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WO2007065533A1 - Préparations blanchissantes liquides aqueuses - Google Patents

Préparations blanchissantes liquides aqueuses Download PDF

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Publication number
WO2007065533A1
WO2007065533A1 PCT/EP2006/010942 EP2006010942W WO2007065533A1 WO 2007065533 A1 WO2007065533 A1 WO 2007065533A1 EP 2006010942 W EP2006010942 W EP 2006010942W WO 2007065533 A1 WO2007065533 A1 WO 2007065533A1
Authority
WO
WIPO (PCT)
Prior art keywords
container
composition
compositions
aqueous liquid
hypochlorite
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/EP2006/010942
Other languages
English (en)
Inventor
Julie R Das
Andrew S Jamieson
Philip M Ryan
Katherine M Thompson
David R Ward
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.)
Hindustan Unilever Ltd
Unilever NV
Original Assignee
Hindustan Lever Ltd
Unilever NV
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 Hindustan Lever Ltd, Unilever NV filed Critical Hindustan Lever Ltd
Publication of WO2007065533A1 publication Critical patent/WO2007065533A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions
    • 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
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • 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
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • the present invention relates to aqueous liquid bleach and disinfectant compositions comprising hypochlorite, Cetyl Trimethylammonium salt surfactant and amine oxide
  • the invention also relates to the use of such compositions for cleaning and disinfecting hard surfaces.
  • Aqueous liquid hypochlorite bleach compositions are well known in the art . On the one hand they are used for
  • bleaching and stain removal on laundry are used for cleaning and disinfecting hard surfaces such as kitchen surfaces, floors and in particular toilets.
  • bleach compositions intended for cleaning hard surfaces preferably have a relatively high viscosity and such compositions are
  • thick bleach generally known as "thick bleach” .
  • thickening systems for hypochlorite have been described in the prior art involving a large variety of combinations of surfactants.
  • these GB 1,466,560 describes thickening systems comprising an alkali metal sarcosinate or tauride surfactant and another surfactant chosen from amine oxides, quaternary ammonium compounds, betaines, alkanolamides and fatty acid soaps. From this latter list only combinations involving an amine oxide or a soap are exemplified.
  • 5,336,426 all disclose thickening mixtures comprising a quaternary ammonium compound and an organic counter ion which may be a Ci-C 10 alkyl or aromatic sulphonate or
  • hypochlorite are known to be powerful disinfectants for hard surfaces, this disinfectant activity is short-lived, i.e. after a surface has been treated with an active
  • compositions were said to lead to phase separation such as emulsions or precipitates.
  • the compositions are particularly suitable for treating textiles and fibres and are therefore preferably thin liquids.
  • EP 844827 discloses that aqueous compositions comprising up to 0.25% active chlorine compound and up to 0.08%
  • bactericidal quaternary ammonium compound are able to kill tubercule bacilli on hard surfaces.
  • Preferred quaternary ammonium compounds are the di (C8-C12) alkyl-dimethylammonium salts and the (C12-C18) alkyl-dimethyl -benzylammonium salts Didecyl-dimethylammonium chloride and (C12-C16) alkyl- dimethyl -benzylammonium chloride are specifically mentioned. It is said to be advisable to keep the active chlorine solution and the quaternary ammonium salt solution separate until the moment of use to prevent the active chlorine solution to lose part of its active chlorine content.
  • compositions of the prior art above have two major drawbacks. Firstly, in the long term most quaternary compounds of the prior art above have two major drawbacks. Firstly, in the long term most quaternary compounds of the prior art above have two major drawbacks. Firstly, in the long term most quaternary compounds of the prior art above have two major drawbacks. Firstly, in the long term most quaternary compounds of the prior art above have two major drawbacks. Firstly, in the long term most quaternary
  • ammonium compounds are not stable in hypochlorite solution. Such solutions tend to lose a significant part of the active chlorine as well as of the quaternary ammonium content after weeks of storage. Secondly, in all the above disclosures, it is the thickening that is supposed to improve the hygiene effect .
  • An aqueous liquid hygiene composition giving enhanced antimicrobial effect without extensive thickening remains to be desired.
  • Desirable methods for oxidative cleaning/bleaching of any surface should provide powerful initial disinfectancy as well as give sufficient residual antimicrobial activity on a surface to prevent bacterial regrowth for extended periods of time, also after rinsing with water.
  • Compositions suitable for use in such methods should be sufficiently stable to be manufactured, shipped and stored, on the shelf as well as by the consumer, without appreciable loss of active chlorine.
  • compositions with slightly different quaternary ammonium compounds show a significant synergistic effect when comparing any combination of two of the three compounds of the invention.
  • compositions further show thorough oxidative cleaning and removal of stains, improved disinfecting of the surface and antimicrobial activity on the cleaned surface for an extended period of time.
  • the compositions may be stored for long periods of time without appreciable loss of active chlorine or quaternary ammonium compound.
  • the invention provides aqueous liquid hygiene
  • compositions comprising hypochlorite, Cetyl - trimethylammonium salts and amine oxide surfactant.
  • the invention provides a method of cleaning and disinfecting hard surfaces, comprising applying to the surface an aqueous liquid hygiene compositions comprising hypochlorite, Cetyl Trimethylammonium salts and amine oxide surfactant .
  • the invention provides the use of a composition comprising 0.001 to 0.5 mol/1 Cetyl Trimethylammonium salt, 0.02 to 10%w amineoxide surfactant and 0.01 to 10%w of an alkali metal hypochlorite for enhanced anti -bacterial activity.
  • the invention further provides a method for disinfecting hard surfaces, comprising of treating the surface with an aqueous liquid hygiene composition, comprising 0.001 to 0.5 mol/1 Cetyl Trimethylammonium chloride, 0.02 to 10%w
  • an aqueous liquid hygiene composition comprising:
  • the hypochlorite salt is generally an alkali metal or alkaline earth metal salt although other salts may be used.
  • the Na and Ca salts are most widely used.
  • the compositions used for the purposes of the invention generally comprise
  • hypochlorite salt 0.01-10% NaClO or an equivalent amount of other hypochlorite salt, which is equivalent to about 0.0095-9.5% available chlorine and to 0.0014-1.4 mol/1 of hypochlorite ion.
  • hypochlorite ion content is 0.005-1.0 mol/1, more preferably at least 0.01 mol/1, most preferably at least 0.05 mol/1 or even 0.1 mol/1.
  • the Cetyl-trimethylammonium salts according to the present invention may comprise organic and inorganic anions.
  • the inorganic anions are preferably halide, sulphate, hydrogen sulphate, phosphate, hydrogen phosphates,
  • organic anions are preferably tosylate, methylsulphate or acetate. More preferably the anion is the halide, sulphate, hydrogen sulphate or OH " . The most preferred anion is chloride.
  • compositions according to, and used in the methods of the invention generally comprise 0.001-0.5 mol/1 of the cetyl trimethylammonium ion (CTA + ), preferably 0.005-0.1 mol/1, more preferably at least 0.01 mol/1.
  • CTA + cetyl trimethylammonium ion
  • the molar ratio between hypochlorite ion and CTA + is usefully kept between 500:1 and 1:1, preferably between 200:1 and 2:1. Even more useful ratios are at or below 100:1.
  • the halide ion is preferably chloride or bromide, more preferably chloride.
  • Suitable amine oxide are tertiary amine oxides of structure
  • RRRNO where one R is an alkyl group of 8 to 20 carbon atoms and the other R's are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, preferably methyl groups.
  • the large alkyl group preferably has at least 12, more preferably at least 14 carbon atoms.
  • the amine oxide is preferably used in an amount of at least 0.02%, more preferably at least 0.05%, most preferably at least 0.1 or even at least 0.5%, but preferably not above 10%, more preferably at most 5%.
  • compositions used for the purposes of the invention need to be alkaline, i.e. have pH above 7.
  • pH is kept at or above 8, more preferably at least 9 or even 10.
  • compositions may not be suitable to come into contact with the human skin on account of their high content of hypochlorite, they can be applied to a surface manually (e.g. with a wipe or cloth or other implement) after proper dilution.
  • Suitable dilution factors are generally between 1:5 and 1:500
  • compositions according to the invention either dilute, but preferably pure are applied to the surface to be treated and are left in contact with that surface for a sufficiently long time to oxidatively clean and disinfect that surface, whereafter the surface may be rinsed if desired.
  • contact times of 1 minute are sufficient for initial disinfectancy, with contact times of at least 5 minutes being used to obtain long term
  • a composition according to the invention with a spraying device such as a trigger spray or similar as well known in the art of hard surface cleaning.
  • foam dispenser and squeeze bottles are also suitable to hold the formulation of the invention.
  • Another embodiment of the invention involves applying a squirt of the product according to the invention straight from the container in which it is provided to the surface to be treated.
  • the invention particularly provides a method for cleaning and disinfecting toilet surfaces comprising applying to the surface a composition as described above.
  • a composition as described above is applied directly from the container to the bowl, either above the water table to the surface of the bowl e.g. under the rim, or to the water in the bowl.
  • Particularly suitable toilet surfaces comprising applying to the surface a composition as described above.
  • the longitudinal axis of the dispensing opening in the cap makes an angle of generally less than 90° (preferably 10-80°) with the longitudinal axis of the bottle to enable easy application of the composition under the rim of the toilet bowl .
  • An example of such a bottle is depicted in the UK Industrial Design registration no. 1057823. Applying the concentrated composition to the water in the bowl will generate a diluted solution according to the invention. As outlined above, treating a surface with a bleaching composition according to the invention will not only
  • the composition oxidatively clean and disinfect that surface, but also provides extended antimicrobial activity on that surface such that regrowth of micro-organisms is prevented for many hours after the treatment is completed, particularly if the composition is left to dry out on the surface.
  • the antimicrobial activity remains after rinsing, even repeated rinsing, of the surface, in spite of the fact that the hypochlorite and quaternary ammonium salt in the composition are soluble in water and would be expected to be rinsed away .
  • compositions according to the invention can optionally contain many other components known in the art to be useful in bleach compositions.
  • hypochlorite stable surfactants may be added to improve cleaning properties, provided they do not adversely affect the properties of the thickening system.
  • Colourants, dyes and pigments may be added to impart a desired colour to the compositions and perfumes to give the compositions a desired odour, particularly to overcome the hypochlorite odour which many people do not appreciate.
  • the components should be chosen to be bleach-stable, as is well known in the art .
  • compositions could also usefully contain buffer to ensure long term pH stability. Alkali metal carbonates/bicarbonates and silicates are particularly useful for that purpose.
  • Aqueous liquid hygiene compositions were prepared according to the formulations 1-5 in Table 1.
  • the used amine oxide is Empigen OD (Ci 0 -Ci 8 alkyl-dimethylamine oxide, trademark ex Huntsman) .
  • the used CTA + Cl " (Cetyl- trimethylammonium chloride) is available from Clariant as Genamin CTAC.
  • the test uses a high throughput screening method to assess the hygienic properties of standard samples of lO ⁇ l of product dispensed in microtitre plate wells that have been left to dry (at 30 0 C overnight) and are thereafter subjected to a number of automatic rinses. Each test is done in 8 replicates. The rinses were done with a Ascent WellwashTM plate washer with sterile water of standard hardness. After a set number of rinses the plates were dried at 30 0 C for 45 minutes and left to cool at 20 0 C for 15 minutes.
  • compositions were prepared from the base formulation of Table 3 below (amounts in % by weight) :
  • pH was adjusted to pH 12.5 with NaOH and demineralised water was added to 100%.
  • the residual available chlorine present was analysed iodometrically, using the following procedure: A known weight of the test solution (w) was placed in an iodine flask. The sample was diluted with approximately 20 ml distilled water. 10 g of 5% potassium iodide solution was added followed by 10 ml of 0.5 M sulphuric acid. The flask was stoppered and swirled to mix the contents before placing in dark for 5 minutes, until the brown colour of the evolved iodine had fully developed. The liberated iodine was
  • the test uses a high throughput screening method to assess the hygienic properties of standard samples of lO ⁇ l of product dispensed in microtitre plate wells that have been left to dry (at 30 0 C overnight) and are thereafter subjected to a number of automatic rinses. Each test is done in 8 replicates. The rinses were done with a Ascent WellwashTM plate washer with sterile water of standard hardness. After a set number of rinses the plates were dried at 30 0 C for 45 minutes and left to cool at 20 0 C for 15 minutes.
  • Each well was thereafter incubated with 50 ⁇ l of an aqueous suspension of E.coli (0.5xl0 8 cfu) in 0.3% protein (BSA) soil and left in contact for Ih at 20 0 C.
  • the wells were then washed by adding lOO ⁇ l water of standard hardness and shaking for lOsec, whereafter the wash liquour and unattached cells were aspirated off. Thereafter 270 ⁇ l of tryptone soya broth growth medium is placed in each well and the plates are incubated for 24h at 37°C to allow remaining bacteria to re- grow.
  • a test is classified as successful after the set number of rinses if at least 80% of the samples show no regrowth. The highest number of rinses that lead to a successful test is taken as the hygiene score.
  • Hygiene score expressed as the number of rinses that a microtitre plate well remained bacteria- free .

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

Abstract

L'objet de l'invention est de fournir une préparation hygiénique liquide aqueuse conférant un effet antimicrobien amélioré sans épaississement excessif. De façon surprenante, il a été découvert qu’une préparation comprenant un sel de cétyltriméthylammonium, un tensioactif de type aminoxyde et un hypochlorite de métal alcalin présentait une activité antibactérienne améliorée.
PCT/EP2006/010942 2005-12-09 2006-11-15 Préparations blanchissantes liquides aqueuses Ceased WO2007065533A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP05077838.0 2005-12-09
EP05077838 2005-12-09

Publications (1)

Publication Number Publication Date
WO2007065533A1 true WO2007065533A1 (fr) 2007-06-14

Family

ID=36028114

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/010942 Ceased WO2007065533A1 (fr) 2005-12-09 2006-11-15 Préparations blanchissantes liquides aqueuses

Country Status (2)

Country Link
AR (1) AR056844A1 (fr)
WO (1) WO2007065533A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3876718A4 (fr) * 2018-11-06 2022-08-24 The Clorox Company Compositions de blanchiment
US11845916B2 (en) 2020-06-24 2023-12-19 The Clorox Company Burstable sporicidal cleaning wipe system containing stabilized hypochlorite

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998059029A1 (fr) * 1997-06-23 1998-12-30 Unilever Plc Procede de traitement de surfaces
DE10206172A1 (de) * 2001-02-15 2002-08-29 Kao Corp Flüssige Bleichreinigungszusammensetzung
WO2006087099A1 (fr) * 2005-02-16 2006-08-24 Unilever N.V. Compositions de blanchiment liquides aqueuses

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998059029A1 (fr) * 1997-06-23 1998-12-30 Unilever Plc Procede de traitement de surfaces
DE10206172A1 (de) * 2001-02-15 2002-08-29 Kao Corp Flüssige Bleichreinigungszusammensetzung
WO2006087099A1 (fr) * 2005-02-16 2006-08-24 Unilever N.V. Compositions de blanchiment liquides aqueuses

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KOKKE-HALL S ET AL: "BLEACH AND SURFACTANTS DO MIX", HAPPI HOUSEHOLD AND PERSONAL PRODUCTS INDUSTRY, RODMAN PUBLISHING, RAMSEY, NJ, US, vol. 35, no. 6, June 1998 (1998-06-01), pages 122,124,126,12, XP000766103, ISSN: 0090-8878 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3876718A4 (fr) * 2018-11-06 2022-08-24 The Clorox Company Compositions de blanchiment
US11596152B2 (en) 2018-11-06 2023-03-07 The Clorox Company Bleach compositions
US11737465B2 (en) 2018-11-06 2023-08-29 The Clorox Company Bleach compositions
US12082586B2 (en) 2018-11-06 2024-09-10 The Clorox Company Bleach compositions
AU2019377791B2 (en) * 2018-11-06 2025-01-02 The Clorox Company Bleach compositions
US11845916B2 (en) 2020-06-24 2023-12-19 The Clorox Company Burstable sporicidal cleaning wipe system containing stabilized hypochlorite
US12234433B2 (en) 2020-06-24 2025-02-25 The Clorox Company Burstable sporicidal cleaning wipe system with a hypochlorite/surfactant mixture

Also Published As

Publication number Publication date
AR056844A1 (es) 2007-10-24

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