US3923456A - Method of washing textile materials with surface-active agent and catalyst-containing micelles - Google Patents
Method of washing textile materials with surface-active agent and catalyst-containing micelles Download PDFInfo
- Publication number
- US3923456A US3923456A US389542A US38954273A US3923456A US 3923456 A US3923456 A US 3923456A US 389542 A US389542 A US 389542A US 38954273 A US38954273 A US 38954273A US 3923456 A US3923456 A US 3923456A
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- US
- United States
- Prior art keywords
- catalyst
- alkali metal
- aqueous medium
- preparing
- per liter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000004753 textile Substances 0.000 title claims abstract description 32
- 239000000693 micelle Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 53
- 238000005406 washing Methods 0.000 title description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000012736 aqueous medium Substances 0.000 claims abstract description 67
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 47
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 44
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 44
- 239000000725 suspension Substances 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 238000004519 manufacturing process Methods 0.000 claims description 37
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 235000012239 silicon dioxide Nutrition 0.000 claims description 21
- 239000004359 castor oil Substances 0.000 claims description 20
- 235000019438 castor oil Nutrition 0.000 claims description 20
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims description 19
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 16
- 150000001340 alkali metals Chemical group 0.000 claims description 14
- 239000004115 Sodium Silicate Substances 0.000 claims description 10
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 10
- 239000002689 soil Substances 0.000 claims description 10
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 3
- 239000003599 detergent Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 19
- 239000004744 fabric Substances 0.000 description 18
- 238000013019 agitation Methods 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- 229960001866 silicon dioxide Drugs 0.000 description 13
- -1 nitrogen-containing compound Chemical class 0.000 description 11
- 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 10
- 239000000344 soap Substances 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000007900 aqueous suspension Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 150000004668 long chain fatty acids Chemical class 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 235000019219 chocolate Nutrition 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000002979 fabric softener Substances 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000019674 grape juice Nutrition 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical class [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- VTIBBOHXBURHMD-UHFFFAOYSA-N 1,2,3,4,4a,5,10,10a-octahydroanthracene Chemical compound C1=CCC2CC(CCCC3)C3=CC2=C1 VTIBBOHXBURHMD-UHFFFAOYSA-N 0.000 description 1
- BGLLQCPSNQUDKF-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)CCCC2=C1 BGLLQCPSNQUDKF-UHFFFAOYSA-N 0.000 description 1
- YDYPLIFGTHYLCZ-UHFFFAOYSA-N 2,3-dihydroxypropyl dodecanoate;sodium Chemical compound [Na].CCCCCCCCCCCC(=O)OCC(O)CO YDYPLIFGTHYLCZ-UHFFFAOYSA-N 0.000 description 1
- BMRVLXHIZWDOOK-UHFFFAOYSA-N 2-butylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(CCCC)=CC=C21 BMRVLXHIZWDOOK-UHFFFAOYSA-N 0.000 description 1
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- SWKVSFPUHCMFJY-UHFFFAOYSA-N 6-methyl-2-oxo-5-pyridin-4-yl-1h-pyridine-3-carboxamide Chemical compound N1C(=O)C(C(N)=O)=CC(C=2C=CN=CC=2)=C1C SWKVSFPUHCMFJY-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 244000056139 Brassica cretica Species 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 241001397173 Kali <angiosperm> Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 208000032376 Lung infection Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 235000015241 bacon Nutrition 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- 229960001950 benzethonium chloride Drugs 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- JXRVKYBCWUJJBP-UHFFFAOYSA-L calcium;hydrogen sulfate Chemical compound [Ca+2].OS([O-])(=O)=O.OS([O-])(=O)=O JXRVKYBCWUJJBP-UHFFFAOYSA-L 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- MLXJANQMZFAJBH-AGZDHKJJSA-L dipotassium;(z)-12-sulfonatooxyoctadec-9-enoate Chemical compound [K+].[K+].CCCCCCC(OS([O-])(=O)=O)C\C=C/CCCCCCCC([O-])=O MLXJANQMZFAJBH-AGZDHKJJSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AAJBNRZDTJPMTJ-UHFFFAOYSA-L magnesium;dinitrite Chemical compound [Mg+2].[O-]N=O.[O-]N=O AAJBNRZDTJPMTJ-UHFFFAOYSA-L 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004028 organic sulfates Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- 235000008476 powdered milk Nutrition 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003307 slaughter Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0291—Micelles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
-
- 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 ; Methods for using cleaning compositions
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- C11D2111/12—
Definitions
- ABSTRACT Textile materials are washed in water containing a surface active agent and a catalytically effective amount of a novel catalyst.
- the catalyst is prepared by steps including admixing a water soluble alkali metal silicate with an aqueous medium containing carefully controlled amounts of dissolved water soluble substances which are sources of calcium ion and magnesium ion, reacting the same to produce an aqueous colloidal suspension of the reaction product, admixing a micelleforming surfactant with the aqueous medium, and agitating the aqueous medium containing the colloidal particles and surfactant to form catalyst-containing micelles.
- This invention relates to a novel method of removing dirt, grease, stains and foreign materials in general from soiled textile materials.
- a wide variety of surface active agents have been used heretofore in washing soiled textile materials. Examples include the alkali metal soaps of long chain fatty acids, the alkali metal soaps of rosin acids and the derivatives of rosin acids, synthetic detergents of the anionic, cationic or nonionic types, and mixtures of one or more of the foregoing surface active agents. It has also been common practice to use inert diluents such as sodium sulfate, or builders such as polyphosphates, polysilicates or sodium carboxymethylcellulose in combination with one or more of the foregoing surface active agents. A number of nitrogen-containing sequestering agents, anti-bacterial agents and surface active agents, and enzymes capable of removing certain stains from fabrics have also been added to laundry detergents heretofore.
- Laundry detergents often include a phosphorus or nitrogen-containing compound which either directly or indirectly results in a pollution problem.
- the phosphates and nitrogen-containing compounds promote the growth of microorganisms and alga in streams and other bodies of water into which sewage is introduced and this results in an adverse change in the ecology.
- the presence of a high concentration of sodium sulfate and other soluble fillers also is undesirable when the water is to be reused downstream for purposes which require a low sodium or solubles content.
- textile materials are washed in water containing a surface active agent and a catalytic amount of a novel catalyst to be described more fully hereinafter.
- the soiled textile materials are intimately contacted with water containing the surface active agent and the catalyst, and preferably with agitation and/or following the recommended prior art washing cycle.
- Suitable surface active agents of the prior art may be used in washing the textile materials.
- surface active agents include the alkali metal soaps of long chain fatty acids and especially the sodium and potassium soaps of fatty acids containing about 14-25 carbon atoms and preferably about 16-18 carbon atoms.
- Other surface active agents include detergents which are not derived directly from fatty acids such as synthetic anionic, cationic and nonionic detergents.
- synthetic anionic detergents include the alkali metal salts of organic sulfonates or organic sulfates, and especially the alkali metal salts of high molecular weight alkyl and alkylaryl sulfonates such as sodium or potassium dodecyl benzene sulfonate, and the sodium and potassium sulfates of straight chain primary alcohols such as sodium lauryl sulfate and other sodium and potassium sulfates of fatty alcohols or products of the 0x0 process.
- Specific examples of cationic detergents include the quaternary ammonium halides such as benzethonium chloride, and often members of this group have outstanding germicidal activity as well as surface active properties.
- nonionic detergents include compounds having a polyoxyethylene or other oxygenated side chain and the remainder of the molecule may be derived from fatty acids, alcohols, phenols, amides or amines.
- the above surface active agents are given by way of example only, and that numerous other suitable surface active agents may be used. A mixture of one or more of the above surface active agents may be used when desired. It it also common practice to admix therewith inert diluents such as sodium sulfate, or builders such as polyphosphates, polysilicates and sodium carboxymethyl cellulose. However, these substances are not essential and it is ususally preferred that the textile materials be washed with a surface active agent or composition which is free of substances presenting a pollution problem, such as phosphorus and nitrogen-containing compounds.
- inert diluents such as sodium sulfate, or builders such as polyphosphates, polysilicates and sodium carboxymethyl cellulose.
- these substances are not essential and it is ususally preferred that the textile materials be washed with a surface active agent or composition which is free of substances presenting a pollution problem, such as phosphorus and nitrogen-containing compounds.
- the surface active agent or composition selected for use in a given instance is often determined by the nature' of the specific textile material to be washed, and may be in accordance with prior art practice.
- the textile materials may be natural or synthetic, and in the form of fiber, roving, thread, woven fabric, unwoven fabric or articles prepared therefrom such as clothing.
- Naturally ocurring textile materials include silk, cotton, flax, hemp and jute.
- synthetic textile materials include regenerated cellulose such as rayon, polymeric amides such as Nylon, and polyesters such as Dacron.
- the water used in washing the textile materials also may be in accordance with the prior art and in most instances is untreated or softened tap water derived from municipal water sources, wells or springs. A soft water usually gives better results and is preferred.
- the surface active composition may be added to the water in the quantity recommended in accordance with prior art practice when desired, such as about 541-2 cups, and preferably about %-1 cup, for each 8-9 pounds of textile material.
- the catalyst of the invention increases the effectiveness of a given quantity of surface active agent very markedly. Only about Bs-l as much surface active agent is required to obtain equally satisfactory results, and often about M1 as much is used in most household and industrial applications.
- the amount of water to be used may be in accordance with prior art practice and is often about -20 gallons and preferably about 10-15 gallons for each 8-9 pounds of textile material.
- the catalyst is present in the water that is intimately contacted with the textile material in a quantity providing sufficient catalytic activity to aid in removing stains and insoluble materials such as soil.
- the water contains about 0.00001-0. 1 weight percent of the catalyst, and preferably about 0.00040.001 weight percent for many applications. often about 0.00002 weight percent of the catalyst based upon the weight of the water v gives very good results when washing clothing in household automatic washers, but it is understood that much larger or smaller quantities may be employed when desired.
- washing equipment It is not necessary to use special washing equipment and ordinary small automatic washing machines are preferred for household use and industrial washing machines for larger scale use such as in laundries. It also is not necessary to change the surface active agent, the amount of water and surface active agent, washing cycle, or other operating procedure with the exception of adding the catalyst or as otherwise noted herein. However, often it is preferred to allow the textile materials to soak in water containing the surface active agent and the catalyst prior to commencing the washing cycle.
- the textile materials may be soaked, for example, for about five minutes to several hours and preferably for about 15 minutes to 1 hour.
- the washing cycle may be, for example, over a period of about 5-60 minutes and preferably about lO-30 minutes.
- a preformed laundry detergent composition for use in practicing the invention may contain a major proportion by weight of a surface active agent and a catalytically effective amount of the novel catalyst.
- the composition may contain, for example, the catalyst and one or more of the surface active agents previously mentioned for use in washing textile materials.
- the catalyst may be added to commercially available solid or liquid surface active compositions such as Ivory Snow, Tide and Thrill, or the compositions disclosed in the patents listed herein.
- the catalyst is present in a quantity to provide a catalytic amount when the composition is admixed with water in the recommended ratio for washing clothing.
- the catalyst is present in an amount to provide about 0.000010.1 weight percent, and preferably about 0.00040.000l weight per cent in the water that is added thereto at the time of use. Often the catalyst is present in an amount of about 0.01-1 weight percent based upon the weight of the concentrated surface active composition. Larger or smaller amounts may be present as it is only necessary to provide the catalyst in effective catalytic amounts in the wash water prepared by diluting the composition with water.
- the surface active agent may be admixed with the aqueous catalyst suspension produced in the catalyst preparation step discussed hereinafter.
- the aqueous catalyst suspension as prepared may be diluted with l00-l0,000 volumes of water, and for better results with about 2502,000 volumes of water and for best results with about 500-l,000 volumes of water, either before, during or after adding the surface active agent.
- the catalyst used in practicing the present invention may be prepared as described below. 1n the presently preferred process for preparing an aqueous suspension of the catalyst, a water soluble alkali metal silicate is admixed and reacted with an aqueous solution of a water soluble dissolved substance which is a source of calcium ion and a water soluble dissolved substance which is a source of magnesium ion to produce a finely divided or colloidal suspension of the reaction product.
- the aqueous solution contains the dissolved substances initially in amounts to provide between about 1 X 10 and l X 10 mole per liter each of calcium ion and magnesium ion, preferably between about 1 X 10 and l X 10' mole per liter, and for still better results between 1 X 10 and 6 X 10 mole per liter.
- the dissolved substances should also be present in amounts to provide a molar ratio of calcium ion to magnesium ion betwwen about 2.0:l.0 and l.0:2.0, and preferably about 1.5: l .0 and 1.0: l .5.
- the aqueous medium should contain the dissolved substances in amounts to provide between about 2.5 X 10 and 3.0 X 10 mole per liter each of calcium ion and magnesium ion, and the molar ratio of calcium ion to magnesium ion should be about 10:10, e.g., 2.9 X 10 mole per liter of calcium ion and 2.7 X 10 mole per liter of magnesium ion.
- the alkali metal silicate should have an alkali metal oxide to silicon dioxide ratio between about 0.9:] .0 and less than 2.011 .0. and preferably between about O.9:1.0 and 1211.0.
- the alkali metal silicate should be admixed with the aqueous medium in an amount of about 0.05-2 moles per liter, preferably about 0.1-1 mole per liter, and for still better results about 0.2-0.5 mole per liter.
- the alkali metal silicate should be an alkali metal meta-silicate having an alkali metal oxide to silicon dioxide ratio of about 1:1, and it should be admixed with the aqueous medium in an amount to provide about 0.2-0.3 mole per liter, e.g., about 0.25 mole per liter.
- sources of calcium ion and magnesium ion for use'in preparing the aqueous solution include mineral acid salts such as the halides, sulfates, bisulfates, nitrites, and nitrates of calcium and magnesium.
- the chlorides are usually the preferred halides, and both calcium and magnesium chloride are soluble and may be used.
- Magnesium sulfate and bisulfate are soluble and often are the preferred sources of magnesium ion.
- Calcium sulfate is only slightly soluble in water and usually is not a preferred source of calcium ion, but calcium bisulfate is somewhat more soluble. While calcium and magnesium nitrite or nitrate are soluble in water and may be used, these substances are not preferred in most instances.
- the sources of calcium ion and magnesium ion are dissolved in the aqueous medium in amounts to provide calcium ion and magnesium ion within the above ranges. Complete ionization is assumed when calculating the quantities to be dissolved and any desired order of addition is satisfactory.
- the source of calcium ion may be added to the aqueous medium before, during or after the source of magnesium ion.
- the alkali metal silicate to be admixed with the aqueous medium is preferably a water soluble sodium or potassium silicate having an alkali metal oxide (M 0) to silicon dioxide (SiO mole ratio between about 0.9: 1 .0 and less than 2.0:1.0, and preferably between about 0.9:l.0 and 1.2:1.0.
- M 0 alkali metal oxide
- silicon dioxide SiO mole ratio between about 0.9: 1 .0 and less than 2.0:1.0, and preferably between about 0.9:l.0 and 1.2:1.0.
- the best results are usually obtained with an alkali metal metasilicate having an alkali metal oxide to silicon dioxide ratio of about 1:1. Hydrated alkali metal silicates dissolve faster and should be used for best results when the alkali metal silicate is added in solid form. In instances where an anhydrous alkali metal silicate is used, it may be desirable to dissolve it in water and then add the solution to the aqueous medium. Sodium metasilicate is preferred and usually
- Carbonate ion and/or bicarbonate ion should not be present in the aqueous medium in substantial concentrations as the calcium ion and magnesium ion are precipitated in the form of their respective carbonates.
- the free carbonate ion and/or bicarbonate ion concentrations in the aqueous medium should not exceed about parts per million by weight based upon the combined weight of the water and the ingredients added thereto and for this reason, the alkali metal silicates should be substantially free of carbonate ion and bicarbonate ion.
- a small amount of preciptated calcium carbonate and/or magnesium carbonate may be present in the aqueous medium provided additional calcium ion and magnesium ion are available to meet the above defined concentrations.
- Distilled water and/or deionized water are usually preferred over a natural or untreated water when preparing the aqueous medium.
- water 6 which contains substantial initial concentrations of alkaline earth metal ions, then this should be taken into consideration in calculating the amounts of the sources of calcium ion and magnesium ion which are necessary to arrive at the final concentrations previously discussed.
- An electrolyte which aids in the preparation of colloidal suspensions may be present in the aqueous medium at the time of admixing the alkali metal silicate therewith.
- electrolytes include those used in preparing prior art colloidal suspensions such as the alkali metal halides, sulfates and bisulfates. Sodium chloride, sodium sulfate and sodium bisulfate are usually preferred.
- the electrolyte should be added in small amounts such as, for example, about 0.00001-0.l mole per liter, but often larger or smaller amounts may be present.
- the conditions under which the alkali metal silicate is admixed with the aqueous medium and reacted with the sources of calcium ion and magnesium ion are not critical provided the reaction mixture is maintained in the liquid phase.
- the reaction temperature may be, for example, between the freezing point and boiling point of water under the existing pressure conditions. At atmospheric pressure, the temperature is usually about 10-90C and often a more convenient temperature is about 2050C. In many instances, ambient or normal room temperature is satisfactory.
- the degree of agitation is not critical, and mild to vigorous agitation may be employed during addition of the alkali metal silicate.
- the aqueous medium should be agitated sufficiently to assure rapid and uniform admixing of the alkali metal silicate.
- the agitation may be continued for a sufficient period of time to assure complete reaction and aging of the resulting colloidal suspension, such as for approximately 1-5 minutes to one hour or longer.
- the colloidal suspension of the reaction product thus produced should be strongly basic and may have a pH value of, for example, approximately 10-14 and preferably about 1 1-13, and for best results about 12.
- the initial pH value of the aqueous medium containing the dissolved sources of calcium ion and magnesium ion is of importance and should be about 6-9 and preferably about 7-8.
- the colloidal suspension may be stored for several weeks or longer while awaiting the further treatment described hereinafter. ln instances where the colloidal suspension is to be stored over a substantial period of time, the pH value should be maintained at the above described level and the storage vessel is preferably a tightly capped polyethylene bottle or other inert plastic container which prevents the contents from absorbing carbon dioxide from the atmosphere.
- the colloidal suspension of the reaction product is not suitable for use as a catalyst as prepared and it shuld be agitated sufficiently in the presence of a micelle-forming surfactant to form catalyst-containing micelles.
- the degree of agitation, the length of the agitation period, and the amount of the micelle-forming surfactant that is present in the colloidal suspension are controlled at levels favorable to the formation of micelles.
- the surfactant may be present in an amount of about 0.001-O.1 mole per liter and preferably about 0.03-0.07 mole per liter for most surfactants. Smaller or larger amounts may be effective with some surfactants such as 0.0001 mole per liter or less, or 0.2 mole per liter or more. About 0.05 mole per liter often gives the best results with many surfactants.
- the minimum period of agitation and the minimum degree of agitation that are required for micelle formation varies somewhat with temperature and the type and amount of surfactant. As is well understood in this art, gradually increasing these variants in the presence of an effective amount of the micelle-forming surfactant will result in micelle formation when the proper levels are reached. As a general rule, longer periods of agitation and/or more vigorous agitation are required to form micelles at lower temperatures approaching the freezing point of the colloidal suspension than at higher temperatures approaching the boiling point. In instances where the aqueous suspension has a temperature of approximately 50-90C., then mild agitation over a period of about 10-60 minutes is satisfactory.
- agitation may be continued long after the catalyst-containing micelles are formed as continued agitation does not seem to have an adverse affect.
- the micelle-forming surfactants known in the prior art may be used in practicing the present invention.
- Micelle-forming surfactants used in the emulsion polymerization of monomeric organic compounds are disclosed in the text Synthetic Rubber, by G. S. Whitby, et al., John Wiley & Sons Incorporated, New York (1954), and surface active agents in general are disclosed on pages 418-424 of the text Organic Chemistry, Fieser and Fieser, 2nd Edition, Reinhold Publishing Corporation, New York, New York (1950), the disclosures of which are incorporated herein by reference.
- surfactants disclosed in the above texts include the alkali metal soaps of long chain fatty acids, and especially the sodium and potassium soaps of fatty acids containing about 14-25 carbon atoms and preferably about 16-18 carbon atoms, and the sodium and potassium soaps of the rosin acids, abietic acid and the derivatives thereof.
- Other micelleforming surfactants include fats and oils such as corn oil, cotton seed oil, castor oil, soy bean oil and safflower oil which have been fully or partially saponified with alkali metal bases to produce mixtures including saponified long chain fatty acids, the monoor di-glycerides thereof, and glycerin.
- Examples of synthetic micelle-forming surfactants include the sulfonates of long chain alcohols prepared by hydrogenation of naturally ocurring fats and oils of the above types and especially sulfonated long chain alcohols containing about -20 and preferably about 12-14 carbon atoms, the alkali metal salts of the monosulfonates of monoglycerides such as sodium glyceryl monolaurate sulfonate, the sulfonates of succinic acid esters such as dioctyl sodium sulfosuccinate and the alkylaryl alkali metal sulfonates.
- micelle-forming surfactants include 8 sodium and potassium sulforicinoleate, tetrahydronaphthalene sulfonate, octahydroanthracene sulfonic acid, butyl naphthalene sulfonic acid, sodium xylene sulfonate, alkyl benzene sulfonic acid and potassium benzene sulfonate.
- Sulfated long chain hydroxycarboxylic acids containing about 14-25 carbon atoms and preferably about 16-18 carbon atoms, and sulfated fats and oils containing hydroxycarboxylic acids of this type produce exceptionally good micelle-forming surfactants. At least 25 percent of the hydroxyl groups and preferably at least 50 percent should be sulfated, and up to 95-100 percent may be sulfated. It is usually preferred that the sulfated oils and/or long chain hydroxycarboxylic acids be neutralized with an alkali metal base, and that the corresponding alkali metal salts be added to the colloidal suspension in the form of an aqueous solution.
- the aqueous solution may contain at least 25 percent of water and preferably at least 35-40 percent by weight. Much larger percentages of water may be present when desired such as -80 percent or more by weight.
- a very active catalyst is produced when using sulfated castor oil as the micelle-forming surfactant (Turkey Red oil).
- Sulfated castor oil which has been purified sufficiently to be of U.S.P. or medicinal grade produces an exceptionally active catalyst.
- the castor oil is reacted with about an equal weight of concentrated sulfuric acid (e.g., 20 percent by weight) at a temperature of approximately 25-30C.
- the mixture may be reacted for about 2 hours with stirring and is then neutralized with sodium hydroxide solution.
- the reaction mixture separates into three layers, i.e., an upper layer which is a water solution, an intermediate or oily layer, and a white curdy precipitate.
- the intermediate oily layer is separated from the upper and lower layers, and may be added to the colloidal suspension as the micelle-forming surfactant in an amount, for example, of 0001-01 mole per liter, and preferably about 0.005 mole per liter.
- the activity of the catalyst may be increased very markedly by cooling the aqueous catalyst suspension to a temperature approaching the freezing point such as about 0-l0C., and then warming over one or more cycles. For best results, the aqueous catalyst suspension should be frozen and thawed over one or more cycles. The reason for the increased catalytic activity is not fully understood at the present time but cooling and then warming the aqueous catalyst suspension seems to increase the concentration of the catalyst-containing micelles and/or increases the catalytic activity thereof.
- the aqueous suspension of the catalyst contains a relatively small percentage by weight of the active catalyst as produced. When desired, it may be concentrated by evaporating a portion of the water to produce a concentrated liquid catalyst suspension which may be stored and used more conveniently. It is also possible to prepare a dry catalyst concentrate by evaporating substantially all of the water.
- the preferred method of producing the dry catalyst concentrate is by flash evaporation using a technique analogous to that employed in preparing powdered milk.
- the catalyst concentrates produced upon partial or complete evaporation of the water content of the initially prepared aqueous suspension may be reconstituted by addition of water with little or no loss of catalytic activity.
- the water is added to the dry catalyst concentrate under sufficiently vigorous conditions of agitation to assure that the catalyst micelles are resuspended and uniformly distributed.
- the aqueous catalyst suspension may be used as produced in practicing the invention, but preferably it is diluted with approximately lOl0,000 parts by weight of water and then used. For better results, the catalyst suspension should be diluted with about 2502,000 parts by weight of water before use, and for best results it should be diluted with about 500l,000 parts by weight of water before use.
- the surface active agent may be added thereto when desired as previously discussed. Alternatively the dry catalyst or liquid catalyst concentrate may be admixed with water and/or the surface active agent to provide an effective catalyst concentration in the quantities previously discussed.
- the weight of the catalyst is calculated on a dry solids basis, i.e., the weight of the catalyst ingredients in the aqueous suspension as produced after removal of the water.
- Anhydrous calcium chloride in an amount of 0.66 gram and magnesium sulfate heptahydrate in an amount of I .32 grams were dissolved in two liters of deionized water with stirring and warming until solution was complete. Then 95 grams of sodium silicate pentahydrate having a molecular ratio of sodium oxide to sil icon dioxide of 111 were added to the solution with stirring and continued warming to produce a white colloidal suspension of the reaction product.
- the colloidal suspension was heated to 80C. and sulfated castor oil in an amount of 50 grams was added with stirring.
- the average molecular weight of the sulfated castor oil was 940 and it contained 50 percent of water.
- the turbidity lessened somewhat as the colloidal suspension was heated at 8090C. for one hour with vigorous stirring to produce catalyst micelles.
- the aqueous suspension of catalyst micelles thus prepared had a viscosity similar to that of water and it was used as the catalyst in certain Examples as noted hereinafter.
- a dry or solid catalyst concentrate was prepared in a further run by evaporating water from the initially pre' pared aqueous catalyst suspension.
- the resulting dry catalyst concentrate was resuspended in water and there was no substantial loss of catalytic activity.
- the catalytic activity of the aqueous suspension of catalyst as initially prepared, the diluted aqueous suspension of catalyst, and the reconstituted aqueous catalyst suspension was enhanced by freezing and thawing.
- EXAMPLE III This example illustrates the use of the catalyst prepared in accordance with Example I in treating fabrics.
- the fabrics washed in water containing the catalyst suspension were softer and brighter.
- the catalyst suspension is useful as a fabric softener and brightner as well as a stain remover.
- Example IV The general procedure of Example III was repeated in a series of runs with the exception of reducing the amount of laundry detergent to between one half and one eighth of the recommended amount employed in Example III. It was found that only one-fourth as much laundry detergent was required when washing clothing in the presence of a catalytic amount of the catalyst.
- EXAMPLE VI A catalyst suspension was prepared in accordance with the procedure of Example I. The water content was removed by evaporation to produce a dried catalyst concentrate.
- the dried catalyst concentrate and commercially available laundry detergent (Tide-XK) are admixed in proportions to provide I weight percent of the catalyst in, the resulting catalyzed surface active composition. A portion of the admixture is tested following the general washing procedure of Example III. The admixture is as effective in washing soiled clothing as separate additions of catalyst and detergent.
- White cloth was treated in accordance with prior art practices to prepare a standard stained and soiled cloth for use in testing the effectiveness of laundry detergents.
- the cloth was saturated with an admixture of soil, mustard, catsup, milk, grape juice, vegetable oil, mineral oil and bacon grease.
- the admixture was dried and the initially white cloth took on a dark brown color.
- the cloth washed in the first run with ordinary laundry soap and diluted catalyst suspension was substantially the same color as the original white cloth.
- the cloth washed in the second run with heavy duty detergent without catalyst was somewhat lighter in color than the stained and soiled cloth, but markedly darker in color than the washed cloth from the first run. It was obvious that the stains and soil were not removed effectively from the cloth washed in the second run, whereas they were in the cloth washed in the first run.
- EXAMPLE VIII A catalyst suspension was prepared following the general procedure in Example I and then diluted with 1,000 volumes of water. The resulting dilute solution is referred to as catalytic solution/1000 in this Example and in Example IX, and it was used in the following test:
- a standard household automatic washer and the recommended washing cycle was used.
- a representitive family wash was also used consisting of baby diapers, bibs, and other articles of clothing for a mechanics family.
- the housewife used V4 cup of Tide XK and A cup of catalytic solution/1000. She used no bleach or fabric softener.
- the Tide XK and catalyst were added at the start of the washing cycle. The results were as good as in similar washes using l A cups of Tide XK, a chlorine bleach, and a fabric softener.
- EXAMPLE IX A woman whose husband worked in the slaughter room of a meat packing plant, was unable to clean her husbands work clothes of blood and slime stains when using the recommended amount of a commercial detergent and following the recommeded washing cycle.
- a method of washing soil from soiled textile material wherein the textile material is intimately contacted with water containing a surface active agent
- the improvement in combination therewith comprising washing the soil from the soiled textile material with water containing the said surface active agent and a catalyst, the catalyst being present in a catalytically effect amount which increases the rate of removal of the soil from the textile material, the catalyst being prepared by a process comprising admixing a water soluble alkali metal silicate with an aqueous medium containing a dissolved substance which is a source of calcium ion and a dissolved substance which is a source of magnesium ion,
- the aqueous medium containing said dissolved substances in amounts to provide between about I X 10 and l X 10 mole per liter each of calcium ion and magnesium ion,
- the aqueous medium containing said dissolved substances in amounts to provide a molar ratio of calcium ion to magnesium ion between about 2.0:l.0 and 1.0120,
- the alkali metal silicate having an alkali metal oxide to silicon dioxide ratio between about 09:10 and less than 2.0: l .0 and being admixed with the aqueous medium in an amount of about 0.05-2 mole per liter,
- a micelle-forming surfactant with the aqueous medium in an amount to form catalyst micelles comprising said colloidal particles upon agitating the aqueous medium
- the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio between about 0921.0 and l.2:l.0.
- the alkali metal silicate is alkali metal metasilicate having an alkali metal oxide to silicon dioxide ratio of about 1.0:1 .0.
- the surfactant comprises sulfated castor oil.
- the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 1 X and 6 X 10 mole per liter each of calcium ion and magnesium ion, the ratio of calcium ion to magnesium ion is between about l.5:1.0 and 1021.5, about 0.2-0.5 mole per liter of the alkali metal silicate is admixed with the aqueous medium, and the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio between about 0921.0 and l.2:l.0.
- the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 2.5 X 10 and 3.0 X 10 mole per liter each of calcium ion and magnesium ion, the aqueous medium contains about equimolar amounts of calcium ion and magnesium ion, about 0.2-0.3 mole per liter of the al kali metal silicate is admixed with the aqueous medium, and the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio of about l.0:l.O.
- the alkali metal metasilicate is sodium metasilicate having an alkali metal oxide to silicon dioxide ratio of about 10:1 .0.
- the surfactant comprises sulfated castor oil.
- the alkali metal metasilicate is sodium metasilicate having a sodium oxide to silicon dioxide ratio of about 1.0:l'.0.
- the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide about 2.9 X 10" mole per liter of calcium ion and about 2.7 X 10* mole per liter of magnesium ion, about 0.25 mole per liter of sodium metasilicate having a sodium oxide to silicon dioxide ratio of about l.0:l.0 is admixed with the aqueous medium, the aqueous medium contains not more than 10 parts per million by weight of carbonate ion and bicarbonate ion, the surfactant comprises sulfated castor oil and at least 50 percent of the hydroxy groups of the castor oil are sulfated, and about 0.05 mole per liter of the sulfated castor oil is admixed with the aqueous medium.
Abstract
Textile materials are washed in water containing a surface active agent and a catalytically effective amount of a novel catalyst. The catalyst is prepared by steps including admixing a water soluble alkali metal silicate with an aqueous medium containing carefully controlled amounts of dissolved water soluble substances which are sources of calcium ion and magnesium ion, reacting the same to produce an aqueous colloidal suspension of the reaction product, admixing a micelle-forming surfactant with the aqueous medium, and agitating the aqueous medium containing the colloidal particles and surfactant to form catalyst-containing micelles.
Description
lliteol States atet 1 91 Willard, Sr.
[ Dec. 2, 1975 METHOD OF WASHING TEXTILE MATERIALS WITH SURFACE-ACTIVE AGENT AND CATALYST-CONTAINING MICELLES Inventor: John W. Willard, Sr., Rapid City, S.
Dak.
Assignee: Caw Industries, Inc., Rapid City, S.
. Dak.
Filed: Aug. 20, 1973 Appl. No.: 389,542
Related US. Application Data Continuation-impart of Ser. No. 317,097, Dec. 20, 1972, which is a continuation of Ser. No. 108,198, Jan. 20, 1971, abandoned.
US. Cl. 8/1375; 252/313 S; 252/428; 252/449; 252/457 Int. Cl. D06F 11/00 Field of Search 8/137, 137.5; 252/313 S, 252/428, 429 B, 449, 451, 452, 455 R, 454, 457, 532
References Cited UNITED STATES PATENTS 3,272,753 9/1966 Wixon 252/532 X 3,350,319 10/1967 Schonfeldt 252/532 X 3,351,558 11/1967 Zimmerer... 252/532 X 252/313 S 3,377,293 4/1968 Shepard 3,453,144 7/1969 Morgan et a1. 252/532 X 3,657,151 4/1972 Noble 252/453 X 3,799,893 3/1974 Quinlan 8/137 X 3,827,857 8/1974 Boulus 8/137 X Primary ExaminerStephen C. Bentley Assistant Examiner-P. A. Nelson Attorney, Agent, or Firm-L. S. Van Landingham, Jr.
[57] ABSTRACT Textile materials are washed in water containing a surface active agent and a catalytically effective amount of a novel catalyst. The catalyst is prepared by steps including admixing a water soluble alkali metal silicate with an aqueous medium containing carefully controlled amounts of dissolved water soluble substances which are sources of calcium ion and magnesium ion, reacting the same to produce an aqueous colloidal suspension of the reaction product, admixing a micelleforming surfactant with the aqueous medium, and agitating the aqueous medium containing the colloidal particles and surfactant to form catalyst-containing micelles.
18 Claims, No Drawings METHOD OF WASHING TEXTILE MATERIALS WITH SURFACE-ACTIVE AGENT AND CATALYST-CONTAINING MICELLES RELATED APPLICATIONS This application is a continuation-in-part of pending application Ser. No. 317,097, filed Dec. 20, 1972 on behalf of John W. Willard, Sr. for Novel Catalyst and Process For Preparing The Same. Application Ser. No. 371,097, in turn, is a continuation of application Ser. No. 108,198 filed Jan. 20, 1971, now abandoned.
BACKGROUND OF THE INVENTION This invention relates to a novel method of removing dirt, grease, stains and foreign materials in general from soiled textile materials.
A wide variety of surface active agents have been used heretofore in washing soiled textile materials. Examples include the alkali metal soaps of long chain fatty acids, the alkali metal soaps of rosin acids and the derivatives of rosin acids, synthetic detergents of the anionic, cationic or nonionic types, and mixtures of one or more of the foregoing surface active agents. It has also been common practice to use inert diluents such as sodium sulfate, or builders such as polyphosphates, polysilicates or sodium carboxymethylcellulose in combination with one or more of the foregoing surface active agents. A number of nitrogen-containing sequestering agents, anti-bacterial agents and surface active agents, and enzymes capable of removing certain stains from fabrics have also been added to laundry detergents heretofore.
Many of the commercially available surface active compositions presently recommended for household and industrial uses are not entirely satisfactory for a number of reasons. Laundry detergents often include a phosphorus or nitrogen-containing compound which either directly or indirectly results in a pollution problem. The phosphates and nitrogen-containing compounds promote the growth of microorganisms and alga in streams and other bodies of water into which sewage is introduced and this results in an adverse change in the ecology. The presence of a high concentration of sodium sulfate and other soluble fillers also is undesirable when the water is to be reused downstream for purposes which require a low sodium or solubles content. In instances where laundry detergents contain synthetic surfactants which are not destroyed by microrganisms at a sufficiently rapid rate, the surfactant concentration in streams tends to increase to an objectionable level. The enzymes presently added to laundry detergents are not effective for removing many stubborn stains and thus do not always produce the desired results. Additionally, all of the enzyme-producing microganisms may not be killed prior to adding the enzyme to the laundry detergent. It has been reported that the live microrganisms are capable of causing lung infections when finely divided particles of the laundry detergent are inhaled.
As a result of the above mentioned and other disadvantages, the art has long sought an entirely satisfactory surface active composition for general household and industrial use which does not require the presence of phosphorus or nitrogen-containing compounds, inert fillers, enzymes and the like. However, prior to the present invention an entirely satisfactory heavy duty surface active composition was not available which 2 overcomes the pollution problems of the prior art and yet is capable of removing stubborn stains and deeply embedded soil from textile materials.
It is an object of the present invention to provide a novel method of removing stains and foreign materials in general from textile materials.
It is a further object to provide a novel method of washing soiled textile materials with water containing a surface active agent and a catalytically effective amount of the novel catalyst of the invention.
Still other objects and advantages of the invention will be apparent to those skilled in the art upon reference to the following detailed description and the specific examples.
DETAILED DESCRIPTION OF THE INVENTION INCLUDING PREFERRED VARIANTS THEREOF In accordance with the present invention, textile materials are washed in water containing a surface active agent and a catalytic amount of a novel catalyst to be described more fully hereinafter. In practicing the method, the soiled textile materials are intimately contacted with water containing the surface active agent and the catalyst, and preferably with agitation and/or following the recommended prior art washing cycle.
Suitable surface active agents of the prior art may be used in washing the textile materials. Examples of surface active agents include the alkali metal soaps of long chain fatty acids and especially the sodium and potassium soaps of fatty acids containing about 14-25 carbon atoms and preferably about 16-18 carbon atoms. Other surface active agents include detergents which are not derived directly from fatty acids such as synthetic anionic, cationic and nonionic detergents. Specific examples of synthetic anionic detergents include the alkali metal salts of organic sulfonates or organic sulfates, and especially the alkali metal salts of high molecular weight alkyl and alkylaryl sulfonates such as sodium or potassium dodecyl benzene sulfonate, and the sodium and potassium sulfates of straight chain primary alcohols such as sodium lauryl sulfate and other sodium and potassium sulfates of fatty alcohols or products of the 0x0 process. Specific examples of cationic detergents include the quaternary ammonium halides such as benzethonium chloride, and often members of this group have outstanding germicidal activity as well as surface active properties. Specific examples of nonionic detergents include compounds having a polyoxyethylene or other oxygenated side chain and the remainder of the molecule may be derived from fatty acids, alcohols, phenols, amides or amines.
Further examples of surface active agents are disclosed in the section on detergency appearing in the Kirk-Othmer Encyclopedia of Chemical Technology (2nd Edition), Volume 6, pages 853-895, the disclosure of which is incorporated herein by reference. Still additional specific examples of detergent compositions for industrial or household use are found in numerous United States patents, including the following which are incorporated herein by reference:
-continued It is understood that the above surface active agents are given by way of example only, and that numerous other suitable surface active agents may be used. A mixture of one or more of the above surface active agents may be used when desired. It it also common practice to admix therewith inert diluents such as sodium sulfate, or builders such as polyphosphates, polysilicates and sodium carboxymethyl cellulose. However, these substances are not essential and it is ususally preferred that the textile materials be washed with a surface active agent or composition which is free of substances presenting a pollution problem, such as phosphorus and nitrogen-containing compounds.
The surface active agent or composition selected for use in a given instance is often determined by the nature' of the specific textile material to be washed, and may be in accordance with prior art practice. The textile materials may be natural or synthetic, and in the form of fiber, roving, thread, woven fabric, unwoven fabric or articles prepared therefrom such as clothing. Examples of naturally ocurring textile materials include silk, cotton, flax, hemp and jute. Examples of synthetic textile materials include regenerated cellulose such as rayon, polymeric amides such as Nylon, and polyesters such as Dacron.
The water used in washing the textile materials also may be in accordance with the prior art and in most instances is untreated or softened tap water derived from municipal water sources, wells or springs. A soft water usually gives better results and is preferred. The surface active composition may be added to the water in the quantity recommended in accordance with prior art practice when desired, such as about 541-2 cups, and preferably about %-1 cup, for each 8-9 pounds of textile material. However, the catalyst of the invention increases the effectiveness of a given quantity of surface active agent very markedly. Only about Bs-l as much surface active agent is required to obtain equally satisfactory results, and often about M1 as much is used in most household and industrial applications. The amount of water to be used may be in accordance with prior art practice and is often about -20 gallons and preferably about 10-15 gallons for each 8-9 pounds of textile material.
The catalyst is present in the water that is intimately contacted with the textile material in a quantity providing sufficient catalytic activity to aid in removing stains and insoluble materials such as soil. Usually the water contains about 0.00001-0. 1 weight percent of the catalyst, and preferably about 0.00040.001 weight percent for many applications. often about 0.00002 weight percent of the catalyst based upon the weight of the water v gives very good results when washing clothing in household automatic washers, but it is understood that much larger or smaller quantities may be employed when desired.
It is not necessary to use special washing equipment and ordinary small automatic washing machines are preferred for household use and industrial washing machines for larger scale use such as in laundries. It also is not necessary to change the surface active agent, the amount of water and surface active agent, washing cycle, or other operating procedure with the exception of adding the catalyst or as otherwise noted herein. However, often it is preferred to allow the textile materials to soak in water containing the surface active agent and the catalyst prior to commencing the washing cycle. The textile materials may be soaked, for example, for about five minutes to several hours and preferably for about 15 minutes to 1 hour. The washing cycle may be, for example, over a period of about 5-60 minutes and preferably about lO-30 minutes.
A preformed laundry detergent composition for use in practicing the invention may contain a major proportion by weight of a surface active agent and a catalytically effective amount of the novel catalyst. The composition may contain, for example, the catalyst and one or more of the surface active agents previously mentioned for use in washing textile materials. If desired, the catalyst may be added to commercially available solid or liquid surface active compositions such as Ivory Snow, Tide and Thrill, or the compositions disclosed in the patents listed herein. The catalyst is present in a quantity to provide a catalytic amount when the composition is admixed with water in the recommended ratio for washing clothing. Usually the catalyst is present in an amount to provide about 0.000010.1 weight percent, and preferably about 0.00040.000l weight per cent in the water that is added thereto at the time of use. Often the catalyst is present in an amount of about 0.01-1 weight percent based upon the weight of the concentrated surface active composition. Larger or smaller amounts may be present as it is only necessary to provide the catalyst in effective catalytic amounts in the wash water prepared by diluting the composition with water. Alternatively, the surface active agent may be admixed with the aqueous catalyst suspension produced in the catalyst preparation step discussed hereinafter. For example, the aqueous catalyst suspension as prepared may be diluted with l00-l0,000 volumes of water, and for better results with about 2502,000 volumes of water and for best results with about 500-l,000 volumes of water, either before, during or after adding the surface active agent.
PREPARATION OF THE CATALYST The catalyst used in practicing the present invention may be prepared as described below. 1n the presently preferred process for preparing an aqueous suspension of the catalyst, a water soluble alkali metal silicate is admixed and reacted with an aqueous solution of a water soluble dissolved substance which is a source of calcium ion and a water soluble dissolved substance which is a source of magnesium ion to produce a finely divided or colloidal suspension of the reaction product. The aqueous solution contains the dissolved substances initially in amounts to provide between about 1 X 10 and l X 10 mole per liter each of calcium ion and magnesium ion, preferably between about 1 X 10 and l X 10' mole per liter, and for still better results between 1 X 10 and 6 X 10 mole per liter. The dissolved substances should also be present in amounts to provide a molar ratio of calcium ion to magnesium ion betwwen about 2.0:l.0 and l.0:2.0, and preferably about 1.5: l .0 and 1.0: l .5. For best results, the aqueous medium should contain the dissolved substances in amounts to provide between about 2.5 X 10 and 3.0 X 10 mole per liter each of calcium ion and magnesium ion, and the molar ratio of calcium ion to magnesium ion should be about 10:10, e.g., 2.9 X 10 mole per liter of calcium ion and 2.7 X 10 mole per liter of magnesium ion. The alkali metal silicate should have an alkali metal oxide to silicon dioxide ratio between about 0.9:] .0 and less than 2.011 .0. and preferably between about O.9:1.0 and 1211.0. The alkali metal silicate should be admixed with the aqueous medium in an amount of about 0.05-2 moles per liter, preferably about 0.1-1 mole per liter, and for still better results about 0.2-0.5 mole per liter. For best results, the alkali metal silicate should be an alkali metal meta-silicate having an alkali metal oxide to silicon dioxide ratio of about 1:1, and it should be admixed with the aqueous medium in an amount to provide about 0.2-0.3 mole per liter, e.g., about 0.25 mole per liter.
Examples of sources of calcium ion and magnesium ion for use'in preparing the aqueous solution include mineral acid salts such as the halides, sulfates, bisulfates, nitrites, and nitrates of calcium and magnesium. The chlorides are usually the preferred halides, and both calcium and magnesium chloride are soluble and may be used. Magnesium sulfate and bisulfate are soluble and often are the preferred sources of magnesium ion. Calcium sulfate is only slightly soluble in water and usually is not a preferred source of calcium ion, but calcium bisulfate is somewhat more soluble. While calcium and magnesium nitrite or nitrate are soluble in water and may be used, these substances are not preferred in most instances. The sources of calcium ion and magnesium ion are dissolved in the aqueous medium in amounts to provide calcium ion and magnesium ion within the above ranges. Complete ionization is assumed when calculating the quantities to be dissolved and any desired order of addition is satisfactory. For example, the source of calcium ion may be added to the aqueous medium before, during or after the source of magnesium ion.
The alkali metal silicate to be admixed with the aqueous medium is preferably a water soluble sodium or potassium silicate having an alkali metal oxide (M 0) to silicon dioxide (SiO mole ratio between about 0.9: 1 .0 and less than 2.0:1.0, and preferably between about 0.9:l.0 and 1.2:1.0. The best results are usually obtained with an alkali metal metasilicate having an alkali metal oxide to silicon dioxide ratio of about 1:1. Hydrated alkali metal silicates dissolve faster and should be used for best results when the alkali metal silicate is added in solid form. In instances where an anhydrous alkali metal silicate is used, it may be desirable to dissolve it in water and then add the solution to the aqueous medium. Sodium metasilicate is preferred and usually a hydrated sodium metasilicate such as the pentahydrate gives the best results.
Carbonate ion and/or bicarbonate ion should not be present in the aqueous medium in substantial concentrations as the calcium ion and magnesium ion are precipitated in the form of their respective carbonates. The free carbonate ion and/or bicarbonate ion concentrations in the aqueous medium should not exceed about parts per million by weight based upon the combined weight of the water and the ingredients added thereto and for this reason, the alkali metal silicates should be substantially free of carbonate ion and bicarbonate ion. A small amount of preciptated calcium carbonate and/or magnesium carbonate may be present in the aqueous medium provided additional calcium ion and magnesium ion are available to meet the above defined concentrations.
Distilled water and/or deionized water are usually preferred over a natural or untreated water when preparing the aqueous medium. In instances where water 6 is used which contains substantial initial concentrations of alkaline earth metal ions, then this should be taken into consideration in calculating the amounts of the sources of calcium ion and magnesium ion which are necessary to arrive at the final concentrations previously discussed.
An electrolyte which aids in the preparation of colloidal suspensions may be present in the aqueous medium at the time of admixing the alkali metal silicate therewith. Examples of electrolytes include those used in preparing prior art colloidal suspensions such as the alkali metal halides, sulfates and bisulfates. Sodium chloride, sodium sulfate and sodium bisulfate are usually preferred. The electrolyte should be added in small amounts such as, for example, about 0.00001-0.l mole per liter, but often larger or smaller amounts may be present.
The conditions under which the alkali metal silicate is admixed with the aqueous medium and reacted with the sources of calcium ion and magnesium ion are not critical provided the reaction mixture is maintained in the liquid phase. The reaction temperature may be, for example, between the freezing point and boiling point of water under the existing pressure conditions. At atmospheric pressure, the temperature is usually about 10-90C and often a more convenient temperature is about 2050C. In many instances, ambient or normal room temperature is satisfactory.
The degree of agitation is not critical, and mild to vigorous agitation may be employed during addition of the alkali metal silicate. For the best results, the aqueous medium should be agitated sufficiently to assure rapid and uniform admixing of the alkali metal silicate. After completing the addition of the alkali metal silicate, when desired the agitation may be continued for a sufficient period of time to assure complete reaction and aging of the resulting colloidal suspension, such as for approximately 1-5 minutes to one hour or longer.
Upon admixing the alkali metal silicate with the aqueous medium, it takes on a turbid appearance but in most instances no significant amount of visible precipitate is formed. The colloidal suspension of the reaction product thus produced should be strongly basic and may have a pH value of, for example, approximately 10-14 and preferably about 1 1-13, and for best results about 12. In view of this, the initial pH value of the aqueous medium containing the dissolved sources of calcium ion and magnesium ion is of importance and should be about 6-9 and preferably about 7-8. When necessary, it is possible to adjust the pH value of the aqueous medium to the foregoing levels either before during or after addition of the alkali metal silicate by adding bases such as sodium or potassium hydroxide, or mineral acids such as sulfuric or hydrochloric acid.
The colloidal suspension may be stored for several weeks or longer while awaiting the further treatment described hereinafter. ln instances where the colloidal suspension is to be stored over a substantial period of time, the pH value should be maintained at the above described level and the storage vessel is preferably a tightly capped polyethylene bottle or other inert plastic container which prevents the contents from absorbing carbon dioxide from the atmosphere.
The colloidal suspension of the reaction product is not suitable for use as a catalyst as prepared and it shuld be agitated sufficiently in the presence of a micelle-forming surfactant to form catalyst-containing micelles. The degree of agitation, the length of the agitation period, and the amount of the micelle-forming surfactant that is present in the colloidal suspension are controlled at levels favorable to the formation of micelles. For example, the surfactant may be present in an amount of about 0.001-O.1 mole per liter and preferably about 0.03-0.07 mole per liter for most surfactants. Smaller or larger amounts may be effective with some surfactants such as 0.0001 mole per liter or less, or 0.2 mole per liter or more. About 0.05 mole per liter often gives the best results with many surfactants.
The minimum period of agitation and the minimum degree of agitation that are required for micelle formation varies somewhat with temperature and the type and amount of surfactant. As is well understood in this art, gradually increasing these variants in the presence of an effective amount of the micelle-forming surfactant will result in micelle formation when the proper levels are reached. As a general rule, longer periods of agitation and/or more vigorous agitation are required to form micelles at lower temperatures approaching the freezing point of the colloidal suspension than at higher temperatures approaching the boiling point. In instances where the aqueous suspension has a temperature of approximately 50-90C., then mild agitation over a period of about 10-60 minutes is satisfactory. Often longer or shorter periods of mild to vigorous agitation may be employed such as from about lminutes to several hours at temperature varying, respectively, between the boiling point and the freezing point. When desired, the agitation may be continued long after the catalyst-containing micelles are formed as continued agitation does not seem to have an adverse affect.
As a general rule, the micelle-forming surfactants known in the prior art may be used in practicing the present invention. Micelle-forming surfactants used in the emulsion polymerization of monomeric organic compounds are disclosed in the text Synthetic Rubber, by G. S. Whitby, et al., John Wiley & Sons Incorporated, New York (1954), and surface active agents in general are disclosed on pages 418-424 of the text Organic Chemistry, Fieser and Fieser, 2nd Edition, Reinhold Publishing Corporation, New York, New York (1950), the disclosures of which are incorporated herein by reference. Examples of surfactants disclosed in the above texts include the alkali metal soaps of long chain fatty acids, and especially the sodium and potassium soaps of fatty acids containing about 14-25 carbon atoms and preferably about 16-18 carbon atoms, and the sodium and potassium soaps of the rosin acids, abietic acid and the derivatives thereof. Other micelleforming surfactants include fats and oils such as corn oil, cotton seed oil, castor oil, soy bean oil and safflower oil which have been fully or partially saponified with alkali metal bases to produce mixtures including saponified long chain fatty acids, the monoor di-glycerides thereof, and glycerin.
Examples of synthetic micelle-forming surfactants include the sulfonates of long chain alcohols prepared by hydrogenation of naturally ocurring fats and oils of the above types and especially sulfonated long chain alcohols containing about -20 and preferably about 12-14 carbon atoms, the alkali metal salts of the monosulfonates of monoglycerides such as sodium glyceryl monolaurate sulfonate, the sulfonates of succinic acid esters such as dioctyl sodium sulfosuccinate and the alkylaryl alkali metal sulfonates. Specific examples of presently preferred micelle-forming surfactants include 8 sodium and potassium sulforicinoleate, tetrahydronaphthalene sulfonate, octahydroanthracene sulfonic acid, butyl naphthalene sulfonic acid, sodium xylene sulfonate, alkyl benzene sulfonic acid and potassium benzene sulfonate.
Sulfated long chain hydroxycarboxylic acids containing about 14-25 carbon atoms and preferably about 16-18 carbon atoms, and sulfated fats and oils containing hydroxycarboxylic acids of this type produce exceptionally good micelle-forming surfactants. At least 25 percent of the hydroxyl groups and preferably at least 50 percent should be sulfated, and up to 95-100 percent may be sulfated. It is usually preferred that the sulfated oils and/or long chain hydroxycarboxylic acids be neutralized with an alkali metal base, and that the corresponding alkali metal salts be added to the colloidal suspension in the form of an aqueous solution. The aqueous solution may contain at least 25 percent of water and preferably at least 35-40 percent by weight. Much larger percentages of water may be present when desired such as -80 percent or more by weight.
A very active catalyst is produced when using sulfated castor oil as the micelle-forming surfactant (Turkey Red oil). Sulfated castor oil which has been purified sufficiently to be of U.S.P. or medicinal grade produces an exceptionally active catalyst. For the best results, the castor oil is reacted with about an equal weight of concentrated sulfuric acid (e.g., 20 percent by weight) at a temperature of approximately 25-30C. The mixture may be reacted for about 2 hours with stirring and is then neutralized with sodium hydroxide solution. The reaction mixture separates into three layers, i.e., an upper layer which is a water solution, an intermediate or oily layer, and a white curdy precipitate. The intermediate oily layer is separated from the upper and lower layers, and may be added to the colloidal suspension as the micelle-forming surfactant in an amount, for example, of 0001-01 mole per liter, and preferably about 0.005 mole per liter.
The activity of the catalyst may be increased very markedly by cooling the aqueous catalyst suspension to a temperature approaching the freezing point such as about 0-l0C., and then warming over one or more cycles. For best results, the aqueous catalyst suspension should be frozen and thawed over one or more cycles. The reason for the increased catalytic activity is not fully understood at the present time but cooling and then warming the aqueous catalyst suspension seems to increase the concentration of the catalyst-containing micelles and/or increases the catalytic activity thereof.
The aqueous suspension of the catalyst contains a relatively small percentage by weight of the active catalyst as produced. When desired, it may be concentrated by evaporating a portion of the water to produce a concentrated liquid catalyst suspension which may be stored and used more conveniently. It is also possible to prepare a dry catalyst concentrate by evaporating substantially all of the water. The preferred method of producing the dry catalyst concentrate is by flash evaporation using a technique analogous to that employed in preparing powdered milk. The catalyst concentrates produced upon partial or complete evaporation of the water content of the initially prepared aqueous suspension may be reconstituted by addition of water with little or no loss of catalytic activity. Preferably, the water is added to the dry catalyst concentrate under sufficiently vigorous conditions of agitation to assure that the catalyst micelles are resuspended and uniformly distributed.
The aqueous catalyst suspension may be used as produced in practicing the invention, but preferably it is diluted with approximately lOl0,000 parts by weight of water and then used. For better results, the catalyst suspension should be diluted with about 2502,000 parts by weight of water before use, and for best results it should be diluted with about 500l,000 parts by weight of water before use. The surface active agent may be added thereto when desired as previously discussed. Alternatively the dry catalyst or liquid catalyst concentrate may be admixed with water and/or the surface active agent to provide an effective catalyst concentration in the quantities previously discussed. The weight of the catalyst is calculated on a dry solids basis, i.e., the weight of the catalyst ingredients in the aqueous suspension as produced after removal of the water.
The invention is further illustrated by the following specific examples.
EXAMPLE I This example illustrates one presently preferred process for preparing the novel catalyst used in practicing the invention.
Anhydrous calcium chloride in an amount of 0.66 gram and magnesium sulfate heptahydrate in an amount of I .32 grams were dissolved in two liters of deionized water with stirring and warming until solution was complete. Then 95 grams of sodium silicate pentahydrate having a molecular ratio of sodium oxide to sil icon dioxide of 111 were added to the solution with stirring and continued warming to produce a white colloidal suspension of the reaction product.
After setting for 10 minutes, the colloidal suspension was heated to 80C. and sulfated castor oil in an amount of 50 grams was added with stirring. The average molecular weight of the sulfated castor oil was 940 and it contained 50 percent of water. The turbidity lessened somewhat as the colloidal suspension was heated at 8090C. for one hour with vigorous stirring to produce catalyst micelles. The aqueous suspension of catalyst micelles thus prepared had a viscosity similar to that of water and it was used as the catalyst in certain Examples as noted hereinafter.
A dry or solid catalyst concentrate was prepared in a further run by evaporating water from the initially pre' pared aqueous catalyst suspension. The resulting dry catalyst concentrate was resuspended in water and there was no substantial loss of catalytic activity. In still other runs, the catalytic activity of the aqueous suspension of catalyst as initially prepared, the diluted aqueous suspension of catalyst, and the reconstituted aqueous catalyst suspension was enhanced by freezing and thawing.
EXAMPLE II Ingredient Amount of Ingredient Run 1 Run 2 Run 3 Run 4 Run 5 Deionized water 2 I I5 l L5 1 L5 l 0.25 l CaCl 0.66 g 0.5 g 0.5 g 1.0 g 05 g MgSO 7H O L32 g 1.0 g 1.0 g 2.0 g [.0 g
-continued Ingredient Amount of Ingredient Run 1 Run 2 Run 3 Run 4 Run 5 Na SiO SH O 165 g I32 g 71g 185 g 7l g Sulfated Castor ml ml I50 ml 200 ml 150 ml oil (approximately 50% by weight H O) The catalyst suspensions prepared by the above five runs were used in certain examples as noted hereinafter.
EXAMPLE III This example illustrates the use of the catalyst prepared in accordance with Example I in treating fabrics.
A standard household automatic washer (9 pounds capacity) was used in obtaining the datafor this example. The recommended washing cycle for the stained fabrics was also used.
In one run, an attempt was made to remove chocolate stains from a cotton shirt using commercially available laundry detergents (laundry detergents sold under the trademarks Biz and Tide-XK) and an oxidizing agent (Clorox). The chocolate stains were not removed by this treatment. However, chocolate stains were easily removed in a second run when washing with a catalytic amount of the diluted catalyst suspension prepared in accordance with Example I.
In subsequent runs, six fluid ounces of the catalyst suspension prepared in accordance with Example I were added to the washer along with the recommended amount of cold water, laundry detergent and stained clothing. Blood, grape juice, catsup, grease and grass stains were easily removed. It was not possible to remove stains of this type when using only a laundry detergent and Clorox.
The fabrics washed in water containing the catalyst suspension were softer and brighter. Thus, the catalyst suspension is useful as a fabric softener and brightner as well as a stain remover.
EXAMPLE IV The general procedure of Example III was repeated in a series of runs with the exception of reducing the amount of laundry detergent to between one half and one eighth of the recommended amount employed in Example III. It was found that only one-fourth as much laundry detergent was required when washing clothing in the presence of a catalytic amount of the catalyst.
EXAMPLE V The general proceduresof Examples III and IV were repeated in a series of runs with the exception of using the catalysts prepared in accordance with Example II. The'catalysts of Example II were found to be active and produced comparable results.
EXAMPLE VI A catalyst suspension was prepared in accordance with the procedure of Example I. The water content was removed by evaporation to produce a dried catalyst concentrate.
The dried catalyst concentrate and commercially available laundry detergent (Tide-XK) are admixed in proportions to provide I weight percent of the catalyst in, the resulting catalyzed surface active composition. A portion of the admixture is tested following the general washing procedure of Example III. The admixture is as effective in washing soiled clothing as separate additions of catalyst and detergent.
EXAMPLE VII A catalyst suspension was prepared following the general procedure of Example I and then diluted with 1,000 volumes of water.
White cloth was treated in accordance with prior art practices to prepare a standard stained and soiled cloth for use in testing the effectiveness of laundry detergents. The cloth was saturated with an admixture of soil, mustard, catsup, milk, grape juice, vegetable oil, mineral oil and bacon grease. The admixture was dried and the initially white cloth took on a dark brown color.
A portion of the stained and soiled cloth was washed in the diluted catalyst suspension prepared above using the recommended amount of ordinary laundry soap. A standard household automatic washer and the recommended washing cycle were used.
A second portion of the stained and soiled cloth was washed in soft tap water to which had been added the recommended amount of a commercially available heavy duty laundry detergent. The manufacturer considered the laundry detergent to be the best formula available. The washer, washing cycle, and other variables were the same in the two'runs with the exception of using laundry soap and catalyst in the first run, and the heavy duty laundry detergent without catalyst in the second run.
Following washing, the two test cloths were dried and examined in daylight. The cloth washed in the first run with ordinary laundry soap and diluted catalyst suspension was substantially the same color as the original white cloth. The cloth washed in the second run with heavy duty detergent without catalyst was somewhat lighter in color than the stained and soiled cloth, but markedly darker in color than the washed cloth from the first run. It was obvious that the stains and soil were not removed effectively from the cloth washed in the second run, whereas they were in the cloth washed in the first run.
EXAMPLE VIII A catalyst suspension was prepared following the general procedure in Example I and then diluted with 1,000 volumes of water. The resulting dilute solution is referred to as catalytic solution/1000 in this Example and in Example IX, and it was used in the following test:
A standard household automatic washer and the recommended washing cycle was used. A representitive family wash was also used consisting of baby diapers, bibs, and other articles of clothing for a mechanics family. The housewife used V4 cup of Tide XK and A cup of catalytic solution/1000. She used no bleach or fabric softener. The Tide XK and catalyst were added at the start of the washing cycle. The results were as good as in similar washes using l A cups of Tide XK, a chlorine bleach, and a fabric softener.
EXAMPLE IX A woman whose husband worked in the slaughter room of a meat packing plant, was unable to clean her husbands work clothes of blood and slime stains when using the recommended amount of a commercial detergent and following the recommeded washing cycle. In
12 this test, she washed in her usual manner with the exception of using only A; of the amount of detergent previously used, and cup of catalyst solution/1000". Surprisingly, even the dried in stains were removed and the washed clothing was free of all blood and slime stains.
I claim: 1. In a method of washing soil from soiled textile material wherein the textile material is intimately contacted with water containing a surface active agent, the improvement in combination therewith comprising washing the soil from the soiled textile material with water containing the said surface active agent and a catalyst, the catalyst being present in a catalytically effect amount which increases the rate of removal of the soil from the textile material, the catalyst being prepared by a process comprising admixing a water soluble alkali metal silicate with an aqueous medium containing a dissolved substance which is a source of calcium ion and a dissolved substance which is a source of magnesium ion,
the aqueous medium containing said dissolved substances in amounts to provide between about I X 10 and l X 10 mole per liter each of calcium ion and magnesium ion,
the aqueous medium containing said dissolved substances in amounts to provide a molar ratio of calcium ion to magnesium ion between about 2.0:l.0 and 1.0120,
the alkali metal silicate having an alkali metal oxide to silicon dioxide ratio between about 09:10 and less than 2.0: l .0 and being admixed with the aqueous medium in an amount of about 0.05-2 mole per liter,
reacting the alkali metal silicate with said dissolved substances providing calcium ion and magnesium ion to produce an aqueous colloidal suspension of particles of the reaction product,
admixing a micelle-forming surfactant with the aqueous medium in an amount to form catalyst micelles comprising said colloidal particles upon agitating the aqueous medium, and
agitating the aqueous medium containing the colloidal particles and surfactant to form said catalyst micelles.
2. The method of claim 1 wherein in the process for preparing the catalyst, said ratio of calcium ion to magnesium ion is between about 1.5110 and l.0:l.5.
3. The method of claim 1 wherein in the process for preparing the catalyst, said ratio of calcium ion to magnesium ion is about l.0:l.0.
4. The method of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about l X 10 and 6 X 10 mole per liter each of calcium ion and magnesium ion.
5. The method of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 2.5 X 10 and 3.0 X 10' mole per liter each of calcium ion and magnesium ion.
6. The method of claim 1 wherein in the process for preparing the catalyst, about 0.2-0.5 mole per liter of the alkali metal silicate is admixed with the aqueous medium.
7. The method of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio between about 0921.0 and l.2:l.0.
8. The method of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is alkali metal metasilicate having an alkali metal oxide to silicon dioxide ratio of about 1.0:1 .0.
9. The method of claim 1 wherein in the process for preparing the catalyst, about 0.0l0.1 mole per liter of the surfactant is admixed with the aqueous medium.
10. The method of claim 1 wherein in the process for preparing the catalyst, the surfactant comprises sulfated castor oil.
11. The method of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 1 X and 6 X 10 mole per liter each of calcium ion and magnesium ion, the ratio of calcium ion to magnesium ion is between about l.5:1.0 and 1021.5, about 0.2-0.5 mole per liter of the alkali metal silicate is admixed with the aqueous medium, and the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio between about 0921.0 and l.2:l.0.
12. The method of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 2.5 X 10 and 3.0 X 10 mole per liter each of calcium ion and magnesium ion, the aqueous medium contains about equimolar amounts of calcium ion and magnesium ion, about 0.2-0.3 mole per liter of the al kali metal silicate is admixed with the aqueous medium, and the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio of about l.0:l.O.
13. The method of claim 12 wherein in the process for preparing the catalyst, the alkali metal metasilicate is sodium metasilicate having an alkali metal oxide to silicon dioxide ratio of about 10:1 .0.
14. The method of claim 12 wherein in the process for preparing the catalyst, about 0.010.l mole per liter of the surfactant is admixed with the aqueous medium.
15. The method of claim 14 wherein in the process for preparing the catalyst, the surfactant comprises sulfated castor oil.
16. The method of claim 15 wherein in the process for preparing the catalyst, the alkali metal metasilicate is sodium metasilicate having a sodium oxide to silicon dioxide ratio of about 1.0:l'.0.
17. The method of claim 16 wherein in the process for preparing the catalyst, at least 25 percent of the hydroxy groups of the castor oil are sulfated, and about 0.03-0.07 mole per liter of the sulfated castor oil is admixed with the aqueous medium.
18. The method of claim 12 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide about 2.9 X 10" mole per liter of calcium ion and about 2.7 X 10* mole per liter of magnesium ion, about 0.25 mole per liter of sodium metasilicate having a sodium oxide to silicon dioxide ratio of about l.0:l.0 is admixed with the aqueous medium, the aqueous medium contains not more than 10 parts per million by weight of carbonate ion and bicarbonate ion, the surfactant comprises sulfated castor oil and at least 50 percent of the hydroxy groups of the castor oil are sulfated, and about 0.05 mole per liter of the sulfated castor oil is admixed with the aqueous medium.
Claims (18)
1. IN A METHOD OF WASHING SOIL FROM SOILED TEXTILE MATERIAL WHEREIN THE TEXTILE MATERIAL IS INTIMATELY CONTACTED WITH WATER CONTAINING A SURFACE ACTIVE AGENT, THE IMPROVEMENT IN COMBINATION THEREWITH COMPRISING WASHING THE SOIL FROM THE SOILED TEXTILE MATERIAL WITH WATER CONTAINING THE SAID SURFACE ACTIVE AGENT AND A CATALYST, THE CATALYST BEING PRESENT IN A CATALYTICALLY EFFECT AMOUNT WHICH INCREASE THE RATE OF REMOVAL OF THE SOIL FROM THE TEXTILE MATERIAL, THE CATALYST BEING PREPARED BY A PROCESS COMPRISING ADMIXING A WATER SOLUBLE ALKALI METAL SILICATE WITH AN AQUEOUS MEDIUM CONTAINING A DISSOLVED SUBSTANCE WHICH IS A SOURCE OF CALCIUM ION AND A DISSOLVED SUBSTANCE WHICH IS A SOURCE OF MAGNESIUM ION, THE AQUEOUS MEDIUM CONTAINING SAID DISSOLVED SUBSTANCES IN AMOUNTS TO PROVIDE BETWEEN ABOUT 1 X 10**4 AND 1 x 10**1 MOLE PER LITER EACH OF CALCIUM ION AND MAGNESIUM ION, THE AQUEOUS MEDIUM CONTAINING SAID DISSOLVED SUBSTANCES IN AMOUNTS TO PROVIDE A MOLAR RATIO OF CALCIUM ION TO MAGNESIUM ION BETWEEN ABOUT 2.0:1.0 AND 1.0:2.0, THE ALKALI METAL SILICATE HAVING AN ALKALI METAL OXIDE TO SILICON DIOXIDE RATIO BETWEEN ABOUT 0.9:1.0 AND LESS THAN 2.0:1.0 AND BEING ADMIXED WITH THE AQUEOUS MEDIUM IN AN AMOUNT OF ABOUT 0.05-2 MOLE PER LITER, REACTING THE ALKALI METAL SILICATE WITH SAID DISSOLVED SUBSTANCES PROVIDING CALCIUM ION AND MAGNESIUM ION TO PRODUCE AN AQUEOUS COLLOIDAL SUSPENSION OF PARTICLES OF THE REACTION PRODUCT, ADMIXING A MICELLE-FORMING SURFACTANT WITH THE AQUEOUS MEDIUM IN AN AMOUNT TO FORM CATALYST MICELLES COMPRISING SAID COLLOIDAL PARTICLES UPON AGITATING THE AQUEOUS MEDIUM, AND AGITATING THE AQUEOUS MEDIUM CONTAINING THE COLLIODAL PARTICLES AND SURFACTANT TO FORM SAID CATALYST MICELLES.
2. The method of claim 1 wherein in the process for preparing the catalyst, said ratio of calcium ion to magnesium ion is between about 1.5:1.0 and 1.0:1.5.
3. The method of claim 1 wherein in the process for preparing the catalyst, said ratio of calcium ion to magnesium ion is about 1.0:1.0.
4. The method of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 1 X 10 3 and 6 X 10 3 mole per liter each of calcium ion and magnesium ion.
5. The method of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 2.5 X 10 3 and 3.0 X 10 3 mole per liter each of calcium ion and magnesium ion.
6. The method of claim 1 wherein in the process for preparing the catalyst, about 0.2-0.5 mole per liter of the alkali metal silicate is admixed with the aqueous medium.
7. The method of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio between about 0.9:1.0 and 1.2:1.0.
8. The method of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is alkali metal metasilicate having an alkali metal oxide to silicon dioxide ratio of about 1.0:1.0.
9. The method of claim 1 wherein in the process for preparing the catalyst, about 0.01-0.1 mole per liter of the surfactant is admixed with the aqueous medium.
10. The method of claim 1 wherein in the process for preparing the catalyst, the surfactant comprises sulfated castor oil.
11. The method of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 1 X 10 3 and 6 X 10 3 mole per liter each of calcium ion and magnesium ion, the ratio of calcium ion to magnesium ion is between about 1.5:1.0 and 1.0:1.5, about 0.2-0.5 mole per liter of the alkali metal silicate is admixed with the aqueous medium, and the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio between about 0.9:1.0 and 1.2:1.0.
12. The method of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 2.5 X 10 3 and 3.0 X 10 3 mole per liter each of calcium ion and magnesium ion, the aqueous medium contains about equimolar amounts of calcium ion and magnesium ion, about 0.2-0.3 mole per liter of the alkali metal silicate is admixed with the aqueous medium, and the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio of about 1.0: 1.0.
13. The method of claim 12 wherein in the process for preparing the catalyst, the alkali metal metasilicate is sodium metasilicate having an alkali metal oxide to silicon dioxide ratio of about 1.0:1.0.
14. The method of claim 12 wherein in the process for preparing the catalyst, about 0.01-0.1 mole per liter of the surfactant is admixed with the aqueous medium.
15. The method of claim 14 wherein in the process for preparing the catalyst, the surfactant comprises sulfated castor oil.
16. The method of claim 15 wherein in the process for preparing the catalyst, the alkali metal metasilicate is sodium metasilicate having a sodium oxide to silicon dioxide ratio of about 1.0:1.0.
17. The method of claim 16 wherein in the process for preparing the catalyst, at least 25 percent of the hydroxy groups of the castor oil are sulfated, and about 0.03-0.07 mole per liter of the sulfated castor oil is admixed with the aqueous medium.
18. The method of claim 12 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide about 2.9 X 10 3 mole per liter of calcium ion and about 2.7 X 10 3 mole per liter of magnesium ion, about 0.25 mole per liter of sodium metasilicate having a sodium oxide to silicon dioxide ratio of about 1.0:1.0 is admixed with the aqueous medium, the aqueous medium contains not more than 10 parts per million by weight of carbonate ion and bicarbonate ion, the surfactant comprises sulfated castor oil and at least 50 percent of the hydroxy groups of the castor oil are sulfated, and about 0.05 mole per liter of the sulfated castor oil is admixed with the aqueous medium.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US05/388,774 US3931031A (en) | 1973-08-16 | 1973-08-16 | Surface active compositions |
US388776A US3874927A (en) | 1973-08-16 | 1973-08-16 | Method of washing soiled culinary articles |
US388775A US3864475A (en) | 1973-08-16 | 1973-08-16 | Method of treating human hair to enhance softness and improve the general appearance thereof |
US389542A US3923456A (en) | 1973-08-16 | 1973-08-20 | Method of washing textile materials with surface-active agent and catalyst-containing micelles |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US05/388,774 US3931031A (en) | 1973-08-16 | 1973-08-16 | Surface active compositions |
US388776A US3874927A (en) | 1973-08-16 | 1973-08-16 | Method of washing soiled culinary articles |
US388775A US3864475A (en) | 1973-08-16 | 1973-08-16 | Method of treating human hair to enhance softness and improve the general appearance thereof |
US389542A US3923456A (en) | 1973-08-16 | 1973-08-20 | Method of washing textile materials with surface-active agent and catalyst-containing micelles |
Publications (1)
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US3923456A true US3923456A (en) | 1975-12-02 |
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US388775A Expired - Lifetime US3864475A (en) | 1973-08-16 | 1973-08-16 | Method of treating human hair to enhance softness and improve the general appearance thereof |
US388776A Expired - Lifetime US3874927A (en) | 1973-08-16 | 1973-08-16 | Method of washing soiled culinary articles |
US05/388,774 Expired - Lifetime US3931031A (en) | 1973-08-16 | 1973-08-16 | Surface active compositions |
US389542A Expired - Lifetime US3923456A (en) | 1973-08-16 | 1973-08-20 | Method of washing textile materials with surface-active agent and catalyst-containing micelles |
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US388775A Expired - Lifetime US3864475A (en) | 1973-08-16 | 1973-08-16 | Method of treating human hair to enhance softness and improve the general appearance thereof |
US388776A Expired - Lifetime US3874927A (en) | 1973-08-16 | 1973-08-16 | Method of washing soiled culinary articles |
US05/388,774 Expired - Lifetime US3931031A (en) | 1973-08-16 | 1973-08-16 | Surface active compositions |
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US5466680A (en) * | 1992-03-26 | 1995-11-14 | Cytologics, Inc. | Method and compositions for enhancing white blood cell functioning on a mucosal or cutaneous surface |
US5929008A (en) * | 1997-09-29 | 1999-07-27 | The Procter & Gamble Company | Liquid automatic dishwashing compositions providing high pH wash solutions |
US5895781A (en) * | 1997-12-22 | 1999-04-20 | S. C. Johnson & Son, Inc. | Cleaning compositions for ceramic and porcelain surfaces and related methods |
US6376456B1 (en) | 1998-10-27 | 2002-04-23 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Wrinkle reduction laundry product compositions |
US6426328B2 (en) | 1998-10-27 | 2002-07-30 | Unilever Home & Personal Care, Usa Division Of Conopco Inc. | Wrinkle reduction laundry product compositions |
US6403548B1 (en) | 1998-10-27 | 2002-06-11 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Wrinkle reduction laundry product compositions |
US6457481B1 (en) * | 2000-09-28 | 2002-10-01 | Gaylord Industries, Inc. | Wash water recirculation unit and system for kitchen ventilators and related ventilation equipment |
US7104269B2 (en) * | 2000-12-08 | 2006-09-12 | Appliance Scientific, Inc. | Residential dishwasher |
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US9752105B2 (en) | 2012-09-13 | 2017-09-05 | Ecolab Usa Inc. | Two step method of cleaning, sanitizing, and rinsing a surface |
US9994799B2 (en) | 2012-09-13 | 2018-06-12 | Ecolab Usa Inc. | Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use |
US8871699B2 (en) | 2012-09-13 | 2014-10-28 | Ecolab Usa Inc. | Detergent composition comprising phosphinosuccinic acid adducts and methods of use |
US20140308162A1 (en) | 2013-04-15 | 2014-10-16 | Ecolab Usa Inc. | Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing |
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Also Published As
Publication number | Publication date |
---|---|
US3864475A (en) | 1975-02-04 |
US3874927A (en) | 1975-04-01 |
US3931031A (en) | 1976-01-06 |
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