- the nonwoven fibrous material can be made of fibers deposited in a random manner as well as fibers oriented or aligned along a particular axis.
- Nonwoven fibrous materials in the form of two-dimensional webs can be prepared by the following methods. Oriented webs are produced using conventional web-style machines, such as openers, pickers, cards, or garnetts. Cross-laid webs are made in a manner similar to oriented webs, except that the fibers are carefully placed at right angles to the machine direction to improve cross-wise strength.
- Random webs are produced in air-lay machines, and the nonwoven fibrous material has equal strength in all directions.
- continuous filaments are fed through a cutter or breaker which discharges the fibers into the discharge side of a blower.
- Suitable conduits are provded to guide the fibers to a collecting screen or airpervious structure for collecting the fibers in the form desired.
- the screen may be in the form of an endless traveling belt passing through the lower portion of a tower into the upper portion of which the blown fibers are introduced by the conduit.
- a suction box may be placed beneath the traveling screen to assist in the deposition of the fibers thereon.
- a stationary formed screen may be used.
- the screen may take the form of a hat shaped cone, such as that used in the felt hat-making industry. Alternatively it may have any other form which is suitable to produce the desired shape of the bonded nonwoven fibrous product such as a rectangular tray. As is the case with the endless traveling belt, suction may also be applied beneath the stationary screen to assist deposition of the fibers thereon.
- Random webs are also produced by the direct spray method from a solution or molten mass of the fiber material.
- This is the conventional procedure for the formation of glass fibers or mineral wool fibers, as well as those of nylon or thermoplastic materials, adapted to be dissolved in a suitable solvent or to be melted.
- the solution or melt is directed to suitable nozzles or jet-forming orifices and a high pressure fluid stream, such air, nitrogen or steam, is directed against the stream or streams of filament-forming material to disrupt them and coagulate them as fibers in the vicinity of the orifices.
- Electrostatic spinning methods can also be employed for this purpose.
- the disrupted and dispersed fibers can be directed to the top of the settling tower and allowed to settle with the aid of suction devices upon a suitable traveling or stationary screen at the bottom of the tower.
- This procedure is particularly adapted to the production of fibers of siliceous materials such as glass or mineral wool, as well as to thermoplastic resin fibers.
- Spun-bonded webs are made of randomly oriented continuous filament fibers bonded at the cross-over point.
- the method includes extrusion of the continuous filament fibers, drawing to orient the fiber, some fiber entanglement by liquids or air, and bonding at the crossover points.
- the bonded nonwoven fibrous products of this invention are generally prepared by a method which comprises consolidating the loose fibers into nonwoven fibrous material having the structural configuration of the desired bonded nonwoven fibrous product, dispersing the ethylene/vinyl chloride interpolymer bonding agent within the nonwoven fibrous material, and heating the impregnated nonwoven fibrous material to a temperature sufficient to coalesce and fuse the interpolymer, and optionally heating to a temperature sufiicient to cross-link the interpolymer if a sulfur cross-linking agent is employed.
- the bonding agent dispersion or powder can be sprayed directly on the fibers while still hot so that immediately after deposition the bonding agent is set and it bonds and interlocks the fibers in proper relationship.
- the interpolymers which are useful in the preparation of the bonded nonwoven fibrous products of this invention generally contain from about 5 to about 70 weight percent ethylene, from about 30 to about 95 weight percent vinyl chloride, and from about 0.1 to about weight percent of a polar monomer component.
- the polar monomer component can be entirely acrylamide or a portion of the acrylamide can be replaced by one or more polar monomers selected from the group consisting of acrylonitrile, N-(lower alkyl) acrylamide and N-(lower alkyl) methacrylamide containing from 1 to 3 carbon atoms in the lower alkyl groups, N-methylol acrylamide, N[2-(2-methyl-4-oxopentyl)] acrylamide, acrylic acid, methacrylic acid, and alkali metal and ammonium salts of acrylic and methacrylacrylic acids, maleic acid, fumaric acid, half and complete alkali metal and ammonium salts of maleic and fumaric acid, aconitic acid, itaconic acid, citraconic acid, and alkali metal and ammonium salts thereof, acrylyl and methacrylyl esters of hydroxyalkanoic acids having from 2 to about 6 carbon atoms in the alkanoic acid moieties, acryly
- the interpolymers are at least terpolymers containing ethylene, vinyl chloride and acrylamide and may be a quaternary or higher polymer containing one or more of the above exemplified additional polar monomers in small quantities. Generally such additional polar monomers will not be present in the interpolymer in quantities greater than about 3 percent by Weight.
- the interpolymer contain from about 5 percent to about 70 percent ethylene, 30 percent to about percent vinyl chloride, and from about 1 percent to about 5 percent acrylamide.
- a specific example of choice is a terpolymer containing from about 19 to about 23 percent ethylene, about 74 to about 78 percent vinyl chloride, and from about 2 to about 4 percent acrylamide.
- the interpolymers used in accordance with this invention are generally unmodified, but modified interpolymers are also included for use in this invention.
- the interpolymers are particularly amenable to hydrolytic modification by the use of small quantities of a strongly alkaline material such as an alkali metal hydroxide, or a quaternary ammonium hydroxide such as tetramethyl ammonium hydroxide, or by a strong acid such as the mineral acids, e.g., hydrochloric, sulfuric, phosphoric, nitric.
- the base or acid used preferably has an ionization constant higher than 10* at 25 C.
- the hydrolytic modification is carried out by treating an aqueous dispersion or polymer latex of the ethylene, vinyl chloride, and acrylamide with aqueous base or acid in an amount chemically equivalent to from about 0.1% to about percent of the amide equivalent in the interpolymer.
- the ethylene/vinyl chloride interpolymer bonding agents can be applied to the fibers of the nonwoven fibrous material by any means known in the art.
- the ethylene/vinyl chloride interpolymer bonding agents are usually applied to the fibers of the nonwoven fibrous material by application to the surface thereof, or by submersion of the nonwoven fibrous material in a liquid, thickened or foamed dispersion so that the bonding agent penetrates into the interior of the nonwoven fibrous material.
- the nonwoven fibrous material is a two-dimensional fabric in the form of a fleece or web
- the ethylene/vinyl chloride interpolymer bonding agents are usually applied in the form of an aqueous dispersion.
- the fabric is impregnated with the ethylene/vinyl chloride interpolymer bonding agent by dipping or immersing the fabric in the dispersion to provide sufiicient wet pickup of the bonding agent.
- the wetted, nonwoven fibrous material in the form of a fleece or web can be passed between a pair of pressure rolls to effect substantially uniform impregnation and also to control the amount of the bonding agent applied.
- the impregnated nonwoven fibrous material is dried by conventional means known to the art in order to remove all or a portion of the water and to effect coalescence and fusion of the ethylene/vinyl chloride interpolymer within the nonwoven fibrous material.
- the drying temperature and drying time are dependent upon the size, shape and cross-section of the impregnated, nonwoven fibrous material. In general, the drying temperature is controlled so that no appreciable deterioration or degradation of the fibers or the ethylene/vinyl chloride interpolymer occurs.
- the dispersion When the ethylene/vinyl chloride interpolymer bonding agents are used in the form of a dispersion, the dispersion generally contains from about 5% to about 90% of the interpolymer by weight. Such dispersions preferably contain from about to about 60% by weight of interpolymer for ease of application by means of dipping, soaking, spraying and the like.
- the amount of ethylene/vinyl chloride interpolymer bonding agent based on the weight of the fiber component of the bonded nonwoven fibrous product can vary widely depending upon the characteristics desired in the final product and the specific end use.
- the bonded nonwoven fibrous products of this invention generally contain from about 2% to about 200% of interpolymer based on the weight of the fibers.
- the amount of ethylene/vinyl chloride interpolymer bonding agent employed generally falls in the lower part of the above range if the bonding agent is applied primarily adjacent to the surface or surfaces of the product or if it is applied in conjunction with other binders.
- the ethylene/vinyl chloride interpolymer bonding agent is to serve mainly to bond the fibers together to form a bonded nonwoven fibrous product in which the maximum porosity is retained in conjunction with a minimum change of fiber hand and drape characteristics as well as an increase in tensile strength
- the lower portion of this range generally gives the maximum porosity and provides a minimum change in the fiber hand and drape characteristics although in the higher portion of this range porosity is mainly retained and the fiber hand and drape characteristics are still evident.
- the bonded nonwoven fibrous products thus obtained are advantageously used for many sanitary purposes, such as table napkins, bibs, tablecloths, sanitary napkin covers, disposable diapers, disposable sheets, and surgical dressings and compresses.
- this amount of bonding agent is used there is relatively little or no window paning i.e., the interstices between fibers are left open leaving a highly porous bulky product.
- the density of the product can be modified by the application of various amounts of pressure prior to, or in many cases, after the saturated nonwoven fibrous material has been heated for bonding.
- Bonded nonwoven fibrous products containing from about 40% to about 150% by weight of ethylene/vinyl chloride interpolymer bonding agent based on the weight of the fiber generally find use in the garment industry to provide interlining fabrics for coats, dresses, collars, cuffs, and the like, and to provide outer wearing apparel fabrics, such as blouses, skirts, shirts, dresses, and the like. Bonded nonwoven fibrous products containing the bonding agent in this range are also useful as curtain and drapery materials.
- the bonded nonwoven fibrous products of this invention in which 10% to by weight of bonding agent based on the weight of fiber is employed find many light industrial uses as wiping cloths, filters and lining materials for packaging.
- Bonded nonwoven fibrous products of the present invention which contain from about 100% to about 200% by weight of the bonding agent based on the weight of the fiber are particularly useful for heavy industrial uses where durability and resistance to wear are desired.
- Such uses include industrial gaskets, packings, filters, and the like.
- the aqueous dispersion of ethylene/vinyl chloride interpolymer can also contain a wetting agent to assist penetration of the nonwoven fibrous material to which it is applied.
- the aqueous dispersions can also contain a foaming agent or they can contain a defoamer when the ingredients of the aqueous dispersion have a tendency to give rise to foaming and when such foaming is undesirable.
- the conventional wetting agents such as the sodium salt of dioctylsuccinic acid can be used and the conventional foaming and defoaming agents can be employed such as sodium soaps including sodium oleate for foaming and octyl alcohol or certain silicone antifoaming agents for defoaming.
- Ethylene/vinyl chloride interpolymers can be cross-linked with various sulfur containing compounds as is disclosed in United States Patent No. 3,356,658.
- the interpolymers are crosslinked by subjecting the bonded nonwoven fibrous product, after the drying operation, or as a final portion of the drying stage itself, to a curing operation as disclosed in US. 3,356,658.
- the bonded nonwoven fibrous products of this invention are characterized by high tensile strength, good elongat on, softness, good hand and flexibility, good drape and resistance to many common solvents and detergents. With these properties, the bonded nonwoven fibrous products of this invention are suitable for use in a wide variety of end applications, many of which have been noted above and including, for example, paper board, toilet tissues,
- the ethylene/vinyl chloride interpolymer bonding agents have been described as the sole bonding agent for the bonded nonwoven fibrous products of this invention.
- the interpolymers can be employed in combination with thermosetting, precondensate resins, such as aminoplasts, which are capable of cooperating with the ethylene/vinyl chloride interpolymer bonding agents to give enhanced properties of launderability and dry cleaning resistance to the bonded nonwoven fibrous products, particularly when they are in the form of fabric material.
- the preferred aminoplast resins for blending with the ethylene/vinyl chloride interpolymers are the condensation products or pre-condensates of urea and formaldehyde, ethylene, urea and formaldehyde, and of formaldehyde and melamine including alkalated, pre-condensates of urea formaldehyde and melamine formaldehyde.
- Typical of these aminoplasts are the reaction products of formaldehyde and triazines, such as melamine and the alcohol modified melamine formaldehyde condensates which have been etherified by reaction with a lower alcohol, such as methyl or ethyl alcohol.
- auxiliary bonding agent employed with the ethylene/vinyl chloride interpolymers
- it can be used in amounts up to about 50% by weight, based on the weight of the ethylene/vinyl chloride interpolymer bonding agent, with about to by weight of the aminoplast being preferably employed.
- the ethylene/vinyl chloride interpolymers useful in this invention are readily prepared by various means well known to the art.
- the interpolymers can be prepared by first mixing ethylene and vinyl chloride in an aqueous medium in the presence of any suitable anionic or nonionic emulsifier and any initiator capable of generating free radicals in the chemical mixture at the chosen reaction temperature and pressure.
- the acrylamide preferably in aqueous solution either alone or mixed with the appropriate amounts of other polar monomers, is added to the polymerizing ethylene and vinyl chloride mixture gradually throughout the reaction.
- the addition of the acrylamide is preferably begun after about 40 to 50 percent of the desired conversion of the ethylene and vinyl chloride has been reached.
- a shell-core latex in which the polar monomer is concentrated in the outer layers is produced.
- the ethylene/vinyl chloride/acrylamide interpolymers used in this invention are preferably prepared by a process which comprises mixing ethylene and vinyl chloride monomers in the presence of an alkaline buffered reductionoxidation (redox) initiator-catalyst system, water, and from about 1 percent to about 8 percent by weight based upon the monomer feed, or from about 4 percent to about 7 percent based upon the polymer product of an anionic or non-ionic emulsifying agent having a hydrophilic-lipophilic balance (HLB) value of from about 10 to about 40, and reacting the mixture at a temperature and pressure and for a time sufficient to cause polymerization between the ethylene and vinyl chloride, and then to introduce acrylamide, either alone, or mixed with other monomers in minor amounts in an appropriate diluent such as water into the pressurized polymerizing reaction mixture of the ethylene and vinyl chloride.
- redox alkaline buffered reductionoxidation
- Ethylene/vinyl chloride latices prepared by this process have particles sizes of emulsified interpolymer from about 500 to 5000 angstroms, preferably from about 1000 to about 2000 angstroms.
- EXAMPLE 1 This example illustrates the preparation of a 21/76/3 ethylene/vinyl chloride/acrylamide interpolymer latex.
- Reaction vessel initial charge G K S O (KPS) 11.0 NaHCO 15.0 Fe(NO -9H O 0.8 Tetrasodium ethylenediaminetetraacetate (Na EDTA) 1.5 Na lauryl sulfate (SLS) 1.2 H 0 to make 1700 ml. Vinyl chloride (VCl) 450 Ethylene (E) 150
- KPS K S O
- Na EDTA Tetrasodium ethylenediaminetetraacetate
- SLS Na lauryl sulfate
- VCS Vinyl chloride
- E Ethylene
- the above ingredients are charged to a suitable reaction vessel and heated to 30 C. with stirring to give a reaction pressure of 850 p.s.i.g. Polymerization is started by adding a l M sodium formaldehyde sulfoxylate- NaHSO -CH O-2H (SFS) /1.5 M
- ammonium hydroxide (NH OH) solution to the mixture at a rate of 5.2 ml./hr. at the same time 18 ml./hr. of a 25 percent SLS solution is added and the pressure is kept constant by the addition of pure vinyl chloride as required.
- a 50 percent solution of acrylamide in water solution is added at 40 ml./hr.
- the reaction steps after 5.5 hours and the feed streams are turned off.
- a total of 1330 g. of VCl, 95 ml. of the 50 percent acrylamide, 27 ml. of the l M SFS/1.5 M NH OH solution, and 92 ml. of the 25 percent SLS solution are added.
- the resulting polymer latex is vented out the bottom of the autoclave.
- a total of about 3500 g. of the ethylene/ vinyl chloride/acrylamide polymer latex is obtained containing 47 percent total solids, and 1.5 percent sodium lauryl sulfate (based on the weight of the polymer). It has a pH of 7.7
- the composition of the terpolymer is about 21/76/3 ethylene/vinyl chloride/acrylamide.
- EXAMPLE 2 Preweighed samples of Hollingsworth and Vose nonwoven fabric composite comprising weight percent cellulosic fiber and 25 weight percent nylon fiber are immersed in aqueous dispersions of ethylene/vinyl chloride interpolymer bonding agents.
- the aqueous dispersions contain 13.5 weight percent interpolymer solids.
- the impregnated fabrics are passed through a size press, weighed, dried for about two minutes at a temperature of about 118 C. and weighed.
- the bonded nonwoven fabrics are subjected to calendering through a single nip for smoothness and tested for hand and drape characteristics and tensile strength. Hand and drape characteristics are determined qualitatively by touch and results are given on a scale of 1 through 10. Number 1 means very soft and highly flexible.
- Tensile strength is determined by TAPPI T40403-6l with a table model Instron. Results and further details are given in the table below Where the amount of bonding agent in the bonded nonwoven fabric is given in percent by dry weight based on the weight of the nonwoven fabric, tensile strength is given in lb./in. width, and the following abbreviations are used in order to simplify tabular identification of the monomers.
- Bonded nonwoven fibrous product comprising nonwoven fibrous material bonded with a bonding agent consisting essentially of a composition selected from the group consisting of (I) an ethylene/vinyl chloride interpolymer containing from about to about 70 weight percent ethylene, from about 30 to about 95 weight per cent vinyl chloride, and from about 0.1 to about Weight percent of a polar component selected from the group consisting of (A) acrylamide, and
- nonwoven fibrous material is made of synthetic fibers.
- nonwoven fibrous material is a combination of natural fiber and synthetic fiber.
- nonwoven fibrous material is in the form of a two-dimensional web.
- ethylene/vinyl chloride interpolymer contains from about 15 to about 70 percent ethylene, from about 30 to about percent vinyl/ chloride and from about 0.1 to about 10 percent acrylamide.
- ethylene/vinyl chloride interpolymer contains from about 19 to about 23 percent ethylene, from about 74 to about 78 percent vinyl chloride, and from about 2 to about 4 percent acrylamide.
- ethylene/vinyl chloride interpolymer is a quaternary polymer containing from about 15 to about 70% ethylene, from about 30 to about 85 weight percent vinyl chloride, from about 1% to about 5% acrylamide, and from about 0.1 to about 3% by weight of bis-hydroxypropyl fumarate.
- nonwoven fibrous material is a combination of natural and synthetic fibers and the ethylene/vinyl chloride interpolymer contains from about 15 to about 70 percent ethylene, from about 30 to about 85 percent vinyl chloride, and from about 0.1 to about 10 percent acrylamide.
- combination of fibers comprises at least 50% by weight of fibers selected from the group consisting of cellulosic fibers, polyamide fibers, vinyl acetate fibers, fibers of polymers and copolymers of acrylonitrile, poly-(ethylene iglycol-tereph thalate) fibers and mixtures thereof.
- nonwoven fibrous material is composed of wood fibers and the ethylene/ vinyl chloride interpolymer contains from about 15 to about 70 percent ethylene, from about 30' to about 85 percent vinyl chloride, and from about 0.1 to about 10 percent acrylamide.
- nonwoven fibrous material is a combination of polyamide fibers and wood fibers and the ethylene/vinyl chloride interpolymer contains from about 19 to about 23 percent ethylene, from about 74 to about 78 percent vinyl chloride, and from about 2 to about 4 percent acrylamide.
- nonwoven fibrous material is a combination of natural and synthetic fibers and the ethylene/vinyl chloride interpolymer contains from about 15 to about 70 percent ethylene, from about 30 to about 85 percent vinyl chloride and from about 0.1 to about 10 percent of an additional polar component comprising acrylamide and N-methylol acrylamide.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nonwoven Fabrics (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US87241269A | 1969-10-29 | 1969-10-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3752733A true US3752733A (en) | 1973-08-14 |
Family
ID=25359517
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00872412A Expired - Lifetime US3752733A (en) | 1969-10-29 | 1969-10-29 | Bonded nonwoven fibrous product |
Country Status (7)
Country | Link |
---|---|
US (1) | US3752733A (enrdf_load_stackoverflow) |
JP (1) | JPS4822855B1 (enrdf_load_stackoverflow) |
CA (1) | CA940437A (enrdf_load_stackoverflow) |
DE (1) | DE2052926B2 (enrdf_load_stackoverflow) |
FI (1) | FI52597C (enrdf_load_stackoverflow) |
FR (1) | FR2065571B1 (enrdf_load_stackoverflow) |
GB (1) | GB1313170A (enrdf_load_stackoverflow) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3874913A (en) * | 1972-05-12 | 1975-04-01 | Peter Frederick Lofts | Method for making a nonwoven fabric |
US4395306A (en) * | 1980-01-31 | 1983-07-26 | The Dow Chemical Company | Method for preparing fibrous mats from a fibrous suspension |
US5057166A (en) * | 1989-03-20 | 1991-10-15 | Weyerhaeuser Corporation | Method of treating discontinuous fibers |
US5064689A (en) * | 1989-03-20 | 1991-11-12 | Weyerhaeuser Company | Method of treating discontinuous fibers |
US5071675A (en) * | 1989-03-20 | 1991-12-10 | Weyerhaeuser Company | Method of applying liquid sizing of alkyl ketene dimer in ethanol to cellulose fibers entrained in a gas stream |
US5230959A (en) * | 1989-03-20 | 1993-07-27 | Weyerhaeuser Company | Coated fiber product with adhered super absorbent particles |
US5432000A (en) * | 1989-03-20 | 1995-07-11 | Weyerhaeuser Company | Binder coated discontinuous fibers with adhered particulate materials |
US5463007A (en) * | 1985-08-06 | 1995-10-31 | Air Products And Chemicals, Inc. | Polymers of self- and diol reactive formaldehyde-free crosslinking monomers |
US5498478A (en) * | 1989-03-20 | 1996-03-12 | Weyerhaeuser Company | Polyethylene glycol as a binder material for fibers |
US5582644A (en) * | 1991-12-17 | 1996-12-10 | Weyerhaeuser Company | Hopper blender system and method for coating fibers |
EP1093750A3 (de) * | 1999-10-19 | 2003-01-29 | Ridder GmbH | Trennvorhang zum Abtrennen eines Nassbereiches von einem Trockenbereich, insbesondere Dusch- oder Brausebadvorhang |
US20030232559A1 (en) * | 2002-06-17 | 2003-12-18 | Goldstein Joel Erwin | Vinyl chloride/vinyl acetate/ethylene/self-crosslinking polymers for non-cellulosic based substrates |
US20050215158A1 (en) * | 2004-02-09 | 2005-09-29 | Herbert Hartgrove | Flame-retardant cellulosic nonwoven fabric |
US20050239359A1 (en) * | 2004-04-23 | 2005-10-27 | Jones Ronald B | Wet tensile strength of nonwoven webs |
EP1632596A1 (en) | 2004-09-07 | 2006-03-08 | Air Products Polymers, L.P. | Vinyl acetate/ethylene and vinyl chloride polymer blends as binders for nonwoven products |
US20060052017A1 (en) * | 2004-09-07 | 2006-03-09 | Boylan John R | Vinyl acetate/ethylene and ethylene/vinyl chloride blends as binders for nonwoven products |
US20070246180A1 (en) * | 2006-04-20 | 2007-10-25 | Kimberly-Clark Worldwide, Inc. | Tissue products containing triggerable polymeric bonding agents |
US20090225416A1 (en) * | 2008-03-04 | 2009-09-10 | E. I. Du Pont De Nemours And Company | Reflection-type projection screen |
US8152929B1 (en) * | 2009-05-01 | 2012-04-10 | Perring David A | Non-abrasive cleaning products |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3647615A (en) * | 1970-07-16 | 1972-03-07 | Monsanto Co | Ethylene/vinyl chloride/n-methylol acrylamide |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE625497A (enrdf_load_stackoverflow) * | 1961-11-29 | 1900-01-01 | ||
FR1414419A (fr) * | 1963-12-05 | 1965-10-15 | Bayer Ag | Procédé de préparation de matières toisonnées teintes ou imprimées |
FR1490919A (fr) * | 1965-08-02 | 1967-08-04 | Goodrich Co B F | Procédé de durcissement de copolymères d'éthylène-chlorure de vinyle et produits obtenus |
-
1969
- 1969-10-29 US US00872412A patent/US3752733A/en not_active Expired - Lifetime
-
1970
- 1970-10-28 JP JP45094391A patent/JPS4822855B1/ja active Pending
- 1970-10-28 DE DE2052926A patent/DE2052926B2/de not_active Withdrawn
- 1970-10-28 FI FI702895A patent/FI52597C/fi active
- 1970-10-28 GB GB5119270A patent/GB1313170A/en not_active Expired
- 1970-10-28 CA CA096,877A patent/CA940437A/en not_active Expired
- 1970-10-28 FR FR7038881A patent/FR2065571B1/fr not_active Expired
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3874913A (en) * | 1972-05-12 | 1975-04-01 | Peter Frederick Lofts | Method for making a nonwoven fabric |
US4395306A (en) * | 1980-01-31 | 1983-07-26 | The Dow Chemical Company | Method for preparing fibrous mats from a fibrous suspension |
US5463007A (en) * | 1985-08-06 | 1995-10-31 | Air Products And Chemicals, Inc. | Polymers of self- and diol reactive formaldehyde-free crosslinking monomers |
US5498478A (en) * | 1989-03-20 | 1996-03-12 | Weyerhaeuser Company | Polyethylene glycol as a binder material for fibers |
US6270893B1 (en) | 1989-03-20 | 2001-08-07 | Weyerhaeuser Company | Coated fiber product with adhered super absorbent particles |
US5230959A (en) * | 1989-03-20 | 1993-07-27 | Weyerhaeuser Company | Coated fiber product with adhered super absorbent particles |
US5432000A (en) * | 1989-03-20 | 1995-07-11 | Weyerhaeuser Company | Binder coated discontinuous fibers with adhered particulate materials |
US5064689A (en) * | 1989-03-20 | 1991-11-12 | Weyerhaeuser Company | Method of treating discontinuous fibers |
US5057166A (en) * | 1989-03-20 | 1991-10-15 | Weyerhaeuser Corporation | Method of treating discontinuous fibers |
US5516585A (en) * | 1989-03-20 | 1996-05-14 | Weyerhaeuser Company | Coated fiber product with adhered super absorbent particles |
US5071675A (en) * | 1989-03-20 | 1991-12-10 | Weyerhaeuser Company | Method of applying liquid sizing of alkyl ketene dimer in ethanol to cellulose fibers entrained in a gas stream |
US5582644A (en) * | 1991-12-17 | 1996-12-10 | Weyerhaeuser Company | Hopper blender system and method for coating fibers |
EP1093750A3 (de) * | 1999-10-19 | 2003-01-29 | Ridder GmbH | Trennvorhang zum Abtrennen eines Nassbereiches von einem Trockenbereich, insbesondere Dusch- oder Brausebadvorhang |
US20030232559A1 (en) * | 2002-06-17 | 2003-12-18 | Goldstein Joel Erwin | Vinyl chloride/vinyl acetate/ethylene/self-crosslinking polymers for non-cellulosic based substrates |
EP1375542A1 (en) * | 2002-06-17 | 2004-01-02 | Air Products Polymers, L.P. | Vinyl chloride/vinyl acetate/ethylene/self-crosslinking polymers for non-cellulosic based substrates |
US20050215158A1 (en) * | 2004-02-09 | 2005-09-29 | Herbert Hartgrove | Flame-retardant cellulosic nonwoven fabric |
US7638446B2 (en) * | 2004-02-09 | 2009-12-29 | Polymer Group, Inc. | Flame-retardant cellulosic nonwoven fabric |
US20100098919A1 (en) * | 2004-02-09 | 2010-04-22 | Polymer Group, Inc. | Flame-retardant cellulosic nonwoven fabric |
US20050239359A1 (en) * | 2004-04-23 | 2005-10-27 | Jones Ronald B | Wet tensile strength of nonwoven webs |
US7285504B2 (en) | 2004-04-23 | 2007-10-23 | Air Products Polymers, L.P. | Wet tensile strength of nonwoven webs |
EP1632596A1 (en) | 2004-09-07 | 2006-03-08 | Air Products Polymers, L.P. | Vinyl acetate/ethylene and vinyl chloride polymer blends as binders for nonwoven products |
US7247586B2 (en) | 2004-09-07 | 2007-07-24 | Air Products Polymers, L.P. | Vinyl acetate/ethylene and vinyl chloride polymer blends as binders for nonwoven products |
US7153791B2 (en) | 2004-09-07 | 2006-12-26 | Air Products Polymers, L.P. | Vinyl acetate/ethylene and ethylene/vinyl chloride blends as binders for nonwoven products |
US20060052017A1 (en) * | 2004-09-07 | 2006-03-09 | Boylan John R | Vinyl acetate/ethylene and ethylene/vinyl chloride blends as binders for nonwoven products |
US20060052018A1 (en) * | 2004-09-07 | 2006-03-09 | Boylan John R | Vinyl acetate/ethylene and vinyl chloride polymer blends as binders for nonwoven products |
US20070246180A1 (en) * | 2006-04-20 | 2007-10-25 | Kimberly-Clark Worldwide, Inc. | Tissue products containing triggerable polymeric bonding agents |
US7625462B2 (en) * | 2006-04-20 | 2009-12-01 | Kimberly-Clark Worldwide, Inc. | Tissue products containing triggerable polymeric bonding agents |
US20090225416A1 (en) * | 2008-03-04 | 2009-09-10 | E. I. Du Pont De Nemours And Company | Reflection-type projection screen |
WO2009111548A1 (en) * | 2008-03-04 | 2009-09-11 | E. I. Du Pont De Nemours And Company | Improved reflection-type projection screen |
US8014066B2 (en) | 2008-03-04 | 2011-09-06 | E.I. Du Pont De Nemours And Company | Reflection-type projection screen |
US8152929B1 (en) * | 2009-05-01 | 2012-04-10 | Perring David A | Non-abrasive cleaning products |
US10357331B1 (en) * | 2009-05-01 | 2019-07-23 | David A. Perring | Non-abrasive cleaning products |
Also Published As
Publication number | Publication date |
---|---|
FR2065571A1 (enrdf_load_stackoverflow) | 1971-07-30 |
FI52597B (enrdf_load_stackoverflow) | 1977-06-30 |
CA940437A (en) | 1974-01-22 |
FI52597C (fi) | 1977-10-10 |
FR2065571B1 (enrdf_load_stackoverflow) | 1973-11-23 |
JPS4822855B1 (enrdf_load_stackoverflow) | 1973-07-09 |
DE2052926B2 (de) | 1980-06-19 |
DE2052926A1 (de) | 1971-05-06 |
GB1313170A (en) | 1973-04-11 |
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