CN1059572A - 不含甲醛的粘结剂 - Google Patents
不含甲醛的粘结剂 Download PDFInfo
- Publication number
- CN1059572A CN1059572A CN91108608A CN91108608A CN1059572A CN 1059572 A CN1059572 A CN 1059572A CN 91108608 A CN91108608 A CN 91108608A CN 91108608 A CN91108608 A CN 91108608A CN 1059572 A CN1059572 A CN 1059572A
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- binding agent
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- 239000011230 binding agent Substances 0.000 title claims abstract description 50
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title abstract description 66
- 239000004744 fabric Substances 0.000 claims abstract description 46
- 239000011159 matrix material Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 33
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 13
- 239000002585 base Substances 0.000 claims description 36
- 229920005596 polymer binder Polymers 0.000 claims description 26
- 239000002491 polymer binding agent Substances 0.000 claims description 26
- 150000002148 esters Chemical class 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 150000001412 amines Chemical group 0.000 claims description 5
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 26
- 238000011282 treatment Methods 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000000523 sample Substances 0.000 description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 92
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 75
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 40
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 34
- 238000005108 dry cleaning Methods 0.000 description 32
- 239000000243 solution Substances 0.000 description 31
- 238000006386 neutralization reaction Methods 0.000 description 29
- 239000000178 monomer Substances 0.000 description 22
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical class CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 22
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 description 20
- 235000017550 sodium carbonate Nutrition 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 19
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 19
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 18
- 235000019580 granularity Nutrition 0.000 description 18
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 17
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 17
- 239000001530 fumaric acid Substances 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000013068 control sample Substances 0.000 description 14
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 12
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 12
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 235000010352 sodium erythorbate Nutrition 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000012856 packing Methods 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- -1 alkali metal salt Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 229920002994 synthetic fiber Polymers 0.000 description 5
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 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 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007771 core particle Substances 0.000 description 3
- 239000011152 fibreglass Substances 0.000 description 3
- 201000006747 infectious mononucleosis Diseases 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010420 shell particle Substances 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical class [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- 238000004017 vitrification Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
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- 230000008859 change Effects 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 229940043237 diethanolamine Drugs 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 238000002791 soaking Methods 0.000 description 2
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
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- NIONDZDPPYHYKY-SNAWJCMRSA-N (2E)-hexenoic acid Chemical compound CCC\C=C\C(O)=O NIONDZDPPYHYKY-SNAWJCMRSA-N 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
- DRMYLINAGHHBNG-UHFFFAOYSA-N 2-oxo-3h-furan-4-carboxylic acid Chemical compound OC(=O)C1=COC(=O)C1 DRMYLINAGHHBNG-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 1
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 241001093575 Alma Species 0.000 description 1
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- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
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- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 238000002715 modification method Methods 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
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- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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Abstract
提供一种用不含甲醛的水基组合物处理多孔软
基体的方法以及经这样处理的多孔软基体。更具体
地说,本发明指向一种用乳液聚合的粘结剂处理无纺
织物的方法,该粘结剂含有某些共聚的烯属不饱和二
元酸或其衍生物,其中,粘结剂用固定碱部分加以中
和。
Description
本发明涉及一种用不含甲醛的水基组合物处理多孔软基体的改良方法以及这样处理过的多孔软基体。更具体地说,本发明涉及一种用乳液聚合的粘结剂处理无纺织物的方法,该粘结剂含有烯属不饱和二元羧酸或其衍生物,其中,粘结剂用固定碱部分中和。
多孔的软基体常常用聚合粘结剂处理使其固结或增强。诸如纸张,织物,和无纺织物之类的多孔软基体常用含聚合粘结剂的溶液或分散液处理,使其性能得到改进。将聚合物粘结剂涂覆到多孔的软基体,使粘结剂配置在基体中或基体上面,可以改进基体的性能诸如回弹性、耐污性、耐干洗性、耐洗性,撕裂强度、耐折性等。
很多情况下希望用含聚合粘结剂的水溶液或水分散液涂覆多孔软基体,其中的粘结剂以大体为热塑性或未交联的状态存在,从而在粘结剂溶液或分散液与基体接触之后,可发生流动,渗透,成膜等行为。一旦粘结剂已到达其最终位置,或在干燥过程的同时,还常希望粘结剂发生交联,从而提高处理后的基体的性能。很多常用的交联剂诸如共聚的N-羟甲基丙烯酰胺和添加的脲-甲醛树脂总是含有或释放出甲醛,它对皮肤和眼睛有刺激性,是一种致变物,疑有致癌性。因此需要用一种能有效交联而不含甲醛的粘结剂来处理多孔基体。本发明采用不含甲醛的组合物处理多孔软基体的改进方法便解决了这个问题。
美国专利4,405,325公开了用一种水不溶性憎水型粘结剂粘结憎水的无纺织物,该粘结剂选自由50-80份苯乙烯和50-20份丁二烯组成的乳液聚合物,聚合物的玻璃化温度为-5℃-25℃。该专利还公开了加入不超过约5份(重量)的少量亲水型共聚单体诸如丙烯酸,甲基丙烯酸,衣康酸,以及丙烯酰胺。但该专利未公开用一种固定碱部分中和粘结剂。
美国专利3,959,552公开了用以下共聚物的水分散液制造耐洗的无纺材料的方法,这些共聚物是N-羟甲基丙烯酰胺和/或N-羟甲基-甲基丙烯酰胺,丙烯酰胺和/或甲基丙烯酰胺,α,β-单烯属不饱和二元羧酸和/或三元羧酸,以及任选的其它单体的共聚物。这些共聚物中含有0.5-3%(重量)的碳原子数为4-6的二元羧酸或三元羧酸或它们的混合物。羧酸最好是马来酸,富马酸,衣康酸,柠康酸或阿康酸,或者它们的混合物。共聚物的组合物在浸透无纺织物工序中用草酸中和到PH=2.5。
美国专利2,931,749公开了用于纤维质无纺制品的粘结剂,该粘结剂是由含0.5-10%(重量)带羧基单元的单烯属不饱和单体单元组成的水不溶性线型共聚物或其盐的水分散液。这种共聚物能以游离酸的形式,碱金属盐的形式,或者以水溶性胺盐的形式涂覆,水溶性胺的例子有甲胺,二乙胺,三乙胺,一乙醇胺,二乙醇胺或三乙醇胺,或吗啉。该专利还公开了在PH至少约为5,最好在PH为6-10之间涂覆这种共聚物分散液。
美国专利4,059,665公开了用一种水不溶性共聚物的热固产物组成的粘结剂将无纺纤维质制品粘结在一起,该共聚物所含的单元来自不饱和脂肪族酸诸如丙烯酸,甲基丙烯酸,柠康酸,以及优选的衣康酸。可以使用一种酸催化剂。
美国专利4,406,660公开的无纺纤维质制品是用一种乳液共聚物粘结在一起,该共聚物含有0.5-10%(重量)的酸,酸含有至少一种烯属不饱和二元羧酸,并任选配合至少一种烯属不饱和一元羧酸。这种酸组分可含有诸如衣康酸或马来酸之类的二元羧酸,以及任选的诸如丙烯酸或甲基丙烯酸之类的一元羧酸;对改进湿强度来说,优选采用的是衣康酸。酸组分可处于游离酸的形式,或处于碱金属如钠或钾的盐,以及水溶性胺(如甲胺,二乙胺,三乙胺,一乙醇胺,二乙醇胺,或三乙醇胺,或吗啉)盐的形式,或处于铵盐的形式。
美国专利4,929,495公开了由丙烯酸类粘结剂同纤维结合,制成无纺织物。该粘结剂中共聚有约1-约20份(重量)至少一种带4-约10个碳原子的不饱和二元羧酸。但该专利未公开用固定碱部分中和粘结剂。
美国专利4,524,093公开了一种改进的含水的聚合物组合物,采用它作织物的涂层,大大减少了甲醛的释出,并表现出良好的耐干洗性和低温柔韧性。该组合物含有由丙烯酸酯单体与丙烯腈,衣康酸,和N-羟甲基丙烯酰胺共聚而成的水乳液;并含有一种乙二醛固化树脂以及一种路易斯酸式有机酸催化剂。
美国专利4,563,289和4,702,944(相同顺序号的分案)公开了天然或合成纤维的无纺制品,该制品具有良好的热稳定性,湿强度,以及低含量的交联剂诸如脲-甲醛或N-羟甲基丙烯酰胺。这种无纺制品加入了一种聚合物胶乳作粘结剂,该聚合物含有一种羧酸官能团,特别是C3-C9的烯属不饱和羧酸或C4-C9的烯属不饱和二元羧酸的酐,所述的胶乳含有足够的碱金属碱,使PH保持在约5-约9,胶乳中最好连同有一种“潜酸”。合适的烯属不饱和酸包括丙烯酸,甲基丙烯酸,富马酸,衣康酸,丁烯酸,戊烯酸,己烯酸,以及辛烯酸。
没有一篇参考文献公开过用一种水基聚合粘结剂处理多孔软基体的方法,该粘结剂含有经选择的共聚二元羧酸或它们的某些衍生物,其中,粘结剂用固定碱部分中和。
本发明的目的是提供一种处理多孔软基体的改进方法。本发明的另一个目的是,提供用一种乳液聚合的粘结剂处理无纺基体的改进方法。本发明的还有一个目的是,提供用一种不含甲醛的粘结剂处理无纺基体的方法。本发明的又一个目的是,经不含甲醛的处理,制成改进了耐洗性和耐干洗性的涂覆有聚合物的无纺基体。
提供了一种用不含甲醛的水基组合物处理多孔软基体的方法,该组合物含有至少一种聚合粘结剂,在粘结剂中有大约0.5%至约10%(按聚合粘结剂重量计算)为至少一种烯属不饱和二元羧酸,其半酯或酐,其中,粘结剂用固定碱部分中和。还提供了经这样处理过的多孔软基体。
本发明涉及一种用不含甲醛的水基组合物处理多孔软基体的方法,以及由此制得的处理过的基体。
用一种不含甲醛的水基组合物处理的多孔软基体的例子有织物,无纺织物,纸张,皮革等,由此可提高这类基体的强度,外观,或耐用性能。不含甲醛的水基组合物含有聚合粘结剂,它能以聚合粘结剂在含水介质中的溶液状态存在;也能以水分散液状态存在(如乳液聚合的分散液);还能以水悬浮液状态存在。本文中“含水”包括水以及基本上由水和水混溶性溶剂所组成的混合物。优选采用的是由乳液聚合得到的含水的分散液。
本发明所采用的聚合粘结剂在涂覆到基体上时是一种大体上为热塑性的或未交联的聚合物,尽管也可以略有一些故意的或非正常的交联。在粘结剂加热之后或加热的同时使粘结剂干燥和发生固化。这里“固化”的意思是指,将有效量的聚合粘结剂涂覆到多孔软基体上,使其发生足以改变基体性能的结构或形态的变化,例如共价化学反应,离子相互作用或群集,同基体粘结性的改进,相变或倒相,氢键等。
聚合粘结剂含有至少一种共聚的烯属不饱和二元羧酸,其半酯或酐,其含量约占聚合粘结剂重量的0.5-10%。例如,可以采用衣康酸,富马酸,马来酸,衣康酸单甲酯,富马酸单甲酯,富马酸单丁酯,或马来酸酐。衣康酸和富马酸的含量宜占聚合粘结剂重量的约2%-约8%。又以约4%-约6%为更佳。
聚合粘结剂还含有占其重量约90%-约99.5%的至少一种烯属不饱和单体。例如,可采用下列各种单体:丙烯酸酯单体包括丙烯酸甲酯,丙烯酸乙酯,丙烯酸丁酯,丙烯酸2-乙基己酯,丙烯酸癸酯,甲基丙烯酸甲酯,甲基丙烯酸丁酯,丙烯酸羟乙酯,甲基丙烯酸羟乙酯,以及甲基丙烯酸羟丙酯;丙烯酰胺或取代的丙烯酰胺;苯乙烯或取代的苯乙烯;丁二烯;醋酸乙烯酯或其它乙烯基酯;丙烯腈或甲基丙烯腈等。优选采用的是占主要量的丙烯酸乙酯。在提供的粘结剂为粒状的情况下要求有一些预交联或凝胶含量时,可以采用少量多烯属不饱和单体诸如甲基丙烯酸烯丙基酯,邻苯二甲酸二烯丙基酯,1,4-丁二醇二甲基丙烯酸酯,1,6-己二醇二丙烯酸酯等。还可采用少量(如占聚合粘结剂重量的0-5%)烯属不饱和单羧酸如甲基丙烯酸或丙烯酸。
聚合粘结剂的玻璃化温度对浸渍过的多孔基体的硬度,柔韧性,以及“手感”有一定影响。按FOX方程算得的玻璃化温度宜为约+40℃-约-60℃。
在聚合反应混合物中有时可采用链转移剂包括硫醇,多硫醇,以及卤素化合物,以调节聚合粘结剂的分子量。一般说来,可采用占聚合粘结剂重量0%-约3%的C4-C20烷基硫醇,巯基丙酸,或巯基丙酸的酯。最好不使用链转移剂。
本发明涉及用一种不含甲醛的水基组合物处理多孔软基体的方法。本文所述的不含甲醛的组合物,其意思是指该组合物大体上不含甲醛,或不因干燥和/或固化释放出明显量的甲醛。为了使这种水基组合物中的甲醛含量降低到最低值,在制备聚合粘结剂时,宜采用聚合添加剂诸如引发剂,还原剂,链转移剂,生物杀伤剂,表面活性剂等,这些添加剂本身不含甲醛,在聚合过程中并不生成甲醛,而且在处理多孔软基体中也不会产生或放出甲醛。如果水基组合物里容许含有少量的甲醛,或者由于有充分的使人信服的理由可使用会产生或放出甲醛的添加剂,则可以采用大体上不含甲醛的水基组合物。
当聚合粘结剂处于乳液聚合的水分散液形式时,宁可选用较小的粒度诸如60毫微米而不用较大的粒度如250毫微米。在聚合粘结剂按乳液聚合水分散液形式制备时,最好于聚合反应引发之前便将全部二元酸加到反应容器,从而提高它在聚合粘结剂中的含量。处于乳液聚合水分散液状态的聚合粘结剂,其颗粒可由诸如以下这类两种或两种以上的相所组成:芯/壳粒子,芯层未完全被壳层包封的芯/壳粒子,多芯层的芯/壳粒子,互穿网络粒子等。
在处理多孔基体之前,要求用一种固定碱与这种含聚合粘结剂无甲醛的水基组合物相接触,称之为中和作用,该粘结剂中含有共聚的烯属不饱和二元羧酸,其半酯或酐。要求用一种固定碱按当量计算中和约20%-约80%的二元羧酸基团。如果用的是二元羧酸的半酯或二元羧酸的酐,算得酸的当量等于所用二元羧酸衍生物的当量。最好是用一种固定碱按当量计算中和约40%-约60%的二元羧酸基团。本文所用的固定碱或稳定碱指的是在处理的条件下基本上不挥发的一价碱诸如氢氧化钾,碳酸钠,或叔丁基氢氧化铵。诸如氨或低级烷基胺之类的挥发性碱并不起本发明的固定碱的作用,但可以添加到固定碱中使用,而无助于由固定碱中和所要求的程度。多价的固定碱诸如碳酸钙往往会使胶乳失稳,不过可少量使用。
另外,在不含甲醛的水基组合物中还可采用常规的处理用组分,诸如乳化剂,颜料,填充剂,防迁移助剂,固化剂,聚结剂,润湿剂,生物杀伤剂,增塑剂,消泡剂,着色剂,蜡,抗氧剂。优选采用一种防迁移助剂诸如某种无机盐或季胺盐。更优选采用的是一种季胺盐防迁移助剂诸如三甲基脂氯化铵或二烯丙基二甲基氯化铵(“DADMAC”)。最好采用占聚合粘结剂干重约0.5%-约1.0%的DADMAC。
用本发明方法加以处理的多孔软基体包括纸张,皮革,织物或无纺织物等。无纺织物可含有如木浆之类的天然纤维或如聚酯,人造丝之类的合成纤维,以及玻璃或它们的混合物。不含甲醛的水基组合物可采用常规技术涂覆,例如空气喷涂或无空气喷涂,压染,浸渍,辊涂,落帘涂布等。
不含甲醛的水基组合物涂覆到多孔软基体之后,加热使其干燥和固化。加热时间的长短和温度将影响干燥速度,加工性能和挺括性和手感,以及经处理基体的性能改进。热处理宜在150℃进行5分钟,不过对于能经受住更高温度的基体则在180℃热处理5分钟。
下面的实施例是为了具体说明根据本发明处理多孔软基体的方法。它们不是为了限制本发明,因为对于专于此项技术的人来说,本发明的别的应用会是显而易见的。
实施例1
含衣康酸的水基聚合粘结剂的制备
样品1的制备。在3升带搅拌的玻璃反应器中装入710克去离子水(DI水)和65.6克十二烷基硫酸钠,并在室温下用氮气吹扫30分钟,然后加热到57℃,往反应器里加入66克单体乳液#1(“ME#1)和15克DI水。2分钟之后,在56℃温度下再加入5克0.15%硫酸亚铁七水合物的水溶液,3.33克过硫酸铵(溶于20克DI水中),以及0.17克亚硫酸氢钠(溶于20克DI水)。在接着的2分钟内观察到反应放热温升至61.5℃,并开始同时加入其余的ME#1以及0.88克亚硫酸氢钠溶于60克DI水的溶液。加料进行126分钟,同时保持温度为56.5-61.5℃。加料结束时加入30克DI水。在温度已从58℃降到49℃的55分钟时期之后,加入1.0克叔丁基氢过氧化物(溶于10克DI水)和0.7克甲醛次硫酸钠(溶于10克DI水)。15分钟后,保持温度为47℃,再加入同样量的叔丁基氢过氧化物以及甲醛次硫酸钠溶液。又过15分钟后,保持温度为44.5℃,再次加入同样量的上述两种溶液。得到的样品1的固含量为38.2%,粒度60毫微米。
表1.1 用于实施例1的单体乳液#1(ME#1)
650克 DI水
16.5克 十二烷基硫酸钠
950克 丙烯酸乙酯(EA)
50克 衣康酸(IA)
实施例2
含富马酸的水基聚合粘结剂的制备
样品2的制备。在3升带搅拌的玻璃反应器中装入1000克DI水,5克十二烷基硫酸钠,以及50克富马酸(FA),并在室温下用氮气吹扫30分钟,然后加热到55℃,往反应器里加入66克单体乳液#1(“ME#1”)和15克DI水。2分钟之后,在55℃温度下再加入5克0.15%硫酸亚铁七水合物的水溶液,3.3克过硫酸铵(溶于20克DI水),以及0.17克亚硫酸氢钠(溶于20克DI水)。在接着的1分钟内观察到反应放热温升至59℃,并开始同时加入其余的ME#1以及0.88克亚硫酸氢钠溶于60克DI水的溶液。加料进行125分钟,加料中温度保持在55.5-59℃。加料结束时加入30克DI水。在温度已从56℃降到49℃的20分钟期间之后,加入1.0克叔丁基氢过氧化物(溶于10克DI水)和0.7克异抗坏血酸(溶于10克DI水)。15分钟之后,温度保持在45℃,加入同样量的叔丁基氢过氧化物以及异抗坏血酸溶液。又过15分钟之后,温度保持在42℃,再次加入同样量的上述两种溶液。得到的样品2的固含量为39.0%,粒度为100毫微米。
表2.1 用于实施例2的单体乳液#1(ME#1)
300克 DI水
28.3克 十二烷基硫酸钠
950克 丙烯酸乙酯
对照实施例A
含甲基丙烯酸的水基聚合粘结剂的制备
对照样品A的制备。在3升带搅拌的玻璃反应器中装入710克DI水,65.6克十二烷基硫酸钠,并在室温下用氮气吹扫30分钟,然后加热到57℃,往反应器里加入66克单体乳液#1(“ME#1”)和15克DI水。2分钟之后,在56℃温度下再加入5克0.15%硫酸亚铁七水合物的水溶液,3.33克过硫酸铵(溶于20克DI水),以及0.17克亚硫酸氢钠(溶于20克DI水)。在下一分钟内观察到反应放热温升至61℃,并开始同时加入其余的ME#1和0.88克亚硫酸氢钠溶于60克DI水的溶液。加料进行120分钟,在此期间温度保持在56-61℃。加料结束时,加入30克DI水。在温度已从56℃降到48℃的55分钟期间之后,加入1.0克叔丁基氢过氧化物(溶于10克DI水)和0.7克甲醛次硫酸钠(溶于10克DI水),15分钟之后,温度保持在46℃,加入同样量的叔丁基氢过氧化物和甲醛次硫酸钠溶液。又过15分钟之后,温度保持在43.5℃,再次加入同样量的上述两种溶液。所得对照样品A的固含量为38.3%,粒度为60毫微米。
表A.1 用于对照实施例A的单体乳液#1(ME#1)
650克 DI水
16.5克 十二烷基硫酸钠
945克 丙烯酸乙酯(EA)
55克 丙烯酸(AA)
实施例3
含酸的水基聚合粘结剂的中和
按下表所示,将水和固定碱的水溶液边搅拌加到水基聚合物粘结剂中。
表3.1 样品1的配方(所有用量均为克数)
样品 样品1 DI水 5%Na2CO310%KOH 10%DADMAC
1A 125 406.94 0 0 0
1B 75 240.58 2.35 1.24 0
1C 75 236.99 4.71 2.47 0
1D 125 388.84 7.84 4.12 6.14
1E 75 233.4 7.06 3.71 0
1F 125 377.03 19.61 10.30 0
表3.2 样品2的配方(所有用量均为克数)
样品 样品2 DI水 5%NaOH 10%KOH 10%DADMAC
2A 65 216.67 - - -
2B 65 214.58 0.87 1.22 -
2C 65 212.48 1.75 2.44 -
2D 65 209.94 1.75 2.44 2.54
2E 65 211.21 1.75 2.44 1.27
2F 65 210.39 2.62 3.66 -
2G 65 206.2 4.37 6.1 -
2H 65 211.79 - 4.88 -
2I 65 213.18 3.49 -
2J 65 203.58 - 13.09CsOH(10%)
表3.3 对照样品A的配方(所有用量均为克数)
对照
样品 样品A DI水 5%Na2CO310%KOH 10%DADMAC
AA 125 406.94 0 0 0
AB 75 240.58 2.35 1.24 0
AC 75 236.99 4.71 2.47 0
AD 125 388.84 7.84 4.12 6.14
AE 75 233.4 7.06 3.71 0
AF 125 377.03 19.61 10.30 0
注:这里用的DADMAC是二烯丙基二甲基氯化铵。
样品1(含5重量%衣康酸)和对照样品A(含5.5重量%丙烯酸)所共聚的酸的当量为等摩尔;样品2含5重量%富马酸。样品2的共聚酸用等离子量钾和钠的固定碱中和0%,20%,40%,60%或100%;另外,对每种粘结剂(1D,2D,AD)来说均存在一个40%的中和点,其中,中和是采用20%钾,20%钠,以及外加10%DADMAC来实施。样品2E是采用20%钾,20%钠,以及外加5%DADMAC来中和;样品2J是用40%铯中和。样品经中和处理的物理特性示于下面表3.4。
表3.4 经中和处理的样品的特性
样品 共聚酸中和% pH
1A 0 3.00
1B 20 5.88
1C 40 6.76
1D 40 6.75
1E 60 7.21
1F 100 8.01
2A 0 2.51
2B 20 4.48
2C 40 6.26
2D 40 6.40
2E 40 6.49
2F 60 6.98
2G 100 8.19
2H 40 5.97
2I 40 6.41
2J 40 6.28
AA 0 2.76
AB 20 6.51
AC 40 7.06
AD 40 7.12
AE 60 7.43
AF 100 7.86
实施例4
无纺基体的处理以及耐洗性耐干洗性和织物抗拉强度的测试
用作耐用性测试是由DACRON 371W制成的粗梳聚酯无纺织物(纤度1.5旦,纤维长度1.5英寸),每平方码的重量为1盎司。采用的是按实施例3制备的中和处置物,聚合物固含量为9%。将用玻璃纤维稀纱支承的织物浸渍在实施例3处理物的浴中,然后在40psig(每平方英寸磅表压)下通过一台Birch Bros,压染机。从稀纱上取下涂覆过的织物并放置在Mathis烘箱的金属网上于150℃加热5分钟。测得每块织物上加进的粘结剂约占织物重量的45%。在标准的干洗机和洗衣机中测试经处理的无纺织物的耐用性。按下面所述的方法测试织物的抗拉强度。
为干洗起见,将织物缝在一块50/50聚酯/棉布上。把这些样品放入一台带五条厚绒擦布的SPEED QUEEN CD2811型商用干洗机中。采用DOWPER CS干洗溶剂;将样品连续干洗五个循环。然后把样品与一组标准样按1-5的等级额定比较。等级“.5”指的是样品完整,未遭到损坏,而等级“1”是指样品被严重起毛和撕裂。中间的等级相当于中等程度的起毛和织物组织的损坏。
规定在一台KENMORE U1tra Fabric Care Heavy Duty 80系列机中采用PENNWALT PENNICO PLUS洗涤剂的0.15%(重量)水溶液,温度为130°F条件下测定耐洗性。机器中加入十条厚绒擦布。重复测试直到织物被撕裂成不止一片。
采用上面准备的浸渍过的一英寸宽织物条来测定织物的抗拉强度。将样品条固定在一台Thwing-Albert Intellect II INSTRON试验机中。在12英寸/分的拉伸速度条件下用3英寸标距将样品拉伸到断裂。记录高峰负荷。样品是在DOWPER CS或热(130°F)洗涤剂溶液里浸泡30分钟后加以测定。
表4.1 处理过的无纺织物样品的耐洗性和耐干洗性
拉伸强度(克/英寸)
样品 耐洗性(通过 耐干洗性(评定 DOWPER 热水
的循环次数)的等级)
1A 13 3.3 111 215
1B 39 3.5 355 545
1C 40 3.6 410 664
1D 51 4.0 430 656
1E 40 3.8 419 447
1F 7 3.0 290 112
2A 3 3.0 120 193
2B 13 3.75 303 584
2C 29 4.25 393 565
2D >53 5 429 566
2E 44 4.75 427 592
2F 32 4.5 432 415
2G 9 4.0 348 176
2H 42 4.75 467 624
2I 14 3.9 399 518
2J >53 4.25 523 545
AA 2 2.5 66 71
AB 2 2.75 146 125
AC 2 3.0 262 111
AD 4 3.45 251 110
AE 2 3.3 335 87
AF 1 3.0 261 67
本发明的样品1B,1C,1D和1E与用同样聚合物制成但未经固定碱中和到所要求程度的样品(样品1A,1F)相比,显示出提高了耐干洗性,优异的耐洗性,以及较高的湿抗拉强度,尤其与含丙烯酸的对照样品(AA-AF)相比,不管中和程度大小,愈加显示出其良好的性能。
本发明的样品2B,2C,2D,2E,2F,2H,2I和2J与用同样聚合物制成但未经固定碱中和到所要求程度的样品(样品2A,2G)相比,显示出提高了耐干洗性,优异的耐洗性,以及较高的湿抗拉强度,尤其与含丙烯酸的对照样品(AA-AF)相比,不管中和程度大小,愈加显示出其良好的性能。添加阳离子型季铵化合物DADMAC,可影响无纺织物处理过程中的防迁移性,从而改善了性能,尤其是提高了处理过的无纺织物的耐干洗性。
实施例5
用季铵碱固定碱中和的聚合粘结剂的耐洗性和耐干洗性
按实施例3那样用四丁基季铵碱中和样品1,再按实施例4的方法把它涂覆到无纺织物并加以测试,所得结果如下。
表5.1 用四丁基季铵碱固定碱中和处理及所得无纺织物的性能
样品 中和% pH 耐洗性(通过的 耐干洗性(评定的
循环次数) 等级)
5A 0 2.58 10 3
5B 20 4.66 18 3.4
5C 40 5.40 16 3.9
5D 60 6.25 16 3.6
5E 100 8.90 3 1
同未用固定碱中和到所要求程度的样品5A和5E相比,本发明的样品5B,5C和5D显示出优良的耐洗性和耐干洗性。
实施例6
含衣康酸的水基聚合粘结剂经挥发性碱或固定碱中和到40%程度的耐干洗性
配制样品1,涂覆到基体上,并按实施例3和4的方法评价其耐干洗性。
表6.1 用挥发性碱或固定碱中和处理及所得无纺织物的性能
样品 中和%/碱 pH 耐干洗性(评定的等级)
6A 0% 2.9 2.9
6B 50%NH4OH 7.5 3.25
6C 20%Na2CO3+20%KOH 6.7 4.1
6D 20%NaOH+20%KOH 6.7 4.5
6E 40%NaOH 6.9 4.75
样品6C和6D,6E除了中和的碱以外还含有占酸当量10%的DADMAC。
本发明的样品6C,6D和6E经固定碱中和到所要求中和度范围以内的程度。样品6B也被中和到所要求的中和度范围以内的程度,但采用的是一种挥发性碱氢氧化铵,其耐干洗性如未经中和的样品6A一样差。
实施例7
含富马酸的较硬的水基聚合粘结剂的制备,中和,基体的涂覆及评价
样品7的制备。在3升带搅拌的玻璃反应器中装入1000克DI水,30克十二烷基硫酸钠和40克富马酸,并在室温下用氮气吹扫30分钟,然后加热到60℃,往反应器里加入66克单体乳液#1(“ME#1”)和15克DI水。2分钟之后,在60℃温度下再加入5克0.15%的硫酸亚铁七水合物的水溶液,3.3克过硫酸铵(溶于20克DI水),以及0.17克亚硫酸氢钠(溶于20克DI水)。在下一分钟内观察到反应放热温升至63℃,并开始同时加入其余的ME#1以及0.88克亚硫酸氢钠溶于60克DI水的溶液。加料进行124分钟,在此期间温度保持在63-65.5℃。加料结束时,加入20克DI水。在温度从65℃降到55℃的30分钟期间之后,加入1.0克叔丁基氢过氧化物(溶于10克DI水)和0.7克异抗坏血酸(溶于10克DI水),20分钟之后,温度保持在48℃下加入同样量的叔丁基氢过氧化物和异抗坏血酸溶液。又过15分钟之后,温度保持在45℃下,再次加入同样量的上述两种溶液。所得样品7的固含量为38.7%,粒度为60毫微米。
表7.1 用于实施例7的单体乳液#1(ME#1)
300克 DI水
51.6克 十二烷基硫酸钠
560克 丙烯酸乙酯
400克 甲基丙烯酸甲酯
取部分样品7按实施例3的方法用中和剂中和,并达到下面表7.2所示的pH值。
表7.2 经中和的处理物的特性
样品 共聚酸液被中和% pH
7A 0 2.53
7B 10%Na2CO3+10%KOH 4.20
7C 20%Na2CO3+20%KOH 5.07
7D 20%Na2CO3+20%KOH(+10%DADMAC) 5.18
7E 30%Na2CO3+30%KOH 5.73
7F 50%Na2CO3+50%KOH 6.30
将样品7A-7F浸渍入无纺织物,并按实施例4的方法测试。结果示于下面表7.3。
表7.3 经处理的无纺织物样品的耐洗性,耐干洗性以及湿抗拉强度
抗拉强度(克/英寸)
样品 耐洗性(通过 耐干洗性(评 DOWPER 热水
的循环次数)定的等级)
7A 9 1 159 584
7B 11 2.5 322 818
7C 16 3.25 419 897
7D 9 3.7 443 987
7E 16 3.75 520 906
7F 9 3.6 412 519
本发明的样品7用固定碱中和到如样品7B-7E所要求的程度,它们同未被中和到所要求程度的样品7A和7F相比,一般表现出优良的耐洗性,耐干洗性,以及湿抗拉强度。
实施例8
含富马酸的较软的水基聚合粘结剂的制备,中和,基体的涂覆及评价
样品8的制备。在3升带搅拌的玻璃反应器中装入800克DI水,65.6克十二烷基硫酸钠,以及40克富马酸,并在室温下用氮气吹扫30分钟,然后加热到60℃,往反应器里加入66克单体乳液#1(“ME#1”)和15克DI水。2分钟之后,在59℃温度下再加入5克0.15%硫酸亚铁七水合物的水溶液,3.3克过硫酸铵(溶于20克DI水),以及0.17克亚硫酸氢钠(溶于20克DI水)。在下一分钟内观察到反应放热温升至63℃,并开始同时加入其余的ME#1以及0.88克亚硫酸氢钠溶于60克DI水的溶液。加料进行120分钟,加料中温度保持在62-65℃。加料结束时,加入30克DI水。在温度从62.25℃降到60℃的5分钟期间之后,加入1.0克叔丁基氢过氧化物(溶于10克DI水)和0.7克异抗坏血酸(溶于10克DI水)。15分钟之后,温度保持在55℃条件下,加入同样量的叔丁基氢过氧化物以及异抗坏血酸溶液。又过10分钟之后,温度保持在53℃条件下,再次加入同样量的上述两种溶液。得到的样品8的固含量为39.1%,粒度为60毫微米。
表8.1 用于实施例8的单体乳液#1(ME#1)
500克 DI水
16.5克 十二烷基硫酸钠
560克 丙烯酸乙酯
400克 丙烯酸丁酯
取部分样品8按实施例3的方法用下面表8.2所示的中和剂中和。采用样品8A-8E来处理多孔无纺基体,并按实施例4所述方法测试其耐干洗性;结果示于表8.2。
表8.2 样品8的中和以及处理后的无纺织物的测试
耐干洗性
样品 中和的共聚物酸的% (评定的
等级)
8A 0%(+10%DADMAC) 1
8B 10%Na2CO3+10%KOH(+10%DADMAC) 1.8
8C 20%Na2CO3+20%KOH(+10%DADMAC) 2
8D 30%Na2CO3+30%KOH(+10%DADMAC) 3.5
8E 50%Na2CO3+50%KOH(+20%DADMAC) 1
中和到所要求程度的本发明的样品8B,8C和8D,在同未被中和到所要求程度的样品8A和8E相比较时,表现出优良的耐干洗性。
实施例9
含富马酸半酯(富马酸单丁酯)的水基聚合粘结剂的制备,中和,基体的涂覆,以及评价
样品9的制备。在3升带搅拌的玻璃反应器中装入900克DI水,40克十二烷基硫酸钠,并加热到80℃。加入2.2克过硫酸铵(溶于20克DI水)。同时开始加入ME#1以及2.2克过硫酸铵溶于75克DI水的溶液。加料进行105分钟,在此期间温度保持在78-85℃。加料结束时,加入35克DI水。在温度从83℃降到53℃的65分钟期间之后,加入1.0克叔丁基氢过氧化物(溶于5克DI水)和0.5克异抗坏血酸(溶于10克DI水)。30分钟之后,于47℃温度条件下加入同样量的叔丁基氢过氧化物和异抗坏血酸溶液。又过15分钟之后,于44℃温度条件下再次加入同样量的上述两种溶液。所得样品9的固含量为41.6%,粒度为90毫微米。
表9.1 用于实施例9的单体乳液#1(ME#1)
275克 DI水
20克 十二烷基硫酸钠
950克 丙烯酸乙酯
50克 富马酸单丁酯
取部分样品9用中和剂按实施例3的方法中和,并达到下面表9.2所示的PH值。所用酸的有效当量数与等摩尔富马酸中酸的当量数相同。
表9.2 经中和的处理物的特性
样品 中和的共聚物酸的% pH
9A 0 2.67
9B 5%Na2CO3+5%KOH 5.06
9C 10%Na2CO3+10%KOH 5.80
9D 10%Na2CO3+10%KOH(+10%DADMAC) 5.86
9E 20%Na2CO3+20%KOH 7.40
9F 20%Na2CO3+20%KOH(+10%DADMAC) 7.54
9G 30%Na2CO3+30%KOH 8.26
9H 50%Na2CO3+50%KOH 9.41
将样品9A-9H浸渍入无纺织物,并按实施例4的方法测试。所得结果示于下面表9.3。
表9.3 处理过的无纺织物样品的耐洗性及耐干洗性
样品 耐洗性(通过 耐干洗性(评定 抗拉强度(克/英寸)
的循环次数) 的等级) DOWPER 热水
9A 3 1 38 135
9B 3 1 73 253
9C 7 2 145 319
9D 18 2.1 205 342
9E 10 2.75 190 306
9F 18 3.25 237 318
9G 5 2 162 244
9H 2 1 79 141
本发明的样品9用固定碱中和到如样品9C-9H所要求的程度,它们同未被中和到所要求程度的样品9A、9B和9F相比,一般表现出优良的耐洗性、耐干洗性,以及湿抗拉强度。
实施例10
粒度对含衣康酸和丙烯酸的聚合粘结剂性能的影响
用0.25%十二烷基硫酸钠代替实施例1和对照实施例A里所用的2.3%十二烷基硫酸钠,重新制备样品1和对照样品A,以此来制备那些样品的粒度较大的相似物。样品1的粒度较大的相似物被称作样品10A。对照样品A的粒度较大的相似物被称作对照样品10B。
表10.1 粒度变化的特性
样品 组合物 粒度(毫微米)
1 95EA/5IA 60
10A 95EA/5IA 297
对照样品A 94.5EA/5.5AA 60
对照样品10B 94.5EA/5.5AA 257
表10.1所示的各个样品均用Na2 CO3中和到20%的程度,并再用KOH又中和20%;另外,还按实施例3的方法加入占酸当量10%的DADMAC。用各个被中和的样品处理无纺织物,并按实施例4的方法测试。所得结果示于表10.2。
表10.2 经处理的无纺织物的耐洗性及耐干洗性
样品 耐洗性(通过的 耐干洗性(评定的
循环次数) 等级)
1 30 4.5
10A 12 3.2
对照样品A 0 2.2
对照样品10B 0 2.7
所有样品均用固定碱中和到所要求的中和度范围内某个中和度。经中和到所要求中和度的本发明的组合物样品1和10A,与两个对照样品A和10B相比,均表现出优良的耐洗性和耐干洗性。本发明的粒度较小的样品1,其性能要比本发明的粒度较大的样品10A更为优异。
实施例11
含富马酸的水基聚合粘结剂的制备,人造纤维无纺织物的处理及评价
样品11的制备。在3升带搅拌的玻璃反应器中装入1000克DI水,2.5克十二烷基硫酸钠,以及50克富马酸(FA),并在室温下用氮气吹扫30分钟,然后加热到55℃,往反应器里加入66克单体乳液#1(“ME#1”)和15克DI水。2分钟之后,在52.5℃温度下再加入5克0.15%硫酸亚铁七水合物的水溶液,3.3克过硫酸铵(溶于20克DI水),以及0.17克亚硫酸氢钠(溶于20克DI水)。在下一分钟内观察到反应放热温升至56.5℃,并开始同时加入其余的ME#1以及0.88克亚硫酸氢钠溶于60克DI水的溶液,加料进行126分钟,加料中温度保持在56.5-57.5℃。加料结束时,加入30克DI水。在温度从57℃降到55℃的20分钟期间之后,加入1.0克叔丁基氢过氧化物(溶于10克DI水),0.7克异抗坏血酸(溶于10克DI水)。15分钟之后,在52.5℃温度条件下,加入同样量的叔丁基氢过氧化物以及异抗坏血酸溶液。又过30分钟之后,在42℃温度条件下,再次加入同样量的上述两种溶液。得到的样品的固含量为39.1%,粒度为110毫微米。
表11.1 用于实施例11的单体乳液#1(ME#1)
300克 DI水
30.8克 十二烷基硫酸钠
950克 丙烯酸乙酯
样品11按实施例3的方法用Na2CO3和KOH各中和至20%的程度。另外还加入占酸当量10%的DADMAC。无纺织物的处理和测试按实施例4方法进行,不同的是采用了人造纤维织物。用Courtalds 100%粘胶纤维(纤度1.5旦,纤维长度19/16英寸,经皱缩的无光丝)制成标称重量为每平方码一盎司的粗梳无纺织物。
表11.2 用部分中和的样品11处理过的人造纤维无纺织物性能的评价
耐洗性 >35
耐干洗性(评定的等级) 5
抗拉强度(克/英寸)DOWPER湿处理 142
用固定碱中和到所要求程度的本发明的样品11经浸渍入人造纤维无纺织物,显示出优良的性能。
实施例12
衣康酸粘结剂的制备,部分中和,在玻璃纤维无纺织物上涂覆及评价
样品12的制备。在5升带搅拌的玻璃反应器中装入775克DI水和12克十二烷基硫酸钠(28%),并用氮气吹扫47分钟,同时加热到88℃,往反应器里加入89克单体乳液#1(“ME#1”)和25克DI水。2分钟之后,在85℃温度下再加入4.2克过硫酸铵在42克DI水中制成的溶液。在下一分钟内观察到反应放热温升至87℃,并开始同时加入其余的ME#1和2.5克过硫酸钠溶于120克DI水的溶液。加料进行120分钟,在此期间温度保持在85℃。加料结束时,加入30克DI水。当反应混合物于35分钟里冷却到80℃之后,加入12克硫酸亚铁七水合物的溶液(0.1%)以及1克过硫酸钠(溶于25克DI水)。20分钟之后,于温度为63℃的条件下加入1.7克叔丁基氢过氧化物(溶于15克DI水)以及0.85克异抗坏血酸(溶于25克DI水)。又过15分钟之后,于温度为58℃的条件下,再次加入同样量的上述两种溶液。再过15分钟之后,于55℃温度下,又一次加入同样量的上述两种溶液。得到的样品12的固含量为44.1%,粒度为105毫微米,PH=1.92。
表12.1 用一实施例12的单体乳液#1(ME#1)
900克 DI水
48.0克 十二烷基硫酸钠(28%)
857克 丙烯酸乙酯(EA)
67.2克 衣康酸(IA)
747.4克 甲基丙烯酸甲酯(MMA)
8.4克 甲基丙烯酸羟乙酯(HEMA)
按照衣康酸的当量用Na2CO3和KOH将样品12各中和其20%;另外,还加入酸当量10%的DADMAC。采用Owens-Corning FIBERGLAS OCF6851英寸M-玻璃,按2磅/100平方英尺的基重制备湿法敷涂的手抄片。将手抄片浸渍入20%(干重)的样品12,并在200℃固化3分钟。
从浸渍过的手抄片上切下1英寸×4英寸大小的试条,用它来测定干抗拉强度。以2英寸标距,滑块速度为2英寸/分的条件下测定抗拉强度。湿抗拉强度的测定方法与干抗拉强度相同,差别在于,它的试条在测试之前要放入PH=7的水里(温度为180°F)浸泡10分钟。热抗拉强度的测定方法与干抗拉强度相同,差别在于试条于测试之前放入350°F的测试室里停留一分钟之后以1英寸/分的滑块速度条件下测定。
表12.2 经处理的玻璃纤维无纺织物的抗拉强度测试
干抗拉强度(磅) 28.5
湿抗拉强度(磅) 14.2
热抗拉强度(磅) 2.5
采用经固定碱中和到所要求程度的本发明组合物处理的玻璃纤维无纺织物,显示出一组实用的强度性能。
Claims (8)
1、一种处理多孔软基体的方法,它包括:
(a)制成一种不含甲醛的水基组合物,该组合物由至少一种聚合粘结剂组成,所述的粘结剂含有至少一种共聚的烯属不饱和二元酸,它的半酯或酐,其含量占所述粘结剂重量的约0.5%-约10%;
(b)使所述组合物同至少一种固定碱相接触,碱的用量要足以使上述共聚的二元酸,其半酯或酐的计算的酸当量中和20%-约80%;
(c)在所述基体上涂覆上述组合物;
(d)加热所述组合物。
2、根据权利要求1的方法,其中所述的粘结剂含有至少一种共聚的烯属不饱和二元酸,它的半酯或酐,其含量占所述粘结剂重量约2%-约8%。
3、根据权利要求1的方法,其中所述粘结剂含有至少一种共聚的烯属不饱和二元酸,它的半酯或酐,其含量占所述粘结剂重量约4%-约6%。
4、根据权利要求1的方法,其中所述的固定碱的用量足以中和计算的酸当量的约40%-约60%。
5、根据权利要求1的方法,其中所述的组合物还含有一种季铵盐。
6、根据权利要求5的方法,其中所述的季胺盐为二烯丙基二甲基氯化铵。
7、根据权利要求1的方法,其中所述的基体是一种无纺织物。
8、根据权利要求1的方法制成的多孔软基体。
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IL (1) | IL99350A (zh) |
NO (1) | NO913280L (zh) |
NZ (1) | NZ239525A (zh) |
PH (1) | PH30742A (zh) |
PT (1) | PT98837A (zh) |
TW (1) | TW197463B (zh) |
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CN102101929A (zh) * | 2009-12-18 | 2011-06-22 | 罗门哈斯公司 | 可固化水性组合物 |
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US5427587A (en) * | 1993-10-22 | 1995-06-27 | Rohm And Haas Company | Method for strengthening cellulosic substrates |
US6165919A (en) * | 1997-01-14 | 2000-12-26 | University Of Georgia Research Foundation, Inc. | Crosslinking agents of cellulosic fabrics |
DE19741184A1 (de) | 1997-09-18 | 1999-03-25 | Basf Ag | Verfahren zur Verminderung von Restmonomeren in Flüssigsystemen unter Zugabe eines Redoxinitiatorsystems |
EP1038433B1 (fr) | 1999-03-19 | 2008-06-04 | Saint-Gobain Cultilene B.V. | Substrat de culture hors-sol |
US20040158214A1 (en) * | 2003-02-10 | 2004-08-12 | The Procter & Gamble Company | Disposable absorbent article comprising a durable hydrophilic topsheet |
US20040158213A1 (en) * | 2003-02-10 | 2004-08-12 | The Procter & Gamble Company | Disposable absorbent article comprising a durable hydrophilic acquisition layer |
CA2433059C (en) * | 2001-01-30 | 2009-05-12 | The Procter & Gamble Company | Coating compositions for modifying surfaces |
US20040158212A1 (en) * | 2003-02-10 | 2004-08-12 | The Procter & Gamble Company | Disposable absorbent article comprising a durable hydrophilic core wrap |
US7070854B2 (en) * | 2001-03-22 | 2006-07-04 | Kimberly-Clark Worldwide, Inc. | Water-dispersible, cationic polymers, a method of making same and items using same |
US20040048531A1 (en) * | 2002-09-09 | 2004-03-11 | Hector Belmares | Low formaldehyde emission panel |
AT501416B1 (de) * | 2005-02-15 | 2007-11-15 | Leopold Franzens Uni Innsbruck | Verfahren und stoffgemisch zur erhöhung der oberflächenleitfähigkeit von hydrophoben polymeren |
US20070054072A1 (en) * | 2005-09-08 | 2007-03-08 | Lexmark International, Inc. | Packaging material for a developing agent cartridge |
US8309231B2 (en) * | 2006-05-31 | 2012-11-13 | Usg Interiors, Llc | Acoustical tile |
BRPI0820560B1 (pt) | 2007-11-15 | 2023-01-17 | Rutgers, The State University Of New Jersey | Método para produzir um corpo monolítico a partir de uma matriz porosa |
EP2454289A1 (en) * | 2009-07-14 | 2012-05-23 | The Sherwin-Williams Company | Starch hybrid polymers |
CN102040794B (zh) * | 2009-10-21 | 2014-10-08 | 罗门哈斯公司 | 可固化水性组合物 |
US8536259B2 (en) | 2010-06-24 | 2013-09-17 | Usg Interiors, Llc | Formaldehyde free coatings for panels |
CN102453447B (zh) | 2010-10-26 | 2014-02-26 | 罗门哈斯公司 | 可移除的胶粘贴 |
JP5241901B2 (ja) * | 2010-10-28 | 2013-07-17 | ローム アンド ハース カンパニー | 水性不織物バインダーおよびこれから製造された処理された不織物 |
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-
1990
- 1990-08-31 US US07/576,574 patent/US5451432A/en not_active Expired - Lifetime
-
1991
- 1991-08-07 TW TW080106218A patent/TW197463B/zh not_active IP Right Cessation
- 1991-08-19 CA CA002049474A patent/CA2049474A1/en not_active Abandoned
- 1991-08-22 AU AU82653/91A patent/AU653952B2/en not_active Expired
- 1991-08-22 NO NO91913280A patent/NO913280L/no unknown
- 1991-08-23 EP EP91307789A patent/EP0474415B1/en not_active Expired - Lifetime
- 1991-08-23 ES ES91307789T patent/ES2078454T3/es not_active Expired - Lifetime
- 1991-08-23 AT AT91307789T patent/ATE127869T1/de not_active IP Right Cessation
- 1991-08-23 DE DE69112963T patent/DE69112963T2/de not_active Expired - Lifetime
- 1991-08-23 NZ NZ239525A patent/NZ239525A/xx unknown
- 1991-08-27 PH PH43002A patent/PH30742A/en unknown
- 1991-08-29 KR KR1019910015035A patent/KR100209440B1/ko not_active IP Right Cessation
- 1991-08-30 CS CS912681A patent/CS268191A3/cs unknown
- 1991-08-30 FI FI914090A patent/FI914090A/fi not_active Application Discontinuation
- 1991-08-30 CN CN91108608A patent/CN1046329C/zh not_active Expired - Fee Related
- 1991-08-30 HU HU912829A patent/HUT59730A/hu unknown
- 1991-08-30 PT PT98837A patent/PT98837A/pt not_active Application Discontinuation
- 1991-08-30 IL IL9935091A patent/IL99350A/en not_active IP Right Cessation
- 1991-08-30 JP JP3220413A patent/JPH04270733A/ja active Pending
- 1991-08-30 IE IE306691A patent/IE913066A1/en unknown
-
1992
- 1992-09-21 US US07/961,551 patent/US5385756A/en not_active Expired - Lifetime
-
1996
- 1996-01-11 HK HK4996A patent/HK4996A/xx not_active IP Right Cessation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102101929A (zh) * | 2009-12-18 | 2011-06-22 | 罗门哈斯公司 | 可固化水性组合物 |
CN102101929B (zh) * | 2009-12-18 | 2013-10-16 | 罗门哈斯公司 | 可固化水性组合物 |
Also Published As
Publication number | Publication date |
---|---|
CS268191A3 (en) | 1992-03-18 |
JPH04270733A (ja) | 1992-09-28 |
KR930004573A (ko) | 1993-03-22 |
HUT59730A (en) | 1992-06-29 |
EP0474415A3 (en) | 1992-11-25 |
IE913066A1 (en) | 1992-03-11 |
US5385756A (en) | 1995-01-31 |
ES2078454T3 (es) | 1995-12-16 |
PH30742A (en) | 1997-10-17 |
HK4996A (en) | 1996-01-19 |
AU8265391A (en) | 1992-03-05 |
EP0474415A2 (en) | 1992-03-11 |
CN1046329C (zh) | 1999-11-10 |
DE69112963T2 (de) | 1996-03-21 |
EP0474415B1 (en) | 1995-09-13 |
AU653952B2 (en) | 1994-10-20 |
FI914090A (fi) | 1992-03-01 |
HU912829D0 (en) | 1992-01-28 |
FI914090A0 (fi) | 1991-08-30 |
TW197463B (zh) | 1993-01-01 |
ATE127869T1 (de) | 1995-09-15 |
NZ239525A (en) | 1993-11-25 |
CA2049474A1 (en) | 1992-03-01 |
KR100209440B1 (ko) | 1999-07-15 |
IL99350A0 (en) | 1992-07-15 |
DE69112963D1 (de) | 1995-10-19 |
NO913280L (no) | 1992-03-02 |
PT98837A (pt) | 1992-08-31 |
US5451432A (en) | 1995-09-19 |
NO913280D0 (no) | 1991-08-22 |
IL99350A (en) | 1995-03-30 |
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