NO773724L - ENZYMATIC LIQUID DETERGENT. - Google Patents
ENZYMATIC LIQUID DETERGENT.Info
- Publication number
- NO773724L NO773724L NO773724A NO773724A NO773724L NO 773724 L NO773724 L NO 773724L NO 773724 A NO773724 A NO 773724A NO 773724 A NO773724 A NO 773724A NO 773724 L NO773724 L NO 773724L
- Authority
- NO
- Norway
- Prior art keywords
- mixture
- weight
- stated
- detergent
- mixtures
- Prior art date
Links
- 239000003599 detergent Substances 0.000 title claims description 32
- 239000007788 liquid Substances 0.000 title claims description 21
- 230000002255 enzymatic effect Effects 0.000 title claims description 16
- 239000000203 mixture Substances 0.000 claims description 40
- 102000004190 Enzymes Human genes 0.000 claims description 20
- 108090000790 Enzymes Proteins 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 229910021538 borax Inorganic materials 0.000 claims description 11
- 239000004328 sodium tetraborate Substances 0.000 claims description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 230000001580 bacterial effect Effects 0.000 claims description 8
- 108091005804 Peptidases Proteins 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 230000006641 stabilisation Effects 0.000 claims description 6
- 238000011105 stabilization Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 102000035195 Peptidases Human genes 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 239000004386 Erythritol Substances 0.000 claims description 3
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 3
- 235000019414 erythritol Nutrition 0.000 claims description 3
- 229940009714 erythritol Drugs 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 230000002797 proteolythic effect Effects 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 235000010356 sorbitol Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000001461 cytolytic effect Effects 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 claims 1
- 239000011149 active material Substances 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- 229940088598 enzyme Drugs 0.000 description 19
- -1 alkali metal borates Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000004365 Protease Substances 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 108010056079 Subtilisins Proteins 0.000 description 4
- 102000005158 Subtilisins Human genes 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 239000000271 synthetic detergent Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000002538 fungal effect Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- 241000194108 Bacillus licheniformis Species 0.000 description 2
- 102000005575 Cellulases Human genes 0.000 description 2
- 108010084185 Cellulases Proteins 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 102000004139 alpha-Amylases Human genes 0.000 description 2
- 108090000637 alpha-Amylases Proteins 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 108700003601 dimethylglycine Proteins 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 108010003855 mesentericopeptidase Proteins 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229940024171 alpha-amylase Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003625 amylolytic effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940079919 digestives enzyme preparation Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2044—Dihydric alcohols linear
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/221—Mono, di- or trisaccharides or derivatives thereof
-
- 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
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2065—Polyhydric alcohols
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)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Detergent Compositions (AREA)
Description
Enzymatisk flytende vaskemiddel.Enzymatic liquid detergent.
Oppfinnelsen vedrører et enzymatisk flytende•produktThe invention relates to an enzymatic liquid product
og mer spesielt en enzymatisk vaskemiddelblanding med forbedret lagrihgsstabilitet . and more particularly an enzymatic detergent composition with improved storage stability.
Flytende vaskemiddelblandinger er velkjente på området, og etter- gjenopplivelse av interessen for enzymer for innlemmelse i vaskemiddelblandinger er det fremsatt flere forslag vedrørende enzymatisk flytende vaskemiddelblandinger. Liquid detergent mixtures are well known in the art, and following the revival of interest in enzymes for incorporation into detergent mixtures, several proposals have been made regarding enzymatic liquid detergent mixtures.
Til tross for disse forslag er slike enzymatiske flytende vaskemiddelblandinger ikke blitt bragt på markedet i noen særlig utstrekning , først og fremst på grunn av at det opptrer alvorlige ustabilitetsproblemer ved innlemmelse av enzymer i flytende vaskemiddelblandinger. Dette problem er velkjent på området, og det er f.eks. blitt foreslått å redusere ustabiliteten hos enzymer i flytende vaskemiddelblandinger ved innlemmelse av stabiliseringssystemer i slike produkter. Despite these proposals, such enzymatic liquid detergent mixtures have not been brought to the market to any particular extent, primarily because serious instability problems occur when enzymes are incorporated into liquid detergent mixtures. This problem is well known in the field, and it is e.g. have been proposed to reduce the instability of enzymes in liquid detergent mixtures by incorporating stabilization systems into such products.
Således er det f.eks. i japansk patentsøknad nr. 47/35192, utlagt 24. november 1972, foreslått å fremstille flytende, stabile enzympreparater, inklusive enzymatiske flytende vaskemiddelblandinger, ved i slike å innblande en kombinasjon av polyalkoholer og boraks. I henhold til den nevnte japanske søknad anvendes disse polyalkoholer, eksemplifisert ved sorbitol og glycerol, i en mengde av minst 5 vekt% av den endelige blanding, fortrinnsvis 10-30 vekt%. Boraksen anvendes i-en mengde av minst 20 %, fortrinnsvis 50-100 vekt% av polyalkoholen. Vekt forholdet mellom polyalkohol og boraks i blandingen bør derfor være lik eller over 1. " Thus, it is e.g. in Japanese patent application no. 47/35192, laid out on 24 November 1972, proposed to produce liquid, stable enzyme preparations, including enzymatic liquid detergent mixtures, by mixing in such a combination of polyalcohols and borax. According to the aforementioned Japanese application, these polyalcohols, exemplified by sorbitol and glycerol, are used in an amount of at least 5% by weight of the final mixture, preferably 10-30% by weight. The borax is used in an amount of at least 20%, preferably 50-100% by weight of the polyalcohol. The weight ratio of polyalcohol to borax in the mixture should therefore be equal to or above 1."
Produktene i henhold til dette tidligere forslag har videre, hvilket er blitt eksperimentelt bestemt ved en gjentagel-se av eksempel I, en pH-verdi i området 3,9-7,4. The products according to this previous proposal also have, which has been experimentally determined by a repetition of example I, a pH value in the range 3.9-7.4.
Det er nå funnet at lagringsstabilitéten til' enzymatiske flytende vaskemiddelblandinger med en pH-verdi over 7,5, fortrinns vis mellom 8,5 og 11,0 (ved 25<0>c'! kan forbedres signifikant ved innlemmelse av et stabiliseringssystem som omfatter'en.eller flere polyhydroksyforbindelser, som skal defineres mer. spesifikt i det følgende, og borsyre eller en bor-ekvivalent derav, idet vektforholdet mellom polyhydroksyforbindelsene og borsyren eller ekvivalenten derav er mindre enn 1 (beregnet på basis av boraks). I sammenligning med kombinasjoner i henhold til den ovennevnte japanske patentsøknad viser systemene i henhold til foreliggende oppfinnelse en signifikant forbedret enzymstabiliserende effekt. It has now been found that the storage stability of enzymatic liquid detergent compositions with a pH value above 7.5, preferably between 8.5 and 11.0 (at 25<0>c'! can be significantly improved by incorporating a stabilization system comprising one or more polyhydroxy compounds, to be defined more specifically in the following, and boric acid or a boron equivalent thereof, the weight ratio between the polyhydroxy compounds and the boric acid or equivalent thereof being less than 1 (calculated on the basis of borax). In comparison with combinations according to the above-mentioned Japanese patent application, the systems according to the present invention show a significantly improved enzyme stabilizing effect.
Polyhydroksyforbindelsene som skal anvendes i forbindelse med oppfinnelsen, inneholder bare C-, H- og 0-atomer. De er fri for andre (funksjonelle)substituerende atomer så som N-, S- The polyhydroxy compounds to be used in connection with the invention contain only C, H and O atoms. They are free of other (functional) substituting atoms such as N-, S-
og lignende.Polyhydroksyforbindelsene bør inneholde minst to hydroksygrupper, og kan inneholde endog opp til 6 hydroksygrupper. Typiske eksempler på polyhydroksyforbindelser som er spesielt godt egnet for anvendelse i forbindelse med oppfinnelsen, er slike dioler som 1,2-propandiol, etylenglykol, erytritan, polyoler, f.eks. gly-c erol, sorbitol og mannitol. and the like. The polyhydroxy compounds should contain at least two hydroxy groups, and may even contain up to 6 hydroxy groups. Typical examples of polyhydroxy compounds which are particularly well suited for use in connection with the invention are such diols as 1,2-propanediol, ethylene glycol, erythritol, polyols, e.g. glycerol, sorbitol and mannitol.
Generelt er polyhydroksyforbind eisen til stede i en mengde av minst 4 vekt% av den endelige blanding, opp til 25 vekt%. Mengden varierer fortrinnsvis fra 5 til 15 vekt% av den endelige blanding Generally, the polyhydroxy compound is present in an amount of at least 4% by weight of the final composition, up to 25% by weight. The amount preferably ranges from 5 to 15% by weight of the final mixture
Borsyren eller borekvivalenten derav, f.eks. boroksyd, boraks og andre alkalimetallborater som er i stand til å reagere med en polyhydroksyf orbindelse f.eks. natrium-, orto-, meta- og pyroborater, anvendes i en slik mengde at vektforholdet mellom polyhydroksyforbindelsen og borforbindelsen er mindre enn 1 (beregnet på basis.av boraks). Dette betyr at borforbindelsen anvendes i en mengde av mer enn 100 % av mengden av polyhydroksyforbindelsen. Generelt varierer mengden fra y 100 til 200 vekt%, og fortrinnsvis y 100 til 160 vekt% av polyhydroksyforbindelsen. The boric acid or boron equivalent thereof, e.g. boron oxide, borax and other alkali metal borates which are capable of reacting with a polyhydroxy compound, e.g. sodium, ortho-, meta- and pyroborates, are used in such an amount that the weight ratio between the polyhydroxy compound and the boron compound is less than 1 (calculated on the basis of borax). This means that the boron compound is used in an amount of more than 100% of the amount of the polyhydroxy compound. In general, the amount varies from y 100 to 200% by weight, and preferably y 100 to 160% by weight of the polyhydroxy compound.
Vektforholdet mellom polyhydroksyforbindelse og borsyre eller -ekvivalent er mindre enn 1, generelt fra 0,5 og opp til like under 1. The weight ratio between polyhydroxy compound and boric acid or equivalent is less than 1, generally from 0.5 up to just under 1.
De enzymatiske flytende blandinger hvor stabiliseringssystemene i henhold til oppfinnelsen.innblandes, kan være vandige flytende systemer, f.eks. enkle løsninger, men de er fortrinnsvis vandige flytende' vaskemiddelblandinger som som essensielle ingre-dienser omfatter enzymer, aktive vaskemidler og' vann, idet pH-verdien ér over 7,5, fortrinnsvis mellom 8,5 og 11.,0, eller The enzymatic liquid mixtures into which the stabilization systems according to the invention are mixed can be aqueous liquid systems, e.g. simple solutions, but they are preferably aqueous liquid detergent mixtures whose essential ingredients include enzymes, active detergents and water, with the pH value being above 7.5, preferably between 8.5 and 11.0, or
justeres til dette område ved egnede midler.adjusted to this area by suitable means.
Enzymene som skal innblandes, kan være proteolytiske, amylolytiske og cellulolytiske enzymer så-vel som blandinger av-disse. De kan være av hvilken som helst opprinnelse, f.eks., av vegetabilsk, animalsk, bakteriell, fungal og gjæropprinnelse. Imidlertid styres valget av dem av forskjellige faktorer så som pH-aktivitet og/eller stabilitetsoptima, termostabilitet, stabi-litet overfor aktive vaskemidler, byggere og så videre. I denne henseende foretrekkes bakterielle eller fungale enzymer, f.eks. bakterielle amylaser og proteaser, samt fungale cellulaser. The enzymes to be mixed in can be proteolytic, amylolytic and cellulolytic enzymes as well as mixtures of these. They may be of any origin, for example, of vegetable, animal, bacterial, fungal and yeast origin. However, their selection is governed by various factors such as pH activity and/or stability optima, thermostability, stability to active detergents, builders and so on. In this regard, bacterial or fungal enzymes are preferred, e.g. bacterial amylases and proteases, as well as fungal cellulases.
Foreliggende oppfinnelse er av spesiell nytte for.enzymatiske flytende vaskemidler som omfatter bakterielle proteaser hvis pH-optima ligger i området mellom 8,0 og 11,0, men det skal forstås at enzymer med et noe lavere eller høyere pH-optimum fremdeles kan anvendes i produktene i henhold til oppfinnelsen, idet det dras fordel av dette. The present invention is of particular use for enzymatic liquid detergents which comprise bacterial proteases whose pH-optimum lies in the range between 8.0 and 11.0, but it should be understood that enzymes with a slightly lower or higher pH-optimum can still be used in the products according to the invention, taking advantage of this.
Egnede eksempler på proteaser er subtilisinene som oppnås fra spesielle stammer av B. subtilis og.B. licheniformis, f.eks. de kommersielt tilgjengelige subtilisiner "Maxatase" fra Gist-Brocades' N.V. , Delft, Nederland) og "Alcalase" fra Novo Industri A/S, København, Danmark). .Som angitt ovenfor., er foreliggende oppfinnelse av. spesiell nytte for enzymatiske flytende vaskemidler som omfatter enzymer med pH-aktivitets- og/eller stabilitetsoptima på over 8,0, f. eks. enzymer som vanligvis også er kalt høy-alkaliske enzymer. Suitable examples of proteases are the subtilisins obtained from particular strains of B. subtilis and.B. licheniformis, e.g. the commercially available subtilisins "Maxatase" from Gist-Brocades' N.V. , Delft, The Netherlands) and "Alcalase" from Novo Industri A/S, Copenhagen, Denmark). .As indicated above., the present invention is of. particular benefit for enzymatic liquid detergents comprising enzymes with pH activity and/or stability optima above 8.0, e.g. enzymes which are usually also called high-alkaline enzymes.
Spesielt egnet er en protease, oppnådd fra en stamme avBacillus, som har maksimal aktivitet gjennom pH-området 8-12, ut-viklet og solgt av Novo Industri A/S under handelsbetegnelsen "Esperase". Fremstillingen av dette enzym og analoge enzymer er beskrevet i britisk patentskrift nr. 1 243 784 (Novo). Particularly suitable is a protease, obtained from a strain of Bacillus, which has maximum activity through the pH range 8-12, developed and sold by Novo Industri A/S under the trade name "Esperase". The production of this enzyme and analogous enzymes is described in British Patent No. 1 243 784 (Novo).
Høyalkaliske amylaser og cellulaser kan også anvendes, f.eks. a-amylaser oppnådd fra en spesiell stamme av B. licheniformis, beskrevet mer detaljert i britisk patentskrift nr. 1 296 839 (Novo). Highly alkaline amylases and cellulases can also be used, e.g. α-amylases obtained from a particular strain of B. licheniformis, described in more detail in British Patent No. 1,296,839 (Novo).
Mengden av enzymer som er til stede i den flytende blanding kan variere fra 0,001 til 10 vekt%, og fortrinnsvis fra 0,01 til. 5 vekt%. The amount of enzymes present in the liquid mixture may vary from 0.001 to 10% by weight, and preferably from 0.01 to. 5% by weight.
, De'flytende vaskemiddelblandinger i henhold til oppfinnelsen omfatter videre som essensiell ingrediens et aktivt vaskemiddelmateriale, som kan være en alkalimétall- eller alkanolamin-såpe av en Clo-c24-fettsyre , inklusive polymeriserte fettsyrer , The liquid detergent mixtures according to the invention further comprise as an essential ingredient an active detergent material, which can be an alkali metal or alkanolamine soap of a Clo-c24 fatty acid, including polymerized fatty acids
eller et anionisk, ikke-ionisk, kationisk, zwitterionisk eller amfotært syntetisk vaskemiddelmateriale, eller blandinger ay hvilke som helst av disse. or an anionic, nonionic, cationic, zwitterionic or amphoteric synthetic detergent material, or mixtures of any of these.
Eksempler på anioniske syntetiske vaskemidler er salter (inklusive natrium-, kalium-, ammonium- og substituert ammonium-salter, f.eks. mono-, di- og trietanolaminsalter) av<Cg>-<C>2o-alkylbenzensulfonater, Cg-C^-primære eller sekundære alkansulfonater, Cg-C24-olefinsulfonater, sulfonerte polykarbok-sylsyre , fremstilt ved sulfonering' av det pyrolyserte produkt av jordalkalimetallcitrater, f.eks. som beskrevet i britisk patentskrift nr. 1082 179 ,Cg-C22-alkylsulfater,Cg-C^-alkylpolygly-koletersulfater (inneholdende opp til 10 mol etylenoksyder); ytterligere eksempler er beskrevet i "Surface Active Agents and Detergents" (bind I og II) av Schwartz, Perry og Berch. Examples of anionic synthetic detergents are salts (including sodium, potassium, ammonium and substituted ammonium salts, e.g. mono-, di- and triethanolamine salts) of<Cg>-<C>2o-alkylbenzene sulfonates, Cg-C ^-primary or secondary alkanesulfonates, C8-C24-olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g. as described in British Patent No. 1082 179, C8-C22-alkyl sulfates, C8-C4-alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxides); additional examples are described in "Surface Active Agents and Detergents" (Volumes I and II) by Schwartz, Perry and Berch.
Eksempler på ikke-ioniske syntetiske vaskemidler er kon-densasjonsproduktene av etylenoksyd, propylenoksyd og/eller buty-lenoksyd med C0-Cn0-alkylfenoler, CQ-C,Q-prim.- eller sek.-alifa-tiske alkoholer, Cg-C-^.g-f ett syreamider; ytterligere eksempler på ikke-ioniske stoffer.inkluderer tertiære aminoksyder' med en Cg-C^g-alkylk jede og to C-^ 2-al^yl'<:jeder . Ovennevnte henvisning beskriver også ytterligere eksempler på ikke-ioniske stoffer. Examples of non-ionic synthetic detergents are the condensation products of ethylene oxide, propylene oxide and/or butylene oxide with C0-Cn0-alkylphenols, CQ-C,Q-primary or sec.-aliphatic alcohols, Cg-C- ^.g-f one acid amides; further examples of nonionic substances include tertiary amine oxides with one C 8 -C 8 -alkyl chain and two C 1 -C 2 -alkyl chains. The above reference also describes further examples of non-ionic substances.
Det gjennomsnittlige antall mol etylenoksyd og/eller propylenoksyd som er til stede i de ovennevnte .ikke-ioniske stoffer, varierer fra 1 til 30; blandinger av forskjellige ikke-ioniske stoffer, inklusive blandinger av ikke-ioniske stoffer med en lavere og en høyere grad av alkoksylering, kan også anvendes. The average number of moles of ethylene oxide and/or propylene oxide present in the above non-ionic substances varies from 1 to 30; mixtures of different non-ionic substances, including mixtures of non-ionic substances with a lower and a higher degree of alkylation, can also be used.
Eksempler-på kationiske vaskemidler er de kvaterriære ammoniumforbindelser, f.eks. alkyldimetylammoniumhalogenider, men slike kationiske stoffer foretrekkes mindre for innlemmelse i enzymatiske vaskemiddelblandinger. Examples of cationic detergents are the quaternary ammonium compounds, e.g. alkyldimethylammonium halides, but such cationic substances are less preferred for incorporation into enzymatic detergent compositions.
Eksempler på amfotæré eller zwitterioniske vaskemidler er N-alkylaminosyrer, sulfobetainer, kondensasjonsprodukter av fettsyrer og proteinhydrolysater, men på grunn av deres relativt høye pris anvendes de vanligvis i kombinasjon med et anionisk eller ikke-ionisk vaskemiddel.Blandinger av de forskjellige typer av aktive vaskemidler kan også anvendes, og det gis preferanse til blandinger av et anionisk og et ikke-ionisk vaskeaktivt stoff. Såper "(i form av deres natrium-, kalium- og substituert ammonium-salter, f.eks. trietanolaminsalter) av C^o-C24-fettsyrer, så vel som av'polymeriserte fettsyrer, kan også anvendes, fortrinnsvis Examples of amphoteric or zwitterionic detergents are N-alkyl amino acids, sulfobetaines, condensation products of fatty acids and protein hydrolysates, but due to their relatively high price they are usually used in combination with an anionic or non-ionic detergent. Mixtures of the different types of active detergents can are also used, and preference is given to mixtures of an anionic and a non-ionic detergent active substance. Soaps (in the form of their sodium, potassium and substituted ammonium salts, e.g. triethanolamine salts) of C 20 -C 24 fatty acids, as well as depolymerized fatty acids, can also be used, preferably
i tilknytning til et . anionisk og/eller et ikke-ionisk syntetisk vaskemiddel, og kan utøve velgjørende innflytelse på skumme-oppførselen til sluttproduktet. in connection with a . anionic and/or a nonionic synthetic detergent, and can exert a beneficial influence on the foaming behavior of the final product.
Mengden av det aktive- vaskemiddelmateriale variererThe amount of active detergent material varies
fra 10 til 60% ; hvis blandinger av. f.eks. anionisk og ikke-from 10 to 60%; if mixtures of. e.g. anionic and non-
ionisk materiale anvendes, varierer det relative vektforhold fra 1:1 til 1:10. Hvis en såpe også innblandes, er mengden av dén fra 1 til 40 vekt%. ionic material is used, the relative weight ratio varies from 1:1 to 1:10. If a soap is also mixed in, the amount thereof is from 1 to 40% by weight.
Selv om væskene kan inneholde opp til 40 % av.en egnet bygger, f.eks. natrium-, kalium- og ammonium- eller substituert ammonium-pyro- og -tripolyfosfater, -nitriltriacetater, -eterpoly-karboksylater , -eitrater, -karbonater, -ortofosfater, polyelektro-lytter, f.eks. polyvinylmetyleter/maleinsyreanhydrid-kopolymerer og så videre,, er foreliggende oppfinnelse av spesiell nytte for anvendelse i .ubyggede flytende vaskemidler. Although the liquids may contain up to 40% of a suitable builder, e.g. sodium, potassium and ammonium or substituted ammonium pyro- and -tripolyphosphates, -nitrile triacetates, -ether polycarboxylates, -eitrates, -carbonates, -orthophosphates, polyelectrolytes, e.g. polyvinyl methyl ether/maleic anhydride copolymers and so on, the present invention is of particular use for use in unstructured liquid detergents.
Den vannmengde som er til stede i vaskemiddelblandingeneThe amount of water present in the detergent mixtures
i henhold til oppfinnelsen, varierer fra 5 til 70 vekt%. according to the invention, varies from 5 to 70% by weight.
André konvensjonelle materialer kan også være til stedeAndré conventional materials may also be present
i de flytende vaskemiddelblandinger i henhold til oppfinnelsen, f. eks. smussbærende midler, hydrot roper,1korrosjonsinhibitorer, farvestoffer, parfymer, silikater, optiske hvitemidler, skumfor-sterkende midler, skumnedsettende midler, germicider, anti-flekkdannelsesmidler, opaktgjørende midler, tøymykningsmidler, oksygenfrigivende blekemidler, f.eks. natriumperborat eller -per-'karbonat med eller uten blekeforløpere, puffere og lignende. in the liquid detergent mixtures according to the invention, e.g. dirt carriers, hydrotropes,1 corrosion inhibitors, dyes, perfumes, silicates, optical brighteners, foam boosters, defoamers, germicides, anti-stain agents, opacifiers, fabric softeners, oxygen-releasing bleaches, e.g. sodium perborate or -per-'carbonate with or without bleach precursors, buffers and the like.
pH-verdien til sluttproduktet er høyere enn 7,5 og bør fortrinnsvis ligge i området fra'8,5 til 11,0, og er om nødvendig pufret til en verdi i nevnte område ved tilsetning av et egnet puffersystem (f.eks. med dimetylglycin). The pH value of the final product is higher than 7.5 and should preferably lie in the range from 8.5 to 11.0, and is, if necessary, buffered to a value in the aforementioned range by adding a suitable buffer system (e.g. with dimethylglycine).
Oppfinnelsen skal i det følgende illustreres ved hjelpIn the following, the invention will be illustrated with help
av eksempler. I eksemplene angir prosentene vekt. I eksemplene ble lengden av den halve levetid for enzymet bestemt på følgende måte: En kontinuerlig uttatt prøve fra en løsning som skal tettes, ble kontinuerlig fortynnet (1:200) og kontinuerlig under-søkt angående enzymatisk aktivitet (for proteolytisk aktivitet.ble kasein anvendt som substrat). Logaritmene for den resterende aktivitet ble avmerket mot tiden, og hastighetskbnstanten K-^av første orden ble beregnet. of examples. In the examples, the percentages indicate weight. In the examples, the length of the half-life of the enzyme was determined as follows: A continuously taken sample from a solution to be sealed was continuously diluted (1:200) and continuously examined for enzymatic activity (for proteolytic activity, casein was used as substrate). The logarithms of the remaining activity were plotted against time, and the first-order rate constant K-^ was calculated.
Enzymets faktor Ft for den halve levetids lengde defineresThe enzyme's factor Ft for the half-life length is defined
■ som: 2 tid, ved hvilken den enzymatiske aktivitet y er halvparten av den opprinnelige enzymatiske aktivitet. ■ as: 2 time, at which the enzymatic activity y is half of the original enzymatic activity.
EKSEMPEL IEXAMPLE I
I dette eksempel ble det testet vandige systemer som inneholdt en bakteriell protease, "Alcalase" fra Novo.. Disse vandige systemer inneholdt pr., liter: In this example, aqueous systems containing a bacterial protease, "Alcalase" from Novo, were tested. These aqueous systems contained per liter:
6,2 molar pentanatriumtripolyfosfat6.2 molar pentasodium tripolyphosphate
0,12 molar dimetylglycin0.12 molar dimethylglycine
1,7 g "Alcala.se" (aktivitet 10,6 AU/g) .1.7 g "Alcala.se" (activity 10.6 AU/g) .
Løsningens pH-verdi var 10, og temperaturen '57°C... Hastighetene for tap av aktivitet hos enzymet ble målt i dette system med og uten de stabiliseringssystemer som er angitt neden-under og enzymets faktor for halv levetidsutstrekning ble bestemt. Følgende resultater ble oppnådd: The pH of the solution was 10, and the temperature '57°C... The rates of loss of activity of the enzyme were measured in this system with and without the stabilization systems indicated below and the enzyme's half-life extension factor was determined. The following results were obtained:
Disse resultater viser de økede Ft~verdier oppnådd med stabiliseringssystemene i henhold til oppfinnelsen.Tester nr. 8 og 11 er ikke i henhold til oppfinnelsen, (—p-forhold > 1) og viser at med disse forhold oppnås det reduserte F,-verdier, These results show the increased Ft~ values obtained with the stabilization systems according to the invention. Tests no. 8 and 11 are not according to the invention, (—p ratio > 1) and show that with these conditions reduced F, values are achieved ,
i sammenligning med —-forhold > 1. Tester hr. 7-9 og 10-12 viser at .et reduserende —-forhold gir bedre F,-verdier, i motsetning in comparison with — ratio > 1. Tests hr. 7-9 and 10-12 show that a decreasing ratio gives better F, values, in contrast
B t B t
til det som er kjent fra teknikkens stand som foreskriver —B-for-hold å være ^ .1. Med bare 2 %, 4 %, 8 % og 9,45 % boraks (ingen tilsetning av polyhydroksyforbindelse), ble følgende Ft~verdier oppnådd: 1,0, 1,3, 1,8 og 2,4. to what is known from the state of the art which prescribes —B-for-hold to be ^ .1. With only 2%, 4%, 8% and 9.45% borax (no addition of polyhydroxy compound), the following Ft values were obtained: 1.0, 1.3, 1.8 and 2.4.
EKSEMPEL II..EXAMPLE II..
I denne forsøksserie ble det anvendt en bakteriell protease,"Esperase" fra Novo (aktivitet 41,5 KNPU/g). Det vandige system var identisk med det fra eksempel I, men temperaturen var nå 60°G. Med 4 %. erytritan og 7,4 % boraks (-| = 0,54) ble det oppnådd en F^på 2,5. In this series of experiments, a bacterial protease, "Esperase" from Novo (activity 41.5 KNPU/g) was used. The aqueous system was identical to that of Example I, but the temperature was now 60°C. With 4%. erythritol and 7.4% borax (-| = 0.54) an F^ of 2.5 was obtained.
EKSEMPEL IIIEXAMPLE III
på en måte som var analog med den fra eksempel I , ble det testet systemer med en bakteriell a-amylase ("Thermamyl"). Det vandige system inneholdt pr. liter: in a manner analogous to that of Example I, systems with a bacterial α-amylase ("Thermamyl") were tested. The aqueous system contained per liters:
0,12 m pentanatriumtripolyfosfat0.12 m pentasodium tripolyphosphate
0,1 m glycin0.1 m glycine
0,5 g "Thermamyl" (aktivitet 450 KNU/g).0.5 g "Thermamyl" (activity 450 KNU/g).
pH-verdien var 9,95 og temperaturen 59,3°C. Med- et sta-biliserende system som inneholdt 6 % etylenglykol + 9,2 % boraks B -forhold = 0,65) , ble det oppnådd en F t-verdi på 2,2. The pH value was 9.95 and the temperature 59.3°C. With a stabilizing system containing 6% ethylene glycol + 9.2% borax B ratio = 0.65), an F t value of 2.2 was achieved.
EKSEMPEL IVEXAMPLE IV
Eksempel I ble gjentatt med et stabiliæringssystem som inneholdt 10 % glycerol og varierende mengder boraks. Føl-gende resultater ble oppnådd: Example I was repeated with a stabilizer system containing 10% glycerol and varying amounts of borax. The following results were obtained:
Claims (8)
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DE3063434D1 (en) | 1979-05-16 | 1983-07-07 | Procter & Gamble Europ | Highly concentrated fatty acid containing liquid detergent compositions |
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 |
JPS59157641A (en) * | 1983-02-28 | 1984-09-07 | Fuji Photo Film Co Ltd | Enzymatically treating liquid agent |
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 |
US4537707A (en) * | 1984-05-14 | 1985-08-27 | The Procter & Gamble Company | Liquid detergents containing boric acid and formate to stabilize enzymes |
DE3574729D1 (en) * | 1984-05-14 | 1990-01-18 | Procter & Gamble | LIQUID CLEANING AGENTS CONTAINING BORIC ACID FOR STABILIZING ENZYMS. |
US4537706A (en) * | 1984-05-14 | 1985-08-27 | The Procter & Gamble Company | Liquid detergents containing boric acid to stabilize enzymes |
US4797362A (en) | 1985-06-06 | 1989-01-10 | Lion Corporation | Alkaline proteases and microorganisms producing same |
SE468518B (en) * | 1985-07-26 | 1993-02-01 | Colgate Palmolive Co | STABILIZED TEXTILE SOFTWARE ENZYMINE CONTINUOUS PREPARED LIQUID DETERGENT COMPOSITION AND ITS APPLICATION IN WASHING TEXTILES |
ZA865095B (en) * | 1985-07-26 | 1988-02-24 | Colgate Palmolive Co | Fabric softening liquid detergent |
ZA865096B (en) * | 1985-07-26 | 1988-02-24 | Colgate Palmolive Co | Stabilized built liquid detergent composition containing enzymes |
GB8810822D0 (en) * | 1988-05-06 | 1988-06-08 | Unilever Plc | Liquid detergent compositions |
AU3667189A (en) * | 1988-06-23 | 1990-01-04 | Unilever Plc | Enzyme-containing liquid detergents |
US5089163A (en) * | 1989-01-30 | 1992-02-18 | Lever Brothers Company, Division Of Conopco, Inc. | Enzymatic liquid detergent composition |
US4959179A (en) * | 1989-01-30 | 1990-09-25 | Lever Brothers Company | Stabilized enzymes liquid detergent composition containing lipase and protease |
EP0385526A3 (en) * | 1989-02-27 | 1991-09-11 | Unilever N.V. | Enzymatic liquid detergent composition |
US4992194A (en) * | 1989-06-12 | 1991-02-12 | Lever Brothers Company, Division Of Conopco Inc. | Stably suspended organic peroxy bleach in a structured aqueous liquid |
DE3921839A1 (en) * | 1989-07-03 | 1991-01-17 | Henkel Kgaa | ENZYMATIC CLEANER |
JPH0775620B2 (en) * | 1991-04-08 | 1995-08-16 | トーメー産業株式会社 | Liquid formulation for hydrous contact lens and method for washing hydrous contact lens |
AU3151293A (en) * | 1991-12-04 | 1993-06-28 | Procter & Gamble Company, The | Liquid laundry detergents with citric acid, cellulase, and boric-diol complex to inhibit proteolytic enzyme |
IL117948A0 (en) * | 1995-04-18 | 1996-08-04 | Horiuchi Co Ltd | Reusable cleaning solutions containing stabilized enzymes |
US5723421A (en) * | 1995-06-07 | 1998-03-03 | Alcon Laboratories, Inc. | Stable liquid enzyme compositions and methods of use in contact lens cleaning and disinfecting systems |
US5604190A (en) * | 1995-06-07 | 1997-02-18 | Alcon Laboratories, Inc. | Stable liquid enzyme compositions and methods of use in contact lens cleaning and disinfecting systems |
JP2624641B2 (en) * | 1996-05-20 | 1997-06-25 | ホーヤ株式会社 | Cleaning solution for contact lenses |
DE19857543A1 (en) * | 1998-12-14 | 2000-06-15 | Henkel Kgaa | Use of protease in liquid to gel detergents |
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- 1977-10-27 FR FR7732530A patent/FR2369338A1/en active Granted
- 1977-10-29 GR GR54667A patent/GR66056B/el unknown
- 1977-10-31 LU LU78424A patent/LU78424A1/xx unknown
- 1977-10-31 ZA ZA00776455A patent/ZA776455B/en unknown
- 1977-10-31 DK DK482577A patent/DK146910C/en not_active IP Right Cessation
- 1977-10-31 SE SE7712284A patent/SE431558B/en unknown
- 1977-10-31 AT AT0776477A patent/AT365229B/en not_active IP Right Cessation
- 1977-10-31 CA CA289,879A patent/CA1092036A/en not_active Expired
- 1977-10-31 CH CH1322777A patent/CH630406A5/en not_active IP Right Cessation
- 1977-10-31 PT PT67225A patent/PT67225B/en unknown
- 1977-10-31 BE BE182264A patent/BE860374A/en not_active IP Right Cessation
- 1977-10-31 NL NL7711925A patent/NL7711925A/en not_active Application Discontinuation
- 1977-10-31 NO NO773724A patent/NO773724L/en unknown
- 1977-10-31 BR BR7707290A patent/BR7707290A/en unknown
- 1977-10-31 IT IT69438/77A patent/IT1093027B/en active
- 1977-11-01 JP JP13038677A patent/JPS5357209A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
SE431558B (en) | 1984-02-13 |
BE860374A (en) | 1978-05-02 |
FR2369338A1 (en) | 1978-05-26 |
DE2748211A1 (en) | 1978-05-11 |
PT67225B (en) | 1979-11-12 |
ZA776455B (en) | 1979-06-27 |
BR7707290A (en) | 1978-07-25 |
SE7712284L (en) | 1978-05-02 |
FI61715B (en) | 1982-05-31 |
FI61715C (en) | 1982-09-10 |
JPS5357209A (en) | 1978-05-24 |
AU513442B2 (en) | 1980-12-04 |
CH630406A5 (en) | 1982-06-15 |
FI773177A (en) | 1978-05-02 |
CA1092036A (en) | 1980-12-23 |
DK146910B (en) | 1984-02-06 |
DK146910C (en) | 1984-07-16 |
GR66056B (en) | 1981-01-14 |
FR2369338B1 (en) | 1981-11-27 |
NL7711925A (en) | 1978-05-03 |
AT365229B (en) | 1981-12-28 |
DK482577A (en) | 1978-05-02 |
ATA776477A (en) | 1981-05-15 |
PT67225A (en) | 1977-11-01 |
AU3005177A (en) | 1979-05-03 |
IT1093027B (en) | 1985-07-19 |
LU78424A1 (en) | 1978-07-12 |
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