CN106471182A - For processing the compositionss of fibrous material - Google Patents
For processing the compositionss of fibrous material Download PDFInfo
- Publication number
- CN106471182A CN106471182A CN201580036196.2A CN201580036196A CN106471182A CN 106471182 A CN106471182 A CN 106471182A CN 201580036196 A CN201580036196 A CN 201580036196A CN 106471182 A CN106471182 A CN 106471182A
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- represent
- compositionss
- vii
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000012545 processing Methods 0.000 title claims abstract description 10
- 239000002657 fibrous material Substances 0.000 title claims description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 23
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004744 fabric Substances 0.000 claims abstract description 21
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- -1 polyoxy Polymers 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 17
- 150000001721 carbon Chemical group 0.000 claims description 17
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 229920001296 polysiloxane Polymers 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 12
- 229920000742 Cotton Polymers 0.000 claims description 11
- 229920002678 cellulose Polymers 0.000 claims description 10
- 235000010980 cellulose Nutrition 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 230000000903 blocking effect Effects 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 239000006081 fluorescent whitening agent Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000005202 decontamination Methods 0.000 claims description 5
- 230000003588 decontaminative effect Effects 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 238000005282 brightening Methods 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 4
- 229920002994 synthetic fiber Polymers 0.000 claims description 4
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical compound N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 claims description 3
- 229940123457 Free radical scavenger Drugs 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 241000283898 Ovis Species 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920000297 Rayon Polymers 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 239000003444 phase transfer catalyst Substances 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000012209 synthetic fiber Substances 0.000 claims description 3
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 239000004202 carbamide Substances 0.000 abstract description 7
- 150000007974 melamines Chemical class 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 208
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 166
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 137
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 114
- 239000000243 solution Substances 0.000 description 96
- 239000000047 product Substances 0.000 description 84
- 235000011121 sodium hydroxide Nutrition 0.000 description 70
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 61
- 235000019441 ethanol Nutrition 0.000 description 32
- 239000007788 liquid Substances 0.000 description 32
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 28
- 238000012360 testing method Methods 0.000 description 28
- 229960004279 formaldehyde Drugs 0.000 description 27
- 238000004821 distillation Methods 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 239000006185 dispersion Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 19
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 14
- 239000003995 emulsifying agent Substances 0.000 description 13
- 229940015043 glyoxal Drugs 0.000 description 13
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 13
- 229950005308 oxymethurea Drugs 0.000 description 13
- 239000012071 phase Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000004753 textile Substances 0.000 description 8
- 239000004435 Oxo alcohol Substances 0.000 description 7
- 235000019256 formaldehyde Nutrition 0.000 description 7
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 7
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- 235000011837 pasties Nutrition 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000006266 etherification reaction Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- DJIFOLVSJVNNSG-UHFFFAOYSA-N 1-ethylidene-3-hydroxyurea Chemical compound ONC(N=CC)=O DJIFOLVSJVNNSG-UHFFFAOYSA-N 0.000 description 3
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 3
- ZEYUSQVGRCPBPG-UHFFFAOYSA-N 4,5-dihydroxy-1,3-bis(hydroxymethyl)imidazolidin-2-one Chemical compound OCN1C(O)C(O)N(CO)C1=O ZEYUSQVGRCPBPG-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 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
- 241001597008 Nomeidae Species 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000013008 moisture curing Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 108010022579 ATP dependent 26S protease Proteins 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000170916 Paeonia officinalis Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000007760 free radical scavenging Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 210000004247 hand Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002955 immunomodulating agent Substances 0.000 description 1
- 229940121354 immunomodulator Drugs 0.000 description 1
- 230000002584 immunomodulator Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000037380 skin damage Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- QVLMUEOXQBUPAH-VOTSOKGWSA-N trans-stilben-4-ol Chemical class C1=CC(O)=CC=C1\C=C\C1=CC=CC=C1 QVLMUEOXQBUPAH-VOTSOKGWSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/165—Ethers
- D06M13/17—Polyoxyalkyleneglycol ethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/372—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing etherified or esterified hydroxy groups ; Polyethers of low molecular weight
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/423—Amino-aldehyde resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/423—Amino-aldehyde resins
- D06M15/427—Amino-aldehyde resins modified by alkoxylated compounds or alkylene oxides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
Described compositionss are particularly useful for processing the fabric donning properties favourable to give them, particularly enhanced hydrophilic.Said composition comprises urea, thiourea or melamine derivative, the compound comprising polyalkylene oxide groups and optional alcohol, and these components also can optionally react with each other.
Description
Following the present invention relates to compositionss and they be used for processing fibrous material, particularly comprise the fibrous material of cellulose
Purposes.
The known textile material comprising cellulose with so-called cellulose crosslinked dose of process is to reduce wrinkling trend.These trees
Fat finishing technique is especially using the N- methylolation product of following formula：
It can be obtained with Biformyl with the reaction of formaldehyde by urea.The methylolated melamine derivant of following formula also has been used for
This：
Be previously mentioned product the disadvantage is that, the heat treatment in resin-finishing processes makes Form aldehyde release to surrounding
In.Therefore develop the product of etherificate at one or more hydroxyls.Methanol is mainly used in this.
The product of the type being previously mentioned and their purposes are especially described inWO 2004/033170 A1、US 6 123 739 AWithDE 196 33 625 A1In.
US 6 102 973 A discloses and comprises dihydroxy methyl two hydroxy ethylidene urea（DMDHEU）Make with ethoxylated alcohol
Waterborne compositions for wetting agent.Said composition also can comprise polysiloxanes.
US 5 242 463 A disclose comprise DMDHEU, hydroxyalkyl amine and/or season hydroxyalkyl ammonium compoundss, glycol ethers and
The waterborne compositions of optional alcohol
US 5 358 535 A discloses the waterborne compositions comprising Lauxite and ethoxylated nonylphenol, wherein using poly- Asia
Alkyl diol diester is as formaldehyde collecting agent.
US 5 614 591 A discloses and comprises DMDHEU and catalyst and optionally, in other probabilities, wetting agent
Waterborne compositions, the preferred alkylphenol ethoxylate of described wetting agent, straight-chain alcohol ethoxylate or fatty acid ethoxy
Thing.
But, or even the property of methanol etherification product wholly or in part is still undesirable.For example, as demonstrate,proved in wetting test
Cellulosicss that are real, having been arranged with this product, particularly contain the hydrophilic nmature of cotton products not all the time for desired Gao Shui
Flat.The resin finishing technique that cotton products are solidified under wet condition is especially true.
The problem to be solved in the present invention is to improve existing product to realize giving while keeping desirable soft feel
The enhanced hydrophilic of cellulosic material being processed with it.When under wet condition during solidification using this product especially such as
This.The problem to be solved in the present invention also resides in finds out the new easily scattered reactive products that can remove free radical.The present invention
To be solved is problematic in that offer novel chemically-reactive fluorine-containing surfactant.The problem to be solved in the present invention also resides in offer tool
There is the novel chemically-reactive compound of fluorescent brightening property.
Solve this problem, described combination by a kind of compositionss with by the waterborne compositions comprising such compositionss
Thing comprises at least one formula (II) or the compound of formula (III) or formula (IV) or formula (V)：
With the amine of the compound of at least one formula (VII) or a kind of formula (VIII) or (IX) or a kind of logical formula (X) there is polyoxy
Change oligomeric or polysiloxane or a kind of formula (XI) of alkenyl group, the compound of preferred formula (XIa)：
And optionally comprise the alcohol of formula (VI) further：
R4―OH (VI)
Wherein all R1And R2Represent H independently of one another or represent the straight or branched alkyl with 1 to 5 carbon atom, preferably
Represent CH3Or C2H5Or C3H7, or represent
Or represent
Wherein m be 4 to 8 numerical value and t be 0 or 1 and p be 8 to 20 numerical value and q be 1 to 3 numerical value,
All R3Represent H or representative-CH independently of one another2―O―R2,
Wherein in formula (V), at least one R3Representative-CH2―O―R2,
X represents O or S,
Wherein in the formula (V) that X represents S, R3Also-CH can be represented2-O-R14, wherein R14Represent by phenolsulfonic acid or phenolsulfonic acid
Salt, particularly one of p-phenolsulfonic acid or its salt obtained by the etherificate of methylolation thiourea and described phenolsulfonic acid or its salt
Part, or R3Also-CH can be represented2-R15, wherein R15Represent by the salt of phenolsulfonic acid or phenolsulfonic acid, particularly Pyrogentisinic Acid's sulphur
One of acid or its salt are reacted in thiourea with the methine of described phenolsulfonic acid or its salt by the methylol of methylolation thiourea
Nitrogen-atoms and phenolsulfonic acid or the carbon atom of its salt between formed methylene bridge obtained by part,
R4Representative has 1 to 18, the straight chain of preferably 1 to 4 carbon atom or optional branched alkyl, more preferably represents CH3Or C2H5,
R5Representative has 4 to 18, the straight or branched alkyl of preferably 8 to 18 carbon atoms or thiazolinyl, more preferably represents and has 13
The branched alkyl of individual carbon atom or represent the aromatic fractions that optionally replaced by one or more hydrocarbyl portions, special representative's phenyl,
Tolyl or benzyl,
Wherein k+y=2 and k has value 1 or 2, R6And R7One of represent H, and another represents H or represents CH3, l represent 0 to
20, preferably 2 to 20, more preferably 2 to 8, particularly 2 to 6 numerical value, wherein in the presence of the compound of the formula (VII) of l=0,
Also there must be l>The compound of=2 formula (VII), n represents 2 to 20, preferably 2 to 8, more preferably 2 to 6 numerical value, and R8Generation
Table H or representative
Wherein R9And R10One of represent H, and another represents H or CH3Or C2H5Or CH2OH,
Wherein r is 2 to 15 numerical value, and s is 0 to 20 numerical value, and v is 1 to 18 numerical value and R11Represent H or CH3And wherein in formula
(X) in siloxanes, not only dimethyl silyloxy units, also comprise the methyl first of the part including polyalkylene oxide groups
Silicon oxyalkyl units can be randomly dispersed in siloxane chain,
Wherein R12Represent H or there is the straight chain of 1 to 4 carbon atom or optional branched alkyl, preferably represent CH3Or t-C4H9, more
Preferably represent H,
Wherein R13Represent H or there is the straight chain of 1 to 4 carbon atom or optional branched alkyl, preferably represent H or n-C4H9,
Wherein w represents 2 to 9, preferably 3 to 8 numerical value, u be 0 or preferably 1, Y be comprise carbon and hydrogen and optional sulfur and/or nitrogen and/
Or the divalent moiety of oxygen,
Wherein said composition comprises the compound of one or more formula (II) to (V) and the compound of one or more formula (VII)
Optionally, at least in the case of there is the compound of formula (VII) of l=6-8 and t=0, the compound of formula (VI) anti-
Answer product.
Example is the R derived from p-phenolsulfonic acid14And R15Part（One is acid, and one is salt）Although, R15Part also may be used
It is substituted by reacting with the molecule of formaldehyde and phenolsulfonic acid or its salt further.Available salt includes those of conventional alkali,
Such as sodium, potassium and/or ammonium salt.
Such compositionss not only have the imparting enhanced hydrophilic advantage of cellulosicss, also result in relatively low R2−
The discharge of OH alcohol.Additionally, less easily crack the ehter bond of presence according to the compositionss of the present invention, this causes relatively low oligomeric to incline
To thus producing more stable product.They are therefore particularly useful for process and comprise natural fiber（Preferred cellulose or Pilus Caprae seu Oviss）
Or synthetic fibers（Particularly polyester, polyamide, polyacrylonitrile, polyacrylate and viscose glue）And its fibrous material of mixture,
Particularly contain the fibrous material of 50 to 100 weight % celluloses.Cotton products are particularly because rely on its surface with described compositions-treated
Surfactant properties and obtain excellent property.Involved fibrous material is specifically for woven fabric form.
One of compositionss according to the present invention and/or the waterborne compositions that comprise such compositionss specially suitable should
It is the moisturecuring of the product comprising cellulose fibre with field.
Many compositionss according to the present invention and relatively long chain alkoxy primary amine, including from Huntsman's
JEFFAMINE®The primary amine of series is miscible.This compatibility means that gained preparation can be used on this finishing agent as in supercritical
In the method that solution in carbon dioxide uses.Using the solution finishing fiber product in liquid supercritical carbon dioxide and use
Water-based system arranges compares the various advantages of offer.Such method is especially described inWO 94/18264 A1、EP 1 126 072 A2WithEP 846 803 B1In.
Urea derivative as the melamine derivative of formula (III) or formula (II) or (V)Group
When under etherificate state, arranged with the product according to the present invention and lead to minimum formaldehyde emissions.Additionally, also dropping compared with the conventional method
The discharge of low lower alcohol, particularly methanol, because the OH group of this urea or melamine derivative is not to use methanol etherification completely.
Lead to the desirable of end article with the cotton products that the compositionss according to the present invention and/or its waterborne compositions arrange
Soft feel.Its cotton content product in the range of 50 to 100 weight % is obtained in particular with outstanding property.This product is preferably machine
Woven fabric.
Mixture according to the present invention can be obtained by following conventional method：
Make the N of following formula, N '-dimethylol urea
React in the presence of water to form the dihydroxy methyl two hydroxy ethylidene urea of formula (I) under about pH 5 with Biformyl
.
It is mixed into excessive R4OH alcohol and the compound being simultaneously mixed into formula (VII)
Lead to etherificate to produce the mixture of the present invention.
According to other compositionss of the present invention, for example comprise formula (II), the compound of (III), (IV) or (V) and/or it
Obtain with the similar approach familiar to those Tong Guo chemists of the alcohol of formula (VI) and the product of the compound of formula (VII)
?.Similarly can also prepare the amine comprising formula (VIII) or (IX) or logical formula (X) have the oligomeric of polyalkylene oxide groups or
Polysiloxane or formula (XI), the compound of preferred formula (XIa) and/or the combination according to the present invention of their product
Thing.When the compound of formula (VII) or the siloxanes of formula (X) or formula (XI), the compound of preferred formula (XIa) is more than adding, also
It is necessary to use, there is R during chemical reaction12Such compound of=H.
R4R in OH alcohol4Representative has 1 to 18, the straight chain of preferably 1 to 4 carbon atom or optional branched alkyl, more preferably
Represent CH3Or C2H5, R4OH is preferably methanol.
R in the compound of formula (VII)5Representative has 4 to 18, the straight or branched alkyl of preferably 8 to 18 carbon atoms
Or thiazolinyl, and isotridecyl is particularly preferred.Additionally, in formula (VII), R6And R7One of represent hydrogen, and another represent hydrogen or
Methyl.In formula (VII), l is 0 to 20, preferably 2 to 20, more preferably 2 to 8, particularly 2 to 6 numerical value, and in l=0
It is necessary to there is l in the presence of the compound of formula (VII)>The compound of=2 formula (VII).
Above-mentioned reaction can be carried out as follows：Glyoxal water solution and N, N '-dimethylol urea under about pH 5 will be set up,
Then with 37% formalin and R4OH alcohol is mixed and heated to 40 DEG C.Then in excessive addition R4OH alcohol and formula (VII)
With NaOH by pH regulator to about 7 before compound.Hereafter add number acid, such as hydrochloric acid, and raise with temperature and ether occurs
Change.Then stop etherificate by being mixed into NaOH.Advantageously it is then mixed into alkanolamine, such as triethanolamine.Preferably then distill out
Excessive R4OH alcohol.After pH regulator to about 6, distilled to remove excess at a temperature of 60 DEG C to 70 DEG C under reduced pressure
Alcohol R4OH and water.R4OH is preferably methanol.
When parent material used is the urea derivative of formula (II), (IV) or (V) or the melamine derivative of formula (III)
When, this synthesis is in a similar manner by using R4The mixture etherificate of the compound of OH alcohol and formula (VII) is carried out.But, replace formula
(VII) compound, it is possible to use the siloxanes of the amine of formula (VIII) or (IX) or formula (X) or formula (XI), preferred formula (XIa)
Compound.
Because etherificate leads to the known fact of balance, the OH group of initial compounds and final compound is generally not complete
Portion, but only a part in the preparation process according to the mixture of the present invention under etherificate state.Above-mentioned synthesis also has
May the initial not compound with formula (VII), but only with alcohol R4OH is etherified.In this case only in R4OH alcohol
Be distilled off during occur with the compound of formula (VII) partial ethers.In the mixture of the present invention, subsequently, necessarily
The original OH group of ratio has used R4OH is etherified, and another part has been reacted with the compound of formula (VII), that is, in this feelings
It is etherified under condition.
In siloxanes or the formula (XI) of the amine using formula (VIII) or (IX) or formula (X), the compound of preferred formula (XIa)
When, this is equally applicable.
Analysis and research are it has been shown that work as R4OH be methanol and formula (VII) compound be formula (VIIa) alcohol,
Comprise average 3 moles of ethylene oxide isotrideyl alcohol when, following compounds are in the present compositions may be used
Those detecting（By Gas Chromatography/Mass Spectrometry Analysis）：
And its derivant（In each, one or more free OH are rolled into a ball by methanol etherification）, and the oligomer of described compound.
The compositionss of the present invention and the known compositions using such as dihydroxy methyl two hydroxy ethylidene urea and methanol preparation
Difference be, in addition to low-molecular-weight alcohol, the present invention is further using compound or its ether of the formula (VII) of relatively high molecular weight
And/or the amine of formula (VIII) or (IX) or the oligomeric or polysiloxane of logical formula (X) or formula (XI), the change of preferred formula (XIa)
The fact that compound.
Formula R4The mixture of the compound of the alcohol of OH and formula (VII) usually contains excessive formula R4The alcohol of OH.
Preferably for every mole of R4OH alcohol, make 0.01 to 0.5 mole of the compound of formula (VII) or formula (VIII) or
(IX) amine or logical formula (X) there is the oligomeric of polyalkylene oxide groups or polysiloxane or formula (XI), preferred formula (XIa)
Compound reacts.
In formula (VII), R5Preferably representative has the branched alkyl of 13 carbon atoms and l preferably represents 2 to 20, more preferably
The numerical value of 2 to 8, particularly 2 to 6.
Compositionss according to the present invention easily can be by the change of at least one described formula (II), (III), (IV) and (V)
The compound of the alcohol of compound and at least one formula (VI) and at least one formula (VII) or the amine or one of a kind of formula (VIII) or (IX)
That plants logical formula (X) has the oligomeric of polyalkylene oxide groups or polysiloxane or a kind of formula (XI), the chemical combination of preferred formula (XIa)
The mixing of the mixture of thing and/or reaction obtain.This at 30 to 130 DEG C, preferably 30 to 80 DEG C, more preferably 40 to 70 DEG C of temperature
Under carry out, and final distilation steps are equally carried out in this temperature range.
Ether is occurred to exchange or respectively amination during being distilled off of alcohol of formula (VI).Advantageously, temperature, pressure are selected
Power and pH so that the distillation removing of the alcohol of formula (VI) make reaction balance towards be conducive to comprising greater proportion with formula (VII) extremely
One of (XIa) direction of the product of compound to one of (V) for the formula (II) of compound reaction is moved, and preferably only exists
After the alcohol of formula (VI) having distilled out part excess, the compound of formula (VII) to one of (XIa) is mixed in this reaction.
With the etherificate of the alcohol of formula (VI) 0.3 to 1, carry out under preferably 0.45 to 0.75 pH.Can be for example dense by being mixed into
Hydrochloric acid realizes this pH.Subsequently and R12The amine of the compound of formula (VII) of=H or formula (VIII) or (IX) or R12=H's is logical
Formula (X) there is the oligomeric of polyalkylene oxide groups or polysiloxane or R12The formula (XI) of=H, the chemical combination of preferred formula (XIa)
The reaction of thing 5 to 7, is carried out under preferably 5.6 to 6.4 pH.Can be by being for example mixed into sodium hydrate aqueous solution and triethanolamine
As buffer agent with terminate with formula (VI) etherified and realize this pH.With R12The compound of formula (VII) of=H or formula
Or the amine of (IX) or R (VIII)12The logical formula (X) of=H there is the oligomeric of polyalkylene oxide groups or polysiloxane or R12
The formula (XI) of=H, the reaction of the compound of preferred formula (XIa) advantageously in a vacuum at 50 to 1000 millibars, preferably 50 to 175
Carry out under the absolute pressure of millibar.This reaction is using R12The amine of the compound of formula (VII) of=H or formula (IX) or R12=
The logical formula (X) of H there is the oligomeric of polyalkylene oxide groups or polysiloxane or R12The formula (XI) of=H, preferred formula (XIa)
Compound when be that ether exchanges, or be amination in the amine using formula (VIII).
One particularly preferred form of the present invention is to comprise can be by making formula (II) or formula (III) or formula (IV) or formula
(V) having of the amine of compound and the alcohol of formula (VI) and the compound of formula (VII) or formula (VIII) or (IX) or logical formula (X) is poly-
The oligomeric or polysiloxane of oxyalkylene group or formula (XI), the mixture reaction acquisition of the compound of preferred formula (XIa)
The compositionss of product.This reaction is carried out preferably at a temperature of 40 to 70 DEG C and at acidic.In reality favourable further
Apply in scheme, the product obtaining after the reaction is neutralized, hereafter distills out the alcohol of excessive formula (VI).
The compositionss of the present invention particularly advantageously can comprise one or more with preferably have 20 to 60 weight % water contents
The form of the waterborne compositions of above-mentioned composition uses.
In some cases when the combination beyond the region of objective existence that this waterborne compositions removes the present invention also comprises the amount of preferably 0.5 to 5 weight %
NaCl, KCl or LiCl when be favourable because this can produce more preferable result especially for cellulose crosslinked aspect.
According to the compositionss of the present invention, natural fiber is comprised for process（Preferred cellulose or Pilus Caprae seu Oviss）Or synthetic fibers（Special
It is not polyester, polyamide, polyacrylonitrile, polyacrylate and viscose glue）And its fibrous material of mixture, particularly contain 50 to
The fibrous material of 100 weight % celluloses is highly useful.Particularly preferred material is for various applications, for example, use
Cotton products in the woven fabric form of skyteens.Other materials are for example to be used for manufacturing the synthetic textiles of sunshade.
The compositionss of the present invention and/or its waterborne compositions are highly useful for the moisturecuring of cotton material.This wet
Solidification can be carried out according to known method.
Compositionss according to the present invention can comprise well known by persons skilled in the art to be usually used in realizing various works to fabric
Other products.
When the product according to the present invention and hydrophobic polymer, the such as hydrophilic polysiloxanes of unfunctionalized one-tenth or and polyethylene
When wax is used on fabric together, the further enhancing of the hydrophilic nmature of achievable fabric.One of reason is probably to live in surface
The reversion of property orientation on the fibrous material thus arranging for the immunomodulator compounds.
In a possible purposes of the compositionss according to the present invention, using comprise a certain proportion of at least one formula
(VII) or (VIII) or (IX) or (X) or preferred (XI), particularly compositionss of conversion compound of one of (XIa) and suitable
For producing the polymer of blocking effect on fabric, and thus obtained compositionss are used for processing fibrous material to produce increasing
Strong blocking effect.Blocking effect refers to that fabric repels some media, particularly aqueouss and oil-based liquid, and the energy of dirt
Power, prevents when coming in contact in their infiltrated fibers.Various polymer are applied to this.These are included with perfluoroalkyl base
The polymer of group, such as polyurethane or poly- (methyl) acrylate and their copolymer also containing other monomers.For example
The polysiloxane with some functional groups is also applied for this.
In a possible purposes of the compositionss according to the present invention, using comprise a certain proportion of at least one formula
(VII) or (VIII) or (IX) or (X) or (XI), preferred compositionss of conversion compound of one of (XIa) and being applied to
The polymer of blocking effect is produced on fabric, and thus obtained compositionss are used for processing fibrous material to produce or to strengthen
Dirty effect.Therefore itself can not be provided that and appoint with being applied to generation blocking effect on fabric using the compositionss of the present invention
The polymer of what decontamination effect is to realize a certain degree of decontamination property on fabric.Intercepting with being applied to produce on fabric
Effect and itself when being provided that the compositionss that the polymer of decontamination effect is used together the present invention, can be further enhanced this
A little decontamination effects.
In latter two purposes, the compositionss of the present invention can be used as surfactant in the emulsifying of this polymer or
Cosurfactant, but they also can be added in polymer emulsion after emulsification, and wherein they are subsequently at the place of fibrous material
Serve as carrier in reason to provide, this polymer to be preferably input in fibrous material.
In another possible purposes, the compositionss according to the present invention are used for for free radical scavenger being transported to fibrous material
On, particularly comprise the compositionss of the conversion compound of the formula (II), (IV) or (V) of a certain proportion of X=S, free radical scavenging
The example of agent is vitamin C or the Vitamin E with antioxidation.
In another possible purposes, comprise fluorescent whitening agent, be based particularly on fluorescent whitening agent or the ultraviolet of stilbene structure
Light absorbers（It is preferably reformulationses）Compositionss be used for by fluorescent whitening agent, be based particularly on the fluorescent whitening agent of stilbene structure
Or UV absorbent is transported on fibrous material.
One example of suitable UV absorbent is the TINUVIN from BASF®1130.Suitable ultraviolet is inhaled
Receive agent further include compound 2- (2- hydroxy-5-methyl base phenyl) benzotriazole and ESCALOL 567 with
And polyethyleneglycol (diphenylethyllene phenyl) ether.
Many also is used as defoamer according to the compositionss of the present invention.
Compositionss according to selected by the present invention also are used as the additive of binding agent, and advantage is for example to make molecular structure
Crosslinking time and the polarity of side chain（This affects evaporation of water speed）Meet particular requirement.
Compositionss according to selected by the present invention also similarly are used as phase transfer catalyst.In the compositionss according to the present invention
In the case of above-mentioned product, the latter can be fixed by the reaction with hydroxyl and/or amino.
Known can its quality and expressive ability and optimize in terms of its processing and designability individually and with
The timber that other materials combine.This is meaningful, because the 26S Proteasome Structure and Function material based on timber, such as laminated veneer lumber
Become more stable, more flexible, more elastic, weight lighter, in terms of rate of utilization of strength more effectively and more resistant to waiting and prevent fires.
It is advantageously for example viscous based on polyvinyl acetate and muf resin according to the product here that the present invention suitably selects
The additive form of mixture composite, because their use can adjust not yet crosslinked adhesive composition in a desired manner
Porosity, agglomeration characteristics and flushing characteristics.The laminated veneer lumber that the larger porosity enhancing of layer is for example made up of multilamellar
Heat-insulating properties.The point form of adhesive composition（punctuately）Stronger agglomeration larger contact pressure is led to a form
And therefore lead to stronger point to bond.Compositionss according to the present invention also can be used for for example in the manufacture of particieboard crosslinked or
It is used as the additive of binding agent in the manufacture of laminated veneer lumber.
It also is used as the component in the manufacture of amino resins according to the compositionss of the present invention.
Another aspect of the present invention is the compound of formula (XII),
Wherein R3Represent H or representative-CH2―O―R2,
All R1And R2Represent H independently of one another or represent the straight or branched alkyl with 1 to 5 carbon atom, preferably represent
CH3Or C2H5Or C3H7, or represent
Or represent
Wherein m be 4 to 8 numerical value and q be 1 to 3 numerical value and
Wherein R13Represent H or there is the straight chain of 1 to 4 carbon atom or optional branched alkyl, preferably represent H or n-C4H9,
Condition is the R existing1Or R2Partial at least one does not represent H.
The compound of formula (XII) can be by obtaining with the similar method of preparing of the prior art compound of following formula：
Thiourea is wherein selected to replace urea as initial compounds.
The following example illustrates the present invention.
Embodiment 1（The present invention）
207.3 gram of 60% glyoxal water solution of initial handling being adjusted to pH 5.0 with diluted sodium hydroxide solution at room temperature.
It is mixed into 279.9 grams of dimethylol urea now by stirring.This produces white paste material.Hereafter, it is mixed into 21.8 grams
This mixture is simultaneously heated to 40 DEG C by 37% formalin solution and 72.6 grams of methanol.
This initial charge is subsequently adjusted to pH 7.0 with diluted sodium hydroxide solution and/or hydrochloric acid and is heated to 70 DEG C.This is first
Begin charging rarefaction, limpid and glassy yellow liquid in this process.
At 70 DEG C after 1 hour, this batch of material is cooled to 50 DEG C.
Hereafter, it is mixed into 183.7 grams of MARLIPAL®O 13/50（Oxo alcohol C13 containing 5 moles of EO, available from
Sasol）With 265.9 grams of methanol.
By being mixed into 5.0 grams of concentrated hydrochloric acid at 50 DEG C（31-33 weight %）Start to be etherified.This exothermic reaction leads to about 8 DEG C
Intensification.After 7 minutes, by being mixed into 2.0 gram of 50% sodium hydroxide solution and 0.3 gram of triethanolamine（99% concentration）Terminate this ether
Change.
This initial charge is subsequently adjusted to pH 5.9 with diluted sodium hydroxide solution and/or hydrochloric acid.Hereafter at 70 DEG C of highest
In the vacuum of as little as 100 millibars of absolute pressures 6 hours to be removed by distillation 228 grams of methanol-water mixtures.
Obtain relatively lean, limpid, glassy yellow product liquid after cooling to room temperature.
In order to test the property of the compositionss according to the present invention, by 220 g/l according to the compositionss of embodiment 1,110 g/l
KNITTEX CATALYST UMP（Available from Huntsman）With 1 g/l concentrated hydrochloric acid（31-33 weight %）Make aqueouss dressing liquid.
In order to compare, by 220 g/l KNITTEX®FA CONC（Dihydroxy methyl two hydroxy ethylidene urea, methanol etherification, available from
Huntsman）、110 g/l KNITTEX CATALYST UMP（Several organic aqueous solutions with inorganic acidic compound, can obtain
From Huntsman）With 1 g/l concentrated hydrochloric acid（31-33 weight %）Make aqueouss dressing liquid.Bleaching but non-fluorescent brightening have 110
Gram/m the woven galatea of 100% cotton of basic weight sample in laboratory mangle（pad-mangle）On use above-mentioned group
The aqueous solution becoming impregnates to the wet uptake of 66 weight %, is then dried to 7% residual moisture content, hereafter stores at 30 DEG C
20 hours.Hereafter, this sample is washed with 10 g/l aqueous sodium carbonates 10 minutes at 40 DEG C, is then neutralized once with hot water,
Hereafter neutralized once with cold water, further with 0.5 g/l INVATEX®AC aqueous solution（There is the citric acid of low polymer content
Aqueous solution, available from Huntsman）Neutralization, is then dried 10 minutes with cold water flush and finally at 110 DEG C.Subsequently according to water
Drip test AATCC test method 79, the absorbability of textile（Water drop test）Assess the textile sample thus arranging and every
Kind in the case of unfinished textile sample hydrophilic nmature and according to wicking test, AATCC test method 197-2011（For commenting
Estimate the capillary lifting height test of fabric）Assessment wicking property.In water drop test, lower value in seconds represents relatively
Good hydrophilic nmature.In this test, a water is applied on fabric and observes the moistening of fabric.Value in seconds describes quilt
The time of this water droplet complete wetting.In wicking test, the lower edge of textile sample is vertically dipped in water and observes liquid one
The height rising in the fabric after fixing time.This fabric is tested once in vertical direction with warp-wise, with broadwise in Vertical Square
Test upwards once.Shown according to the compositionss here of embodiments of the invention 1 and be substantially better than based on KNITTEX FA CONC
Contrast test hydrophilic effects, be shown in Table 1 and 2.
Methanol according to embodiment 1 be distilled off can through different time interval carry out.Increase with distillation time,
MARLIPAL®O 13/50 and dihydroxy methyl two hydroxy ethylidene urea（DMDHEH）The extent of reaction also improve.Therefore, this reaction
Controlled have product of different nature to manufacture.
Distillation time is used different time interval repeat embodiment 1, its corresponding value is found in table 3 below.
Table 3
| Run numbering | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Distillation time (hour) | 0 | 3.5 | 5.5 | 7.5 | 9.5 | 11.5 | 13.5 | 15.5 |
In products therefrom, preparation has the aqueous dispersion of the content of 200 g/l.This aqueous dispersion is acutely shaken
Shake, then stand 30 minutes.Be can be seen that by this aqueous dispersion increases with distillation time, and their foaming improves, and sees Fig. 1.
It will be seen that this aqueous dispersion increases with distillation time and/or ether exchanges journey after long-time standing and lather collapse
Degree improves and becomes limpider and/or more transparent, sees Fig. 2.
This two tests all show, the distillation time of increase and therefore bigger MARLIPAL®O 13/50 conversion ratio produces
Life has the product of enhanced surfactant properties.Increase with distillation time, the product obtaining in each case
Viscosity also improve.
Embodiment 2（The present invention）
150.0 gram of 60% glyoxal water solution of initial handling being adjusted to pH 5.0 with diluted sodium hydroxide solution at room temperature.
It is mixed into 202.5 grams of dimethylol urea now by stirring.This produces white paste material.Hereafter, it is mixed into 15.8 grams
This mixture is simultaneously heated to 40 DEG C by 37% formalin solution and 52.5 grams of methanol.
This initial charge is subsequently adjusted to pH 7.0 with diluted sodium hydroxide solution and/or hydrochloric acid and is heated to 70 DEG C.This is first
Begin charging rarefaction, limpid and glassy yellow liquid in this process.
At 70 DEG C after 1 hour, this batch of material is cooled to 50 DEG C.
Hereafter, it is mixed into 202.5 grams of methanol.
By being mixed into 3.6 grams of concentrated hydrochloric acid at 50 DEG C（31-33 weight %）Start to be etherified.This exothermic reaction leads to about 8 DEG C
Intensification.After 7 minutes, by being mixed into 1.4 gram of 50% sodium hydroxide solution and 0.2 gram of triethanolamine（99% concentration）Terminate this ether
Change.
This initial charge is subsequently adjusted to pH 5.9 with diluted sodium hydroxide solution and/or hydrochloric acid.Hereafter at 70 DEG C of highest
In the vacuum of as little as 100 millibars of absolute pressures 2 hours to be removed by distillation 197 grams of methanol-water mixtures.
After cooling to room temperature, 132.9 grams of MARLIPAL are stirred into®O 13/50.Essential distinction with embodiment 1 therefore exists
In being mixed into the oxo alcohol C13 containing 5 moles of EO after distillation for removing methanol, that is, without the oxo alcohol containing 5 moles of EO
C13 is etherified.
Obtain relatively lean, limpid and glassy yellow product liquid.
In order to test the property of the compositionss according to the present invention, by 220 g/l according to the compositionss of embodiment 2,100 g/l
KNITTEX CATALYST UMP, 1 g/l concentrated hydrochloric acid（31-33 weight %）With 50 g/l TURPEX®ACN NEW（The moisture of wax
A prose style free from parallelism, for the crosslinked conventional formulation component of bafta, available from Huntsman）Make aqueouss dressing liquid.In order to compare, by
220 g/l KNITTEX®FA CONC, 100 g/l KNITTEX CATALYST UMP, 1 g/l concentrated hydrochloric acid（31-33 weight %）
With 50 g/l TURPEX®ACN NEW makes aqueouss dressing liquid.Dye but the woven shirt of 100% cotton poplin of non-fluorescent brightening
The sample of cloth is impregnated with the aqueous solution of above-mentioned composition to the wet uptake of 66 weight % on laboratory mangle, is then dried extremely
7% residual moisture content, hereafter stores 20 hours at 30 DEG C.Hereafter, this sample is water-soluble with 10 g/l sodium carbonate at 40 DEG C
Liquid washs 10 minutes, then with hot wash once, hereafter be washed once with cold water, further with 0.5 g/l INVATEX®
AC aqueous solution neutralizes, and is then dried 10 minutes with cold water flush and finally at 110 DEG C.Subsequently tried according to water drop test AATCC
Proved recipe method 79, the absorbability of textile（Water drop test）Assess the textile sample thus arranging and do not arrange in each case
The hydrophilic nmature of textile sample and according to wicking test, AATCC test method 197-2011（Capillary for assessing fabric is made
Lifting height is tested）Assessment wicking property.In addition also according to JIS L 1041:2011（Nippon Standard）（Be equivalent to ISO
14184-1:1998）Content of formaldehyde in test fabric.Shown substantially excellent according to the compositionss here of embodiments of the invention 2
In hydrophilic effects and the lower content of formaldehyde of the contrast test based on KNITTEX FA CONC, it is shown in Table 4 and 5.
Embodiment 3（The present invention）
177.5 gram of 60% glyoxal water solution of initial handling being adjusted to pH 5.0 with diluted sodium hydroxide solution at room temperature.
It is mixed into 239.6 grams of dimethylol urea now by stirring.This produces white paste material.Hereafter, it is mixed into 18.7 grams
This mixture is simultaneously heated to 40 DEG C by 37% formalin solution and 62.2 grams of methanol.
This initial charge is subsequently adjusted to pH 7.0 with diluted sodium hydroxide solution and/or hydrochloric acid and is heated to 70 DEG C.This is first
Begin charging rarefaction, limpid and glassy yellow liquid in this process.
At 70 DEG C after 1 hour, this batch of material is cooled to 50 DEG C.
Hereafter, it is mixed into 78.6 grams of MARLIPAL®O 13/50（Oxo alcohol C containing 5 moles of EO13）With 227.6 grams of first
Alcohol.
By being mixed into 4.3 grams of concentrated hydrochloric acid at 50 DEG C（31-33%）Start to be etherified.This exothermic reaction leads to about 9 DEG C of liter
Temperature.After 8 minutes, by being mixed into 1.7 gram of 50% sodium hydroxide solution and 0.2 gram of triethanolamine（99% concentration）Terminate this etherificate.
This initial charge is subsequently adjusted to pH 5.9 with diluted sodium hydroxide solution and/or hydrochloric acid.
Hereafter it is mixed into 36.7 grams of trans -4- hydroxystilbenes 98%.During being subsequently heated to 70 DEG C, this initial charge
Outward appearance is from muddy and orange become limpid and glassy yellow.
Hereafter at 70 DEG C of highest in the vacuum of as little as 100 millibars of absolute pressures 6 hours to be removed by distillation 195.2
Gram methanol-water mixtures.
Then cool down this batch of material.When reaching about 45 DEG C, it is mixed with 45 grams of softened waters.
Hereafter, this initial charge diluted sodium hydroxide solution is adjusted to pH 6.5 from pH 5.2.
Obtain pasty state, milkiness and lacteous product when being cooled to room temperature.
Embodiment 4（The present invention）
80.2 grams of methanol of initial handling, 243.2 gram of 37 weight % formalin and 114.3 grams of sulfur in the reactor at room temperature
Urea.With diluted sodium hydroxide solution by pH regulator to 8.2.This batch of material is heated under pH 8.2 54 DEG C through 5 hours.
Hereafter, it is mixed into 137 grams of MARLIPAL®O 13/50（Oxo alcohol C containing 5 moles of EO13）With 174.3 grams of first
Alcohol.Temperature is 47 DEG C.
By being mixed into 19.5 grams of concentrated hydrochloric acid（32%）Start to be etherified.This exothermic reaction leads to 9 DEG C of intensification.After 9 minutes,
Terminate this etherificate by being mixed into 7.5 gram of 50% sodium hydroxide solution.
This initial charge is subsequently adjusted to pH 6.0 with diluted sodium hydroxide solution and/or hydrochloric acid.Hereafter at 70 DEG C of highest
At the end of this time interval as little as in the vacuum of 90 millibars of absolute pressures 6.5 hours be removed by distillation 445 ml methanol/
Aqueous mixtures.
Obtain extremely thick, the muddy product of the dry matter content with 98 weight % after cooling to room temperature.
Use example:
1. dye:
Mercerising cotton piece is with containing 2.4 g/l NOVACRON Blue C-R（Reactive dye from HUNTSMAN）、15 ml/l
36 ° of B of sodium hydroxide, 70 38-40 ° of B of ml/l sodium silicate, 2 g/l LYOPRINT RG（Dyeing assistant from HUNTSMAN）
With 1 g/l CIBAFLOW PAD（Dyeing assistant from HUNTSMAN）Dye solution pass through dip-heap dye（pad-
batch）Method（Using mangle）Dyeing.Mangling to the wet uptake of 70 weight %, piece of cloth is being stored at room temperature 16 little
When, then use water（Cold, boiling, cold）Flush three times and be dried.
2. Wako test
Use " Wako Test "（The closed test method of HUNTSMAN）Measure BPO fastness.BPO here represents benzoyl peroxide first
Acyl, or more precisely, dibenzoyl peroxide, it is used for department of dermatologry product and inclines because of it after being applied on skin
Damage the color of fabric in formation free radical.For this reason, by 50 grams of water, 0.1 gram of Wako V50（Double [the 2- methyl of 2,2'- azo
Third amidine] dihydrochloride, CAS 2997-92-4）, the compositionss of 0.15 gram of present invention being made as described above and 1 gram of stained specimens
Stir 2 hours at 65 70 DEG C.Then rinse sample and be dried.Hereafter, this sample is in slight decolored state.
As reference, 50 grams of water, 0.1 gram of Wako V50 and 1 gram of stained specimens are stirred 2 hours at 65 70 DEG C.Then
Rinse sample and be dried.Hereafter this sample is in very serious decolored state.
Colorimetric evaluation.
| Reference | Product using the present invention | |
| Scoring | 1 | 3 |
Grade:Scoring 1 to 5 (1=extreme difference, 5=fabulous)
This test shows that the compositionss of the present invention being made as described above clearly have the property of free radical scavenger.
3. post processing
The compositionss of the present invention that the sample of dyeing is made as described above with 20 g/l are passed through to dip-dry-thermosetting color（pad-
dry-thermofix）Method（For example it is described in DE 4133995）Arrange under the wet uptake of the pH 4 to 8 and 100 weight %,
Then it is dried 1 minute at 110 DEG C and thermosetting color 2 minutes at 170 DEG C.
Embodiment 5（The present invention）
159.7 gram of 60% glyoxal water solution of initial handling being adjusted to pH 5.0 with diluted sodium hydroxide solution at room temperature.
It is mixed into 215.8 grams of dimethylol urea now by stirring.This produces white paste material.Hereafter, it is mixed into 16.8 grams
This mixture is simultaneously heated to 40 DEG C by 37% formalin solution and 56.0 grams of methanol.
This initial charge is subsequently adjusted to pH 7.0 with diluted sodium hydroxide solution and/or hydrochloric acid and is heated to 70 DEG C.This is first
Begin charging rarefaction, limpid and glassy yellow liquid in this process.
At 70 DEG C after 1 hour, this batch of material is cooled to 50 DEG C.
Hereafter, in succession it is mixed into 107.6 grams of MARLIPAL®O 13/50（Oxo alcohol C containing 5 moles of EO13）With 109.7
Gram ZONYL Fluorosurfactant FS-300（40% in water, ethoxylation perfluoroalkyl ethyl alcohol, available from
DuPont）With 203.5 grams of methanol.
By being mixed into 7.8 grams of concentrated hydrochloric acid at 50 DEG C（31-33 weight %）Start to be etherified.This exothermic reaction leads to about 9 DEG C
Intensification.After 9 minutes, by being mixed into 4.8 gram of 50% sodium hydroxide solution and 0.2 gram of triethanolamine（99% concentration）Terminate this ether
Change.
This initial charge is subsequently adjusted to pH 5.8 with diluted sodium hydroxide solution and/or hydrochloric acid.
Hereafter, this initial charge is heated to 70 DEG C.
Hereafter at 70 DEG C of highest in the vacuum of as little as 100 millibars of absolute pressures 6 hours to be removed by distillation 175.8
Gram methanol-water mixtures.
Hereafter, this batch of material is cooled down.After reaching about 45 DEG C, it is mixed with 47 grams of softened waters.
Hereafter, this initial charge diluted sodium hydroxide solution is adjusted to pH 5.2 to pH 6.5.
Obtain the limpid product of glassy yellow after cooling to room temperature.
Embodiment 6a)（The present invention）
107.6 gram of 60% glyoxal water solution of initial handling being adjusted to pH 5.0 with diluted sodium hydroxide solution at room temperature.
Now 145.3 grams of dimethylol urea are mixed into by stirring.This produces white paste material.Hereafter, it is mixed into 11.3 grams
This mixture is simultaneously heated to 40 DEG C by 37% formalin solution and 37.9 grams of methanol.
This initial charge is subsequently adjusted to pH 7.0 with diluted sodium hydroxide solution and/or hydrochloric acid and is heated to 70 DEG C.This is first
Begin charging rarefaction, limpid and glassy yellow liquid in this process.
At 70 DEG C after 1 hour, this batch of material is cooled to 50 DEG C.
Hereafter, it is mixed into 130.0 grams of JEFFAMINE portionwise®M-600（Containing 9 mol propylenoxy and 1 moles of ethylene oxide
Polyetheramine, methyl etherified and pH 12, available from Huntsman）, pass through to be mixed into concentrated hydrochloric acid portionwise simultaneously（31-33%）PH is kept
In the range of 5.1-6.4.It is being mixed into 18.0 grams of concentrated hydrochloric acid altogether for this（31-33%）Afterwards, this initial charge has 5.3 pH.
It is then mixed into 132.0 grams of methanol.By being mixed into 10.7 grams of concentrated hydrochloric acid at 50 DEG C（31-33%）Start to be etherified.This exothermic reaction is led
Cause about 7 DEG C of intensification.After 9 minutes, by being mixed into 4.1 gram of 50% sodium hydroxide solution and 0.2 gram of triethanolamine（99%）Eventually
Stop this etherificate.
This initial charge is subsequently adjusted to pH 5.9 with diluted sodium hydroxide solution and/or hydrochloric acid.Hereafter at 65 DEG C of highest
In the vacuum of as little as 100 millibars of absolute pressures 6 hours to be removed by distillation 163 grams of methanol-water mixtures.
After cooling to room temperature obtain have the relatively sticky, limpid of the viscosity of 7000 mPa s recording at 25 DEG C and
Dark red liquid product.
Embodiment 6b)（The present invention）
Repeat embodiment 6a), simplyAfter the reaction rather than it is mixed into JEFFAMINE before reaction ® M-600.
107.6 gram of 60% glyoxal water solution of initial handling being adjusted to pH 5.0 with diluted sodium hydroxide solution at room temperature.
It is mixed into 145.3 grams of dimethylol urea now by stirring.This produces white paste material.Hereafter, it is mixed into 11.3 grams
This mixture is simultaneously heated to 40 DEG C by 37% formalin solution and 37.9 grams of methanol.
This initial charge is subsequently adjusted to pH 7.0 with diluted sodium hydroxide solution and/or hydrochloric acid and is heated to 70 DEG C.This is first
Begin charging rarefaction, limpid and glassy yellow liquid in this process.
At 70 DEG C after 1 hour, this batch of material is cooled to 50 DEG C.
It is then mixed into 132.0 grams of methanol.
By being mixed into 5.5 grams of concentrated hydrochloric acid at 50 DEG C（31-33 weight %）Start to be etherified.This exothermic reaction leads to about 8 DEG C
Intensification.After 9 minutes, by being mixed into 3.5 gram of 50% sodium hydroxide solution and 0.2 gram of triethanolamine（99%）Terminate this etherificate.
This initial charge is subsequently adjusted to pH 5.9 with diluted sodium hydroxide solution and/or hydrochloric acid.Hereafter at 70 DEG C of highest
In the vacuum of as little as 100 millibars of absolute pressures 3 hours to be removed by distillation 156 grams of methanol-water mixtures.
After cooling to room temperature obtain have the relatively lean, limpid of the viscosity of 500 mPa s recording at 25 DEG C and
Glassy yellow product liquid.
Hereafter, it is mixed into 130.0 grams of JEFFAMINE portionwise®M-600, passes through to be mixed into concentrated hydrochloric acid portionwise simultaneously（31-33%）Will
PH is maintained in the range of 5.1-6.4.It is being mixed into 18.0 grams of concentrated hydrochloric acid altogether for this（31-33%）Afterwards, this initial charge has
5.3 pH.Final product is in limpid peony the viscosity with the 600 mPa s recording at 25 DEG C.
Table 6 below shows embodiment 6a again) and embodiment 6b) between essential distinction.
Table 6
| Embodiment 6a) | Embodiment 6b) | |
| JEFFAMINE®M-600 | React with DMDHEH | Only it is mixed into, unreacted |
| Viscosity (25 DEG C) | 7000 mPa•s | 600 mPa•s |
Products therefrom is used for the aqueous dispersion that preparation has the content of 200 g/l.By violent for these dispersions shake, so
Stand 30 minutes afterwards.Hereafter, by this aqueous dispersion in a water bath homoiothermic to 45 DEG C.Embodiment 6a) product in relatively strong
Turbidity shows that this reaction reduces HLB value, sees Fig. 3.
Embodiment 7a)（The present invention）
168.14 grams of tripolycyanamide of initial handling at room temperature.It is mixed into 0.53 gram of triethanolamine now by stirring（99%）With
342.16 gram of 37% formalin solution and 84.07 grams of diethylene glycols.Then stir into 0.14 gram of 25% sodium hydroxide solution.This is initial
The pH of charging rises to 10.0 from 9.0 in this process.
Hereafter, this initial charge is heated to 70 DEG C and keeps 10 minutes at 70 DEG C.
Subsequently by this batch of material be cooled to 65 DEG C and with 254.5 grams of methanol mixed.
Batch temperature is down to about 55 DEG C in this process.After batch temperature goes back up to 65 DEG C, by being mixed into 17.5 grams
50% sodium hydroxide solution starts alkalescence etherificate.
Hereafter, this initial charge is heated to 70 DEG C and keeps 40 minutes at 70 DEG C.
Subsequently terminate this etherificate by being mixed into 17.7 gram of 60% acetic acid.In this process by pH regulator to 10.7（Tolerance +/-
0.3%）.
Hereafter, 157.0 grams of MARLIPAL are stirred into®O 13/50.Hereafter in as little as 100 millibars of absolute pressure at 65 DEG C of highest
In the vacuum of power 6 hours to be removed by distillation 380 grams of methanol-water mixtures.
Obtain after cooling to room temperature have the viscosity of 35 000 mPa s recording at 25 DEG C and 9.2 pH viscous
Thick, limpid and colorless liquid product.
Embodiment 7b)（The present invention）
Repeat embodiment 7a), simplyAfter the reaction rather than it is mixed into MARLIPAL before reaction ® O 13/50.
168.14 grams of tripolycyanamide of initial handling at room temperature.It is mixed into 0.53 gram of triethanolamine now by stirring（99%）
With 342.16 gram of 37% formalin solution and 84.07 grams of diethylene glycols.Then stir into 0.14 gram of 25% sodium hydroxide solution.This is first
The pH beginning to feed rises to 10.0 from 9.0 in this process.
Hereafter, this initial charge is heated to 70 DEG C and keeps 10 minutes at 70 DEG C.
Subsequently by this batch of material be cooled to 65 DEG C and with 254.5 grams of methanol mixed.
Batch temperature is down to about 55 DEG C in this process.After batch temperature goes back up to 65 DEG C, by being mixed into 17.5 grams
50% sodium hydroxide solution starts alkalescence etherificate.
Hereafter, this initial charge is heated to 70 DEG C and keeps 40 minutes at 70 DEG C.
Subsequently terminate this etherificate by being mixed into 17.7 gram of 60% acetic acid.In this process by pH regulator to 10.7（Tolerance +/-
0.3%）.
Hereafter at 65 DEG C of highest in the vacuum of as little as 100 millibars of absolute pressures 3 hours to be removed by distillation 351 grams
Methanol-water mixtures.
After cooling to room temperature obtain have the relatively lean, limpid of the viscosity of 600 mPa s recording at 25 DEG C and
Glassy yellow product liquid.
Hereafter, 157.0 grams of MARLIPAL are stirred into®O 13/50.Final product is equally to have 800 recording at 25 DEG C
The viscosity of mPa s and 9.3 pH relatively lean, limpid and colourless liquid.
Table 7 below shows embodiment 7a again) and embodiment 7b) between essential distinction.
Table 7
| Embodiment 7a) | Embodiment 7b) | |
| MARLIPAL®O 13/50 | React with tripolycyanamide | Only it is mixed into, unreacted |
| Viscosity (25 DEG C) | 35 000 mPa•s | 800 mPa•s |
Products therefrom is used for the aqueous dispersion that preparation has the content of 200 g/l.By violent for these dispersions shake, so
Stand 30 minutes afterwards.Hereafter, by this aqueous dispersion in a water bath homoiothermic to 53 DEG C.Embodiment 7a) product relatively clear appearance
Show that this reaction improves HLB value, see Fig. 4.
Embodiment 8a)（The present invention）
116.8 gram of 60% glyoxal water solution of initial handling being adjusted to pH 5.0 with diluted sodium hydroxide solution at room temperature.
It is mixed into 157.7 grams of dimethylol urea now by stirring.This produces white paste material.Hereafter, it is mixed into 12.2 grams
This mixture is simultaneously heated to 40 DEG C by 37% formalin solution and 41.1 grams of methanol.
This initial charge is subsequently adjusted to pH 7.0 with diluted sodium hydroxide solution and/or hydrochloric acid and is heated to 70 DEG C.This is first
Begin charging rarefaction, limpid and glassy yellow liquid in this process.
At 70 DEG C after 1 hour, this batch of material is cooled to 50 DEG C.
Hereafter, it is mixed into 123.2 grams of Emulgator EL emulsifying agents（Oleum Ricini polyglycol ether containing 36 moles of EO, can obtain
From Sch rer ＆ Schl pfer AG）With 144.0 grams of methanol.
By being mixed into 5.5 grams of concentrated hydrochloric acid at 50 DEG C（31-33%）Start to be etherified.This exothermic reaction leads to about 9 DEG C of liter
Temperature.After 9 minutes, by being mixed into 3.4 gram of 50% sodium hydroxide solution and 0.2 gram of triethanolamine（99%）Terminate this etherificate.
This initial charge is subsequently adjusted to pH 5.9 with diluted sodium hydroxide solution and/or hydrochloric acid.Hereafter at 65 DEG C of highest
In the vacuum of as little as 100 millibars of absolute pressures 5 hours to be removed by distillation 177 grams of methanol-water mixtures.
Obtain after cooling to room temperature have the viscosity of 24 000 mPa s recording at 25 DEG C and 6.1 pH viscous
Thick, limpid and glassy yellow product liquid.
Embodiment 8b)（The present invention）
Repeat embodiment 8a), simply after the reaction rather than reaction before be mixed into Emulgator EL emulsifying agent.
116.8 gram of 60% glyoxal water solution of initial handling being adjusted to pH 5.0 with diluted sodium hydroxide solution at room temperature.
It is mixed into 157.7 grams of dimethylol urea now by stirring.This produces white paste material.Hereafter, it is mixed into 12.2 grams
This mixture is simultaneously heated to 40 DEG C by 37% formalin solution and 41.1 grams of methanol.
This initial charge is subsequently adjusted to pH 7.0 with diluted sodium hydroxide solution and/or hydrochloric acid and is heated to 70 DEG C.This is first
Begin charging rarefaction, limpid and glassy yellow liquid in this process.
At 70 DEG C after 1 hour, this batch of material is cooled to 50 DEG C.
Subsequently it is mixed into 144.0 grams of methanol.
By being mixed into 5.9 grams of concentrated hydrochloric acid at 50 DEG C（31-33 weight %）Start to be etherified.This exothermic reaction leads to about 10
DEG C intensification.After 9 minutes, by being mixed into 3.6 gram of 50% sodium hydroxide solution and 0.2 gram of triethanolamine（99%）Terminate this ether
Change.This initial charge is subsequently adjusted to pH 5.9 with diluted sodium hydroxide solution and/or hydrochloric acid.Hereafter as little as at 65 DEG C of highest
In the vacuum of 100 millibars of absolute pressures 3 hours to be removed by distillation 169 grams of methanol-water mixtures.
After cooling to room temperature obtain have the relatively sticky, limpid of the viscosity of 500 mPa s recording at 25 DEG C and
Glassy yellow product liquid.
Hereafter, 123.2 grams of Emulgator EL emulsifying agents are stirred into, then by being mixed into dilute hydrochloric acid by pH regulator to pH
6.1.
Final product is in limpid glassy yellow the viscosity with 3500 mPa s at 25 DEG C.
Table 8 shows embodiment 8a again) and embodiment 8b) between essential distinction.
Table 8
| Embodiment 8a) | Embodiment 8b) | |
| Emulgator EL emulsifying agent | React with DMDHEH | Only it is mixed into, unreacted |
| Viscosity (25 DEG C) | 24 000 mPa•s | 3500 mPa•s |
Products therefrom is used for the sample that preparation has the composition enumerated in table 9.
Table 9
At the same time acutely after shake, sample A, B and C produce the dispersion with pasty consistency.
Sample A, B are identical with the amount of Emulgator EL emulsifying agent in C.
Sample D is the comparison of non-invention, and it is based on embodiment 8b) but without Emulgator EL emulsifying agent.?
After shake, sample D is still wash and is immediately split into 2 limpid phases.See Fig. 5.
After standing 6 hours, find that dispersion A of initial pasty state and B liquefy, and dispersion C is still pasty state, sees Fig. 6.
Standing 1 day after, be clear that embodiment 8a) the present invention product（In sample A）And enforcement
Example 8b) the present invention mixture（In sample B）It is phase transfer catalyst, see Fig. 7.
This is by MIBK phase in sample A and B（Top）Volume increase（By Fig. 7 is depicted in centimetre phase height recording
In）It is evident that and embodiment 8a) product with microemulsion（Limpid top phase）Form makes water emulsification and embodiment 8b)
Mixture is with thick emulsion（Emulsus top phase）Form makes water emulsification, in contrast to this, only contains the non-invention of Oleum Ricini polyglycol ether
Mixture C keep pasty state, and 8b containing embodiment) product but without emulsifying agent in the solvent mixture of MIBK and water
Mixture D does not lead to the volume of MIBK phase to increase.
As shown in Figure 8, the visual pattern of sample A-F is supported additionally by infrared spectrum analysiss.
3000-4000 cm-1Spectrum in wavelength zone shows, different from sample D and E, the present invention sample A and B each
MIBK phase in be clearly present water.
Do not have to measure the mixture C only containing the non-invention of Oleum Ricini polyglycol ether, because it keeps pasty state.
Embodiment 9a)（The present invention）
120.2 gram of 60% glyoxal water solution of initial handling being adjusted to pH 5.0 with diluted sodium hydroxide solution at room temperature.
It is mixed into 162.3 grams of dimethylol urea now by stirring.This produces white paste material.Hereafter, it is mixed into 12.6 grams
This mixture is simultaneously heated to 40 DEG C by 37% formalin solution and 42.3 grams of methanol.
This initial charge is subsequently adjusted to pH 7.0 with diluted sodium hydroxide solution and/or hydrochloric acid and is heated to 70 DEG C.This is first
Begin charging rarefaction, limpid and glassy yellow liquid in this process.
At 70 DEG C after 1 hour, this batch of material is cooled to 50 DEG C.
Hereafter, it is mixed into 114.7 grams of Genamin portionwise®C 050（There is 5 moles of ethylene oxide and the C8/C18 of pH 9-10
Coconut oil fat amine ethoxylate, available from Clariant）, pass through to be mixed into concentrated hydrochloric acid portionwise simultaneously（31-33%）PH is maintained at
5.1-6.4 in the range of.It is being mixed into 28.9 grams of concentrated hydrochloric acid altogether for this（31-33%）Afterwards, this initial charge has 5.3 pH.
It is then mixed into 148.0 grams of methanol.
By being mixed into 7.5 grams of concentrated hydrochloric acid at 50 DEG C（31-33%）Start to be etherified.This exothermic reaction leads to about 7 DEG C of liter
Temperature.After 9 minutes, by being mixed into 3.7 gram of 50% sodium hydroxide solution and 0.2 gram of triethanolamine（99%）Terminate this etherificate.
This initial charge is subsequently adjusted to pH 5.9 with diluted sodium hydroxide solution and/or hydrochloric acid.Hereafter at 65 DEG C of highest
In the vacuum of as little as 100 millibars of absolute pressures 5 hours to be removed by distillation 182 grams of methanol-water mixtures.
After cooling to room temperature obtain have the relatively sticky, limpid of the viscosity of 4100 mPa s recording at 25 DEG C and
Bright brown liquid product.
Embodiment 9b)（The present invention）
Repeat embodiment 9a) simplyAfter the reaction rather than it is mixed into Genamin before reaction ® C 050.
120.2 gram of 60% glyoxal water solution of initial handling being adjusted to pH 5.0 with diluted sodium hydroxide solution at room temperature.
It is mixed into 162.3 grams of dimethylol urea now by stirring.This produces white paste material.Hereafter, it is mixed into 12.6 grams
This mixture is simultaneously heated to 40 DEG C by 37% formalin solution and 42.3 grams of methanol.
This initial charge is subsequently adjusted to pH 7.0 with diluted sodium hydroxide solution and/or hydrochloric acid and is heated to 70 DEG C.This is first
Begin charging rarefaction, limpid and glassy yellow liquid in this process.
At 70 DEG C after 1 hour, this batch of material is cooled to 50 DEG C.
It is then mixed into 132.0 grams of methanol.
By being mixed into 6.1 grams of concentrated hydrochloric acid at 50 DEG C（31-33 weight %）Start to be etherified.This exothermic reaction leads to about 8 DEG C
Intensification.After 9 minutes, by being mixed into 3.7 gram of 50% sodium hydroxide solution and 0.2 gram of triethanolamine（99%）Terminate this etherificate.
This initial charge is subsequently adjusted to pH 5.9 with diluted sodium hydroxide solution and/or hydrochloric acid.Hereafter at 65 DEG C of highest
In the vacuum of as little as 100 millibars of absolute pressures 3 hours to be removed by distillation 173 grams of methanol-water mixtures.
After cooling to room temperature obtain have the relatively lean, limpid of the viscosity of 500 mPa s recording at 25 DEG C and
Glassy yellow product liquid.
Hereafter, it is mixed into 114.7 grams of Genamin portionwise®C 050, passes through to be mixed into concentrated hydrochloric acid portionwise simultaneously（31-33%）By pH
It is maintained in the range of 5.1-6.4.It is being mixed into 28.9 grams of concentrated hydrochloric acid altogether for this（31-33%）Afterwards, this initial charge has 5.3
PH.
Final product is in limpid bright brown the viscosity with the 550 mPa s recording at 25 DEG C.
Table 10 below shows embodiment 9a again) and embodiment 9b) between essential distinction.
Table 10
| Embodiment 9a) | Embodiment 9 is b) | |
| Genamin®C 050 | React with DMDHEH | Only it is mixed into, unreacted |
| Viscosity (25 DEG C) | 4100 mPa•s | 550 mPa•s |
Products therefrom be used for by with by 335 milliliters of water and 335 milliliters of methyl iso-butyl ketone (MIBK)s（MIBK）The mixture of composition
It is mixed with the dispersion of the content with 330 g/l.
At the same time acutely after shake, embodiment 9a) product and embodiment 9b) product all show phase transfer catalysis
Agent acts on.
Directly after shake, embodiment 9a) produce creamy emulsion, and embodiment 9b) product slight haze, see Fig. 9.
After standing 1 minute and/or 2 minutes, in embodiment 9a) in can be seen that and be clearly separated, see Figure 10.
After standing 5 minutes, embodiment 9a) and embodiment 9b) each there is the limpid top phase mainly containing MIBK.
The bottom of primary aqueous is in embodiment 9a) in still slight haze, but in embodiment 9b) in limpid, see Figure 11.
Embodiment 10a)（The present invention）
115.7 gram of 60% glyoxal water solution of initial handling being adjusted to pH 5.0 with diluted sodium hydroxide solution at room temperature.
It is mixed into 156.2 grams of dimethylol urea now by stirring.This produces white paste material.Hereafter, it is mixed into 12.1 grams
This mixture is simultaneously heated to 40 DEG C by 37% formalin solution and 40.7 grams of methanol.
This initial charge is subsequently adjusted to pH 7.0 with diluted sodium hydroxide solution and/or hydrochloric acid and is heated to 70 DEG C.This is first
Begin charging rarefaction, limpid and glassy yellow liquid in this process.
At 70 DEG C after 1 hour, this batch of material is cooled to 50 DEG C.
Hereafter, it is mixed into 123.6 grams of TEGOPREN®5847（Polyethers-methyl polysilicone alkyl copolymer, has in polyethers
80:The EO/PO of 20 weight %, available from Evonik）With 144.5 grams of methanol.
By being mixed into 4.0 grams of concentrated hydrochloric acid at 50 DEG C（31-33%）Start to be etherified.This exothermic reaction leads to about 9 DEG C of liter
Temperature.After 9 minutes, by being mixed into 2.5 gram of 50% sodium hydroxide solution and 0.2 gram of triethanolamine（99%）Terminate this etherificate.
This initial charge is subsequently adjusted to pH 5.9 with diluted sodium hydroxide solution and/or hydrochloric acid.Hereafter at 65 DEG C of highest
In the vacuum of as little as 100 millibars of absolute pressures 6 hours to be removed by distillation 176 grams of methanol-water mixtures.
After cooling to room temperature obtain have the relatively sticky, limpid of the viscosity of 6300 mPa s recording at 25 DEG C and
Glassy yellow product liquid.
Embodiment 10b)（The present invention）
Repeat embodiment 10a), simply after the reaction rather than reaction before be mixed into TEGOPREN®5847.
115.7 gram of 60% glyoxal water solution of initial handling being adjusted to pH 5.0 with diluted sodium hydroxide solution at room temperature.
It is mixed into 156.2 grams of dimethylol urea now by stirring.This produces white paste material.Hereafter, it is mixed into 12.1 grams
This mixture is simultaneously heated to 40 DEG C by 37% formalin solution and 40.7 grams of methanol.
This initial charge is subsequently adjusted to pH 7.0 with diluted sodium hydroxide solution and/or hydrochloric acid and is heated to 70 DEG C.This is first
Begin charging rarefaction, limpid and glassy yellow liquid in this process.
At 70 DEG C after 1 hour, this batch of material is cooled to 50 DEG C.
It is then mixed into 144.5 grams of methanol.
By being mixed into 5.9 grams of concentrated hydrochloric acid at 50 DEG C（31-33 weight %）Start to be etherified.This exothermic reaction leads to about 8 DEG C
Intensification.After 9 minutes, by being mixed into 3.7 gram of 50% sodium hydroxide solution and 0.2 gram of triethanolamine（99%）Terminate this etherificate.
This initial charge is subsequently adjusted to pH 5.9 with diluted sodium hydroxide solution and/or hydrochloric acid.Hereafter at 65 DEG C of highest
In the vacuum of as little as 100 millibars of absolute pressures 3 hours to be removed by distillation 168 grams of methanol-water mixtures.
After cooling to room temperature obtain have the relatively lean, limpid of the viscosity of 500 mPa s recording at 25 DEG C and
Glassy yellow product liquid.
Hereafter, 123.6 grams of TEGOPREN are stirred into®5847, then by being mixed into dilute hydrochloric acid by pH regulator to pH 6.1.
Final product is in limpid glassy yellow the viscosity with the 880 mPa s recording at 25 DEG C.
Table 11 below shows embodiment 10a again) and embodiment 10b) between essential distinction.
Table 11
| Embodiment 10a) | Embodiment 10b) | |
| TEGOPREN®5847 | React with DMDHEH | Only it is mixed into, unreacted |
| Viscosity (25 DEG C) | 6300 mPa•s | 880 mPa•s |
Products therefrom is used for content and the 2 g/l concentrated hydrochloric acid that preparation has 200 g/l（31-33 weight %）Moisture dissipate
Body.
At the same time and after being stirred vigorously, embodiment 10a) product and as blend components, non-reactant is mixed thereto
Enter TEGOPREN®5847 embodiment 10b) product there is similar outward appearance, and there is suitable bubble in each case
Foam height and clear water phase, are shown in Figure 12.
Standing 1 minute after, embodiment 10 a) in foam height significantly reduce and there is certain visible muddiness,
See Figure 13.
After standing 15 minutes, embodiment 10a) product so that foam and turbidity is improved.On the contrary, in embodiment 10b)
Product in, foam is still clearly visible and lower section aqueous phase is still limpid.Figure 14 is it is therefore evident that be used this product as froth breaking
The probability of agent.
In order to test property when as additive in wood adhesive for the embodiments of the invention, using a series of
Inventive embodiment prepares the mixture of table 12.
In fact, in each case the product of 10 weight % fraction is stirred to Ponal Express（Based on poly- acetic acid
The aqueous wood adhesive dispersion of vinyl acetate, available from Henkel）In until uniformly.
Table 12
| A | B | C | D | E | F | G | |
| Embodiment 8 is a) | 1 g | - | - | - | - | - | - |
| Embodiment 8 is b) | - | 1 g | - | - | - | - | - |
| Embodiment 7 is a) | - | - | - | 1 g | - | - | - |
| Embodiment 1 | - | - | - | - | 1 g | - | - |
| Embodiment 10 is a) | - | - | - | - | - | 1 g | - |
| Embodiment 10 is b) | - | - | - | - | - | - | 1 g |
| Ponal Express bonding wood materials agent dispersion from Henkel | 9 g | 9 g | 9 g | 9 g | 9 g | 9 g | 9 g |
Different structure in order to make adhesive composition in terms of porosity and agglomeration visualizes, and these binding agents are combined
Each 0.1 gram of thing is applied on a glass with point mode.Then the second glass plate is laid on the first glass plate and with handss gently
Press down.Hereafter, by top board mobile about 5 centimetres parallel to base plate, and at a right angle with top board after about 1 minute lift, see
Figure 15 A to G.
The known heat-insulating properties strengthening the laminated veneer lumber being for example made up of multilamellar of the larger porosity of layer.
Especially, Figure 15 B, D and E shows for respective mixture B, D and E, and with regard to the timber using adhesive-free
Figure 15 C of the comparative example of adhesive dispersion compares, the relatively strong structure of this adhesive composition.This shows and comparative example phase
Than the more macroporosity obtaining adhesive phase and therefore advantageously more preferable heat-insulating properties.
It is also known that the stronger agglomeration of the compositionss of binding agent leads to larger contact pressure with a form and therefore leads
Cause stronger point bonding.
Especially, Figure 15 G with regard to mixture G shows clearly more powerful binding agent compared with Figure 15 C with regard to comparative example
Compositionss agglomeration.
This means that this produces higher point bonding.
Mixture A, B have the advantages that before solidification to be easier to be removed with water with D to G compared with comparative example C.
Embodiment 11（The present invention）
32 grams of methanol of initial handling, 97.3 gram of 37.5 weight % formalin and 45.7 grams of thiourea in the reactor at room temperature.
Use diluted sodium hydroxide solution（10 weight %）By pH regulator to 8.2.This batch of material is heated under pH 8.2 54 DEG C through 5 hours.
Hereafter, it is mixed into 54.8 grams of JEFFAMINE®M-600 and 60 gram of methanol.It is 9.6 that temperature is 50 DEG C and pH.
It is then mixed into 18 grams of concentrated hydrochloric acid（32 weight %）.This exothermic reaction leads to about 8 DEG C of intensification.After 9 minutes, lead to
Cross and be mixed into 15.6 gram of 30 weight % sodium hydroxide solution and terminate this reaction.Hereafter heat 90 minutes for 6 times in pH at 50 DEG C.This is molten
Liquid becomes cloudy after about twenty minutes.
Then distill out first alcohol and water in the vacuum of as little as 90 millibars of absolute pressures at 70 DEG C of highest.
Obtain slightly sticky, muddy product after cooling to room temperature.Standing when, salt gradually settles, be isolated out with
Obtain slightly sticky, the muddy product of the solids content with 88 weight %.
Embodiment 12（The present invention）
133.8 gram of 65 weight % phenolsulfonic acid aqueous solution of initial handling and 134.2 grams of water in the reactor.Add about 166 grams
16% sodium hydroxide solution is to realize neutral pH 7.Temperature rises to about 40 DEG C.
Now, it is mixed into 76.1 grams of thiourea and 120 gram of 37.5 weight % formalin.
With 16% sodium hydroxide solution, pH regulator is heated to 70 DEG C through 3 hours to 8.5 and by this batch of material under pH 8.5.
Obtain limpid product when being cooled to room temperature.
By itself and 34.2 grams of MARLIPAL®O 13/70（Oxo alcohol C13 containing 7 moles of EO, available from Sasol）Mixed
Close, be then stirred at room temperature 30 minutes to obtain limpid product.
Embodiment 13（The present invention）
66.9 gram of 65 weight % phenolsulfonic acid aqueous solution of initial handling and 33 grams of water in the reactor.Add about 83 grams of 16% hydrogen-oxygens
Change sodium solution to realize neutral pH 7.1.Temperature rises to about 39 DEG C.
Now, it is mixed into 38 grams of thiourea, 50 ml methanol and 60 gram of 37.5 weight % formalin.Molten with 16% sodium hydroxide
PH regulator is heated to 70 DEG C through 3 hours to 8.5 and by this batch of material under pH 8.5 by liquid.
Now, it is mixed into 15 grams of MARLIPAL®O 13/70 and 50 ml methanol.
At 50 DEG C, subsequently it is mixed into 23.1 grams of about 32 weight % hydrochloric acid.PH be down to 0.8 and product after about 7 minutes
Sink as precipitate.
Hereafter stir 1 hour at 65 DEG C.With 21.1 gram of 30% sodium hydroxide solution, pH regulator to 7.6 is fine to obtain
Homogeneous dispersion.
Then distill out methanol with 120 grams of methanol/water total amounts.
This fine product dispersion is in 3% BAYKANOL SL（Available from Lanxess）In the presence of grind until to reach 5 micro-
The granularity of rice.
This product is the aqueous dispersion with 26.5 weight % activated product contents.
Embodiment 14（The present invention）
66.9 gram of 65 weight % phenolsulfonic acid aqueous solution of initial handling and 33 grams of water in the reactor.Add about 84.9 grams of 16% hydrogen
Sodium hydroxide solution is to realize neutral pH 7.3.
Now, it is mixed into 38.05 grams of thiourea and 60 gram of 37.5 weight % formalin.With 16% sodium hydroxide solution, pH is adjusted
Save to 8.5 and this batch of material be heated under pH 8.5 70 DEG C through 3 hours.
Now, it is mixed into 15 grams of MARLIPAL®O 13/70.
At 50 DEG C, subsequently it is mixed into 25.9 grams of about 32 weight % hydrochloric acid.PH be down to 0.6 and product as under precipitate
Heavy.
Hereafter stir 2 hours at 70 DEG C.It is mixed into 13.9 gram of 30% sodium hydroxide solution to obtain pH 7 and slightly dispersed
Body.
This product dispersion grinds until reaching 2 microns of granularity in the presence of 3% BAYKANOL SL.
This product is the aqueous dispersion with 25 weight % activated product contents.
Wako tests
Product from embodiment 11 to 14 is also carried out as mentioned above（To embodiment 4）Wako test.In each case,
Using x gram（It is shown in Table 13）As above described in embodiment 11 to 14 preparation compositionss and 1 gram of blue dyeing sample, reference substance
As described in example 4 above.
Assessed by colorimetric measurement.Result is shown in table 13.
Table 13
| Product | Consumption (g) | Scoring |
| No product（Reference） | -- | 1 |
| Embodiment 11 | 0.2 | 4 - 5 |
| Embodiment 12 | 0.3 | 4 - 5 |
| Embodiment 13 | 0.3 | 3 |
| Embodiment 4 | 0.3 | 3 - 4 |
Grade:Scoring 1 to 5 (1=extreme difference, 5=fabulous).
Chlorine tests (ISO 105/E03,20 ppm active chlorine)
Carry out chlorine test using with Wako test identical blue dyeing sample.
By dipping-dry-product is applied on sample thermosetting color method：
- consumption：40 g/l products
- pH 5
- 15 g/l KNITTEX CAT MO（Available from Huntsman）
- wet uptake 70%
- be dried：2 minutes at 110 DEG C
- fixation：2 minutes at 170 DEG C.
The sample part thus processing is washed at 50 DEG C 30 minutes with soaping to test its wash resistant color fastness.
The sample that do not have post processing is used as reference.
Assessed by colorimetric measurement.Result is shown in table 14.
Table 14
Grade:Scoring 1 to 5 (1=extreme difference, 5=fabulous).
Claims (19)
1. compositionss, it comprises at least one formula (II) or the compound of formula (III) or formula (IV) or formula (V)
With the amine of the compound of at least one formula (VII) or a kind of formula (VIII) or (IX) or a kind of logical formula (X) there is polyoxy
The oligomeric or polysiloxane of change alkenyl group or a kind of formula (XI), the compound of preferred formula (XIa),
And optionally comprise the alcohol of formula (VI) further,
R4―OH (VI)
Wherein all R1And R2Represent H independently of one another or represent the straight or branched alkyl with 1 to 5 carbon atom, preferably generation
Table CH3Or C2H5Or C3H7, or represent
Or represent
Wherein m be 4 to 8 numerical value and t be 0 or 1 and p be 8 to 20 numerical value and q be 1 to 3 numerical value,
All R3Represent H or representative-CH independently of one another2―O―R2,
Wherein in formula (V), at least one R3Representative-CH2―O―R2,
X represents O or S,
Wherein in the formula (V) that X represents S, R3Also-CH can be represented2-O-R14, wherein R14Represent by phenolsulfonic acid or phenolsulfonic acid
Salt, particularly one of p-phenolsulfonic acid or its salt obtained by the etherificate of methylolation thiourea and described phenolsulfonic acid or its salt
Part, or R3Also-CH can be represented2-R15, wherein R15Represent the salt by phenolsulfonic acid or by phenolsulfonic acid, particularly Pyrogentisinic Acid
The methylol groups that one of sulfonic acid or its salt pass through methylolation thiourea are anti-with the methin groups of described phenolsulfonic acid or its salt
Should between the nitrogen-atoms and phenolsulfonic acid or the carbon atom of its salt of thiourea formed methylene bridge obtained by part,
R4Representative has 1 to 18, the straight chain of preferably 1 to 4 carbon atom or optional branched alkyl, more preferably represents CH3Or C2H5,
R5Representative has 4 to 18, the straight or branched alkyl of preferably 8 to 18 carbon atoms or thiazolinyl, more preferably represents and has 13
The branched alkyl of carbon atom or represent the aromatic fractions that optionally replaced by one or more hydrocarbyl portions, special representative's phenyl, first
Phenyl or benzyl,
Wherein k+y=2 and k has value 1 or 2, R6And R7One of represent H, and another represents H or represents CH3, l represent 0 to
20, preferably 2 to 20, more preferably 2 to 8, particularly 2 to 6 numerical value, wherein in the presence of the compound of the formula (VII) of l=0,
Also there must be l>The compound of=2 formula (VII), n represents 2 to 20, preferably 2 to 8, more preferably 2 to 6 numerical value, and R8Generation
Table H or representative
Wherein R9And R10One of represent H, and another represents H or CH3Or C2H5Or CH2OH,
Wherein r is 2 to 15 numerical value, and s is 0 to 20 numerical value, and v is 1 to 18 numerical value and R11Represent H or CH3And wherein in formula
(X) in siloxanes, not only dimethyl silyloxy units, also comprise the methyl first of the part including polyalkylene oxide groups
Silicon oxyalkyl units can be randomly dispersed in siloxane chain,
Wherein R12Represent H or there is the straight chain of 1 to 4 carbon atom or optional branched alkyl, preferably represent CH3Or t-C4H9, more excellent
Choosing represents H,
Wherein R13Represent H or there is the straight chain of 1 to 4 carbon atom or optional branched alkyl, preferably represent H or n-C4H9,
Wherein w represents 2 to 9, preferably 3 to 8 numerical value, u be 0 or preferably 1, Y be comprise carbon and hydrogen and optional sulfur and/or nitrogen and/
Or the divalent moiety of oxygen,
Wherein said compositionss comprise the compound of one or more formula (II) to (V) and the chemical combination of one or more formula (VII)
Thing and optionally, at least in the case of there is the compound of formula (VII) of l=6-8 and t=0, the compound of formula (VI)
Product.
2. compositionss according to claim 1 are it is characterised in that R5Represent there is the branched alkyl of 13 carbon atoms and l represent 2 to
The numerical value of 8, particularly 2 to 6, and t=0.
3. the compositionss according to claim 1 or 2 it is characterised in that its comprise can be by making at least one formula (II) or formula
Or the compound of formula (IV) or formula (V) and the alcohol of at least one formula (VI) and at least one R (III)12The change of the formula (VII) of=H
The amine of compound or formula (VIII) or (IX) or R12The logical formula (X) of=H there is the oligomeric of polyalkylene oxide groups or poly organo
Alkane or R12The formula (XI) of=H, the product of the mixture reaction acquisition of the compound of preferred formula (XIa), wherein every mole formula (VI)
Alcohol preferably use the compound of 0.01 to 0.5 mole of at least one formula (VII) to (XIa).
4. the compositionss of one or more according to claims 1 to 3 are it is characterised in that it comprises fluorescent whitening agent, particularly
Based on the fluorescent whitening agent of stilbene structure, or the UV absorbent of preferred reformulationses.
5. the compositionss according to claim 3 or 4, it is characterised in that the product that will obtain after described reacting neutralizes, are hereafter distilled
Go out the alcohol of excessive formula (VI).
6. comprise the waterborne compositions of one or more one or more of compositions according to claim 1 to 5, it preferably has
There is the water content of 20 to 60 weight %.
7. the method preparing compositionss according to claim 3, wherein makes formula (II) or formula (III) or formula (IV) or formula (V)
Compound is reacted it is characterised in that in addition making R with the alcohol of formula (VI)12The compound of formula (VII) of=H or formula (VIII) or
(IX) amine or R12The logical formula (X) of=H there is the oligomeric of polyalkylene oxide groups or polysiloxane or R12The formula of=H
(XI), the compound reaction of preferred formula (XIa), and can be when the alcohol of the compound of formula (I) to (V) and formula (VI) reacts beginning
Or add the compound with formula (VII) to one of (XIa) afterwards.
8. method according to claim 7 is it is characterised in that select temperature, pressure and pH to make being distilled off of the alcohol of formula (VI)
Reaction is made to balance towards beneficial to the formula (II) to (V) reacted with the compound of formula (VII) to one of (XIa) comprising greater proportion
One of the product of compound direction move, and preferably only distill out a part excess formula (VI) alcohol after will
The compound of formula (VII) to one of (XIa) is mixed in described reaction.
9. the method according to claim 7 or 8 is it is characterised in that it is at 30 to 130 DEG C, preferably 30 to 80 DEG C, more preferably 40 to
Carry out at a temperature of 70 DEG C.
10. one or more according to claim 7 to 9 method it is characterised in that with the etherificate of the alcohol of formula (VI) 0.3 to
1, carry out under preferably 0.45 to 0.75 pH, and and R12The compound of formula (VII) of=H or the amine of formula (VIII) or (IX)
Or R12The logical formula (X) of=H there is the oligomeric of polyalkylene oxide groups or polysiloxane or R12The formula (XI) of=H, preferably
The reaction of the compound of formula (XIa) 5 to 7, is carried out under preferably 5.6 to 6.4 pH, and uses in the case of rear one reaction
50 to 1000 millibars, preferably 50 to 175 millibars of absolute pressure.
11. according to claim 1 to 6 one or more of compositionss comprise natural fiber for process, preferred cellulose or
Pilus Caprae seu Oviss, or synthetic fibers, particularly polyester, polyamide, polyacrylonitrile, polyacrylate and viscose glue, and its fiber of mixture
The purposes of material.
12. purposes according to claim 11 are it is characterised in that described fibrous material contains 50 to 100 weight % celluloses, particularly
Cotton.
13. according to the purposes of claim 11 or 12 it is characterised in that using comprise a certain proportion of at least one formula (VII) or
(VIII) or (IX) or (X) or preferred (XI), particularly compositionss of conversion compound of one of (XIa) and being applied to are being knitted
The polymer of blocking effect is produced on thing, and thus obtained compositionss are used for processing fibrous material to produce enhanced obstruct
Effect.
14. according to the purposes of claim 11 or 12 it is characterised in that using comprise a certain proportion of at least one formula (VII) or
(VIII) or (IX) or (X) or (XI), preferably compositionss of conversion compound of one of (XIa) and being applied to are produced on fabric
Give birth to the polymer of blocking effect, and thus obtained compositionss are used for processing fibrous material to produce or to strengthen decontamination effect.
15. according to the purposes of claim 11 or 12 it is characterised in that described compositionss are used for being transported to free radical scavenger
On fibrous material, particularly comprise the compositionss of the conversion compound of the formula (II), (IV) or (V) of a certain proportion of X=S.
16. according to the purposes of claim 11 or 12 it is characterised in that compositionss according to claim 4 are used for fluorescent brightening
Agent, is based particularly on the fluorescent whitening agent of stilbene structure or UV absorbent is transported on fibrous material.
17. according to claim 1 to 6 one or more compositionss as phase transfer catalyst purposes.
18. according to claim 1 to 6 one or more compositionss as the additive of binding agent purposes.
The compound of 19. formulas (XII),
Wherein R3Represent H or representative-CH2―O―R2,
All R1And R2Represent H independently of one another or represent the straight or branched alkyl with 1 to 5 carbon atom, preferably represent
CH3Or C2H5Or C3H7, or represent
Or represent
Wherein m be 4 to 8 numerical value and q be 1 to 3 numerical value and
Wherein R13Represent H or there is the straight chain of 1 to 4 carbon atom or optional branched alkyl, preferably represent H or n-C4H9,
Condition is the R existing1Or R2Partial at least one does not represent H.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14179257.2 | 2014-07-31 | ||
| EP14179257.2A EP2980308A1 (en) | 2014-07-31 | 2014-07-31 | Compositions for the treatment of fibrous materials |
| PCT/EP2015/067332 WO2016016282A2 (en) | 2014-07-31 | 2015-07-29 | Compositions for treatment of fiber materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106471182A true CN106471182A (en) | 2017-03-01 |
| CN106471182B CN106471182B (en) | 2019-05-31 |
Family
ID=51257366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580036196.2A Active CN106471182B (en) | 2014-07-31 | 2015-07-29 | For handling the composition of fibrous material |
Country Status (4)
| Country | Link |
|---|---|
| EP (2) | EP2980308A1 (en) |
| CN (1) | CN106471182B (en) |
| ES (1) | ES2949983T3 (en) |
| WO (1) | WO2016016282A2 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62104986A (en) * | 1985-10-29 | 1987-05-15 | 東海染工株式会社 | Enhancement of dyeing fastness of cellulosic fiber-containing structure to chlorine treatment water |
| US5242463A (en) * | 1991-03-06 | 1993-09-07 | The United States Of America As Represented By The Secretary Of Agriculture | Anionically dyeable smooth-dry crosslinked cellulosic material created by treatment of cellulose with non-reactive glycol ether swelling agents and nitrogen based compounds |
| US5358535A (en) * | 1992-05-07 | 1994-10-25 | Societe Francaise Hoechst | Use of polyalkyleneglycol diesters as formaldehyde collectors and finishing process for the textile industry |
| US5614591A (en) * | 1994-12-15 | 1997-03-25 | The Virkler Company | Process and composition for imparting durable press properties to textile fabrics |
| US6102973A (en) * | 1993-07-20 | 2000-08-15 | Morales; Rodolfo A. | Process for treating garments |
| CN1922360A (en) * | 2004-02-25 | 2007-02-28 | 凯米罗总公司 | A process for the treatment of fibre material and new composition |
| CN102767106A (en) * | 2012-05-29 | 2012-11-07 | 凯米罗总公司 | Method for treating fiber material and novel composition |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH1702468D (en) * | 1967-12-02 | |||
| US3620821A (en) * | 1968-09-18 | 1971-11-16 | Union Carbide Corp | Treatment of fibers with siloxane-polyoxyalkylene block copolymers containing methoxysiloxy groups |
| US5252233A (en) * | 1990-08-10 | 1993-10-12 | Union Carbide Chemicals & Plastics Technology Corporation | Silicone textile finishes |
| DE4133995A1 (en) | 1990-10-17 | 1992-04-23 | Ciba Geigy Ag | Two=stage two bath dyeing of cellulose hydrophobic fibre mixt. - using reactive dyestuff then disperse dyestuff in bath contg. neutral salt to prevent sepn. |
| US5340614A (en) | 1993-02-11 | 1994-08-23 | Minnesota Mining And Manufacturing Company | Methods of polymer impregnation |
| US6123739A (en) | 1995-06-19 | 2000-09-26 | Westpoint Stevens Inc. | Method to impart wrinkle free properties to sheeting and other fabrics made from cotton |
| DE19633625A1 (en) | 1996-08-21 | 1998-02-26 | Basf Ag | Process for the preparation of aqueous concentrated solutions of N-methylol ethers suitable for the finishing of cellulose-containing textile materials |
| ATE241722T1 (en) | 1996-12-04 | 2003-06-15 | Amann & Soehne | METHOD FOR DYEING TEXTILE SUBSTRATES |
| NL1014395C2 (en) | 2000-02-16 | 2001-08-20 | Stork Brabant Bv | Method for dyeing textile materials in a supercritical fluid. |
| DE10246401A1 (en) | 2002-10-04 | 2004-08-05 | Georg-August-Universität Göttingen | Process for improving the durability, dimensional stability and surface hardness of a wooden body |
| EP1947233A1 (en) * | 2007-01-19 | 2008-07-23 | Basf Se | Method for producing a coated textile |
-
2014
- 2014-07-31 EP EP14179257.2A patent/EP2980308A1/en not_active Withdrawn
-
2015
- 2015-07-29 CN CN201580036196.2A patent/CN106471182B/en active Active
- 2015-07-29 EP EP15744199.9A patent/EP3175033B1/en active Active
- 2015-07-29 ES ES15744199T patent/ES2949983T3/en active Active
- 2015-07-29 WO PCT/EP2015/067332 patent/WO2016016282A2/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62104986A (en) * | 1985-10-29 | 1987-05-15 | 東海染工株式会社 | Enhancement of dyeing fastness of cellulosic fiber-containing structure to chlorine treatment water |
| US5242463A (en) * | 1991-03-06 | 1993-09-07 | The United States Of America As Represented By The Secretary Of Agriculture | Anionically dyeable smooth-dry crosslinked cellulosic material created by treatment of cellulose with non-reactive glycol ether swelling agents and nitrogen based compounds |
| US5358535A (en) * | 1992-05-07 | 1994-10-25 | Societe Francaise Hoechst | Use of polyalkyleneglycol diesters as formaldehyde collectors and finishing process for the textile industry |
| US6102973A (en) * | 1993-07-20 | 2000-08-15 | Morales; Rodolfo A. | Process for treating garments |
| US5614591A (en) * | 1994-12-15 | 1997-03-25 | The Virkler Company | Process and composition for imparting durable press properties to textile fabrics |
| CN1922360A (en) * | 2004-02-25 | 2007-02-28 | 凯米罗总公司 | A process for the treatment of fibre material and new composition |
| CN100593600C (en) * | 2004-02-25 | 2010-03-10 | 凯米罗总公司 | A process for the treatment of fibre material and new composition |
| CN102767106A (en) * | 2012-05-29 | 2012-11-07 | 凯米罗总公司 | Method for treating fiber material and novel composition |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2949983T3 (en) | 2023-10-04 |
| WO2016016282A2 (en) | 2016-02-04 |
| EP3175033B1 (en) | 2023-04-26 |
| EP2980308A1 (en) | 2016-02-03 |
| WO2016016282A3 (en) | 2016-06-02 |
| CN106471182B (en) | 2019-05-31 |
| EP3175033A2 (en) | 2017-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1129158A (en) | Treatment of textile fabrics with epoxy-polyoxyalkylene modified organosilicones | |
| EP0135471B1 (en) | Process for treating textile materials | |
| CN101910504B (en) | Textiles treated with copolymers of epoxy compounds and amino silanes having enhanced wet-strength | |
| US8916511B2 (en) | Polysiloxanes having quaternary ammonium groups and use thereof | |
| EP1401920B1 (en) | Modified polyorganosiloxanes, aqueous emulsions thereof, their production and their use | |
| CN105949468B (en) | A kind of anionic is linearly copolymerized the preparation method of organosilicon flexible finishing agent | |
| CN114517411A (en) | Preparation method and application of washable cotton fabric softener | |
| CN1950141A (en) | Rapid low-foam wetting agents for hydrophobic surfaces | |
| CN103261390A (en) | Cleaning compositions with amphoteric polycarboxylate polymers | |
| JP4542895B2 (en) | Liquid laundry composition comprising a silicone additive | |
| US9605151B2 (en) | Microemulsion composition and a fiber treating agent | |
| CN101506274A (en) | Aminosiloxane oil-in-water emulsion | |
| DE2952287A1 (en) | METHOD FOR PRODUCING A POLYSILOXANE BLOCK POLYMERISATE AND THE USE THEREOF AS A FOAM INHIBITOR | |
| CA2627140A1 (en) | Polysiloxane and textile auxiliary containing a polysiloxane | |
| CN1364955A (en) | Method for reducing textile crease and improving textile contact feel | |
| CN111234255A (en) | Hyperbranched organic silicon wetting agent for waterborne polyurethane and preparation method thereof | |
| EP2980126A1 (en) | Process for making an aminosiloxane polymer nanoemulsion | |
| CN106471182A (en) | For processing the compositionss of fibrous material | |
| US10626223B2 (en) | Polyurethane-organopolysiloxanes | |
| JPH01229072A (en) | Low foaming composition for processing synthetic fiber | |
| CN114855461A (en) | Organic silicon softening agent, preparation method thereof and application thereof in deep color fabric | |
| KR102577428B1 (en) | Emulsions of aminosiloxanes and silicates | |
| JPH02221238A (en) | Styrene oxide adduct | |
| SE503556C2 (en) | New cationic surfactants of quaternary ammonium type, process for their preparation and use thereof, especially for the treatment of textile and cellulose materials | |
| KR0134183B1 (en) | Micro-emulsion of aminopolysiloxans |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |