EP0028866B1 - Stabilised aqueous enzyme composition containing formate and calcium ions - Google Patents
Stabilised aqueous enzyme composition containing formate and calcium ions Download PDFInfo
- Publication number
- EP0028866B1 EP0028866B1 EP19800201059 EP80201059A EP0028866B1 EP 0028866 B1 EP0028866 B1 EP 0028866B1 EP 19800201059 EP19800201059 EP 19800201059 EP 80201059 A EP80201059 A EP 80201059A EP 0028866 B1 EP0028866 B1 EP 0028866B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- enzyme
- composition
- compositions
- calcium
- per litre
- 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
Links
- 239000000203 mixture Substances 0.000 title claims description 112
- 102000004190 Enzymes Human genes 0.000 title claims description 44
- 108090000790 Enzymes Proteins 0.000 title claims description 44
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims description 24
- 229910001424 calcium ion Inorganic materials 0.000 title claims description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 title description 10
- 239000003599 detergent Substances 0.000 claims description 28
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 235000019253 formic acid Nutrition 0.000 claims description 13
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 102000035195 Peptidases Human genes 0.000 claims description 8
- 108091005804 Peptidases Proteins 0.000 claims description 8
- 239000004280 Sodium formate Substances 0.000 claims description 5
- 159000000007 calcium salts Chemical class 0.000 claims description 5
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 5
- 235000019254 sodium formate Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000006172 buffering agent Substances 0.000 claims description 3
- 150000003138 primary alcohols Chemical class 0.000 claims description 3
- 150000003333 secondary alcohols Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- 229940088598 enzyme Drugs 0.000 description 36
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 17
- 239000011575 calcium Substances 0.000 description 17
- 229910052791 calcium Inorganic materials 0.000 description 17
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 9
- 229940044170 formate Drugs 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 7
- 239000002736 nonionic surfactant Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 239000003605 opacifier Substances 0.000 description 5
- 150000004671 saturated fatty acids Chemical class 0.000 description 5
- 239000003352 sequestering agent Substances 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- -1 ethoxylated ammonium sulfonates Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000002797 proteolythic effect Effects 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000004365 Protease Substances 0.000 description 3
- 102000005158 Subtilisins Human genes 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 235000003441 saturated fatty acids Nutrition 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 108010056079 Subtilisins Proteins 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 150000004675 formic acid derivatives Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 201000011243 gastrointestinal stromal tumor Diseases 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- SGHSRBYSXCNJLP-UHFFFAOYSA-N 2-methyl-4,6-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC(C)=C(O)C(CCCCCCCCC)=C1 SGHSRBYSXCNJLP-UHFFFAOYSA-N 0.000 description 1
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical class CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- IMOYOUMVYICGCA-UHFFFAOYSA-N 2-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C=C1C(C)(C)C IMOYOUMVYICGCA-UHFFFAOYSA-N 0.000 description 1
- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RIADTAAHKZOZHP-UHFFFAOYSA-L C(=O)[O-].[K+].[Li+].C(=O)[O-] Chemical compound C(=O)[O-].[K+].[Li+].C(=O)[O-] RIADTAAHKZOZHP-UHFFFAOYSA-L 0.000 description 1
- 0 C*(C)[N+]([O-])OC Chemical compound C*(C)[N+]([O-])OC 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LASVAZQZFYZNPK-UHFFFAOYSA-N Cc1nc(C)nc(C)n1 Chemical compound Cc1nc(C)nc(C)n1 LASVAZQZFYZNPK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003625 amylolytic effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 235000010331 calcium propionate Nutrition 0.000 description 1
- 239000004330 calcium propionate Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- FDKLLWKMYAMLIF-UHFFFAOYSA-N cyclopropane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CC1 FDKLLWKMYAMLIF-UHFFFAOYSA-N 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- 229940079919 digestives enzyme preparation Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 150000004674 formic acids Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229940096405 magnesium cation Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- XNQULTQRGBXLIA-UHFFFAOYSA-O phosphonic anhydride Chemical compound O[P+](O)=O XNQULTQRGBXLIA-UHFFFAOYSA-O 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—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
Definitions
- the present invention relates to stabilised aqueous enzyme compositions which contain detergent compounds.
- a stabilised aqueous enzyme composition containing a detergent, surfactant, an enzyme, a low molecular weight primary or secondary alcohol, and a water-soluble calcium salt derived from an organic acid, characterised in that:
- the detergent surfactant can be a nonionic, anionic, cationic, zwitterionic, amphoteric or semi-polar nonionic surfactant, or a mixture thereof.
- the surfactant comprises a substantial portion of nonionic surfactant together with either an anionic surfactant, a semi-polar nonionic surfactant, or a cationic surfactant or a mixture thereof.
- the surfactants preferably comprise from 10% to 75%, more preferably from 20% to 50%, of the composition.
- Nonionic surfactants are conventionally produced by condensing ethylene oxide with a hydrocarbon having a reactive hydrogen atom, e.g., a hydroxyl, carboxyl, amino, or amido group, in the presence of an acidic or basic catalyst.
- Nonionic surfactants have the general formula RA(CH 2CH 20)nH wherein R represents the hydrophobic moiety, A represents the group carrying the reactive hydrogen atom and n represents the average number of ethylene oxide moieties.
- R typically contains from 8 to 22 carbon atoms, but can also be formed by the condensation of propylene oxide with a lower molecular weight compound. n usually varies from 2 to 24.
- the hydrophobic moiety of the nonionic compound is preferably a primary or secondary, straight or slightly branched, aliphatic alcohol having from 8 to 24, preferably from 12 to 20 carbon atoms.
- suitable nonionic surfactants can be found in U.S. Patent 4,111,855.
- Synthetic anionic surfactants can be represented by the general formula R'S0 3 M wherein R 1 represents a hydrocarbon group such as a straight or branched alkyl radical containing from 8 to 24 carbon atoms or an alkyl phenyl radical containing from 9 to 15 carbon atoms in the alkyl group.
- M is a salt forming cation which typically is sodium, potassium, ammonium, monoalkanol-ammonium, di- alkanolammonium, trialkanolammonium, or magnesium cation or a mixture thereof.
- a preferred synthetic anionic surfactant is a water-soluble salt of an alkylbenzene sulfonic acid containing from 9 to 15 carbon atoms in the alkyl group.
- Another preferred synthetic anionic surfactant is a water-soluble salt of an alkyl polyethoxylate ether sulfate wherein the alkyl group contains from 8 to 24, preferably from 10 to 18 carbon atoms and there are from 1 to 20, preferably from 1 to 12 ethoxy groups.
- Other suitable anionic surfactants are disclosed in U.S. Patent 4,170,565, Flesher et al, issued October 9, 1979.
- Suitable anionic surfactants can include soaps and fatty acids containing from 8 to 24 carbon atoms, but it should be recognised that such soaps and fatty acids to tend to tie up calcium ions and thus are preferably limited to from 1% to 25%, most preferably from 10% to 20%.
- Suitable cationic surfactants have the general formula wherein each R 2 is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to three phenyl or hydroxy groups and optionally interrupted by up to four structures selected from and mixtures thereof, each R 2 containing from 8 to 22 carbon atoms, and which may additionally contain up to 12 ethylene oxide groups, m is a number from 1 to 3, each R 3 is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one R 3 in a molecule being benzyl, x is a number from 0 to 11, the remainder of any carbon atom positions being filled by hydrogens, Y is selected from: wherein p is from 1 to 12, wherein p is from 1 to 12, and (9) mixtures thereof.
- Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulphonium compounds in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic substituents contains from 8 to 24 carbon atoms and one contains an anionic water-solubilising group.
- Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patents 3,925,262, Laughlin et al, issued December 9, 1975 and 3,929,678, Laughlin et al, issued December 30, 1975.
- Ampholytic surfactants include derivatives of aliphatic heterocylic secondary and ternary amines in which the aliphatic moieth can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 24 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Semi-polar nonionic surfactants include water-soluble amine oxides containing 1 alkyl or hydroxy alkyl moiety of from 8 to 28 carbon atoms and 2 moieties of alkyl groups or hydroxy alkyl groups, containing from 1 to 3 carbon atoms which can optionally be joined into ring structures; water-soluble phosphine oxides containing 1 alkyl or hydroxy alkyl moiety of from 8 to 28 carbon atoms and 2 moieties of alkyl groups or hydroxyl alkyl groups, containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing 1 alkyl or hydroxy alkyl moiety of from 8 to 28 carbon atoms and an alkyl or hydroxy alkyl moiety of from 1 to 3 carbon atoms.
- the enzyme component herein is incorporated in an amount of from 0.025 to 1 %, preferably from 0.05% to 0.2%.
- the preferred proteolytic enzyme component should give to the composition a proteolytic activity of at least 4 Anson units per litre, preferably from 15 to 70 Anson units per litre, most preferably from 20 to 40 Anson units per litre. A proteolytic activity of from 3 to 5 Anson units per gram of product is desirable.
- Other enzymes, including amylolytic enzymes can also be included.
- the enzyme component is characterised by an isoelectric point of from 8.5 to 10, preferably from 9 to 9.5.
- suitable protoelytic enzymes include many species which are known to be adapted for use in detergent compositions and, in fact, have been used in detergent compositions.
- Sources of the enzymes include commercial enzyme preparations such as "Alcalase”* sold by Novo Industries, and “Maxatase”(s sold by Gist-Brocades, Delft, The Netherlands, which contain from 10% to 20% enzyme.
- Another preferred enzyme composition for use herein is available, under the trade mark ESPERASEc, from Novo Industries A/S, Copenhagen, Denmark.
- the low molecular weight primary or secondary alcohol is exemplified by methanol, ethanol, propanol, or isopropanol.
- Monohydric alcohols are preferred for solubilising the surfactant but polyols containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups can be used and can provide improved enzyme stability.
- polyols include propylene glycol, ethylene glycol and glycerine.
- Ethanol is a particular preferred alcohol.
- the composition contains from 0% to 20%, preferably from 5% to 15%, most preferably from 9% to 11.4% of the alcohol.
- the formate is either formic acid or a water-soluble salt thereof, e.g. sodium formate.
- the formates are surprisingly much more effective than other short chain carboxylic salts like the acetates and the propionates.
- the formic acid or formate is used at a level from 0.1% to 10%, preferably from 0.3% to 3%, more preferably from 0.5% to 1.5% when the product pH is below 8.5 and from 3% to 10%, preferably from 4% to 8%, when the product pH is from 8.5 to 10.
- Any water-soluble calcium salt can be used as a source of enzyme-accessible calcium ions, including calcium acetate, calcium formate and calcium propionate.
- the level of enzyme-accessible calcium ions in the composition is from 0.1 to 10 millimoles of calcium ion per litre, provided that the amount of calcium ion per litre of the composition is from 0.1 to 2 millimoles at pHs below 8.5.
- soap or fatty acid is present, the preferred level is from 2 to 6 millimoles of calcium ion per litre.
- the pH of the composition is from 6.5 to 10, preferably from 7 to 8.5 to obtain a combination of enzyme stability and detergency.
- a pH of from 8.5 to 10 preferably 9 to 10 is best for detergency. Both high and low pH adversely affects enzyme stability and low pH gives up too much detergent effectiveness.
- Suitable pH buffers include mono-, di- and tri-ethanolamines. When the composition pH is from 8.5 to 10 triethanolamine is the best buffer. When soap or fatty acid is present, the preferred pH is from 7 to 7.5.
- the balance of the composition is water.
- the composition can contain optional ingredients, including perfumes, dyes, opacifiers, optical brighteners, suds, suppressors, pH adjusting agents, etc. Disclosures of suitable ingredients can be found in the patents and patent applications referred to above.
- the composition is essentially free of materials such as detergent builders which tie up calcium ions to permit sufficient enzyme-accessible calcium ions to be present, although with the formate, excellent stability is achieved with very low levels of calcium ions, especially in the low pH range.
- homogeneous aqueous detergent compositions of this invention comprise: (a) from 20% to 50% by weight of an organic synthetic surface-active agent; (b) from 3% to 15% by weight of a saturated fatty acid having 10 to 16 carbon atoms in the alkyl chain; (c) from 0.025% to about 1% by weight of an enzyme; (d) from 0.1 % to 3% by weight of formic acid or a water-soluble salt thereof; and (e) less than 2 millimoles of enzyme-accessible calcium per litre of the detergent composition, the pH of the composition, measured as is at 20°C, being from 6.5 to 8.5.
- the saturated fatty acids preferably have from 12 to 14 carbon atoms in the alkyl chain
- the detergent enzymes are represented by proteases or mixtures of proteases and amylases
- formate is represented by formic acid
- the enzyme-accessible calcium is present in an amount of from 0.5 to 1.5 millimoles per litre of the detergent composition
- the pH of the composition as is, in the range from 7 to 7.5.
- the saturated fatty acid component is incorporated in an amount of from 3% to 15%, preferably from 5% to 11 %.
- the saturated fatty acids have from 10 to 16, preferably 12 or 14 carbon atoms in the alkyl chain.
- the most preferred fatty acids are either lauric acid or lauric and myristic fatty acid in a mixture of 5:1 to 1 :1.
- the compositions herein can comprise certain amounts of unsaturated fatty acids having, for example, 16 or 18 carbon atoms in the alkyl chain.
- unsaturated fatty acids are oleic fatty acid and palmitoleic fatty acid.
- the enzyme component is incorporated in an amount of from 0.025 to 1 %, preferably from 0.05% to 0.2%.
- the preferred proteolytic enzyme component should give to the composition a proteolytic activity of at least 4 Anson units, preferably from 10 to 20 Anson units, per litre of the liquid detergent composition.
- the enzyme component can be represented by a mixture of proteases and amylases. The proteolytic activity of that mixture is as defined hereinbefore.
- the enzyme component is characterised by an isoelectric point of from 8.0 to 10, preferably from 8.5 to 9.5.
- the formic acid or water-soluble salt thereof is used in an amount from 0.1% to 3%, preferably from 0.5% to 1.5%.
- compositions herein comprise from 0.1 to 2, 'preferably from 0.5 to 1.5, millimoles of enzyme-accessible calcium per litre of the homogeneous enzyme containing detergent composition.
- the preferred compositions are substantially free of sequestrants, for example, polyacids capable of forming calcium complexes which are soluble in the composition. However, minor amounts of sequestrants such as polyacids or mixtures of polyacids can be used.
- the enzyme-accessible calcium is defined as the amount of calcium ions effectively available to the enzyme component.
- the calcium sequestration resulting from e.g., 0.5% of a mixture of polyphosphonates and polyacids as exemplified hereinafter can represent 1 to 1.5 millimoles of calcium per litre of product.
- the total calcium incorporated into the compositions is thus comprised of the enzyme-accessible calcium and also the calcium sequestered by the low levels of polyacids. From a practical standpoint the enzyme-accessible calcium is therefore the soluble calcium in the composition in the absence of any strong sequestrants, e.g., having an equilibrium constant of complexation with calcium equal to or greater than 1.5 at 20°C.
- the pH of these preferred compositions is 6.5 to 8.5, preferably from 7 to 7.5 to obtain a combination of enzyme stability and detergency. Both high and low pH can adversely affect enzyme stability.
- compositions herein frequently contain a series of optional ingredients which are used for the known functionality in conventional levels. While the inventive compositions are premised on aqueous enzyme-containing detergent compositions containing a critical ternary system as fully explained above, it is frequently desirable to use a phase regulant. This component together with water constitutes then the solvent matrix for the claimed liquid compositions.
- Suitable phase regulants are well-known in liquid detergent technology and, for example, can be represented by lower aliphatic alcohols having from 2 to 6 carbon atoms and from 1 to 3 hydroxyl groups, ethers of diethylene glycol and lower aliphatic monoalcohols having from 1 to 4 carbon atoms.
- phase regulants are: ethanol; n-propanol; isopropanol; butanol; 1,2-propanediol; 1,3-propanediol; n-hexanol; monomethyl-, -ethyl-, -propyl, and mono-butyl ethers and di-ethylene glycol.
- a low molecular weight alcohol which may already be present can also function as a phase regulant.
- Additional phase regulants having a relatively high boiling point and low vapor pressure can also be used provided they do not react with the other ingredients of the compositions.
- phase regulants suitable for use herein.
- these hydrotropes include salts of alkylarylsulfonates having up to 3 carbon atoms in the alkylgroup, e.g., sodium, potassium, ammonium and ethanolamine salts of xylene-, toluene-, ethylbenzene-, cumene-, and isopropylbenzene sulfonic acids.
- the phase regulant is frequently used in an amount from 5% to 20%; the sum of phase regulant and water is normally in the range from 65% to 35%.
- compositions herein can contain a series of further optional ingredients which are mostly used in additive levels, usually below 5%.
- additives include; polyacids, suds regulants, opacifiers, antioxidants, bactericides, dyes, perfumes, and brighteners.
- a preferred additive is represented by a polyacid or mixture of polyacids in an amount below 1 %.
- Suitable polyacids can include: citric, cyclohexane-1,1-dicarboxylic, cyclopropane-1,1-dicarboxylic, dimethylmalic, glutaric, o-hydroxybenzoic, m-hydroxybenzoic, p-hydroxybenzoic, itaconic, methyl- succinic, sodium tripolyphosphates, and nitrilotriacetic acid.
- Preferred polyacid species for use herein can be represented by citric acid and organo-phosphonic acids and mixtures thereof.
- alkylene-polyamino-polyalkylene phosphonic acids are ethylene diamine tetramethylene- phosphonic acid, hexamethylene diaminetetramethylene-phosphonic acid, diethylene triaminepenta- methylenephosphonic acid, and amino-trimethylenephosphonic acid or the salts thereof.
- organo-phosphonic acids/salts are preferably used in an amount from 0.1 %-0.8%.
- compositions under various usage conditions can require the utilisation of a suds regulant. While generally all detergent suds regulants can be utilised, preferred for use herein are alkylated polysiloxanes such as dimethylpolysiloxanes such as dimethylpolysiloxane also frequently termed silicones. The silicones are frequently used in a level not exceeding 0.5%, most preferably between 0.01% and 0.2%.
- opacifiers it can also be desirable to utilise opacifiers inasmuch as they contribute to create a uniform appearance of the concentrated liquid detergent compositions.
- suitable opacifiers include: polystyrene commercially known as LYTRON 621 ⁇ 9 manufactured by MONSANTO CHEMICAL CORPORATION. The opacifiers are frequently used in an amount from 0.3% to 1.5%.
- compositions herein can also contain known antioxidants for their known utility, frequently radical scavengers, in the art established levels i.e. 0.001% to 0.25% (by reference to total composition). These antioxidants are frequently introduced in conjunction with the fatty acids. While many suitable antioxidants are readily known and available for that purpose especially preferred for use in the compositions herein are: 2,6 ditertiary butyl-p-cresol, more commonly known as butylated hydroxytoluene, BHT, and 2-tertiarybutyl-4-hydroxyanisole or 3-tertiarybutyl-4-hydroxyanisole more commonly known as BHA or butylated hydroxyanisole. Other suitable antioxidants are: 4,4'-thiobis (6-tert-butyl-m-cresol) and 2-methyl-4,6-dinonyl phenol.
- 21 day stability data follows the same general trend. As can be seen from the above data, the formate is best, followed by the acetate, which is followed by the propionate. The total amount of Ca ++ present is about 1.5 millimoles/litre, (some is added with the enzyme slurry).
- Liquid detergent compositions were prepared by mixing the individual ingredients listed hereinafter in the stated proportions.
- compositions 1-4 contained 3 millimoles and compositions 5-7 5 millimoles total of calcium/litre of the composition. However, some of the calcium ion is sequestrated by the phosphonic and sulphonic acid components so that the amount of enzyme-accessible calcium ion in each composition is from 0.1 to 2 millimoles per litre.
- compositions 2 to 4, 6 and 7 in accordance with this invention were markedly superior vs. comparable compositions 1 and 5 which did not contain the formate stabiliser.
- compositions 3 and 6 wherein the sodium formate is replaced by a substantially equivalent molar level of triethanolammonium formate, diethanolammonium formate, monoethanolammonium formate, potassium formate lithium formate or ammonium formate.
- Liquid detergent compositions were prepared by mixing the listed ingredients in the stated proportions.
- composition A is representative of the prior art.
- Compositions B and C are reference compositions based on routine variations vs. the art compositions.
- Composition I is an example of the invention herein.
- the level of calcium in compositions A and B represents, based on current art khowledge, the minimum needed to achieve acceptable enzyme stability.
- the amount of calcium in composition C was lowered to the point where phase instability and precipitation would not anymore occur.
- the testing data are summarised below.
- composition I in accordance with this invention vs. formulationwise closely related art composition ⁇ A ⁇ or what could be technical variations ⁇ B, C ⁇ of known art formulations.
- compositions were prepared by mixing the listed components in the indicated proportions.
- Composition D is what could be a technical variation of the state of art whereas formula IV is an execution of the claimed invention.
- Composition V is a comparative example using acetic acid instead of formic acid.
- the residual enzymatic activity (expressed in % of initial activity) were measured following exposure to accelerated storage conditions (48 hours at 40°C).
- compositions of this invention are prepared by mixing the listed ingredients in a conventional manner.
- compositions VI ⁇ XII are clear, homogeneous products having a markedly improved enzyme stability, especially upon storage.
- the above general formula was modified by adding the indicated percentages of alkaline buffering agents (citric acid to trim) to provide the indicated product pH's and by adding the indicated percentages of CaCl 2 and sodium formate.
- the individual compositions were tested and gave the indicated stability results.
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Description
- The present invention relates to stabilised aqueous enzyme compositions which contain detergent compounds.
- This application is related to concurrently filed European Patent Application No. 80201058.7, filed on 7th November, 1980. (EP-A1-0 028 865)
- The formulation of enzyme-containing aqueous liquid detergent compositions is very difficult due to the rapid decrease in enzymatic activity in aqueous media during storage. U.S. Patent 4,111,855, Barrat et al., for Liquid Enzyme Containing Detergent Composition, issued September 5, 1978, discloses one solution to stabilisation of enzymes in aqueous media. The patent utilises a combination of a polyacid, free calcium ions, and a lower aliphatic alcohol to stabilise the enzymes.
- According to the present invention, there is provided a stabilised aqueous enzyme composition containing a detergent, surfactant, an enzyme, a low molecular weight primary or secondary alcohol, and a water-soluble calcium salt derived from an organic acid, characterised in that:
- the detergent surfactant is present in a level up to 75%;
- the alcohol is present in a level up to 20%;
- the enzyme is present in a level from 0.025% to 1%;
- the composition contains from 0.1% to 10% of formic acid or a water soluble salt thereof;
- the soluble calcium salt provides from 0.1 to 10 millimoles of enzyme-accessible calcium ion per litre of the composition, and
- the pH of the composition is in the range from 6.5 to 10; provided that the amount of enzyme-accessible calcium ion per litre of the composition is from 0.1 to 2 millimoles when the pH of the composition is below 8.5.
- In the present description and in the claims, all parts, percentages and ratios are by weight unless otherwise specified.
- The detergent surfactant can be a nonionic, anionic, cationic, zwitterionic, amphoteric or semi-polar nonionic surfactant, or a mixture thereof. Preferably, the surfactant comprises a substantial portion of nonionic surfactant together with either an anionic surfactant, a semi-polar nonionic surfactant, or a cationic surfactant or a mixture thereof. The surfactants preferably comprise from 10% to 75%, more preferably from 20% to 50%, of the composition.
- Nonionic surfactants are conventionally produced by condensing ethylene oxide with a hydrocarbon having a reactive hydrogen atom, e.g., a hydroxyl, carboxyl, amino, or amido group, in the presence of an acidic or basic catalyst. Nonionic surfactants have the general formula RA(CH 2CH 20)nH wherein R represents the hydrophobic moiety, A represents the group carrying the reactive hydrogen atom and n represents the average number of ethylene oxide moieties. R typically contains from 8 to 22 carbon atoms, but can also be formed by the condensation of propylene oxide with a lower molecular weight compound. n usually varies from 2 to 24.
- The hydrophobic moiety of the nonionic compound is preferably a primary or secondary, straight or slightly branched, aliphatic alcohol having from 8 to 24, preferably from 12 to 20 carbon atoms. A more complete disclosure of suitable nonionic surfactants can be found in U.S. Patent 4,111,855.
- Synthetic anionic surfactants can be represented by the general formula R'S03M wherein R1 represents a hydrocarbon group such as a straight or branched alkyl radical containing from 8 to 24 carbon atoms or an alkyl phenyl radical containing from 9 to 15 carbon atoms in the alkyl group. M is a salt forming cation which typically is sodium, potassium, ammonium, monoalkanol-ammonium, di- alkanolammonium, trialkanolammonium, or magnesium cation or a mixture thereof.
- A preferred synthetic anionic surfactant is a water-soluble salt of an alkylbenzene sulfonic acid containing from 9 to 15 carbon atoms in the alkyl group. Another preferred synthetic anionic surfactant is a water-soluble salt of an alkyl polyethoxylate ether sulfate wherein the alkyl group contains from 8 to 24, preferably from 10 to 18 carbon atoms and there are from 1 to 20, preferably from 1 to 12 ethoxy groups. Other suitable anionic surfactants are disclosed in U.S. Patent 4,170,565, Flesher et al, issued October 9, 1979.
- Other suitable anionic surfactants can include soaps and fatty acids containing from 8 to 24 carbon atoms, but it should be recognised that such soaps and fatty acids to tend to tie up calcium ions and thus are preferably limited to from 1% to 25%, most preferably from 10% to 20%.
- Suitable cationic surfactants have the general formula
- A more complete disclosure can be found in U.S. Patent 4,228,044 by Cushman M. Cambre for Laundry Detergent Composition Having Enhanced Particulate Soil Removal and Antiredeposition Performance, issued October 14, 1980. Care should be taken in including cationic materials, including surfactants since some cationic materials have been found to decrease enzyme effectiveness.
- Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulphonium compounds in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic substituents contains from 8 to 24 carbon atoms and one contains an anionic water-solubilising group. Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patents 3,925,262, Laughlin et al, issued December 9, 1975 and 3,929,678, Laughlin et al, issued December 30, 1975.
- Ampholytic surfactants include derivatives of aliphatic heterocylic secondary and ternary amines in which the aliphatic moieth can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 24 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Semi-polar nonionic surfactants include water-soluble amine oxides containing 1 alkyl or hydroxy alkyl moiety of from 8 to 28 carbon atoms and 2 moieties of alkyl groups or hydroxy alkyl groups, containing from 1 to 3 carbon atoms which can optionally be joined into ring structures; water-soluble phosphine oxides containing 1 alkyl or hydroxy alkyl moiety of from 8 to 28 carbon atoms and 2 moieties of alkyl groups or hydroxyl alkyl groups, containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing 1 alkyl or hydroxy alkyl moiety of from 8 to 28 carbon atoms and an alkyl or hydroxy alkyl moiety of from 1 to 3 carbon atoms.
- For a more complete disclosure of compounds which are suitable for incorporation in detergent compositions, one can consult U.S. Patents 4,056,481, Tate (November 1, 1977); 4,049,586, Collier (September 20, 1977); 4,040,988, Vincent et al (August 9, 1977); 4,035,257, Cherney (July 12, 1977); 4,033,718, Holcolm et al (July 5, 1977); 4,019,999, Ohren et al (April 26, 1977); 4,019,998, Vincent et al (April 26, 1977); and 3,985,669, Krummel et al (October 12, 1976).
- The enzyme component herein is incorporated in an amount of from 0.025 to 1 %, preferably from 0.05% to 0.2%. The preferred proteolytic enzyme component should give to the composition a proteolytic activity of at least 4 Anson units per litre, preferably from 15 to 70 Anson units per litre, most preferably from 20 to 40 Anson units per litre. A proteolytic activity of from 3 to 5 Anson units per gram of product is desirable. Other enzymes, including amylolytic enzymes can also be included.
- Preferably the enzyme component is characterised by an isoelectric point of from 8.5 to 10, preferably from 9 to 9.5.
- Examples of suitable protoelytic enzymes include many species which are known to be adapted for use in detergent compositions and, in fact, have been used in detergent compositions. Sources of the enzymes include commercial enzyme preparations such as "Alcalase"* sold by Novo Industries, and "Maxatase"(s sold by Gist-Brocades, Delft, The Netherlands, which contain from 10% to 20% enzyme. Another preferred enzyme composition for use herein is available, under the trade mark ESPERASEc, from Novo Industries A/S, Copenhagen, Denmark.
- A more complete disclosure of suitable enzymes can be found in U.S. Patent 4,101,457, Place et al issued July 18, 1978.
- The low molecular weight primary or secondary alcohol is exemplified by methanol, ethanol, propanol, or isopropanol. Monohydric alcohols are preferred for solubilising the surfactant but polyols containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups can be used and can provide improved enzyme stability. Examples of polyols include propylene glycol, ethylene glycol and glycerine. Ethanol is a particular preferred alcohol. The composition contains from 0% to 20%, preferably from 5% to 15%, most preferably from 9% to 11.4% of the alcohol.
- The formate is either formic acid or a water-soluble salt thereof, e.g. sodium formate. The formates are surprisingly much more effective than other short chain carboxylic salts like the acetates and the propionates. The formic acid or formate is used at a level from 0.1% to 10%, preferably from 0.3% to 3%, more preferably from 0.5% to 1.5% when the product pH is below 8.5 and from 3% to 10%, preferably from 4% to 8%, when the product pH is from 8.5 to 10.
- Any water-soluble calcium salt can be used as a source of enzyme-accessible calcium ions, including calcium acetate, calcium formate and calcium propionate. The level of enzyme-accessible calcium ions in the composition is from 0.1 to 10 millimoles of calcium ion per litre, provided that the amount of calcium ion per litre of the composition is from 0.1 to 2 millimoles at pHs below 8.5. Preferably, there are from 0.5 to 1.5 millimoles of enzyme-accessible calcium ion per litre when the product pH is below 8.5 and from 4 to 8 millimoles when the product pH is from 8.5 to 1'0. When soap or fatty acid is present, the preferred level is from 2 to 6 millimoles of calcium ion per litre.
- The pH of the composition is from 6.5 to 10, preferably from 7 to 8.5 to obtain a combination of enzyme stability and detergency. A pH of from 8.5 to 10 preferably 9 to 10 is best for detergency. Both high and low pH adversely affects enzyme stability and low pH gives up too much detergent effectiveness. Suitable pH buffers include mono-, di- and tri-ethanolamines. When the composition pH is from 8.5 to 10 triethanolamine is the best buffer. When soap or fatty acid is present, the preferred pH is from 7 to 7.5.
- The balance of the composition is water. The composition can contain optional ingredients, including perfumes, dyes, opacifiers, optical brighteners, suds, suppressors, pH adjusting agents, etc. Disclosures of suitable ingredients can be found in the patents and patent applications referred to above. Preferably, the composition is essentially free of materials such as detergent builders which tie up calcium ions to permit sufficient enzyme-accessible calcium ions to be present, although with the formate, excellent stability is achieved with very low levels of calcium ions, especially in the low pH range.
- In a preferred embodiment homogeneous aqueous detergent compositions of this invention comprise: (a) from 20% to 50% by weight of an organic synthetic surface-active agent; (b) from 3% to 15% by weight of a saturated fatty acid having 10 to 16 carbon atoms in the alkyl chain; (c) from 0.025% to about 1% by weight of an enzyme; (d) from 0.1 % to 3% by weight of formic acid or a water-soluble salt thereof; and (e) less than 2 millimoles of enzyme-accessible calcium per litre of the detergent composition, the pH of the composition, measured as is at 20°C, being from 6.5 to 8.5. In these preferred embodiments of this invention, the saturated fatty acids preferably have from 12 to 14 carbon atoms in the alkyl chain, the detergent enzymes are represented by proteases or mixtures of proteases and amylases, formate is represented by formic acid, the enzyme-accessible calcium is present in an amount of from 0.5 to 1.5 millimoles per litre of the detergent composition, and the pH of the composition, as is, in the range from 7 to 7.5. These preferred compositions of this invention are substantially builder free. While the fatty acids and/or soaps are not considered as detergent builders/sequestrants in the context of this invention, the claimed compositions do not contain more than minor amounts of sequestrants.
- In this preferred embodiment, the saturated fatty acid component is incorporated in an amount of from 3% to 15%, preferably from 5% to 11 %. The saturated fatty acids have from 10 to 16, preferably 12 or 14 carbon atoms in the alkyl chain. The most preferred fatty acids are either lauric acid or lauric and myristic fatty acid in a mixture of 5:1 to 1 :1. It is understood that in addition to the saturated fatty acids, the compositions herein can comprise certain amounts of unsaturated fatty acids having, for example, 16 or 18 carbon atoms in the alkyl chain. Known examples of the like unsaturated fatty acids are oleic fatty acid and palmitoleic fatty acid.
- In this preferred embodiment the enzyme component is incorporated in an amount of from 0.025 to 1 %, preferably from 0.05% to 0.2%. The preferred proteolytic enzyme component should give to the composition a proteolytic activity of at least 4 Anson units, preferably from 10 to 20 Anson units, per litre of the liquid detergent composition. In another preferred embodiment the enzyme component can be represented by a mixture of proteases and amylases. The proteolytic activity of that mixture is as defined hereinbefore.
- Preferably the enzyme component is characterised by an isoelectric point of from 8.0 to 10, preferably from 8.5 to 9.5.
- In this preferred embodiment the formic acid or water-soluble salt thereof is used in an amount from 0.1% to 3%, preferably from 0.5% to 1.5%.
- Preferred is, formic acid or the formates such as sodium, potassium, lithium, ammonium and substituted ammonium, inclusive of mono-, di-, and tri-ethanolammonium.
- These preferred compositions herein comprise from 0.1 to 2, 'preferably from 0.5 to 1.5, millimoles of enzyme-accessible calcium per litre of the homogeneous enzyme containing detergent composition. The preferred compositions are substantially free of sequestrants, for example, polyacids capable of forming calcium complexes which are soluble in the composition. However, minor amounts of sequestrants such as polyacids or mixtures of polyacids can be used. The enzyme-accessible calcium is defined as the amount of calcium ions effectively available to the enzyme component. The calcium sequestration resulting from e.g., 0.5% of a mixture of polyphosphonates and polyacids as exemplified hereinafter can represent 1 to 1.5 millimoles of calcium per litre of product. The total calcium incorporated into the compositions is thus comprised of the enzyme-accessible calcium and also the calcium sequestered by the low levels of polyacids. From a practical standpoint the enzyme-accessible calcium is therefore the soluble calcium in the composition in the absence of any strong sequestrants, e.g., having an equilibrium constant of complexation with calcium equal to or greater than 1.5 at 20°C.
- The pH of these preferred compositions is 6.5 to 8.5, preferably from 7 to 7.5 to obtain a combination of enzyme stability and detergency. Both high and low pH can adversely affect enzyme stability.
- In addition to the essential ingredients described hereinbefore the preferred compositions herein frequently contain a series of optional ingredients which are used for the known functionality in conventional levels. While the inventive compositions are premised on aqueous enzyme-containing detergent compositions containing a critical ternary system as fully explained above, it is frequently desirable to use a phase regulant. This component together with water constitutes then the solvent matrix for the claimed liquid compositions. Suitable phase regulants are well-known in liquid detergent technology and, for example, can be represented by lower aliphatic alcohols having from 2 to 6 carbon atoms and from 1 to 3 hydroxyl groups, ethers of diethylene glycol and lower aliphatic monoalcohols having from 1 to 4 carbon atoms. Specific examples of phase regulants are: ethanol; n-propanol; isopropanol; butanol; 1,2-propanediol; 1,3-propanediol; n-hexanol; monomethyl-, -ethyl-, -propyl, and mono-butyl ethers and di-ethylene glycol. Clearly, a low molecular weight alcohol which may already be present can also function as a phase regulant. Additional phase regulants having a relatively high boiling point and low vapor pressure can also be used provided they do not react with the other ingredients of the compositions.
- Known detergent hydrotropes are a further class of phase regulants suitable for use herein. Examples of these hydrotropes include salts of alkylarylsulfonates having up to 3 carbon atoms in the alkylgroup, e.g., sodium, potassium, ammonium and ethanolamine salts of xylene-, toluene-, ethylbenzene-, cumene-, and isopropylbenzene sulfonic acids. The phase regulant is frequently used in an amount from 5% to 20%; the sum of phase regulant and water is normally in the range from 65% to 35%.
- The preferred compositions herein can contain a series of further optional ingredients which are mostly used in additive levels, usually below 5%. Examples of the like additives include; polyacids, suds regulants, opacifiers, antioxidants, bactericides, dyes, perfumes, and brighteners.
- A preferred additive is represented by a polyacid or mixture of polyacids in an amount below 1 %. Suitable polyacids can include: citric, cyclohexane-1,1-dicarboxylic, cyclopropane-1,1-dicarboxylic, dimethylmalic, glutaric, o-hydroxybenzoic, m-hydroxybenzoic, p-hydroxybenzoic, itaconic, methyl- succinic, sodium tripolyphosphates, and nitrilotriacetic acid. Preferred polyacid species for use herein can be represented by citric acid and organo-phosphonic acids and mixtures thereof. Particularly preferred alkylene-polyamino-polyalkylene phosphonic acids are ethylene diamine tetramethylene- phosphonic acid, hexamethylene diaminetetramethylene-phosphonic acid, diethylene triaminepenta- methylenephosphonic acid, and amino-trimethylenephosphonic acid or the salts thereof. These organo-phosphonic acids/salts are preferably used in an amount from 0.1 %-0.8%.
- The beneficial utilisation of the claimed compositions under various usage conditions can require the utilisation of a suds regulant. While generally all detergent suds regulants can be utilised, preferred for use herein are alkylated polysiloxanes such as dimethylpolysiloxanes such as dimethylpolysiloxane also frequently termed silicones. The silicones are frequently used in a level not exceeding 0.5%, most preferably between 0.01% and 0.2%.
- It can also be desirable to utilise opacifiers inasmuch as they contribute to create a uniform appearance of the concentrated liquid detergent compositions. Examples of suitable opacifiers include: polystyrene commercially known as LYTRON 621<9 manufactured by MONSANTO CHEMICAL CORPORATION. The opacifiers are frequently used in an amount from 0.3% to 1.5%.
- The compositions herein can also contain known antioxidants for their known utility, frequently radical scavengers, in the art established levels i.e. 0.001% to 0.25% (by reference to total composition). These antioxidants are frequently introduced in conjunction with the fatty acids. While many suitable antioxidants are readily known and available for that purpose especially preferred for use in the compositions herein are: 2,6 ditertiary butyl-p-cresol, more commonly known as butylated hydroxytoluene, BHT, and 2-tertiarybutyl-4-hydroxyanisole or 3-tertiarybutyl-4-hydroxyanisole more commonly known as BHA or butylated hydroxyanisole. Other suitable antioxidants are: 4,4'-thiobis (6-tert-butyl-m-cresol) and 2-methyl-4,6-dinonyl phenol.
- The following examples illustrate the invention and facilitate its understanding.
-
- 21 day stability data follows the same general trend. As can be seen from the above data, the formate is best, followed by the acetate, which is followed by the propionate. The total amount of Ca++ present is about 1.5 millimoles/litre, (some is added with the enzyme slurry).
-
- The compositions 1-4 contained 3 millimoles and compositions 5-7 5 millimoles total of calcium/litre of the composition. However, some of the calcium ion is sequestrated by the phosphonic and sulphonic acid components so that the amount of enzyme-accessible calcium ion in each composition is from 0.1 to 2 millimoles per litre.
- The storage stability of the listed compositions was determined under high temperature conditions (35°C. 2 and 4 weeks; 40°C. 48 hours). It was found that compositions 2 to 4, 6 and 7 in accordance with this invention were markedly superior vs. comparable compositions 1 and 5 which did not contain the formate stabiliser.
- Substantially comparable results are also provided by compositions 3 and 6 wherein the sodium formate is replaced by a substantially equivalent molar level of triethanolammonium formate, diethanolammonium formate, monoethanolammonium formate, potassium formate lithium formate or ammonium formate.
-
- (a) MAXATASE@ supplied by GIST-BROCADES expressed on 100% active basis.
- (b) Added as calcium chloride and expressed as millimoles of calcium ion per litre of composition.
- (c) The level of enzyme-accessible calcium is: composition A: 2.5; B: 2.5; C: 0.5; and I: 0.5.
- The enzyme and physical stability of the listed compositions were determined under accelerated storage conditions after 2 weeks at 35°C. Composition A is representative of the prior art. Compositions B and C are reference compositions based on routine variations vs. the art compositions. Composition I is an example of the invention herein. The level of calcium in compositions A and B represents, based on current art khowledge, the minimum needed to achieve acceptable enzyme stability. The amount of calcium in composition C was lowered to the point where phase instability and precipitation would not anymore occur. The testing data are summarised below.
- These results confirm the overall performance benefits provided by composition I in accordance with this invention vs. formulationwise closely related art composition ―A― or what could be technical variations ―B, C― of known art formulations.
-
- (a) MAXATASEe supplied by GIST-BROCADES and expressed on a 100% active basis
- (b) Total calcium added as calcium chloride and expressed in millimoles of enzyme-accessible calcium ion per litre of solution.
- (c) Formic and acetic acids are used in the same molar concentrations.
- Composition D is what could be a technical variation of the state of art whereas formula IV is an execution of the claimed invention. Composition V is a comparative example using acetic acid instead of formic acid.
- The residual enzymatic activity (expressed in % of initial activity) were measured following exposure to accelerated storage conditions (48 hours at 40°C).
-
- These results verify the superiority of the claimed techn .ogy vs. closely related compositions and also show that formic acid is superior to acetic acid.
-
- Compositions VI―XII are clear, homogeneous products having a markedly improved enzyme stability, especially upon storage.
-
- The above general formula was modified by adding the indicated percentages of alkaline buffering agents (citric acid to trim) to provide the indicated product pH's and by adding the indicated percentages of CaCl2 and sodium formate. The individual compositions were tested and gave the indicated stability results.
- The stability of each individual composition was compared to that of the control sample A, which is at low pH and contains no added buffering agent. Samples containing TEA (B, C, D) are more stable than their MEA counterparts (F, G, H), which in turn are much superior to formulas containing Na2C03 (K-P). Enzyme degradation is retarded with increasing levels of sodium formate, particularly in ethanolamine-buffered systems (compare B to F, C to G, and D to H). Added Ca++ (in the form of CaCl2) to the point of saturation retards the degradation rate (compare G to I and H to J).
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT80201059T ATE8406T1 (en) | 1979-11-09 | 1980-11-07 | A STABLE, AQUEOUS ENZYME COMPOSITION CONTAINING FORMATS AND CALCIUM IONS. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US9290679A | 1979-11-09 | 1979-11-09 | |
US12385780A | 1980-02-22 | 1980-02-22 | |
US123857 | 1980-02-22 | ||
US92906 | 1987-09-04 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0028866A1 EP0028866A1 (en) | 1981-05-20 |
EP0028866B1 true EP0028866B1 (en) | 1984-07-11 |
Family
ID=26786177
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19800201059 Expired EP0028866B1 (en) | 1979-11-09 | 1980-11-07 | Stabilised aqueous enzyme composition containing formate and calcium ions |
Country Status (2)
Country | Link |
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EP (1) | EP0028866B1 (en) |
DE (1) | DE3068554D1 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4529525A (en) * | 1982-08-30 | 1985-07-16 | Colgate-Palmolive Co. | Stabilized enzyme-containing detergent compositions |
GR81415B (en) * | 1983-02-14 | 1984-12-11 | Procter & Gamble | |
US4661287A (en) * | 1983-10-05 | 1987-04-28 | Colgate-Palmolive Company | Stable soil release promoting enzymatic liquid detergent composition |
US4486329A (en) * | 1983-10-17 | 1984-12-04 | Colgate-Palmolive Company | Liquid all-purpose cleaner |
CA2006527A1 (en) * | 1988-12-30 | 1990-06-30 | Martin S. Cardinali | Enzymatic liquid detergent compositions |
US5447649A (en) * | 1990-03-01 | 1995-09-05 | Novo Nordisk A/S | Lipase containing liquid pre-spotter and use of such pre-spotter |
US5358656A (en) * | 1991-12-31 | 1994-10-25 | Lever Brothers Company, Division Of Conopco, Inc. | Compositions comprising glyceroglycolipids having an amine linkage as a surfactant or cosurfactant |
US5635464A (en) * | 1992-02-19 | 1997-06-03 | The Procter & Gamble Company | Aqueous hard surface detergent compositions containing calcium ions |
CA2181125A1 (en) * | 1995-07-14 | 1997-01-15 | Gladys S. Gabriel | Stabilization of enzymes in laundry detergent compositions |
JP2000506930A (en) * | 1996-09-24 | 2000-06-06 | ザ、プロクター、エンド、ギャンブル、カンパニー | Liquid detergent containing proteolytic enzymes, peptide aldehydes and calcium ions |
US20060270571A1 (en) * | 2005-05-26 | 2006-11-30 | Burke Peter A | Deactivation of mineral encapsulated nanobacteria |
WO2024012894A1 (en) * | 2022-07-15 | 2024-01-18 | Basf Se | Alkanolamine formates for enzyme stabilization in liquid formulations |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA940070A (en) * | 1968-12-23 | 1974-01-15 | Jim S. Berry | Stabilized aqueous enzyme composition |
BE759360A (en) * | 1969-11-25 | 1971-05-24 | Procter & Gamble Europ | |
DE2709476A1 (en) * | 1976-03-08 | 1977-09-15 | Procter & Gamble Europ | LIQUID, ENZYME-BASED DETERGENT AND DETERGENT |
-
1980
- 1980-11-07 EP EP19800201059 patent/EP0028866B1/en not_active Expired
- 1980-11-07 DE DE8080201059T patent/DE3068554D1/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
DE3068554D1 (en) | 1984-08-16 |
EP0028866A1 (en) | 1981-05-20 |
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