US3761420A - Stabilized liquid enzyme stain remover - Google Patents
Stabilized liquid enzyme stain remover Download PDFInfo
- Publication number
- US3761420A US3761420A US00044630A US3761420DA US3761420A US 3761420 A US3761420 A US 3761420A US 00044630 A US00044630 A US 00044630A US 3761420D A US3761420D A US 3761420DA US 3761420 A US3761420 A US 3761420A
- Authority
- US
- United States
- Prior art keywords
- enzyme
- water
- composition
- stain
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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
-
- 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
- C11D3/38618—Protease or amylase in liquid compositions only
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/96—Stabilising an enzyme by forming an adduct or a composition; Forming enzyme conjugates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
Definitions
- Enzymes are naturally occurring proteins with certain catalytic properties due to their power to activate specific substrates or substances to cause breakdown of more complex molecules into smaller fragments. Enzymes are normally produced by living cells, and can be easily obtained from natural sources by solvent extraction or other well known methods with full retention of their catalytic prop erties. The crude enzyme solutions are clarified as necessary by filtration or centrifugation, or concentrated by vacuum evaporation at low temperatures.
- Solid enzyme products may then be provided by spray drying the enzyme concentrate or the enzyme may be precipitated from solution by means of an aliphatic ketone or alcohol. Precipitated enzyme products are recovered by filtration or centrifugation and dried in vacuum dryers.
- Dried or powdered enzyme products have been used in laundry detergent products for their stain removing properties, but until now, there has been no liquid enzyme laundry product known to applicant.
- the detergent products incorporating dried enzyme products are packaged while dry and are desirably stored dry, being protected from absorption of moisture until placed in use. Dry storage for these products was thought necessary, because moisture tends to destabilize the enzymes and it is generally believed that enzymes stored in the presence of water tend to lose activity after a short period of time.
- the typical dry enzyme detergent products are added to water at the time of use to provide a relatively dilute enzyme solution. Articles of clothing having stains must then be soaked for extended long periods of time for the relatively weak enzyme solution to catalyze the breakdown and removal of the stain.
- This invention eliminates the extended soak time necessary when using the dry powder products and provides a relatively concentrated liquid enzyme product that is applied directly onto a stain from a storage container without first adding water.
- the liquid storage problem has been solved by applicant by providing an enzyme stabilizer which makes possible a stabilized aqueous enzyme produce with excellent shelf storage life.
- Applicants stabilized aqueous enzyme product overcomes the need for dispersing enzyme in water just prior to use, and applicants aqueous enzyme products eliminates the dust exposure hazard inherent with dry powder detergent products.
- the relatively concentrated aqueous enzyme preparations can also be poured directly onto stains on clothing to further accelerate the stain removal process with even higher concentrations of enzyme thus being applied to the stain substrate in the presence of less diluting water.
- the liquid enzyme composition of the invention can be included as part of a liquid laundry detergent while retaining the advantages listed above.
- This invention is directed to a stain-hydrolyzing aqueous enzyme composition which is particularly useful for dissolving stains on washable fabrics which has an excellent shelf storage life in an aqueous media because of the addition of certain enzyme stabilizing agents.
- a proteolytic enzyme is employed which is stabilized by a polyhydric alcohol such as glycerin.
- a chelating agent such as sodium hexametaphosphate is normally included in the product to increase its effectiveness and to maintain the pH of the aqueous solution in a controlled range.
- a stabilized enzyme composition which contains an enzyme, water and a polyhydric organic stabilizing agent.
- the organic stabilizing agent is present at a level suflicient to stabilize the enzyme and to prevent inactivation of the enzyme when stored for long periods of time.
- the polyhydric organic stabilizing agent is present at particular levels with respect to the water so as to provide a stabilized aqueous enzyme system which is effective in treating and removing stains from clothing.
- the stabilizing agent of the invention is preferably selected from polyhydric organic compounds having a carbon chain length of from 2 to 6.
- polyhydric is meant that the organic compound has at least two hydroxyl groups and may contain up to 6 hydroxyl groups per molecule. More specifically, those polyhydric organic compounds having a hydroxyl group on the initial and terminal carbon atom of the molecule are preferred.
- Such compounds include ethylene glycol, propylene glycol, glycerol, sorbitol and mannitol. Glycerol is the presently preferred stabilizing agent, but certain other less expensive polyols may also be used.
- Monosaccharide aldose and ketose sugars may also be used as the polyhydric organic stabihzmg agent, but their use depends on the particular use intended for the stabilized enzyme product and whether a particular chelating agent is to be used.
- Suitable sugars include dextrose, fructose, galactose, mannose and sorbitose.
- the polyhydric organic stabilizing agent should be present at particular ratios with respect to the water in the composition in order to obtain a stable liquid enzyme WhlCh also retains the catalytic ability of the enzyme to treat stains on clothing.
- a mole ratio of the stabilizing agent to water of from about 10:1 to about 1:37 is preferred.
- water should be present in the composition at levels of from about 25 percent to about 60' percent by weight of the composltion, and the stabilizing agent would then comprise about 15 percent to about 40 percent by weight of the composition.
- the mole ratio of the polyhydric organic stabilizing agent to Water in the range set forth above is more important when a chelating agent such as a glassy phosphate is used, because when an excess of the stabilizmg agent over this range is used, some of the glassy phosphate tends to fiocculate and precipitate from the liquid composltion. It is not necessary in all instances to include chelating agents, for example, where the product will be used in pre-softened water. In such situations, the concentration of stabilizing agent can be considerably higher, that is, up to by weight of the total liquid composition, the remainder being water and enzyme.
- the enzyme to be employed is usually selected based on the intended use for the stabilized liquid enzyme composition.
- a protease enzyme is preferred, because the usual stains on clothing are proteinaceous in character.
- Proteases and similar enzymes employed for stain removal normally lose their potency after a very short time in water, so the presence of the stabilizing agent is most important to maintain the effectiveness of these enzymes.
- composition of the present invention is particularly useful for treating stains on clothing by applying the composition directly to the stain until the enzyme has catalyzed breakdown of the stain.
- the composition of the invention may also be used as an active component of a liquid detergent product, or as a supplement to standard washing procedures, being combined with detergent products at the time of preparing the wash water.
- the recommended concentration of the enzyme when used in a liquid detergent product is in the range of .5 percent to 2.0 percent by weight of the total product, and the enzyme containing liquid detergent is normally applied directly to the stains as set forth above.
- the water used in preparing the aqueous enzyme composition of the enzyme is preferably softened to remove polyvalent cations prior to use.
- a chelating agent may be combined with the composition in the event that softened water is not available, and particularly when used in hard water.
- the chelating agent is selected so as to provide a pH in the aqueous enzyme system of 9.0, and should normally not be above this to prevent loss of activity of the enzyme, which is sensitive to excessive alkalinity.
- the chelating agent is preferably present in a range from about 20 percent to about 40 percent by Weight of the composition.
- the enzyme is first mixed with the polyhydric organic stabilizing agent prior to combining the enzyme with water. While the step of combining the enzyme with the polyhydric organic stabilizing agent prior to addition to water is not necessary, it has been found that activity of the enzyme tends to remain higher when this is done.
- the polyhydric organic stabilizing agent becomes intertwined with the protein molecule of the enzyme and acts to prevent water degradation of the enzyme during storage.
- combining the polyhydric organic stabilizing agent with the enzyme prior to adding the water appears to enable the intertwining reaction to become completed prior to the time that the enzyme is contacted with water.
- suitable levels of activity can also be attained when the enzyme is first added to water and the polyhydric organic stabilizing agent is added shortly thereafter.
- aqueous enzyme composition is prepared in accordance with the present invention.
- the composltion contains the following ingredients at the indicated levels.
- the above composition had a shelf life stability of more than seven months when stored at an ambient temperature of about 77 F.
- the composition is then used to treat a blood stain on a cotton fabric.
- the composition is applied directly to the blood stain and is permitted to remain in contact with the blood stain for a period of about three minutes before washing actually commences. At the end of this time, the blood stain has been broken down by the catalytic activity of the enzyme and the blood stain is easily removed from the fabric during normal wash cycles.
- a blood stain is treated by preparing a pre-soak from a commercially available dry powder enzyme-containing detergent in accordance with instructions supplied therewith, treatment for a period of one-half to two hours is needed to effect any appreciable breakdown of the blood stain.
- a stabilized aqueous enzyme preparation for dissolving stains on fabrics consisting essentially of by weight of the preparation:
- Cited ganic stabilizing agents selected from the group con- UNITED STATES PATENTS sisting of ethylene glycol, propylene glycol, and 3,557,002 1/1971 McCarty H 12 glycerol; 3,627,688 12/1971 McCarty et a1.
- 252Dig. 12 said aqueous enzyme preparation having a pH in the 5 3,553,139 1/ 1971 McCarty 252-439 range of about 5.5 to 9.0, and capable of effective stain 2,164,914 7/1939 Gore et 5- removing for more than seven months at a temperature ggg iffi l of about 77 F.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Genetics & Genomics (AREA)
- Zoology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biomedical Technology (AREA)
- Biotechnology (AREA)
- Molecular Biology (AREA)
- Microbiology (AREA)
- Medicinal Chemistry (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US4463070A | 1970-06-08 | 1970-06-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3761420A true US3761420A (en) | 1973-09-25 |
Family
ID=21933427
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00044630A Expired - Lifetime US3761420A (en) | 1970-06-08 | 1970-06-08 | Stabilized liquid enzyme stain remover |
Country Status (8)
Country | Link |
---|---|
US (1) | US3761420A (en) |
BE (1) | BE768228A (en) |
CA (1) | CA981606A (en) |
DE (1) | DE2128135A1 (en) |
FR (1) | FR2097842A5 (en) |
GB (1) | GB1323819A (en) |
IT (1) | IT942116B (en) |
NL (1) | NL7107664A (en) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4238345A (en) * | 1978-05-22 | 1980-12-09 | Economics Laboratory, Inc. | Stabilized liquid enzyme-containing detergent compositions |
US4250254A (en) * | 1978-09-11 | 1981-02-10 | Modrovich Ivan Endre | Stabilized liquid enzyme and coenzyme compositions |
US4261868A (en) * | 1979-08-08 | 1981-04-14 | Lever Brothers Company | Stabilized enzymatic liquid detergent composition containing a polyalkanolamine and a boron compound |
US4271264A (en) * | 1976-09-13 | 1981-06-02 | Modrovich Ivan Endre | Stabilized liquid enzyme and coenzyme compositions |
US4372874A (en) * | 1976-09-13 | 1983-02-08 | Modrovich Ivan Endre | Stabilization of hydrolysis prone labile organic reagents in liquid media |
US4511490A (en) * | 1983-06-27 | 1985-04-16 | The Clorox Company | Cooperative enzymes comprising alkaline or mixtures of alkaline and neutral proteases without stabilizers |
US4515705A (en) * | 1983-11-14 | 1985-05-07 | The Procter & Gamble Company | Compositions containing odor purified proteolytic enzymes and perfumes |
US4684615A (en) * | 1983-06-06 | 1987-08-04 | Ciba Corning Diagnostics Corp. | Stabilized isoenzyme control products |
US4711739A (en) * | 1986-12-18 | 1987-12-08 | S. C. Johnson & Son, Inc. | Enzyme prespotter composition stabilized with water insoluble polyester or polyether polyol |
US4747977A (en) * | 1984-11-09 | 1988-05-31 | The Procter & Gamble Company | Ethanol-free liquid laundry detergent compositions |
US5176292A (en) * | 1986-03-21 | 1993-01-05 | The Dow Chemical Company | Combined closure and measuring device |
US5589448A (en) * | 1993-02-17 | 1996-12-31 | The Clorox Company | High water liquid enzyme prewash composition |
US5614484A (en) * | 1991-08-21 | 1997-03-25 | The Procter & Gamble Company | Detergent compositions containing lipase and terpene |
US5714363A (en) * | 1989-09-26 | 1998-02-03 | Eli Lilly And Company | Deacetoxycephalosporin C hydroxylase |
US5789364A (en) * | 1993-02-17 | 1998-08-04 | The Clorox Company | High water liquid enzyme prewash composition |
US5858117A (en) * | 1994-08-31 | 1999-01-12 | Ecolab Inc. | Proteolytic enzyme cleaner |
WO2003035827A2 (en) | 2001-09-07 | 2003-05-01 | Brigham Young University | Plasticized hydrophilic glasses for improved stabilization of biological agents |
US20130143297A1 (en) * | 2010-07-27 | 2013-06-06 | Henkel Ag & Co. Kgaa | Stabilized liquid tenside preparation comprising enzymes |
US20140094398A1 (en) * | 2012-10-03 | 2014-04-03 | The Procter & Gamble Company | Stable enzyme stabilizer premix |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK289083A (en) * | 1983-06-23 | 1984-12-24 | Novo Industri As | LIPASE, PROCEDURE FOR PREPARING THEREOF AND ITS APPLICATION |
AU3722984A (en) * | 1984-01-05 | 1985-07-11 | Manlab Pty. Ltd. | Reagents for immunoassay at elevated temperatures |
US4810638A (en) * | 1986-07-24 | 1989-03-07 | Miles Inc. | Enzyme-labeled antibody reagent with polyalkyleneglycol linking group |
FR2626373B1 (en) * | 1988-01-22 | 1993-10-15 | Stabiligen | PROCESS FOR THE PREPARATION OF A STABLE PLOTTER AND OBTAINED PLOTTER |
US4959179A (en) * | 1989-01-30 | 1990-09-25 | Lever Brothers Company | Stabilized enzymes liquid detergent composition containing lipase and protease |
EP0973875B1 (en) * | 1997-03-12 | 2006-06-14 | Novozymes A/S | Storage-stable liquid formulation comprising a laccase |
EP4039806A1 (en) * | 2021-02-04 | 2022-08-10 | Henkel AG & Co. KGaA | Detergent composition comprising xanthan lyase and endoglucanase variants with im-proved stability |
-
1970
- 1970-06-08 US US00044630A patent/US3761420A/en not_active Expired - Lifetime
-
1971
- 1971-05-10 CA CA112,580A patent/CA981606A/en not_active Expired
- 1971-05-25 GB GB1693271A patent/GB1323819A/en not_active Expired
- 1971-06-03 NL NL7107664A patent/NL7107664A/xx unknown
- 1971-06-04 IT IT50794/71A patent/IT942116B/en active
- 1971-06-05 DE DE19712128135 patent/DE2128135A1/en active Pending
- 1971-06-08 BE BE768228A patent/BE768228A/en unknown
- 1971-06-08 FR FR7120725A patent/FR2097842A5/fr not_active Expired
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4271264A (en) * | 1976-09-13 | 1981-06-02 | Modrovich Ivan Endre | Stabilized liquid enzyme and coenzyme compositions |
US4372874A (en) * | 1976-09-13 | 1983-02-08 | Modrovich Ivan Endre | Stabilization of hydrolysis prone labile organic reagents in liquid media |
US4238345A (en) * | 1978-05-22 | 1980-12-09 | Economics Laboratory, Inc. | Stabilized liquid enzyme-containing detergent compositions |
US4250254A (en) * | 1978-09-11 | 1981-02-10 | Modrovich Ivan Endre | Stabilized liquid enzyme and coenzyme compositions |
US4261868A (en) * | 1979-08-08 | 1981-04-14 | Lever Brothers Company | Stabilized enzymatic liquid detergent composition containing a polyalkanolamine and a boron compound |
US4684615A (en) * | 1983-06-06 | 1987-08-04 | Ciba Corning Diagnostics Corp. | Stabilized isoenzyme control products |
US4511490A (en) * | 1983-06-27 | 1985-04-16 | The Clorox Company | Cooperative enzymes comprising alkaline or mixtures of alkaline and neutral proteases without stabilizers |
US4515705A (en) * | 1983-11-14 | 1985-05-07 | The Procter & Gamble Company | Compositions containing odor purified proteolytic enzymes and perfumes |
US4747977A (en) * | 1984-11-09 | 1988-05-31 | The Procter & Gamble Company | Ethanol-free liquid laundry detergent compositions |
US5176292A (en) * | 1986-03-21 | 1993-01-05 | The Dow Chemical Company | Combined closure and measuring device |
US4711739A (en) * | 1986-12-18 | 1987-12-08 | S. C. Johnson & Son, Inc. | Enzyme prespotter composition stabilized with water insoluble polyester or polyether polyol |
US5714363A (en) * | 1989-09-26 | 1998-02-03 | Eli Lilly And Company | Deacetoxycephalosporin C hydroxylase |
US5614484A (en) * | 1991-08-21 | 1997-03-25 | The Procter & Gamble Company | Detergent compositions containing lipase and terpene |
US5589448A (en) * | 1993-02-17 | 1996-12-31 | The Clorox Company | High water liquid enzyme prewash composition |
US5789364A (en) * | 1993-02-17 | 1998-08-04 | The Clorox Company | High water liquid enzyme prewash composition |
US5858117A (en) * | 1994-08-31 | 1999-01-12 | Ecolab Inc. | Proteolytic enzyme cleaner |
US6197739B1 (en) | 1994-08-31 | 2001-03-06 | Ecolab Inc. | Proteolytic enzyme cleaner |
WO2003035827A2 (en) | 2001-09-07 | 2003-05-01 | Brigham Young University | Plasticized hydrophilic glasses for improved stabilization of biological agents |
US20040014164A1 (en) * | 2001-09-07 | 2004-01-22 | Cicerone Marcus T. | Plasticized hydrophilic glasses for improved stabilization of biological agents |
EP1430117A2 (en) * | 2001-09-07 | 2004-06-23 | Brigham Young University | Plasticized hydrophilic glasses for improved stabilization of biological agents |
EP1430117A4 (en) * | 2001-09-07 | 2006-01-25 | Univ Brigham Young | Plasticized hydrophilic glasses for improved stabilization of biological agents |
US7101693B2 (en) | 2001-09-07 | 2006-09-05 | Brigham Young University | Plasticized hydrophilic glasses for improved stabilization of biological agents |
US20130143297A1 (en) * | 2010-07-27 | 2013-06-06 | Henkel Ag & Co. Kgaa | Stabilized liquid tenside preparation comprising enzymes |
US20140094398A1 (en) * | 2012-10-03 | 2014-04-03 | The Procter & Gamble Company | Stable enzyme stabilizer premix |
Also Published As
Publication number | Publication date |
---|---|
NL7107664A (en) | 1971-12-10 |
GB1323819A (en) | 1973-07-18 |
CA981606A (en) | 1976-01-13 |
IT942116B (en) | 1973-03-20 |
FR2097842A5 (en) | 1972-03-03 |
DE2128135A1 (en) | 1971-12-16 |
BE768228A (en) | 1971-12-08 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: PUREX CORPORATION, LAKEWOOD, CA A CORP. OF CA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:A. E. STALEY MANUFACTURING COMPANY, DECATUR, IL A CORP. OF DE;REEL/FRAME:003906/0124 Effective date: 19810831 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED FILE - (OLD CASE ADDED FOR FILE TRACKING PURPOSES) |
|
AS | Assignment |
Owner name: PUREX CORPORATION, A CORP. OF DE. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:PII AQUISITIONS, INC.;REEL/FRAME:005172/0592 Effective date: 19820813 |
|
AS | Assignment |
Owner name: PII ACQUISITIONS, INC., A CORP. OF DE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:PUREX CORPORATION;REEL/FRAME:005011/0686 Effective date: 19820813 |