CA2345737C - Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability - Google Patents
Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability Download PDFInfo
- Publication number
- CA2345737C CA2345737C CA002345737A CA2345737A CA2345737C CA 2345737 C CA2345737 C CA 2345737C CA 002345737 A CA002345737 A CA 002345737A CA 2345737 A CA2345737 A CA 2345737A CA 2345737 C CA2345737 C CA 2345737C
- Authority
- CA
- Canada
- Prior art keywords
- chelant
- inorganic compound
- transition metal
- agglomerate
- process according
- 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 184
- 239000013522 chelant Substances 0.000 title claims abstract description 99
- 239000003599 detergent Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 66
- 230000008569 process Effects 0.000 title claims abstract description 59
- 238000003860 storage Methods 0.000 title claims description 11
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 33
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 31
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 31
- 150000003624 transition metals Chemical class 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000001694 spray drying Methods 0.000 claims abstract description 10
- 239000012736 aqueous medium Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 44
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 32
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 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 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000010457 zeolite Substances 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims description 13
- 238000005342 ion exchange Methods 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- MPJQXAIKMSKXBI-UHFFFAOYSA-N 2,7,9,14-tetraoxa-1,8-diazabicyclo[6.6.2]hexadecane-3,6,10,13-tetrone Chemical compound C1CN2OC(=O)CCC(=O)ON1OC(=O)CCC(=O)O2 MPJQXAIKMSKXBI-UHFFFAOYSA-N 0.000 claims description 6
- 229940071087 ethylenediamine disuccinate Drugs 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 150000004760 silicates Chemical class 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 claims description 2
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 claims 4
- 235000012239 silicon dioxide Nutrition 0.000 claims 3
- 229910009112 xH2O Inorganic materials 0.000 claims 3
- -1 aluminosilicate ion Chemical class 0.000 description 48
- 239000007844 bleaching agent Substances 0.000 description 35
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- 235000014113 dietary fatty acids Nutrition 0.000 description 15
- 239000000194 fatty acid Substances 0.000 description 15
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- 150000003839 salts Chemical class 0.000 description 15
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- 239000002245 particle Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000003945 anionic surfactant Substances 0.000 description 10
- 239000000975 dye Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 102000004882 Lipase Human genes 0.000 description 9
- 108090001060 Lipase Proteins 0.000 description 9
- 239000002738 chelating agent Substances 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
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- 239000004367 Lipase Substances 0.000 description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 8
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Natural products O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 6
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- 239000004365 Protease Substances 0.000 description 6
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- 125000003118 aryl group Chemical class 0.000 description 6
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- 235000010338 boric acid Nutrition 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 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 5
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- 150000001298 alcohols Chemical class 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
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- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 3
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- 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
- 239000003607 modifier Substances 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical class CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- ONHFWHCMZAJCFB-UHFFFAOYSA-N myristamine oxide Chemical compound CCCCCCCCCCCCCC[N+](C)(C)[O-] ONHFWHCMZAJCFB-UHFFFAOYSA-N 0.000 description 1
- BZDOEVMUXJTHPS-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)hexadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCC[N+]([O-])(CCO)CCO BZDOEVMUXJTHPS-UHFFFAOYSA-N 0.000 description 1
- CBLJNXZOFGRDAC-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)octadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCCCC[N+]([O-])(CCO)CCO CBLJNXZOFGRDAC-UHFFFAOYSA-N 0.000 description 1
- ITFGZZGYXVHOOU-UHFFFAOYSA-N n,n-dimethylmethanamine;methyl hydrogen sulfate Chemical compound C[NH+](C)C.COS([O-])(=O)=O ITFGZZGYXVHOOU-UHFFFAOYSA-N 0.000 description 1
- UTTVXKGNTWZECK-UHFFFAOYSA-N n,n-dimethyloctadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)[O-] UTTVXKGNTWZECK-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 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
- 150000004965 peroxy acids Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 229940024999 proteolytic enzymes for treatment of wounds and ulcers Drugs 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
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 229920002545 silicone oil Polymers 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying 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
- 230000001180 sulfating effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical class OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DTOSIQBPPRVQHS-UHFFFAOYSA-N α-Linolenic acid Chemical compound CCC=CCC=CCC=CCCCCCCCC(O)=O DTOSIQBPPRVQHS-UHFFFAOYSA-N 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
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/364—Organic compounds containing phosphorus containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Glanulating (AREA)
Abstract
The present invention provides a process for preparation of a chelant composition by a non-spray-drying process, a process for improving one or more of flowability and scoopability of a laundry detergent composition, and a chelant agglomerate useful as an ad-mix in a particulate laundry detergent. In one aspect of the present invention, the process for preparation of a chelant composition by a non-spray-drying process includes the steps of admixing a transition metal chelant and an inorganic compound to form a mixture, agllomerating the mixture in an aqueous medium to form a chelant agglomerate and drying the chelant agglomerate.
Description
PROCESS FOR DELIVERING CHELANT AGGLOMERATE INTO DETERGENT
COMPOSITION FOR IMPROVING ITS STORAGE STABILITY;
FLOWABILITY AND SCOOPABILITY
TECHNICAL FIELD
The present invention relates to a laundry detergent compositions and more particularly, to a process for improving storage stability and scoopability of laundry detergent compositions by incorporation of useful levels of a concentrated chelant agglomerate into a laundry detergent composition.
BACKGROUND OF THE INVENTION
It has been extremely desirable to have a process for increasing the storage stability and scoopability of detergent compositions. This is a characteristic that most consumers are very desirous of because consumers do not want to have to deal with detergent compositions that "clump" together after the detergent box has been laid open for an extended period of time due to the inadvertent absorption of moisture.
It has beer. recognized that the incorporation of a transition metal chelant into the base granules of the laundry detergent composition causes the promotion of interlocking crystalline needle growth which is suspected to detrimentally affect the resultant particulate laundry detergent composition's flowability and scoopability properties. Thus it has been recognized by the inventors of this particular invention that it is extremely advantageous to devise a method of separating the transition metal chelant from the base granule of the laundry detergent composition, so that any useful level of the transition metal chelant may be incorporated in the overall laundry detergent composition without adversely affecting its flowability and scoopability properties. It has thus been extremely desirable to have a process or a method whereby any useful level of a chelant agglomerate can be ad-mixed into a laundry detergent composition such that the chelant agglomerate desirably improves the solubility and storage stability of the resultant ad-mixed detergent composition formulation and at the very least, does not detrimentally affect the laundry detergent composition's flowability and scoopability characteristics. The present invention overcomes the problems, as set forth above.
BACKGROUND ART
U.S. Patent 5,108,646 discloses a process for making detergent builder agglomerates by mixing a detergent builder with a selected binder to form free flowing agglomerates.
International Publication Number WO 97/09415 discloses a non-spray-dried particulate detergent composition prepared by mixing and granulating liquid and solid ingredients in a high-speed mixer/granulator, containing a builder polymer and/or a soil-release polymer, wherein the polymer is incorporated during the mixing and granulating process in the form of a non-aqueous premix with a non-aqueous diluent.
SUMMARY OF THE INVENTION
The invention meets the needs above by providing a process for preparation of a chelant composition by a non-spray-drying process, a process for improving one or more of storage stability, flowability and scoopability of a laundry detergent composition, and a chelant agglomerate useful as an ad-mix in a particulate laundry detergent.
In one aspect of the present invention, a process for preparation of a chelant composition by a non-spray-drying process includes the steps of admixing a transition metal chelant and an inorganic compound to form a mixture, agglomerating the mixture in an aqueous medium to form a chelant agglomerate and drying the chelant agglomerate.
In another aspect of the invention there is provided a process for preparation of a chelant composition by a non-spray-drying process, comprising the steps of:
a)admixing a transition metal chelant and an inorganic compound to form a mixture; b) agglomerating said mixture in an aqueous medium to form a chelant agglomerate; and c) drying said chelant agglomerate wherein the inorganic compound is selected from the group consisting of sulfates, carbonates, silicates, aluminosilicates and mixtures thereof; and wherein the transition metal chelant is selected from the group consisting of diethylenetriaminepentaacetates;
ethylenediamine disuccinate; and mixtures thereof; and wherein the chelant agglomerate resulting from step c) consists of said transition metal chelant and said inorganic compound.
In a further aspect of the present invention, a process for improving one or more of storage stability, flowability and scoopability of a laundry detergent composition includes the steps of providing a chelant composition prepared by a non-spray-drying process and incorporating the chelant composition into a particulate laundry detergent material in a weight ratio in a range of from about 0.05:99.95 to about 2:98, chelant composition to particulate laundry detergent material. The non-spray-drying process includes the steps of admixing a transition metal chelant and an inorganic compound to form a mixture, agglomerating the 2a mixture in an aqueous medium to form a chelant agglomerate, and drying the chelant agglomerate.
In yet another aspect of the present invention, a chelant agglomerate useful as an ad-mix in a particulate laundry detergent is disclosed. The chelant agglomerate has a composition including a transition metal chelant, an inorganic compound and water. The chelant agglomerate is formed by admixing the transition metal chelant and the inorganic compound to form a mixture, agglomerating the mixture in the water to form the chelant agglomerate, and drying the chelant agglomerate.
These and other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment and the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
In the preferred embodiment of the present invention, the process for preparation of a chelant composition by a non-spray-drying process includes the steps of admixing a transition S metal chelant and an inorganic compound to form a mixture, agglomerating the mixture in an aqueous medium to form a chelant agglomerate, and drying the chelant agglomerate. in the preferred embodiment, the transition metal chelant is sodium ditriaminepentaacetate and the inorganic compound is selected from the group consisting of sulfates, carbonates, silicates, aluminosilicates and mixtures thereof. Desirably, the inorganic compound is an aluminosilicate material and preferably, the inorganic compound is an aluminosilicate ion exchange material of the formula. Mm/n[(A10~)m(Si02)y]~xH,p where n is the valence of the cation M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y/m is 1 to 100, and wherein M is selected from the group consisting of sodium, potassium, magnesium, and calcium. Most preferably, the inorganic compound is zeolite.
In the preferred embodiment, the step of admixing includes mixing and granulating the transition metal chelant and the inorganic compound in one or more of a high-speed mixer and granulator, desirably in a weight ratio in a range of from about 10:90 to about 80:20 respectively, preferably in a weight ratio in a range of from about 15:85 to about 60:40 respectively and most preferably in a weight ratio in a range of from about 25:75 to about 35:65 respectively 2p In the preferred embodiment, the step of agglomerating includes forming a chelant-inorganic compound pre-mix with water before agglomerating, desirably in a weight ratio in a range of from about 10:90 to about 80:20 respectively, preferably in a weight ratio in a range of from about 15:85 to about 60:40 respectively and most preferably in a weight ratio in a range of from about 25:75 to about 35:65 respectively In another preferred embodiment of the present invention, a process for improving storage stability and scoopability of a laundry detergent composition is disclosed. In this preferred embodiment of the present invention, the process includes the first step of forming a chelant agglomerate. It has very surprisingly been found that when the chelant particles are separated from the rest of the laundry detergent composition and chelant agglomerates are formed and then the chelant agglomerates are incorporated into a particulate laundry detergent composition, there is a dramatic increase in the resultant laundry detergent composition's storage stability and scoopability when the chelant agglomerate is eventually ad-mixed with the detergent powder in a desired weight ratio in a range of from about 0.05:99.95 to about 2:98, a preferred weight ratio in a range of from about 0.3:99.7 to about 1.5:98.5, and a most preferred weight ratio in a range of from about 0.1:99.9 chelant agglomerate:laundry detergent composition. Thus it has been surprisingly found that by expressly separating the chelant particles from the laundry detergent composition and only incorporating a chelant agglomerate into a laundry detergent composition, the finish product, i.e., the laundry detergent composition , has much improved "lump cake" properties, i.e., that the detergent composition having a chelant, has improved storage stability and scoopabiliry. Without being bound to any speciftc theory, it is believed that this improvement is achieved as a result of having separated the hygroscopic transition metal chelant from the rest of the "sticky" laundry composition.
For the purposes herein, the tern "lump cake" property is meant to include composition storage stability and powder sotubiiiry in water. The term "sticky" components is meant to include a mixture of one or more of surfactants, polyethylene glycol, polyacrylates and water.
The term "builder" is intended to mean all materials which tend to remove calcium ion from solution, either by ion exchange, complexation, sequestration or precipitation. The term "scoopability" is defined on a scale of 1 to 5, I being the least desirable value and 5 being the most desirable value, of the ability or characteristic of a laundry composition to be scooped up in a spoon without exhibiting tackiness or clumpiness.
Cheiants The chelaUng agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents, sodium ditriaminepentaacetate and mixtures thereof Without intending to be bound by theory, it is believed that the benefit of these materials is due in pan 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, nitrilo-triacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, 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 TM
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.
Polyfunetionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3.8 i 2,044, issued May 21, 1974, to Connor et al.
Preferred compounds ~$-of this type in acid fotirt are 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 4,704,233, November 3, 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.05%
to about 10°i°
by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will compnse from about O.OS% to about 3.0°~o by weight of such compositions.
The most preferred transition metal chelant used to carry out the present invention is sodium ditriaminepentaacetate (DTPA). The DTPA is preferably used in a weight ratio of from about 0.1:99.9 to about 1.5:98.5. DTPA agglomerate:laundry detergent composition and most preferably. in a weight ratio of 0.4:99.6. Preferably the chelant agglomerate consists of DTPA
and zeolite in a preferred weight ratio ir, a range of from about 15:85 to about 25:75, DTPA:zeoiite.
1 s Aluminosilicate material in the preferred embodiment of the present invention, the structural formula of an aluminosiltcate material is based on the crystal unit cell, the smallest unit of structure represented by:
Mm/n[(A10,)m(S~O:)y]~xH~O
?0 where n is the valence of the canon M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y/m is 1 to 100. Most preferably, y/m is 1 to 5. The canon M can be Group lA and Group lIA elements, such as sodium, potassium, magnesium. and calcium. The preferred aluminosilicate materials are zeolites_ The most preferred zeolites are zeolite A, zeolite X, zeolite Y, zeolite P, zeolite MAP
and mixtures thereof.
25 The aluminosilicate ion exchange materials used herein for chelant agglomerates have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange materials used herein are 30 preferably produced in accordance with Corkill et al, U.S. Patent No.
COMPOSITION FOR IMPROVING ITS STORAGE STABILITY;
FLOWABILITY AND SCOOPABILITY
TECHNICAL FIELD
The present invention relates to a laundry detergent compositions and more particularly, to a process for improving storage stability and scoopability of laundry detergent compositions by incorporation of useful levels of a concentrated chelant agglomerate into a laundry detergent composition.
BACKGROUND OF THE INVENTION
It has been extremely desirable to have a process for increasing the storage stability and scoopability of detergent compositions. This is a characteristic that most consumers are very desirous of because consumers do not want to have to deal with detergent compositions that "clump" together after the detergent box has been laid open for an extended period of time due to the inadvertent absorption of moisture.
It has beer. recognized that the incorporation of a transition metal chelant into the base granules of the laundry detergent composition causes the promotion of interlocking crystalline needle growth which is suspected to detrimentally affect the resultant particulate laundry detergent composition's flowability and scoopability properties. Thus it has been recognized by the inventors of this particular invention that it is extremely advantageous to devise a method of separating the transition metal chelant from the base granule of the laundry detergent composition, so that any useful level of the transition metal chelant may be incorporated in the overall laundry detergent composition without adversely affecting its flowability and scoopability properties. It has thus been extremely desirable to have a process or a method whereby any useful level of a chelant agglomerate can be ad-mixed into a laundry detergent composition such that the chelant agglomerate desirably improves the solubility and storage stability of the resultant ad-mixed detergent composition formulation and at the very least, does not detrimentally affect the laundry detergent composition's flowability and scoopability characteristics. The present invention overcomes the problems, as set forth above.
BACKGROUND ART
U.S. Patent 5,108,646 discloses a process for making detergent builder agglomerates by mixing a detergent builder with a selected binder to form free flowing agglomerates.
International Publication Number WO 97/09415 discloses a non-spray-dried particulate detergent composition prepared by mixing and granulating liquid and solid ingredients in a high-speed mixer/granulator, containing a builder polymer and/or a soil-release polymer, wherein the polymer is incorporated during the mixing and granulating process in the form of a non-aqueous premix with a non-aqueous diluent.
SUMMARY OF THE INVENTION
The invention meets the needs above by providing a process for preparation of a chelant composition by a non-spray-drying process, a process for improving one or more of storage stability, flowability and scoopability of a laundry detergent composition, and a chelant agglomerate useful as an ad-mix in a particulate laundry detergent.
In one aspect of the present invention, a process for preparation of a chelant composition by a non-spray-drying process includes the steps of admixing a transition metal chelant and an inorganic compound to form a mixture, agglomerating the mixture in an aqueous medium to form a chelant agglomerate and drying the chelant agglomerate.
In another aspect of the invention there is provided a process for preparation of a chelant composition by a non-spray-drying process, comprising the steps of:
a)admixing a transition metal chelant and an inorganic compound to form a mixture; b) agglomerating said mixture in an aqueous medium to form a chelant agglomerate; and c) drying said chelant agglomerate wherein the inorganic compound is selected from the group consisting of sulfates, carbonates, silicates, aluminosilicates and mixtures thereof; and wherein the transition metal chelant is selected from the group consisting of diethylenetriaminepentaacetates;
ethylenediamine disuccinate; and mixtures thereof; and wherein the chelant agglomerate resulting from step c) consists of said transition metal chelant and said inorganic compound.
In a further aspect of the present invention, a process for improving one or more of storage stability, flowability and scoopability of a laundry detergent composition includes the steps of providing a chelant composition prepared by a non-spray-drying process and incorporating the chelant composition into a particulate laundry detergent material in a weight ratio in a range of from about 0.05:99.95 to about 2:98, chelant composition to particulate laundry detergent material. The non-spray-drying process includes the steps of admixing a transition metal chelant and an inorganic compound to form a mixture, agglomerating the 2a mixture in an aqueous medium to form a chelant agglomerate, and drying the chelant agglomerate.
In yet another aspect of the present invention, a chelant agglomerate useful as an ad-mix in a particulate laundry detergent is disclosed. The chelant agglomerate has a composition including a transition metal chelant, an inorganic compound and water. The chelant agglomerate is formed by admixing the transition metal chelant and the inorganic compound to form a mixture, agglomerating the mixture in the water to form the chelant agglomerate, and drying the chelant agglomerate.
These and other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment and the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
In the preferred embodiment of the present invention, the process for preparation of a chelant composition by a non-spray-drying process includes the steps of admixing a transition S metal chelant and an inorganic compound to form a mixture, agglomerating the mixture in an aqueous medium to form a chelant agglomerate, and drying the chelant agglomerate. in the preferred embodiment, the transition metal chelant is sodium ditriaminepentaacetate and the inorganic compound is selected from the group consisting of sulfates, carbonates, silicates, aluminosilicates and mixtures thereof. Desirably, the inorganic compound is an aluminosilicate material and preferably, the inorganic compound is an aluminosilicate ion exchange material of the formula. Mm/n[(A10~)m(Si02)y]~xH,p where n is the valence of the cation M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y/m is 1 to 100, and wherein M is selected from the group consisting of sodium, potassium, magnesium, and calcium. Most preferably, the inorganic compound is zeolite.
In the preferred embodiment, the step of admixing includes mixing and granulating the transition metal chelant and the inorganic compound in one or more of a high-speed mixer and granulator, desirably in a weight ratio in a range of from about 10:90 to about 80:20 respectively, preferably in a weight ratio in a range of from about 15:85 to about 60:40 respectively and most preferably in a weight ratio in a range of from about 25:75 to about 35:65 respectively 2p In the preferred embodiment, the step of agglomerating includes forming a chelant-inorganic compound pre-mix with water before agglomerating, desirably in a weight ratio in a range of from about 10:90 to about 80:20 respectively, preferably in a weight ratio in a range of from about 15:85 to about 60:40 respectively and most preferably in a weight ratio in a range of from about 25:75 to about 35:65 respectively In another preferred embodiment of the present invention, a process for improving storage stability and scoopability of a laundry detergent composition is disclosed. In this preferred embodiment of the present invention, the process includes the first step of forming a chelant agglomerate. It has very surprisingly been found that when the chelant particles are separated from the rest of the laundry detergent composition and chelant agglomerates are formed and then the chelant agglomerates are incorporated into a particulate laundry detergent composition, there is a dramatic increase in the resultant laundry detergent composition's storage stability and scoopability when the chelant agglomerate is eventually ad-mixed with the detergent powder in a desired weight ratio in a range of from about 0.05:99.95 to about 2:98, a preferred weight ratio in a range of from about 0.3:99.7 to about 1.5:98.5, and a most preferred weight ratio in a range of from about 0.1:99.9 chelant agglomerate:laundry detergent composition. Thus it has been surprisingly found that by expressly separating the chelant particles from the laundry detergent composition and only incorporating a chelant agglomerate into a laundry detergent composition, the finish product, i.e., the laundry detergent composition , has much improved "lump cake" properties, i.e., that the detergent composition having a chelant, has improved storage stability and scoopabiliry. Without being bound to any speciftc theory, it is believed that this improvement is achieved as a result of having separated the hygroscopic transition metal chelant from the rest of the "sticky" laundry composition.
For the purposes herein, the tern "lump cake" property is meant to include composition storage stability and powder sotubiiiry in water. The term "sticky" components is meant to include a mixture of one or more of surfactants, polyethylene glycol, polyacrylates and water.
The term "builder" is intended to mean all materials which tend to remove calcium ion from solution, either by ion exchange, complexation, sequestration or precipitation. The term "scoopability" is defined on a scale of 1 to 5, I being the least desirable value and 5 being the most desirable value, of the ability or characteristic of a laundry composition to be scooped up in a spoon without exhibiting tackiness or clumpiness.
Cheiants The chelaUng agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents, sodium ditriaminepentaacetate and mixtures thereof Without intending to be bound by theory, it is believed that the benefit of these materials is due in pan 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, nitrilo-triacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, 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 TM
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.
Polyfunetionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3.8 i 2,044, issued May 21, 1974, to Connor et al.
Preferred compounds ~$-of this type in acid fotirt are 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 4,704,233, November 3, 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.05%
to about 10°i°
by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will compnse from about O.OS% to about 3.0°~o by weight of such compositions.
The most preferred transition metal chelant used to carry out the present invention is sodium ditriaminepentaacetate (DTPA). The DTPA is preferably used in a weight ratio of from about 0.1:99.9 to about 1.5:98.5. DTPA agglomerate:laundry detergent composition and most preferably. in a weight ratio of 0.4:99.6. Preferably the chelant agglomerate consists of DTPA
and zeolite in a preferred weight ratio ir, a range of from about 15:85 to about 25:75, DTPA:zeoiite.
1 s Aluminosilicate material in the preferred embodiment of the present invention, the structural formula of an aluminosiltcate material is based on the crystal unit cell, the smallest unit of structure represented by:
Mm/n[(A10,)m(S~O:)y]~xH~O
?0 where n is the valence of the canon M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y/m is 1 to 100. Most preferably, y/m is 1 to 5. The canon M can be Group lA and Group lIA elements, such as sodium, potassium, magnesium. and calcium. The preferred aluminosilicate materials are zeolites_ The most preferred zeolites are zeolite A, zeolite X, zeolite Y, zeolite P, zeolite MAP
and mixtures thereof.
25 The aluminosilicate ion exchange materials used herein for chelant agglomerates have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange materials used herein are 30 preferably produced in accordance with Corkill et al, U.S. Patent No.
4,605,509 (Procter & Gamble).
Preferably, the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit the as high of an exchange rate and capacity as provided by the sodium form. Additionally, the aluminosilicate ion WO 00!20550 ~ PCT/US99/22922 exchange material preferably is in over dried form so as to facilitate production of crisp chelant agglomerates as described herein. The aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
The term "particle size diameter" as used herein represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM). The preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
l0 In a preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Nal2[(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 1 ~ has a particle size of about 0.1-10 microns in diameter.
Laundry detergent comnosit~on In the preferred embodiment, the laundry detergent composition has a composition including a chelant agglomerate made according to the present invention and incorporated into the laundry detergent composition. The laundry detergent composition also comprises a builder '0 made by agglomeration or spray dried process, sodium carbonate, sodium sulfate, sodium tripolyphosphate, anionic and nonionic surfactants and balance water. Laundry detergent compositions are well known in the art and various examples of various laundry detergent compositions are disclosed, for example in U.S. Patent No. 5,554,587, issued to Scott W. Capeci, and assigned to The Procter & Gamble Company.
25 Chelant aeQlomerates made by aa~lomeration process In the preferred embodiment of she present invention, the chelant agglomerates are made by an agglomeration process.
T_he aaalomeration process The agglomeration process comprises the steps of:
30 i) admixing one or more ingredients to form a mixture; and ii) agglomerating the mixture to form agglomerated particles or "agglomerates", and iii) drying the agglomerate.
Typically, such an agglomeration process involves mixing the ingredients in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably in-line mixers, _7_ preferably two, such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn I, Elsenerstrasse 7-9, Postfach 2050, Germany. Preferably a high shear mixer is used, such as a Lodige CB (Trade Mark). Most preferably, a high shear mixer is used in combination with a low shear mixer, such as a Lodige CB (Trade Mark) and a Lodige KM (Trade Mark) or Schugi KM
(Trade Mark). Optionally, only one or more low shear mixer are used.
Preferably, the agglomerates are thereafter dried and/ or cooled. An excellent description of an agglomeration process is contained in U.S. Patent No. 5,554,587. issued to Scott W. Capeci, and assigned to The Procter ZC Gamble Company.
Another agglomeration process involves mixing of various components of the ftnal agglomorate in different stages, using an fluidized bed. For example, a detergent powder can be agglomerated by spraying on of surfactants and optionally a wax, or mixtures thereof. to the acid source in powdered form and other optional ingredients. Then, additional components, including the perborate bleach and optionally the alkali source or part thereof, can be added and 1 ~ agglomerated in one or more stages, thus forming the final agglomerate particle.
The agglomerates may take the form of flakes, prills, marumes, noodles.
ribbons, but preferably take the form of granules. A preferred way to process the particles is by agelomerating dry material (e_g. aluminosilicate, carbonate) with high active surfactant pastes and to control the panicle size of the resulting agglomerates within specified limits. Typical ?0 particle sizes are from 0.10 mm to 5.0 mm in diameter, preferably from 0.25 mm to 3.0 mm in diameter, most preferably from 0.40 mm to 1.00 mm in diameter. Typically, the "agglomerates"
have a bulk density desirably .of at least 700 g/1 and preferably, in a range of from about 700 g/1 to about 900 g11.
AdLunct Detergent Ingredients ?5 The adjunct ingredients include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smecnte clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S.
Patent 3,936,537, issued February 3, 1976 to Baskerville,1r. et al.
30 Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, Chelating agents are also described in U.S.
Patent 4,663,071, Bush et al., from Column 17, tine 54 through Column 18, line 68.
Suds modifiers are also optional ingredients and are described in U.S.
_$_ Patents 3,933,672, issued 3anuary 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23.
1979 to Gault et al.
Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24.
Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4.663,071, Bush et al, issued May 5, 1987.
Surfactants :Anionic Surfactant - The preferred anionic surfactants include C 11-C1 g alkyl benzene sulfonates (LAS) and primary, branched-chain and random C10-C20 alkyl sulfates (AS), the CIO-Clg secondary (2.3) alky.~l sulfates of the formula CH3(CH2)x(CHOS03 M+) CH3 and CH3 (CH2)y(CHOS03 M+) CH2CH3 where x and (y + 1 ) are integers of at least about 7, preferably at least about 9, and M is a water-soiubilizing canon, especially sodium, unsaturated sulfates such as oleyl sulfate, the C 10-C 1 g alkyl alkoxy sulfates ("AEXS";
especially EO 1-7 1 ~ ethoxy sulfates), C 10-C 1 g allyl alkoxv carboxylates (especially the EO
I-S
ethoxycarboxylates). the C l 0-1 g glycerol ethers, the C 10-C 18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and CI~-C18 alpha-sulfonated fatty acid esters.
Generally speaking, anionic surfactants useful herein are disclosed in U.S.
Patent No.
4.285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent No.
3,919,678, Laughlin et ~0 al. issued December 30, 1975.
Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester ?5 group. (Included in the term "alkyl" is the alkyl portion of aryl groups.) Examples of this group of synthetic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-C 1 g carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil.
Other anionic surfactants herein are the water-soluble salts of alkyl phenol ethylene oxide 30 ether sulfates containing from about I to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group.
Other useful anionic surfactants herein include the water-soluble salts of esters of a-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; 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 b-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 moiet)-.
Other useful anionic surfactants herein are the alkyl polyethoxylate sulfates of the formula RO(C~H40)xS03-M+
wherein R is an alkyl chain having from about 10 to about 22 carbon atoms, saturated or unsaturated. M is a canon which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium canon, and x averages from about 1 to about 15.
Other alkyl sulfate surfactants are the non-ethoxylated C12-15 Pnmary and secondary.
allyl sulfates. Under cold water washing conditions, i.e., less than abut 65°F (18.3°C), it is preferred that there be a mixture of such ethoxylated and non-ethoxylated alkyl sulfates.
Examples of fatty acids include capric, lauric, myristic, palmitic, stearic, arachidic, and behenic acid. Other fatty acids include palmitoleic, oleic, linoleic, linolenic, and ricinoleic acid.
Nonionic Surfactant - Conventional nonionic and amphoteric surfactants include C 12-C 1 g alkyl ethoxylates (AE) including the so-called narrow peaked alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy). The C 10-C 1 g N-alkyl potyhydroxy fatty acid amides can also be used. Typical examples include the C
12-C 1 g N-methylglucamides. See WO 92/06154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10-C 1 g N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C 12-C 18 glucamides can be used for low sudsing. C 10-conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Examples of nonionic surfactants are described in U.S.
Patent No.
4,285.841, Barrat et al, issued August 25, 1981.
Examples of surfactants also include ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(OC2H4)nOH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about I S carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15. These surfactants are more fully described in U.S. Patent No. 4,284,532, Leikhim et al, issued August 18, 1981. Other surfactants include ethoxylated alcohols having an average of from about 10 to abut 15 carbon atoms in the alcohol and an average degree of ethoxylation of from about 6 to about 12 moles of ethylene oxide per mole of alcohol. Mixtures of anionic and nonionic surfactants are especially useful.
Other conventional useful surfactants are listed in standard texts, including polyhydroxy fatty acid amides, alkyl glucosides, polyalkyl glucosides, C12-Clg betaines and _ sulfobetaines (sultaines). Examples include the C12-Clg N-methylglucamides.
See WO
9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10-C I g N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C 12-C I g glucamides can be used for low sudsing.
Cationic Surfactants One class of useful cationic surfactants are the mono alkyl quaternary ammonium surfactants although any cationic surfactant useful in detergent compositions are suitable for use herein.
The cationic surfactants which can be used herein include quaternary ammonium surfactants of the formula:
R4\ / R~
/ \
wherein R 1 and R2 are individually selected from the group consisting of C 1-C4 alkyl, C 1-C4 hydroxy alkyl, benryl, and -(C2H40)xH where x has a value from about 2 to about S; X is an anion; and ( 1 ) R3 and R4 are each a C6-C 14 alkyl or (2) R3 is a C6-C 1 g alkyl, and R4 is selected from the group consisting of C I-C l0 alkyl, C I -C 10 hydroxyalkyl, benryl, and -(C2H40)xH where x has a value from 2 to 5.
Other useful quaternary ammonium surfactants are the chloride, bromide, and methylsulfate salts. Examples of desirable mono-long chain alkyl quaternary ammonium surfactants are those wherein R I , R2, and R4 are each methyl and R3 is a Cg-C 16 alkyl; or wherein R3 is Cg-1 g alkyl and R1, R2, and R4 are selected from methyl and hydroxyalkyl moieties. Lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, coconut trimethylammonium chloride, coconut trimethylammonium methylsulfate, coconut dimethyl-monohydroxy-ethylammonium chloride, coconut dimethyl-monohydroxyethylammonium methylsulfate, steryl dimethyl-monohydroxy--I I-ethylammonium chloride, steryl dimethyl-monohydroxyethylammonium methylsulfate, di- C12-C 14 alkyl dimethyl ammonium chloride, and mixtures thereof are also desirable. ADOGEN
412T"", a lauryl trimethyl ammonium chloride commercially available from Witco, is also desirable. Other desirable surfactants are lauryl trimethyl ammonium chloride and myristyl trimethyl ammonium chloride.
Another group of suitable cationic surfactants are the alkanol amidal quaternary surfactants of the formula:
O
R 1-Ci-N-( CH2 ) n-Y-( CH2 ) n-X
wherein RI can be C10-18 alkyl or a substituted or unsubstituted phenyl; R2 can be a C1~
alkyl, H, or (EO)y, wherein y is from about 1 to about 5; Y is O or -N(R3)(R4); R3 can be H, C 1 ~ alkyl, or (EO)y, wherein y is from about 1 to about S; R4, if present, can be C 1 ~ alkyl or (EO)y, wherein y is from about 1 to about S; each n is independently selected from about 1 to about 6, preferably from about 2 to about 4; X is hydroxyl or -N(RS)(R6)(R~), wherein R5, R6, R~ are independently selected from C1~ alkyl, H, or (EO)y, 1 > wherein y is from about 1 to about 5.
Amine Oxide Surfactants - The laundry detergent compositions herein also contain amine oxide surfactants of the formula:
R1(EO)x(PO)y(BO)zN(O)(CH2R')2.qH2O (I) In general, it can be seen that the structure (I) provides one long-chain moiety Rl(EO)x(PO)y(BO)z and two short chain moieties, CH2R'. R' is preferably selected from hydrogen, methyl and -CH20H. In general R1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, Rl is a primary alkyl moiety. When x+y+z =
0, RI is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
When x+y+z is different from 0. Rl may be somewhat longer, having a chainlength in the range C12-C24~ The general formula also encompasses amine oxides wherein x+y+z = 0, R1 = Cg-C 1 g, R' is H and q is 0-2, preferably 2. These amine oxides are illustrated by C12-l4 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the -12_ dehydrates as disclosed in U.S. Patents 5,075,501 and 5,071,594.
The invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R1 is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y +
z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO
represents buryleneoxy. Such amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
Desirable amore oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30°C to 90°C. Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter &
Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers. Other desirable commercially available amine oxides are the solid, TM
dehydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp.
Other embodiments include dodecyldimethylamine oxide dehydrate, hexadecyldimethylamine oxide dehydrate. octadecyldimethylamine oxide dehydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide, tetradecyldimethylamine oxide dehydrate, and mixtures thereof. Whereas in certain embodiments R' is H, there is some latitude with respect to having R' slightly larger than H. Alternate embodiments include wherein R' is CH20H. such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
Enzymes Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or trigiyceride-based stains, for example, and for fabric restoration. The enzymes to be incorporated include proteases, amylases, lipases, and cellulases, 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, thermostabiliry, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are 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 % to 1 % 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 proteases are the subtilisins which are obtained from particular strains of B. 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 A/S under the registered trademark ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No.
1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the trade marks ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc.
(The 1 S Netherlands). Other proteases include Protease A (see European Patent Application 130,756, .
published January 9, 1985) and Protease B (see European Patent Application published January 7, 1988, and European Patent Application 130,756, Bott et al, published January 9, 1985).
Amylases include, for example, a-amylases described in British Patent Specification No.
TM TM
1,296.839 (Novo), RAP)DASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
The cellulase usable in the present invention include both bacterial or fungal cellulase.
Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSMI800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricuia Solander). Suitable cellulases are also TM
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 enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 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. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S.
Biochemical Corp., U.S.A. and Diosynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The L)pOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein.
A wide range of enzyme 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 1 fi, 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, 1981.
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 I 5 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.
The enzymes employed herein may be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. (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 art-disclosed stabilizers, especially borate species. See Severson, U.S. 4,537,706. Typical detergents, especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about S to about 15, and ?S 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 enzyme 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 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 pcr liter, is often also present in the composition due to calcium in the enzyme slurry and formula water. In -1$-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, as a general proposition the compositions herein will typically comprise from about 0.0$% 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 enzyme employed in the composition.
The laundry detergent compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers. Typically, such stabiEizers will be used at levels in the compositions from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 4%, by weight of boric acid or I $ 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-, meta- 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.
Polymeric Soil Release Aeent 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 adhcred 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.
Examples of polymeric soil release agents useful herein include U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink; U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.; European Patent Application 0 219 048, published April 22, 1987 by Kud, et al.;
U.S. Patent 4,702,8$7, issued October 27, 1987 to Gosselink; U.S. Patent 4,968,4$ l, issued November 6, 1990 to J.J. Scheibel. Commercially available soil release agents include the TM
SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
Also see U.S. Patent 3,9$9.230 to Hays, issued May ?$, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, I 975. Examples of this polymer include the commercially available TM TM
material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). 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 3anuary 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, I987 to Gosselink.
Preferred polymeric soil release agents also include the soil release agents of U.S.
Patent 4,877,896, issued October 31, 1989 to Maldonado et al.
If utilized, soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0_I% to about 5%, preferably from about 0.2% to about 3_0%.
Clay Soil Removal/Anti-redeposition Agents The laundry detergent compositions of the present invention can also optionally contair~
water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
IS Liquid detergent compositions typically contain about 0.01% to about S%.
The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removai-antiredeposition agents are the cationic compounds disclosed in European Patent Application 1 I 1,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 11 1.984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, i98S.
Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
Polymeric Dispersing Agents Polymeric dispersing agents can advantageously be utilized at levels from about 0.1°i° to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates 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 enhance 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 ran=es from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably 1 ~ 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 la~town 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 d~spersing/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 I:1, more preferably 2S from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic 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 maieic/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 S00 to about 100.000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
Brightener Any optical brighteners or other brightening or whitening agents lmown in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent t 0 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 I S 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. Patcnt 4,790,856, issued to Wixon on December 13, 1988. These 'rM
br~ghteners include the PHORWHITE sencs of brighteners from Verona. Other brighteners 'rM
20 disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal SBM: available 'rM
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-dJtriazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil-benes: 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-yi)ethylene;
25 1,3-Biphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-[1,2-dJoxazole; and 2-(stilbene-4-yl)-2H-naphtho- { 1,2-dJtriazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.
Suds Suppressors Compounds for reducing or suppressing the formation of suds can be incorporated into 30 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 4,489,574 and in front-loading European-style washing machines.
A wide variety of materials may be used as suds suppressors, and suds suppressors are welt known to those skiiled 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 suppressor of particular interest encompasses monocarboxylic 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 suppressor 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 laundry detergent compositions herein may also contain non-surfactant suds suppressors. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 1 g-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino tnazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines 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 I ~ monostearyl alcohol phosphate ester and monostearyi di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin 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 ~l0°C and about SO°C, and a minimum boiling point not less than about 110°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 ?5 12 to about 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors 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 are, 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 siianated silica are described, for instance, in German Patent Application DOS 2,124,526.
In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked 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 suppressor, 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. See also U.S. Patents 4,978,471, Starch, issued 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 suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all 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 5 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 glycol/polypropylene 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 suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers T"M
of ethylene oxide and propylene oxide, like PLUROIVIC LI01.
Other suds suppressors 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, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C 16 alkyl alcohols having a C1-C16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures 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 sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic Laundry washing machines.
The laundry detergent 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. 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 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.
Dye Transfer lnhibiting,Aaents The laundry detergent 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 polymers, 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 s%, and more preferably from about O.OS%
to about 2%.
More specifically, the polyamine N-oxide polymers preferred 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 polymerizable unit or the N-O
group can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; 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:
O O
I I
(Rt )x- j -~2)y; =N'.'(R~ )x (R3 )z is wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned 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-soluble 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 2s 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 can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinyfpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI") are also preferred 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. "Modem Methods of Polymer Characterization".) The PVPVI copolymers typically have a molar ratio u: N-vinylimidazole to N-vinylpyrtolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
The laundry detergent compositions also may employ 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. incorporated herein by reference. Compositions containing PVP 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 ?0 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.
The laundry detergent compositions herein may also optionally contain from about 0.005% to S% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those having the structural formula:
R~
~N H Ii N
N N C C N N
~N H H N \
RI, S03M S03M Ry wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2.2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the trademark Tinopal-iJNPA-GX by Ciba-Geigy Corporation.
Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a canon such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2.2'-stilbenedisulfonic acid disodium salt.
This particular brightener species is commercially marketed under the trademark Tinopal SBM-GX
by Ciba--Geigy Corporation.
1 ~ When in the above formula, RI is anilmo, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2.2'-sUlbened~sulfonic acid, sodium salt. This particular brightener species is commercially marketed udder the trademark Tinopal AMS-GX by Ciba Geigy Corporation.
The specific optical brightener species selected for use in the present invention provide ?0 especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brtghteners (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these 25 two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the 30 brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
Of course, it will be appreciated that other, conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations.
Bleaching Compounds - Bleachine Aeents and Bleach Activators The laundry detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one ar more bleach activators. Whey present, bleaching agents will typically be at levels of from about I% 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 useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now 1~ known or become irnow~n. These include oxygen bleaches as well as other bleaching agents.
Perborate bleaches, e.g.. sodium perborate (e.g., mono- or tetra-hydrate) and percarbonate bleaches can be used herein.
Another category of bleaching agent that can be used without restriction 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-nonyiaminoji-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U_S. Patent 4.483.781, Hartman. issued November 20, 1984, U.S. Patent No. 4,634,551 issued January 6, 1987, European Patent Application 0.133.354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et ai, vssucd November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycapro~c 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 pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Persulfate bleach TM
(e.g., OXONE, manufactured commercially by DuPont) can also be used.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents. the perborates. the percarbonates, etc., are preferably combined with bleach activators. which lead to the in situ production in aquec::,s solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao 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 are those of the formulae:
R1N(R5)C(O)R2C(O)L or RIC(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an allylene containing from 1 to about 6 carbon atoms, R~ is H or alkyl, aryl, or alkaryl containing from about 1 to about f 0 carbon atoms, and L is any suitable leaving group. A
leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leavins group is phenyl sul fonate_ Preferred examples of bleach activators of the above formulae include (6-I S octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesul-fonate, (6-decanamidocaproyl)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 Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990.
Still another class of preferred bleach activators includes the acyl lactam activators.
especially acyl caprolactams and acyl valerolactams. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl vaieroiactam, decanoyl vaierolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching 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. 549,271A1, 549,272A1, 544,440A2, and 544,490A 1. 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.
Anti-Static Age., nts The laundry detergent compositions can also comprise anti-static agents as illustrated in U.S. Pat. 4,861.502. Preferred examples of anti-static agents include alkyl amine-anionic surfactant ion pairs, such as distearyl amine-cumene sulfonate ion pairs. If present, anti-static agents are present in an amount of from about 0.5% to about 20%, preferably from about 1 % to about 10°ro, more preferably from about 1% to about 5%, by weight of the detergent composition.
In the following Example A, an embodiment of the present invention of a chelant agglomerate is exemplified:
p EXAMPLE A
In e, rg-d'~ent Wt%
Zeolite 85.00 DTPA 15.00 Total 100.0%
Accordingly, having thus described the invention in detail, it will be obvious to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.
Preferably, the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit the as high of an exchange rate and capacity as provided by the sodium form. Additionally, the aluminosilicate ion WO 00!20550 ~ PCT/US99/22922 exchange material preferably is in over dried form so as to facilitate production of crisp chelant agglomerates as described herein. The aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
The term "particle size diameter" as used herein represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM). The preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
l0 In a preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Nal2[(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 1 ~ has a particle size of about 0.1-10 microns in diameter.
Laundry detergent comnosit~on In the preferred embodiment, the laundry detergent composition has a composition including a chelant agglomerate made according to the present invention and incorporated into the laundry detergent composition. The laundry detergent composition also comprises a builder '0 made by agglomeration or spray dried process, sodium carbonate, sodium sulfate, sodium tripolyphosphate, anionic and nonionic surfactants and balance water. Laundry detergent compositions are well known in the art and various examples of various laundry detergent compositions are disclosed, for example in U.S. Patent No. 5,554,587, issued to Scott W. Capeci, and assigned to The Procter & Gamble Company.
25 Chelant aeQlomerates made by aa~lomeration process In the preferred embodiment of she present invention, the chelant agglomerates are made by an agglomeration process.
T_he aaalomeration process The agglomeration process comprises the steps of:
30 i) admixing one or more ingredients to form a mixture; and ii) agglomerating the mixture to form agglomerated particles or "agglomerates", and iii) drying the agglomerate.
Typically, such an agglomeration process involves mixing the ingredients in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably in-line mixers, _7_ preferably two, such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn I, Elsenerstrasse 7-9, Postfach 2050, Germany. Preferably a high shear mixer is used, such as a Lodige CB (Trade Mark). Most preferably, a high shear mixer is used in combination with a low shear mixer, such as a Lodige CB (Trade Mark) and a Lodige KM (Trade Mark) or Schugi KM
(Trade Mark). Optionally, only one or more low shear mixer are used.
Preferably, the agglomerates are thereafter dried and/ or cooled. An excellent description of an agglomeration process is contained in U.S. Patent No. 5,554,587. issued to Scott W. Capeci, and assigned to The Procter ZC Gamble Company.
Another agglomeration process involves mixing of various components of the ftnal agglomorate in different stages, using an fluidized bed. For example, a detergent powder can be agglomerated by spraying on of surfactants and optionally a wax, or mixtures thereof. to the acid source in powdered form and other optional ingredients. Then, additional components, including the perborate bleach and optionally the alkali source or part thereof, can be added and 1 ~ agglomerated in one or more stages, thus forming the final agglomerate particle.
The agglomerates may take the form of flakes, prills, marumes, noodles.
ribbons, but preferably take the form of granules. A preferred way to process the particles is by agelomerating dry material (e_g. aluminosilicate, carbonate) with high active surfactant pastes and to control the panicle size of the resulting agglomerates within specified limits. Typical ?0 particle sizes are from 0.10 mm to 5.0 mm in diameter, preferably from 0.25 mm to 3.0 mm in diameter, most preferably from 0.40 mm to 1.00 mm in diameter. Typically, the "agglomerates"
have a bulk density desirably .of at least 700 g/1 and preferably, in a range of from about 700 g/1 to about 900 g11.
AdLunct Detergent Ingredients ?5 The adjunct ingredients include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smecnte clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S.
Patent 3,936,537, issued February 3, 1976 to Baskerville,1r. et al.
30 Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, Chelating agents are also described in U.S.
Patent 4,663,071, Bush et al., from Column 17, tine 54 through Column 18, line 68.
Suds modifiers are also optional ingredients and are described in U.S.
_$_ Patents 3,933,672, issued 3anuary 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23.
1979 to Gault et al.
Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24.
Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4.663,071, Bush et al, issued May 5, 1987.
Surfactants :Anionic Surfactant - The preferred anionic surfactants include C 11-C1 g alkyl benzene sulfonates (LAS) and primary, branched-chain and random C10-C20 alkyl sulfates (AS), the CIO-Clg secondary (2.3) alky.~l sulfates of the formula CH3(CH2)x(CHOS03 M+) CH3 and CH3 (CH2)y(CHOS03 M+) CH2CH3 where x and (y + 1 ) are integers of at least about 7, preferably at least about 9, and M is a water-soiubilizing canon, especially sodium, unsaturated sulfates such as oleyl sulfate, the C 10-C 1 g alkyl alkoxy sulfates ("AEXS";
especially EO 1-7 1 ~ ethoxy sulfates), C 10-C 1 g allyl alkoxv carboxylates (especially the EO
I-S
ethoxycarboxylates). the C l 0-1 g glycerol ethers, the C 10-C 18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and CI~-C18 alpha-sulfonated fatty acid esters.
Generally speaking, anionic surfactants useful herein are disclosed in U.S.
Patent No.
4.285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent No.
3,919,678, Laughlin et ~0 al. issued December 30, 1975.
Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester ?5 group. (Included in the term "alkyl" is the alkyl portion of aryl groups.) Examples of this group of synthetic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-C 1 g carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil.
Other anionic surfactants herein are the water-soluble salts of alkyl phenol ethylene oxide 30 ether sulfates containing from about I to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group.
Other useful anionic surfactants herein include the water-soluble salts of esters of a-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; 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 b-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 moiet)-.
Other useful anionic surfactants herein are the alkyl polyethoxylate sulfates of the formula RO(C~H40)xS03-M+
wherein R is an alkyl chain having from about 10 to about 22 carbon atoms, saturated or unsaturated. M is a canon which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium canon, and x averages from about 1 to about 15.
Other alkyl sulfate surfactants are the non-ethoxylated C12-15 Pnmary and secondary.
allyl sulfates. Under cold water washing conditions, i.e., less than abut 65°F (18.3°C), it is preferred that there be a mixture of such ethoxylated and non-ethoxylated alkyl sulfates.
Examples of fatty acids include capric, lauric, myristic, palmitic, stearic, arachidic, and behenic acid. Other fatty acids include palmitoleic, oleic, linoleic, linolenic, and ricinoleic acid.
Nonionic Surfactant - Conventional nonionic and amphoteric surfactants include C 12-C 1 g alkyl ethoxylates (AE) including the so-called narrow peaked alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy). The C 10-C 1 g N-alkyl potyhydroxy fatty acid amides can also be used. Typical examples include the C
12-C 1 g N-methylglucamides. See WO 92/06154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10-C 1 g N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C 12-C 18 glucamides can be used for low sudsing. C 10-conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Examples of nonionic surfactants are described in U.S.
Patent No.
4,285.841, Barrat et al, issued August 25, 1981.
Examples of surfactants also include ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(OC2H4)nOH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about I S carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15. These surfactants are more fully described in U.S. Patent No. 4,284,532, Leikhim et al, issued August 18, 1981. Other surfactants include ethoxylated alcohols having an average of from about 10 to abut 15 carbon atoms in the alcohol and an average degree of ethoxylation of from about 6 to about 12 moles of ethylene oxide per mole of alcohol. Mixtures of anionic and nonionic surfactants are especially useful.
Other conventional useful surfactants are listed in standard texts, including polyhydroxy fatty acid amides, alkyl glucosides, polyalkyl glucosides, C12-Clg betaines and _ sulfobetaines (sultaines). Examples include the C12-Clg N-methylglucamides.
See WO
9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10-C I g N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C 12-C I g glucamides can be used for low sudsing.
Cationic Surfactants One class of useful cationic surfactants are the mono alkyl quaternary ammonium surfactants although any cationic surfactant useful in detergent compositions are suitable for use herein.
The cationic surfactants which can be used herein include quaternary ammonium surfactants of the formula:
R4\ / R~
/ \
wherein R 1 and R2 are individually selected from the group consisting of C 1-C4 alkyl, C 1-C4 hydroxy alkyl, benryl, and -(C2H40)xH where x has a value from about 2 to about S; X is an anion; and ( 1 ) R3 and R4 are each a C6-C 14 alkyl or (2) R3 is a C6-C 1 g alkyl, and R4 is selected from the group consisting of C I-C l0 alkyl, C I -C 10 hydroxyalkyl, benryl, and -(C2H40)xH where x has a value from 2 to 5.
Other useful quaternary ammonium surfactants are the chloride, bromide, and methylsulfate salts. Examples of desirable mono-long chain alkyl quaternary ammonium surfactants are those wherein R I , R2, and R4 are each methyl and R3 is a Cg-C 16 alkyl; or wherein R3 is Cg-1 g alkyl and R1, R2, and R4 are selected from methyl and hydroxyalkyl moieties. Lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, coconut trimethylammonium chloride, coconut trimethylammonium methylsulfate, coconut dimethyl-monohydroxy-ethylammonium chloride, coconut dimethyl-monohydroxyethylammonium methylsulfate, steryl dimethyl-monohydroxy--I I-ethylammonium chloride, steryl dimethyl-monohydroxyethylammonium methylsulfate, di- C12-C 14 alkyl dimethyl ammonium chloride, and mixtures thereof are also desirable. ADOGEN
412T"", a lauryl trimethyl ammonium chloride commercially available from Witco, is also desirable. Other desirable surfactants are lauryl trimethyl ammonium chloride and myristyl trimethyl ammonium chloride.
Another group of suitable cationic surfactants are the alkanol amidal quaternary surfactants of the formula:
O
R 1-Ci-N-( CH2 ) n-Y-( CH2 ) n-X
wherein RI can be C10-18 alkyl or a substituted or unsubstituted phenyl; R2 can be a C1~
alkyl, H, or (EO)y, wherein y is from about 1 to about 5; Y is O or -N(R3)(R4); R3 can be H, C 1 ~ alkyl, or (EO)y, wherein y is from about 1 to about S; R4, if present, can be C 1 ~ alkyl or (EO)y, wherein y is from about 1 to about S; each n is independently selected from about 1 to about 6, preferably from about 2 to about 4; X is hydroxyl or -N(RS)(R6)(R~), wherein R5, R6, R~ are independently selected from C1~ alkyl, H, or (EO)y, 1 > wherein y is from about 1 to about 5.
Amine Oxide Surfactants - The laundry detergent compositions herein also contain amine oxide surfactants of the formula:
R1(EO)x(PO)y(BO)zN(O)(CH2R')2.qH2O (I) In general, it can be seen that the structure (I) provides one long-chain moiety Rl(EO)x(PO)y(BO)z and two short chain moieties, CH2R'. R' is preferably selected from hydrogen, methyl and -CH20H. In general R1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, Rl is a primary alkyl moiety. When x+y+z =
0, RI is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
When x+y+z is different from 0. Rl may be somewhat longer, having a chainlength in the range C12-C24~ The general formula also encompasses amine oxides wherein x+y+z = 0, R1 = Cg-C 1 g, R' is H and q is 0-2, preferably 2. These amine oxides are illustrated by C12-l4 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the -12_ dehydrates as disclosed in U.S. Patents 5,075,501 and 5,071,594.
The invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R1 is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y +
z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO
represents buryleneoxy. Such amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
Desirable amore oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30°C to 90°C. Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter &
Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers. Other desirable commercially available amine oxides are the solid, TM
dehydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp.
Other embodiments include dodecyldimethylamine oxide dehydrate, hexadecyldimethylamine oxide dehydrate. octadecyldimethylamine oxide dehydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide, tetradecyldimethylamine oxide dehydrate, and mixtures thereof. Whereas in certain embodiments R' is H, there is some latitude with respect to having R' slightly larger than H. Alternate embodiments include wherein R' is CH20H. such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
Enzymes Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or trigiyceride-based stains, for example, and for fabric restoration. The enzymes to be incorporated include proteases, amylases, lipases, and cellulases, 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, thermostabiliry, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are 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 % to 1 % 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 proteases are the subtilisins which are obtained from particular strains of B. 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 A/S under the registered trademark ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No.
1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the trade marks ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc.
(The 1 S Netherlands). Other proteases include Protease A (see European Patent Application 130,756, .
published January 9, 1985) and Protease B (see European Patent Application published January 7, 1988, and European Patent Application 130,756, Bott et al, published January 9, 1985).
Amylases include, for example, a-amylases described in British Patent Specification No.
TM TM
1,296.839 (Novo), RAP)DASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
The cellulase usable in the present invention include both bacterial or fungal cellulase.
Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSMI800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricuia Solander). Suitable cellulases are also TM
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 enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 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. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S.
Biochemical Corp., U.S.A. and Diosynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The L)pOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein.
A wide range of enzyme 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 1 fi, 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, 1981.
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 I 5 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.
The enzymes employed herein may be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. (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 art-disclosed stabilizers, especially borate species. See Severson, U.S. 4,537,706. Typical detergents, especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about S to about 15, and ?S 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 enzyme 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 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 pcr liter, is often also present in the composition due to calcium in the enzyme slurry and formula water. In -1$-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, as a general proposition the compositions herein will typically comprise from about 0.0$% 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 enzyme employed in the composition.
The laundry detergent compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers. Typically, such stabiEizers will be used at levels in the compositions from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 4%, by weight of boric acid or I $ 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-, meta- 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.
Polymeric Soil Release Aeent 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 adhcred 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.
Examples of polymeric soil release agents useful herein include U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink; U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.; European Patent Application 0 219 048, published April 22, 1987 by Kud, et al.;
U.S. Patent 4,702,8$7, issued October 27, 1987 to Gosselink; U.S. Patent 4,968,4$ l, issued November 6, 1990 to J.J. Scheibel. Commercially available soil release agents include the TM
SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
Also see U.S. Patent 3,9$9.230 to Hays, issued May ?$, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, I 975. Examples of this polymer include the commercially available TM TM
material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). 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 3anuary 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, I987 to Gosselink.
Preferred polymeric soil release agents also include the soil release agents of U.S.
Patent 4,877,896, issued October 31, 1989 to Maldonado et al.
If utilized, soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0_I% to about 5%, preferably from about 0.2% to about 3_0%.
Clay Soil Removal/Anti-redeposition Agents The laundry detergent compositions of the present invention can also optionally contair~
water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
IS Liquid detergent compositions typically contain about 0.01% to about S%.
The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removai-antiredeposition agents are the cationic compounds disclosed in European Patent Application 1 I 1,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 11 1.984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, i98S.
Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
Polymeric Dispersing Agents Polymeric dispersing agents can advantageously be utilized at levels from about 0.1°i° to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates 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 enhance 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 ran=es from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably 1 ~ 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 la~town 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 d~spersing/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 I:1, more preferably 2S from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic 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 maieic/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 S00 to about 100.000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
Brightener Any optical brighteners or other brightening or whitening agents lmown in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent t 0 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 I S 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. Patcnt 4,790,856, issued to Wixon on December 13, 1988. These 'rM
br~ghteners include the PHORWHITE sencs of brighteners from Verona. Other brighteners 'rM
20 disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal SBM: available 'rM
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-dJtriazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil-benes: 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-yi)ethylene;
25 1,3-Biphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-[1,2-dJoxazole; and 2-(stilbene-4-yl)-2H-naphtho- { 1,2-dJtriazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.
Suds Suppressors Compounds for reducing or suppressing the formation of suds can be incorporated into 30 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 4,489,574 and in front-loading European-style washing machines.
A wide variety of materials may be used as suds suppressors, and suds suppressors are welt known to those skiiled 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 suppressor of particular interest encompasses monocarboxylic 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 suppressor 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 laundry detergent compositions herein may also contain non-surfactant suds suppressors. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 1 g-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino tnazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines 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 I ~ monostearyl alcohol phosphate ester and monostearyi di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin 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 ~l0°C and about SO°C, and a minimum boiling point not less than about 110°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 ?5 12 to about 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors 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 are, 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 siianated silica are described, for instance, in German Patent Application DOS 2,124,526.
In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked 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 suppressor, 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. See also U.S. Patents 4,978,471, Starch, issued 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 suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all 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 5 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 glycol/polypropylene 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 suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers T"M
of ethylene oxide and propylene oxide, like PLUROIVIC LI01.
Other suds suppressors 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, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C 16 alkyl alcohols having a C1-C16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures 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 sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic Laundry washing machines.
The laundry detergent 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. 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 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.
Dye Transfer lnhibiting,Aaents The laundry detergent 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 polymers, 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 s%, and more preferably from about O.OS%
to about 2%.
More specifically, the polyamine N-oxide polymers preferred 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 polymerizable unit or the N-O
group can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; 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:
O O
I I
(Rt )x- j -~2)y; =N'.'(R~ )x (R3 )z is wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned 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-soluble 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 2s 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 can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinyfpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI") are also preferred 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. "Modem Methods of Polymer Characterization".) The PVPVI copolymers typically have a molar ratio u: N-vinylimidazole to N-vinylpyrtolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
The laundry detergent compositions also may employ 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. incorporated herein by reference. Compositions containing PVP 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 ?0 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.
The laundry detergent compositions herein may also optionally contain from about 0.005% to S% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those having the structural formula:
R~
~N H Ii N
N N C C N N
~N H H N \
RI, S03M S03M Ry wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2.2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the trademark Tinopal-iJNPA-GX by Ciba-Geigy Corporation.
Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a canon such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2.2'-stilbenedisulfonic acid disodium salt.
This particular brightener species is commercially marketed under the trademark Tinopal SBM-GX
by Ciba--Geigy Corporation.
1 ~ When in the above formula, RI is anilmo, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2.2'-sUlbened~sulfonic acid, sodium salt. This particular brightener species is commercially marketed udder the trademark Tinopal AMS-GX by Ciba Geigy Corporation.
The specific optical brightener species selected for use in the present invention provide ?0 especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brtghteners (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these 25 two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the 30 brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
Of course, it will be appreciated that other, conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations.
Bleaching Compounds - Bleachine Aeents and Bleach Activators The laundry detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one ar more bleach activators. Whey present, bleaching agents will typically be at levels of from about I% 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 useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now 1~ known or become irnow~n. These include oxygen bleaches as well as other bleaching agents.
Perborate bleaches, e.g.. sodium perborate (e.g., mono- or tetra-hydrate) and percarbonate bleaches can be used herein.
Another category of bleaching agent that can be used without restriction 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-nonyiaminoji-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U_S. Patent 4.483.781, Hartman. issued November 20, 1984, U.S. Patent No. 4,634,551 issued January 6, 1987, European Patent Application 0.133.354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et ai, vssucd November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycapro~c 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 pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Persulfate bleach TM
(e.g., OXONE, manufactured commercially by DuPont) can also be used.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents. the perborates. the percarbonates, etc., are preferably combined with bleach activators. which lead to the in situ production in aquec::,s solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao 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 are those of the formulae:
R1N(R5)C(O)R2C(O)L or RIC(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an allylene containing from 1 to about 6 carbon atoms, R~ is H or alkyl, aryl, or alkaryl containing from about 1 to about f 0 carbon atoms, and L is any suitable leaving group. A
leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leavins group is phenyl sul fonate_ Preferred examples of bleach activators of the above formulae include (6-I S octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesul-fonate, (6-decanamidocaproyl)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 Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990.
Still another class of preferred bleach activators includes the acyl lactam activators.
especially acyl caprolactams and acyl valerolactams. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl vaieroiactam, decanoyl vaierolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching 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. 549,271A1, 549,272A1, 544,440A2, and 544,490A 1. 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.
Anti-Static Age., nts The laundry detergent compositions can also comprise anti-static agents as illustrated in U.S. Pat. 4,861.502. Preferred examples of anti-static agents include alkyl amine-anionic surfactant ion pairs, such as distearyl amine-cumene sulfonate ion pairs. If present, anti-static agents are present in an amount of from about 0.5% to about 20%, preferably from about 1 % to about 10°ro, more preferably from about 1% to about 5%, by weight of the detergent composition.
In the following Example A, an embodiment of the present invention of a chelant agglomerate is exemplified:
p EXAMPLE A
In e, rg-d'~ent Wt%
Zeolite 85.00 DTPA 15.00 Total 100.0%
Accordingly, having thus described the invention in detail, it will be obvious to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.
Claims (22)
1. A process for preparation of a chelant composition by a non-spray-drying process, comprising the steps of:
a) admixing a transition metal chelant and an inorganic compound to form a mixture;
b) agglomerating said mixture in an aqueous medium to form a chelant agglomerate;
and c) drying said chelant agglomerate wherein the inorganic compound is selected from the group consisting of sulfates, carbonates, silicates, aluminosilicates and mixtures thereof; and wherein the transition metal chelant is selected from the group consisting of diethylenetriaminepentaacetates;
ethylenediamine disuccinate; and mixtures thereof; and wherein the chelant agglomerate resulting from step c) consists of said transition metal chelant and said inorganic compound.
a) admixing a transition metal chelant and an inorganic compound to form a mixture;
b) agglomerating said mixture in an aqueous medium to form a chelant agglomerate;
and c) drying said chelant agglomerate wherein the inorganic compound is selected from the group consisting of sulfates, carbonates, silicates, aluminosilicates and mixtures thereof; and wherein the transition metal chelant is selected from the group consisting of diethylenetriaminepentaacetates;
ethylenediamine disuccinate; and mixtures thereof; and wherein the chelant agglomerate resulting from step c) consists of said transition metal chelant and said inorganic compound.
2. The process according to claim 1, wherein said transition metal chelant is selected from the group consisting of sodium diethylenetriaminepentaacetate, ethylenediamine disuccinate, and mixtures thereof.
3. The process according to claim 1, wherein said transition metal chelant is sodium diethylenetriaminepentaacetate.
4. The process according to claim 1, wherein said inorganic compound is an aluminosilicate ion exchange material of the formula, M m/n[(AlO2)m (SiO2)y].xH2O where n is the valence of the cation M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y/m is 1 to 100, and wherein M
is selected from the group consisting of sodium, potassium, magnesium, and calcium.
is selected from the group consisting of sodium, potassium, magnesium, and calcium.
5. The process according to claim 1, wherein said inorganic compound is zeolite.
6. The process according to claim 1, wherein said step of admixing includes mixing and granulating said transition metal chelant and said inorganic compound in one or more of a high-speed mixer and granulator.
7. The process according to claim 1, wherein said step of agglomerating includes forming a chelant-inorganic compound pre-mix with water.
8. The process according to claim 1, wherein said transition metal chelant and said inorganic compound are admixed in a weight ratio in a range of from about 10:90 to about 80:20 respectively.
9. The process according to claim 1, wherein said mixture and said aqueous medium are pre-mixed before agglomerating, in a weight ratio in a range of from about 10:90 to about 80:20 respectively.
10. A process for improving one or more of storage stability, flowability and scoopability of a laundry detergent composition, comprising the steps of:
(a) providing a chelant composition prepared by a non-spray-drying process, comprising the steps of:
(i) admixing a transition metal chelant and an inorganic compound to form a mixture;
(ii) agglomerating said mixture in an aqueous medium to form a chelant agglomerate; and (iii) drying said chelant agglomerate;
wherein the transition metal chelant is selected from the group consisting of diethylenetriaminepentaacetates, ethylenediamine disuccinate; and mixtures thereof; and wherein the chelant agglomerate resulting from step iii) consists of said transition metal chelant and said inorganic compound; and (b) incorporating said chelant composition into a particulate laundry detergent material in a weight ratio in a range of from about 0.05:99.95 to about 2:98, chelant composition to particulate laundry detergent material.
(a) providing a chelant composition prepared by a non-spray-drying process, comprising the steps of:
(i) admixing a transition metal chelant and an inorganic compound to form a mixture;
(ii) agglomerating said mixture in an aqueous medium to form a chelant agglomerate; and (iii) drying said chelant agglomerate;
wherein the transition metal chelant is selected from the group consisting of diethylenetriaminepentaacetates, ethylenediamine disuccinate; and mixtures thereof; and wherein the chelant agglomerate resulting from step iii) consists of said transition metal chelant and said inorganic compound; and (b) incorporating said chelant composition into a particulate laundry detergent material in a weight ratio in a range of from about 0.05:99.95 to about 2:98, chelant composition to particulate laundry detergent material.
11. The process according to claim 10, wherein said laundry detergent composition has at least increased scoopability.
12. The process according to claim 10, wherein said transition metal chelant is sodium diethylenetriaminepentaacetate.
13. The process according to claim 10, wherein said inorganic compound is selected from the group consisting of sulfates, carbonates, silicates, aluminosilicates and mixtures thereof.
14. The process according to claim 10, wherein said inorganic compound is an aluminosilicate material of the formula, M m/n[(AlO2)m (SiO2)Y].xH2O where n is the valence of the canon M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y/m is 1 to 100, and wherein M is selected from the group consisting of sodium, potassium, magnesium, and calcium.
15. The process according to claim 14, wherein said inorganic compound is zeolite.
16. The process according to claim 10, wherein said transition metal chelant and said inorganic compound are admixed in a weight ratio in a range of from about 10:90 to about 80:20 respectively.
17. The process according to claim 10, wherein said mixture and said aqueous medium are premixed before agglomerating, in a weight ratio in a range of from about 10:90 to about 80:20 respectively.
18. A chelant agglomerate useful as an admix in a particulate laundry detergent, the chelant agglomerate consisting of:
a transition metal chelant selected from the group consisting of diethylenetriaminepentaacetates; ethylenediamine disuccinate; and mixtures thereof;
an inorganic compound selected from the group consisting of sulfates, carbonates, silicates, aluminosilicates and mixtures thereof; and water;
said chelant agglomerate being formed by admixing said transition metal chelant and said inorganic compound to form a mixture, agglomerating said mixture in said water to form said chelant agglomerate and drying the chelant agglomerate.
a transition metal chelant selected from the group consisting of diethylenetriaminepentaacetates; ethylenediamine disuccinate; and mixtures thereof;
an inorganic compound selected from the group consisting of sulfates, carbonates, silicates, aluminosilicates and mixtures thereof; and water;
said chelant agglomerate being formed by admixing said transition metal chelant and said inorganic compound to form a mixture, agglomerating said mixture in said water to form said chelant agglomerate and drying the chelant agglomerate.
19. The chelant composition according to claim 18, wherein said transition metal chelant is sodium diethylenetriaminepentaacetate.
20. The chelant composition according to claim 18, wherein said inorganic compound is an aluminosilicate material of the formula, M m/n[(AlO2)m (SiO2)y].xH2O where n is the valence of the canon M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y/m is 1 to 100, and wherein M is selected from the group consisting of sodium, potassium, magnesium, and calcium.
21. The chelant composition according to claim 20, wherein said aluminosilicate material is zeolite.
22. The chelant composition according to claim 18, wherein said transition metal chelant and said inorganic compound are present in a weight ratio in a range of from about 10:90 to about 80:20 respectively.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10319198P | 1998-10-05 | 1998-10-05 | |
US60/103,191 | 1998-10-05 | ||
PCT/US1999/022922 WO2000020550A1 (en) | 1998-10-05 | 1999-10-01 | Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability |
Publications (2)
Publication Number | Publication Date |
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CA2345737A1 CA2345737A1 (en) | 2000-04-13 |
CA2345737C true CA2345737C (en) | 2005-04-19 |
Family
ID=22293868
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002345737A Expired - Fee Related CA2345737C (en) | 1998-10-05 | 1999-10-01 | Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1119605A1 (en) |
JP (1) | JP2002526642A (en) |
CN (1) | CN1329660A (en) |
AR (1) | AR020710A1 (en) |
AU (1) | AU1311200A (en) |
BR (1) | BR9914614A (en) |
CA (1) | CA2345737C (en) |
WO (1) | WO2000020550A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE10339164A1 (en) † | 2003-08-26 | 2005-03-31 | Henkel Kgaa | Stabilization of hydrogen peroxide during the dissolution of alkalizing solids in hydrogen peroxide-containing systems |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE374762B (en) * | 1968-03-04 | 1975-03-17 | Monsanto Co | |
DE3120744A1 (en) * | 1981-05-25 | 1982-12-09 | Joh. A. Benckiser Gmbh, 6700 Ludwigshafen | Non-friable granules based on alkali metal aluminium silicate with good dispersibility in aqueous liquor |
JPS59157194A (en) * | 1983-02-28 | 1984-09-06 | ライオン株式会社 | Manufacture of small bulk density detergent builder granules |
GB8918984D0 (en) * | 1989-08-21 | 1989-10-04 | Unilever Plc | Detergent compositions |
ATE121129T1 (en) * | 1990-11-14 | 1995-04-15 | Procter & Gamble | METHOD FOR PRODUCING OXYGEN BLEACHING SYSTEMS CONTAINING PHOSPHATE-FREE DISHWASHING DETERGENT COMPOSITIONS. |
DE4311440A1 (en) * | 1993-04-07 | 1994-10-13 | Henkel Kgaa | Builder for detergents or cleaners |
PT796911E (en) * | 1996-03-23 | 2002-10-31 | Procter & Gamble | A DETERGENT DRY DETERGENT COMPONENT FOR SPRAY SPRAY CONTAINING A QUELATING AGENT |
DE19651072A1 (en) * | 1996-12-09 | 1998-06-10 | Henkel Kgaa | Additive for detergents or cleaning agents |
-
1999
- 1999-10-01 WO PCT/US1999/022922 patent/WO2000020550A1/en not_active Application Discontinuation
- 1999-10-01 EP EP99956515A patent/EP1119605A1/en not_active Withdrawn
- 1999-10-01 AU AU13112/00A patent/AU1311200A/en not_active Abandoned
- 1999-10-01 CN CN 99814084 patent/CN1329660A/en active Pending
- 1999-10-01 CA CA002345737A patent/CA2345737C/en not_active Expired - Fee Related
- 1999-10-01 JP JP2000574649A patent/JP2002526642A/en not_active Withdrawn
- 1999-10-01 BR BR9914614-2A patent/BR9914614A/en not_active IP Right Cessation
- 1999-10-04 AR ARP990105028 patent/AR020710A1/en unknown
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BR9914614A (en) | 2001-10-02 |
AR020710A1 (en) | 2002-05-22 |
CA2345737A1 (en) | 2000-04-13 |
WO2000020550A1 (en) | 2000-04-13 |
JP2002526642A (en) | 2002-08-20 |
CN1329660A (en) | 2002-01-02 |
EP1119605A1 (en) | 2001-08-01 |
AU1311200A (en) | 2000-04-26 |
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