CN1094512C - Oitnment detergent composition - Google Patents
Oitnment detergent composition Download PDFInfo
- Publication number
- CN1094512C CN1094512C CN99110039A CN99110039A CN1094512C CN 1094512 C CN1094512 C CN 1094512C CN 99110039 A CN99110039 A CN 99110039A CN 99110039 A CN99110039 A CN 99110039A CN 1094512 C CN1094512 C CN 1094512C
- Authority
- CN
- China
- Prior art keywords
- stilbene
- composition
- amino
- benzene
- dyestuff
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 239000003599 detergent Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 claims description 57
- 239000000975 dye Substances 0.000 claims description 50
- 239000004094 surface-active agent Substances 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- LHYQAEFVHIZFLR-UHFFFAOYSA-L 4-(4-diazonio-3-methoxyphenyl)-2-methoxybenzenediazonium;dichloride Chemical compound [Cl-].[Cl-].C1=C([N+]#N)C(OC)=CC(C=2C=C(OC)C([N+]#N)=CC=2)=C1 LHYQAEFVHIZFLR-UHFFFAOYSA-L 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- VIFBEEYZXDDZCT-UHFFFAOYSA-N 2-(2-phenylethenyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=CC=C1 VIFBEEYZXDDZCT-UHFFFAOYSA-N 0.000 claims description 2
- FSSXWBIXRQXSHH-UHFFFAOYSA-N N1N=CCC1.C1(=CC=CC=C1)C=1C=CC=CC1 Chemical class N1N=CCC1.C1(=CC=CC=C1)C=1C=CC=CC1 FSSXWBIXRQXSHH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 claims 2
- 239000008187 granular material Substances 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 6
- 239000002245 particle Substances 0.000 description 42
- 238000002156 mixing Methods 0.000 description 37
- 239000000463 material Substances 0.000 description 27
- 239000013543 active substance Substances 0.000 description 26
- 239000003945 anionic surfactant Substances 0.000 description 24
- -1 polyoxyethylene Polymers 0.000 description 24
- 239000011734 sodium Substances 0.000 description 24
- 125000000217 alkyl group Chemical group 0.000 description 23
- 239000000843 powder Substances 0.000 description 23
- 229910052708 sodium Inorganic materials 0.000 description 23
- 238000005406 washing Methods 0.000 description 23
- 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 19
- 229910052799 carbon Inorganic materials 0.000 description 19
- 239000006071 cream Substances 0.000 description 19
- 150000001721 carbon Chemical group 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 238000005342 ion exchange Methods 0.000 description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 13
- 238000005054 agglomeration Methods 0.000 description 12
- 230000002776 aggregation Effects 0.000 description 12
- 230000009257 reactivity Effects 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000003760 tallow Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000007859 condensation product Substances 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 150000004665 fatty acids Chemical class 0.000 description 9
- 238000005469 granulation Methods 0.000 description 9
- 230000003179 granulation Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000006210 lotion Substances 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 241000282326 Felis catus Species 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 229910021653 sulphate ion Inorganic materials 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 4
- 150000003818 basic metals Chemical class 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229940077388 benzenesulfonate Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000019864 coconut oil Nutrition 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
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- 238000005562 fading Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910017090 AlO 2 Inorganic materials 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 2
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
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- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- 235000017550 sodium carbonate Nutrition 0.000 description 2
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 1
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- 125000005341 metaphosphate group Chemical group 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 229910052674 natrolite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A high active detergent paste composition which is suitable for making detergent granules which have an excellent white appearance making them suitable for use in consumer products. The paste compositions comprise a dye or optical brightener.
Description
The application is the dividing an application of No. 93109880.7 applications for a patent for invention of " detergent composition " by name submitted on July 15th, 1993.
At present, exist the trend to compact detergent development, this washing composition provides a kind of product of transporting and storing of being more convenient for to the human consumer, and has alleviated the weight of used wrapping material.In order to prepare these compact detergents, need to use high-density, high-activity particle/agglomerate.
A problem relevant with this high-activity particle is the COLOR FASTNESS PROBLEM of organic surface active agent material.This phenomenon of fading is very disagreeable in the finished product washing composition, and can make the detergent particles yellowing that slurry by anionic detergent salt makes, and this is unacceptable to the human consumer, therefore, these washing composition commercial be infeasible.This problem is especially severe in the particle that contains the high reactivity organic surface active agent.
A kind of method of preparation high active detergent granules is to contain the high reactivity slurry and the detergent powder agglomeration of the salt of anion surfactant.In the past, for various reasons, seldom use this slurry in detergent industry, these reasons are included in to be used the practical difficulty that runs in the high viscosity slurry and needs to keep high temperature in order to prevent that material from solidifying, and with the relevant problem of fading.
From the viewpoint that the human consumer accepts, need preparation to be white in color or approaching white high active detergent granules.According to Herman de Groot, W. " sulfonation technology in the detergent industry " (Kluwer Academic Publishers, 1991), a kind of to improve painted common treatment process be the dark organic compound of bleaching, especially resembles alkyl group benzene sulfonate (LAS) or the such anion surfactant of methyl ester sulfonate (MES).Bleaching action is the reagent by a kind of conjugated carbon-carbon double bond that ruptures, by with conjugated double bond in two keys reaction or the oxidation and/or the reductive action of chromophore realized.Have many SYNTHETIC OPTICAL WHITNER may be applicable to this purpose, but have only clorox and hydrogen peroxide to have commercial value, clorox is than the more convenient and more effective SYNTHETIC OPTICAL WHITNER of hydrogen peroxide.Yet, owing in the process of some charging, may produce sensitizer, so the chloro SYNTHETIC OPTICAL WHITNER is not desirable SYNTHETIC OPTICAL WHITNER, another kind of selection is to use hydrogen peroxide, but hydrogen peroxide has lower cost-efficient, and owing to the release of oxygen in bleaching process causes that excessive foaming makes process be difficult to control.
On October 2nd, 1974, disclosed GB 1369269 described a kind of preparing washing agent particulate dry neutralization method.It has mentioned all difficulties that run into, and comprises fading in the part of organic detergent.But concrete solution is not proposed this problem.
February 14 nineteen ninety, disclosed GB 2221695 also described a kind of dry neutralization method.It is mentioned and various auxilliary adding assistants can be added with neutralizing agent, still, except this method concerning many auxilliary adding assistants is a kind of common working method, adds whitening agent or dyestuff in the method and does not bring benefit.
On May 8th, 1986, disclosed GB 2166452 described a kind of working method, and it comprises with inorganic component particles dispersed organic substance formation solid globules, this solid ball can be made particle then.And the detergent component of the wide range of choice that can add according to neutralizing effect is provided, has comprised adding blue agent, fluorescence dye and pigment.Yet, do not point out any particular advantage that from these components of selecting, obtains yet.
On August 16th, 1989, disclosed EPA 327963 disclosed a kind of method, and this method is a pre-neutralization surfactant acid in slip, and this slip of spraying drying forms powder, and these powder of compacting.The available ordinary method that whitening agent is joined in the final product composition having joins whitening agent in the slip, but the benefit that this method has the color of dense granule is not mentioned in this patent application.
European application 92870026.9,92200994.9 and 92200993.1 to be examined jointly, according to the regulation of clause 54 (3) EPC, these patent applications have formed the part of prior art.These patent applications have disclosed detergent composition and by the method for high-activity detergent Paste Preparation said composition, with white dyes is joined in the finished product detergent composition, use dyestuff or white dyes to avoid COLOR FASTNESS PROBLEM but mention in the high-activity detergent lotion, also do not mention dyestuff or whitening agent are joined in the high-shear mixer.Can prepare than former particle based on these novel methods of high-activity detergent lotion and to have the more active particle of high surfactant, but these methods will cause the COLOR FASTNESS PROBLEM that caused by the raw material that forms with hot surface promoting agent lotion.
The composition that the purpose of this invention is to provide the high reactivity lotion of the washing composition salt that contains particular components, these particular components make the finished product detergent particles demonstrate complete acceptable white.
Another object of the present invention provides a kind of method for preparing the concentrated cleaning powder, and this detergent powder has the acceptable color of high reactivity, high volume density and human consumer.
The high-activity detergent paste composition contains the composition of the salt of at least 40% (weight) anion surfactant, and said composition was 70 ℃ temperature and 25 seconds
-1Shearing rate under have the viscosity of at least 10 handkerchiefs (Pa.S) when measuring, said composition also contains dyestuff or white dyes or their mixture.
Have been found that some dyestuff and white dyes joined to make fresh detergent particles obtain extraordinary color in the particle that makes with agglomeration method, and keep color characteristic, even improved storage case.
Preferably dyestuff or white dyes before agglomeration process or during join in the composition with liquid form.A preferred embodiment of the present invention is to use the aqueous solution or organic carrier medium.Organic carrier is nonionogenic tenside or polyoxyethylene glycol in a most preferred embodiment.The preparation high active detergent granules
Particle of the present invention is to mix with the washing composition powder by the high reactivity paste that will contain anion surfactant to make in high-shear mixer/tablets press (agglomeration machine).The effect of mixing tank/tablets press at first is a fluidized powder, then the paste tensio-active agent is distributed to rapidly in these fluidized powders.The mixture that obtains is gone up substantially and is always remained dispersed particles, does not allow to form dough/pasta, and this dough/pasta can cause that high-shear mixer/tablets press blocks.Be installed under cutting on the axle and the mixing tool effect in mixing tank/tablets press inside and carrying out finely divided mixing and pelletization.The paste composition and the method that are fit to will be described in more detail below.The particle that obtains has high surfactivity and high volume density, but still has good flowability and non-caked characteristic.Preferred surfactants content is greater than 40% of particle weight, and volume density is at least 600g/l.
When coating or white dyes are liquid form; they can by with the batch mixed jar enter extrusion machine continuously or enter in and recirculation reactor and with the pre-mixing of high-activity detergent lotion; perhaps can or directly pump in high-shear mixer/tablets press dyestuff or white dyes spraying, dyestuff or white dyes are scattered in the particle that forms therein in mixing tank/tablets press.In a special preferred process, during dyestuff or white dyes are directly pumped into and in the recirculation reactor, the sour form of tensio-active agent is neutralized in this recirculation reactor.
Suitable dyestuff and white dyes
For purposes of the invention, suitable dyestuff and white dyes are those dyestuff and white dyess luminous in spectrographic purple or blue color range.For the present invention, preferably, the wide part (at least 70%) that these dyestuffs send is in the visible-range that is lower than the 500nm wavelength.The example of useful dyestuff comprises Levanyl Violet BNZ (trade(brand)name) and Special Fast Blue G Fw Ground (trade(brand)name), provides by Bayer AG..
Preferred white dyes is selected from the sodium salt of following compounds:
4,4 '-two-(2-diethanolamino-4-phenylamino-S-triazine-6-base is amino) Stilbene-2:2 ' stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonates 4,4 '-two-(2-morpholino-4-phenylamino-S-triazine-6-base is amino) Stilbene-2:2 ' stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonates 4,4 '-two-(2,4-diphenylamino-S-triazine-6-base is amino) Stilbene-2:2 ' stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate 4 ', 4 " two-(2; 4-diphenylamino-S-triazine-6-base is amino) Stilbene-2-sulfonate 4; 4 '-two-(2-phenylamino-4-(N-methyl N-2-hydroxyethyl amino)-S-triazine-6-base is amino) Stilbene-2; 2 ' stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate 4; 4 '-two-(4-phenyl-2; 1,3-triazole-2-yl) Stilbene-2,2 ' stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate 4,4 '-two-(2-phenylamino-4-(1-methyl-2-hydroxyethyl amino)-S-triazine-6-base is amino) Stilbene-2,2 ' stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate 4,4-two-(2-sulfo group styryl) phenylbenzene 4,4-two (4-chloro-3-sulfo group styryl) phenylbenzene
Be preferred for other white dyess of the present invention equally and comprise 2-benzoxazolyls and 1, the derivative of 3-phenylbenzene-2-pyrazoline.
The dyestuff content that is used for the washing composition lotion is less than 20ppm, preferred 0.1 to 20ppm (these content are meant the PPM of pure dye, though these dyestuffs are to provide with solution usually).
The content of the white dyes in the surfactant paste is usually less than 5%, preferably less than 2%.The content of the white dyes in granular detergent component or the composition is generally less than 2%, preferably less than 1%.
Paste
The moisture paste of one or more of the salt of anion surfactant is preferred among the present invention, preferably uses the sodium salt of anion surfactant.In a preferred embodiment, anion surfactant preferably concentrates (that is, contain can make it with the minimum possible moisture of liquid mode mobile) as much as possible, but so that it is keeping pumping under the stable temperature.Though it is known carrying out process for granulating with various pure or blended tensio-active agents, but for the present invention that will be actually used in the industry, for the particle that obtains to join in the granulated detergent with suitable physical character, anion surfactant must be with greater than 40%, preferred 40-95%, most preferably the concentration of 60-95% is as the part of paste.
Preferably, the moisture in the moisture paste of tensio-active agent is low as much as possible, will keep the flowability of paste simultaneously, because low amount of moisture will cause in the finished particle surfactant concentrations higher.Preferred paste contains the water of 5-40%, the more preferably water of 5-30%, the most preferably water of 5-20%.A kind of operating method that haves a great attraction that reduced moisture wherein but very high viscosity problem can not occur before paste enters the agglomeration machine is that normal pressure or the anxious poly-moisture eliminator of decompression are installed on production line, and the outlet of this moisture eliminator links to each other with the agglomeration machine.
Preferably use high active surfactant paste, so that the Total Water minimum in the system in mixing, granulation and the drying process.Lower water-content can bring: the ratio of (1) higher surface activity agent and washing assistant, for example 1: 1; (2) other liquid of high level in the prescription can not produce the adhesion of dough body or particle; (3) less cooling, this is because higher admissible prilling temperature; (4) less particle drying is to satisfy final moisture restriction.
Two important parameters that can influence the surfactant paste of mixing and granulation step are temperature and viscosity.Wherein, viscosity especially becomes with concentration and temperature, and range of viscosities is 10 handkerchief to 10000 handkerchiefs in this application, and preferably, the viscosity that enters the surfactant paste in the system is about 20 to about 100 handkerchiefs, and more preferably about 30 to about 70 handkerchiefs.The viscosity of surfactant paste of the present invention was 70 ℃ of temperature and 25 seconds
-1Shearing rate under measure.
Tensio-active agent cream can join in the mixing tank under the initial temperature between its softening temperature (usually in 40-60 ℃ of scope) and its degraded point (chemical property that depends on cream, for example alkyl-sulphate is tending towards degraded being higher than under 75-85 ℃).High temperature has reduced viscosity, is convenient to the pumping of paste, but has produced more SA agglomerate.Yet, use the step (for example flash drying) that on production line, reduces moisture to need to use higher temperature (being higher than 100 ℃).In the present invention, owing to limited moisture, agglomerate keeps high reactivity.
Available many modes join paste in the mixing tank, and from simply being poured into before entering mixing tank, the aperture by pipe end pumps into the paste high pressure wherein.Though all these methods can both prepare the agglomerate with good physical properties, but have been found that, in a preferred embodiment of the invention, can cause it in mixing tank, better to distribute the paste ejection, improve productive rate like this with required size particles.Before entering mixing tank, use the high-pressure pump pressurization to improve the activity of final agglomerate.In conjunction with these two effects, the hole (ejection) by being small enough to obtain required flow rate but in system, keep pumping pressure to the bar of maximum feasible value to appoint adding paste down, just can reach very favorable result.High active surfactant paste
The active part of aqueous surfactant lotion is at least 40% also can be up to 95%; Preferred active part is 60-95% and 65-80%.The equipoise of this cream mainly is a water, but also can comprise various processing materials.Under higher active concentration, need or do not need washing assistant hardly for the cold granulation of cream.The spissated surfactant granules that obtains can be added in dried washing assistant or the powder, or is used for conventional agglomeration operation.Aqueous surfactant cream contains the organic surface active agent that is selected from negatively charged ion, zwitter-ion, both sexes and cats product and their mixture.Anion surfactant preferably.Nonionogenic tenside is used as accessory tensio-active agent or processing material, or as the organic carrier of white dyes, nonionogenic tenside does not comprise in this article as " activity " tensio-active agent.The effective tensio-active agent of the present invention list in the United States Patent (USP) 3664961 of the Norris that issued May 23 in 1972 and the people's such as Laughlin that issued on December 30th, 1975 United States Patent (USP) 3919678 in.Effectively cats product also be included in the United States Patent (USP) 4222905 of the Cockrell that issued on September 16th, 1980 and the United States Patent (USP) 4239659 of the Murphy that issued on December 16th, 1980 described in those tensio-active agents.Yet cats product is less usually compatible with alumino-silicate materials herein, and therefore, it preferably uses with low amount (if desired) in the present composition.Be the representative example that is used for the tensio-active agent of the present composition below.
The water-soluble salt of higher fatty acid, i.e. " soap " is effective anion surfactant in this paper composition.It comprises alkali metal soap, for example contains to have an appointment 8 to about 24 carbon atoms, preferred about 12 sodium, potassium, ammonium and alkylammonium salts to the higher fatty acid of about 18 carbon atoms.These soaps can by direct saponified fat and oil or by in and free fatty acids make.Especially effectively soap is the sodium and the sylvite of the mixture of the lipid acid that obtained by Oleum Cocois and tallow, i.e. tallow and coconut sodium or potash soap.
Effectively anion surfactant also comprises water-soluble salt, preferably has to contain about 10 basic metal, ammonium and alkylammonium salts to the organosulfur reaction product of the alkyl of about 20 carbon atoms and sulfonic acid or sulfate group (be included in being the moieties of acyl group in the term " alkyl ") in its molecular structure.The example of this class synthetic surfactant is sodium alkyl sulfate and alkylsurfuric acid potassium, especially by sulfation higher alcohols (C8-C
18) those alcohol of for example obtaining through the glyceryl ester of reduction tallow or Oleum Cocois and those compounds of making; And sodium alkyl benzene sulfonate and alkyl benzene sulphonate (ABS) potassium, wherein alkyl contains and has an appointment 9 to about 15 carbon atoms, and with the straight or branched configuration, for example the compound of those types of being narrated in the United States Patent (USP) 2220099 and 2477383.Useful especially is linear alkylbenzene sulfonate, and wherein carbon atom mean number is about 11 to 13 in the alkyl, is abbreviated as C11-C13LAS.
Other anion surfactant of this paper is an alkyl glycerol base ether sulfonic acid sodium, especially those ethers of the higher alcohols that is obtained by tallow and Oleum Cocois; Coco-nut oil fatty acid coconut monoglyceride and coco-nut oil fatty acid direactive glyceride sodium sulfate; Per molecule contains 1 sodium or the sylvite to the alkyl phenol epoxy ethane ether salt of about 10 unit oxyethane of having an appointment, and wherein alkyl contains and has an appointment 8 to about 12 carbon atoms; And per molecule contains 1 sodium or the sylvite to the alkyl epoxy ethane ether sulfate of about 10 unit oxyethane of having an appointment, and wherein alkyl contains and has an appointment 10 to about 20 carbon atoms.
Other effective anion surfactants comprise the water-soluble salt that contains the ester of the α-alpha-sulfonated fatty acid that contains 1 to 10 carbon atom in have an appointment 6 to 20 carbon atoms and the ester group in fatty acid-based herein; Contain the water-soluble salt that contains 9 the 2-acyloxy-alkane-1-sulfonic acid of having an appointment in have an appointment 2 to 9 carbon atoms and the paraffin section in the acyl group to about 23 carbon atoms; Contain in the alkyl and have an appointment 10 to 20 carbon atoms and contain the sulfated alkyl ether of 1 to 30 moles of ethylene oxide of having an appointment; The water-soluble salt that contains the alkene sulfonate of 12 to 24 carbon atoms of having an appointment; Contain in the alkyl in have an appointment 1 to 3 carbon atom and the paraffin section and contain 8 the β-alkoxy alkane sulfonate of having an appointment to about 20 carbon atoms.Though these sour salt generally all come into question and used, deacidification can be used as the part of finely divided mixing step to carry out.
Have been found that the present invention is effective especially when anion surfactant cream contains decolourization effective tensio-active agent especially, for example contain those cream of at least 5% (weight) linear alkylbenzene sulfonate, methyl ester sulfonate or paraffin sulfonate or their mixture.
Preferred anionic surfactants tensio-active agent cream is to contain the straight or branched alkylbenzene sulfonate of 10-16 carbon atom alkyl and the mixture of the alkyl-sulphate of the alkyl that contains 10-18 carbon atom.These tensio-active agent cream normally prepare like this: fluid organic material matter and sulphur trioxide reaction are made sulfonic acid or sulfuric acid, and neutralizing acid makes this sour salt then.This salt is exactly the tensio-active agent cream that this document is discussed in the whole text.Sodium salt is preferred, and to have a final performance cost good and NaOH low because compare it with other neutralizing agents, but be not to use other reagent, for example can use KOH.
Water soluble nonionic surfactant also can be used as the minor surface promoting agent in the present composition.Really, preferable methods is used the adulterant of anionic/nonionic tensio-active agent.Particularly preferred tensio-active agent cream contains and has about 0.01: 1 to about 1: 1, more preferably from about the adulterant of 0.05: 1 nonionic and anion surfactant.The consumption of nonionogenic tenside can be up to equating with the amount of main organic surface active agent.These nonionic comprise by oxyalkylene group (is hydrophilic in nature) and organic hydrophobic compound (its can be in nature aliphatic series or alkyl aromatic) condensation and the compound that makes.And the length of the polyoxyalkylene of any specific hydrophobic base condensation can easily be regulated the water-soluble cpds that has the required degree of equilibrated between hydrophilic and hydrophobic part with generation.
Suitable ionic surfactant pack is drawn together the polyethylene oxide condensation compound of alkylphenol, for example, contain with containing of straight or branched configuration about 6 to 16 carbon atoms the alkylphenol of alkyl and the condensation product of oxyethane (every mole alkylphenol and alkyl glucose amide and about 4 to 25 moles of ethylene oxide).
Preferred nonionic is the water-soluble condensed product with the fatty alcohol that contains 8 to 22 carbon atoms of straight or branched configuration and oxyethane (every mol of alcohol and 4 to 100 moles of ethylene oxide).Particularly preferably be the alcohol of the alkyl that contains 9-15 the carbon atom of having an appointment and the condensation product of oxyethane (every mol of alcohol and about 4-80 moles of ethylene oxide); And the condensation product of propylene glycol and oxyethane.
The semi-polarity nonionic shows that promoting agent comprises that the moieties that contains about 10-18 carbon atom and 2 are selected from alkyl and contain 1 water-soluble amine oxides to the hydroxyalkyl part of about 3 carbon atoms; Moieties and 2 water soluble oxidized phosphines that are selected from the alkyl and the part of the hydroxyalkyl that contains 1-3 the carbon atom of having an appointment of containing about 10-18 carbon atom; And moieties and a sulfoxide that is selected from the alkyl and the part of the hydroxyalkyl that contains about 1-3 carbon atom of containing about 10-18 carbon atom.
Amphoterics comprises aliphatic series or heterocycle is secondary and the derivative of the aliphatic derivatives of tertiary amine, wherein the aliphatic series part can be a straight or branched, a substituting group in the wherein aliphatic substituting group contains 8-18 the carbon atom of having an appointment, and at least one aliphatic substituting group contains the anionic water-soluble group.
Zwitterionics comprises the derivative of aliphatic series season ammonium Phosphonium and sulfonium compound, and a substituting group in the wherein aliphatic substituting group contains 8-18 the carbon atom of having an appointment.
The particularly preferred tensio-active agent of this paper comprises the linear alkylbenzene sulfonate that contains 11 to 14 carbon atoms of having an appointment in alkyl; Tallow alkyl sulfate; The coconut alkyl glycerol ether sulfonate; Sulfated alkyl ether, wherein moieties contains 14-18 the carbon atom of having an appointment, average degree of ethoxylation is about 1-4; The alkene or the paraffin sulfonate that contain 14-16 the carbon atom of having an appointment; Alkyl dimethyl amine oxide, wherein alkyl contains 11-16 the carbon atom of having an appointment; Alkyl dimethyl ammonium propane sulfonate and alkyl dimethyl ammonium hydroxypropanesulfonic acid salt, wherein alkyl contains 14-18 the carbon atom of having an appointment; The soap that contains the higher fatty acid of 12-18 the carbon atom of having an appointment; C
9-C
15The condensation product of alcohol and about 3-8 moles of ethylene oxide, and their mixture.
Effectively cats product comprises water-soluble quaternary ammonium compound, and its general formula is R
4R
5R
6R
7N
+X
-, R wherein
4Be to contain 10-20, the alkyl of preferred 12-18 carbon atom, R
5, R
6And R
7C respectively does for oneself
1-C
7Alkyl, preferable methyl; X
-Be negatively charged ion, chlorine for example.The example of this trimethyl ammonium compound comprises C
12-14Alkyl trimethyl ammonium chloride and Ke Ka alkyl trimethyl ammonium methyl sulfate.Also can use other cats products, comprise the coline ester.
Being used for particularly preferred tensio-active agent of the present invention comprises: straight chain C
11-C
13Sodium alkyl benzene sulfonate; Sulfonated; Triethanol ammonium C
11-C
13Alkylbenzene sulfonate; Alkyl-sulphate, (tallow, Oleum Cocois, plam oil, synthesis material, for example C
45Deng); Sodium alkyl sulfate; Methyl ester sulfonate; Oleum Cocois alkyl glycerol base ether sulfonic acid sodium; The sodium salt of the sulfation condensation product of tallow alcohol and about 4 moles of ethylene oxide; The condensation product of coco-nut oil fatty acid and 6 moles of ethylene oxide; The condensation product of tallow fatty alcohol and about 11 moles of ethylene oxide; Contain the Fatty Alcohol(C12-C14 and C12-C18) of about 15 carbon atoms of the 14-that has an appointment and the condensation product of about 7 moles of ethylene oxide; C
12-C
13The condensation product of Fatty Alcohol(C12-C14 and C12-C18) and about 3 moles of ethylene oxide; 3-(N, N-dimethyl-N-Oleum Cocois alkylammonium)-2-hydroxy propane-1-sulfonate; 3-(N, N-dimethyl-N-Oleum Cocois alkylammonium)-propane-1-sulfonate; 6-(N-dodecylbenzyl-N, N-Dimethyl Ammonium) caproate; Oxidation dodecyl dimethyl amine; Oxidation Oleum Cocois alkyl dimethyl amine; And the water-soluble sodium and the sylvite of Oleum Cocois and tallow fatty acid.
(except as otherwise noted, term used herein " tensio-active agent " is meant non----nonionogenic tenside.Tensio-active agent (not comprising nonionogenic tenside) is 0.005: 1 to 19: 1 with the ratio of dry cleaning washing assistant or powder, preferred 0.05: 1 to 10: 1, and more preferably 0.1: 1 to 5: 1.Preferred tensio-active agent is 0.15: 1 to 1: 1 and 0.2: 1 to 0.5: 1 with the ratio of washing assistant).Flow of powder
Though the preferred embodiment of the inventive method comprises anion surfactant is added by aforesaid paste form, also can be by flow of powder as blowing out the anion surfactant that powder type adds a tittle.In these embodiments, the tackiness of flow of powder and water content must be remained on low-levelly, increase and the agglomerate that prevents to make contains the tensio-active agent of excessive concentrations with " load " that prevents anion surfactant.The liquid stream of preferred agglomeration method also can be used for adding other tensio-active agents and/or polymkeric substance.This can be by being premixed into tensio-active agent in a kind of liquid stream or also can being undertaken by various logistics are joined in the reunion machine.These two kinds of process implementing schemes can make the different finished particle of performance (distributivity, gelling, dissolution rate, etc.), if particularly allowed the blended tensio-active agent form before particle forms.For each preferred method, these differences all can utilize the application to help expecting.
Observe, the described technology of the application of the invention, can some chemical (as non-ionic, citric acid) be joined in the last prescription, and some key property (caking, compression etc.) of matrix is had no adverse effect than any other known processes higher level ground.Finely divided mixing and granulation
Except as otherwise noted; Term used herein " finely divided mixing and/or granulation " is meant in finely divided mixing tank/tablets press mixing and/or the granulation at the blade tip speed mixture that is about 5 meter per seconds to about 50 meter per seconds.Total residence time of mixing and granulation process is preferably about 0.1-10 minute, more preferably 0.1-5 minute, most preferably is 0.2-4 minute.The blade tip speed of preferred mixing and granulation is about 10-45 meter per second and about 15-40 meter per second.
Be applicable to any unit of finished surface promoting agent or the enforcement that apparatus all can be used for the inventive method.The equipment that is fit to comprises, for example, and falling film type sulfonation reactor, digestor, esterifier etc.For mixing/nodulizing, can use many any mixing tanks/agglomeration machine.In a preferred embodiment, method of the present invention is carried out continuously.Particularly preferably be Fukae Powtech Kogyo Co., the Fukae that Japan makes
RFS-G series mixing tank; This equipment is actually spherical vessel, and the branch mouth by the top can enter this container, near its bottom an agitator with basic Z-axis being housed, blade is housed on sidewall.Agitator and blade can operations independently of each other under variable velocity separately.This container can be equipped with cooling jacket, or is necessary, cryogenic unit is housed.
We find to be applicable to that other similar mixing tank/tablets presss of the inventive method comprise Dierks ﹠amp; S hne, the Diosna that Germany makes
RV series; With T K Fielder Ltd., the Pharma Matrix that England makes
RWe think that other mixing tank/tablets presss that are applicable to the inventive method are Fuji Sangyo Co., the Fuji that Japan makes
RVG-C series; With Zanchetta ﹠amp; Co srl, the RotoR that Italy makes
Other equipment that preferably are fit to comprise Gustau Eirich Hardheim, the Eirich that Germeny makes
R, serial RV; By L dige Machinenbau Gmbh, the L dige that is used for batch mixing that PaderbornGermany makes
R, serial FM is used for continuous mixing/agglomerant serial Baud KM; By Drais Werke Gmbh, the Drais that Mannheim Germany makes
RT160 series and Winkworth Machinery Ltd., Berkshire, the Winkworth that Englandr makes
RRT 25 series.
Littleford Mixer with inner cut-off blade, model #FM-130-D-12 and have the Cuisinart Food Processor of 7.75 inches (19.7cm) blades, model #DCX-Plus are two examples of mixing tank/tablets press of being fit to.Having finely divided mixing and granulation performance and a residence time all can use for any other mixing tank/tablets press of about 0.1-10 minute." Scroll-type " impeller mixing tank that preferably on turning axle, has several blades.The present invention can be intermittently or successive processes carry out.Service temperature
Preferred service temperature should be low as much as possible, because this can produce the higher surface activity agent concentration in finished particle.Preferred temperature is lower than 80 ℃ in agglomeration process, more preferably is 0 ℃-70 ℃, is more preferably 10 ℃-60 ℃, and most preferred is 20 ℃-50 ℃.The lower service temperature of Shi Yonging can be passed through various known method such as nitrogen cooling, the watercooling jacket that installs in the prior art, add solid CO in the methods of the invention
2Reach similar method and obtain, preferable methods is to add solid CO
2, most preferred method is the nitrogen cooling.
By in the liquid flow that contains anion surfactant and/or other tensio-active agents, adding other compositions that cause paste viscosity and/or fusing point rising and/or tackiness to reduce, finish the more attractive scheme that in the preferred embodiment of the invention, further increases surfactant concentration in the final particle.In a preferred embodiment of the inventive method, these compositions can resemble to be pumped the shape thing on production line and enter in the agglomeration machine.The example of these compositions can be various powder, and it will further be described hereinafter.Final agglomerate composition
The present invention's preparation is used for the high density granular of detergent composition.The preferred final agglomerate composition that is used for joining granulated detergent has the high surface agent concentration.By increasing surfactant concentrations, particle/agglomerate that the present invention makes more is applicable to various prescription.These less final processing technologies of high surfactant needs that contain particle agglomerates just can be made into final agglomerate, therefore saved other procedure of processings (spraying drying, the dedusting that is used for all washing composition production processes in a large number, Deng) in processing aid (inorganic powder, etc.).
The particle that makes according to the present invention is big, low dirt and free-pouring, preferably has volume density up to about 1.0g/cc, more preferably from about the about 0.8g/cc of 0.6-.Particulate weight average particle diameter of the present invention is about 1000 microns of about 200-, and the particle diameter that the preferred particulates that so makes has is at 200 to 2000 micrometer ranges.Preferred prilling temperature is about 10 ℃-60 ℃, and most preferred is about 20 ℃ to about 50 ℃.Dry
The required moisture of free flowing powder of the present invention can be suitable for expecting the level of using as dry being adjusted in the fluidized bed dryer by at conventional powder for drying device.If adopt warm air fluidisation bed dryer, must be careful in order to avoid temperature-sensitive component degradation in the particle.It also is favourable before extensive the storage cooling step being arranged.This step also can be carried out in the conventional fluidized-bed with the cooling air operation.Drying/the cooling of agglomerate also can be carried out in any other is suitable for the equipment (as rotatory drier etc.) of powder for drying.
For the use of washing composition, but the final moisture of agglomerate need keep below the level of stored in bulk and this agglomerate of transportation.Definite moisture content depends on the component of polymers and decides, but generally be enter the 1-8% free-water (be water not with agglomerate in any crystal combination), 1-4% preferably.Detergent builder compound and powder
The mixture of any compatible detergent builder compound or washing assistant or powder all can be used in the method and composition of the present invention.
The detergent composition of this paper can contain the crystal aluminosilicate ion exchange material of following formula:
Naz[(AlO
2) z (SiO
2) y] XH
2O wherein Z and Y is at least about 6, and the mol ratio of Z and Y is about 1.0-0.4, and Z is about 10-264.Be used for amorphous hydrated silico-aluminate thing of the present invention and have following empirical formula:
Mz (zAlO
2YSiO
2) wherein M be the ammonium of sodium, potassium, ammonium or replacement, z is about 0.5 to 2, y is 1, the magnesium ion exchange capacity that this material has is that the anhydrous silico-aluminate of every gram is at least about 50 milligramequivalent CaCO
3Hardness.Preferably have the hydration natrolite A of particle diameter for about 1-10 micron.
The silico-aluminate ion-exchange builder material of this paper is a hydrated form, if the crystalline words, it contains the water (weight) of the 10%-that has an appointment about 28%, the water yield possibility even higher if right and wrong are unbodied.Most preferred crystal aluminosilicate ion exchange material contains the water of the 18%-that has an appointment about 22% in its crystal substrate.The other feature of this crystal aluminosilicate ion exchange material is that particle diameter is about 0.1 micron to about 10 microns, and amorphous substance is often littler, and is for example little extremely less than about 0.01 micron, and the particle diameter that preferred ion exchange material has is about 0.2 micron to about 4 microns.Conventional method of analysis is used in the term of this paper " particle diameter " expression, for example utilizes the micro-measuring method of scanning electronic microscope to measure the median size of given ion exchange material weight.Usually, its calcium ion exchange capacity that is characterised in that in addition of the crystal aluminosilicate ion exchange material of this paper is at least about 200mg equivalent CaCO
3The water hardness/g silico-aluminate (calculating with moisture-free basis) is usually at about 300mg eq./g about 352mg eq./g extremely.Another of the silico-aluminate ion exchange material of this paper is characterised in that its calcium ion exchange rate is at least about 2 grain Ca
2+/ gpm/gram/gallon silico-aluminate (moisture-free basis), usually at about 2 grains/gpm/gram/gallon to about 6 grains/gpm/gram/gallon (based on calcium ion hardness) scope.The calcium ion exchange rate that demonstrates for the silico-aluminate of the best of washing assistant purposes is at least about 4 grains/gpm/gram/gallon.
The Mg that the amorphous aluminosilicate ion exchange material has usually
++Exchange capacity is at least about 50mg eq.CaCO
3/ g (12mg Mg
++/ g) and Mg
++Exchange velocity is at least about 1 grain/gpm/gram/gallon.Amorphous substance does not demonstrate observable diffraction spectrogram when detecting with Cu radiation method (1.54 atomic meter).
It is commercially available being actually used in silico-aluminate ion exchange material of the present invention.Being used for silico-aluminate of the present invention can be crystallization or amorphous structure, and can be the silico-aluminate or synthetic the obtaining of natural formation.The method for preparing the silico-aluminate ion exchange material is described in the people's such as Krummel that issued on October 12nd, 1976 the United States Patent (USP) 3985669 (being incorporated herein by reference).It can be obtaining of zeolite A, zeolite B and X zeolite by model that preferred synthetic crystallization silico-aluminate ion used herein is handed over material.In an especially preferred embodiment, the crystal aluminosilicate ion exchange material has following chemical formula:
Na
12[(AlO
2)
12(SiO
2)
12] XH
2O wherein X is about 20 to about 30, is preferably approximately 27, and its particle diameter that has is usually less than about 5 microns.
Granulated detergent of the present invention can contain neutrality or basic salt, and the pH value that this salt has in solution is 7 or higher, and can be organic or inorganic in nature.Builder salt helps to provide required density and loose density to granulated detergent of the present invention.Though some salt is inert, wherein many salt also play the effect of detergent builder compound material in washing soln.
The example of neutral water-soluble salt comprises muriate, fluorochemical and the vitriol of the ammonium of basic metal, ammonium or replacement, preferred as alkali in the above-mentioned salt, especially sodium salt.Sodium sulfate generally is used for detergent particles, and is particularly preferred salt.Usually, citric acid and any other organic acid or mineral acid can join in the granulated detergent of the present invention, as long as it can with other component chemical compatibilities in the agglomeration composition.
Other effective water-soluble salts comprise usually known compound as the detergent builder compound material.Washing assistant is selected from phosphoric acid salt, polyphosphate, phosphonate, polyphosphonic acid salt, carbonate, silicate, borate and the polyhydroxy sulfonate of the ammonium of various water miscible basic metal, ammonium or replacement usually.Preferably above-mentioned basic metal, especially sodium salt.
The object lesson of inorganic phosphate builders be sodium and potassium tri-polyphosphate, pyrophosphate salt, have the polymerization degree and be polymeric metaphosphate and the orthophosphoric acid salt of about 6-21.The example of polyphosphonic acid salt washing assistant is the sodium of ethylidene diphosphonic acid and sylvite, ethane 1-hydroxyl-1, the sodium of 1-di 2 ethylhexyl phosphonic acid and sylvite and ethane 1,1, the sodium of 2-tri methylene phosphonic acid and sylvite.Other phosphorous washing-aid compounds are disclosed in United States Patent (USP) 3159581; 3213030; 3422021; 3422137; 3400176 and 3400148, quote these patents as a reference at this.
The example of non-phosphorus inorganic builders has carbonate, the supercarbonate of sodium and potassium, sesquicarbonate, tetraborate+hydrate, has SiO
2Be the preferred silicate of about 1.0-2.4 of about 0.5-4.0 with the mol ratio of alkalimetal oxide.The composition of the inventive method preparation does not need excessive carbonate to handle, United States Patent (USP) 4196093 as the people such as Clarke that issued on April 1st, 1980 is disclosed, said composition does not preferably contain and surpasses 2% finely divided lime carbonate and preferably do not contain lime carbonate.
As mentioned above, usually with the powder in the washing composition such as zeolite, carbonate, silicon-dioxide, silicate, Citrate trianion, phosphoric acid salt, perborate etc. with handle auxiliary agent such as starch and can be used in the preferred embodiments of the invention.Polymkeric substance
Also can use various organic polymers, wherein some also can be as washing assistant to improve washing effect.Be included in can be referred in these polymkeric substance---low alkyl group sodium cellulosate, low alkyl group sodium cellulosate and hydroxyl---the low alkyl group sodium cellulosate that is carboxyl, for example, Xylo-Mucine, sodium carboxymethylcellulose pyce and HPMC, polyvinyl alcohol (also often comprising some acetate polyvinyl esters), polyacrylamide, polyacrylic ester and various multipolymer, for example toxilic acid and acrylic acid multipolymer.The molecular weight of these polymkeric substance alters a great deal, but majority is between 2000-100000.
Aggretion type polycarboxylate washing assistant be disclosed in Diehl in the United States Patent (USP) of issuing on March 7th, 1,967 3308067.These materials comprise aliphatic carboxylic acid such as the homopolymer of toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citric acid and methylene radical propanedioic acid or the water-soluble salt of multipolymer.Optional components
Normally used other components also can be included in the composition of the present invention in detergent composition.These materials comprise: flow promotor, lentigo grain, SYNTHETIC OPTICAL WHITNER and bleach activator, suds booster or suds suppressor, the anti-dark agent of enzyme and sanitas, soil-suspending agent, stain remover, filler, sterilant, PH conditioning agent.Non-auxiliary agent alkali source, hydrotropic agent, enzyme, enzyme stabilizers, sequestrant and spices.
Special suds suppressor can directly join in the agglomerate of the present invention with the method that flow of powder joins in the agglomerating device, or joins in the final product composition having by dried addition method.It is active in lipid acid or siloxanes that these particles preferably press down bubble.
Embodiment
Term used herein " LAS " and " AS " are meant " sodium lauryl benzene sulfonate " and " alkyl-sulphate " respectively, and " MES " is meant the methyl ester sodium sulfonate.Except as otherwise noted, resemble " C
45" such term is meant C
14And C
15Alkyl.TAS is meant tallow alkyl sodium sulfate.Dobanol 45E7 is the C that contains 7 unit oxyethane
14/ C
15The ethoxylate of alcohol, it is prepared by Shell Co..AE3S is meant that each molecule on average has the sodium alkylether sulphate of 3 oxyethyl groups.
High reactivity base particle (agglomerate) is to use a pot foods handler (Braun[TM] Multipractic Plus Electronic de luxe) to be made by high active surfactant cream and powdered mixture.Powdered mixture is made up of following material:
Water glass (3Na) 11.5%
Yellow soda ash 50.5%
Carboxy methyl cellulose 1.6%
Zeolite A 36.4% high active surfactant cream contains 18% water, and total surfactant activity thing (when existing, comprising white dyes) is 78%.Anion surfactant is 74: 24: 2 ratio existence with LAS: TAS: AE3S.
In each experiment, this powdered mixture of 300g is put into the bowl of mixing tank, and the high reactivity paste of 110.5g is slowly added under 50 ℃, simultaneously with the operation under the most at a high speed of the mixing tank of food processor.After 30 seconds, the cutter prompt drop is extremely minimum, and add entry at leisure up to nodulizing takes place, the mean diameter that the particle that obtains has is between 400 microns and 600 microns.In fluidized-bed, be that 60 ℃ air was with dry about 15 minutes of wet agglomerate then with temperature in.The equivalent relative humidity (eRH) that obtains agglomerate is 10-15%.
In the following example 1 to 5, before food processor carries out nodulizing, with nonionogenic tenside of difference amount (obtain Dobanol 45E7[TM]) and white dyes (4 by Shell, 4 '-two { [2-morpholinoes-4-anilino-1,3,5-triazine-6-yl] amino } Stilbene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate)
*Be processed into paste.The particulate color that mensuration obtains.
*The color index white dyes No.71 that the Society of Dyers and Colorists and the AmericanAssociation of Textile Chemists and Colorists announce.
In the % high reactivity paste in the % high reactivity paste in the % high reactivity paste
Brightening agent embodiment 1 76.8 0 1.2 embodiment 2 73.2 3.7 1.1 embodiment 3 70.0 7.0 1.0 comparative examples 4 78.0 00 comparative examples 5 70.9 7.1 0 of non-ionic surface active agent of anion surfactant
In embodiment 1, in Drais (TM) kneader (planetary-type mixer and the kneader model FH1.55 that make by Draiswerke GmbH), keeping 50 ℃ and prevent under some vacuum tightness of paste inflation with powdery white dyes and high active surfactant cream thorough mixing 15 minutes.In embodiment 2 and 3, use super mixer under 50 ℃, the powdery white dyes at first to be well-dispersed in the nonionogenic tenside.Use the method identical should disperse thing to sneak in the high reactivity anion surfactant cream then with embodiment 1.In comparative example 4, as previously described in the embodiment, paste is handled in kneader, but do not added nonionogenic tenside or whitening agent.In comparative example 5, in kneader, nonionogenic tenside is mixed with anion surfactant cream, but do not add white dyes.
In each embodiment, agglomerate sieved between Tyler 20 orders and Tyler 35 orders remove thin and thick particle, utilize commercially available Hunterlab color/difference meter model D25-2 of Elscoserv N.V manufacturing to measure the color of remainder by Hunter Lab method (Hunter, R.S.J.Opt.Soc.Amer 48597 (1958)).The color readings of agglomerate is as follows:
Hunter (Hunter) value
L a b embodiment 1 92.2 0.0 5.5 embodiment 2 91.3 0.6 5.0 embodiment 3 90.8 1.2 4.6 comparative example 4 91.8-0.4 6.9 comparative examples 5 91.2-0.4 7.6
Learn the jade-green agglomerate that is tending towards of have low-L value (＜85%) and/or negative value (a＜0) from human consumer's outward appearance test, and/or the flaxen agglomerate that is tending towards with high b value (b＞6) is easy to tell from granular composition, makes the product appearance variation.
In embodiment 6 and 7, agglomerate prepares in Loedig FM mixing tank/reunion machine.Powdered mixture is made up of following material:
Water glass (3Na) 17.5%
Yellow soda ash 32.5%
Carboxy methyl cellulose 2.4%
Zeolite A 47.6%
High active surfactant cream contains 18% water, and total surfactant actives (comprising dye solution, when existing) is 78%.Anion surfactant is 74: 24: 2 ratio existence with LAS: TAS: AE3S.
In these two tests, the 25.8kg powdered mixture is put into mixing tank/reunion machine with 14.3kg high active surfactant cream under 50 ℃, make the ploughshare and the knife mill of mixing tank/reunion machine all operate about 100 seconds, make and have the agglomerate that median size is the 400-600 micron.In fluidized-bed with temperature in be 80 ℃ air with dry about 15 minutes of agglomerate, then, before agglomerate is discharged, it is cooled to 35 ℃ with ambient air.The eRH of this agglomerate is between 10%-15%.
2 parts of concentration that provided by Bayer UK Ltd are provided the dye solution that makes in embodiment 6 is that 25% extraordinary fast blue (Special Fast Blue) G FW color base (Blue VRS 27/1) and 1 part of concentration that is provided by Bayer UK Ltd are 25% LevauylViolet BNZ (pigment purple 23).
With before high active surfactant cream mixes, this dye mixture is diluted to 0.1% the aqueous solution then, is processed into agglomerate with aforesaid method then, the solution of 90ml this 0.1% is mixed with the 15kg paste.
In each embodiment, agglomerate sieves between Tyler 20 orders and Tyler 35 orders to remove thin and thick particle, utilize the commercially available Hunterab color/difference meter model D25-2 that provides by Elscoserv N.V to measure the color of remainder by Hunter Lab method (Hunter, R.S.J.Opt.Soc.Amer 48 597 (1958)).The color readings of agglomerate is as follows:
The Hunter value
The agglomerate (containing dyestuff) of L a b embodiment comparative example's 6 (containing dyestuff) 87.4-0.2 4.3 89.6-0.5 9.4 embodiment 6,7 (not containing dyestuff) has still less yellow color than the agglomerate of the embodiment 7 that does not add dyestuff.
Claims (3)
1. one kind is used as the high-activity detergent paste composition for preparing the intermediate in the granulated detergent process, comprise dyestuff or white dyes, it is characterized in that described paste composition contains the salt of at least 40 weight % anion surfactants, is 25 seconds when being 70 ℃ with shearing rate in temperature
-1The viscosity that this paste composition has when measuring down was 10 handkerchief seconds to 10,000 handkerchief second; And the water of paste composition 5 to 40 weight %; And the amount of wherein said dyestuff be paste composition weight 0.1 to 20ppm, and be selected from the commodity that provide by Bayer AG Levanyl Violet BNZ by name, dyestuff of Special Fast Blue G FWGround and composition thereof, perhaps the amount of wherein said white dyes is the 1-5 weight % of paste composition weight, and be selected from the sodium salt of following compounds: 4,4 '-two-(2-diethanolamino-4-phenylamino-S-triazine-6-base is amino)-Stilbene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, 4,4 '-two-(2-morpholino-4-phenylamino-S-triazine-6-base is amino)-Stilbene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, 4,4 '-two-(2,4-diphenylamino-S-triazine-6-base is amino) Stilbene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, 4,4 '-two-(2,4-diphenylamino-S-triazine-6-base is amino) Stilbene-2-sulfonate, 4,4 '-two-(2-phenylamino-4-(N-methyl-N-2-hydroxyethyl amino)-S-triazine-6-base is amino) Stilbene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, 4,4 '-two-(4-phenyl-2,1,3-triazole-2-yl) Stilbene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, 4,4 '-two-(2-phenylamino-4-(1-methyl-2-hydroxyethyl amino)-S-triazine-6-base is amino)-Stilbene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, 4,4-two (2-sulfo group styryl) phenylbenzene sulfonate, 4,4-two (4-chloro-3-sulfo group styryl) phenylbenzene sulfonate; 2-benzoxazolyls and 1, the derivative of 3-phenylbenzene-2-pyrazoline.
2. according to the composition of claim 1, the amount of described dyestuff be paste composition 0.1 to 5ppm.
3. according to the composition of claim 1, it is characterized in that dyestuff joins in the composition with aqueous solution form.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92202170.4 | 1992-07-15 | ||
| EP92202170A EP0578872B1 (en) | 1992-07-15 | 1992-07-15 | Detergent compositions |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93109880A Division CN1054631C (en) | 1992-07-15 | 1993-07-15 | Detergent compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1243867A CN1243867A (en) | 2000-02-09 |
| CN1094512C true CN1094512C (en) | 2002-11-20 |
Family
ID=8210786
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93109880A Expired - Fee Related CN1054631C (en) | 1992-07-15 | 1993-07-15 | Detergent compositions |
| CN99110039A Expired - Fee Related CN1094512C (en) | 1992-07-15 | 1999-06-25 | Oitnment detergent composition |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93109880A Expired - Fee Related CN1054631C (en) | 1992-07-15 | 1993-07-15 | Detergent compositions |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0578872B1 (en) |
| JP (1) | JP3560340B2 (en) |
| CN (2) | CN1054631C (en) |
| AT (1) | ATE172240T1 (en) |
| AU (1) | AU4642193A (en) |
| CA (1) | CA2140285C (en) |
| DE (1) | DE69227311T2 (en) |
| DK (1) | DK0578872T3 (en) |
| EG (1) | EG20369A (en) |
| ES (1) | ES2121814T3 (en) |
| IE (1) | IE930520A1 (en) |
| MA (1) | MA22931A1 (en) |
| MX (1) | MX9304261A (en) |
| PH (1) | PH31248A (en) |
| TR (1) | TR28449A (en) |
| WO (1) | WO1994002574A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0660873B2 (en) † | 1992-09-01 | 2006-05-31 | The Procter & Gamble Company | High density granular detergent composition |
| GB9323250D0 (en) * | 1993-11-11 | 1994-01-05 | Unilever Plc | Process for the production of a detergent composition |
| US5714456A (en) * | 1996-03-15 | 1998-02-03 | Amway Corporation | Process for making discrete whitening agent particles |
| AU2075097A (en) | 1996-03-15 | 1997-10-01 | Amway Corporation | Discrete whitening agent particles, method of making, and powder detergent containing same |
| US5714452A (en) * | 1996-03-15 | 1998-02-03 | Amway Corporation | Whitening agent particle composition |
| IT1283044B1 (en) * | 1996-05-21 | 1998-04-07 | 3V Sigma Spa | METHOD FOR THE CLEANING OF DETERGENTS |
| GB9618877D0 (en) * | 1996-09-10 | 1996-10-23 | Unilever Plc | Process for preparing high bulk density detergent compositions |
| DE19855677A1 (en) * | 1998-12-02 | 2000-06-08 | Henkel Kgaa | Production of detergent granules containing brighteners |
| GB2364065A (en) * | 2000-06-28 | 2002-01-16 | Procter & Gamble | Fabric treatment composition |
| DE10208773A1 (en) * | 2002-02-28 | 2003-09-04 | Clariant Gmbh | Aqueous liquid formulations of pyrazoline brighteners |
| DE10260833B4 (en) * | 2002-12-23 | 2007-08-16 | Henkel Kgaa | Process for the treatment of detergents or cleaners |
| EP2343359A1 (en) * | 2010-01-07 | 2011-07-13 | Unilever PLC | Detergent formulation containing spray dried granule |
| RU2650892C2 (en) * | 2016-04-07 | 2018-04-18 | Наталия Тимофеевна Тараненко | “ya mama” paste for washing |
| EP3611247B1 (en) * | 2018-08-14 | 2021-03-10 | The Procter & Gamble Company | Fabric treatment compositions comprising benefit agent capsules |
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|---|---|---|---|---|
| US3986987A (en) * | 1974-05-15 | 1976-10-19 | Canada Packers Limited | Light-density, low phosphate, puffed borax-containing detergent compositions |
| US4082682A (en) * | 1972-04-06 | 1978-04-04 | Colgate-Palmolive Company | Detergent composition containing distinctive, colored, non-staining soap particles |
| US5080848A (en) * | 1988-12-22 | 1992-01-14 | The Proctor & Gamble Company | Process for making concentrated surfactant granules |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1072348B (en) * | 1956-10-01 | 1960-06-02 | The Procter & Gamble Company, Cincinnati, Ohio (V. St. A.) | laundry detergent |
| FR1214578A (en) * | 1958-07-17 | 1960-04-11 | Process for manufacturing a solid detergent and product obtained by this process | |
| US3959340A (en) * | 1969-06-05 | 1976-05-25 | Ciba-Geigy Ag | Cyano-distyrylbenzenes |
| NL7013268A (en) * | 1970-09-08 | 1970-11-25 | Fluorescing compounds in organic materials | |
| CA980957A (en) * | 1971-11-26 | 1976-01-06 | Randall B. Hall | Substantially uncolored detergent products containing coloring materials |
| ES8707290A1 (en) * | 1985-01-23 | 1987-07-16 | Henkel Iberica | Detergent paste prodn. |
| IN170991B (en) * | 1988-07-21 | 1992-06-27 | Lever Hindustan Ltd | |
| JPH0633439B2 (en) * | 1988-07-28 | 1994-05-02 | 花王株式会社 | High-density granular concentrated detergent composition |
| GB8922018D0 (en) * | 1989-09-29 | 1989-11-15 | Unilever Plc | Detergent compositions and process for preparing them |
| EP0510746A3 (en) * | 1991-04-12 | 1993-09-08 | The Procter & Gamble Company | Process for preparing condensed detergent granules |
| EP0508543B1 (en) * | 1991-04-12 | 1997-08-06 | The Procter & Gamble Company | Chemical structuring of surfactant pastes to form high active surfactant granules |
-
1992
- 1992-07-15 DK DK92202170T patent/DK0578872T3/en active
- 1992-07-15 ES ES92202170T patent/ES2121814T3/en not_active Expired - Lifetime
- 1992-07-15 DE DE69227311T patent/DE69227311T2/en not_active Expired - Fee Related
- 1992-07-15 EP EP92202170A patent/EP0578872B1/en not_active Expired - Lifetime
- 1992-07-15 AT AT92202170T patent/ATE172240T1/en not_active IP Right Cessation
-
1993
- 1993-06-18 JP JP50445894A patent/JP3560340B2/en not_active Expired - Fee Related
- 1993-06-18 WO PCT/US1993/005888 patent/WO1994002574A1/en active Application Filing
- 1993-06-18 AU AU46421/93A patent/AU4642193A/en not_active Abandoned
- 1993-06-18 CA CA002140285A patent/CA2140285C/en not_active Expired - Fee Related
- 1993-07-08 PH PH46485A patent/PH31248A/en unknown
- 1993-07-13 MA MA23231A patent/MA22931A1/en unknown
- 1993-07-13 EG EG43693A patent/EG20369A/en active
- 1993-07-14 MX MX9304261A patent/MX9304261A/en unknown
- 1993-07-14 IE IE052093A patent/IE930520A1/en not_active IP Right Cessation
- 1993-07-15 TR TR00613/93A patent/TR28449A/en unknown
- 1993-07-15 CN CN93109880A patent/CN1054631C/en not_active Expired - Fee Related
-
1999
- 1999-06-25 CN CN99110039A patent/CN1094512C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4082682A (en) * | 1972-04-06 | 1978-04-04 | Colgate-Palmolive Company | Detergent composition containing distinctive, colored, non-staining soap particles |
| US3986987A (en) * | 1974-05-15 | 1976-10-19 | Canada Packers Limited | Light-density, low phosphate, puffed borax-containing detergent compositions |
| US5080848A (en) * | 1988-12-22 | 1992-01-14 | The Proctor & Gamble Company | Process for making concentrated surfactant granules |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2121814T3 (en) | 1998-12-16 |
| ATE172240T1 (en) | 1998-10-15 |
| EG20369A (en) | 1999-01-31 |
| CN1083859A (en) | 1994-03-16 |
| WO1994002574A1 (en) | 1994-02-03 |
| AU4642193A (en) | 1994-02-14 |
| CA2140285C (en) | 1999-01-26 |
| CN1243867A (en) | 2000-02-09 |
| DK0578872T3 (en) | 1999-06-23 |
| DE69227311T2 (en) | 1999-06-02 |
| JPH07509268A (en) | 1995-10-12 |
| DE69227311D1 (en) | 1998-11-19 |
| IE930520A1 (en) | 1994-01-26 |
| PH31248A (en) | 1998-06-18 |
| CN1054631C (en) | 2000-07-19 |
| MX9304261A (en) | 1994-05-31 |
| EP0578872A1 (en) | 1994-01-19 |
| EP0578872B1 (en) | 1998-10-14 |
| MA22931A1 (en) | 1994-04-01 |
| CA2140285A1 (en) | 1994-02-03 |
| JP3560340B2 (en) | 2004-09-02 |
| TR28449A (en) | 1996-07-04 |
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