CA2434273A1 - Stable solid enzyme compositions and methods employing them - Google Patents

Stable solid enzyme compositions and methods employing them Download PDF

Info

Publication number
CA2434273A1
CA2434273A1 CA002434273A CA2434273A CA2434273A1 CA 2434273 A1 CA2434273 A1 CA 2434273A1 CA 002434273 A CA002434273 A CA 002434273A CA 2434273 A CA2434273 A CA 2434273A CA 2434273 A1 CA2434273 A1 CA 2434273A1
Authority
CA
Canada
Prior art keywords
composition
bicarbonate
carbonate
enzyme
weight ratio
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.)
Granted
Application number
CA002434273A
Other languages
French (fr)
Other versions
CA2434273C (en
Inventor
James J. Tarara
Sally K. Swart
Tareasa Lynn Bradley
Reid Rabon
Denise Chandler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab Inc
Original Assignee
Ecolab Inc.
James J. Tarara
Sally K. Swart
Tareasa Lynn Bradley
Reid Rabon
Denise Chandler
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ecolab Inc., James J. Tarara, Sally K. Swart, Tareasa Lynn Bradley, Reid Rabon, Denise Chandler filed Critical Ecolab Inc.
Publication of CA2434273A1 publication Critical patent/CA2434273A1/en
Application granted granted Critical
Publication of CA2434273C publication Critical patent/CA2434273C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • 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
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
    • 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
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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
    • C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase
    • C11D2111/20—

Abstract

The present invention relates to a solid enzyme cleaning composition in which the enzyme is stable in the presence of mixtures of carbonate and bicarbonate at alkaline pH, and methods employing this composition. The enzyme cleaning composition preferably employs weight ratios of carbonate and bicarbonate to stabilize one or more enzymes in a solid, a concentrate, and/or a use composition, and at temperatures higher than ambient.

Claims (31)

1. A solid enzyme cleaning composition comprising detersive enzyme and a mixture of carbonate and bicarbonate; the carbonate and bicarbonate being present in a weight ratio of about 0.5:1 to about 4.75:1;
wherein the ratio of carbonate to bicarbonate is selected to increase stability of the detersive enzyme.
2. The composition of claim 1, wherein the weight ratio of carbonate to bicarbonate is in the range of about 1:1 to about 3:1.
3. The composition of claim 2, wherein the weight ratio of carbonate to bicarbonate is about 2:1, or about 3:1.
4. The composition of claim 1, wherein the carbonate comprises sodium carbonate.
5. The composition of claim 4, comprising about 30 to about 50 weight percent carbonate.
6. The composition of claim 1, wherein the bicarbonate comprises sodium bicarbonate.
7. The composition of claim 6, comprising about 10 to about 20 weight percent bicarbonate.
8. The composition of claim 1, wherein the mixture of carbonate and bicarbonate stabilizes the enzyme in use compositions at use temperatures.
9. The composition of claim 8, wherein the detersive enzyme retains at least about 50% of its initial activity at 120 °F for at least about 30 minutes after forming a use composition.
10. The composition of claim 1, wherein the mixture of carbonate and bicarbonate stabilizes the enzyme in the solid composition at ambient temperature.
11. The composition of claim 1, further comprising an E-form hydrate.
12. The composition of claim 1, wherein the detersive enzyme comprises protease, amylase, lipase, cellulase, peroxidase, gluconase, or a combination thereof.
13. The composition of claim 12, wherein the detersive enzyme comprises alkaline protease, lipase, amylase, or a combination thereof.
14. The composition of claim 1, further comprising nonionic surfactant, builder, and chelating agent.
15. The composition of claim 14, wherein the nonionic surfactant comprises nonyl phenol ethoxylate, the builder comprises tripolyphosphate, and the chelating agent comprises amino tri(methylene phosphonic acid) (ATMP).
16. The composition of claim 15, comprising about 8 wt-% nonyl phenol ethoxylate, about 18 wt-% tripolyphosphate, about 4 wt-% protease, and about 5 wt-%ATMP.
17. The composition of claim 15, comprising about 8 wt-% nonyl phenol ethoxylate 9.5, about 17 wt-% tripolyphosphate, about 8 wt-% protease, and about 5 wt-% ATMP.
18. The composition of claim 15, comprising about 7.5 wt-% nonyl phenol ethoxylate 9.5, about 20 wt-% tripolyphosphate, about 1 wt-% protease, and about 7 wt-% ATMP.
19. A method of cleaning an instrument, comprising:

dissolving a solid enzyme cleaning composition in water, the solid enzyme cleaning composition comprising detersive enzyme and a mixture of carbonate and bicarbonate; the carbonate and bicarbonate being present in a weight ratio of about 0.5:1 to about 4.75:1;
contacting the instrument with the dissolved solid enzyme cleaning composition at a temperature at or above ambient temperature.
20. The method of claim 19, wherein the weight ratio of carbonate to bicarbonate is in the range of about 1:1 to about 3:1.
21. The method of claim 20, wherein the composition comprises about 3 to about 73 weight percent carbonate.
22. The method of claim 20, wherein the composition comprises about 1 to about 30 weight percent bicarbonate.
23. The method of claim 19, wherein the composition further comprises an E-form hydrate.
24. The method of claim 19, wherein the detersive enzyme retains at least about 50% of its initial activity at 120 °F for at least about 30 minutes after dissolving the composition.
25. The method of claim 19, wherein the detersive enzyme comprises protease, amylase, lipase, cellulase, peroxidase, gluconase, or a combination thereof.
26. The method of claim 19, wherein the composition further comprises nonionic surfactant, builder, and chelating agent.
27. The method of claim 26, wherein the nonionic surfactant comprises nonyl phenol ethoxylate, the builder comprises tripolyphosphate, and the chelating agent comprises amino tri(methylene phosphoric acid) (ATMP).
28. A liquid concentrate composition comprising water, detersive enzyme, and a mixture of carbonate and bicarbonate; the carbonate and bicarbonate being present in a weight ratio of about 0.5:1 to about 4.75:1.
29. The liquid concentrate composition of claim 28, comprising about 0.3 to about 4 wt-% water.
30. A use composition comprising water, detersive enzyme, and a mixture of carbonate and bicarbonate; the carbonate and bicarbonate being present in a weight ratio of about 0.5:1 to about 4.75:1.
31. The use composition of claim 30, comprising about 99 to about 99.97 wt-% water.
CA2434273A 2001-02-01 2001-12-21 Stable solid enzyme compositions and methods employing them Expired - Lifetime CA2434273C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/773,965 2001-02-01
US09/773,965 US6638902B2 (en) 2001-02-01 2001-02-01 Stable solid enzyme compositions and methods employing them
PCT/US2001/050778 WO2002061026A1 (en) 2001-02-01 2001-12-21 Stable solid enzyme compositions and methods employing them

Publications (2)

Publication Number Publication Date
CA2434273A1 true CA2434273A1 (en) 2002-08-08
CA2434273C CA2434273C (en) 2011-11-15

Family

ID=25099848

Family Applications (1)

Application Number Title Priority Date Filing Date
CA2434273A Expired - Lifetime CA2434273C (en) 2001-02-01 2001-12-21 Stable solid enzyme compositions and methods employing them

Country Status (8)

Country Link
US (2) US6638902B2 (en)
EP (1) EP1356016B1 (en)
AT (1) ATE340237T1 (en)
CA (1) CA2434273C (en)
DE (1) DE60123284T2 (en)
ES (1) ES2273908T3 (en)
PL (1) PL199653B1 (en)
WO (1) WO2002061026A1 (en)

Families Citing this family (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6010729A (en) 1998-08-20 2000-01-04 Ecolab Inc. Treatment of animal carcasses
US7795199B2 (en) * 2000-06-29 2010-09-14 Ecolab Inc. Stable antimicrobial compositions including spore, bacteria, fungi, and/or enzyme
US7150884B1 (en) 2000-07-12 2006-12-19 Ecolab Inc. Composition for inhibition of microbial growth
US6514556B2 (en) 2000-12-15 2003-02-04 Ecolab Inc. Method and composition for washing poultry during processing
US20030136942A1 (en) * 2001-11-30 2003-07-24 Smith Kim R. Stabilized active oxygen compositions
US7179781B2 (en) * 2003-05-02 2007-02-20 Ecolab Inc. Heterogeneous cleaning composition
US7504123B2 (en) * 2004-01-09 2009-03-17 Ecolab Inc. Methods for washing poultry during processing with medium chain peroxycarboxylic acid compositions
JP2007520479A (en) 2004-01-09 2007-07-26 イーコラブ インコーポレイティド Medium chain peroxycarboxylic acid composition
US7507429B2 (en) 2004-01-09 2009-03-24 Ecolab Inc. Methods for washing carcasses, meat, or meat products with medium chain peroxycarboxylic acid compositions
US7771737B2 (en) 2004-01-09 2010-08-10 Ecolab Inc. Medium chain peroxycarboxylic acid compositions
US8999175B2 (en) 2004-01-09 2015-04-07 Ecolab Usa Inc. Methods for washing and processing fruits, vegetables, and other produce with medium chain peroxycarboxylic acid compositions
US7887641B2 (en) 2004-01-09 2011-02-15 Ecolab Usa Inc. Neutral or alkaline medium chain peroxycarboxylic acid compositions and methods employing them
US7135449B2 (en) * 2004-02-20 2006-11-14 Milliken & Company Composition for removal of odors and contaminants from textiles and method
US20060019859A1 (en) * 2004-07-23 2006-01-26 Melani Duran Powder dilutable multi-surface cleaner
US20060293212A1 (en) * 2005-05-05 2006-12-28 Ecolab Inc. Stable solid compositions of spores, bacteria, fungi and/or enzyme
US7754670B2 (en) 2005-07-06 2010-07-13 Ecolab Inc. Surfactant peroxycarboxylic acid compositions
EP1876226B1 (en) * 2006-07-07 2011-03-23 The Procter & Gamble Company Detergent compositions
US7547421B2 (en) 2006-10-18 2009-06-16 Ecolab Inc. Apparatus and method for making a peroxycarboxylic acid
US8075857B2 (en) 2006-10-18 2011-12-13 Ecolab Usa Inc. Apparatus and method for making a peroxycarboxylic acid
US7888303B2 (en) * 2007-05-04 2011-02-15 Ecolab Inc. Solidification matrix
US7763576B2 (en) * 2008-01-04 2010-07-27 Ecolab Inc. Solidification matrix using a polycarboxylic acid polymer
US7893012B2 (en) * 2007-05-04 2011-02-22 Ecolab Inc. Solidification matrix
US8338352B2 (en) * 2007-05-07 2012-12-25 Ecolab Usa Inc. Solidification matrix
US7759300B2 (en) * 2007-07-02 2010-07-20 Ecolab Inc. Solidification matrix including a salt of a straight chain saturated mono-, di-, or tri- carboxylic acid
US8759269B2 (en) * 2007-07-02 2014-06-24 Ecolab Usa Inc. Solidification matrix including a salt of a straight chain saturated mono-, di-, and tri- carboxylic acid
US8999912B2 (en) * 2007-07-09 2015-04-07 The Procter & Gamble Company Detergent compositions
US8198228B2 (en) * 2008-01-04 2012-06-12 Ecolab Usa Inc. Solidification matrix using an aminocarboxylate
US8138138B2 (en) * 2008-01-04 2012-03-20 Ecolab Usa Inc. Solidification matrix using a polycarboxylic acid polymer
US8951956B2 (en) 2008-01-04 2015-02-10 Ecolab USA, Inc. Solid tablet unit dose oven cleaner
US8772221B2 (en) 2008-01-04 2014-07-08 Ecolab Usa Inc. Solidification matrices using phosphonocarboxylic acid copolymers and phosphonopolyacrylic acid homopolymers
US20090263884A1 (en) * 2008-04-22 2009-10-22 Organica Biotech, Inc. Multi-action drain cleaning composition and method
US7964548B2 (en) * 2009-01-20 2011-06-21 Ecolab Usa Inc. Stable aqueous antimicrobial enzyme compositions
US7723281B1 (en) 2009-01-20 2010-05-25 Ecolab Inc. Stable aqueous antimicrobial enzyme compositions comprising a tertiary amine antimicrobial
JP5624127B2 (en) * 2009-05-26 2014-11-12 エコラボ ユーエスエー インコーポレイティド Pot and pan soaking composition
US8530403B2 (en) * 2009-11-20 2013-09-10 Ecolab Usa Inc. Solidification matrix using a maleic-containing terpolymer binding agent
US20110124547A1 (en) * 2009-11-23 2011-05-26 Ecolab Inc. Solidification matrix using a sulfonated/carboxylated polymer binding agent
US20110174340A1 (en) * 2010-01-20 2011-07-21 Ecolab USA Low and high temperature enzymatic system
US9388369B2 (en) 2010-08-20 2016-07-12 Ecolab Usa Inc. Wash water maintenance for sustainable practices
US9949477B2 (en) 2010-12-30 2018-04-24 Kimberly-Clark Worldwide, Inc. Durable antimicrobial composition
WO2013024143A1 (en) * 2011-08-18 2013-02-21 Unilever Plc Enzyme system
US8748365B2 (en) * 2012-09-13 2014-06-10 Ecolab Usa Inc. Solidification matrix comprising phosphinosuccinic acid derivatives
US8871699B2 (en) 2012-09-13 2014-10-28 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US20140308162A1 (en) 2013-04-15 2014-10-16 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing
US9133420B2 (en) 2013-01-08 2015-09-15 Ecolab Usa Inc. Methods of using enzyme compositions
JP2017503061A (en) 2013-11-11 2017-01-26 エコラボ ユーエスエー インコーポレイティド Multi-purpose enzyme detergent and method for stabilizing use solution
US9353335B2 (en) 2013-11-11 2016-05-31 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
EP3167037A1 (en) * 2014-07-08 2017-05-17 Novozymes A/S Organic film removal from plastic objects
EP3381284A1 (en) * 2015-09-17 2018-10-03 Ecolab USA Inc. Triamine solidification using diacids
US11021680B2 (en) * 2016-09-07 2021-06-01 Ecolab Usa Inc. Detergent compositions containing a stabilized enzyme by phosphonates
MX2019004601A (en) 2016-10-18 2019-06-17 Sterilex LLC Ambient moisture-activated surface treatment powder.
JP6982092B2 (en) 2017-03-29 2021-12-17 エコラボ ユーエスエー インコーポレイティド Detergent composition and aluminum discoloration prevention method
JP6955030B2 (en) 2017-04-27 2021-10-27 エコラボ ユーエスエー インコーポレイティド Solid Control Release Carbonate Detergent Composition
US10633616B2 (en) 2017-05-01 2020-04-28 Ecolab Usa Inc. Alkaline warewash detergent for aluminum surfaces
EP3710569A1 (en) 2017-11-14 2020-09-23 Ecolab USA Inc. Solid controlled release caustic detergent compositions
AU2019222696B2 (en) 2018-02-14 2024-02-29 Ecolab Usa Inc. Compositions and methods for the reduction of biofilm and spores from membranes
CA3093298C (en) * 2018-03-08 2024-01-23 Ecolab Usa Inc. Solid enzymatic detergent compositions and methods of use and manufacture
CA3093389C (en) 2018-03-13 2024-02-13 Ecolab Usa Inc. Alkaline warewash detergent composition comprising a terpolymer
US11607323B2 (en) 2018-10-15 2023-03-21 Howmedica Osteonics Corp. Patellofemoral trial extractor
CA3128363A1 (en) 2019-01-31 2020-08-06 Ecolab Usa Inc. Laundry machine kit to enable control of water levels, recirculation, and spray of chemistry
US20200248383A1 (en) 2019-01-31 2020-08-06 Ecolab Usa Inc. Rinse water reuse system and methods of use
US11572652B2 (en) 2019-01-31 2023-02-07 Ecolab Usa Inc. Controlling water levels and detergent concentration in a wash cycle
WO2020160429A1 (en) 2019-01-31 2020-08-06 Ecolab Usa Inc. Controller for a rinse water reuse system and methods of use
CN113490735A (en) 2019-02-28 2021-10-08 埃科莱布美国股份有限公司 Hardness additive and detergent bar containing same for improving edge hardening
WO2022140505A1 (en) 2020-12-23 2022-06-30 Ecolab Usa Inc. Soil removal on cotton via treatment in the rinse step for enhanced cleaning in the subsequent wash
WO2022140522A1 (en) 2020-12-23 2022-06-30 Ecolab Usa Inc. Laundry sour softener with extra stability and additional benefits of laundry fire mitigation and sunscreen removal
WO2023122196A1 (en) 2021-12-22 2023-06-29 Ecolab Usa Inc. Compositions comprising multiple charged cationic compounds for soil release

Family Cites Families (154)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US561452A (en) * 1896-06-02 Harrow
US363852A (en) * 1887-05-31 Moeeis l
US297183A (en) * 1884-04-22 Sidney f
US364840A (en) * 1887-06-14 Mold for blowing turned bottles
US501375A (en) * 1893-07-11 Ball-bearing
US161596A (en) * 1875-04-06 Improvement in preparing fish for market
US1580576A (en) 1924-03-08 1926-04-13 Weidner Edmund Perfumed soap cake
US1596756A (en) * 1925-03-05 1926-08-17 Grace W Murphy Auto semishade
US1949264A (en) 1929-03-20 1934-02-27 R M Hollingshead Co Method of making soap solution
US1976567A (en) * 1931-02-21 1934-10-09 Leg O Matic Company Folding chair
US2003913A (en) * 1933-12-01 1935-06-04 Bell Telephone Labor Inc Position controlling device
US2271120A (en) * 1938-10-27 1942-01-27 Honeywell Regulator Co Compensated two-stage hot air control system
US2412819A (en) 1945-07-21 1946-12-17 Mathieson Alkali Works Inc Detergent briquette
US2927900A (en) 1951-07-10 1960-03-08 Gen Aniline & Film Corp Solid detergent composition and process for preparation thereof
US2987483A (en) 1956-07-02 1961-06-06 Pennsalt Chemicals Corp Cleaning composition
US2920417A (en) 1958-01-22 1960-01-12 Sylvia T Wertheimer Detergent-solution dispensing container
US3048548A (en) 1959-05-26 1962-08-07 Economics Lab Defoaming detergent composition
NL285082A (en) 1962-02-28
NL293412A (en) 1962-06-06
US3392121A (en) 1962-11-05 1968-07-09 Procter & Gamble Built detergent compositions
US3356612A (en) 1965-02-01 1967-12-05 Petrolite Corp Stable detergent compositions
US3390092A (en) 1965-03-30 1968-06-25 Fmc Corp Dishwashing detergent preparations containing sodium or potassium dichloroisocyanurate
US3306858A (en) 1965-06-17 1967-02-28 Economics Lab Process for the preparation of storage stable detergent composition
US3441511A (en) 1965-12-20 1969-04-29 Wyandotte Chemicals Corp Alkali metal hydroxide-containing agglomerates
CA813301A (en) 1966-09-06 1969-05-20 E. Zimmerer Roger Detergent composition
US3442242A (en) 1967-06-05 1969-05-06 Algonquin Shipping & Trading Stopping and manoeuvering means for large vessels
US3557003A (en) 1967-06-21 1971-01-19 Procter & Gamble Detergent tablet
GB1240058A (en) 1968-04-12 1971-07-21 Procter & Gamble Enzyme-containing detergent compositions
US3639286A (en) 1968-05-28 1972-02-01 Mario Ballestra Synthetic detergent in bar or cake form and the method to manufacture same
US3491028A (en) 1969-06-03 1970-01-20 Grace W R & Co Chlorine stable machine dishwashing composition
JPS4835329B1 (en) 1969-12-03 1973-10-27
US3856932A (en) 1969-12-16 1974-12-24 M May Tablet of a chlorine releasing solid compound
US3695989A (en) 1970-08-12 1972-10-03 Robert E Albert Cold water soluble foam plastic package
CA959370A (en) 1970-09-08 1974-12-17 William G. Mizuno Machine dishwashing detergent having a reduced condensed phosphate content
US3846346A (en) 1971-01-25 1974-11-05 Philadelphia Quartz Co Detergent composition with controlled alkalinity
US3941710A (en) 1972-04-24 1976-03-02 Lever Brothers Company Phosphate - free dishwashing compositions containing an alkyl polyether carboxylate surfactant
US3816320A (en) 1972-11-24 1974-06-11 Fmc Corp Stable dishwashing compositions containing sodium dichloroisocyanurate dihydrate
US4605509A (en) 1973-05-11 1986-08-12 The Procter & Gamble Company Detergent compositions containing sodium aluminosilicate builders
US3965989A (en) * 1973-09-24 1976-06-29 International Harvester Company Flexible plow
US3933670A (en) 1973-11-12 1976-01-20 Economic Laboratories, Inc. Process for making agglomerated detergents
US4274975A (en) 1974-03-11 1981-06-23 The Procter & Gamble Company Detergent composition
US3985669A (en) 1974-06-17 1976-10-12 The Procter & Gamble Company Detergent compositions
US4148603A (en) 1974-10-04 1979-04-10 Henkel Kommanditgesellschaft Auf Aktien Method of washing textiles and composition containing inorganic silicates and polycarboxylates and/or polyphosphonates
US4000080A (en) 1974-10-11 1976-12-28 The Procter & Gamble Company Low phosphate content detergent composition
GB1516848A (en) 1974-11-13 1978-07-05 Procter & Gamble Ltd Detergent composition
FR2298599A2 (en) 1975-01-24 1976-08-20 Sifrance NEW SOLID NON-CORROSIVE DETERGENT COMPOSITIONS
US3961754A (en) 1975-09-12 1976-06-08 Economics Laboratory, Inc. Spray and foam producing nozzle apparatus
CA1092476A (en) 1976-02-23 1980-12-30 Philip M. Sabatelli Detergent composition and its use in a dishwashing machine
US4105573A (en) 1976-10-01 1978-08-08 The Procter & Gamble Company Dishwasher detergent composition
USRE32762E (en) 1977-01-17 1988-10-11 Ballantine Laboratories, Inc. Adjustable instrument case
GB1596756A (en) 1977-04-22 1981-08-26 Procter & Gamble Ltd Detergent compositions
CA1120819A (en) 1977-06-01 1982-03-30 Jurgen W.K. Gromer Detergent tablet
NZ188209A (en) 1977-09-12 1980-04-28 Colgate Palmolive Co Free-flowing, phosphate-free, particulate, heavy-duty laundry detergent
NZ188469A (en) 1977-10-06 1980-12-19 Colgate Palmolive Co Detergent composition comprising a univalent cation-exchanging zeolite a nonionic detergent and builder salts
US4329246A (en) 1977-11-07 1982-05-11 The Procter & Gamble Company Alkaline dishwasher detergent
USRE32818E (en) 1978-02-07 1989-01-03 Ecolab Inc. Cast detergent-containing article and method of using
USRE32763E (en) 1978-02-07 1988-10-11 Ecolab Inc. Cast detergent-containing article and method of making and using
US4212761A (en) * 1978-03-06 1980-07-15 Novo Laboratories, Inc. Method and composition for cleaning dairy equipment
US4238345A (en) 1978-05-22 1980-12-09 Economics Laboratory, Inc. Stabilized liquid enzyme-containing detergent compositions
US4289815A (en) 1978-06-26 1981-09-15 Airwick Industries, Inc. Cold water-insoluble polyvinyl alcohol pouch for the controlled release of active ingredients
MX151028A (en) 1978-11-17 1984-09-11 Unilever Nv IMPROVEMENTS IN INSOLUBLE BAG BUT PERMEABLE TO WATER THAT HAS A DISPERSIBLE PROTECTIVE LAYER OR SOLUBLE IN WATER, WHICH CONTAINS A PARTICULATE DETERGENT COMPOSITION
US4211517A (en) 1978-11-27 1980-07-08 Bender Machine Works, Inc. Detergent supply control for automatic dishwasher
US4426362A (en) 1978-12-05 1984-01-17 Economics Laboratory, Inc. Solid block detergent dispenser
US4216125A (en) 1978-12-07 1980-08-05 Pq Corporation Detergent compositions with silane-zeolite silicate builder
US4243543A (en) 1979-05-11 1981-01-06 Economics Laboratory, Inc. Stabilized liquid enzyme-containing detergent compositions
US4261868A (en) 1979-08-08 1981-04-14 Lever Brothers Company Stabilized enzymatic liquid detergent composition containing a polyalkanolamine and a boron compound
US4284532A (en) 1979-10-11 1981-08-18 The Procter & Gamble Company Stable liquid detergent compositions
US4276205A (en) 1980-02-04 1981-06-30 The Procter & Gamble Company Detergent compositions containing amine oxide and nonionic surfactants and polyethylene glycol
US4268406A (en) 1980-02-19 1981-05-19 The Procter & Gamble Company Liquid detergent composition
US4481167A (en) 1980-04-11 1984-11-06 The Dow Chemical Company Sanitizing complexes of polyoxazolines or polyoxazines and polyhalide anions
US4692494A (en) 1980-12-15 1987-09-08 Colgate-Palmolive Company Water soluble films of polyvinyl alcohol and polyacrylic acid and packages comprising same
US4359413A (en) 1981-03-17 1982-11-16 The Procter & Gamble Company Solid detergent compositions containing alpha-amine oxide surfactants
GR77642B (en) 1981-09-25 1984-09-25 Procter & Gamble
DE3232616A1 (en) 1982-09-02 1984-03-08 Henkel KGaA, 4000 Düsseldorf LIQUID, INORGANIC FRUIT SALT, IN ESSENTIAL FREE DETERGENT AND CLEANING AGENT
US4664848A (en) 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
DE3315950A1 (en) 1983-05-02 1984-11-15 Henkel KGaA, 4000 Düsseldorf METHOD FOR PRODUCING DETERGENT TABLETS
US4474976A (en) 1983-08-29 1984-10-02 General Electric Company Method of producing phenyl silanes
JPS60189108A (en) 1984-03-08 1985-09-26 日本石油化学株式会社 Electrically insulating oil and oil-immersed electric device
US4608187A (en) 1984-04-02 1986-08-26 The Clorox Company Rubber toughened polyvinyl alcohol film compositions
US4537706A (en) 1984-05-14 1985-08-27 The Procter & Gamble Company Liquid detergents containing boric acid to stabilize enzymes
DE3418494A1 (en) 1984-05-18 1985-11-21 Hoechst Ag, 6230 Frankfurt DETERGENT AND CLEANING AGENT
GB8415302D0 (en) 1984-06-15 1984-07-18 Unilever Plc Fabric washing process
US4594175A (en) 1984-08-29 1986-06-10 Economics Laboratory, Inc. Mechanical dishwashing rinse composition having a low foaming sulfonic acid rinsing agent, a hydrotrope and a source of active halogen
US4680134A (en) 1984-10-18 1987-07-14 Ecolab Inc. Method for forming solid detergent compositions
US4595520A (en) 1984-10-18 1986-06-17 Economics Laboratory, Inc. Method for forming solid detergent compositions
US5254287A (en) 1985-08-21 1993-10-19 The Clorox Company Encapsulated enzyme in dry bleach composition
US4677130A (en) 1985-10-07 1987-06-30 Great Lakes Chemical Corporation Process of densification of N-halohydantoin compositions and products thereof
US4715979A (en) 1985-10-09 1987-12-29 The Procter & Gamble Company Granular detergent compositions having improved solubility
US4690305A (en) 1985-11-06 1987-09-01 Ecolab Inc. Solid block chemical dispenser for cleaning systems
US4687121A (en) 1986-01-09 1987-08-18 Ecolab Inc. Solid block chemical dispenser for cleaning systems
US4858449A (en) 1986-01-09 1989-08-22 Ecolab Inc. Chemical solution dispenser apparatus and method of using
US4836951A (en) 1986-02-19 1989-06-06 Union Carbide Corporation Random polyether foam control agents
US4725376A (en) 1986-04-23 1988-02-16 Ecolab Inc. Method of making solid cast alkaline detergent composition
US4826661A (en) 1986-05-01 1989-05-02 Ecolab, Inc. Solid block chemical dispenser for cleaning systems
US4698181A (en) 1986-06-30 1987-10-06 The Procter & Gamble Company Detergent compositions containing triethylenetetraminehexaacetic acid
US4753755A (en) 1986-08-25 1988-06-28 Diversey Wyandotte Corporation Solid alkaline detergent and process for making the same
US4845965A (en) 1986-12-23 1989-07-11 Ecolab Inc. Method and apparatus for dispensing solutions
US4965012A (en) 1987-04-17 1990-10-23 Olson Keith E Water insoluble encapsulated enzymes protected against deactivation by halogen bleaches
US5019292A (en) 1987-06-30 1991-05-28 The Procter & Gamble Company Detergent compositions
US4830773A (en) 1987-07-10 1989-05-16 Ecolab Inc. Encapsulated bleaches
US5078301A (en) 1987-10-02 1992-01-07 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5034147A (en) 1988-01-19 1991-07-23 Colgate-Palmolive Company Process for manufacture of built synthetic organic detergent composition patties
US4895667A (en) 1988-05-24 1990-01-23 The Dial Corporation Fabric treating compositions
US5080819A (en) 1988-05-27 1992-01-14 Ecolab Inc. Low temperature cast detergent-containing article and method of making and using
US4846993A (en) 1988-07-11 1989-07-11 Ecolab Inc. Zero phosphate warewashing detergent composition
US4970058A (en) 1988-10-06 1990-11-13 Fmc Corporation Soda ash peroxygen carrier
US4966762A (en) 1988-10-06 1990-10-30 Fmc Corporation Process for manufacturing a soda ash peroxygen carrier
DE4010533A1 (en) 1990-04-02 1991-10-10 Henkel Kgaa Prodn. of high-density detergent granules
US4983315A (en) 1989-08-10 1991-01-08 The Procter & Gamble Company N,N'-(1-oxo-1,2-ethanediyl)-bis(aspartic acid), salts and use in detergent compositions
DD297183A5 (en) * 1989-08-22 1992-01-02 Joh. A. Benckiser Gmbh,De MASCHINENGESCHIRRSPUELMITTEL
US5061392A (en) 1990-02-07 1991-10-29 Dubois Chemicals, Inc. Method of making paste detergent and product produced
DE4007601A1 (en) 1990-03-09 1991-09-12 Henkel Kgaa METHOD FOR PRODUCING GRANULES OF A DETERGENT OR CLEANING AGENT
DE69133526T2 (en) 1990-04-05 2006-09-07 Kao Corp. Detergent composition
US5064561A (en) 1990-05-09 1991-11-12 Diversey Corporation Two-part clean-in-place system
US5358653A (en) 1990-06-25 1994-10-25 Ecolab, Inc. Chlorinated solid rinse aid
AU687075B2 (en) 1990-07-09 1998-02-19 Amrad Operations Pty. Limited Enhanced implantation, development and maintenance of embryos using leukaemia inhibitory factor
US5122538A (en) 1990-07-23 1992-06-16 Ecolab Inc. Peroxy acid generator
US5118426A (en) 1990-07-26 1992-06-02 Olin Corporation Process for purifying impotable water with hypochlorous acid
DE69229806T2 (en) 1991-01-22 1999-12-16 Kao Corp Detergent composition
JPH04271785A (en) 1991-02-28 1992-09-28 Kao Corp Enzymic solid pharmaceutical and its production
US5316688A (en) 1991-05-14 1994-05-31 Ecolab Inc. Water soluble or dispersible film covered alkaline composition
US5173207A (en) 1991-05-31 1992-12-22 Colgate-Palmolive Company Powered automatic dishwashing composition containing enzymes
US5234719A (en) 1991-06-04 1993-08-10 Ecolab Inc. Food additive sanitizing compositions
DE4134078A1 (en) 1991-10-15 1993-04-22 Henkel Kgaa CONCENTRATED AQUEOUS LIQUID DETERGENT
US5559089A (en) 1992-03-12 1996-09-24 The Procter & Gamble Company Low-dosage automatic dishwashing detergent with monopersulfate and enzymes
EP0561452A1 (en) 1992-03-20 1993-09-22 Unilever N.V. Machine dishwashing composition containing polyaminoacids as builders
US5223179A (en) 1992-03-26 1993-06-29 The Procter & Gamble Company Cleaning compositions with glycerol amides
US5516449A (en) 1992-04-03 1996-05-14 The Procter & Gamble Company Detergent compositions
US5691292A (en) 1992-04-13 1997-11-25 The Procter & Gamble Company Thixotropic liquid automatic dishwashing composition with enzyme
GB9220669D0 (en) 1992-09-30 1992-11-11 Unilever Plc Detergent composition
US5292525A (en) 1992-10-14 1994-03-08 Merck & Co., Inc. Method and composition for removing an alginate from a cutaneous substrate
US5589099A (en) 1993-04-20 1996-12-31 Ecolab Inc. Low foaming rinse agents comprising ethylene oxide/propylene oxide block copolymer
US5858299A (en) 1993-05-05 1999-01-12 Ecolab, Inc. Process for consolidating particulate solids
US5370729A (en) 1993-09-15 1994-12-06 Ecolab Inc. Food safe composition to facilitate soil removal
US5494817A (en) 1993-12-06 1996-02-27 Allergan, Inc. Sugar-based protease composition for use with constant-PH borate buffers
AU1516795A (en) 1993-12-30 1995-07-17 Ecolab Inc. Method of making non-caustic solid cleaning compositions
US5474698A (en) 1993-12-30 1995-12-12 Ecolab Inc. Urea-based solid alkaline cleaning composition
US5578134A (en) 1994-04-19 1996-11-26 Ecolab Inc. Method of sanitizing and destaining tableware
AU2925495A (en) 1994-07-04 1996-01-25 Unilever Plc Washing process and composition
US5665694A (en) 1994-07-22 1997-09-09 Monsanto Company Block detergent containing nitrilotriacetic acid
US5419850A (en) 1994-07-22 1995-05-30 Monsanto Company Block detergent containing nitrilotriacetic acid
US5858117A (en) 1994-08-31 1999-01-12 Ecolab Inc. Proteolytic enzyme cleaner
US5861366A (en) 1994-08-31 1999-01-19 Ecolab Inc. Proteolytic enzyme cleaner
ATE195001T1 (en) 1995-04-17 2000-08-15 Procter & Gamble PRODUCTION AND USE OF COMPOSITE PARTICLES CONTAINING DIACYL PEROXIDE
GB9519607D0 (en) * 1995-09-26 1995-11-29 Procter & Gamble Detergent composition
WO1997033957A1 (en) 1996-03-15 1997-09-18 Amway Corporation Powder detergent composition having improved solubility
MA25183A1 (en) 1996-05-17 2001-07-02 Arthur Jacques Kami Christiaan DETERGENT COMPOSITIONS
ZA974226B (en) * 1996-05-17 1998-12-28 Procter & Gamble Detergent composition
CA2251779A1 (en) * 1996-06-20 1997-12-24 Bruno Suri Method for the prevention and treatment of mastitis
US6156715A (en) * 1997-01-13 2000-12-05 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6177392B1 (en) * 1997-01-13 2001-01-23 Ecolab Inc. Stable solid block detergent composition
US5876514A (en) 1997-01-23 1999-03-02 Ecolab Inc. Warewashing system containing nonionic surfactant that performs both a cleaning and sheeting function and a method of warewashing
US6017864A (en) 1997-12-30 2000-01-25 Ecolab Inc. Alkaline solid block composition
US6551981B1 (en) * 1998-07-17 2003-04-22 Patrizio Ricci Detergent tablet

Also Published As

Publication number Publication date
DE60123284D1 (en) 2006-11-02
US20020177541A1 (en) 2002-11-28
WO2002061026A1 (en) 2002-08-08
PL199653B1 (en) 2008-10-31
US6638902B2 (en) 2003-10-28
US20040072714A1 (en) 2004-04-15
EP1356016B1 (en) 2006-09-20
DE60123284T2 (en) 2007-01-11
EP1356016A1 (en) 2003-10-29
ES2273908T3 (en) 2007-05-16
ATE340237T1 (en) 2006-10-15
PL365817A1 (en) 2005-01-10
CA2434273C (en) 2011-11-15

Similar Documents

Publication Publication Date Title
CA2434273A1 (en) Stable solid enzyme compositions and methods employing them
EP0544777B1 (en) Enzymatic detergent composition and method for enzyme stabilization
US4965012A (en) Water insoluble encapsulated enzymes protected against deactivation by halogen bleaches
US4566985A (en) Method of cleaning using liquid compositions comprising stabilized mixtures of enzymes
US7326674B2 (en) Household cleaning composition in self-sustaining body form and essentially free of zeolite and clay
US8454757B2 (en) Phosphate and phosphonate-free automatic gel dishwashing detergent providing improved spotting and filming performance
WO2003029393A3 (en) Alkaline metal cleaner
EP2844729B1 (en) Detergent formulation for dishwashing machine
SK94296A3 (en) Enzymic preparation
US5527487A (en) Enzymatic detergent composition and method for enzyme stabilization
CA2458338A1 (en) Cleaning composition and method for using the same
EP1036840A2 (en) Detergent composition
EP0286773A2 (en) Water insoluble encapsulated enzymes protected against deactivation by halogen bleaches
CA2428069A1 (en) Compositions and methods for mitigating corrosion of applied color designs
WO1994023006A1 (en) Lavatory blocks containing enzymes
JP2009034062A (en) Alkaline protease
US5759984A (en) Enzyme stabilization
JPH07103394B2 (en) Detergent for automatic dishwasher
JP2714495B2 (en) Nonionic powder detergent composition
Wilkesman et al. HEAT STABLE PROTEASE FROM THE MARINE SPONGE GEODIA CJIDOVIUM
JP3429701B2 (en) Detergent composition
JPH07179900A (en) Detergent composition for automatic dishwasher
JP3069088B1 (en) Detergent composition
JP3771079B2 (en) Cleaning composition
WO2005097958A1 (en) Detergent composition and method of using same

Legal Events

Date Code Title Description
EEER Examination request
MKEX Expiry

Effective date: 20211221