CA1213541A - Stabilized aqueous enzyme composition - Google Patents
Stabilized aqueous enzyme compositionInfo
- Publication number
- CA1213541A CA1213541A CA000447238A CA447238A CA1213541A CA 1213541 A CA1213541 A CA 1213541A CA 000447238 A CA000447238 A CA 000447238A CA 447238 A CA447238 A CA 447238A CA 1213541 A CA1213541 A CA 1213541A
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- composition
- calcium
- acid
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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
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Enzymes And Modification Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
STABILIZED AQUEOUS ENZYME COMPOSITION
Abstract of the Disclosure .alpha.-Amylase derived from B.licheniformis is stabil-ized in aqueous liquid detergent compositions containing surfactants and sequestering agents by the inclusion of a calcium-containing component that provides at least about 1x10-4.5 millimole of enzyme-accessible calcium per liter of composition.
Abstract of the Disclosure .alpha.-Amylase derived from B.licheniformis is stabil-ized in aqueous liquid detergent compositions containing surfactants and sequestering agents by the inclusion of a calcium-containing component that provides at least about 1x10-4.5 millimole of enzyme-accessible calcium per liter of composition.
Description
~Z~5~
SI~BILIZE~D AS~OIÆ; ENZY~E COME'O~;ITIC2 TECHNIC~L FIELD
1. Field of the Invention The present invention relates to stabilized aqueous enzyrne compositions which o~ntain detergent components.
SI~BILIZE~D AS~OIÆ; ENZY~E COME'O~;ITIC2 TECHNIC~L FIELD
1. Field of the Invention The present invention relates to stabilized aqueous enzyrne compositions which o~ntain detergent components.
2.
The formulation of enzyme-containing aqueous liquid detergent compositions is difficult due to the tendency toward rapid decrease in enzymatic activity in aqueous media during storage. U.S. Patent 4,111,855, ~arrat et al, issued September 5, 1978, U.S. Patent 4,287,082, Tolfo et al, issued September 1, 1981, U.S. Patent 4,305,837, Kaminsky et al, issued December 15, 1981, and U.S. Patent 4,318,818, Letton et al, issued March 9, 1982, all disclose approaches to the stabilization of enzymes in aqueous media.
DISCLO6URE CF T~E rNVENTICN
The stabilized aqueous enzyme cnpositions of this invention c~n-prise: (a) fran about 10% to about 65% by weight of a non-soap deter-gent surfactant or mixtures thereof; (b) from about 0.01~ to akout 5%
by weight on a standard enzyme basis of an ~-amylolytic enzyme derived from B. licheniformis; (c) from atout 3% to about 30% of a combination of citric acid or water-soluble salts thereof and a nitrogen-o~ntaining sequestering agent selected from the group oonsisting of ethylenedi-amine tetramethylene phosphonic acid, diethylenetriamine pentamethy-lenephosphonic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediarninetriaoetic acid, and diethylenetriamine-pentaacetic acid, or mixtures of water-soluble salts thereof, wherein the ratio of citric acid or water-soluble salt thereof to nitrogen-oontaining sequestering agent is at least about 2:1 by weight; (d) a calcium-containing o~nponent to provide at least about lxlO 4~5 milli~
moles of enzyme available calcium ion per liter o said composition;
(e) from about 10% to akout 80~ water by weight; and (f) from akout 3%
to akout 25% by weight of a fatty acid having fran about 10 to about 22 carbon atoms, said composition having a ~1 Oe fran about 6.5 to about 9Ø
The stabilization of enzymes in aqueous media has keen the subject of substantial study with particular effort directed to ccmpositions such as liquid detergent comFositions that Eaoe relatively prolonged storage and possible extremes of ternperature before use. Proteolytic enzymes (protease) and amylolytic enzymes (~-amylase) have proven to be very useful detergency adjuvants because oE their ability to solu-bilize or otherwise degrade soils o~ntaining, respectively, protein and carkohydrate ccmponents.
~h ~ ~13~
The use of calcium to stabilize enzymes in aqueous media is well known, but this method of stabilization is in conflict with the incorporation of detergency builder componen-ts into liquid detergent compositions. A major function of effective detergency builder components is to remove metal ions other than alkali metal ions from washing solutions by sequestration or precipitation.
These und~sirable metal ions, calcium and magnesium ions in particular, are generally designated water hardness.
The incorporation of such detergency builder components in a liqùid detergent composition clearly complicates enzyme stability considerations.
By practice of the present invention, it is now surprisingly found that an -amylase can be stabil_zed in liquid detergent compositions containing calcium sequestering agents when said -amylase is derived from Bacillus licheniformis (B. licheniformis) and a very low minimum level of "enzyme-accessible" calcium ion, as hereinafter defined, is provided by incorporation of a calcium-containing component in accordance with a mathematical formula involving the equilibrium constants of complexation of said calcium sequestering agents.
DETAILED DESCRIPTION OF THE INVENTION
Non-Soap Detergent Surfactants The non-soap detergent surfactant can be selected from nonionic, anionic, cationic, zwitterionic, amphoteric and semi-polar nonionic surfactants and mixtures thereof. The surfactants preferably comprise from about 10% to about 65~, more preferably from about 20% to about 50% o~ the ~ormula by weight.
Nonionic Surfactants One useful type of nonionic surfactant is produced by condensing ethylene oxide with a hydrocarbon having a reactive hydrogen atom, e.g., a hydroxyl, carboxyl, 35~1 amino, or amido group, in the presence of an acidic or basic catalyst. Such nonionic surfactants have the general forrnula RA(CH2CH2O)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 about 8 to 22 carbon atoms, but can also be formed by the condensation of propylene oxide with a lower molecular weight compound. n can vary from about 2 to about 24 depending on the desired physical and detergency proper-ties. The hydrophobic moiety of the nonionic compound is preferably a pri~ary or secondary, straight or slightly branched, aliphatic alcohol having from about 8 to about 24, preferably from about 12 to about 20 carbon atoms.
Alkyl amine oxides and other semi-polar nonionic surfactants are hereinafter described. Another class of useful nonionic surfactants are alkylpolysaccharides having a hydrophobic group containing from about'~ to about 20 carbon atoms and a polysaccharide hydrophilic group containing from about 1.5 to about 10 saccharide units.
A more complete disclosure of suitable nonionic surfactants can be found in U.S. Patent 4,111,855.
Anionic Surfactants Synthetic anionic surfactant.s can be represented by the general formula R SO M wherein R represents a hydrocarbon group selected from the group consisting oE straight or branched alkyl radicals conkaining fram 3a ~;~
4 ~L2:~3S~l about 3 to about 24 carbon atoms and alkyl phenyl radicals containing from about 9 to about 15 carbon atoms in the alkyl group. M is a salt forming cation which typically is selected from the group consisting of sodium, potassium, ammonium, monoalkanolammonium, dialkanolammonium, trialkanolammonium, and magnesium cations and mixtures thereof.
Preferred synthetic anionic surfactants include the water-goluble salts of alkylbenzene sulfonic acid containing from about 9 to about 15 carbon atoms in the alkyl group and water-soluble alkyl sulfates containing from about 10 to about 18 carbon atoms.
Another preferred synthetic anionic surfactant is a water-soluble salt of an alkyl polyethoxylate ether sulfate wherein the alkyl group contains from about 8 to about 24~ preferably from about 10 to about 18 carbon atoms and there are from about 1 to about 20, preferably from about 1 to about 12 ethoxy groups. Other suitable anionic surfactants are disclosed in U.S. Patent 4,170,565, Flesher et al, issued October 9, 1979.
Cationic_Surfactants Suitable cationlc surfactants have the general formula R2R3y z wherein each R 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 interruptad by up to four structures selected from the group consisting of O O O R R O
~ C-O-, ~O-C-, -C-N-, -N-C-, O H H O O H H O
li I I 1l 11 1 i 11 -C-N-, -N-C-, -O-, -O-C-N-, -N-C-O-, `!
35~
and mixtures thereof, each R2 containing from about ~ to 22 carbon atoms, and which may additionally contain up to about 12 ethylane oxide groups, m is a number from 1 to 3, each R3 is an alkyl or hydroxyalkyl group S containing from 1 to 4 carbon atoms or a benzyl group with no more than one R3 in a molecule being ~enzyl, x is a number from 0 to 11, the remainder of any carbon atoms positions being filled by hydrogens, Y is selected from the group consisting of:
I
(1) -N -I
~ / I
N - C
/
(2) -C
N - C
I
The formulation of enzyme-containing aqueous liquid detergent compositions is difficult due to the tendency toward rapid decrease in enzymatic activity in aqueous media during storage. U.S. Patent 4,111,855, ~arrat et al, issued September 5, 1978, U.S. Patent 4,287,082, Tolfo et al, issued September 1, 1981, U.S. Patent 4,305,837, Kaminsky et al, issued December 15, 1981, and U.S. Patent 4,318,818, Letton et al, issued March 9, 1982, all disclose approaches to the stabilization of enzymes in aqueous media.
DISCLO6URE CF T~E rNVENTICN
The stabilized aqueous enzyme cnpositions of this invention c~n-prise: (a) fran about 10% to about 65% by weight of a non-soap deter-gent surfactant or mixtures thereof; (b) from about 0.01~ to akout 5%
by weight on a standard enzyme basis of an ~-amylolytic enzyme derived from B. licheniformis; (c) from atout 3% to about 30% of a combination of citric acid or water-soluble salts thereof and a nitrogen-o~ntaining sequestering agent selected from the group oonsisting of ethylenedi-amine tetramethylene phosphonic acid, diethylenetriamine pentamethy-lenephosphonic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediarninetriaoetic acid, and diethylenetriamine-pentaacetic acid, or mixtures of water-soluble salts thereof, wherein the ratio of citric acid or water-soluble salt thereof to nitrogen-oontaining sequestering agent is at least about 2:1 by weight; (d) a calcium-containing o~nponent to provide at least about lxlO 4~5 milli~
moles of enzyme available calcium ion per liter o said composition;
(e) from about 10% to akout 80~ water by weight; and (f) from akout 3%
to akout 25% by weight of a fatty acid having fran about 10 to about 22 carbon atoms, said composition having a ~1 Oe fran about 6.5 to about 9Ø
The stabilization of enzymes in aqueous media has keen the subject of substantial study with particular effort directed to ccmpositions such as liquid detergent comFositions that Eaoe relatively prolonged storage and possible extremes of ternperature before use. Proteolytic enzymes (protease) and amylolytic enzymes (~-amylase) have proven to be very useful detergency adjuvants because oE their ability to solu-bilize or otherwise degrade soils o~ntaining, respectively, protein and carkohydrate ccmponents.
~h ~ ~13~
The use of calcium to stabilize enzymes in aqueous media is well known, but this method of stabilization is in conflict with the incorporation of detergency builder componen-ts into liquid detergent compositions. A major function of effective detergency builder components is to remove metal ions other than alkali metal ions from washing solutions by sequestration or precipitation.
These und~sirable metal ions, calcium and magnesium ions in particular, are generally designated water hardness.
The incorporation of such detergency builder components in a liqùid detergent composition clearly complicates enzyme stability considerations.
By practice of the present invention, it is now surprisingly found that an -amylase can be stabil_zed in liquid detergent compositions containing calcium sequestering agents when said -amylase is derived from Bacillus licheniformis (B. licheniformis) and a very low minimum level of "enzyme-accessible" calcium ion, as hereinafter defined, is provided by incorporation of a calcium-containing component in accordance with a mathematical formula involving the equilibrium constants of complexation of said calcium sequestering agents.
DETAILED DESCRIPTION OF THE INVENTION
Non-Soap Detergent Surfactants The non-soap detergent surfactant can be selected from nonionic, anionic, cationic, zwitterionic, amphoteric and semi-polar nonionic surfactants and mixtures thereof. The surfactants preferably comprise from about 10% to about 65~, more preferably from about 20% to about 50% o~ the ~ormula by weight.
Nonionic Surfactants One useful type of nonionic surfactant is produced by condensing ethylene oxide with a hydrocarbon having a reactive hydrogen atom, e.g., a hydroxyl, carboxyl, 35~1 amino, or amido group, in the presence of an acidic or basic catalyst. Such nonionic surfactants have the general forrnula RA(CH2CH2O)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 about 8 to 22 carbon atoms, but can also be formed by the condensation of propylene oxide with a lower molecular weight compound. n can vary from about 2 to about 24 depending on the desired physical and detergency proper-ties. The hydrophobic moiety of the nonionic compound is preferably a pri~ary or secondary, straight or slightly branched, aliphatic alcohol having from about 8 to about 24, preferably from about 12 to about 20 carbon atoms.
Alkyl amine oxides and other semi-polar nonionic surfactants are hereinafter described. Another class of useful nonionic surfactants are alkylpolysaccharides having a hydrophobic group containing from about'~ to about 20 carbon atoms and a polysaccharide hydrophilic group containing from about 1.5 to about 10 saccharide units.
A more complete disclosure of suitable nonionic surfactants can be found in U.S. Patent 4,111,855.
Anionic Surfactants Synthetic anionic surfactant.s can be represented by the general formula R SO M wherein R represents a hydrocarbon group selected from the group consisting oE straight or branched alkyl radicals conkaining fram 3a ~;~
4 ~L2:~3S~l about 3 to about 24 carbon atoms and alkyl phenyl radicals containing from about 9 to about 15 carbon atoms in the alkyl group. M is a salt forming cation which typically is selected from the group consisting of sodium, potassium, ammonium, monoalkanolammonium, dialkanolammonium, trialkanolammonium, and magnesium cations and mixtures thereof.
Preferred synthetic anionic surfactants include the water-goluble salts of alkylbenzene sulfonic acid containing from about 9 to about 15 carbon atoms in the alkyl group and water-soluble alkyl sulfates containing from about 10 to about 18 carbon atoms.
Another preferred synthetic anionic surfactant is a water-soluble salt of an alkyl polyethoxylate ether sulfate wherein the alkyl group contains from about 8 to about 24~ preferably from about 10 to about 18 carbon atoms and there are from about 1 to about 20, preferably from about 1 to about 12 ethoxy groups. Other suitable anionic surfactants are disclosed in U.S. Patent 4,170,565, Flesher et al, issued October 9, 1979.
Cationic_Surfactants Suitable cationlc surfactants have the general formula R2R3y z wherein each R 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 interruptad by up to four structures selected from the group consisting of O O O R R O
~ C-O-, ~O-C-, -C-N-, -N-C-, O H H O O H H O
li I I 1l 11 1 i 11 -C-N-, -N-C-, -O-, -O-C-N-, -N-C-O-, `!
35~
and mixtures thereof, each R2 containing from about ~ to 22 carbon atoms, and which may additionally contain up to about 12 ethylane oxide groups, m is a number from 1 to 3, each R3 is an alkyl or hydroxyalkyl group S containing from 1 to 4 carbon atoms or a benzyl group with no more than one R3 in a molecule being ~enzyl, x is a number from 0 to 11, the remainder of any carbon atoms positions being filled by hydrogens, Y is selected from the group consisting of:
I
(1) -N -I
~ / I
N - C
/
(2) -C
N - C
I
(3) _p+_
(4) S+-~L2135~.
I
I
(5) -N - , wherein p is from 1 to 12, _ ( 2 4 )p (C2H4)pH
(6) -N - , wherein p is from 1 to 12, I
(C2H4O)pH
\ C~ \ N
(C2H4O)pH
\ C~ \ N
(7) 1 1I r / ~C/ \
I
/ ~ /
N .~ N
( 8 ) ¦¦ ¦ , and / N
(9) mixtures thereoE and Z is an anion such as halide, methyl sulfate or hydroxide.
One R3 can also be a proton. The resultant ter-tiary amines can have characteristics similar to cat-ionic surfactants at washing soultion pH values lessthan about 8.5.
A more complete disclosure of cationic surfactants can be found in U.S. Patent 4,228,044 by Cushman M.
Cambre for Laundry Detergent Composition Having Enhanced _ 7 - ~ ~ ~35~
Particulate Soil Removal and ~ntiredeposition Performance, issued October 14, 1980.
When cationic surfactants are used in combination with anionic surfactants, compatibility must be consider-ed. A type of cationic surfactant generally compatiblewith anionic surfactants is a C8 18 alkyl tri Cl_3 alkyl ammonium chloride or methyl sulfate.
Zwitterionic Surfactants zwitterionic surfactants include derivatives of ali-phatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic sub-stituents contains from about 8 to 24 carbon atoms and one contains an anionic water-solubilizing group. Parti-cularly preferred zwitterionic materials are the ethoxy-lated amrnonium 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, 1~75~
~hol~tic ~5urfactants Ampholytic surfactants include derivatives of ali-phatic heterocyclic secondary and ternary amines in 2S which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 2~ carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
Semi-Polar Nonionic Surfactants Semi-polar nonionic surEactants inclucle water-solu-ble amine oxides containing 1 alkyl or hydroxy alkyl moiety of Erom about 8 to about 28 carbon atoms and 2 moieties selected ~rom the group consisting of alkyl 3S groups and hydroxy alkyl groups, containing from 1 to about 3 carbon atoms which can optionally be joined into ring structures; water-soluble phosphine oxides
I
/ ~ /
N .~ N
( 8 ) ¦¦ ¦ , and / N
(9) mixtures thereoE and Z is an anion such as halide, methyl sulfate or hydroxide.
One R3 can also be a proton. The resultant ter-tiary amines can have characteristics similar to cat-ionic surfactants at washing soultion pH values lessthan about 8.5.
A more complete disclosure of cationic surfactants can be found in U.S. Patent 4,228,044 by Cushman M.
Cambre for Laundry Detergent Composition Having Enhanced _ 7 - ~ ~ ~35~
Particulate Soil Removal and ~ntiredeposition Performance, issued October 14, 1980.
When cationic surfactants are used in combination with anionic surfactants, compatibility must be consider-ed. A type of cationic surfactant generally compatiblewith anionic surfactants is a C8 18 alkyl tri Cl_3 alkyl ammonium chloride or methyl sulfate.
Zwitterionic Surfactants zwitterionic surfactants include derivatives of ali-phatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic sub-stituents contains from about 8 to 24 carbon atoms and one contains an anionic water-solubilizing group. Parti-cularly preferred zwitterionic materials are the ethoxy-lated amrnonium 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, 1~75~
~hol~tic ~5urfactants Ampholytic surfactants include derivatives of ali-phatic heterocyclic secondary and ternary amines in 2S which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 2~ carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
Semi-Polar Nonionic Surfactants Semi-polar nonionic surEactants inclucle water-solu-ble amine oxides containing 1 alkyl or hydroxy alkyl moiety of Erom about 8 to about 28 carbon atoms and 2 moieties selected ~rom the group consisting of alkyl 3S groups and hydroxy alkyl groups, containing from 1 to about 3 carbon atoms which can optionally be joined into ring structures; water-soluble phosphine oxides
- 8 - ~2~3~
containing 1 alkyl or hydroxy alkyl moiety of from about 8 to about 28 and 2 moieties selected from the group consisting of alkyl groups and hydroxy alkyl groups, containing from about 1 tc about 3 carbon atoms; and water-soluble sulfoxides containing 1 alkyl or hydroxy alkyl moiety of from about 8 to about 28 carbon atoms and a moiety selected from the group consisting of alkyl and hyd~rpxy alkyl moieties of from 1 to 3 carbon atoms.
For a more complete disclosure of compounds which are suitable for incorporation in detergent compo-sitions, one can consult U.S. Patents 4,056,481, Tate (November 1, 1977); 4,049,586, Collier (Septe~ber 20, 1977); 4,040,988, Vincent et al (August 9, 1977);
4,035,257, Cherney ~July 12, 1977); 4,033,718, ~olcolm 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, Xrummel et al (October 12, 1976).
The Enzyme The compositions of the invention contain from about 0.01~ to about 5% by weight on a standard enzyme basis of an ~-amylolytic enzyme (~-amylase) derived from B. licheniformis, preferably from about 0.05% to about 2~ by weight and most preferably from about 0.1~ to about 1.0% by weight. Commercial enzyme preparations, particularly those prepared for use in detergent compositions, are rarely pure enzyme and are, in an~
case, generally mixed with various inert materials.
Commercial enzyme preparations will typically have a low calcium metal content complexed with the enzyme and as part of the inert portion of the preparation ~s described hereinafter, this calcium content must be recognized for stability considerations. For purposes of describing the present invention and preferred enzyme levels, standard enzyme basis is defined as an enzyme J~
containing 1 alkyl or hydroxy alkyl moiety of from about 8 to about 28 and 2 moieties selected from the group consisting of alkyl groups and hydroxy alkyl groups, containing from about 1 tc about 3 carbon atoms; and water-soluble sulfoxides containing 1 alkyl or hydroxy alkyl moiety of from about 8 to about 28 carbon atoms and a moiety selected from the group consisting of alkyl and hyd~rpxy alkyl moieties of from 1 to 3 carbon atoms.
For a more complete disclosure of compounds which are suitable for incorporation in detergent compo-sitions, one can consult U.S. Patents 4,056,481, Tate (November 1, 1977); 4,049,586, Collier (Septe~ber 20, 1977); 4,040,988, Vincent et al (August 9, 1977);
4,035,257, Cherney ~July 12, 1977); 4,033,718, ~olcolm 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, Xrummel et al (October 12, 1976).
The Enzyme The compositions of the invention contain from about 0.01~ to about 5% by weight on a standard enzyme basis of an ~-amylolytic enzyme (~-amylase) derived from B. licheniformis, preferably from about 0.05% to about 2~ by weight and most preferably from about 0.1~ to about 1.0% by weight. Commercial enzyme preparations, particularly those prepared for use in detergent compositions, are rarely pure enzyme and are, in an~
case, generally mixed with various inert materials.
Commercial enzyme preparations will typically have a low calcium metal content complexed with the enzyme and as part of the inert portion of the preparation ~s described hereinafter, this calcium content must be recognized for stability considerations. For purposes of describing the present invention and preferred enzyme levels, standard enzyme basis is defined as an enzyme J~
9 ~35~
preparation having an activity measured in Xilo Novo -amylase Units (KNU) of 120 KNU/gram. One Kilo Novo ~-amylase Unit (1 KNU) is the amount of enzyme which breaks down 5.26 grams of starch (Merc~, Amylum Solubile Erg. s. 6, Batch 3947275) per hour at Novo's standard method for determination of ~-amylase based upon the following starldard conditions:
Substrate soluble starch Calcium content in solvent 0.0043M
Reaction time 7-20 min.
Temperature 37C
pH 5.6 As described in sritish Patent S~ecification 1,296,839, the Novo method (Novo Industri A/S, Baqsvaerd, Denmark) is a modification of the SKB
method performed at 37C without the addition of ~amy1ase. The S~B method i`s descri~bed in Cereal C~emistry, 16, 712 (1939).
-Amylases derived from B. licheniformis have been characterized as carbohydrases and more particularly 1,4--D-Glucan Glucanohydrolase. -Amylases for use in detergent compositions, granule detergent compositions in particular, have been generally derived from Bacillus subtilis, but -amylase derived from B. licheniformis suitable for use in the compositions of the present invention is available from a number of sources.
Termamylo 120L, Novo Industri A/S, Bagsvaerd, Denmark;
Taka-ThermO L-340, Miles Laboratories, Elkhart, Indiana;
Rohalase ATo, Rohm & Haas, West Philadelphia, PA;
Maxamyl HT, Gist Brocades, Delft, The Netherlands, are -amylases derived from B. licheniformis and suitable for use in the compositions of the present invention.
Reported deposit numbers for Bacillus licheniformis capable of producing ~-amylase are NCIB 8061, NCIB 8059, ATCC 6634, ATCC 6598, ATCC 11945, ATCC 8480, and ATCC
J ~13~
9945a~ sritish Patent Specification 1,296,839, published November 22, 1972, discloses methods of making ~-amylases derived ~rom ~. licheniformis.
Se~uestering Agent The compositions of the invention contain from about 0.25~ to about 40~, preferably from about 3% to about ,30~ and most preferably from about 5~ to about 25~
of a calcium ion sequestering agent. These sequesterinq agents act as detergency builders to improve cleaning, particularly when the washing solution will contain metal ions other than alkali metal ions. Sequestra~ion involves the formation of a coordination complex of the sequestering agent and metallic ions in solution to reduce the interactions of calcium with other materials in the wash solution. As used herein, the term sequest-ering age~t includes multidentate ligands which can act as chelating agents and can include some ion e~change materials, but not those detergency builde'r materials which remove calcium ions from solutions only by pre-cipitation reactions.
The sequestering agents used in the compositions of this invention include polyphosphates, polyphosphonates and polycarboxylates in soluble salt or acid form.
Polyphosphates which can sequester calcium ions are characterized by the general formula:
(Monovalent Cation) nt2PnO3ntl and comprise the acid form and alkali metal, ammonium and substituted ammonium salts of pyrophosphoric acid and tripolyphosphoric acid and the water soluble poly-metaphosphates. For use ln aqueous liquid detergent compositions, pyrophosphoric acid and its salts are preferred because of their stability. Water solutions of tripolyphosphates and polymetaphosphates tend to degrade to a mixture of pyrophosphate and orthophos phate, the latter having the ability to precipitate but ~213S~
not sequester calcium.
Polyphosphonates comprise a large range of organic compounds having two or more - C - PO3M groups, I
wherein M is a hydrogen or a salt-~orming radical.
Suitable phosphonates include ethane-l-hydroxy-l,l-di-phosphonates, ethanehydxoxy-1,1,2-triphosphonates and their oligomeric ester chain condensates. Particularly suitable polyphosphonates for use in the compositions of the invention are nitrogen containing polyphosphonates such as ethylenediaminetetramethylene phosphonic acid and diethylenetriaminepentamethylene phosphonic acid and al~ali metal, ammonium and substituted ammonium salts thereof.
Suitable polycarboxylates include the acid form and alkali metal, ammonium and substituted ammonium salts of citric, ascorbic, phytic, mellitic, benzene ,pentacar-boxylic, oxydiacetic, carboxymethyloxysuccinic, car-boxymethyloxymalonic, cis-cyclohexanehexacarboxylic, cis-cyclopentanetetracarboxylic and oxydisuccinic acids.
Also suitable are the polycarboxylate materials de-scribed in U.S. Patent 3,364,103 and polycarboxylate polymers and copolymers described in U.S. Patent 25 3,308,067, Diehl, issued March 7, 1967.
With due regard to their stability in aqueous media, the polyacetal carboxylates disclosed in U.S. Patent 4~j144,226 issuecl March 13, 1979, to Crutchfield et al and U.S. Patent 4,146,~95 issued March 27, 1979 to Crutchfield et al can be incorporated in the compositions of the inven-tion.
Particularlv suitable polycarboxylates are -those containin~ nitroqen such as ethylenediaminetetraacetic ~ ..3.
~2~35~ -acid, hydroxyethylenediaminetriacetic acid, diethylene-triaminepentaacetic acid and nitrilotriacetic acid and alklai metal, ammonium and substituted ammonium salts thereof.
S As detailed by examples hereinafter, combinztions of sequestering agents with different degrees of calcium ion sequestering power are particularly useful in the practice o~ this invention. The combinations of citric acid and a nitrogen-containing sequestering agent selected from the group consisting of ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenephosphonic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediamine-triacetic acid, diethylenetriaminepentaacetic acid or mixtures and suitable salts thereof are particularly preferred. Citric acid has a relatively lower equilib-rium constant of complexation with calcium than the nitrogen-containing sequestering agents recited above.
Preferred ratios of citric acid to the nitrogen-con-taining sequestering agent are from about 50:1 to about ~ 1:2 by weight and, more preferably, from about 30:1 to about 2:1 by.weight.
Enzyme-Accessible Calcium Ion The stabilized aqueous enzyme compositions of this invention comprise a calcium-containing component to provide at least about lxlO 4 5 millimoles of enzyme-ac-cessible calcium, as hereinafter defined, per liter of said composition. Pre~erably, sufficient calcium-con-taining component is incorporated to provide at least about lxlO millimoles of enzyme-accessible calcium and more preferably at least about lxlO 3 millimoles. Most preferably the compositions contain at least about lxlO 2 millimoles of enzyme-accessible calcium per liter of said composition.
The calcium-containing component can be or can be S~
part of other essential or optional components, for example, an anionic surfactant in the form of a calcium salt or a calcium-sequestering agent complex. More typically, water-soluble or solubilizable calciuo salts such as calcium chloride are employed. In the aqueous liquid detergent compositions of the present invention, calcium in different forms, insoluble, sequestered and enzyme-accessible, will reach an equilibrium as a function of the composition components and pH without regard to the initial nature of the calci~n-containing component.
A upper limit of enzyme-accessible calcium in compositions of the invention can be set by practical considerations not related to enz~ne stability. There is little improvement in the stability of alpha-amylase derived from B.licheniformis in compositions of the invention at enzyme-accessible calcium levels above lxlO 2 millimoles per liter. In the preferred compo-sitions of the invention this level of enzyme-accessible calcium is provided by total calcium levels of no more than about from 0.1% to about 0.3~ of the composition by weiyht. At a recommended usage of 1/2 cup of the compo-sition in a washing machine with a 18 gallon washing solution capacity, 0.18~ total calcium (from 0.5% CaC12) increases water hardness of the washing solution by about 1/2 grain per gallon (as CaC03). Calcium is generally detrimental to detergency, but 1/2 grain/gaL-lon is almost negligible. The calcium-containing compo-nent partiaLly depletes the sequestering capaci-ty of the sequestering agent or agents of the composition in so far as calcium is concerned. However, in washing solu tions, a calcium-sequestering agen-t complex is never-theless capable of sequestering heavy metal ions such as iron, manganese and copper which are associated with certain staining problems. This is a result of higher 3~
complexation and ormation constants of said seques~
tering agents with heavy metal ions relative to the constants with calcium.
~nzyme-accessible calcium is analagous to free or ionic calcium in aqueous solutions of less complexity than the compositions of the invention.
Fo~ the purposes of this invention, enzyme-ac-cessible calcium is determined by the method described in the following publication:
J. Morgan, F. Morel, Env. Sci. Tech. 6, 58-67 (1972), "A Numerical Method for Computing Equilibria in Aqueous Chemical Systems".
For the purposes of this invention said method is used to calculate enzyme-accessible calcium in compo-sitions of the invention by use of the following assump-tions:
1) ionic strength fixed at 0.5;
2) pH fixed at the pH of the composition;
3) only divalent (e.g., calcium) metals and multidentate ligands (the sequestering agents of this invention) are considered;
4) the free or uncomplexed calcium concentrationis the enzyme-accessible calcium concentra-tion.
Other methods of calculating equilibrlum concen-trations of all species in aqueous solutions provide essentially equivalent results and are also known to those skilled in the art.
It should be no-ted that alkaline earth rnetals other than calcium are substantially less effective for sta-bilizing the compositions of the invention.
Water The compositions of this invention contain from about 10~ to about 80~ water, preferably from about 15~
to about 60% water, by weight. Preferred compositions have a pH of from about 6.5 to about 9Ø
- 15 - ~213~
Optional Ingredients Tjhe compositions of this invention can contain components other than those disclosed as essential The compositions of this invention can contain enzymes other than -amylase derived from B.licheni-formis, proteolytic enzymes in particular. Examples of suitable proteolytic enzymes include many enzyme prepa-rations adapted for use in detergent compositions and, in fact, used in detergent compositions. Sources of the enzymes include commercial enzyme preparations such as AlcalaseO sold by Novo Industries, A/S, Copenhagen, Denmark an~d ~axatase~ sold by Gist-Brocades, Delft, The Netherlands. Other preferred enzyme compositions include those commercially available under the trade-names EsperaseO, manufactured and sold by Novo Indus-tries, A/S, Copenhagen, Denmark and "AZ-Protease" man-ufactured and sold by Gist-~rocades, Delft, The Nether-lands.
It should be noted that levels of enzyme accessible ~ calcium above about lx10 2 millimoles per liter provide excellent stability to proteolytic enzymes (proteases) incorporated in the compositions of the invention and the inclusion of a proteolytic enzyme is a pre~erred embodiment. There is, however, no dramatic increase in proteolytic enzyme stability over any narrow range of enzyme-accessible calcium levels as is seen with ~-amylase ~derived from B.licheniformis) between lx10 5 and lx10 A more complete disclosure of suitable enzymes can 30 be found in U.S. Patent 4,101,457, Place et al issued July 18, 1978.
The compositions of this invention can contain solvents other than water. Low molecul~r weight primary or secondary alcohol exemplified by methanol, ethanol, ~g 3S~
propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing the surfactant but polyols containing from 2 to about 6 carbon atoms and from 2 to abou-t 6 hydroxy groups can be used and can provide improved enzyme stability. Examples oE polyols include propylene glycol, ethylene glycol, glycerine and 1,2-propanediol. Ethanol is a particularly preferred alcohol. The compositions contain from 0~ to about 30%, preferably from about 1% to about 15%, of alcohols.
A short chain carboxylic acid salt can be used to stabilize enzymes, particularly proteolytic enzymes, as disclosed in U.S. Patent 4,318,818, issued March 9, 1982. The short chain carboxylic acid salt preferably is a formate, e.g., formic acid and its salts. The formates are surprisingly much more effective than other short chain carboxylic salts such as the acetates and the propionates. The short chain carboxylic acid salt is used at a level from about 0.1% to about 10%, preferably from about 0.3% to about 3%, more preferably from about 0.5% to about 2.0% when the product pH is below about 8.5 and from about 3% to about 10~, preferably from about 4% to about 8~, when the product pH is from about 8.5 to about 10.
In a preferred embodiment, a fatty acid component is incorporated in an amount of from about 3% to about 25% by weight, preferably from about 5% to about 20% by weigh-t. The fatty acids have from 10 -to 22, preferabl~
from 12 to 18 carbon atoms in the alkyl chain.
Compositions containing fatty acids, will have a pH of from about 6.5 to about 9Ø
The compositions of the invention can contain such materials as fabric whiteners and brighteners, sudsing control agents, hydrotropes such as sodium toluene or ~Z3~35~L~
xylene sulfonate, perfumes, colorants, opacifiers, anti-redeposition agents and alkalinity control or buffering agents such as monoethanolamine and trieth-anolamine. The use of these materials is well known in the detergent art.
Materials ox anions that tend to precipitate cal-cium should preferably be restricted to minimum levels.
Examples are carbonates, sulfates, and orthophosphates.
Although the fatty acids of preferred compositions act to precipitate calcium in a washing solution, they have no such effect in the undiluted compositons of the invention if calcium levels are rontrolled carefully.
The fatty acid content of the compositions of the invention, at least at pH values below 8.5, does not substantially affect the enzyme-accessible calciu~ level of said compositions and can be neglected when calculating the enzyme-accessible calcium level as disclosed hereinbefore.
The following examples illustrate the invention and facilitate its understanding.
All parts, percentages and ratios herein are by weight unless otherwise specified.
EXAMPI.E I
Liquid detergent compositions were prepared by mixing the components listed hereinafter in the stated proportions.
A B
Surfactants C13 linear alkyl benzene sulfonic acid 9.25~ 5.8 30 Coco alkyl sulfate-acid form - 8.8 Cl2-1~ alkyl ether (ethoxy 1.0) sulfate-acid form 8.75 C12 alkyltrimethylammonium chloride 1.2 1.2 C12 13 alcohol ethoxy 6.5 condensate 6.5 lO.0 s~
Fatty Acids Lauric acid 10.1 7.5 Myristic acid 4.1 2.5 --Oleic acid - 5.0 Sequestering Agents Citric Acid 4.0 6.9 Sodium diethylenetriaminepentaacetate (DTPA) (1) 0.6 Enzymes
preparation having an activity measured in Xilo Novo -amylase Units (KNU) of 120 KNU/gram. One Kilo Novo ~-amylase Unit (1 KNU) is the amount of enzyme which breaks down 5.26 grams of starch (Merc~, Amylum Solubile Erg. s. 6, Batch 3947275) per hour at Novo's standard method for determination of ~-amylase based upon the following starldard conditions:
Substrate soluble starch Calcium content in solvent 0.0043M
Reaction time 7-20 min.
Temperature 37C
pH 5.6 As described in sritish Patent S~ecification 1,296,839, the Novo method (Novo Industri A/S, Baqsvaerd, Denmark) is a modification of the SKB
method performed at 37C without the addition of ~amy1ase. The S~B method i`s descri~bed in Cereal C~emistry, 16, 712 (1939).
-Amylases derived from B. licheniformis have been characterized as carbohydrases and more particularly 1,4--D-Glucan Glucanohydrolase. -Amylases for use in detergent compositions, granule detergent compositions in particular, have been generally derived from Bacillus subtilis, but -amylase derived from B. licheniformis suitable for use in the compositions of the present invention is available from a number of sources.
Termamylo 120L, Novo Industri A/S, Bagsvaerd, Denmark;
Taka-ThermO L-340, Miles Laboratories, Elkhart, Indiana;
Rohalase ATo, Rohm & Haas, West Philadelphia, PA;
Maxamyl HT, Gist Brocades, Delft, The Netherlands, are -amylases derived from B. licheniformis and suitable for use in the compositions of the present invention.
Reported deposit numbers for Bacillus licheniformis capable of producing ~-amylase are NCIB 8061, NCIB 8059, ATCC 6634, ATCC 6598, ATCC 11945, ATCC 8480, and ATCC
J ~13~
9945a~ sritish Patent Specification 1,296,839, published November 22, 1972, discloses methods of making ~-amylases derived ~rom ~. licheniformis.
Se~uestering Agent The compositions of the invention contain from about 0.25~ to about 40~, preferably from about 3% to about ,30~ and most preferably from about 5~ to about 25~
of a calcium ion sequestering agent. These sequesterinq agents act as detergency builders to improve cleaning, particularly when the washing solution will contain metal ions other than alkali metal ions. Sequestra~ion involves the formation of a coordination complex of the sequestering agent and metallic ions in solution to reduce the interactions of calcium with other materials in the wash solution. As used herein, the term sequest-ering age~t includes multidentate ligands which can act as chelating agents and can include some ion e~change materials, but not those detergency builde'r materials which remove calcium ions from solutions only by pre-cipitation reactions.
The sequestering agents used in the compositions of this invention include polyphosphates, polyphosphonates and polycarboxylates in soluble salt or acid form.
Polyphosphates which can sequester calcium ions are characterized by the general formula:
(Monovalent Cation) nt2PnO3ntl and comprise the acid form and alkali metal, ammonium and substituted ammonium salts of pyrophosphoric acid and tripolyphosphoric acid and the water soluble poly-metaphosphates. For use ln aqueous liquid detergent compositions, pyrophosphoric acid and its salts are preferred because of their stability. Water solutions of tripolyphosphates and polymetaphosphates tend to degrade to a mixture of pyrophosphate and orthophos phate, the latter having the ability to precipitate but ~213S~
not sequester calcium.
Polyphosphonates comprise a large range of organic compounds having two or more - C - PO3M groups, I
wherein M is a hydrogen or a salt-~orming radical.
Suitable phosphonates include ethane-l-hydroxy-l,l-di-phosphonates, ethanehydxoxy-1,1,2-triphosphonates and their oligomeric ester chain condensates. Particularly suitable polyphosphonates for use in the compositions of the invention are nitrogen containing polyphosphonates such as ethylenediaminetetramethylene phosphonic acid and diethylenetriaminepentamethylene phosphonic acid and al~ali metal, ammonium and substituted ammonium salts thereof.
Suitable polycarboxylates include the acid form and alkali metal, ammonium and substituted ammonium salts of citric, ascorbic, phytic, mellitic, benzene ,pentacar-boxylic, oxydiacetic, carboxymethyloxysuccinic, car-boxymethyloxymalonic, cis-cyclohexanehexacarboxylic, cis-cyclopentanetetracarboxylic and oxydisuccinic acids.
Also suitable are the polycarboxylate materials de-scribed in U.S. Patent 3,364,103 and polycarboxylate polymers and copolymers described in U.S. Patent 25 3,308,067, Diehl, issued March 7, 1967.
With due regard to their stability in aqueous media, the polyacetal carboxylates disclosed in U.S. Patent 4~j144,226 issuecl March 13, 1979, to Crutchfield et al and U.S. Patent 4,146,~95 issued March 27, 1979 to Crutchfield et al can be incorporated in the compositions of the inven-tion.
Particularlv suitable polycarboxylates are -those containin~ nitroqen such as ethylenediaminetetraacetic ~ ..3.
~2~35~ -acid, hydroxyethylenediaminetriacetic acid, diethylene-triaminepentaacetic acid and nitrilotriacetic acid and alklai metal, ammonium and substituted ammonium salts thereof.
S As detailed by examples hereinafter, combinztions of sequestering agents with different degrees of calcium ion sequestering power are particularly useful in the practice o~ this invention. The combinations of citric acid and a nitrogen-containing sequestering agent selected from the group consisting of ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenephosphonic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediamine-triacetic acid, diethylenetriaminepentaacetic acid or mixtures and suitable salts thereof are particularly preferred. Citric acid has a relatively lower equilib-rium constant of complexation with calcium than the nitrogen-containing sequestering agents recited above.
Preferred ratios of citric acid to the nitrogen-con-taining sequestering agent are from about 50:1 to about ~ 1:2 by weight and, more preferably, from about 30:1 to about 2:1 by.weight.
Enzyme-Accessible Calcium Ion The stabilized aqueous enzyme compositions of this invention comprise a calcium-containing component to provide at least about lxlO 4 5 millimoles of enzyme-ac-cessible calcium, as hereinafter defined, per liter of said composition. Pre~erably, sufficient calcium-con-taining component is incorporated to provide at least about lxlO millimoles of enzyme-accessible calcium and more preferably at least about lxlO 3 millimoles. Most preferably the compositions contain at least about lxlO 2 millimoles of enzyme-accessible calcium per liter of said composition.
The calcium-containing component can be or can be S~
part of other essential or optional components, for example, an anionic surfactant in the form of a calcium salt or a calcium-sequestering agent complex. More typically, water-soluble or solubilizable calciuo salts such as calcium chloride are employed. In the aqueous liquid detergent compositions of the present invention, calcium in different forms, insoluble, sequestered and enzyme-accessible, will reach an equilibrium as a function of the composition components and pH without regard to the initial nature of the calci~n-containing component.
A upper limit of enzyme-accessible calcium in compositions of the invention can be set by practical considerations not related to enz~ne stability. There is little improvement in the stability of alpha-amylase derived from B.licheniformis in compositions of the invention at enzyme-accessible calcium levels above lxlO 2 millimoles per liter. In the preferred compo-sitions of the invention this level of enzyme-accessible calcium is provided by total calcium levels of no more than about from 0.1% to about 0.3~ of the composition by weiyht. At a recommended usage of 1/2 cup of the compo-sition in a washing machine with a 18 gallon washing solution capacity, 0.18~ total calcium (from 0.5% CaC12) increases water hardness of the washing solution by about 1/2 grain per gallon (as CaC03). Calcium is generally detrimental to detergency, but 1/2 grain/gaL-lon is almost negligible. The calcium-containing compo-nent partiaLly depletes the sequestering capaci-ty of the sequestering agent or agents of the composition in so far as calcium is concerned. However, in washing solu tions, a calcium-sequestering agen-t complex is never-theless capable of sequestering heavy metal ions such as iron, manganese and copper which are associated with certain staining problems. This is a result of higher 3~
complexation and ormation constants of said seques~
tering agents with heavy metal ions relative to the constants with calcium.
~nzyme-accessible calcium is analagous to free or ionic calcium in aqueous solutions of less complexity than the compositions of the invention.
Fo~ the purposes of this invention, enzyme-ac-cessible calcium is determined by the method described in the following publication:
J. Morgan, F. Morel, Env. Sci. Tech. 6, 58-67 (1972), "A Numerical Method for Computing Equilibria in Aqueous Chemical Systems".
For the purposes of this invention said method is used to calculate enzyme-accessible calcium in compo-sitions of the invention by use of the following assump-tions:
1) ionic strength fixed at 0.5;
2) pH fixed at the pH of the composition;
3) only divalent (e.g., calcium) metals and multidentate ligands (the sequestering agents of this invention) are considered;
4) the free or uncomplexed calcium concentrationis the enzyme-accessible calcium concentra-tion.
Other methods of calculating equilibrlum concen-trations of all species in aqueous solutions provide essentially equivalent results and are also known to those skilled in the art.
It should be no-ted that alkaline earth rnetals other than calcium are substantially less effective for sta-bilizing the compositions of the invention.
Water The compositions of this invention contain from about 10~ to about 80~ water, preferably from about 15~
to about 60% water, by weight. Preferred compositions have a pH of from about 6.5 to about 9Ø
- 15 - ~213~
Optional Ingredients Tjhe compositions of this invention can contain components other than those disclosed as essential The compositions of this invention can contain enzymes other than -amylase derived from B.licheni-formis, proteolytic enzymes in particular. Examples of suitable proteolytic enzymes include many enzyme prepa-rations adapted for use in detergent compositions and, in fact, used in detergent compositions. Sources of the enzymes include commercial enzyme preparations such as AlcalaseO sold by Novo Industries, A/S, Copenhagen, Denmark an~d ~axatase~ sold by Gist-Brocades, Delft, The Netherlands. Other preferred enzyme compositions include those commercially available under the trade-names EsperaseO, manufactured and sold by Novo Indus-tries, A/S, Copenhagen, Denmark and "AZ-Protease" man-ufactured and sold by Gist-~rocades, Delft, The Nether-lands.
It should be noted that levels of enzyme accessible ~ calcium above about lx10 2 millimoles per liter provide excellent stability to proteolytic enzymes (proteases) incorporated in the compositions of the invention and the inclusion of a proteolytic enzyme is a pre~erred embodiment. There is, however, no dramatic increase in proteolytic enzyme stability over any narrow range of enzyme-accessible calcium levels as is seen with ~-amylase ~derived from B.licheniformis) between lx10 5 and lx10 A more complete disclosure of suitable enzymes can 30 be found in U.S. Patent 4,101,457, Place et al issued July 18, 1978.
The compositions of this invention can contain solvents other than water. Low molecul~r weight primary or secondary alcohol exemplified by methanol, ethanol, ~g 3S~
propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing the surfactant but polyols containing from 2 to about 6 carbon atoms and from 2 to abou-t 6 hydroxy groups can be used and can provide improved enzyme stability. Examples oE polyols include propylene glycol, ethylene glycol, glycerine and 1,2-propanediol. Ethanol is a particularly preferred alcohol. The compositions contain from 0~ to about 30%, preferably from about 1% to about 15%, of alcohols.
A short chain carboxylic acid salt can be used to stabilize enzymes, particularly proteolytic enzymes, as disclosed in U.S. Patent 4,318,818, issued March 9, 1982. The short chain carboxylic acid salt preferably is a formate, e.g., formic acid and its salts. The formates are surprisingly much more effective than other short chain carboxylic salts such as the acetates and the propionates. The short chain carboxylic acid salt is used at a level from about 0.1% to about 10%, preferably from about 0.3% to about 3%, more preferably from about 0.5% to about 2.0% when the product pH is below about 8.5 and from about 3% to about 10~, preferably from about 4% to about 8~, when the product pH is from about 8.5 to about 10.
In a preferred embodiment, a fatty acid component is incorporated in an amount of from about 3% to about 25% by weight, preferably from about 5% to about 20% by weigh-t. The fatty acids have from 10 -to 22, preferabl~
from 12 to 18 carbon atoms in the alkyl chain.
Compositions containing fatty acids, will have a pH of from about 6.5 to about 9Ø
The compositions of the invention can contain such materials as fabric whiteners and brighteners, sudsing control agents, hydrotropes such as sodium toluene or ~Z3~35~L~
xylene sulfonate, perfumes, colorants, opacifiers, anti-redeposition agents and alkalinity control or buffering agents such as monoethanolamine and trieth-anolamine. The use of these materials is well known in the detergent art.
Materials ox anions that tend to precipitate cal-cium should preferably be restricted to minimum levels.
Examples are carbonates, sulfates, and orthophosphates.
Although the fatty acids of preferred compositions act to precipitate calcium in a washing solution, they have no such effect in the undiluted compositons of the invention if calcium levels are rontrolled carefully.
The fatty acid content of the compositions of the invention, at least at pH values below 8.5, does not substantially affect the enzyme-accessible calciu~ level of said compositions and can be neglected when calculating the enzyme-accessible calcium level as disclosed hereinbefore.
The following examples illustrate the invention and facilitate its understanding.
All parts, percentages and ratios herein are by weight unless otherwise specified.
EXAMPI.E I
Liquid detergent compositions were prepared by mixing the components listed hereinafter in the stated proportions.
A B
Surfactants C13 linear alkyl benzene sulfonic acid 9.25~ 5.8 30 Coco alkyl sulfate-acid form - 8.8 Cl2-1~ alkyl ether (ethoxy 1.0) sulfate-acid form 8.75 C12 alkyltrimethylammonium chloride 1.2 1.2 C12 13 alcohol ethoxy 6.5 condensate 6.5 lO.0 s~
Fatty Acids Lauric acid 10.1 7.5 Myristic acid 4.1 2.5 --Oleic acid - 5.0 Sequestering Agents Citric Acid 4.0 6.9 Sodium diethylenetriaminepentaacetate (DTPA) (1) 0.6 Enzymes
10 Maxataseo .75,75 Termamyl~ 120L 0.370.37 olvents Water 30.719.4 Ethanol 7.0 lo0 1,2-Propanediol 5.0 5.0 Other Components Monoethanolamine 2.012.0 Triethanolamine 4.0 6.7 NaOH & KOH 4.9 20 Sodium toluene sulfonate - 5.0 Sodium formate 1.01.0 CaC12 (1) ~1) Perfume, colorants, fabric whiteners and other miscellaneous optional ingredients ----Remainder-----pH 8.4 8.4 (1) as indicated in tabulations below (quantity added is deducted from total water).
Composition A was prepared in thirteen variations with CaCl2 and sodium diethylenekriaminepentaacetate (DTPA) levels as indicated. The variations were stored in airtight containers for 1 week at 100F. a-amylase activity was then measured by Technicon Industrial Method ~500-77P dated September 12, 1977, as revised September 1979, (Technicon Industrial Systems, Tarry-town, N.Y. 10S91), but any suitable method such as the ~2~35~
one described in U.S. Patent 4,284,722 issued August 18, 1981j to Tamuri et al, will give equivalent results. ~-amylase activity at the end of the storag~ period was divided by activity directly after composition prepar~tion to calculate percent retained activity.
Composition A - a-AmylaSe Stability CaC1 ,, DTP~ ~ of ~Ca %Ca Enzyme %
adde~ % compo- seques- seques- acces- retained (2) % sition ted by ted by sible ~-amylase DTPADTPA citrate calci- activity complex~ um (3) 1 week ed with 100F
calcium . ~
0.0 0.0 - ~ 99.7 ~.5020 ~ 0-3 0.299.8 - 7.26trace 0.0 0.6 0.199.9 - 7.56trace 0.0 0.9 0.199.9 - 7.74trace 0.1 0.0 - - 99.7 1.6193 0.1 0.3 99.766.0 33.9 2.09~ 90-0.1 0.6 75.299.7 ~ ~.0847 0.1 0.9 50.399.9 _ 4.56trace 0.2 0.3 99.933.1 66.7 1.4894 0.2 0.6 99.866.1 33.8 1.7898 0.2 0.3 97.997.3 2.7 2.8981 0.3 0~6 99.9~4.2 55.7 1.3799 0.3 0.9 99.966.2 33.7 1.6093 (~) in addition to low levels of calcium in enzyme preparations (3) expressed as the negative log of the millimolar enzyme accessible calcium concentration Composition B was prepared in seven variations wi-th CaC12 levels as indicated. The variations wer~ stored for 1 month at 90F and at 70F and evaluated for -amylase stability in the same manner as the variations of Composltion A.
L35~L~
Composition B - ~-Amylase Stability CaCl % of %Ca ~Ca Enzyme %
adde~ compo- seques- seques- acces- retained (2) % sition ted by ted by sible ~-amylase DTPA DTPA citrate calci- activity complex- um (3) 1 mo./ l mo./
ed with 90F 70F
calcium 0.0 - 99.9 - 7.560.0 5 0.125 93.1 98.6 1.43.44 56 79 0.2599.9 52.9 46.9 1.6089 93 0.5100.0 26.5 73.3 1.0790 93 1.0100.0 13.3 51.6(4) 0.88 91 95 ~2) in addi~ion to low levels of calcium in enzyme preparation (quantity added is deducted from total water) 5 (3) expressed as negative log of millimolar enzyme-accessible calcium concentration (4) plus 34.9% as precipitated calcium citrate These results show the dramatic improvement in ~ amylase (derived from B.licheniformis) stability in an aqueous liquid detergent composition when a calcium-containing component is incorporated that provides at least about lxlO 4-5 millimoles of enzyme-accessible calcium. The results also point out the advantage of mixtures of sequestering agents. A
sequestering agent with high equilibrium constant of complexation, e.g., the nitrogen-containing sequestering agents disclosed hereinbefore, will tend to sequester all available calcium to the poin-t of theoretical capacity, but can release such calcium in washing solutions to in turn sequester heavy rnetal ions such as copper, iron and manganese. A s~questeriny agent with a lower equilibrium constant of complexation such as alkali metal citrates or citric acid can be incorporated L3~
in the compositions of the invention without addition of calcium-containing components at a level to satisfy theoretical capacity. Thus, such sequestering agents are available to act as detergency builders efective in the presence of alkaline earth metal ions in washing solutions.
Apparently, -amylase derived from B.licheniformis has, in effect, an equilibrium constant of complexation with calcium somewhat greater than citrate, or more precisely, an equilibrium constant thak can hold suf-ficient calcium for stabilization in an aqueous solution containing at least about lxlO 4 5 millimoles of enzyme accessible calcium.
EXAMPLE II
The commercial enzymes Taka-ThermO L-340, Rohalase AT~ and Maxamyl HTo are incorporated in the compositions of Example I replacing the TermamylO 120L. Comparable ! a-amylase stability results are obtained at equi~alent enzyme-accessible calcium levels.
EXAMPLE III
a-amylases derived by B.subtilis, Ban~ from Novo Industri and RapidaseO from Gist Brocade, are incor-porated in the compositions of Example I replaci~g the Termamyl R120L. It is not possible to add a sufficient amount of a calcium-containing component to stabilize said a-amylases derived from B.subtilis without pre-cipita-tion of calcium citrate in the aqueous liquid detergent compositions.
EXAMPLE IV
Dodecyldimethyamine oxide replaces C12 alkyltri-methylammonium chloride in the compositions of Example I. Equivalent results are obtained.
3~
EXAMPLE V
The following compositions are prepared by mixing the ingredients listed.
A B C
C13 linear alkyl benzene sulfonic acid 12.1~ 10.56%
C14_15 alkyl ethoxy-l ether sulfate 3.9 - 10.0 Triethanolamine coco alkyl sulfate ~ 4.0 C12-1a, alkyltrimethyl-ammonium chloride 1.4 14O15 alcohol ethoxylate-7 7 8 12.0 20.0 Lauric acid 9.08 7.5 Myristic acid 3.03 2.5 Oleic acid 2.4 5.0 Citric acid 5.3 0.2 0.05 Maxataseo 0.97 0O97 1.0 TermamylO 120L 0.3 0 4 3 0.3 Diethylenetriaminepenta methylene phosphonic acid 0.29 0.3 0.3 Monoethanolamine 1.9 -Triethanolamine 3.6 4.5 NaOH & KOH 4.19 1.65 Ethanol 4.8 8.63 7.0 1,2-Propanediol 7.2 3.0 Sodium formate 0.97 1.0 2.0 Calcium chloride 0.02 0.02 0.02 Water 29.2 35.5 58.0 Perfume, colorant, suds control agent ~abric whiteners and other miscellaneous optional ingredients ----Remainder----pH 8.0 7.7 7-5 The incorporation of 0.02~ calcium chloride in each composition provides an enzyme accessible calcium level of at least lx10 5 millimoles per liter.
~L2~L35~
EXAMPLE VI
Potassium pyrophosphate, potassium carboxymethyl-oxymalonate and potassium carboxymethyloxysuccinate are each substituted for citric acid in Examples I, II and IV. Composition pH is adjusted to 8Ø A calcium chloride level of 0.3% by weight is sufficient to pro-vide an enzyme-accessible calcium level greater than lxlO 4'5 millimoles and stabilize the ~-amylase derived from B.licheniformis incorporated in said compositions.
WHAT IS CLAIMED IS:
Composition A was prepared in thirteen variations with CaCl2 and sodium diethylenekriaminepentaacetate (DTPA) levels as indicated. The variations were stored in airtight containers for 1 week at 100F. a-amylase activity was then measured by Technicon Industrial Method ~500-77P dated September 12, 1977, as revised September 1979, (Technicon Industrial Systems, Tarry-town, N.Y. 10S91), but any suitable method such as the ~2~35~
one described in U.S. Patent 4,284,722 issued August 18, 1981j to Tamuri et al, will give equivalent results. ~-amylase activity at the end of the storag~ period was divided by activity directly after composition prepar~tion to calculate percent retained activity.
Composition A - a-AmylaSe Stability CaC1 ,, DTP~ ~ of ~Ca %Ca Enzyme %
adde~ % compo- seques- seques- acces- retained (2) % sition ted by ted by sible ~-amylase DTPADTPA citrate calci- activity complex~ um (3) 1 week ed with 100F
calcium . ~
0.0 0.0 - ~ 99.7 ~.5020 ~ 0-3 0.299.8 - 7.26trace 0.0 0.6 0.199.9 - 7.56trace 0.0 0.9 0.199.9 - 7.74trace 0.1 0.0 - - 99.7 1.6193 0.1 0.3 99.766.0 33.9 2.09~ 90-0.1 0.6 75.299.7 ~ ~.0847 0.1 0.9 50.399.9 _ 4.56trace 0.2 0.3 99.933.1 66.7 1.4894 0.2 0.6 99.866.1 33.8 1.7898 0.2 0.3 97.997.3 2.7 2.8981 0.3 0~6 99.9~4.2 55.7 1.3799 0.3 0.9 99.966.2 33.7 1.6093 (~) in addition to low levels of calcium in enzyme preparations (3) expressed as the negative log of the millimolar enzyme accessible calcium concentration Composition B was prepared in seven variations wi-th CaC12 levels as indicated. The variations wer~ stored for 1 month at 90F and at 70F and evaluated for -amylase stability in the same manner as the variations of Composltion A.
L35~L~
Composition B - ~-Amylase Stability CaCl % of %Ca ~Ca Enzyme %
adde~ compo- seques- seques- acces- retained (2) % sition ted by ted by sible ~-amylase DTPA DTPA citrate calci- activity complex- um (3) 1 mo./ l mo./
ed with 90F 70F
calcium 0.0 - 99.9 - 7.560.0 5 0.125 93.1 98.6 1.43.44 56 79 0.2599.9 52.9 46.9 1.6089 93 0.5100.0 26.5 73.3 1.0790 93 1.0100.0 13.3 51.6(4) 0.88 91 95 ~2) in addi~ion to low levels of calcium in enzyme preparation (quantity added is deducted from total water) 5 (3) expressed as negative log of millimolar enzyme-accessible calcium concentration (4) plus 34.9% as precipitated calcium citrate These results show the dramatic improvement in ~ amylase (derived from B.licheniformis) stability in an aqueous liquid detergent composition when a calcium-containing component is incorporated that provides at least about lxlO 4-5 millimoles of enzyme-accessible calcium. The results also point out the advantage of mixtures of sequestering agents. A
sequestering agent with high equilibrium constant of complexation, e.g., the nitrogen-containing sequestering agents disclosed hereinbefore, will tend to sequester all available calcium to the poin-t of theoretical capacity, but can release such calcium in washing solutions to in turn sequester heavy rnetal ions such as copper, iron and manganese. A s~questeriny agent with a lower equilibrium constant of complexation such as alkali metal citrates or citric acid can be incorporated L3~
in the compositions of the invention without addition of calcium-containing components at a level to satisfy theoretical capacity. Thus, such sequestering agents are available to act as detergency builders efective in the presence of alkaline earth metal ions in washing solutions.
Apparently, -amylase derived from B.licheniformis has, in effect, an equilibrium constant of complexation with calcium somewhat greater than citrate, or more precisely, an equilibrium constant thak can hold suf-ficient calcium for stabilization in an aqueous solution containing at least about lxlO 4 5 millimoles of enzyme accessible calcium.
EXAMPLE II
The commercial enzymes Taka-ThermO L-340, Rohalase AT~ and Maxamyl HTo are incorporated in the compositions of Example I replacing the TermamylO 120L. Comparable ! a-amylase stability results are obtained at equi~alent enzyme-accessible calcium levels.
EXAMPLE III
a-amylases derived by B.subtilis, Ban~ from Novo Industri and RapidaseO from Gist Brocade, are incor-porated in the compositions of Example I replaci~g the Termamyl R120L. It is not possible to add a sufficient amount of a calcium-containing component to stabilize said a-amylases derived from B.subtilis without pre-cipita-tion of calcium citrate in the aqueous liquid detergent compositions.
EXAMPLE IV
Dodecyldimethyamine oxide replaces C12 alkyltri-methylammonium chloride in the compositions of Example I. Equivalent results are obtained.
3~
EXAMPLE V
The following compositions are prepared by mixing the ingredients listed.
A B C
C13 linear alkyl benzene sulfonic acid 12.1~ 10.56%
C14_15 alkyl ethoxy-l ether sulfate 3.9 - 10.0 Triethanolamine coco alkyl sulfate ~ 4.0 C12-1a, alkyltrimethyl-ammonium chloride 1.4 14O15 alcohol ethoxylate-7 7 8 12.0 20.0 Lauric acid 9.08 7.5 Myristic acid 3.03 2.5 Oleic acid 2.4 5.0 Citric acid 5.3 0.2 0.05 Maxataseo 0.97 0O97 1.0 TermamylO 120L 0.3 0 4 3 0.3 Diethylenetriaminepenta methylene phosphonic acid 0.29 0.3 0.3 Monoethanolamine 1.9 -Triethanolamine 3.6 4.5 NaOH & KOH 4.19 1.65 Ethanol 4.8 8.63 7.0 1,2-Propanediol 7.2 3.0 Sodium formate 0.97 1.0 2.0 Calcium chloride 0.02 0.02 0.02 Water 29.2 35.5 58.0 Perfume, colorant, suds control agent ~abric whiteners and other miscellaneous optional ingredients ----Remainder----pH 8.0 7.7 7-5 The incorporation of 0.02~ calcium chloride in each composition provides an enzyme accessible calcium level of at least lx10 5 millimoles per liter.
~L2~L35~
EXAMPLE VI
Potassium pyrophosphate, potassium carboxymethyl-oxymalonate and potassium carboxymethyloxysuccinate are each substituted for citric acid in Examples I, II and IV. Composition pH is adjusted to 8Ø A calcium chloride level of 0.3% by weight is sufficient to pro-vide an enzyme-accessible calcium level greater than lxlO 4'5 millimoles and stabilize the ~-amylase derived from B.licheniformis incorporated in said compositions.
WHAT IS CLAIMED IS:
Claims (13)
1. An aqueous liquid detergent composition comprising:
(a) from about 10% to about 65% by weight of a non-soap detergent surfactant or mixtures thereof;
(b) from about 0.01% to about 5% by weight on a standard enzyme basis of an .alpha.-amylolytic enzyme derived from B. licheniformis;
(c) from about 3% to about 30% of a combination of citric acid or water-soluble salts thereof and a nitrogen-containing sequestering agent selected from the group consisting of ethylenediamine tetramethylene phosphonic acid, diethylenetri-amine pentamethylenephosphonic acid, nitrilo-triacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, and di-ethylenetriaminepentaacetic acid, or mixtures of water-soluble salts thereof, wherein the ratio of citric acid or water-soluble salt thereof to nitrogen-containing sequestering agent is at least about 2:1 by weight;
(d) a calcium-containing component to provide at least about 1x10-4.5 millimoles of enzyme available calcium ion per liter of said composition;
(e) from about 10% to about 80% water by weight; and (f) from about 3% to about 25% by weight of a fatty acid having from about 10 to about 22 carbon atoms, said composition having a pH of from about 6.5 to about 9Ø
(a) from about 10% to about 65% by weight of a non-soap detergent surfactant or mixtures thereof;
(b) from about 0.01% to about 5% by weight on a standard enzyme basis of an .alpha.-amylolytic enzyme derived from B. licheniformis;
(c) from about 3% to about 30% of a combination of citric acid or water-soluble salts thereof and a nitrogen-containing sequestering agent selected from the group consisting of ethylenediamine tetramethylene phosphonic acid, diethylenetri-amine pentamethylenephosphonic acid, nitrilo-triacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, and di-ethylenetriaminepentaacetic acid, or mixtures of water-soluble salts thereof, wherein the ratio of citric acid or water-soluble salt thereof to nitrogen-containing sequestering agent is at least about 2:1 by weight;
(d) a calcium-containing component to provide at least about 1x10-4.5 millimoles of enzyme available calcium ion per liter of said composition;
(e) from about 10% to about 80% water by weight; and (f) from about 3% to about 25% by weight of a fatty acid having from about 10 to about 22 carbon atoms, said composition having a pH of from about 6.5 to about 9Ø
2. The composition of claim 1 wherein said calcium-containing component provides at least about 1x10-3 millimoles of enzyme-available calcium ion per liter of said composition.
3. The composition of claim 1 wherein said calcium-containing component provides at least about 1x10-2 millimoles of enzyme-available calcium ion per liter of said composition.
4. The composition of claim 1 wherein said composition comprises a proteolytic enzyme.
5. The composition of claim 4 wherein said composition comprises formic acid or water soluble salts of formic acid or mixtures thereof.
6. The composition of claim 1 wherein water comprises from about 15% to about 60% of said composition by weight.
7. The composition of claim 1 wherein said calcium-containing component comprises a salt of calcium or mixtures thereof.
8. The composition of claim 1 wherein said calcium-containing component comprises a calcium-sequestering agent complex or mixtures thereof.
9. The composition of claim 1 comprising from about 20% to about 50% by weight of the non-soap detergent surfactant.
10. The composition of claim 9 wherein the non-soap detergent surfactant comprises water-soluble salts of alkylbenzene sulfonic acid containing from about 9 to about 15 carbon atoms in the alkyl group and water-soluble alkylsulfates containing from about 10 to about 18 carbon atoms.
11. The composition of claim 10 comprising from about 5 to about 20% by weight of a fatty acid having from about 12 to about 18 carbon atoms.
12. The composition of claim 11 wherein the ratio of citric acid or water-soluble salt thereof to nitrogen-containing sequestering agent is from about 30:1 to about 2:1 by weight.
13. The composition of claim 12 having a total calcium level of from about 0.1% to about 0.3% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46624383A | 1983-02-14 | 1983-02-14 | |
| US466,243 | 1983-02-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1213541A true CA1213541A (en) | 1986-11-04 |
Family
ID=23851028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000447238A Expired CA1213541A (en) | 1983-02-14 | 1984-02-13 | Stabilized aqueous enzyme composition |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0118933B1 (en) |
| JP (1) | JPS59206497A (en) |
| AT (1) | ATE34767T1 (en) |
| AU (1) | AU575313B2 (en) |
| CA (1) | CA1213541A (en) |
| DE (1) | DE3471687D1 (en) |
| GR (1) | GR81415B (en) |
| IE (1) | IE57055B1 (en) |
| MX (1) | MX161307A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3685768T2 (en) * | 1985-04-15 | 1993-01-21 | Procter & Gamble | LIQUID CLEANING AGENT WITH AN ANIONIC SURFACE ACTIVE COMPOUND, AN AMPLIFIER AND A PROTEOLYTIC ENZYME. |
| US5223166A (en) * | 1986-11-17 | 1993-06-29 | Henkel Kommanditgesellschaft Auf Aktien | Preparations and processes for cleaning and disinfecting endoscopes |
| DE3639322A1 (en) * | 1986-11-17 | 1988-05-26 | Henkel Kgaa | METHOD FOR CLEANING AND DISINFECTING ENDOSCOPES AND MEANS FOR IMPLEMENTING THE METHOD |
| DE3816734A1 (en) * | 1988-05-17 | 1989-11-30 | Henkel Kgaa | METHOD FOR CLEANING AND DISINFECTING HEAT AND CORROSION-SENSITIVE MEDICAL DEVICES, ESPECIALLY ENDOSCOPES, AND MEANS FOR IMPLEMENTING THE METHOD |
| US5269960A (en) * | 1988-09-25 | 1993-12-14 | The Clorox Company | Stable liquid aqueous enzyme detergent |
| US5605881A (en) * | 1993-09-03 | 1997-02-25 | Minolta Co., Ltd. | Cleaning liquid for recycling copy medium for electrophotography |
| JP3081534B2 (en) * | 1995-12-22 | 2000-08-28 | 花王株式会社 | Enzyme-containing granules, method for producing the same, and compositions containing the same |
| KR20200010268A (en) * | 2017-04-25 | 2020-01-30 | 뉴트레코 아이피 애셋츠 비.브이. | Compositions for Use in Pregnant Animals |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1296839A (en) * | 1969-05-29 | 1972-11-22 | ||
| DE2709476A1 (en) * | 1976-03-08 | 1977-09-15 | Procter & Gamble Europ | LIQUID, ENZYME-BASED DETERGENT AND DETERGENT |
| DE2633601A1 (en) * | 1976-07-27 | 1978-02-02 | Henkel Kgaa | LIQUID, ENZYMATIC CONCENTRATE CAN BE USED AS A WASHING AGENT AND CLEANING AGENT |
| US4305837A (en) * | 1980-10-30 | 1981-12-15 | The Procter & Gamble Company | Stabilized aqueous enzyme composition |
| US4287082A (en) * | 1980-02-22 | 1981-09-01 | The Procter & Gamble Company | Homogeneous enzyme-containing liquid detergent compositions containing saturated acids |
| EP0028866B1 (en) * | 1979-11-09 | 1984-07-11 | THE PROCTER & GAMBLE COMPANY | Stabilised aqueous enzyme composition containing formate and calcium ions |
| US4529525A (en) * | 1982-08-30 | 1985-07-16 | Colgate-Palmolive Co. | Stabilized enzyme-containing detergent compositions |
-
1984
- 1984-02-06 GR GR73724A patent/GR81415B/el unknown
- 1984-02-06 AT AT84200157T patent/ATE34767T1/en not_active IP Right Cessation
- 1984-02-06 DE DE8484200157T patent/DE3471687D1/en not_active Expired
- 1984-02-06 EP EP84200157A patent/EP0118933B1/en not_active Expired
- 1984-02-13 JP JP59024920A patent/JPS59206497A/en active Pending
- 1984-02-13 CA CA000447238A patent/CA1213541A/en not_active Expired
- 1984-02-13 IE IE321/84A patent/IE57055B1/en not_active IP Right Cessation
- 1984-02-13 AU AU24538/84A patent/AU575313B2/en not_active Ceased
- 1984-02-14 MX MX200321A patent/MX161307A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59206497A (en) | 1984-11-22 |
| IE57055B1 (en) | 1992-04-08 |
| EP0118933B1 (en) | 1988-06-01 |
| MX161307A (en) | 1990-09-06 |
| EP0118933A1 (en) | 1984-09-19 |
| AU2453884A (en) | 1984-08-23 |
| AU575313B2 (en) | 1988-07-28 |
| ATE34767T1 (en) | 1988-06-15 |
| DE3471687D1 (en) | 1988-07-07 |
| GR81415B (en) | 1984-12-11 |
| IE840321L (en) | 1984-08-14 |
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