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WO1996040856A1 - Nettoyeurs de cuvettes de w.c. contenant des inhibiteurs de l'urease - Google Patents

Nettoyeurs de cuvettes de w.c. contenant des inhibiteurs de l'urease Download PDF

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Publication number
WO1996040856A1
WO1996040856A1 PCT/US1996/007737 US9607737W WO9640856A1 WO 1996040856 A1 WO1996040856 A1 WO 1996040856A1 US 9607737 W US9607737 W US 9607737W WO 9640856 A1 WO9640856 A1 WO 9640856A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
urease
hydrogen
diaminophosphinyl
composition
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.)
Ceased
Application number
PCT/US1996/007737
Other languages
English (en)
Inventor
Henry Cheng Na
Karen Smith Howard-Nordan
Rodney Dean Bush
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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 Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of WO1996040856A1 publication Critical patent/WO1996040856A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D3/26—Organic compounds containing nitrogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0056—Lavatory cleansing blocks
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen

Definitions

  • This invention relates to toilet bowl cleaners containing an effective amount of urease enzyme inhibitor to prevent the build-up of soapy scums, bacterial slime and/or mineral deposits on the surface of toilet bowls and urinals.
  • the present compositions comprise a urease inhibitor and optional ingredients such as surfactants, builders, perfumes, abrasives, dyes, enzymes, biocides, oxidizing agents, reducing agents, and/or other carrier and adjunct materials.
  • This invention relates to a method of cleaning and sanitizing toilet bowls and urinals.
  • the invention is also directed to maintaining toilet bowls, urinals, sinks, showers and other hard surface areas in a state of sanitation. More particularly, it relates to a method wherein a urease enzyme inhibitor is employed in an effective amount to retard the bacterial mediated deposition of minerals, dirt and waste products onto the surface of a toilet bowl or urinal.
  • urease enzymes associated with microorganisms are inhibited in vitro, thereby retarding the cycle of bacterial growth/mineralization of toilet bowls or urinals. There has been a long standing need to retard the growth of bacteria associated with human waste receptacles.
  • ammonia causes an increase in the alkalinity of the urine affording an environment favorable to the formation of minerals such as struvite, (MgNH 4 PO 4 • 6H-O) and calcium phosphate (Ca ⁇ PO -), which are predominant components of infected urinary calculi, also known as "kidney stones".
  • minerals such as struvite, (MgNH 4 PO 4 • 6H-O) and calcium phosphate (Ca ⁇ PO -), which are predominant components of infected urinary calculi, also known as "kidney stones".
  • compositions of these articles typically include water soluble salts in the form of surfactants, buffers and builders.
  • water soluble salts in the form of surfactants, buffers and builders.
  • the cations of water soluble salts present in the "sanitizer” formulations will increase the concentration of dissolved "minerals" in the toilet bowl water, and depending on the inherent conditions of the urinal or toilet bowl, may provide a further source of "minerals" for deposition onto the surface of the toilet bowl.
  • Buffers are inco ⁇ orated into these "sanitizer" formulations for the purpose of mediating the toilet water pH levels but, due largely to the prodigious activity of urease enzymes, these attempts at alkalinity management can only be marginally effective. Indeed, given the amount of dissolved urea and other bacterial nutrients present in only one urinary void volume, an un-flushed toilet will soon overwhelm the buffer capacity of normal toilet tank introduced sanitizers.
  • Liquid cleaners that are used to scrub or scour urinals or toilet bowls may leave behind various levels of minerals or bacteria depending on the efficiency of the cleaning.
  • this act of sanitizing urinals and toilet bowls is not performed with any great deal of pleasure, but instead is a task of necessity, done primarily to ensure hygiene. It is therefore a matter of circumstance that the effectiveness of a liquid or solid cleaner used for scrubbing and scouring be as broadly effective as possible.
  • the inclusion of urease enzyme inhibitors will act on all urease present in the bowl or urinal and therefore render inactive any urease that remains adhered to the toilet bowl after cleaning.
  • a urinal or toilet bowl cleaned with the present invention will not leave behind active urease enzymes which will be in a position to further accelerate the already inexorable process of toilet soiling and mineral deposition.
  • the present invention provides for the cleaning and sanitation of toilets/ urinals by the in vitro inhibition of urease enzymes.
  • the goals/benefits to be observed by inhibition of urease enzymes in the toilet or urinal include one or more of:
  • An object of this invention is to provide an improved method for cleaning and sanitizing toilet bowls, urinals and other sanitary waste receptacles. It is another object herein to provide cleaners which deliver a urease inhibitor to toilet bowls or to the flush tanks thereby affecting the ability of bacteria to mediate the environment of toilet bowl water. It is a further object herein to provide cleaning compositions and processes which employ a urease inhibitor to increase the time that toilets can remain in a sanitary condition by inhibiting the urease enzymes associated with bacteria from creating a hospitable environment for growth.
  • the present invention also encompasses a method of inhibiting urease enzymes in a toilet bowl or urinal comprising contacting the surface of a toilet bowl or urinal with a composition comprising at least about 0.001 % by weight of a urease inhibitor, from about 1% to about 99%, preferably from about 1% to about 85%, by weight of a surfactant, the balance comprising an effective carrier and adjunct ingredients.
  • Adjunct ingredients can optionally include but are not limited to builders, bleaches, buffers, filler salts, perfumes, dyes and abrasives. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise noted.
  • hydroxamic acid and the substituted hydroxamic acids are hydroxamic acids and the substituted hydroxamic acids.
  • Acetohydroxamic and propionhydroxamic acid are the most common of the acyl substituted hydroxamic acids.
  • These two compounds, as well as the parent hydroxamic acid and the alkali or alkaline earth salts of said acids, are particularly efficacious in inhibiting urease enzyme activity in vitro. They are also particularly compatible with surfactants and other detersive ingredients that are found in common toilet bowl cleaners and flush tank additives.
  • phosphorus compounds have been prepared for in vivo use against urease activity.
  • phosphorus compounds found wide use in the laundry industry as detergent builders until environmental concerns predicated their removal.
  • the level of phosphorus compound needed to prevent substantial urease activity in toilet bowls and urinals described in the present invention does not begin to approach the quantity once used in laundry product.
  • Many of the pharmaceutical industry generated products are compatible with the environment due to their bio-degradability and the structure and oxidation state of the phosphorus containing moiety.
  • R HPfNH ⁇ wherein R is hydrogen, phenyl, substituted phenyl, alkyl, alkenyl, and other suitable moieties or preferably N-(diarr__nophospninyl)arylcarboxamides of the formula:
  • R is 3-pyridyl, 2-furanyl, 2-naphthyl, cinnamenyl, benzyl, phenyl, and substituted phenyl are efficacious as urease inhibitors in a toilet bowl cleaner and flush tank additive when added in an amount sufficient to inhibit the enzyme urease.
  • Other preferred urease inhibitors have the general formula:
  • R 1 and R 2 are the same or different and are hydrogen or alkyl having from 1 to about 4 carbon atoms;
  • the furanyl substituents can be substituted by one or more alkyl, amino, cyano, nitro, alkylamino, dialkylamino, aryl mercapto, isocyanato, trihalomethyl, alkoxy, thiocyano, alkanoyl and halogen moieties and mixtures thereof.
  • R or R 2 may each comprise the same or different di-substituted aryl or heterocyclic moiety such as 2,4-dichlorofuranyl, 2-chloro-4-methylfuranyl, or a tri-substituted moiety such as 2,4,6-trichlorophenyl, or 3,4,5-trichlorofuranyl.
  • a urease inhibitor in an effective amount to inhibit the urease enzyme is formulated into a solid cake for use in urinals, toilet bowls, or toilet flush tanks.
  • the following description of this embodiment of the invention, the manner and process of making and using it, pertains to magnesium alkyl sulfate. It will be understood that other alkali earth metal alkyl sulfates and other selected non-alkali metal alkyl sulfates can be used.
  • Cakes can contain alkali metal alkyl sulfates at levels of 2% to 25%, more or less, of the total cake surfactant content.
  • the cake compositions of the present invention comprise from about 20% to about 90% of an alkali earth metal and/or suitable transition metal alkyl sulfate surfactant wherein the alkyl group has a carbon chain length of from 8 to 22 carbon atoms, preferably from 10 to 16 carbon atoms.
  • Preferred surfactants are buffered; magnesium alkyl sulfate, calcium alkyl sulfate, tin alkyl sulfate, aluminum alkyl sulfate, and zinc alkyl sulfate.
  • the cakes of this embodiment of the invention contain at least 0.001 % to about 20 % of hydroxamic acid or a suitable alkyl substituted hydroxamic acid.
  • the embodiment of this invention as a cake may contain various optional materials in the compositions herein. See U.S. Pat. No. 4,278,571, Choy, issued July 14, 1981, and inco ⁇ orated herein by reference, for an extensive list of them. Steps for Making the "Surfactant -Cake” Embodiment of This Invention
  • the following method for making the "surfactant-cake” embodiment of this invention is herein provided and is not meant to be limiting or exclusive in its description.
  • the formulator may also wish to substitute materials and adjust the formulation as conditions dictate based on several factors such as, the nature of the urease inhibitor, the final desired pH of the cake, the surfactant, and the amount and content of optional ingredients.
  • Hardness readings are taken directly from the gauge, in units of tenths of millimeters.
  • Dispensing Means of Solid Cake Embodiment Dispensing means which can be used to dispense compositions of the present invention Solid Cake Embodiment into the toilet flush water are exemplified by those described in U.S. Pat. Nos. 3,831,205, 3,241,074, 3,504,384, 2,688,754, 4,036,407, 4, 171,546, 4,208,747, and 4,186,856, above noted and inco ⁇ orated herein by reference.
  • a liquid toilet bowl/urinal cleaner comprising an effective amount of a urease inhibitor to inhibit the enzyme urease is prepared by standard methods and comprises the following:
  • R j , R 2 , R 3 , R 4 , R 5 , and R ⁇ are as defined herein above.
  • N-(diaminophosphinyl)acylcarboxamides N-(diaminophosphinyl)-3-methylbutanamide 14 g of 3-methylbutanamide is dissolved in 300 mL of carbon tetrachloride. 14 g of phosphorous pentachloride is added to the resulting solution at room temperature and the mixture is stirred for 30 minutes. 3.1 g of 99% formic acid is added dropwise to the mixture for 30 minutes. Then, gaseous ammonia is introduced therein under cooling to - 20° C. The mixture is warmed to room temperature and stirred at room temperature for 30 minutes.
  • a suspension of 68 g (0.44 mole) of 4-chlorobenzamide, 91 g (0.44 mole) of phosphorous pentachloride and 700 mL of carbon tetrachloride is heated at 65 - 70° C for 25 min.
  • the solution is cooled to 20° C and 20.7 g (0.44 mole) of 97% formic acid is added dropwise.
  • the precipitate is collected by filtration, washed with carbon tetrachloride and air- dried to give 103 g, mp 114.5 -115.5° C.
  • Aryl Keto Oximes di-(5-methyl-2-furyl)ethanedione monooxime 5-methylfurfural ( 1 1.0 gm, 0.1 mole) is dissolved in 30 mL of absolute ethanol and placed into a 100 mL flask equipped with a magnetic stirring bar and positive nitrogen pressure. 3,4-dimethyl-5-(2-hydroxyethyl)thiazolium iodide catalyst (0.1 gm) is added to the reaction flask along with triethylamine (0.8 gm). The flask is heated in an oil bath at 85° C for 2 hours. An additional 0.1 gm of catalyst and 0 8 gm of triethylamine is added and heating is continued for an additional 4 hours.
  • the crude reaction mixture is cooled and filtered to remove the catalyst and is placed in a freezer at -5° C for 24 hours.
  • the resulting crystals are filtered and washed with ethanol and dried under vacuum (0.1 mmHg). This affords approximately 8.2 gm of a yellow solid di-l,2-(5-methyl-2-furyl) 2-hydroxyethanone
  • the di-l,2-(5-methyl-2-furyl) 2-hydroxyethanone (8.0 gm) is dissolved in 80 mL of absolute ethanol and placed in a 250 mL flask equipped with a magnetic stirrer.
  • Di-(5-methyl-2-furyl) ethanedione (4.0 gm) is dissolved in 20 mL of methanol and placed in a 250 mL flask equipped with a magnetic stirring bar.
  • a solution of hydroxylamine hydrochloride (1.3 gm) in 8 mL of deionized water is added to the flask and then cooled to -5° C.
  • a solution of sodium hydroxide (2.26 gm) in 10 mL of water is added to the flask dropwise and stirred for 1 hour.
  • Acetic acid (2.3 gm) is added followed by 100 mL of saturated sodium chloride and 200 mL of methylene chloride.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention décrit des produits de nettoyage de surfaces dures contenant des inhibiteurs d'uréase. Ces produits renferment des nettoyeurs de cuvettes de w.c. et d'urinoirs contenant une quantité efficace d'un inhibiteur d'uréase pour inhiber l'uréase et permettent avantageusement d'assainir et/ou de nettoyer davantage les cuvettes de w.c. et les urinoirs. L'invention décrit aussi des produits manufacturés comprenant des inhibiteurs d'uréase à utiliser dans le réservoir de chasse d'urinoirs ou des toilettes.
PCT/US1996/007737 1995-06-07 1996-05-28 Nettoyeurs de cuvettes de w.c. contenant des inhibiteurs de l'urease Ceased WO1996040856A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US48159095A 1995-06-07 1995-06-07
US08/481,590 1995-06-07

Publications (1)

Publication Number Publication Date
WO1996040856A1 true WO1996040856A1 (fr) 1996-12-19

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PCT/US1996/007737 Ceased WO1996040856A1 (fr) 1995-06-07 1996-05-28 Nettoyeurs de cuvettes de w.c. contenant des inhibiteurs de l'urease

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006010389A1 (fr) * 2004-07-23 2006-02-02 Skw Stickstoffwerke Piesteritz Gmbh Triamides d'acide n-phenyl-phosphorique, procedes pour les produire et leur utilisation comme agents pour reguler ou inhiber l'hydrolyse enzymatique de l'uree
US7074925B1 (en) * 1998-05-26 2006-07-11 Rimma Lliinichna Ashkinazi N-substituted derivatives of 5-oxyiminobarbituric acid
WO2008022919A1 (fr) * 2006-08-24 2008-02-28 Basf Se Utilisation de triamides d'acide phosphorique dans les toilettes
WO2008022925A1 (fr) * 2006-08-24 2008-02-28 Basf Se Utilisation de triamides d'acide phosphorique dans des détergents et des applications hygiéniques
US7377983B2 (en) 2004-11-04 2008-05-27 The Clorox Company Prevention of deposits on ceramics

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3978208A (en) * 1974-01-07 1976-08-31 Eisai Co., Ltd. Deodorizing compositions
JPS57119997A (en) * 1981-01-19 1982-07-26 Lion Corp Hydroxamic acid type amphoteric surfactant
US4396522A (en) * 1981-05-13 1983-08-02 The Proctor & Gamble Company Polyethylene oxide cake with reduced gelling for flush toilet wastewater sanitation
JPH0335097A (ja) * 1989-06-30 1991-02-15 Kao Corp 水洗トイレ用清浄剤組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3978208A (en) * 1974-01-07 1976-08-31 Eisai Co., Ltd. Deodorizing compositions
JPS57119997A (en) * 1981-01-19 1982-07-26 Lion Corp Hydroxamic acid type amphoteric surfactant
US4396522A (en) * 1981-05-13 1983-08-02 The Proctor & Gamble Company Polyethylene oxide cake with reduced gelling for flush toilet wastewater sanitation
JPH0335097A (ja) * 1989-06-30 1991-02-15 Kao Corp 水洗トイレ用清浄剤組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8235, Derwent World Patents Index; Class D25, AN 82-73567E, XP002014613 *
DATABASE WPI Section Ch Week 9113, Derwent World Patents Index; Class D25, AN 91-090741, XP002014614 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7074925B1 (en) * 1998-05-26 2006-07-11 Rimma Lliinichna Ashkinazi N-substituted derivatives of 5-oxyiminobarbituric acid
WO2006010389A1 (fr) * 2004-07-23 2006-02-02 Skw Stickstoffwerke Piesteritz Gmbh Triamides d'acide n-phenyl-phosphorique, procedes pour les produire et leur utilisation comme agents pour reguler ou inhiber l'hydrolyse enzymatique de l'uree
US7377983B2 (en) 2004-11-04 2008-05-27 The Clorox Company Prevention of deposits on ceramics
WO2008022919A1 (fr) * 2006-08-24 2008-02-28 Basf Se Utilisation de triamides d'acide phosphorique dans les toilettes
WO2008022925A1 (fr) * 2006-08-24 2008-02-28 Basf Se Utilisation de triamides d'acide phosphorique dans des détergents et des applications hygiéniques

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