IE59691B1 - Stabilized built liquid detergent composition containing enzymes - Google Patents
Stabilized built liquid detergent composition containing enzymesInfo
- Publication number
- IE59691B1 IE59691B1 IE197486A IE197486A IE59691B1 IE 59691 B1 IE59691 B1 IE 59691B1 IE 197486 A IE197486 A IE 197486A IE 197486 A IE197486 A IE 197486A IE 59691 B1 IE59691 B1 IE 59691B1
- Authority
- IE
- Ireland
- Prior art keywords
- detergent composition
- liquid detergent
- enzyme
- alkali metal
- sodium
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 131
- 239000003599 detergent Substances 0.000 title claims abstract description 84
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 66
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 66
- 239000007788 liquid Substances 0.000 title claims abstract description 63
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 65
- -1 alkali metal borate Chemical class 0.000 claims abstract description 37
- 235000011187 glycerol Nutrition 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 239000000440 bentonite Substances 0.000 claims abstract description 15
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 15
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000008961 swelling Effects 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004327 boric acid Substances 0.000 claims abstract description 5
- 239000004927 clay Substances 0.000 claims abstract description 5
- 229910011255 B2O3 Inorganic materials 0.000 claims abstract description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940088598 enzyme Drugs 0.000 claims description 63
- 229910021538 borax Inorganic materials 0.000 claims description 29
- 239000004328 sodium tetraborate Substances 0.000 claims description 29
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 19
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 230000000087 stabilizing effect Effects 0.000 claims description 15
- 229940092782 bentonite Drugs 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 13
- 239000002671 adjuvant Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 10
- 229930182556 Polyacetal Natural products 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 239000002304 perfume Substances 0.000 claims description 9
- 229920006324 polyoxymethylene Polymers 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 235000003704 aspartic acid Nutrition 0.000 claims description 6
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001639 boron compounds Chemical class 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims description 4
- 229940080314 sodium bentonite Drugs 0.000 claims description 4
- 229910000280 sodium bentonite Inorganic materials 0.000 claims description 4
- KRTNITDCKAVIFI-UHFFFAOYSA-N tridecyl benzenesulfonate Chemical compound CCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 KRTNITDCKAVIFI-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004900 laundering Methods 0.000 claims description 3
- 108091005658 Basic proteases Proteins 0.000 claims description 2
- 102000004139 alpha-Amylases Human genes 0.000 claims description 2
- 108090000637 alpha-Amylases Proteins 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 235000012216 bentonite Nutrition 0.000 description 24
- 230000000694 effects Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 235000017550 sodium carbonate Nutrition 0.000 description 8
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 8
- 238000013019 agitation Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- 108091005804 Peptidases Proteins 0.000 description 5
- 108010003855 mesentericopeptidase Proteins 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 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 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 102000035195 Peptidases Human genes 0.000 description 3
- 239000004365 Protease Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229940079919 digestives enzyme preparation Drugs 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 108010056079 Subtilisins Proteins 0.000 description 2
- 102000005158 Subtilisins Human genes 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 229940024999 proteolytic enzymes for treatment of wounds and ulcers Drugs 0.000 description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 2
- 239000001433 sodium tartrate Substances 0.000 description 2
- 229960002167 sodium tartrate Drugs 0.000 description 2
- 235000011004 sodium tartrates Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- VOLGAXAGEUPBDM-UHFFFAOYSA-N $l^{1}-oxidanylethane Chemical compound CC[O] VOLGAXAGEUPBDM-UHFFFAOYSA-N 0.000 description 1
- UEJBEYOXRNGPEI-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-(methylamino)propan-1-one Chemical compound CNC(C)C(=O)C1=CC=C(Cl)C=C1 UEJBEYOXRNGPEI-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- HOZBSSWDEKVXNO-DKWTVANSSA-N 2-aminobutanedioic acid;(2s)-2-aminobutanedioic acid Chemical compound OC(=O)C(N)CC(O)=O.OC(=O)[C@@H](N)CC(O)=O HOZBSSWDEKVXNO-DKWTVANSSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000003625 amylolytic effect Effects 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
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- VNWKTOKETHGBQD-AKLPVKDBSA-N carbane Chemical compound [15CH4] VNWKTOKETHGBQD-AKLPVKDBSA-N 0.000 description 1
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- 230000000368 destabilizing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- SKDZEPBJPGSFHS-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)N(CCO)CCO SKDZEPBJPGSFHS-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011083 sodium citrates 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
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 1
- 235000018341 sodium sesquicarbonate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/16—Phosphates including polyphosphates
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38663—Stabilised liquid enzyme compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A stabilized enzyme-containing liquid detergent comprises (a) 5 to 20%, a non-cationic surface active detergent compound (b) 5 to 30%, of a builder salt; (c) 5 to 20%, of a swelling bentonite clay; (d) an effective amount of an enzyme of; (e) an enzyme-stabilizing system containing, based on the weight of the detergent composition, (i) 1% to 10% glycerine; (ii) 1 to 8% of boric acid, boric oxide or an alkali metal borate; and (iii) 0.5 to 8% of a of mono, di and/or polycarboxylic acid having 1 to 8 carbon atoms or a water-soluble salt thereof; and (f) water. e
Description
STABILIZED BUILT LIQUID DETERGENT COMPOSITION CONTAINING ENZYMES b The present invention, relates to stable, built, enzyme-containing liquid detergent compositions suitable for laundry or pre-soak formulations. More particularly, the present invention relates to . aqueous enzyme-containing liquid detergent compositions which contain one or more detergent builders and which are characterised toy toeing physically stable, homogeneous liquid compositions.
The formulation of stabilised enzyme-containing . liquid, detergent compositions has been the focus of much attention in the prior art. The desirability of incorporating enzymes into detergent compositions is primarily due to the effectiveness of proteolytic and amylolytic enzymes in decomposing proteinaceous and . starchy materials found on soiled fabrics, thereby facilitating the removal of stains, such as, gravy stains, blood stains, chocolate stains and the like during laundering. However, enzymatic materials suitable for laundry compositions, particularly . proteolytic enzymes, are relatively expensive.
Indeed, they generally are among the most expensive ingredients in a typical commercial liquid detergent composition, even though they are present in relatively minor amounts. Moreover, enzymes are known to . toe unstable in aqueous compositions. It is for this reason that an excess of enzymes is generally required in liquid detergent formulations to „ compensate for the expected loss of enzyme activity during prolonged periods of storage. Accordingly, the , .., prior art is replete with suggestions for stabilising P12915 , enzyme-containing liquid detergent compositions, and in particular unbuilt liquid compositions by the use of various materials which are incorporated into the composition to function as enzyme stabilizers.
„ In the case of liquid detergent compositions containing a builder, the problem of enzyme instability is particularly acute. Primarily this is because detergent builders have a destabilizing effect on enzymes, even in compositions containing „ enzyme stabilizers which are otherwise effective in unbuilt formulations. Moreover, the incorporation of a builder into a liquid detergent composition poses an additional problem, namely, the ability to form a stable single-phase composition; the solubility of „ sodium tripolvphosphate, for example, being relatively limited in aqueous compositions, and especially in the presence of anionic and nonionic detergents.
In U.K, Patent Application G,„B„ 2,079,305, published 20th January, 1982, there is disclosed an . aqueous built enzyme-containing liquid detergent composition which is stabilized by a mixture of a polyol and boric acid. As noted in the examples of the U.K. application, relatively large amounts of glycerol are required to stabilise the enzymes in the . composition. Yet, as demonstrated hereinafter in the present specification, the enzyme stabilizing effect provided by a mixture of glycerine and borax in a built aqueous liquid detergent composition is relatively modest.
In European Patent Application Publication Mo.
. P12915 3. 0126505, there is disclosed an aqueous enzymecontaining liquid detergent composition containing an enzyme stabilizing mixture consisting of certain dicarboxylic acids and borax. The dicarboxylic acids ,, are recommended as a substitute for a polyol such as glycerol in known enzyme stabilizing mixtures consisting of glycerol and a boron compound.
However, the dicarboxylic acid-borax mixtures of this publication in common with the aforementioned prior . art,mixture of glycerine and borax are incapable of providing anything other than a modest stabilizing effect in the present built liquid detergent compositions .
The present invention provides a stabilized „ fabric softening, enzyme-containing built liquid detergent composition comprising: (a) from about 5 to 20%, by weight, of one or more surface active detergent compounds selected from the group consisting of anionic, nonionic and ampho20. teric detergent compounds; (b) from about 5 to 30%, by weight, of one or more builder salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates, and poly . acetal carboxvlates; (c) from about 5 to 20%, by weight, of a swelling bentonite clay, .
P12S15 4» (d) an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline protease enzymes and alpha-amylase enzymes; (e) an enzyme-stabilizing system containing, . based on the weight of the detergent composition, (i) from about 1 to 10% glycerine; (ii) from about 1 to 8% of a boron compound selected from the group consisting of boric acid, boric oxide and alkali metal borates and; (iii) from about 0.5 to 8% of a . carboxylic acid compound selected from the group consisting of mono, di and/or polycarboxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof; and (f) the balance comprising water and optionally . perfume and other adjuvants.
In a preferred embodiment of the present invention, the liquid detergent composition comprises (a) from about 5 to 15% of an alkali metal alkyl benzene sulphonate wherein the alkyl group contains . 12 to 15 carbon atoms; (b) from about 2 to 5% of an alkali metal alkyl polyethoxy sulphate wherein the alkyl group contains to 18 carbon atoms and the polyethoxy is of 3 to ethylene oxide groups,, the weight ratio of (a) to . (b) being from about 2:1 to about 8:1; (c) from about 5 to 20% of sodium tripolyphosphate ; (d) from about 1 to 10% of sodium carbonate, the weight ratio of (c) to (d) being from about 2:1 to . about 6:1; P12S15 „ (e) from about 10 to 15% of a sodium bentonite; (f) an effective amount of the aforesaid enzyme or enzyme mixture; (g) an enzyme stabilizing system containing, . based on the weight of the detergent composition, (i) from about 3 to 7% glycerine, (ii) from about 1 to 5% of an alkali metal borate and (iii) from about 0.5 to 4% of the said carboxylic acid compound; and (h) the balance comprising water and optionally . perfume and other adjuvants.
In accordance with the process of the present invention, laundering of stained and/or soiled materials is affected by contacting such materials with an aqueous solution of the above-defined liquid 3.5,, detergent compositions.
The described liquid detergent is a commercially acceptable heavy duty laundry detergent, capable of satisfactorily cleaning laundry items containing both oily and particulate soils. Additionally, the . described compositions may be employed for the pretreatment of badly soiled areas, such as collars and cuffs, of items to be laundered.
The present invention is predicated upon the discovery of a three component enzyme stabilizing . system as herein defined which provides an enzyme stabilizing effect to the liquid detergent compositions of the present invention far in, excess of that which can be achieved with conventional enzyme stabilizers. The enzyme stabilizing effect thus . achieved reflects a synergy among the three components. In accordance with the present invention, the enzyme stability provided by a mixture of glycerine and borax or a mixture of borax and a P12915 6, dicarboxylic acid as disclosed in the prior art can be synergistically improved by the use of the three component stabilizing system herein defined in the present liquid compositions so as to raise the level . of enzyme stability significantly above that provided by either the mixture of glycerine and borax or the mixture of borax and dicarboxylic acid when used independently of each other as enzyme stabilizers.
For commercial purposes, a desirable enzyme stability . generally corresponds to about a half-life of one week at a temperature of 110°F (43°C).
The enzyme stabilizing system of the present invention is a mixture of glycerine, a boron compound selected from among boric acid, boric oxide and an . alkali metal borate and a carboxylic acid compound as herein defined. The weight of the stabilizing system in the present built liquid detergent compositions is generally from about 3 to 25%, preferably about 6 to 15%, by weight. The weight ratio of glycerine to . borax in the stabilizing mixtures is generally from about 1 to 3. The preferred amount of glycerine in the composition is from about 1 to 5%, and the preferred amount of carboxylic compound is from about 0.5 to 4% based on the weight of the composition.
. The carboxylic acid compounds which are useful in the enzyme stabilizing system of the present invention encompass saturated as well as unsaturated mono, di and polycarboxylic acids having 1 to 8 carbon atoms among which are included oxalic acid . (HOOCCOOH), malonic acid (HOOCCHjCOOH), maleic acid P12915 7.
(HOOCCH:CHCOOH) and succinic acid (HOOCCH^CHqCOOH). The carboxylic acids may contain hydroxy or amino substituents as exemplified by malic acid (HOOCCHOHCH2COOH), tartaric acid (dihydroxysuceinic . acid) aspartic acid (amino succinic acid) and citric acid. Preferred carboxylic acids of the present invention are aspartic acid, tartaric acid, malonic acid and malic acid. From a commercial standpoint, a particularly preferred carboxylic acid compound is . citric acid and/or its salts because of their relatively low cost.
The alkaline proteolytic enzymes suitable for the compositions of the present invention include the various commercial liquid enzyme preparations which . have been adapted for use in detergent compositions. Enzyme preparations in powdered form are also useful although, as a general rule, less convenient for incorporation into the built liquid detergent eomposi tions. Thus, suitable liquid enzyme preparations . include Alcalase and '"Esperase sold by Novo Industries, Copenhagen, Denmark, and Maxatase and AZ-Protease sold by Gist-Brocades, Delft, The Netherlands.
Among the suitablepC-amylase liquid enzyme . preparations are those sold by Novo Industries and Gist-Brocades under the tradenames ‘’Termamyl10 and Maxamyl", respectively.
Esperase is particularly preferred for the present compositions because of its optimized . activity at the higher pH values corresponding to the built detergent compositions.
P12915 8.
. The preferred detergents for use in the present liquid compositions are the synthetic anionic detergent compounds, and particularly a mixture of higher alkylbenzene sulphonate and alkyl polyethoxy 5. sulphate. While other water soluble higher alkylbenzene sulphonates may also be present in the formulas of the present invention, such as potassium salts and in some instances the ammonium or alkanolammonium salts, where appropriate, it has been found 10. that the sodium salt is highly preferred, which is also the case with respect to the alkyl polyethoxy sulphate detergent component. The alkylbenzene sulphonate is one wherein the higher alkyl group is of 12 to 15 carbon atoms, preferably 13 carbon 15. atoms. The alkyl polyethoxy sulphate, which also may be referred to as a sulphated polyethoxylated higher linear alcohol or the sulphated condensation product of a higher fatty alcohol and ethylene oxide or polyethoxylene glycol, is one wherein the alkyl group is 20. of 10 to 18 carbon atoms, preferably 12 to 15 carbon atoms, e.g. about 13 carbon atoms, and which includes 3 to 11 ethylene oxide groups, preferably 3 to 7, more preferably 3 to 5 and most preferably 3 or about 3 ethylene oxide groups. The ratio of alkylbenzene 25. sulphonate to polyethoxy sulphate in the detergent mixture is preferably from about 2;1 to 5:1 and most preferably from about 2;1 to 4s1, by weight. At ratios above 5si, the physical stability of the product may be adversely affected.
In suitable circumstances other anionic deterP12S15 9. gents, such as fatty alcohol sulphates, paraffin sulphonates, olefin sulphonates, monoglyceride sulphates, sarcosinates and similarly functioning detergents, preferably as the alkali metal, e.g. , sodium salts, can be present, sometimes in partial replacement of the previously mentioned synthetic organic detergents but usually, if present, in addition to such detergents. Normally, the supplementing detergents will be sulphated or „ sulphonated products (usually as the sodium salts) and will contain long chain (8 to 20 carbon atoms) linear or fatty alkyl groups. In addition to any supplementing anionic synthetic organic detergents, there also may be present nonionic and amphoteric . materials, like the Neodols (Registered Trade Mark), sold by Shell Chemical Company, which are condensation products of ethylene oxide and higher fatty alcohols, e.g. Neodol (Registered Trade Mark) 23-6.5, which is a condensation product of a higher fatty alcohol of . about 12 to 13 carbon atoms with about 6.5 moles of ethylene oxide. Illustrations of the various detergents and classes of detergents mentioned may be found in the text Surface Active Agents, Vol. II, by Scwartz, Perry and Serch (Interscience Publishers, . 1958), the descriptions of which are incorporated herein by reference.
The builder salt combination of the present invention, which has been found to satisfactorily improve the detergency of the mixture of synthetic „ anionic organic detergents and produce the desired pH P12915 . in the liquid detergent and in the wash water, is a mixture of sodium tripolyphosphate and sodium carbonate. The builder salts are employed in the compositions of the present invention in amounts , generally of from about 5 to 25%, by weight. For the preferred builder salt combination, sodium tripolyphosphate is present in amounts of from about 5 to 20%, preferably 10 to 16%, and sodium carbonate is present from about 1 to 10%, by weight, preferably 3 . to 7%, the weight ratio of tripolyphosphate to carbonate in the preferred builder mixtures being from about 2;1 to 6si, and most preferably from about 2:1 to 4:1. As used herein, the term alkali metal carbonates or carbonate is meant to include the carbonates, bicarbonates and sesquicarbonates of such alkali metals.
For best processing, easier mixing and good enduse properties it is preferred that the sodium tripolyphosphate be low in content of Phase I type tri20. polyphosphate. Thus, normally the content of Phase I type tripolyphosphate will be less than 30% of the tripolyphosphate employed.. Although in some instances incompletely neutralized tripolyphosphate may be used, normally the phosphate employed may be . considered as being pentasodium tripolyphosphate, Na5P30iQ. Of course, in some instances, as when potassium salts of other materials are present, Ion interchange in an aqueous medium may result in other salts than the sodium tripolyphosphate being present „ but for the purpose of this specification it will be 11.
P12S15 considered that sodium tripolyphosphate, as the pentasodium salt, the material which is normally charged to the mixer to make the present liquid detergent, is the tripolyphosphate employed.
. Other preferred builder salts which may be used in place of sodium tripolyphosphate and sodium carbonate or in addition thereto include a polyacetal carboxylate as herein described and sodium nitrilotriacetate (NTA) ... Of course, various mixtures . of the mentioned water soluble builder salts can be utilised. Yet, the tripolyphosphate-carbonate mixture described has been found to be most preferred, although the other builders and mixtures thereof are also operative. Other builders which may . be employed as supplements, in addition to the proportions of the above-mentioned builders, include other phosphates, such as tetrasodium pyrophosphate or tetrapotassium pyrophosphate, sodium bicarbonate, sodium citrate, sodium gluconate, sodium silicate, . and sodium sesquiearbonate. Among the water insoluble builders r.h.at may be used are the zeolites, such as Zeolite A, usually in the form of its crystalline hydrate, although, amorphous zeolites may also be useful.
. Polyacetal earboxylates are generally described in U.S, Patents 4,144,226 and 4,315,092. U.S. Patent 4,146,495 describes detergent compositions containing polyacetal earboxylates as builders.
The polyacetal earboxylates which are useful » herein as builders may be considered to be those P12915 12. described in U.S. Patent 4,144,226 and may be made by the method mentioned therein. A typical such product will be of the formula . a1 - (CHO)n - R2 I COOM wherein M represents an alkali metal, or ammonium, or » an alkyl group of 1 to 4 carbon atoms, or a tetraalkylammonium group or an alkanolamine group, both of 1 to 4 carbon atoms in the alkyls thereof, n averages at least 4, and R^ and R2 represent any chemically stable group which stabilizes the polymer against . rapid depolymerization in alkaline solution. Preferably the polyacetal carboxylate will be one wherein M is alkali metal, e.g. sodium, n is from 50 to 200, R-*is CH3CH2O MOOC . I I HCO- or H3C-COI I H3C MOOC or a mixture thereof, R2 is . OCH2CH3 I -CH I ch3 . and n averages from 20 to 100, more preferably 30 to P12915 13. 80. The calculated weight average molecular weights of the polymers will normally be within the range of 2,000 to 20,000, preferably 3,500 to 10,000 and more preferably 5,000 to 9,000, e.g. about 8,000.
. A particularly preferred sodium polyacetal carboxylate is supplied by Monsanto Company and is known as Builder U. It has a calculated weight average molecular weight of about 8,000 and an active polymer content of about 80%.
, Although the preferred polyacetal carboxylates have been described above, it is to be understood that they may be wholly or partially replaced by other such polyacetal earboxylates or related organic builder salts described in the previously cited . patents on such compounds, processes for the manufacture thereof and compositions in which they are employed. Also, the chain terminating groups described in the various patents, especially U.S. 4,144,226, may be utilized, providing that they have . the desired stabilizing properties, which allow the mentioned builders to be depolymerised in acidic media, facilitating biodegradation thereof in waste streams, but maintain their stability in alkaline media, such as washing solutions.
. The bentonite employed in the present invention is a colloidal clay (aluminium silicate) containing montmoriiionite. Swelling bentonites are generally characterised as sodium bentonites, i.e. bentonite wherein the predominant cation is sodium. Among the . sodium bentonite clays, those from Wyoming (generally 14.
P12S15 referred to as Western or Wyoming bentonite) are especially preferred.
The swelling capacity of bentonite is generally associated with its fabric softening properties. In . water* the swelling capacity of sodium bentonite is in the range of 3 to 20 millilitres/gram, preferably 7 to 15 ml/gra.m, and its viscosity, at 6% concentration in water, is usually in the range of 3 to 30 centipoises, preferably 8 to 30 centipoises.
. Preferred swelling bentonites are sold under the trademark HI-JEL by Georgia Kaolin Co. These materials are the same as bentonites which were formerly sold under the trademarks MINERAL COLLOID and THIXO-JEL. They are selectively mined and bene15. ficiated bentonites, and those considered to be most useful are available as HI-JEL Nos. 1, 2, 3 etc., corresponding to THIXO-JELs No's 1, 2, 3 and 4. Such materials have a maximum free moisture content (before addition to the liquid medium) of 4% to 8% . and specific gravities of about 2.6. The bentonite is preferably one which will pass through a 200 mesh U.S. Sieve Series sieve, and most preferably at least 90% of the particles will pass through a No. 325 sieve, so that the equivalent diameter of the . bentonite may be considered to be less than 74 microns, and more preferably lass than about 44 microns.
Typical chemical analyses of some bentonites that are useful for making the liquid detergents of . the present invention show that they contain from P12915 . 64„8 to 7 3.0% of SiO2, 14 to 18% of A12O3, 1.6 to 2.7% of MgO, 1.3 to 3.1% of C&O, 2.3 to 3.4% of Fe2O3, 0.8 to 2.8% of Na20 and 0.4 to 7.0% of K2° Although the western bentonites are preferred it 5. is also possible to utilise other bentonites, such as those which may be made by treating Italian or similar bentonites containing relatively small proportions of exchangeable monovalent metals (sodium and potassium) with alkaline materials, such as IQo sodium carbonate, to increase the cation exchange capacities of such products. It is considered that the Na20 content of the bentonite should be at least about 0.5%, preferably at least 1% and more preferably at least 2% so that the clay will be satisfactorily swelling, with good softening and dispersing properties in aqueous suspension.
Preferred swelling bentonites of the types described above are sold under the trade names Laviosa and Winkelmann, e.g. Laviosa AGB and Winkelmann G-13.
. Other bentonites which are particularv useful for the present liquid detergent compositions because of their white or very light colour include American Colloid Company's Polarite KB 325, a California bentonite, and Georgia Kaolin's GK 129, a Mexican . bentonite.
The only other required component of the liquid detergents of the present invention is water.
Normally the hardness content of such water will be less than about 300 ppm, as CaC03, and preferably it . will be less than 150 ppm. Often it may be desirable P12915 16. to utilise deionised water although city water with less than 50 or 100 p.p.m. hardness content will frequently be equally satisfactory.
Various adjuvants may be present in the liquid . detergents of the present invention, such as fluorescent brighteners, perfumes and colourants. The fluorescent brighteners include the well known stilbene derivatives, including the cotton and nylon brighteners, such as those sold under the trademark . Tinopal (5BM Cone.). The perfumes that are employed usually include essential oils, esters, aldehydes and/or alcohols, all of which are known in the perfumery art. The colourants may include dyes and water dispersible pigments of various types, . including ultramarine blue. Inorganic filler salts, such as sodium sulphate and sodium chloride may be present, as may be antiredeposition agents, such as sodium carboxymethylcellulose; dispersing agents, such as sodium polyacrylate; bleaches; bactericides,20. fungicides; anti-foam agents, such as silicones; anti soiling agents, such as copolyesters; preservatives such as formalin; foam stabilizers, such as lauric myristic diethanolamide; and auxiliary solvents, such as ethanol. Normally the individual proportions of . such adjuvants will be less than 3%, often less than 1% and sometimes even less than 0.5%, except for any fillers and solvents, and additional detergents and builder,s for which the proportions may sometimes be as high as 10%. The total proportion of adjuvants, . including non-designated synthetic detergents and builders, will normally be no more than 20% of the P12915 17. product and desirably will be less than 10% thereof, more desirably less than 5% thereof. Of course, the adjuvants employed will be selected so as not to interfere with the washing action of the liquid « detergent and to avoid instability of the product on standing» Also, adjuvants which cause the production of objectionable deposits on the laundry are to be avoided.
The liquid compositions of the present invention » are efficient and easy to use. Compared to heavy duty laundry detergent powders, much smaller volumes of the liquids of the present invention are employed to obtain comparable cleaning of soiled laundry. .For example, using a typical preferred formulation of the » present invention, only about 132 grams or 1/2 cup of liquid is needed for a full tub of wash in a toploading washing machine in which the water volume is 15 to 18 gallons (57 to 68 litres); and even less is needed for front-loading machines. Thus, the . concentration of the liquid detergent composition in the wash water is of the order of about 0.2%.
Usually, the amount of the liquid composition in the wash solution will range from about 0.05 to 0.3%, preferably from 0.15 to 0.25%. The proportions of . the various constituents of the liquid composition may vary accordingly. Equivalent results can be obtained by using greater amounts of a more dilute formulation but the greater quantity needed will require additional packaging and will generally be . less convenient for consumer use and may also result in product separation.
P12915 18.
The viscosity of the liquid detergent composition of the present invention is normally in the range of about 1000 to 10,000 centipoises, preferably 2000-5000 centipoises, but products of other suitable viscosi5. ties may also be useful. At the viscosities mentioned, the liquid detergent is pourable, stable, non-separating and uniform. The pH of the liquid detergent suspension usually in the range of 7 to 11.5, preferably 8 to 10.5, appears to help to » maintain product stability and pourability.
The invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying examples. Unless . otherwise indicated all parts are by weight and temperatures are in °C.
EXAMPLE 1 A liquid detergent composition is made up with the ingredients and proportions shown in Table 1 . below.
TABLE 1 Component Percent Pentasodium tripolvphosphate 11.0 Bentonite (Georgia-Kaolin 129) 12.0 . Sodium carbonate 2.0 Sodium sesquicarhonate 2.0 Sodium linear tridecylbenzene sulphonate 8.0 AEOS(1) 3.0 Carboxymethyl cellulose (CMC) 0.2 . Optical brightener 0.3 Perfume 0.4 Enzyme (Esperase 8.0L)(^) 1.0 Component Percent Glycerine 3.0 Borax 2.5 . Citric Acid 2.0 Water and adjuvants Balance P12S15 IS.
TABLE 1 (cont i nued) Notes on Table 1; Sodium alkyl polyethoxy sulphate wherein the . alkyl group is of 12 to 15 carbon atoms and the polyethoxy is of 3 ethoxy groups. (2) Esperase sold by Novo Industries having an activity of 8.0 KNPU/gram (Kilo Novo Protease . units/gra).
The composition set out in Table 1 was prepared by the following procedures 30.0 parts of deionised water at 40°F (4°C) are added to a suitable mixing . apparatus such as a vertical cylindrical tank equipped with a stirrer. With the stirrer adjusted for medium agitation, a mixture consisting of 2,0 parts anhydrous soda ash, 2.0 parts sodium sesquiearfoonate, and 0.2 parts sodium carboxymethyl » cellulose is incorporated into the water. The stirrer speed is then increased to maximum agitation and a mixture comprised of 11.0 parts pentasodium tripolyphosphate and 12.0 parts bentonite is slowly added to the mixing apparatus over a period of 10-15 » minutes to form an off-white suspension. The P12915 . agitation speed is then decreased to a slow/medium setting while 8.64 parts of a high Al (about 55%) LTBS (linear tridecylbenzene sulphonate) slurry is added. Thereafter the optical brightener/ . colour solution is added consisting of 0.3 parts Tinopal LMS-X (CIBA-GEIGY), 0.99 parts colourant, and 4.02 parts deionised water. Once a uniform blueish-green coloured solution is obtained, 0.4 parts of perfume are added to the mixture under . agitation. This is followed by the slow addition of 3.0 parts glycerine and 2.5 parts borax as a two component slurry. Stirring is continued until the mixture is uniform in appearance and then 2.0 parts of sodium citrate and 9.0 parts water are „ slowly added. Agitation of the mixture is then reduced while 10.95 parts of a mixed Al detergent base consisting of an LTBS slurry (about 30% Al) and AEOS (about 27.5% Al) is added to the mixture. This is followed by the slow addition of 1.0 part . proteolytic enzyme with continuous agitation until all materials are completely dispersed or dissolved.
EXAMPLES 2A to 2G Enzyme-containing built liquid detergent compositions, Examples 2A to 2G, were formulated as . set forth below in Table 2. The percentages shown indicate weight percent. It will be appreciated that the compositions are identical in respect of the first ten components listed in Table 2.
Examples 2A to 2F are comparison examples.
. P12915 21.
TABLE 2 Component 2A 2B 2C 2D 2E 2F 2G Pentasodium tripolyphosphate 11.0 11.0 11.0 11.0 11.0 11.0 11.0 5. Bentonite (Georgia-Kaolin 129) 12.0 12.0 12.0 12.0 12.0 12.0 12.0 Sodium Carbonate 2.0 2.0 2.0 2.0 2.0 2.0 2.0 10. Sodium sesquicar- bonate 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Sodium linear tri- decylbenzene sulphonate 8.0 8.0 8.0 8.0 8.0 8.0 8.0 AEOS^1) 3.0 3.0 3.0 3.0 3.0 3,0 3.0 15. Optical brightener (Tinopal LMS-X) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Perfume 0.4 0 »4 0.4 0.4 0.4 0.4 0.4 CMC 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Enzyme (2) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 20. Glycerine - 3.0 - 3.0 - - 3.0 Borax - 2.5 2.5 - 2.5 2,5 Carboxylic acid compound * n 2.0 2.0 2.0 Water and — — ----Balance — — . adjuvants Notes on Table 2: (1) Sodium alkyl polyethoxy sulphate wherein the alkyl group is of 12 to 15 carbon atoms and the . polyethoxy is 3 of ethoxy groups» (2) Esperase sold by Novo Industries having an activity of 8.0 ΚΝΡϋ/gm (Kilo Novo Protease units/gm).
P12915 22.
» . . » The enzyme activities of the compositions of Examples 2A to 2G were tested after 7 days storage at 110°F (43°C). The measured enzyme activity for each composition after this period of storage is indicated in Tables 3A to 3C and Table 4 as a percent of the initial value. The various carboxylic acids and salts used in the formulas of the compositions of Examples 2A to 2D are shown in Table 3A as well as the enzyme activities corresponding to each composition; for Example 2E in Table 3B (these all being comparison examples) and for Example 3G in Table 3C (this being in accordance with the invention).
TABLE 3A ENZYME STABILITY Percent Active Enzyme After 7 Days at 110 °F Example Composition (43aC)_ 2A (control) HD* 2B (with glycerine) MD 2C (with borax) HD 2D (with glycerine and borax) 45 . 23.
P12S15 .
. . TABLE 3B Composition E (with carboxylic acid compound) wherein the carboxylic acid compound is: Example Composition Percent Active Enzyme After 7 Days at 110 °F (43 °C) 2E (1) Succinic acid MD* 2E (2) Malonic acid MD 2E (3) Malic acid MD 2E (4) Tartaric acid MD 2E (5) Aspartic acid MD 2E (6) Citric acid MD 2E (7) Sodium tartrate MD 2E (3) Sodium citrate MD Mote on Tables 3A and 3B * MD ~ ] Mot detectable (below 10% residual activity).
TABLE 3C .
. Composition G (with glycerine/borax/carboxylic acid compound) wherein the carboxylic acid compound i s: Example Composition Percent Active Enzyme A.fter 7 Days at 110 °F (43°C) 2G (1) Succinic acid 70 2G (2) Malonic acid 70 2G (3) Malic acid 78 2G (4) Tartaric acid 73 2G (5) Aspartic acid SO 2G (6) Citric acid 74 2G (7) Sodium tartrate 56 2G (8) Sodium citrate 52 .
P12915 24.
As is evident from Table 3 A, the control composi tion of Example 2A, as well as the comparison composi tions of Examples 2B and 2C which contained glycerine and borax, respectively, as individual stabilizers, . manifested almost no enzyme activity after the 7 day storage period of 110°F (43°C) . Since enzyme activities below 10% could not be precisely measured they are designated ND„ The comparison composition of Example 2D containing glycerine and borax in the . absence of a carboxylic acid compound provided an improvement in enzyme stability relative to the compositions of Examples 2A to 2C but about 50% of the enzyme was deactivated. The various comparison compositions of Examples 2E(l) to 2E(8) containing a . variety of carboxylic acid compounds but no borax or glycerine, as indicated, manifested absolutely no improvement in enzyme stability relative to the compositions of Examples 2A to 2G. However, the compositions of Examples 2G(1) to 2G(8) formulated in . accordance with the invention (using the same carboxylic acids) demonstrate the unexpected and synergistic improvement in enzyme stability which is achieved with the use of glycerine and borax in combination with a carboxylic acid compound in liquid . detergent compositions as required by the present invention. It is noted that almost every one of the compositions corresponding to Examples 2G(1) to 2G(8) demonstrated a significant improvement in enzyme activity relative to the composition of Example 2D . (containing only glycerine and borax).
P12915 » A comparison of the enzyme activities achieved with the composition of Example 2D (glycerine and borax) and various compositions of Example 2F (borax and carboxylic acid compound) and of Example 2G . (formulated in accordance with the invention) is set forth below in Table 4.
TABLE 4 ENZYME STABILITY .
Percent Active Enzyme After 7 Davs at 110°F (43°C) .
Example Composition . 2D (Glycerine/borax) 59 2F (1) (Sorax/malonic acid) 45 2G (2) (Glycerine/borax/malonic acid) 70 2F (2) (Borax/aspartic acid) 72 2G (5) (Glycerine/borax/aspartic acid) 90 2F (3) (Borax/citric acid) 42 2G (6) (Glycerine/borax/citric acid) 74 Notes on Table 4 2F(1) corresponds to 2G(2); 2F(2) corresponds to 2G(5) and 2F(3) corresponds to 2G(6).
" ’ As shown in Table 4, the various compositions of Example 2G(2), 2G(5) and 2G(6) containing a three component stabilizer system in accordance with the present invention provided a synergistic improvement in enzyme stability relative to the compositions of » Examples 2D and 2F(l), 2F(2) and 2F(3) formulated in accordance with the prior art.
Claims (14)
1. A stabilized fabric softening enzymecontaining built liquid detergent composition comprising; (a) from 5 to 20%, by weight, of one or more surface active detergent compounds selected from the group consisting of anionic, nonionic and amphoteric detergent compounds; (b) from 5 to 30%, by weight, of one or more builder salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal carboxvlates; (c) from 5 to 20%, by weight, of a swelling bentonite clay; (d) an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline protease enzymes and alpha-amylase enzymes; (e) an enzyme-stabilizing system containing, based on the weight of the detergent composition, (1) from 1% to 10% glycerine; (ii) from 1 to 8% of a boron compound selected from the group consisting of boric acid, boric oxide and alkali metal borates; and (iii) from 0.5 to 8% of a carboxylic acid compound selected from the group consisting of mono, di and polycarboxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof; and (f) the balance comprising water and optionally perfume and other adjuvants. 27.
2. A liquid detergents composition as claimed in Claim 1 comprising: (a) from 5 to 15% of an alkali metal alkylbenzene sulphonate in which the alkyl group contains 5 12 to 15 carbon atoms; (b) from 2 to 5% of an alkali metal alkyl polyethoxy sulphate in which the alkyl group contains 10 to 18 carbon atoms and the polyethoxy is of 3 to 11 ethylene oxide groups, the weight ratio of (a) to 10 (b) being from about 2:1 to about 8:H (c) from 5 to 20% of sodium tripolyphosphate ; (d) from 1 to 10% of sodium carbonate, the weight ratio of (c) to (d) being from 2:1 to 6:1; 15 (e) from 10 to 15% of a sodium bentonite; (f) an effective amount of the said enzyme or enzyme mixture; (g) the enzyme stabilizing system containing, based on the weight of the detergent composition, (i) 20 from 3 to 7% glycerine, (ii) from I to 5% of an alkali metal borate and (iii) from 0.5 to 4% of the said carboxylic acid compound; and (h) the balance comprising water and optionally perfume and other adjuvants.
3. A liquid detergent composition as claimed in Claim 2 in which the said alkali metal alkylbenzene sulphonate is sodium linear tridecylbenzene sulphonate and the said alkali metal alkyl 28. polyethoxy sulphate is one in which the alkali metal is sodium, the alkyl group contains 12 to 15 carbon atoms and the polyethoxy is of about 3 ethylene oi^ide' groups.
4. A liquid detergent composition as claimed in Claim 2 or Claim 3 in which the ratio of alkylbenzene sulphonate to polyethoxy sulphate is from 2:1 to 4:1.
5. A liquid detergent composition as claimed in any one of Claims 1 to 4 in which the said boron compound is an alkali metal borate.
6. » A liquid detergent composition as claimed in Claim 5 in which the said borate is borax.
7. A liquid detergent composition as claimed in any one of Claims 2 to 6 which contains from 8 to 16% sodium tripolyphosphate and from 2 to 6% sodium carbonate or sodium bicarbonate or mixtures thereof.
8. A liquid detergent composition as claimed in any one of Claims 1 to 7 in which the said carboxylic acid compound is aspartic acid or a water-soluble salt thereof.
9. A liquid detergent composition as claimed in any one of Claims 1 to 7 in which the said carboxylic acid compound is tartaric acid or a water-soluble salt thereof. 29.
10. A liquid detergent composition as claimed in any one of Claims 1 to 7 in which the said carboxylic acid compound is citric acid or a water-soluble salt thereof.
11. A liquid detergent composition as claimed in any one of Claims 1 to 7 in which the said carboxylic acid compound is malonic acid or a watersoluble salt thereof.
12. A liquid detergent composition as claimed in any one of Claims 1 to 7 in which the said carboxylic acid compound is malic acid or a watersoluble salt thereof.
13. A liquid detergent composition as claimed in Claim 1 substantially as specifically described herein with reference to any one of Example 1 or Examples 2G(1) to 2G(8).
14. A method of laundering comprising contacting the stained and/or soiled fabrics to be laundered with a stabilized enzyme-containing built liquid detergent composition as claimed in any one of Claims 1 to 13.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US75952385A | 1985-07-26 | 1985-07-26 | |
US79271085A | 1985-10-30 | 1985-10-30 |
Publications (2)
Publication Number | Publication Date |
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IE861974L IE861974L (en) | 1987-01-26 |
IE59691B1 true IE59691B1 (en) | 1994-03-23 |
Family
ID=27116693
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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IE197486A IE59691B1 (en) | 1985-07-26 | 1986-07-25 | Stabilized built liquid detergent composition containing enzymes |
Country Status (31)
Country | Link |
---|---|
KR (1) | KR940010118B1 (en) |
AT (1) | AT397810B (en) |
AU (1) | AU590589B2 (en) |
BE (1) | BE905167A (en) |
BR (1) | BR8603479A (en) |
CA (1) | CA1297440C (en) |
CH (1) | CH669958A5 (en) |
DE (1) | DE3623943A1 (en) |
DK (1) | DK165331C (en) |
EG (1) | EG17901A (en) |
ES (1) | ES2001483A6 (en) |
FR (1) | FR2585361B1 (en) |
GB (1) | GB2178055B (en) |
GR (1) | GR861947B (en) |
HK (1) | HK1993A (en) |
IE (1) | IE59691B1 (en) |
IL (1) | IL79450A0 (en) |
IN (1) | IN170204B (en) |
IT (1) | IT1195869B (en) |
LU (1) | LU86526A1 (en) |
MA (1) | MA20741A1 (en) |
MX (1) | MX167431B (en) |
MY (1) | MY101616A (en) |
NL (1) | NL8601927A (en) |
NO (1) | NO165928C (en) |
NZ (1) | NZ216792A (en) |
PH (1) | PH22908A (en) |
PT (1) | PT83023B (en) |
SE (1) | SE468518B (en) |
SG (1) | SG108692G (en) |
ZW (1) | ZW13386A1 (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NZ216791A (en) * | 1985-07-26 | 1988-07-28 | Colgate Palmolive Co | Stabilised, built, enzyme-containing liquid detergents |
GB8519047D0 (en) * | 1985-07-29 | 1985-09-04 | Unilever Plc | Detergent composition |
GB2200132B (en) * | 1986-12-15 | 1991-09-18 | Colgate Palmolive Co | Stabilised enzyme systems and compositions containing them |
DE3704465C2 (en) * | 1987-02-13 | 1995-11-02 | Roehm Gmbh | Liquid formulations of enzymes |
US6287841B1 (en) | 1988-02-11 | 2001-09-11 | Genencor International, Inc. | High alkaline serine protease |
PT89702B (en) | 1988-02-11 | 1994-04-29 | Gist Brocades Nv | PROCESS FOR PREPARING NEW PROTEOLITIC ENZYMES AND DETERGENTS THAT CONTAINS THEM |
AU3667189A (en) * | 1988-06-23 | 1990-01-04 | Unilever Plc | Enzyme-containing liquid detergents |
GB8822374D0 (en) * | 1988-09-23 | 1988-10-26 | Abster Co Ltd | Detergent composition |
US5500151A (en) * | 1988-10-07 | 1996-03-19 | Colgate-Palmolive Co. | Heavy duty fabric softening laundry detergent composition |
DE3911099A1 (en) * | 1989-04-06 | 1990-10-11 | Henkel Kgaa | METHOD FOR CLEANING ENZYME SOLUTIONS |
DE3915277A1 (en) * | 1989-05-10 | 1990-11-15 | Henkel Kgaa | METHOD FOR PURIFYING ENZYME LIQUID CONCENTRATES |
DE68928569D1 (en) * | 1989-11-06 | 1998-03-05 | Colgate Palmolive Co | Softening heavy-duty detergent composition for laundry |
NZ237570A (en) * | 1990-04-13 | 1993-09-27 | Colgate Palmolive Co | Enzyme stabilising composition and stabilised enzyme-containing built detergent compositions |
ES2078738T3 (en) * | 1991-02-12 | 1995-12-16 | Buckman Labor Inc | COMPOSITION AND PROCEDURE TO ELIMINATE OR PREVENT THE APPEARANCE OF BIOFILMS. |
AU669900B2 (en) * | 1992-07-20 | 1996-06-27 | Colgate-Palmolive Company, The | Stabilized built aqueous liquid softergent compositions |
ZA943640B (en) * | 1993-06-07 | 1995-01-26 | Buckman Labor Inc | Synergistically stabilized liquid enzymatic compositions |
GB9822797D0 (en) * | 1998-10-19 | 1998-12-16 | United States Borax Inc | Pourable aqueous boron-containing compositions and their preparation |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FI61715C (en) * | 1976-11-01 | 1982-09-10 | Unilever Nv | ENZYMER INNEHAOLLANDE STABILIZERAD FLYTANDE DETERGENTKOMPOSITION |
IT1129814B (en) * | 1980-07-02 | 1986-06-11 | Unilever Nv | LIQUID ENZYMATIC DETERGENT COMPOSITION |
AU547579B2 (en) * | 1981-11-13 | 1985-10-24 | Unilever Plc | Low foaming liquid detergent composition |
DE3264685D1 (en) * | 1981-11-13 | 1985-08-14 | Unilever Nv | Enzymatic liquid cleaning composition |
US4462922A (en) * | 1981-11-19 | 1984-07-31 | Lever Brothers Company | Enzymatic liquid detergent composition |
US4529525A (en) * | 1982-08-30 | 1985-07-16 | Colgate-Palmolive Co. | Stabilized enzyme-containing detergent compositions |
US4469605A (en) * | 1982-12-13 | 1984-09-04 | Colgate-Palmolive Company | Fabric softening heavy duty liquid detergent and process for manufacture thereof |
GB8305790D0 (en) * | 1983-03-02 | 1983-04-07 | Unilever Plc | Liquid detergent composition |
GB8311314D0 (en) * | 1983-04-26 | 1983-06-02 | Unilever Plc | Aqueous enzyme-containing compositions |
NZ208157A (en) * | 1983-05-31 | 1986-11-12 | Colgate Palmolive Co | Built single-phase liquid detergent compositions containing stabilised enzymes |
NZ208156A (en) * | 1983-05-31 | 1986-11-12 | Colgate Palmolive Co | Built single-phase liquid detergent compositions containing stabilised enzymes |
US4507219A (en) * | 1983-08-12 | 1985-03-26 | The Proctor & Gamble Company | Stable liquid detergent compositions |
DE3574729D1 (en) * | 1984-05-14 | 1990-01-18 | Procter & Gamble | LIQUID CLEANING AGENTS CONTAINING BORIC ACID FOR STABILIZING ENZYMS. |
NZ216791A (en) * | 1985-07-26 | 1988-07-28 | Colgate Palmolive Co | Stabilised, built, enzyme-containing liquid detergents |
-
1986
- 1986-07-08 SE SE8603036A patent/SE468518B/en not_active IP Right Cessation
- 1986-07-08 NZ NZ216792A patent/NZ216792A/en unknown
- 1986-07-10 IN IN606/DEL/86A patent/IN170204B/en unknown
- 1986-07-14 AU AU60132/86A patent/AU590589B2/en not_active Ceased
- 1986-07-16 ZW ZW133/86A patent/ZW13386A1/en unknown
- 1986-07-16 DE DE3623943A patent/DE3623943A1/en not_active Ceased
- 1986-07-17 CA CA000514035A patent/CA1297440C/en not_active Expired - Lifetime
- 1986-07-17 IL IL79450A patent/IL79450A0/en not_active IP Right Cessation
- 1986-07-21 MA MA20969A patent/MA20741A1/en unknown
- 1986-07-21 FR FR868610550A patent/FR2585361B1/en not_active Expired - Lifetime
- 1986-07-21 PT PT83023A patent/PT83023B/en unknown
- 1986-07-22 PH PH34051A patent/PH22908A/en unknown
- 1986-07-22 IT IT48289/86A patent/IT1195869B/en active
- 1986-07-22 CH CH2942/86A patent/CH669958A5/de not_active IP Right Cessation
- 1986-07-23 AT AT0199086A patent/AT397810B/en not_active IP Right Cessation
- 1986-07-23 BR BR8603479A patent/BR8603479A/en not_active IP Right Cessation
- 1986-07-24 GR GR861947A patent/GR861947B/en unknown
- 1986-07-24 ES ES8600598A patent/ES2001483A6/en not_active Expired
- 1986-07-24 EG EG464/86A patent/EG17901A/en active
- 1986-07-24 GB GB8618043A patent/GB2178055B/en not_active Expired
- 1986-07-25 MX MX003265A patent/MX167431B/en unknown
- 1986-07-25 BE BE0/216971A patent/BE905167A/en not_active IP Right Cessation
- 1986-07-25 KR KR1019860006065A patent/KR940010118B1/en active IP Right Grant
- 1986-07-25 LU LU86526A patent/LU86526A1/en unknown
- 1986-07-25 DK DK355186A patent/DK165331C/en not_active IP Right Cessation
- 1986-07-25 NL NL8601927A patent/NL8601927A/en not_active Application Discontinuation
- 1986-07-25 IE IE197486A patent/IE59691B1/en not_active IP Right Cessation
- 1986-07-25 NO NO862996A patent/NO165928C/en unknown
-
1987
- 1987-09-28 MY MYPI87002055A patent/MY101616A/en unknown
-
1992
- 1992-10-14 SG SG1086/92A patent/SG108692G/en unknown
-
1993
- 1993-01-14 HK HK19/93A patent/HK1993A/en unknown
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