CA2231691C - Compositions comprising hydrophilic silica particulates - Google Patents
Compositions comprising hydrophilic silica particulates Download PDFInfo
- Publication number
- CA2231691C CA2231691C CA002231691A CA2231691A CA2231691C CA 2231691 C CA2231691 C CA 2231691C CA 002231691 A CA002231691 A CA 002231691A CA 2231691 A CA2231691 A CA 2231691A CA 2231691 C CA2231691 C CA 2231691C
- Authority
- CA
- Canada
- Prior art keywords
- detergent
- surfactant
- silica
- composition
- compositions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000000203 mixture Substances 0.000 title claims abstract description 188
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 65
- 239000003599 detergent Substances 0.000 claims abstract description 122
- 239000004094 surface-active agent Substances 0.000 claims abstract description 96
- 238000000034 method Methods 0.000 claims abstract description 28
- -1 alkyl ether sulfate Chemical class 0.000 claims description 58
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 16
- 239000003945 anionic surfactant Substances 0.000 claims description 12
- 239000002671 adjuvant Substances 0.000 claims description 9
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 230000009969 flowable effect Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000002563 ionic surfactant Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 125000005011 alkyl ether group Chemical group 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 description 43
- 239000007844 bleaching agent Substances 0.000 description 36
- 239000002689 soil Substances 0.000 description 33
- 239000000463 material Substances 0.000 description 32
- 150000003839 salts Chemical class 0.000 description 29
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 239000012190 activator Substances 0.000 description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 19
- 102000004190 Enzymes Human genes 0.000 description 18
- 108090000790 Enzymes Proteins 0.000 description 18
- 229940088598 enzyme Drugs 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 18
- 239000011734 sodium Substances 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 17
- 229920001296 polysiloxane Polymers 0.000 description 17
- 229910052708 sodium Inorganic materials 0.000 description 17
- 235000014113 dietary fatty acids Nutrition 0.000 description 15
- 239000000194 fatty acid Substances 0.000 description 15
- 229930195729 fatty acid Natural products 0.000 description 15
- 239000004615 ingredient Substances 0.000 description 15
- 229920005646 polycarboxylate Polymers 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 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 14
- 239000002253 acid Substances 0.000 description 14
- 150000001412 amines Chemical class 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 12
- 239000010457 zeolite Substances 0.000 description 12
- 239000002202 Polyethylene glycol Substances 0.000 description 11
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 229910000323 aluminium silicate Inorganic materials 0.000 description 11
- 229910001424 calcium ion Inorganic materials 0.000 description 11
- 239000000975 dye Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000004367 Lipase Substances 0.000 description 9
- 102000004882 Lipase Human genes 0.000 description 9
- 108090001060 Lipase Proteins 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 239000002738 chelating agent Substances 0.000 description 9
- 235000019421 lipase Nutrition 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 8
- 229920002678 cellulose Polymers 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 229910001425 magnesium ion Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 125000002947 alkylene group Chemical group 0.000 description 7
- 125000003118 aryl group Chemical class 0.000 description 7
- 238000004061 bleaching Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 229920000768 polyamine Polymers 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001204 N-oxides Chemical class 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 235000010338 boric acid Nutrition 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000003752 hydrotrope Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 102000003992 Peroxidases Human genes 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 5
- 230000002538 fungal effect Effects 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 150000004760 silicates Chemical class 0.000 description 5
- 235000019832 sodium triphosphate Nutrition 0.000 description 5
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 108091005804 Peptidases Proteins 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 229940025131 amylases Drugs 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000002979 fabric softener Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000004900 laundering Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 4
- WLDGDTPNAKWAIR-UHFFFAOYSA-N 1,4,7-trimethyl-1,4,7-triazonane Chemical compound CN1CCN(C)CCN(C)CC1 WLDGDTPNAKWAIR-UHFFFAOYSA-N 0.000 description 3
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 3
- 108010084185 Cellulases Proteins 0.000 description 3
- 102000005575 Cellulases Human genes 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BCXBKOQDEOJNRH-UHFFFAOYSA-N NOP(O)=O Chemical class NOP(O)=O BCXBKOQDEOJNRH-UHFFFAOYSA-N 0.000 description 3
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 108010056079 Subtilisins Proteins 0.000 description 3
- 102000005158 Subtilisins Human genes 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 235000019418 amylase Nutrition 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000019864 coconut oil Nutrition 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 159000000001 potassium salts Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003333 secondary alcohols Chemical class 0.000 description 3
- 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 3
- 239000007787 solid Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- XMVBHZBLHNOQON-UHFFFAOYSA-N 2-butyl-1-octanol Chemical compound CCCCCCC(CO)CCCC XMVBHZBLHNOQON-UHFFFAOYSA-N 0.000 description 2
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 description 2
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 2
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- 108700020962 Peroxidase Proteins 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical compound CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 230000001851 biosynthetic effect Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000005282 brightening Methods 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
- 150000007942 carboxylates Chemical group 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 229940071087 ethylenediamine disuccinate Drugs 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
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- 239000001530 fumaric acid Substances 0.000 description 1
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- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
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- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 229910052739 hydrogen Chemical group 0.000 description 1
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- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical class OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 108010062085 ligninase Proteins 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- FODOUIXGKGNSMR-UHFFFAOYSA-L magnesium;2-oxidooxycarbonylbenzoate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-]OC(=O)C1=CC=CC=C1C([O-])=O FODOUIXGKGNSMR-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- VPOLVWCUBVJURT-UHFFFAOYSA-N pentadecasodium;pentaborate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] VPOLVWCUBVJURT-UHFFFAOYSA-N 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000002797 proteolythic effect Effects 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- MSLRPWGRFCKNIZ-UHFFFAOYSA-J tetrasodium;hydrogen peroxide;dicarbonate Chemical compound [Na+].[Na+].[Na+].[Na+].OO.OO.OO.[O-]C([O-])=O.[O-]C([O-])=O MSLRPWGRFCKNIZ-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention relates to structured surfactant compositions comprisi ng a detergent surfactant and hydrophilic silica particulates to be used in granular detergent compositions. The preferred silica particulate is hydrophilic precipitated silica. The process for making a structured surfactant composition comprising a detergent surfactant and hydrophilic silica particulates is also included. The present invention encompasses a structured surfactant composition consisting essentially of: (a) from about 35 % to about 60 % of a detergent surfactant; (b) from about 1 % to about 20 % of hydrophylic, finely-divided silica particulate; and (c) from about 15 % to about 25 % moisture.
Description
COMPOSITIONS COMPRISING HYDROPHILIC SILICA PARTICULATES
FIELD OF THE INVENTION
The present invention relates to structured surfactant compositions comprising a detergent surfactant and hydrophilic silica particulates to be used in granular detegent compositions. The preferred silica particulate is hydrophilic precipitated silica. The process for making a structured surfactant composition comprising a detergent surfactant and hydrophilic silica particulates is also included.
BACKGROUND OF THE INVENTION
It is desired to increase the active level of detergent surfactants in compositions comprising said surfactants in order to facilitate the manufacture of detergent compositions containing high active levels. In addition, it is also desirable to have surfactant compositions that are pumpable and generally easy to transport and transfer from one manufacturing location to a granulation site. One way to meet these needs is by mixing a chemical structuring agent to the detergent surfactant. Prior art includes EPO 508 543 published October 14, 1992 and U.S. 4,925,585 granted May I5, 1990.
It has now been found that incorporating hydrophilic, finely-divided silica particulates as a highly-preferred structuring agent with detergent surfactant enables the formation of structured surfactant compositions which have high levels of active. Preferably, the detergent surfactant is in an aqueous paste form. Structuring of the paste means the addition of a chemical in a solid, liquid, or solution form to change the structure of the paste or modify its physical characteristics to facilitate the manufacture of high active detergent agglomerates which otherwise are not easily obtainable under normal operating conditions. In addition, when such structured surfactant compositions are mixed with other detergent adjuvants such as additional surfactants, detergent builders, inorganic salts, silica, and mixtures thereof to form granular detergent compositions, such granules are free flowing and easy to transport and transfer.
SUMMARY OF THE INVENTION
The invention encompasses a structured surfactant composition consisting essentially of (a) from about 35% to about 60% of a detergent surfactant;
(b) from about 1% to about 20% of hydrophilic, finely-divided silica particulate; and (c) from about I S% to about 25% moisture.
SUBSTiTi.~ T E Si~iEcT (RULE 26) The invention further encompasses a granular detergent composition comprising:
(a) from about 2% to about 70% of a structured surfactant composition, the surfactant composition consisting essentially of (i) from about 35% to about 60% of a detergent surfactant;
(ii) from about 1% to about 20% of hydrophilic, finely-divided silica particulate; and (iii) from about 15% to about 25% moisture; and (b) from about 30% to about 98% other detergent adjuvanu selected from the group consisting of other detergent surfactants, detergent builders, silica, and mixtures thereof.
A process for making structured surfactant compositions is also included.
This invention relates to compositions with a detergent surfactant and hydrophilic, finely-divided silica particulate.
ingredients, as well as optional ingredients, as well as the process for making a granular detergent composition or an additive composition for a detergent composition are descrilxd in detail hereinafter.
Structured Surfactant Comtrosition The structured surfactant composition of the present invention comprises by weight:
(a) from about 35% to about 60%, preferably from about 35% to about SO%, most preferably from about 40% to about 45% of a detergent surfactant;
(b) from about I% to about 20%, preferably from about 1% to about 10%, most preferably from about 2% to about 5%, of hydrophilic, finely-divided silica particulate; and (c) from about 15% to about 25% moisture, wherein the ratio of the silica particulate to moisture is from about 1 : 5 to about I : 25, more preferably from about I : 5 to about I : 7.5.
The structured surfactant composition can be mixed with other detergent ingredients to form detergent compositions. If the structured surfactant is directly made into a detergent composition, the detergent composition would comprise from about 20% to about 65%, preferably from about 30% to about 65%, most preferably from about 45% to about 65% structured surfactant composition. The granular detergent composition preferably has a particle size of a maximum of 5% on 14 Tyler mesh.
The particulate silica is added to the surfactant paste, which typically contains 15% to about 25% moisture; as well as salts which are the by-product of neutralization. The particulate silica absorbs the water and a hardened continuous paste is formed. When shear force is applied to the hardened paste, the paste becomes a flowable liquid, which is easily dispersed into fine droplets by using any conventional high-shear agglomerating mixer. The droplets are added with other powder ingredients to form individual particles with have a particle size of a maximum of 5% on 14 Tyler mesh and a minimum of 5% through 100 Tyler mesh. The droplets form particles inside a typical agglomerating mixer. These droplets once formed into a particle, do not re-form a continuous hardened paste. This results in the formation of particle agglomerates to the specific particle size distribution that is required to maintain solubility, handling, etc.
Detereent Surfactant The detergent surfactant is any surfactant selected from the group of consisting of anionics, zwitterionics, ampholytics, cationics, and mixtures thereof. Preferably, the detergent surfactant is anionic surfactant. Most preferably, the detergent surfactant is ethoxylated anionic surfactant.
The anionic surfactant can be selected from:
(a) linear or branched chain alkyl benzene sulfonate having an C8-20 alkyl chain, preferably CIO-18 alkyl chain, and most preferably a C12-16 alkyl chain;
(b) alkyl sulfate having a C8-20 alkyl chain, preferably C 14-18 alkyl chain, most preferably C 12-16 alkyl chain;
(c) mixtures thereof.
Preferred is Alkylalkoxy sulfate comprising an alkyl portion of from 6 to 18 carbon atoms and an alkoxy portion comprising, an average, from about 0.5 to about 20 moles of alkoxy, preferably ethoxy, units, more preferably from about 0.5 to about 5 ethoxy units.
An anionic surfactant that is most preferable is the alkyl ether sulfate of the formula R-EnS03M, wherein:
(i) R is C8-20; and preferably, C12-I5, alkyl chain (mixed chain);
(ii) E is an ethoxy unit;
v (iii) n is from I-20; preferably, n=3; and (iv) M is a suitable cation, preferably sodium ion.
SUBSTITUTE SHEET (RULE 26) Useful anionic surfactants include water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Water-soluble salts of the higher fatty acids, i.e., "soaps", also are useful anionic surfactants herein. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Examples of soaps are the sodium, potassium, ammonium, and alkylolamonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soaps.
Other anionic surfactants useful herein include:
Sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil;
Sodium coconut oil fatty acid monoglyceride sulfonates and sulfates;
Sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates, and sodium or potassium salts of methyl ester R-CH(S03M)-COOR', wherein R is Cg-C22 alkyl or alkenyl, R' is C 1-C4 alkyl, and M is a counter ion, preferably Na or K, such as disclosed in WO-93-05013, published March 18, 1992; sulfonates;
Alpha-sulfonated fatty acid alkyl ether surfactant of the formula R'-C(S03)H-C(O)-OR", wherein R' is C8-20; most preferably C8-18, alkyl chain; and R" is CI-C4 alkyl, preferably methyl;
Secondary alkyl sulfates having an alkyl chain of from i0 to 20 carbon atoms;
and Alkyl ethoxy carboxylates of the formula RO(CH2CH20)xCH2C00-M+, wherein R is a C6 to C I g alkyl; x ranges from 0 to 10, and the ethoxylate distribution is such that on a weight basis, the amount of material where x is 0 is less than 20%, the amount of material where x is greater than 7 is less than 25%, and wherein the average x is 2-4 when the average R
is C13 or less, and is 3-6 when R is greater than C13; and M is an alkali metal, alkali earth metal, ammonium, ' mono-, dl-, and tri-ethanol ammonium.
SUBSTITUTE SHEET (RULE 26) One or various aqueous pastes of the salts of anionic surfactants is preferred for use in the present invention, It is preferred that the moisture in the surfactant aqueous paste is as low as possible, while maintaining paste fluidity, and minimizing the amount of free water that may need to be removed, by drying for example, since low moisture leads to a higher concentration of the surfactant 5 in the finished particle. Preferably the paste contains from about 10% to about 40% water, more preferably from about IS% to about 30% water, and most preferably from about 20% to about 30%
water.
The activity of the surfactant paste is at least 30% and can go up to about 90%; preferred activities are: 70-80%.
Cationic surfactants can also be used as a detergent surfactant herein and suitable quaternary ammonium surfactants are selected from mono C6-C 16, preferably C6-C I0 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
Ampholytic surfactants can also be used as a detergent surfactant herein, which include aliphatic derivatives of heterocyclic secondary and tertiary amines;
zwitterionic surfactants which include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds;
water-soluble salts of esters of alpha-sulfonated fatty acids; alkyl ether sulfates; water-soluble salts of olefin sulfonates; beta-alkyloxy alkane sulfonates; betaines having the formula R(R I )2N+R2C00-, wherein R is a C6-C 1 g hydrocarbyl group, preferably a C I
0-C I 6 alkyl group or Clp-C16 acylamido alkyl group, each RI is typically CI-C3 alkyl, preferably methyl and R2 is a CI-C5 hydrocarbyl group, preferably a CI-C3 alkylene group, more preferably a CI-C2 alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C12-14 acylamidopropylbetaine; Cg_14 acylamidohexyldiethyl betaine; 4[C14-16 acylmethylamidodiethylammonio]-I-carboxybutane; C16-18 acylamidodimethylbetaine;
C12-16 acylamidopentanediethylbetaine; and [C12-16 acylmethylamidodimethylbetaine. Preferred betaines are C12-18 d~ethy!-ammonio hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines; and the sultaines having the formula (R(RI)2N+R2S03- wherein R is a C6-Clg hydrocarbyl group, preferably a C I0-C 16 alkyl group, more preferably a C 12-C 13 amyl ~'oup, each R I is typically C 1-C3 alkyl, preferably methyl, and R2 is a C1-C6 hydrocarbyl group, preferably a CI-C3 alkylene or, preferably, hydroxyalkylene group. Examples of suitable sultaines include C 12-dimethylammonio-2-hydroxypropyl sulfonate, C 12-C 14 arnido propyl ammonio-2-hydroxypropyl sultaine, C 12-C 14 d~Y~oxyethylammonio propane sulfonate, and C 16-18 d~ethylammonio hexane sulfonate, with C12-14 ~ido propyl ammonio-2-hydroxypropyl sultaine being preferred.
SUBSTITUTE SHEET (RULE 26) Hvdrovhilic Silica Particulates The structured surfactant compositions of the present invention contains, in addition to a detergent surfactant, from about 0.2% to about 20%, preferably from about I%
to about 10%, most preferably from about 2% to about 5%, of hydrophilic, finely-divided silica particulate. Preferably, the particulate is a hydrophilic precipitated silica. Such materials are extremely fine-panicle size silicon dioxides. Its surface area ranges preferably from 140 to 550 m2/g as measured by the BET
nitrogen adsorption method. The surface of the silica has both internal and external surface area which allows for the easy. absorption of liquids. Dibutyl Phthlate absorption is the method used to determine the absorptive capability of precepitated silica. Generally, a precipitated silica can adsorb 2 to 3 times its weight.
Precipitated silica materials usually appear in the form of agglomerates. The average agglomerate siu of the silica range from about 50 to 100 microns. The silica agglomerates may be milled by various known methods to reduce the agglomerate size to the range of 2 to I S microns. The pH of the silica is normally from about 5.5 to about 7Ø
The hydrophilic silica can also be a fumed silica. Hydrophilic precipitated silica materials useful herein are commercially available from Degussa Corporation under the trade marks SIPERNAT
22S, 22LS, SOS.
Deterttent Adiuvanu Preferably, the detergent adjuvanu are from about 35% to about 99% of the detergent composition. The compositions herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrsu to be cleaned, or to modify the aesthetics of the detergent composition (e.g..
perfumes, coloranu, dyes, etc.). The following are illustrative examples of such adjunct materials.
Other detergent surfactanu include surfactanu described above. In addition, a hydrotrope, or mixture of hydrotropes, can be present in the laundry detergent bar.
Preferred hydrotropes include the alkali metal, preferably sodium, salts of tolune sulfonate, xylene sulfonate, cumene sulfonate, sulfosuccinate, and mixtures thereof. Preferably, the hydrotrope, in either the acid form or the salt form, and being substantially anhydrous, is added to the linear alkyl benune sulfonic acid prior to iu neutralization. The hydrotrope will preferably be present at from about 0.5% to about 5% of the laundry detergent bar.
FIELD OF THE INVENTION
The present invention relates to structured surfactant compositions comprising a detergent surfactant and hydrophilic silica particulates to be used in granular detegent compositions. The preferred silica particulate is hydrophilic precipitated silica. The process for making a structured surfactant composition comprising a detergent surfactant and hydrophilic silica particulates is also included.
BACKGROUND OF THE INVENTION
It is desired to increase the active level of detergent surfactants in compositions comprising said surfactants in order to facilitate the manufacture of detergent compositions containing high active levels. In addition, it is also desirable to have surfactant compositions that are pumpable and generally easy to transport and transfer from one manufacturing location to a granulation site. One way to meet these needs is by mixing a chemical structuring agent to the detergent surfactant. Prior art includes EPO 508 543 published October 14, 1992 and U.S. 4,925,585 granted May I5, 1990.
It has now been found that incorporating hydrophilic, finely-divided silica particulates as a highly-preferred structuring agent with detergent surfactant enables the formation of structured surfactant compositions which have high levels of active. Preferably, the detergent surfactant is in an aqueous paste form. Structuring of the paste means the addition of a chemical in a solid, liquid, or solution form to change the structure of the paste or modify its physical characteristics to facilitate the manufacture of high active detergent agglomerates which otherwise are not easily obtainable under normal operating conditions. In addition, when such structured surfactant compositions are mixed with other detergent adjuvants such as additional surfactants, detergent builders, inorganic salts, silica, and mixtures thereof to form granular detergent compositions, such granules are free flowing and easy to transport and transfer.
SUMMARY OF THE INVENTION
The invention encompasses a structured surfactant composition consisting essentially of (a) from about 35% to about 60% of a detergent surfactant;
(b) from about 1% to about 20% of hydrophilic, finely-divided silica particulate; and (c) from about I S% to about 25% moisture.
SUBSTiTi.~ T E Si~iEcT (RULE 26) The invention further encompasses a granular detergent composition comprising:
(a) from about 2% to about 70% of a structured surfactant composition, the surfactant composition consisting essentially of (i) from about 35% to about 60% of a detergent surfactant;
(ii) from about 1% to about 20% of hydrophilic, finely-divided silica particulate; and (iii) from about 15% to about 25% moisture; and (b) from about 30% to about 98% other detergent adjuvanu selected from the group consisting of other detergent surfactants, detergent builders, silica, and mixtures thereof.
A process for making structured surfactant compositions is also included.
This invention relates to compositions with a detergent surfactant and hydrophilic, finely-divided silica particulate.
ingredients, as well as optional ingredients, as well as the process for making a granular detergent composition or an additive composition for a detergent composition are descrilxd in detail hereinafter.
Structured Surfactant Comtrosition The structured surfactant composition of the present invention comprises by weight:
(a) from about 35% to about 60%, preferably from about 35% to about SO%, most preferably from about 40% to about 45% of a detergent surfactant;
(b) from about I% to about 20%, preferably from about 1% to about 10%, most preferably from about 2% to about 5%, of hydrophilic, finely-divided silica particulate; and (c) from about 15% to about 25% moisture, wherein the ratio of the silica particulate to moisture is from about 1 : 5 to about I : 25, more preferably from about I : 5 to about I : 7.5.
The structured surfactant composition can be mixed with other detergent ingredients to form detergent compositions. If the structured surfactant is directly made into a detergent composition, the detergent composition would comprise from about 20% to about 65%, preferably from about 30% to about 65%, most preferably from about 45% to about 65% structured surfactant composition. The granular detergent composition preferably has a particle size of a maximum of 5% on 14 Tyler mesh.
The particulate silica is added to the surfactant paste, which typically contains 15% to about 25% moisture; as well as salts which are the by-product of neutralization. The particulate silica absorbs the water and a hardened continuous paste is formed. When shear force is applied to the hardened paste, the paste becomes a flowable liquid, which is easily dispersed into fine droplets by using any conventional high-shear agglomerating mixer. The droplets are added with other powder ingredients to form individual particles with have a particle size of a maximum of 5% on 14 Tyler mesh and a minimum of 5% through 100 Tyler mesh. The droplets form particles inside a typical agglomerating mixer. These droplets once formed into a particle, do not re-form a continuous hardened paste. This results in the formation of particle agglomerates to the specific particle size distribution that is required to maintain solubility, handling, etc.
Detereent Surfactant The detergent surfactant is any surfactant selected from the group of consisting of anionics, zwitterionics, ampholytics, cationics, and mixtures thereof. Preferably, the detergent surfactant is anionic surfactant. Most preferably, the detergent surfactant is ethoxylated anionic surfactant.
The anionic surfactant can be selected from:
(a) linear or branched chain alkyl benzene sulfonate having an C8-20 alkyl chain, preferably CIO-18 alkyl chain, and most preferably a C12-16 alkyl chain;
(b) alkyl sulfate having a C8-20 alkyl chain, preferably C 14-18 alkyl chain, most preferably C 12-16 alkyl chain;
(c) mixtures thereof.
Preferred is Alkylalkoxy sulfate comprising an alkyl portion of from 6 to 18 carbon atoms and an alkoxy portion comprising, an average, from about 0.5 to about 20 moles of alkoxy, preferably ethoxy, units, more preferably from about 0.5 to about 5 ethoxy units.
An anionic surfactant that is most preferable is the alkyl ether sulfate of the formula R-EnS03M, wherein:
(i) R is C8-20; and preferably, C12-I5, alkyl chain (mixed chain);
(ii) E is an ethoxy unit;
v (iii) n is from I-20; preferably, n=3; and (iv) M is a suitable cation, preferably sodium ion.
SUBSTITUTE SHEET (RULE 26) Useful anionic surfactants include water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Water-soluble salts of the higher fatty acids, i.e., "soaps", also are useful anionic surfactants herein. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Examples of soaps are the sodium, potassium, ammonium, and alkylolamonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soaps.
Other anionic surfactants useful herein include:
Sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil;
Sodium coconut oil fatty acid monoglyceride sulfonates and sulfates;
Sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates, and sodium or potassium salts of methyl ester R-CH(S03M)-COOR', wherein R is Cg-C22 alkyl or alkenyl, R' is C 1-C4 alkyl, and M is a counter ion, preferably Na or K, such as disclosed in WO-93-05013, published March 18, 1992; sulfonates;
Alpha-sulfonated fatty acid alkyl ether surfactant of the formula R'-C(S03)H-C(O)-OR", wherein R' is C8-20; most preferably C8-18, alkyl chain; and R" is CI-C4 alkyl, preferably methyl;
Secondary alkyl sulfates having an alkyl chain of from i0 to 20 carbon atoms;
and Alkyl ethoxy carboxylates of the formula RO(CH2CH20)xCH2C00-M+, wherein R is a C6 to C I g alkyl; x ranges from 0 to 10, and the ethoxylate distribution is such that on a weight basis, the amount of material where x is 0 is less than 20%, the amount of material where x is greater than 7 is less than 25%, and wherein the average x is 2-4 when the average R
is C13 or less, and is 3-6 when R is greater than C13; and M is an alkali metal, alkali earth metal, ammonium, ' mono-, dl-, and tri-ethanol ammonium.
SUBSTITUTE SHEET (RULE 26) One or various aqueous pastes of the salts of anionic surfactants is preferred for use in the present invention, It is preferred that the moisture in the surfactant aqueous paste is as low as possible, while maintaining paste fluidity, and minimizing the amount of free water that may need to be removed, by drying for example, since low moisture leads to a higher concentration of the surfactant 5 in the finished particle. Preferably the paste contains from about 10% to about 40% water, more preferably from about IS% to about 30% water, and most preferably from about 20% to about 30%
water.
The activity of the surfactant paste is at least 30% and can go up to about 90%; preferred activities are: 70-80%.
Cationic surfactants can also be used as a detergent surfactant herein and suitable quaternary ammonium surfactants are selected from mono C6-C 16, preferably C6-C I0 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
Ampholytic surfactants can also be used as a detergent surfactant herein, which include aliphatic derivatives of heterocyclic secondary and tertiary amines;
zwitterionic surfactants which include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds;
water-soluble salts of esters of alpha-sulfonated fatty acids; alkyl ether sulfates; water-soluble salts of olefin sulfonates; beta-alkyloxy alkane sulfonates; betaines having the formula R(R I )2N+R2C00-, wherein R is a C6-C 1 g hydrocarbyl group, preferably a C I
0-C I 6 alkyl group or Clp-C16 acylamido alkyl group, each RI is typically CI-C3 alkyl, preferably methyl and R2 is a CI-C5 hydrocarbyl group, preferably a CI-C3 alkylene group, more preferably a CI-C2 alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C12-14 acylamidopropylbetaine; Cg_14 acylamidohexyldiethyl betaine; 4[C14-16 acylmethylamidodiethylammonio]-I-carboxybutane; C16-18 acylamidodimethylbetaine;
C12-16 acylamidopentanediethylbetaine; and [C12-16 acylmethylamidodimethylbetaine. Preferred betaines are C12-18 d~ethy!-ammonio hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines; and the sultaines having the formula (R(RI)2N+R2S03- wherein R is a C6-Clg hydrocarbyl group, preferably a C I0-C 16 alkyl group, more preferably a C 12-C 13 amyl ~'oup, each R I is typically C 1-C3 alkyl, preferably methyl, and R2 is a C1-C6 hydrocarbyl group, preferably a CI-C3 alkylene or, preferably, hydroxyalkylene group. Examples of suitable sultaines include C 12-dimethylammonio-2-hydroxypropyl sulfonate, C 12-C 14 arnido propyl ammonio-2-hydroxypropyl sultaine, C 12-C 14 d~Y~oxyethylammonio propane sulfonate, and C 16-18 d~ethylammonio hexane sulfonate, with C12-14 ~ido propyl ammonio-2-hydroxypropyl sultaine being preferred.
SUBSTITUTE SHEET (RULE 26) Hvdrovhilic Silica Particulates The structured surfactant compositions of the present invention contains, in addition to a detergent surfactant, from about 0.2% to about 20%, preferably from about I%
to about 10%, most preferably from about 2% to about 5%, of hydrophilic, finely-divided silica particulate. Preferably, the particulate is a hydrophilic precipitated silica. Such materials are extremely fine-panicle size silicon dioxides. Its surface area ranges preferably from 140 to 550 m2/g as measured by the BET
nitrogen adsorption method. The surface of the silica has both internal and external surface area which allows for the easy. absorption of liquids. Dibutyl Phthlate absorption is the method used to determine the absorptive capability of precepitated silica. Generally, a precipitated silica can adsorb 2 to 3 times its weight.
Precipitated silica materials usually appear in the form of agglomerates. The average agglomerate siu of the silica range from about 50 to 100 microns. The silica agglomerates may be milled by various known methods to reduce the agglomerate size to the range of 2 to I S microns. The pH of the silica is normally from about 5.5 to about 7Ø
The hydrophilic silica can also be a fumed silica. Hydrophilic precipitated silica materials useful herein are commercially available from Degussa Corporation under the trade marks SIPERNAT
22S, 22LS, SOS.
Deterttent Adiuvanu Preferably, the detergent adjuvanu are from about 35% to about 99% of the detergent composition. The compositions herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrsu to be cleaned, or to modify the aesthetics of the detergent composition (e.g..
perfumes, coloranu, dyes, etc.). The following are illustrative examples of such adjunct materials.
Other detergent surfactanu include surfactanu described above. In addition, a hydrotrope, or mixture of hydrotropes, can be present in the laundry detergent bar.
Preferred hydrotropes include the alkali metal, preferably sodium, salts of tolune sulfonate, xylene sulfonate, cumene sulfonate, sulfosuccinate, and mixtures thereof. Preferably, the hydrotrope, in either the acid form or the salt form, and being substantially anhydrous, is added to the linear alkyl benune sulfonic acid prior to iu neutralization. The hydrotrope will preferably be present at from about 0.5% to about 5% of the laundry detergent bar.
Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about I%
builder. Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about I S% to about SO% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly those having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Si05 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSix02x+I'YH20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2SiOg (NaSKS-6 form) is most preferred for use herein.
Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
- Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
Aluminosilicate builders include those having the empirical formula:
SUBSTITUTE SHEET (RULE 26) Mz(zAt02)y]~xH20 wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about I 5 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring , aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Na 12~(A102) 12(Si02) 12)~xH20 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A.
Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
~5 Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate"
refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of useful materials.
One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S.
Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability.
Citrates can also be used in SUBSTITUTE SHEET (RULE 26) granular compositions. especially in combination with zeolite andlor layered silicate builders.
Oxydisuccinates are also especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the 3,3~dicarboxy-4 oxa-!,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the CS-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myrisrylsuecinate, palmirylsuccinate, 2 dodecenylsuccinate (preferred), 2~pentadecenylsuccinate, and the like.
Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Ctvtchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S.
Patcnt 3,723.322.
Fatty acids, e.g., C12-Clg monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate andlor the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
Phosphonate builders such as ethane-1-hydroxy-1,1~diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3.422,021; 3.400,148 and 3,422,137) can also be used.
Hydrophilic silica particulates as described above is a preferred detergent adjuvant.
her Adiunct lnQredients Ch~latine Aeents ~ The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenedtamtne tetraproprtonates, triethylenetetraaminehexacetaus, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal.
ammonium, and substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUESt. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfvnctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 2I, 1974, to Connor et al.
Preferred compounds of this type in acid form arc dihydroxydisulfobenzenes such as 1.2-dihydroxy-3.5~disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704w33, November 3.
1987, to Harman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1 % to about 3.0% by weight of such compositions.
Clav Soil RemovaUAnti-redeeosition Agents - The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines;
liquid detergent compositions typically contain about 0.01 % to about 5%.
The most preferred soil release and anti-rcdeposition agent is ethoxylated tetraethylene-pentamine. Exemplary ethoxylated amines arc further described in U.S. Patent 4,597.898, VanderMeer, issued July t, 1986. Another group of preferred clay soil removal~antiredeposition agents arc the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removaUantiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published tune 27, 1984; the zwitterionic polymers disclosed in European Patent Appli-cation 112.592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal andlor anti redeposition agenu known in the art can also be utilized in the compositions herein. Another type of preferred antiredcposition agent includes the carboxy methyl cellulose (CMC) materials.
These materials are well known in the art.
Polymeric Disxrsina Aeents - Polymeric dispersing agenu can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite andlor layered silicate builders. Suitable polymeric dispersing agents include polymeric poiycarboxylates and polyethylene glycols, although others known in the art can also be used, It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents snhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can ' be polymerized to form suitable polymeric polycarboxylates include acrylic acid, malefic acid (or malefic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S.
Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and malefic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water soluble salts of such acrylic acidlmaleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG).
PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
SUBSTITUTE SHEET (RULE 26) Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders. Disposing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10.000.
Briehtener - Any optical brighteners or other brightening or whitening agents known in the alt can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5.5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York ( 1982).
Specific examples of optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal C8S and Tinopal SBM; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy:
the 2-(4-stryl-phenyl)-2H-napthol[ 1,2~d]triazoles; 4,4'-bis- ( 1.2,3-aiazol-2-yl}-stil- bones; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl- amino coumarin;
1,2-bis(-venzimidazol-2~yl)ethyiene; 1,3-diphenyl-phrazolines; 2.5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-(l,2-d]oxazole: and 2~(stilbene-4-yl)-2H-naphtho- (1.2-d]triazole.
See also U.S. Patent 3.646,015, issued February 29, 1972 to Hamilton. Anionic brighteners arc preferred herein.
Suds Suwressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489.5?4 and in front-loading European-style washing machines.
A wide variety. of materials may be used as suds suppressers, and suds suppressers are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, inc., 1979). One category of suds suppresser of particular interest encompasses monocarboxyiie fatty acid and soluble salts therein. See U.S. Patent 2.954,347, issued September 27. 1960 to Wayne St.
John. The monocarboxylic fatty acids and salts thereof used as suds suppresser typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds suppressers. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (r.g., fatty acid triglycerides), fatty acid esters of monovaient alcohols. aliphatic Clg-C40 ketones (t.g..
stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlorniazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g.. K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as para~ffm and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 50°C, and a minimum boiling point not less than about 1 10°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions.
Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraf~ins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds supprcssors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds suppressors are well known in the art and arc, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No.
354016, published February 7. 1990, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent 3.455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25°C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3Si01~ units of Si02 units in a ratio of from (CH3)3 SiOln units and to SiO~ units of from about 0.6: I to about 1.2: I; and (iii) from about 1 to about 20 parts per 100 pans by weight of (i) of a solid silica gel.
In the preferred silicone suds suppresser used herein, the solvent for a continuous phase is made up of certain polyethylene glycois or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppresser is branched/crossiinked and preferably not linear.
To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds suppresser, which comprises ( 1 ) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant;
and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol, Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issusd December 18, 1990, and 4,983.316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February 22. 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
The silicone suds suppresser herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycoUpolypropylene glycol, ail having an average molecular weight of less than about 1.000. preferably between about 100 and 800. The polyethylene glycol and polyethylene~polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 3 weight °/..
The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene giycoUpolypropyiene glycol, preferably PPG 200/PEG 300.
Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
The preferred silicone suds suppressers used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of TM
ethylene oxide and propylene oxide, like PLURON1C LI01.
Other suds suppressers useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075, I I 8 and EP 150,872. The secondary aicohols include the C6-C 16 alkyl sicohols having a C 1-C 16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols arc available under the trademark 1SALCHEM 123 from Enichem. Mixed suds suppressers typically comprise mixtwes of alcohol +
silicone at a weight ratio of 1:5 to 5:1.
For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a "suds suppressing amount. By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will 5 sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
The compositions herein will generally comprise from 0% to about 5% of suds suppressor.
When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to about 5%, by weight, of the detergent composition.
Preferably, from about 10 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized.
Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
Preferably from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from 15 about 0.25% to about 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Hams et al, issued September 22, 1981.
Additional Adiunct Ingredients A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the C10-C16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels. The C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, soluble magnesium SUBSTITUTE SHEET (RULE 26) WO 97/10321 PCT/iJS96/13448 salts such as MgCl2, MgS04, and the like, can be added at levels of, typically. 0.1%-2%. to provide additional suds and to enhance grease removal performance.
Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13 15 ethoxylated alcohol (E0 7) nonionic surfactant. Typically, the enryme/surfactant solution is 2.5 X
the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The compositions may contain from 5% to 90%, typically I 0% to 50% of such carriers.
The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about I I, preferably between about 7.5 and 10.5. Liquid dishwashing product formulations preferably have a pH between about 6.8 and about 9Ø Laundry products are typically at pH 9-I
1. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
Dve Transfer Inhibiting Aeents - The compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone poiymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
SUBSTITUTE SHEET (RULE 26) More specifically, the polyamine N-oxide polymers suitable for use herein contain units having the following structural formula: R-Ax-P; wherein P is a polymerizable unit to which an N-O
group can be attached or the N-O group can form part of the potymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC(O)~, -C(O)D-, -S-, -O-, -N=; x is 0 or I; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
The N-O group can be represented by the following general structures:
U~NWy, UDC
,o wherein RI, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or l; and the nitrogen of the N-O group can be attached or form part of any of the aforcmcntioned groups. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is water-sotuble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials cant be referred to as "PVNO".
The most preferred polyamine N-oxide useful as dye aansfer inhibiting polymers in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50.000 and an amine to amine N-oxide ratio of about I :4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI") are also suitable for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200.000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization".) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from I :1 to 0.2: l, more preferably from 0.8: I to 0.3:1, most preferably from 0.6:1 to 0.4: I. Those copolymers can be either linear or branched.
The present invention also may employ as a dye transfer inhibitor a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5.000 to about 400.000, preferably from about 5,000 to about 200.000, and more preferably from about 5.000 to about 50.000. PVP's are known to persons skilled in the detergent field; see, for example. EP-A-262.897 and EP-A-256,696.
Compositions containing PVP dye transfer inhibitors can also contain polyethylene glycol ("PEG") having an average molecular weight from about 500 to about 100.000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
Enzymes - Enrymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride~based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration. The enzymes to be incorporated include professes, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH~activity and/or stability optima, thetmostability, stability versus active detergents, builders and so on. In this respect bactetial or fungal enzymes are preferred, such as bacterial amylases and professes, and fungal cellulases.
Enrymes arc normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition.
Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-I% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
Suitable examples of professes are the subtilisins which arc obtained from particular strains of 8. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries AIS under the registered trade mark ESPERASE. The preparation of this enryme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. Proteolytic enrymes suitable for removing protein-based stains that are commercially available include those sold under the trademarks ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, lnc. (The Netherlands). Other professes include Protease A
(see European Patent Application 130.756, published January 9, 1985) and Protease B (see European Patent Application No. 251446 published January 7, 1988 and European Patent Application 130,756, Bott et al., published January 9, 1985).
Amylases include, for example, -amylases described in British .Patent Specification No.
1, 296.839 (Novo). RAPIDASE. international Bio-Synthetics, Inc. and TERMAMYL.
Novo Industries.
The cellulose usable in the present invention include both bacterial or fungal cellulose.
Preferably, they will have a pH optimum of between S and 9.5. Suitable celtutases arc disclosed in U.S. Patent 4,435,307, Barbesgoard et at, issued March 6, 1984, which discloses fungal cellulose produced from Humicola insolens and Humicota strain DSM 1800 or a cellulose ?
12-producing fungus belonging to the genus Aeromonas, and cellulose extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) is especially useful.
Suitable lipase enrymes for detsrgent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Pstent 1,372.034. See also lipases in Japanese Patent Application 53.20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co.
Ltd., Nagoya, Japan, under the trade mark Lipase P "Amano," hereinafter referred to as "Amano-P."
Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
Iipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagasa, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The rM
Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein.
Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes arc known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT
International Application WO
891099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
A wide range of enryme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al.
Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S.
Patent 4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Patent 4,261.868, Hora et al, issued April 14, i 981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 3.600.319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.
Enzyme Stabilizers - The enrymes employed herein arc stabilized by the presence of water-5 soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enrymes. (Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of canon is being used.) Additional stability can be provided by the presence of various other an-disclosed stabilizers, especially borate species: see Severson, U.S.
4.537,706. 'Typical detergents, especially liquids, will comprise from about I
to about 30, preferably 10 from about 2 to about 20, more preferably from about 5 to about I5. and most preferably from about 8 to about 12, millimoles of calcium ion per liter of finished composition. This can vary somewhat, depending on the amount of enryme present and its response to the calcium or magnesium ions. The level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc.. in the 15 composition. Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate.
calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts. A small amount of calcium ion, generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula 20 water. In solid detergent compositions the formulation may include a sufficient quantity of a water.
soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.
It is to be understood that the foregoing levels of calcium and/or magnesium ions are sufficient to provide enzyme stability. More calcium and/or magnesium ions can be added to the compositions to provide an additional measure of grease removal performance.
Accordingly, ss a general proposition the compositions herein will typically comprise from about 0.05% to about 2% by weight of a water-soluble source of calcium or magnesium ions, or both. The amount can vary, of course, with the amount and type of enryme employed in the composition.
The compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers. Typically, such stabilizers will be used at levels in the compositions from about 0.25% to about t0%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid). Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g..
sodium ortho-, mete. and pyroborate, and sodium pentaborate) are suitable.
Substituted boric acids (e.g.. phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid) can also be used in place of boric acid.
B~achine Comvounds - Bleach~n_gAJ~~r~ts and Bleach Activates . The detergent composit'rons herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or mare bleach activators. When present, bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition.
especially for fabric laundering. if present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents uxful for deter~tent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that arc now known or become known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g.. sodium perborate (e.g.. mono- or tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without rcsaiction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonyhunino-4-oxoperoxybutyric acid and diperoxydodecanedioit acid. Such bleaching agents arc disclosed in U.S. Patent No.4,483,781, Hatttnan, issued November 20, 1984, U.S. P
No. 4,806,632, issued February 21,1989, European Patent Application 0,133,354, Banks et al., published February 20, 1985, and U.S. Patent 4,412.934, Chung et a1, issued November 1, 1983.
Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds -include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphue peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometer, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC. Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably cmnbined with bleach activators, which lead to the in siiw production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
Various nonlimiting examples of activators are discloxd in U.S. Patent 4,915,854, issued April 10, 1990 to Mso et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (HOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4.634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators ate those of the formulae:
R1N(RSIC(O)R2C(O)L or R1C(O)N(RS)R2C(O)L
wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms. RS is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequtnce of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551.
Another class of bleach activators comprises the benzoxazin-type activators disclosed by ~5 Hodge et al. in U.S. Patent No. 4,966,723, issued October 30, 1990. A
highly preferred activator of the benzoxazin-type is:
~g-OO
Still another class of preferred bleach activators includts the aeyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
O
H O ~-C C
O ~-CHT-C ; ~ ~'~2-- H2 .~ CH2 ~--~--~C
'CH2--C!+~ H2-- ~2 , wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyi caprolactam. 3,5,5-trimethylhexanoyl caproiactam, nonanoyl caprolactam, decanoyl caproiactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl vaierolactam, decanoyl valerolactam, undccenoyl vaierolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. Sec also U.S. Patent No. 4,545,784, issued to Sanderson, October 8, 1985, which discloses aryl caprolactams, including benzoyl capmlactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents arc also known in the art and can be utilized herein. One type of non-oxygen bleathing agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines.
See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a manganese compound.
Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416;
U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271 A 1, 549,272A 1, 544,440A2, and 544,490A
1; Preferred examples of these catalysts include MntV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mnttt2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2_(C104)2, MntV4(u-O)6(1,4,7-triazacyclononane)4(C104)4, MnIIIMnIV4(u-O)I(u-OAc)2_(1,4,7-trimethyl-1,4,7 triazacyclononane)2(C104)3, MntV(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944;
5,246,612; 5,256,779;
5,280,117; 5,274,147; 5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
Polymeric Soil Release Agent - Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
The polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, SUBSTITUTE SHEET (RULE 26) said hydrophile segments preferably comprising at last about 25% oxytthyiene units and more preferably, especially for such components having about 20 to 30 oxypropyiene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) Cg oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethyiene tercphthalate, tht ratio of oxyethyiene tercphthaiate:C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C6 alkylene or oxy Cq-C6 alkylene segments, or mixtures therein, (iii) poly (vinyl tster) segments, preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C 1-C4 alkyl ether or Cq hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of Cl-C4 alkyl ether or Cq hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).
Typically, the polyoxyethylene segments of (axi) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable oxy Cq-CS alkylene hydrophobe segments include, but arc not limited to, end-caps of polymeric soil release agents such as M03S(CH2)nOCH2CH20-, when M is sodium and n is an inttger from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
Polymeric soil release agenu useful in the present invention also include cellulosic de-rivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene tercphthalate or propylent terephthalate with polyethylene oxide of polypropylene oxide terephthalate, and the like.
TM
Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL
(Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C 1-Cq alkyl and C4 hydroxyalkyl cellulose: see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et ai.
Soil release agents characterized by polyvinyl ester) hydrophobe segments include graft copolymers of polyvinyl ester), e.g., CI-C6 vinyl esters, preferably polyvinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available soil release TM
agents of this kind include the SOKALAN type of material, e.g.. SOKALAN HP-22, available from BASF (west Germany).
One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from about 25.000 to about 55.000. See U.S.
Patent 3.959.230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-t5% by weight of ethylene terephthalate units togttherwith 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5.000. Examples of this polymer include the commercially available material 5 ZELCON 5126 (from Dupont) and M1LEASE T (from ICl). See also U.S. Patent 4,702,857, issued October 27. 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are 10 described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J.
Scheibel and E.P. Gosselink.
Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4.721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 2?, 1987 to Gosselink.
15 Preferred polymeric soil release agenu also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sul-foarolyl, cnd-capped terephthalate esters.
If utilized, soil release agenu will generally comprise from about 0.01% to about 10.0°/., by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably.from 20 about 0.2% to about 3.0%.
Still another preferred soil release agent is an oligomer with repeat uniu of tercphthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form the backbone of the oligomer and arc preferably terminated with modified isethionate end-caps. A
paniculariy preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 25 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxyrethanesulfonate.
Said soil release agent also comprises from about 0.5% to about 20~/0, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonatc, toluene sulfonate, and mixtures thereof.
PROCESS
Included in the present invention is a process for making a structured detergent composition consisting essentially of the surfactant and the hydrophilic, finely-divided silica. The process comprises the step of mixing an paste of the surfactant with the finely divided hydrophilic silica, under adequate mixing to intimately combine the components into an homogeneous mixture. The silica is well-dispersed in the structured detergent composition. The resultant detergent composition has a hardened or firmer physical structure than the detergent surfactant.
Also included in the present invention is a process for making a structured surfactant composition for a detergent composition comprising the steps of:
a) Mixing from about I% to about 20% of a hydrophilic, finely-divided particulate silica and from about 35% to about 60% of a detergent surfactant, thereby forming a hardened paste;
b) Applying shear force to the hardened paste to form a ilowable liquid; and c) Dispersing the flowable liquid into fine droplets and agglomerting with dry detergent powder comprising other detergent adjuvants selected from the group consisting of other detergent surfactant, detergent builders, silica, and mixtures thereof, to form particles.using a high speed mixer.
The silica particulate is preferably a hydrophilic precipitated silica and the detergent surfactant paste is an anionic surfactant, most preferably alkylaUcoxy sulfate comprising an alkyl portion of from 6 to 18 carbon atoms and an alkoxy portion comprising, an average, from about 0.5 to about 20 moles of alkoxy, preferably ethoxy, units, morn preferably from about 0.5 to about 5 ethoxy units.
In order to make the structured surfactant composition, any suitable apparatus capable of handling viscous paste is required. Suitable apparatus includes, for example, twin-screw extruders, rM
Teledyne compounders, etc.
In order to make a detergent composition comprising the structured surfactant composition, suitable apparatus includes, for example, mixeNagglomerators can be used. In one prtferred embodiment, the process of the invention is continuously carried out.
The process preferably further comprises another step wherein the granulated surfactant composition is dusted with silica or zeolite.
EXAMPLES
xam ie 1 The structured surfactant composition can be made in the following way: the hydrophilic silica particulate is mixed with an alkylethoxy sulfate paste in a single-screw or twin-screw extruder. The pre-mot of soda ash, builder, zeolite and precipitated silica is agglomerated with the structured surfactant composition in a plowshare mixer. The resulting particle has a density of 600 to 800 g11.
xa 1 2 Ingredient %
CFA I
AE45-T O.g Structured Surfactant Composition 3.3 *
of Example 1 STPP 22.5 Zeolite 12.6 Polymer 0.7 Other detergent adjuvants Balance *Structured surfactant composition is comprised of AE3S at 70%, Hydrophilic precipitated silica at 2% and water at 28%.
Example 3 Ingredient %
LAS 20.7 STPP 22.7 Carbonate 22 Zeolite 14 Structured surfactant Composition*3.3 of Example I
Other detergent adjuvants Balance *Structured surfactant composition is comprised of AE3S at 70%, Hydrophilic precipitated silica at 2% and water at 28%.
Examvle 4 Ingredient LAS 24.5 STPP 17.9 Soda Ash 30 Zeolite 11.9 x Surfactant Composition (AE3S)* 3.3 of Example 1 Other detergent adjuvants Balance SUBSTITUTE SHEET (RULE 26) *Structured surfactant composition is comprised of AE3S at 70%, Hydrophilic precipitated silica at 2% and water at 28%.
SUBSTITUTE SHEET (RULE 26)
The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about I%
builder. Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about I S% to about SO% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly those having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Si05 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSix02x+I'YH20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2SiOg (NaSKS-6 form) is most preferred for use herein.
Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
- Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
Aluminosilicate builders include those having the empirical formula:
SUBSTITUTE SHEET (RULE 26) Mz(zAt02)y]~xH20 wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about I 5 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring , aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Na 12~(A102) 12(Si02) 12)~xH20 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A.
Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
~5 Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate"
refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of useful materials.
One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S.
Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability.
Citrates can also be used in SUBSTITUTE SHEET (RULE 26) granular compositions. especially in combination with zeolite andlor layered silicate builders.
Oxydisuccinates are also especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the 3,3~dicarboxy-4 oxa-!,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the CS-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myrisrylsuecinate, palmirylsuccinate, 2 dodecenylsuccinate (preferred), 2~pentadecenylsuccinate, and the like.
Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Ctvtchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S.
Patcnt 3,723.322.
Fatty acids, e.g., C12-Clg monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate andlor the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
Phosphonate builders such as ethane-1-hydroxy-1,1~diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3.422,021; 3.400,148 and 3,422,137) can also be used.
Hydrophilic silica particulates as described above is a preferred detergent adjuvant.
her Adiunct lnQredients Ch~latine Aeents ~ The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenedtamtne tetraproprtonates, triethylenetetraaminehexacetaus, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal.
ammonium, and substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUESt. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfvnctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 2I, 1974, to Connor et al.
Preferred compounds of this type in acid form arc dihydroxydisulfobenzenes such as 1.2-dihydroxy-3.5~disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704w33, November 3.
1987, to Harman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1 % to about 3.0% by weight of such compositions.
Clav Soil RemovaUAnti-redeeosition Agents - The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines;
liquid detergent compositions typically contain about 0.01 % to about 5%.
The most preferred soil release and anti-rcdeposition agent is ethoxylated tetraethylene-pentamine. Exemplary ethoxylated amines arc further described in U.S. Patent 4,597.898, VanderMeer, issued July t, 1986. Another group of preferred clay soil removal~antiredeposition agents arc the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removaUantiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published tune 27, 1984; the zwitterionic polymers disclosed in European Patent Appli-cation 112.592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal andlor anti redeposition agenu known in the art can also be utilized in the compositions herein. Another type of preferred antiredcposition agent includes the carboxy methyl cellulose (CMC) materials.
These materials are well known in the art.
Polymeric Disxrsina Aeents - Polymeric dispersing agenu can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite andlor layered silicate builders. Suitable polymeric dispersing agents include polymeric poiycarboxylates and polyethylene glycols, although others known in the art can also be used, It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents snhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can ' be polymerized to form suitable polymeric polycarboxylates include acrylic acid, malefic acid (or malefic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S.
Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and malefic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water soluble salts of such acrylic acidlmaleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG).
PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
SUBSTITUTE SHEET (RULE 26) Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders. Disposing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10.000.
Briehtener - Any optical brighteners or other brightening or whitening agents known in the alt can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5.5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York ( 1982).
Specific examples of optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal C8S and Tinopal SBM; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy:
the 2-(4-stryl-phenyl)-2H-napthol[ 1,2~d]triazoles; 4,4'-bis- ( 1.2,3-aiazol-2-yl}-stil- bones; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl- amino coumarin;
1,2-bis(-venzimidazol-2~yl)ethyiene; 1,3-diphenyl-phrazolines; 2.5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-(l,2-d]oxazole: and 2~(stilbene-4-yl)-2H-naphtho- (1.2-d]triazole.
See also U.S. Patent 3.646,015, issued February 29, 1972 to Hamilton. Anionic brighteners arc preferred herein.
Suds Suwressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489.5?4 and in front-loading European-style washing machines.
A wide variety. of materials may be used as suds suppressers, and suds suppressers are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, inc., 1979). One category of suds suppresser of particular interest encompasses monocarboxyiie fatty acid and soluble salts therein. See U.S. Patent 2.954,347, issued September 27. 1960 to Wayne St.
John. The monocarboxylic fatty acids and salts thereof used as suds suppresser typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds suppressers. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (r.g., fatty acid triglycerides), fatty acid esters of monovaient alcohols. aliphatic Clg-C40 ketones (t.g..
stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlorniazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g.. K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as para~ffm and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 50°C, and a minimum boiling point not less than about 1 10°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions.
Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraf~ins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds supprcssors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds suppressors are well known in the art and arc, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No.
354016, published February 7. 1990, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent 3.455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25°C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3Si01~ units of Si02 units in a ratio of from (CH3)3 SiOln units and to SiO~ units of from about 0.6: I to about 1.2: I; and (iii) from about 1 to about 20 parts per 100 pans by weight of (i) of a solid silica gel.
In the preferred silicone suds suppresser used herein, the solvent for a continuous phase is made up of certain polyethylene glycois or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppresser is branched/crossiinked and preferably not linear.
To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds suppresser, which comprises ( 1 ) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant;
and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol, Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issusd December 18, 1990, and 4,983.316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February 22. 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
The silicone suds suppresser herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycoUpolypropylene glycol, ail having an average molecular weight of less than about 1.000. preferably between about 100 and 800. The polyethylene glycol and polyethylene~polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 3 weight °/..
The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene giycoUpolypropyiene glycol, preferably PPG 200/PEG 300.
Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
The preferred silicone suds suppressers used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of TM
ethylene oxide and propylene oxide, like PLURON1C LI01.
Other suds suppressers useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075, I I 8 and EP 150,872. The secondary aicohols include the C6-C 16 alkyl sicohols having a C 1-C 16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols arc available under the trademark 1SALCHEM 123 from Enichem. Mixed suds suppressers typically comprise mixtwes of alcohol +
silicone at a weight ratio of 1:5 to 5:1.
For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a "suds suppressing amount. By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will 5 sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
The compositions herein will generally comprise from 0% to about 5% of suds suppressor.
When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to about 5%, by weight, of the detergent composition.
Preferably, from about 10 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized.
Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
Preferably from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from 15 about 0.25% to about 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Hams et al, issued September 22, 1981.
Additional Adiunct Ingredients A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the C10-C16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels. The C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, soluble magnesium SUBSTITUTE SHEET (RULE 26) WO 97/10321 PCT/iJS96/13448 salts such as MgCl2, MgS04, and the like, can be added at levels of, typically. 0.1%-2%. to provide additional suds and to enhance grease removal performance.
Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13 15 ethoxylated alcohol (E0 7) nonionic surfactant. Typically, the enryme/surfactant solution is 2.5 X
the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The compositions may contain from 5% to 90%, typically I 0% to 50% of such carriers.
The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about I I, preferably between about 7.5 and 10.5. Liquid dishwashing product formulations preferably have a pH between about 6.8 and about 9Ø Laundry products are typically at pH 9-I
1. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
Dve Transfer Inhibiting Aeents - The compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone poiymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
SUBSTITUTE SHEET (RULE 26) More specifically, the polyamine N-oxide polymers suitable for use herein contain units having the following structural formula: R-Ax-P; wherein P is a polymerizable unit to which an N-O
group can be attached or the N-O group can form part of the potymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC(O)~, -C(O)D-, -S-, -O-, -N=; x is 0 or I; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
The N-O group can be represented by the following general structures:
U~NWy, UDC
,o wherein RI, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or l; and the nitrogen of the N-O group can be attached or form part of any of the aforcmcntioned groups. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is water-sotuble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials cant be referred to as "PVNO".
The most preferred polyamine N-oxide useful as dye aansfer inhibiting polymers in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50.000 and an amine to amine N-oxide ratio of about I :4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI") are also suitable for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200.000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization".) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from I :1 to 0.2: l, more preferably from 0.8: I to 0.3:1, most preferably from 0.6:1 to 0.4: I. Those copolymers can be either linear or branched.
The present invention also may employ as a dye transfer inhibitor a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5.000 to about 400.000, preferably from about 5,000 to about 200.000, and more preferably from about 5.000 to about 50.000. PVP's are known to persons skilled in the detergent field; see, for example. EP-A-262.897 and EP-A-256,696.
Compositions containing PVP dye transfer inhibitors can also contain polyethylene glycol ("PEG") having an average molecular weight from about 500 to about 100.000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
Enzymes - Enrymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride~based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration. The enzymes to be incorporated include professes, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH~activity and/or stability optima, thetmostability, stability versus active detergents, builders and so on. In this respect bactetial or fungal enzymes are preferred, such as bacterial amylases and professes, and fungal cellulases.
Enrymes arc normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition.
Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-I% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
Suitable examples of professes are the subtilisins which arc obtained from particular strains of 8. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries AIS under the registered trade mark ESPERASE. The preparation of this enryme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. Proteolytic enrymes suitable for removing protein-based stains that are commercially available include those sold under the trademarks ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, lnc. (The Netherlands). Other professes include Protease A
(see European Patent Application 130.756, published January 9, 1985) and Protease B (see European Patent Application No. 251446 published January 7, 1988 and European Patent Application 130,756, Bott et al., published January 9, 1985).
Amylases include, for example, -amylases described in British .Patent Specification No.
1, 296.839 (Novo). RAPIDASE. international Bio-Synthetics, Inc. and TERMAMYL.
Novo Industries.
The cellulose usable in the present invention include both bacterial or fungal cellulose.
Preferably, they will have a pH optimum of between S and 9.5. Suitable celtutases arc disclosed in U.S. Patent 4,435,307, Barbesgoard et at, issued March 6, 1984, which discloses fungal cellulose produced from Humicola insolens and Humicota strain DSM 1800 or a cellulose ?
12-producing fungus belonging to the genus Aeromonas, and cellulose extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) is especially useful.
Suitable lipase enrymes for detsrgent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Pstent 1,372.034. See also lipases in Japanese Patent Application 53.20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co.
Ltd., Nagoya, Japan, under the trade mark Lipase P "Amano," hereinafter referred to as "Amano-P."
Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
Iipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagasa, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The rM
Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein.
Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes arc known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT
International Application WO
891099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
A wide range of enryme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al.
Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S.
Patent 4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Patent 4,261.868, Hora et al, issued April 14, i 981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 3.600.319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.
Enzyme Stabilizers - The enrymes employed herein arc stabilized by the presence of water-5 soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enrymes. (Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of canon is being used.) Additional stability can be provided by the presence of various other an-disclosed stabilizers, especially borate species: see Severson, U.S.
4.537,706. 'Typical detergents, especially liquids, will comprise from about I
to about 30, preferably 10 from about 2 to about 20, more preferably from about 5 to about I5. and most preferably from about 8 to about 12, millimoles of calcium ion per liter of finished composition. This can vary somewhat, depending on the amount of enryme present and its response to the calcium or magnesium ions. The level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc.. in the 15 composition. Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate.
calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts. A small amount of calcium ion, generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula 20 water. In solid detergent compositions the formulation may include a sufficient quantity of a water.
soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.
It is to be understood that the foregoing levels of calcium and/or magnesium ions are sufficient to provide enzyme stability. More calcium and/or magnesium ions can be added to the compositions to provide an additional measure of grease removal performance.
Accordingly, ss a general proposition the compositions herein will typically comprise from about 0.05% to about 2% by weight of a water-soluble source of calcium or magnesium ions, or both. The amount can vary, of course, with the amount and type of enryme employed in the composition.
The compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers. Typically, such stabilizers will be used at levels in the compositions from about 0.25% to about t0%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid). Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g..
sodium ortho-, mete. and pyroborate, and sodium pentaborate) are suitable.
Substituted boric acids (e.g.. phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid) can also be used in place of boric acid.
B~achine Comvounds - Bleach~n_gAJ~~r~ts and Bleach Activates . The detergent composit'rons herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or mare bleach activators. When present, bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition.
especially for fabric laundering. if present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents uxful for deter~tent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that arc now known or become known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g.. sodium perborate (e.g.. mono- or tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without rcsaiction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonyhunino-4-oxoperoxybutyric acid and diperoxydodecanedioit acid. Such bleaching agents arc disclosed in U.S. Patent No.4,483,781, Hatttnan, issued November 20, 1984, U.S. P
No. 4,806,632, issued February 21,1989, European Patent Application 0,133,354, Banks et al., published February 20, 1985, and U.S. Patent 4,412.934, Chung et a1, issued November 1, 1983.
Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds -include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphue peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometer, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC. Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably cmnbined with bleach activators, which lead to the in siiw production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
Various nonlimiting examples of activators are discloxd in U.S. Patent 4,915,854, issued April 10, 1990 to Mso et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (HOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4.634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators ate those of the formulae:
R1N(RSIC(O)R2C(O)L or R1C(O)N(RS)R2C(O)L
wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms. RS is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequtnce of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551.
Another class of bleach activators comprises the benzoxazin-type activators disclosed by ~5 Hodge et al. in U.S. Patent No. 4,966,723, issued October 30, 1990. A
highly preferred activator of the benzoxazin-type is:
~g-OO
Still another class of preferred bleach activators includts the aeyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
O
H O ~-C C
O ~-CHT-C ; ~ ~'~2-- H2 .~ CH2 ~--~--~C
'CH2--C!+~ H2-- ~2 , wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyi caprolactam. 3,5,5-trimethylhexanoyl caproiactam, nonanoyl caprolactam, decanoyl caproiactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl vaierolactam, decanoyl valerolactam, undccenoyl vaierolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. Sec also U.S. Patent No. 4,545,784, issued to Sanderson, October 8, 1985, which discloses aryl caprolactams, including benzoyl capmlactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents arc also known in the art and can be utilized herein. One type of non-oxygen bleathing agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines.
See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a manganese compound.
Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416;
U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271 A 1, 549,272A 1, 544,440A2, and 544,490A
1; Preferred examples of these catalysts include MntV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mnttt2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2_(C104)2, MntV4(u-O)6(1,4,7-triazacyclononane)4(C104)4, MnIIIMnIV4(u-O)I(u-OAc)2_(1,4,7-trimethyl-1,4,7 triazacyclononane)2(C104)3, MntV(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944;
5,246,612; 5,256,779;
5,280,117; 5,274,147; 5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
Polymeric Soil Release Agent - Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
The polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, SUBSTITUTE SHEET (RULE 26) said hydrophile segments preferably comprising at last about 25% oxytthyiene units and more preferably, especially for such components having about 20 to 30 oxypropyiene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) Cg oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethyiene tercphthalate, tht ratio of oxyethyiene tercphthaiate:C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C6 alkylene or oxy Cq-C6 alkylene segments, or mixtures therein, (iii) poly (vinyl tster) segments, preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C 1-C4 alkyl ether or Cq hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of Cl-C4 alkyl ether or Cq hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).
Typically, the polyoxyethylene segments of (axi) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable oxy Cq-CS alkylene hydrophobe segments include, but arc not limited to, end-caps of polymeric soil release agents such as M03S(CH2)nOCH2CH20-, when M is sodium and n is an inttger from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
Polymeric soil release agenu useful in the present invention also include cellulosic de-rivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene tercphthalate or propylent terephthalate with polyethylene oxide of polypropylene oxide terephthalate, and the like.
TM
Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL
(Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C 1-Cq alkyl and C4 hydroxyalkyl cellulose: see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et ai.
Soil release agents characterized by polyvinyl ester) hydrophobe segments include graft copolymers of polyvinyl ester), e.g., CI-C6 vinyl esters, preferably polyvinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available soil release TM
agents of this kind include the SOKALAN type of material, e.g.. SOKALAN HP-22, available from BASF (west Germany).
One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from about 25.000 to about 55.000. See U.S.
Patent 3.959.230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-t5% by weight of ethylene terephthalate units togttherwith 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5.000. Examples of this polymer include the commercially available material 5 ZELCON 5126 (from Dupont) and M1LEASE T (from ICl). See also U.S. Patent 4,702,857, issued October 27. 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are 10 described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J.
Scheibel and E.P. Gosselink.
Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4.721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 2?, 1987 to Gosselink.
15 Preferred polymeric soil release agenu also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sul-foarolyl, cnd-capped terephthalate esters.
If utilized, soil release agenu will generally comprise from about 0.01% to about 10.0°/., by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably.from 20 about 0.2% to about 3.0%.
Still another preferred soil release agent is an oligomer with repeat uniu of tercphthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form the backbone of the oligomer and arc preferably terminated with modified isethionate end-caps. A
paniculariy preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 25 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxyrethanesulfonate.
Said soil release agent also comprises from about 0.5% to about 20~/0, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonatc, toluene sulfonate, and mixtures thereof.
PROCESS
Included in the present invention is a process for making a structured detergent composition consisting essentially of the surfactant and the hydrophilic, finely-divided silica. The process comprises the step of mixing an paste of the surfactant with the finely divided hydrophilic silica, under adequate mixing to intimately combine the components into an homogeneous mixture. The silica is well-dispersed in the structured detergent composition. The resultant detergent composition has a hardened or firmer physical structure than the detergent surfactant.
Also included in the present invention is a process for making a structured surfactant composition for a detergent composition comprising the steps of:
a) Mixing from about I% to about 20% of a hydrophilic, finely-divided particulate silica and from about 35% to about 60% of a detergent surfactant, thereby forming a hardened paste;
b) Applying shear force to the hardened paste to form a ilowable liquid; and c) Dispersing the flowable liquid into fine droplets and agglomerting with dry detergent powder comprising other detergent adjuvants selected from the group consisting of other detergent surfactant, detergent builders, silica, and mixtures thereof, to form particles.using a high speed mixer.
The silica particulate is preferably a hydrophilic precipitated silica and the detergent surfactant paste is an anionic surfactant, most preferably alkylaUcoxy sulfate comprising an alkyl portion of from 6 to 18 carbon atoms and an alkoxy portion comprising, an average, from about 0.5 to about 20 moles of alkoxy, preferably ethoxy, units, morn preferably from about 0.5 to about 5 ethoxy units.
In order to make the structured surfactant composition, any suitable apparatus capable of handling viscous paste is required. Suitable apparatus includes, for example, twin-screw extruders, rM
Teledyne compounders, etc.
In order to make a detergent composition comprising the structured surfactant composition, suitable apparatus includes, for example, mixeNagglomerators can be used. In one prtferred embodiment, the process of the invention is continuously carried out.
The process preferably further comprises another step wherein the granulated surfactant composition is dusted with silica or zeolite.
EXAMPLES
xam ie 1 The structured surfactant composition can be made in the following way: the hydrophilic silica particulate is mixed with an alkylethoxy sulfate paste in a single-screw or twin-screw extruder. The pre-mot of soda ash, builder, zeolite and precipitated silica is agglomerated with the structured surfactant composition in a plowshare mixer. The resulting particle has a density of 600 to 800 g11.
xa 1 2 Ingredient %
CFA I
AE45-T O.g Structured Surfactant Composition 3.3 *
of Example 1 STPP 22.5 Zeolite 12.6 Polymer 0.7 Other detergent adjuvants Balance *Structured surfactant composition is comprised of AE3S at 70%, Hydrophilic precipitated silica at 2% and water at 28%.
Example 3 Ingredient %
LAS 20.7 STPP 22.7 Carbonate 22 Zeolite 14 Structured surfactant Composition*3.3 of Example I
Other detergent adjuvants Balance *Structured surfactant composition is comprised of AE3S at 70%, Hydrophilic precipitated silica at 2% and water at 28%.
Examvle 4 Ingredient LAS 24.5 STPP 17.9 Soda Ash 30 Zeolite 11.9 x Surfactant Composition (AE3S)* 3.3 of Example 1 Other detergent adjuvants Balance SUBSTITUTE SHEET (RULE 26) *Structured surfactant composition is comprised of AE3S at 70%, Hydrophilic precipitated silica at 2% and water at 28%.
SUBSTITUTE SHEET (RULE 26)
Claims (10)
1. A structured surfactant composition consisting essentially of:
(a) from about 35% to about 60% of a detergent surfactant;
(b) from about 1% to about 20% of hydrophilic, finely-divided silica particulate: and (c) from about 15% to about 25% moisture.
(a) from about 35% to about 60% of a detergent surfactant;
(b) from about 1% to about 20% of hydrophilic, finely-divided silica particulate: and (c) from about 15% to about 25% moisture.
2. A surfactant composition according to Claim 1, wherein the detergent surfactant is selected from the group consisting of anionic, cationic, zwitterionic, ampholytic surfactants and mixtures thereof.
3. A surfactant composition according to Claim 2, wherein the silica particulate is hydrophilic precipitated silica.
4. A surfactant composition according to Claim 3, wherein the detergent surfactant is alkyl ether sulfate of the formula R-E n SO3M, wherein:
(i) R is C8-20 alkyl chain;
(ii) E is an ethoxy unit;
(iii) n is from 1-20; and (iv) M is a cation.
(i) R is C8-20 alkyl chain;
(ii) E is an ethoxy unit;
(iii) n is from 1-20; and (iv) M is a cation.
5. A granular detergent composition comprising:
from about 2% to about 70% of a structured surfactant composition, the surfactant composition consisting essentially of:
(i) from about 35% to about 60% of a detergent surfactant;
(ii) from about 1% to about 20% of hydrophilic, finely-divided silica particulate; and (iii) from about 15% to about 25% moisture; and (b) from about 30% to about 98% other detergent adjuvants selected from the group consisting of other detergent surfactants, detergent builders, silica, and mixtures thereof.
from about 2% to about 70% of a structured surfactant composition, the surfactant composition consisting essentially of:
(i) from about 35% to about 60% of a detergent surfactant;
(ii) from about 1% to about 20% of hydrophilic, finely-divided silica particulate; and (iii) from about 15% to about 25% moisture; and (b) from about 30% to about 98% other detergent adjuvants selected from the group consisting of other detergent surfactants, detergent builders, silica, and mixtures thereof.
6. A composition according to Claim 5, wherein the detergent surfactant in (a)(i) is anionic surfactant and the silica particulate in (a)(ii) is hydrophilic precipitated silica.
7. A composition according to Claim 6, wherein the anionic surfactant is an alkyl ether sulfate of the formula R-E n-SO3M, wherein:
(a) R is C12-18, alkyl chain;
(b) E is an ethoxy unit;
(c) n is from 1-20; and (d) M is a cation.
(a) R is C12-18, alkyl chain;
(b) E is an ethoxy unit;
(c) n is from 1-20; and (d) M is a cation.
8. A process for making a surfactant composition for a detergent composition comprising the steps of:
a) mixing from about 1% to about 20% of a hydrophilic, finely-divided particulate silica, from about 35% to about 60% of a detergent surfactant, and from about 15%
to about 25% moisture, thereby forming a hardened paste;
b) applying shear force to the hardened paste to form a flowable liquid; and c) dispersing the flowable liquid into fine droplets and agglomerting with dry detergent powder comprising other detergent adjuvants selected from the group consisting of other detergent surfactant, detergent builders, silica, and mixtures thereof, to form particles using a high speed mixer.
a) mixing from about 1% to about 20% of a hydrophilic, finely-divided particulate silica, from about 35% to about 60% of a detergent surfactant, and from about 15%
to about 25% moisture, thereby forming a hardened paste;
b) applying shear force to the hardened paste to form a flowable liquid; and c) dispersing the flowable liquid into fine droplets and agglomerting with dry detergent powder comprising other detergent adjuvants selected from the group consisting of other detergent surfactant, detergent builders, silica, and mixtures thereof, to form particles using a high speed mixer.
9. A process according to Claim 8, wherein the silica particulate is a hydrophilic precipitated silica and the detergent surfactant is an anionic surfactant paste,
10. A process for making a granular detergent composition comprising the steps of:
a) mixing from about 1% to about 20% of a hydrophilic, finely-divided particulate silica, from about 15% to about 25% moisture, and from about 35% to about 60%
of an alkyl ether sulfate surfactant of the formula R-E n-SO3M, wherein:
R is C12-15, alkyl chain;
E is an ethoxy unit;
n is 3; and M is a sodium ion, thereby forming a structured surfactant composition; and b) granulating the surfactant composition upon mixing with a dry detergent powder comprising ocher detergent adjuvants selected from the group consisting of other detergent surfactant, detergent builders, silica, and mixtures thereof.
a) mixing from about 1% to about 20% of a hydrophilic, finely-divided particulate silica, from about 15% to about 25% moisture, and from about 35% to about 60%
of an alkyl ether sulfate surfactant of the formula R-E n-SO3M, wherein:
R is C12-15, alkyl chain;
E is an ethoxy unit;
n is 3; and M is a sodium ion, thereby forming a structured surfactant composition; and b) granulating the surfactant composition upon mixing with a dry detergent powder comprising ocher detergent adjuvants selected from the group consisting of other detergent surfactant, detergent builders, silica, and mixtures thereof.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPN5350 | 1995-09-12 | ||
AUPN5350A AUPN535095A0 (en) | 1995-09-12 | 1995-09-12 | Compositions comprising hydrophilic silica particulates |
PCT/US1996/013448 WO1997010321A1 (en) | 1995-09-12 | 1996-08-20 | Compositions comprising hydrophilic silica particulates |
Publications (2)
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CA2231691A1 CA2231691A1 (en) | 1997-03-20 |
CA2231691C true CA2231691C (en) | 2003-04-15 |
Family
ID=3789679
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Application Number | Title | Priority Date | Filing Date |
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CA002231691A Expired - Fee Related CA2231691C (en) | 1995-09-12 | 1996-08-20 | Compositions comprising hydrophilic silica particulates |
Country Status (14)
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EP (1) | EP0863968A4 (en) |
JP (1) | JPH11512472A (en) |
AR (1) | AR003549A1 (en) |
AU (1) | AUPN535095A0 (en) |
BR (1) | BR9610542A (en) |
CA (1) | CA2231691C (en) |
CZ (1) | CZ72298A3 (en) |
EG (1) | EG21149A (en) |
HU (1) | HUP9901545A3 (en) |
IL (1) | IL123541A0 (en) |
MX (1) | MX9801940A (en) |
TR (1) | TR199800446T1 (en) |
WO (1) | WO1997010321A1 (en) |
ZA (1) | ZA967117B (en) |
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DE69709746T2 (en) * | 1996-07-26 | 2002-07-18 | THE PROCTER & GAMBLE COMPANY, CINCINNATI | PRODUCTION OF DETERGENT AGGLOMERATES WITH LOW DENSITY CONTAINING SILICA |
ES2196352T3 (en) * | 1996-07-26 | 2003-12-16 | Procter & Gamble | PREPARATION OF LOW DENSITY DETERGENT AGLOMERATES CONTAINING SILICE. |
GB9618875D0 (en) * | 1996-09-10 | 1996-10-23 | Unilever Plc | Process for preparing high bulk density detergent compositions |
GB9618877D0 (en) * | 1996-09-10 | 1996-10-23 | Unilever Plc | Process for preparing high bulk density detergent compositions |
GB9825558D0 (en) | 1998-11-20 | 1999-01-13 | Unilever Plc | Granular detergent components and particulate detergent compositions containing them |
DE10008815A1 (en) * | 2000-02-25 | 2001-08-30 | Sued Chemie Ag | Agglomerates containing layered minerals with non-ionic surfactants |
US6897188B2 (en) | 2001-07-17 | 2005-05-24 | Ecolab, Inc. | Liquid conditioner and method for washing textiles |
DE10212169A1 (en) * | 2002-03-19 | 2003-10-02 | Sued Chemie Ag | Detergent additive with a high content of non-ionic surfactants and quick dissolving power |
US8110537B2 (en) | 2003-01-14 | 2012-02-07 | Ecolab Usa Inc. | Liquid detergent composition and methods for using |
DE60314783T2 (en) * | 2003-05-12 | 2008-04-10 | Unitika Ltd., Amagasaki | BIODEGRADABLE POLYESTER-CONTAINING COMPOSITION, MANUFACTURING METHOD AND FOAM AND FORM BODY USING THEM |
US7682403B2 (en) | 2004-01-09 | 2010-03-23 | Ecolab Inc. | Method for treating laundry |
WO2014198034A1 (en) * | 2013-06-13 | 2014-12-18 | The Procter & Gamble Company | Granular laundry detergent |
WO2015008296A1 (en) * | 2013-07-18 | 2015-01-22 | Galaxy Surfactants Ltd. | Free-flowing, solid, high active alkyl ether sulfates |
MX2016013263A (en) * | 2014-04-10 | 2017-01-16 | Procter & Gamble | Composite detergent granules and laundry compositions comprising the same. |
WO2016041168A1 (en) * | 2014-09-18 | 2016-03-24 | The Procter & Gamble Company | Structured detergent particles and granular detergent compositions containing thereof |
KR102200185B1 (en) | 2014-10-30 | 2021-01-08 | (주)아모레퍼시픽 | Skin or Hair Washing Composition |
EP3271444A1 (en) * | 2015-03-19 | 2018-01-24 | The Procter and Gamble Company | Structured detergent particles and granular detergent compositions containing the same |
US10494591B2 (en) | 2017-06-22 | 2019-12-03 | Ecolab Usa Inc. | Bleaching using peroxyformic acid and an oxygen catalyst |
CN111019777B (en) * | 2019-12-17 | 2021-08-17 | 广州立白企业集团有限公司 | Granular concentrated detergent composition |
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DE3504628A1 (en) * | 1985-02-11 | 1986-08-14 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING GRANULATE GRANULATE |
JPH0726120B2 (en) * | 1988-03-10 | 1995-03-22 | 株式会社ジャパンエナジー | Detergent composition |
US4925585A (en) * | 1988-06-29 | 1990-05-15 | The Procter & Gamble Company | Detergent granules from cold dough using fine dispersion granulation |
US5045225A (en) * | 1988-12-30 | 1991-09-03 | Lever Brothers Co., Division Of Conopco Inc. | Self hydrophobing silicone/hydrocarbon antifoam compositions |
DE69221357T2 (en) * | 1991-04-12 | 1998-03-12 | Procter & Gamble | Chemical structuring of surface-active pastes for the production of highly effective surfactant granules |
US5529722A (en) * | 1992-03-10 | 1996-06-25 | The Procter & Gamble Company | High active detergent pastes |
US5458799A (en) * | 1993-08-03 | 1995-10-17 | Amway Corporation | Mix process for formulating detergents |
-
1995
- 1995-09-12 AU AUPN5350A patent/AUPN535095A0/en not_active Abandoned
-
1996
- 1996-08-20 IL IL12354196A patent/IL123541A0/en unknown
- 1996-08-20 HU HU9901545A patent/HUP9901545A3/en unknown
- 1996-08-20 WO PCT/US1996/013448 patent/WO1997010321A1/en not_active Application Discontinuation
- 1996-08-20 TR TR1998/00446T patent/TR199800446T1/en unknown
- 1996-08-20 EP EP96928248A patent/EP0863968A4/en not_active Withdrawn
- 1996-08-20 JP JP9511960A patent/JPH11512472A/en not_active Ceased
- 1996-08-20 BR BR9610542A patent/BR9610542A/en active Search and Examination
- 1996-08-20 CA CA002231691A patent/CA2231691C/en not_active Expired - Fee Related
- 1996-08-20 CZ CZ98722A patent/CZ72298A3/en unknown
- 1996-08-21 ZA ZA967117A patent/ZA967117B/en unknown
- 1996-09-03 EG EG80696A patent/EG21149A/en active
- 1996-09-11 AR ARP960104301A patent/AR003549A1/en unknown
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1998
- 1998-03-11 MX MX9801940A patent/MX9801940A/en not_active IP Right Cessation
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HUP9901545A3 (en) | 2000-10-30 |
HUP9901545A2 (en) | 1999-08-30 |
AR003549A1 (en) | 1998-08-05 |
CZ72298A3 (en) | 1998-10-14 |
EP0863968A1 (en) | 1998-09-16 |
EG21149A (en) | 2000-12-31 |
EP0863968A4 (en) | 2000-06-21 |
ZA967117B (en) | 1997-03-03 |
CA2231691A1 (en) | 1997-03-20 |
JPH11512472A (en) | 1999-10-26 |
WO1997010321A1 (en) | 1997-03-20 |
IL123541A0 (en) | 1998-10-30 |
TR199800446T1 (en) | 1998-06-22 |
AUPN535095A0 (en) | 1995-10-05 |
MX9801940A (en) | 1998-08-30 |
BR9610542A (en) | 1999-07-06 |
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