US3741901A - Washing compositions and process - Google Patents
Washing compositions and process Download PDFInfo
- Publication number
- US3741901A US3741901A US00062130A US3741901DA US3741901A US 3741901 A US3741901 A US 3741901A US 00062130 A US00062130 A US 00062130A US 3741901D A US3741901D A US 3741901DA US 3741901 A US3741901 A US 3741901A
- Authority
- US
- United States
- Prior art keywords
- sodium
- none
- detergent
- washing
- enzymes
- 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
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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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0042—Reducing agents
-
- 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
- C11D3/38609—Protease or amylase in solid compositions only
Definitions
- Detergent Ingredients Effect on Enzymes published in Soap and Chemical Specialties for September 1969, pages 60, 62, 64, 66, 70, 82, 84, and 90; NTA Gets Big Push in Detergent Powders, published in Chemical and Engineering News, Apr. 6, 1970, pageall; and Nonionics In the 70s, published in Detergents and Specialties, May 1970, pages 33-36.
- a laboratory scale multiple washing machine which simulates the action of the agitator-type home washer is used for the test.
- the conditions set forth in this procedure for laboratory operations are precise and practical and there is a high degree of reproducibility of the test data.
- Two types of swatches are used which are usually called BMI and CMS.
- the BMI swatches are impregnated with blood, milk and India ink and are used where it is desired to determine the effectiveness of bacterial protease enzymes.
- the CMS swatches are impregnated with cocoa, milk and starch and are used where it is desired to determine the effectiveness of bacterial amylase enzymes.
- Detergents are normally composed of surface active agents and chelating agents with or without foam boosters, anti-soil redeposition agents, silicates, optical brighteners, borates, enzymes, fillers, organic solvents, coloring agents and perfume.
- Sodium tripolyphosphate (herein called STP) is the principal chelating agent employed in most present day detergents but recently phosphates have come under attack because of their effect on plant life in streams and ponds and efforts have been made to replace at least a part of the phosphates with other substances, for example, trisodium nitrilotriacetatemonohydrate (herein called NTA). This has resulted in compositions that dissolve in water to give a higher pH.
- washing compositions and a washing process containing ingredients which make it possible to improve washing efficiency over a relatively wide alkaline pH, especially compositions containing bacterial protease and/or bacterial amylase and to give a buffered pH level, particularly where other components give too high a pH which would normally affect the stability of such enzymes.
- one of the objects of the present invention is to provide new and improved washing compositions and a washing process by adding to a detergent composition or to the wash water, especially to detergent compositions or wash waters containing bacterial protease and/or bacterial amylase, an ingredient which gives a buffered pH level, particularly where other components give too high a pH which would normally affect the stability of such enzymes, and which when employed in the proper proportions enhances the washing efficiency.
- a more specific object of the invention is to provide new and improved washing compositions and a new and improved washing process in which water soluble sulfites and bisulfites are employed to increase the washing effectiveness of detergent compositions, especially those containing bacterial protease and/or bacterial amylase.
- water soluble sulfites and bisulfites are employed to increase the washing effectiveness of detergent compositions, especially those containing bacterial protease and/or bacterial amylase.
- water soluble sulfites and/or bisulfites preferably sodium sulfite (Na SO sodium bisulfite (NaHSO and/or sodium metabisulfite (Na S O are added to detergent compositions containing surface active agents and chelating agents with or without other ingredients, or to wash waters containing such compositions, in sufficient amount to increase the washing efiiciency and preferably also in amounts sufficient to give a buffered pH level particularly where other components give too high a pH which would normally affect the stability of bacterial protease and/or bacterial amylase enzymes where such enzymes are present in such compositions or in wash waters involving the use of such compositions.
- Na SO sodium bisulfite NaHSO and/or sodium metabisulfite
- Na S O sodium metabisulfite
- the invention particularly contemplates detergent compositions and wash water wherein the pH is around 8 to 12.0 and especially when it is within the range of 9.0 to 10.5.
- STP is a sequestering agent for calcium and magnesium salts normally found in hard water. It is a member of the class of materials usually known as chelating agents.
- NTA is another member of this class of materials which also includes the disodium salt of ethylene diamine tetraacetic acid, the tetrasodium salt of ethylenediamine tetraacetic acid, the sodium salts of N-(hydroxyethyDethylenediamine tetraacetic acid, and the sodium salts of diethylenetriaminepentaacetic acid. Substances such as STP and NTA are sometimes referred to in the art as builders. The surfactants are sometimes referred to as actives.
- surfactants commonly employed are C alkyl benzene sulfonate, and /15 tallow/coconut soap, a C1245 primary alcohol with 9 moles of ethylene oxide, a polyoxypropylene-ethylene oxide condensate with an approximate molecular weight of 1750 and containing 3 about 80% ethylene oxide, and a cationic surfactant, dimethyldicocoammonium chloride.
- fillter The most commonly used fillter is sodium sulfate.
- Other fillers are sodium carbonate, sodium sesquicarbonate, sodium bicarbonate and sodium borate.
- foam boosters e.g., lauryl alcohol and cocomonoethanolamide
- antisoil redeposition agents e.g., sodium carboxymethyl cellulose
- anticorrosion agents e.g., sodium silicate
- optical brighteners e.g., sodium silicate
- bleaches e.g., sodium perborate
- enzymes e.g., enzymes.
- Table I gives a more specific breakdown of the composition of detergents contemplated in the practice of the present invention, it being understood that a water soluble sulfite and/or bisulfite is added to such detergents or to wash waters containing them in amounts sufiicient to enhance the washing efficiency.
- sodium sulfite, sodium bisulfite and/or sodium metabisulfite are preferred, the corresponding water soluble potassium salts can be used but are normally too expensive for practical purposes.
- Other sulfites which are water soluble and substantially equivalent to sodium sulfite, sodium bisulfite and/ or sodium bisulfite can also be employed.
- the water noluble sulfite, bisulfite and/or metabisulfite preferably constitutes 2 to 0.6 part of the detergent.
- the amount used should be sufficient to produce at least 300 parts per million (p.p.m.) of water soluble sulfite, bisulfite and/or sodium meta-bisulfite in a wash water and preferably at least 400 p.p.m., calculated as Na SO Usually enhanced effectiveness is not obtained beyond 1000 p.p.m. and in most cases no improvement in effectiveness is obtained when the amount is greater than 800 p.p.m. It should be noted that sodium meta-bisulfite reacts in equal molar proportions with water to form 2 moles of sodium bisulfite.
- the invention contemplates the use of mixtures of sodium sulfite and sodium bisulfite (or sodium metabisulfite) so as to give the wash water a buffered pH usually not exceeding and in most cases not exceeding 9.8.
- the optimum washing pH range is usually from about 8 to 10.
- the usual recommended concentration of detergent in the wash water is 1500 p.p.m. (0.15% weight/volume).
- compositions in terms of the major components of various enzyme based detergent products, some of which are used in the specific examples hereinafter given. It will be understood that these compositions also contain as minor components carboxymethyl cellulose, optical brighteners, bleach stabilizers, perfumes, dyes and free moisture. In the table the quantities are given in parts by weight.
- enzymes containing bacterial protease and/or bacterial amylase can be prepared in powdered form having activities within the range of 15,000 to 1,000,000 PV units per gram and 30 to 100,000 DV units per gram. Normally the enzyme powders contain diluents so that the enzyme activity per gram as added to a detergent base is within the range of 15,000 to 150,000 PV units per gram and 0 to 150,000 DV units per gram.
- washing efficiencies were determined with various types of detergents with and without sodium sulfite in various proportions.
- BMI or CMS test swatches were used (6" x 3"). Three swatches were used for each BMI test and five swatches were used for each CMI test.
- the washing cycle was 10 minutes at F.
- the rinse cycle was 5 minutes at 100 F. and pH values are those of the wash solutions at the end of the wash cycle.
- the reflectance was determined with a Hunter D25 Color Reflectometer and the ARd readings represent the difference in reflectance before and after each test.
- the readings were based on average readings taken three times on one side and three times on the other side of each swatch.
- the concentration of detergent in every case was 0.15% (w./v.) which corresponds to 1500 p.p.m., unless otherwise indicated. All of the wash tests described in the following examples were carried out with city water from Milwaukee, Wis., having a hardness of p.p.m.
- EXAMPLE 1 In this example the detergent used was a commercial detergent base known as White Magic. The tests were carried out with and without a fixed percentage of sodium carbonate and with and without various percentages of sodium sulfite. No enzyme was added to the detergent. The following results were obtained.
- Example 3 Comparing the test results of Example 3 with those of Example 4 it will be observed that there was an enhanced etficiency when the sodium sulfite was added where the wash water conatined one gram per liter of STP at pHs of 8.6 or 8.7 and also at pHs of 9.5 and 9.6.
- pHs of 8.6 or 8.7 At a pH of 9.25 when a combination of 0.5 g. of STP and 0.5 g. of NTA was used per liter of wash water there was no significant improvement with the CMS test cloths but there was a very substantial improvement with the BMI test cloths. Also, there was a significant improvement with both types of test cloths at higher pH values of 9.7 and 9.8.
- EXAMPLE 5 In the following series of sixteen tests, the first four tests were carried out with White Magic detergent base, the next four tests with Punch detergent base, the next four tests with Tide detergent base and the last four tests with Colgate-Palmolive NTA-low phosphate deter- 20 gent base. Enzyme M (Table III) was added in all of these tests.
- EXAMPLE 8 This example illustrates the results obtained by combining a particular type of enzyme with White Magic detergent base with and without sodium carbonate and/ or sodium sulfite. The results were as follows.
- EXAMPLE 14 In this series of tests enzyme M (Table III) was added to White Magic detergent base and various proportions of sodium carbonate, sodium sulfite and sodium bisulfite were employed. The results were as follows.
- EXAMPLE 15 The following tests were carried out with various commercial deteregnt bases and a pre-soak base without the addition of any enzyme and at pHs from 8.95 to 9.3 with and without the addition of sodium sulfite. The results were as follows:
- the sodium sulfite and/or sodium bisulfite or their equivalents can be added to the detergent base or to enzymes which are added to the detergent base or directly to the wash water. Usually, it is more practical to make a solid or liquid product in which all of the detergent ingredients are combined so that the user can add the proper proportions to the wash water.
- the improvement which comprises adding to the wash water a quantity of a substance from the group consisting of water soluble sulfites, bisulfites, metabisulfites, and mixtures thereof sufiicient to enhance the washing efficiency of said wash water while maintaining a pH within the range of 8 to 12 in said wash water.
- wash water comprises sodium tripolyphosphate.
- wash water comprises trisodium nitrilotriacetate monohydrate.
- wash water comprises an enzyme from the group consisting of bacterial protease, bacterial amylase and mixtures thereof.
- the improvement which comprises adding to the wash water a quantity of a substance from the group consisting of sodium sulfite, mixtures of sodium sulfite with sodium bisulfite and mixtures of sodium sulfite with sodium metabisulfite, said quantity being within the range of 300 parts per million to 1000 parts per million and being sufiicient to enhance the washing efficiency of said wash water while maintaining a pH within the range of 8 to 12 in said wash water.
- wash water contains a substance from the group consisting of surfactants, chelating agents, sodium sulfate, sodium carbonate, sodium sesquicarbonate, sodium bicarbonate, so dium borate, borax, sodium carboxy methyl cellulose, sodium silicate, sodium perborate, and enzymes from the group consisting of bacterial protease, bacterial amylase and mixtures thereof.
Abstract
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US6213070A | 1970-08-07 | 1970-08-07 |
Publications (1)
Publication Number | Publication Date |
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US3741901A true US3741901A (en) | 1973-06-26 |
Family
ID=22040406
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US00062130A Expired - Lifetime US3741901A (en) | 1970-08-07 | 1970-08-07 | Washing compositions and process |
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Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3940341A (en) * | 1973-03-22 | 1976-02-24 | Colgate-Palmolive Company | Granular detergent compositions |
US4001132A (en) * | 1974-06-17 | 1977-01-04 | The Procter & Gamble Company | Automatic dishwashing detergent composition |
US4115293A (en) * | 1975-10-06 | 1978-09-19 | E. I. Du Pont De Nemours And Company | Denture cleanser |
JPS5482853A (en) * | 1977-12-14 | 1979-07-02 | Lion Fat Oil Co Ltd | Method of cleaning dishes by automatic dish washing machine |
US4285738A (en) * | 1978-04-24 | 1981-08-25 | Senju Pharmaceutical Co., Ltd. | Cleaning composition for contact lenses |
US4421664A (en) * | 1982-06-18 | 1983-12-20 | Economics Laboratory, Inc. | Compatible enzyme and oxidant bleaches containing cleaning composition |
US4446043A (en) * | 1981-09-01 | 1984-05-01 | Lever Brothers Company | Built liquid detergent compositions |
US4462922A (en) * | 1981-11-19 | 1984-07-31 | Lever Brothers Company | Enzymatic liquid detergent composition |
JPS6268898A (en) * | 1985-09-20 | 1987-03-28 | ライオン株式会社 | Granular detergent composition |
EP0233721A2 (en) * | 1986-02-12 | 1987-08-26 | Genencor, Inc. | Protein stain-removing compositions |
US4707287A (en) * | 1985-06-28 | 1987-11-17 | The Procter & Gamble Company | Dry bleach stable enzyme composition |
US4710313A (en) * | 1985-06-26 | 1987-12-01 | Lion Corporation | Detergent composition for contact lenses |
US4767557A (en) * | 1985-06-28 | 1988-08-30 | The Procter & Gamble Company | Dry bleach and stable enzyme granular composition |
EP0293055A1 (en) * | 1987-05-29 | 1988-11-30 | The Procter & Gamble Company | Particles containing ammonium salts as chlorine scavengers for detergent compositions |
US5002684A (en) * | 1987-04-08 | 1991-03-26 | Harris Research, Inc. | Composition and method for removal of stains from fibers |
WO1994010283A1 (en) * | 1992-10-28 | 1994-05-11 | The Procter & Gamble Company | Process for the manufacture of a liquid detergent composition comprising a sulphiting agent and an enzyme system |
US5429765A (en) * | 1993-04-29 | 1995-07-04 | Amway Corporation | Detergent and method for producing the same |
US5705469A (en) * | 1992-10-28 | 1998-01-06 | The Procter & Gamble Company | Process for the manufacture of a liquid detergent composition comprising a sulphiting agent and an enzyme system |
US5726142A (en) * | 1995-11-17 | 1998-03-10 | The Dial Corp | Detergent having improved properties and method of preparing the detergent |
EP2970831A4 (en) * | 2013-03-14 | 2016-11-30 | Ecolab Usa Inc | Enzyme-containing detergent and presoak composition and methods of using |
US20180371381A1 (en) * | 2017-06-26 | 2018-12-27 | Ecolab Usa Inc. | Method of dishwashing comprising detergent compositions substantially free of polycarboxylic acid polymers |
WO2022094265A1 (en) | 2020-10-30 | 2022-05-05 | Ecolab Usa Inc. | Reducing agent as corrosion inhibitor for machine warewash |
-
1970
- 1970-08-07 US US00062130A patent/US3741901A/en not_active Expired - Lifetime
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3940341A (en) * | 1973-03-22 | 1976-02-24 | Colgate-Palmolive Company | Granular detergent compositions |
US4001132A (en) * | 1974-06-17 | 1977-01-04 | The Procter & Gamble Company | Automatic dishwashing detergent composition |
US4115293A (en) * | 1975-10-06 | 1978-09-19 | E. I. Du Pont De Nemours And Company | Denture cleanser |
JPS5482853A (en) * | 1977-12-14 | 1979-07-02 | Lion Fat Oil Co Ltd | Method of cleaning dishes by automatic dish washing machine |
JPS6054358B2 (en) * | 1977-12-14 | 1985-11-29 | ライオン株式会社 | How to wash tableware using an automatic dishwasher |
US4285738A (en) * | 1978-04-24 | 1981-08-25 | Senju Pharmaceutical Co., Ltd. | Cleaning composition for contact lenses |
US4446043A (en) * | 1981-09-01 | 1984-05-01 | Lever Brothers Company | Built liquid detergent compositions |
US4462922A (en) * | 1981-11-19 | 1984-07-31 | Lever Brothers Company | Enzymatic liquid detergent composition |
US4421664A (en) * | 1982-06-18 | 1983-12-20 | Economics Laboratory, Inc. | Compatible enzyme and oxidant bleaches containing cleaning composition |
US4710313A (en) * | 1985-06-26 | 1987-12-01 | Lion Corporation | Detergent composition for contact lenses |
EP0206417A3 (en) * | 1985-06-28 | 1988-11-09 | The Procter & Gamble Company | Dry bleach stable enzyme composition |
US4707287A (en) * | 1985-06-28 | 1987-11-17 | The Procter & Gamble Company | Dry bleach stable enzyme composition |
US4767557A (en) * | 1985-06-28 | 1988-08-30 | The Procter & Gamble Company | Dry bleach and stable enzyme granular composition |
JPS6268898A (en) * | 1985-09-20 | 1987-03-28 | ライオン株式会社 | Granular detergent composition |
EP0233721A3 (en) * | 1986-02-12 | 1988-08-31 | Genencor, Inc. | Protein stain-removing compositions |
EP0233721A2 (en) * | 1986-02-12 | 1987-08-26 | Genencor, Inc. | Protein stain-removing compositions |
US5002684A (en) * | 1987-04-08 | 1991-03-26 | Harris Research, Inc. | Composition and method for removal of stains from fibers |
EP0293055A1 (en) * | 1987-05-29 | 1988-11-30 | The Procter & Gamble Company | Particles containing ammonium salts as chlorine scavengers for detergent compositions |
US4810413A (en) * | 1987-05-29 | 1989-03-07 | The Procter & Gamble Company | Particles containing ammonium salts or other chlorine scavengers for detergent compositions |
WO1994010283A1 (en) * | 1992-10-28 | 1994-05-11 | The Procter & Gamble Company | Process for the manufacture of a liquid detergent composition comprising a sulphiting agent and an enzyme system |
US5705469A (en) * | 1992-10-28 | 1998-01-06 | The Procter & Gamble Company | Process for the manufacture of a liquid detergent composition comprising a sulphiting agent and an enzyme system |
US5429765A (en) * | 1993-04-29 | 1995-07-04 | Amway Corporation | Detergent and method for producing the same |
US5726142A (en) * | 1995-11-17 | 1998-03-10 | The Dial Corp | Detergent having improved properties and method of preparing the detergent |
EP2970831A4 (en) * | 2013-03-14 | 2016-11-30 | Ecolab Usa Inc | Enzyme-containing detergent and presoak composition and methods of using |
US9879206B2 (en) | 2013-03-14 | 2018-01-30 | Ecolab Usa Inc. | Enzyme-containing detergent and presoak composition and methods of using |
US10604726B2 (en) | 2013-03-14 | 2020-03-31 | Ecolab Usa Inc. | Enzyme-containing detergent and presoak composition and methods of using |
US20180371381A1 (en) * | 2017-06-26 | 2018-12-27 | Ecolab Usa Inc. | Method of dishwashing comprising detergent compositions substantially free of polycarboxylic acid polymers |
US10865367B2 (en) * | 2017-06-26 | 2020-12-15 | Ecolab Usa Inc. | Method of dishwashing comprising detergent compositions substantially free of polycarboxylic acid polymers |
US20210062117A1 (en) * | 2017-06-26 | 2021-03-04 | Ecolab Usa Inc. | Method of dishwashing comprising detergent compositions substantially free of polycarboxylic acid polymers |
US11685882B2 (en) * | 2017-06-26 | 2023-06-27 | Ecolab Usa Inc. | Method of dishwashing comprising detergent compositions substantially free of polycarboxylic acid polymers |
WO2022094265A1 (en) | 2020-10-30 | 2022-05-05 | Ecolab Usa Inc. | Reducing agent as corrosion inhibitor for machine warewash |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: FIRST WISCONSIN NATIONAL BANK OF MILWAUKEE, A NATI Free format text: SECURITY INTEREST;ASSIGNOR:PABST BREWING COMPANY A DE CORP.;REEL/FRAME:004129/0649 Effective date: 19830321 Owner name: LAWYERS TITLE COMPANY OF WASHINGTON, INC. (TRUSTEE Free format text: SECURITY INTEREST;ASSIGNOR:PABST BREWING COMPANY A DE CORP.;REEL/FRAME:004129/0649 Effective date: 19830321 |
|
AS | Assignment |
Owner name: PMP ACQUISITION CORPORATION, A DE CORP. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:PAPST BREWING COMPANY;REEL/FRAME:004390/0892 Effective date: 19841231 |