EP0988362A1 - Compositions de nettoyage de tapis et procede de nettoyage de tapis - Google Patents

Compositions de nettoyage de tapis et procede de nettoyage de tapis

Info

Publication number
EP0988362A1
EP0988362A1 EP99909160A EP99909160A EP0988362A1 EP 0988362 A1 EP0988362 A1 EP 0988362A1 EP 99909160 A EP99909160 A EP 99909160A EP 99909160 A EP99909160 A EP 99909160A EP 0988362 A1 EP0988362 A1 EP 0988362A1
Authority
EP
European Patent Office
Prior art keywords
composition
carpet
cleaning
composition according
surfactant
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
EP99909160A
Other languages
German (de)
English (en)
Other versions
EP0988362B1 (fr
Inventor
Valentina Masotti
Renzo Rizzo
Luca Sarcinelli
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
Family has litigation
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Priority claimed from EP98870076A external-priority patent/EP0949325A1/fr
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to DE29923546U priority Critical patent/DE29923546U1/de
Priority to EP99909160A priority patent/EP0988362B1/fr
Publication of EP0988362A1 publication Critical patent/EP0988362A1/fr
Application granted granted Critical
Publication of EP0988362B1 publication Critical patent/EP0988362B1/fr
Anticipated expiration legal-status Critical
Revoked 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0031—Carpet, upholstery, fur or leather cleansers
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention relates to liquid compositions suitable for sanitizing and cleaning carpets.
  • Carpets produced from synthetic or natural fibers and mixtures thereof are commonly used in residential and commercial applications as a floor covering.
  • Various types of fibers can be used in making carpets such as polyamide fibers, polyester fibers as well as wool, cotton or even silk in the case of rugs.
  • carpets irrespective of whether they are made from natural or synthetic fibers are all prone to soiling and staining when contacted with many household items.
  • Foods, grease, oils, beverages in particular such as coffee, tea and soft drinks especially those containing acidic dyes can cause unsightly, often dark stains on carpets.
  • fibers may become soiled as a result of dirt particles, clay, dust, i.e., particulate soils in general, coming into contact with and adhering to the fibers of the carpet.
  • These latter soils often appear in the form of a diffuse layer of soils rather than in the form of spots and tend to accumulate particularly in the so called "high traffic areas" such as near doors as a result of intensive use of the carpets in such areas.
  • peroxygen bleach-containing compositions may damage the colour of the carpets treated therewith, i.e. when applied directly (neat) onto the carpets, and left to act onto said carpets for prolonged periods of time before evaporating and/or being mechanically removed by for example a vacuum cleaner.
  • compositions of the present invention are applicable to all carpet types, especially delicate natural fibres and are safe to all carpet dye types, particularly sensitive natural dyes used therein.
  • the present invention is also suitable to be used to clean upholstery and car seats covering.
  • the compositions herein may suitably be used to treat localised areas of carpets or the whole carpet.
  • Another advantage of the present invention is that excellent overall cleaning performance on various types of stains including particulate stains, greasy stains, bleachable stains and/or enzymatic stains and excellent sanitising performance is provided in an easy and fast way while requiring low amount of composition.
  • compositions of the present invention may be applied directly on the carpet without causing damage to the carpet fibres.
  • cleaning action of the invention commences as soon as the carpet cleaning composition has been applied to the surface of the carpet.
  • compositions according to the present invention further comprise a polymer to further enhance the overall cleaning performance of these compositions. More particularly, in its preferred embodiment the present invention provides liquid compositions comprising a peroxygen bleach and a polymer, which can be used to clean and sanitise a carpet while reducing or even preventing resoiling of the carpet after having been cleaned/sanitised, and reducing or even preventing microbial redeposition and/or microbial re-growth.
  • the present invention provides a composition which delivers excellent sanitising and cleaning performance without requiring manual action (except for the application) by the user while the composition is in a wet state, especially when at least a polymer is present on top of the peroxygen bleach.
  • the preferred liquid compositions of the present invention comprising a peroxygen bleach and a polymer have the ability to dry to non-tacky residues which entrap the soils and the micro-organisms present thereby reducing or even preventing the soils and the micro-organisms re-deposition on the carpet cleaned. These residues (with the entrapped soils and micro-organisms) are easily removed by vacuum cleaning the carpet without the need of any other additional effort by the user such as rinsing or manual action like brushing.
  • EP-A- 629 694 discloses the use of stable aqueous compositions comprising a source of active oxygen, having a pH of from 1 to 6, for the cleaning of carpets.
  • EP-A-751 213 discloses a carpet cleaning composition comprising salicylic acid, and a compound selected from the group consisting of amine oxides, soil suspending polycarboxylate or polyamine polymers, hydroxy-pyridine N-oxides, chelating agents and mixtures thereof. None of these documents discloses the compositions of the present invention comprising a peroxygen bleach and being packaged in a container adapted to deliver the composition in the form of a spray of droplets having a particle size distribution with a mean diameter D(v,0.9) of less than 1500 microns.
  • the present invention encompasses a liquid composition suitable for cleaning and sanitising carpets, comprising a peroxygen bleach, said composition being packaged in a container adapted to deliver the composition onto the carpet in the form of a spray of droplets having a particle size distribution with a mean diameter D(v,0.9) of less than 1500 microns.
  • said composition further comprises at least a polymer or a mixture thereof.
  • the present invention further encompasses a method of cleaning a carpet wherein a composition has described herein before, is applied to said carpet in the form of a spray of droplets having a particle size distribution with a mean diameter D(v,0.9) of less than 1500 microns, left to dry onto said carpet before being optionally removed from said carpet.
  • the present invention also encompasses the use of a liquid composition comprising a peroxygen bleach, said composition being packaged in a container adapted to deliver the composition in the form of a spray of droplets having a particle size distribution with a mean diameter D(v,0.9) of less than 1500 microns, for cleaning and sanitizing a carpet, for reducing the colour damage on said carpet.
  • compositions of the present invention are formulated as liquid compositions.
  • Preferred compositions herein are aqueous compositions.
  • compositions of the present invention comprise a peroxygen bleach or a mixture thereof, as an essential ingredient.
  • a preferred peroxygen bleach for use herein is hydrogen peroxide or a source thereof.
  • a hydrogen peroxide source refers to any compound which produces perhydroxyl ions when said compound is in contact with water.
  • a peroxygen bleach preferably hydrogen peroxide
  • Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, persilicate, persulphate such as monopersulfate, perborates, preformed peroxyacids, alkyl hydroperoxides, peroxides, aliphatic diacyl peroxides and mixtures thereof. Hydrogen peroxide is preferred to be used in the compositions according to the present invention.
  • Suitable preformed peroxyacids for use in the compositions herein include diperoxydodecandioic acid DPDA, magnesium perphthalatic acid, perlauric acid, perbenzoic acid, diperoxyazelaic acid and mixtures thereof.
  • Suitable hydroperoxides for use herein are tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene- monohydroperoxide, tert-amyl hydroperoxide, 2,5-dimethyl-hexane-2,5- dihydroperoxide or mixtures thereof.
  • Suitable aliphatic diacyl peroxides for use herein are dilauroyl peroxide, didecanoyl peroxide, dimyristoyl peroxide or mixtures thereof.
  • the liquid compositions herein comprise from 0.01 % to 20% by weight of the total composition of a peroxygen bleach, or mixtures thereof, preferably from 0.5 % to 10%, and more preferably from 1 % to 7%.
  • composition is packaged in a container adapted to deliver the composition on the carpet in the form of a spray of droplets having a particle size distribution with a mean diameter D(v,0.9) of less than 1500 microns.
  • suitable containers according to the present invention are able to deliver the composition onto the carpet in the form of a spray of droplets having a particle size distribution with a mean diameter D(v,0.9) of less than 1000 microns, preferably of less than 750 microns, more preferably less than 500 microns, and most preferably from 350 microns to 10 microns.
  • the present invention is based on the finding that the colour damage of some kinds of dyes present on carpets, i.e. the colour change and/or decoloration, is reduced when a liquid composition comprising a peroxygen bleach is applied onto the carpet in the form of a spray of droplets having a particle size distribution with a mean diameter D(v,0.9) of less than 1500 microns, as compared to the colour damage observed when treating the carpets by directly pouring thereto the same liquid composition or applying it thereto in the form of a spray of bigger droplets.
  • spraying a liquid composition comprising a peroxygen bleach, as described herein, onto soiled carpets allows to prevent/reduce the decomposition (oxidation) of dyes generally present on the surface of carpet fibres (e.g. bleach sensitive dyes and/or metallized dyes including copper-formazan dyes and/or metal-azo dyes).
  • dyes generally present on the surface of carpet fibres (e.g. bleach sensitive dyes and/or metallized dyes including copper-formazan dyes and/or metal-azo dyes).
  • the colour damage of a carpet sample may be evaluated by measuring the colour deviation (DE) for example by employing the colour damage method, as can be seen in the examples hereinafter.
  • This method consists in measuring the colour deviation (DE) with "The Hunterlab tristimulus MINISCAN".
  • colour deviation it is to be understood the difference when comparing the colour of a carpet sample taken as a reference, e.g., wherein the composition is simply poured or applied via a spray dispenser that delivers the composition in the form of a spray of bigger droplets, e.g. a trigger spray dispenser which delivers the composition in the form of a spray of droplets having a particle size distribution with a mean diameter D(v,0.9) of 1800 microns or more like the S.C. Johnson Shout®.
  • mean diameter D(v,0.9) of less than 1500 microns for a droplet size distribution it is meant that 90% of the spray of droplets dispensed (expressed in volume unit) has a droplet diameter of less than 1500 microns.
  • a D(v,0.9) of less than 1500 microns indicates that 90% of the total sprayed volume is dispensed with droplets whose diameter is less than 1500 microns.
  • a suitable test equipment is the Malvern Mastersizer S LongBed® with 1000mm lens and a maximum particle size range of 3475 microns.
  • the Malvern Mastersizer S LongBed® provides 21 cm opening (between lenses) to accommodate spray flow.
  • the lens surface must remain free of spray contamination.
  • the distance from nozzle to laser was fixed at 8 cm, this to minimise lens contamination.
  • the spray was directed to the laser beam to place the laser center to the spray cone. At least three readings have to be made for each composition sprayed to determine the particle size distribution of the spray of droplets.
  • the sprayer used in the test according to the present invention was an electrically operated sprayer.
  • a reference sprayer used herein is a hand trigger operated sprayer. Hand trigger systems have to be tested against repeatability with three different persons. These persons chosen for their varied ability to actuate the trigger against force: Small female, female with strong finger strength, and medium male. Any container adapted to deliver a spray of droplets as defined herein are suitable for use herein. Several modifications can be made to the conventional, single aperture, spray head to ensure that a spray of such droplets as required herein is formed.
  • Suitable containers to be used herein share the common feature of having at least one aperture or a plurality of apertures also called “dispensing openings” through which the composition is dispensed so as to produce the spray of droplets as defined herein.
  • composition output from the container herein is from 5 ml/minute to 750 ml/minute, preferably from 20ml/minute to 400ml/minute, more preferably from 150ml/minute to 250 ml/minute.
  • spray dispensers may be manually or electrically operated.
  • Typical manually operated spray dispensers include pump operated ones or trigger operated ones.
  • the composition contained in the container is directed through the spray dispenser head via energy communicated to a pumping mechanism by the user as said user activates said pumping mechanism or to an electrically driven pump.
  • the means for delivering the composition comprises an electrically driven pump and a spray arm being either extended or extendible and having at least one dispensing opening so that in operation, the composition is pumped by electrically driven pump from the container, through the spray arm to the dispensing opening from which it is dispensed. It is preferred that the spray arm communicates with the container by means of a flexible connector.
  • the spray arm may have one nozzle or multiple nozzles located along its length.
  • the spray arm makes it easier to control where the composition is sprayed.
  • the electrically driven pump may be, for example, a gear pump, an impeller pump, a piston pump, a screw pump, a peristaltic pump, a diaphragm pump, or any other miniature pump.
  • the pump is a gear pump with a typical speed between 6000 rpm and 12000rpm.
  • the electrically driven pump is driven by a means such as an electric motor which typically produce a torque between 1 and 20 mN.m. The electric motor must in turn be provided with a power source.
  • the power source may be either mains electricity (optionally via transformer), or it may be a throw-away battery or rechargeable battery.
  • the spray arm may be rigidly extended. However such a spray arm can be difficult to store, and the spray arm is preferably extensible either by means of telescopic or foldable configuration.
  • the pH of the liquid compositions according to the present invention can be from 1 to 14.
  • the recommended pH range is from 1 to 8, preferably between pH 1 and 7, more preferably between pH 2 and 6.5 and most preferably between 4 and 6.5.
  • the compositions herein may further comprise an acid or base to adjust pH as appropriate.
  • the acids that may be used for these purposes can be organic or inorganic acids, preferably inorganic acids such as sulphuric acid.
  • the bases to be used herein can be organic or inorganic bases, preferably inorganic bases such as sodium hydroxide.
  • compositions herein may further comprise a number of additional compounds such as polymers, volatile organic compounds, surfactants, stabilising agents, chelating agents, builder systems, perfumes, dyes, suds suppressing agents, enzymes, photobleaching agents, bleach activators and other minors.
  • additional compounds such as polymers, volatile organic compounds, surfactants, stabilising agents, chelating agents, builder systems, perfumes, dyes, suds suppressing agents, enzymes, photobleaching agents, bleach activators and other minors.
  • compositions of the present invention may further comprise a polymer or a mixture thereof, as a highly preferred optional ingredient.
  • compositions herein may comprise from 0.01% to 50% by weight of the total composition of a polymer or a mixture thereof, preferably from 0.1 % to 20%, more preferably from 0.3% to 10% and most preferably from 0.5% to 3%.
  • the polymers desired herein are those which do not dry as tacky residues.
  • Suitable polymers for use herein include any soil suspending polycarboxylate polymer as well as any soil suspending polyamine polymer and mixtures thereof. 10
  • any soil suspending polycarboxylate polymer known to those skilled in the art can be used according to the present invention such as homo- or co-polymeric polycarboxylic acids or their salts including polyacrylates and copolymers of maleic anhydride or/and acrylic acid and the like.
  • soil suspending polycarboxylate polymers can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates to be used herein can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred soil suspending polycarboxylic polymer.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1 :1 , more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 1 1
  • copolymer of maleic / acrylic acid with an average molecular weight of about 70,000.
  • Such copolymers are commercially available from BASF under the trade name SOKALAN CP5.
  • Any soil suspending polyamine polymer known to those skilled in the art may also be used herein.
  • Particularly suitable polyamine polymers for use herein are alkoxylated polyamines. Such materials can conveniently be represented as molecules of the empirical structures with repeating units :
  • R is a hydrocarbyl group, usually of 2-6 carbon atoms;
  • R 1 may be a C-
  • the alkoxy groups are ethoxy, propoxy, and the like, and y is 2-30, most preferably from 10-20;
  • n is an integer of at least 2, preferably from 2- 20, most preferably 3-5;
  • X- is an anion such as halide or methylsulfate, resulting from the quatemization reaction.
  • polyethylene amines i.e., the polymerized reaction product of ethylene oxide with ethyleneimine, having the general formula :
  • y 2-30, preferably 15 and n is 1-30 preferably 4.
  • Particularly preferred for use herein is an ethoxylated polyethylene amine, in particular ethoxylated tetraethylenepentamine, and quatemized ethoxylated hexamethylene diamine.
  • compositions herein further contributes to the overall cleaning performance as well as excellent sanitising performance of the compositions herein, while reducing or even preventing the formation of tacky residues on the surface of the carpet upon drying, as compared to the same compositions but without the polymer.
  • compositions of the present invention which comprise said peroxygen bleach and polymer, more than 90%, preferably more than 95% of the residues left onto the carpet fibres are solid and non tacky. This results in a method of cleaning carpets whereby the residues left onto the carpets are removed more easily as opposed to residues being sticky, and thus difficult to remove by vacuum cleaning said carpets. By almost completely removing the residues the present invention reduces or even prevents soil re-deposition on the carpet.
  • the present invention reduces or even prevents microbial re-deposition and/or microbial re-growth.
  • the present invention allows fast evaporation of the composition when applied in the form of a spray of droplets having a particle size distribution with a mean diameter D(v,0.9) of less than 1500 microns. This results in residues having lower levels of moisture. Thus, these residues do not represent a fertile environment for bacterial re-growth.
  • the present invention provides excellent sanitising on a broad range of bacterial pure strains including Gram positive bacteria like S. aureus 13
  • Gram negative bacteria like E. Coli, Ps. aeruginosa as well as more resistant micro-organisms like fungi like Candida albicans.
  • compositions according to the present invention typically comprise a volatile organic compound (VOC) or a mixture thereof.
  • VOC volatile organic compound
  • the compositions herein comprise up to 90% by weight of the total composition of a volatile organic compound or a mixture thereof, preferably from 0.1 % to 20%, more preferably from 1.5% to 10% and most preferably from 2% to 8%.
  • Suitable volatile organic compounds for use herein include aliphatic and/or aromatic alcohol, glycol ethers and/or derivatives thereof, polyol and mixtures thereof.
  • Suitable aromatic alcohols to be used herein are according to the formula R ⁇
  • a suitable aromatic alcohol to be used herein is benzyl alcohol.
  • Suitable aliphatic alcohols to be used herein are according to the formula R2- OH wherein R2 is a linear or branched saturated or unsaturated hydrocarbon chain of from 1 to 20 carbon atoms, preferably from 1 to 10 and more preferably from 2 to 6. Highly preferred herein are aliphatic alcohols with 2 to 4 carbon atoms and most preferably 4 carbon atoms, or mixtures thereof. Suitable aliphatic alcohols to be used herein include linear alcohol like 2-octanol, decanol, isopropyl alcohol, propyl alcohol, ethanol and/or methanol. Highly preferred herein is isopropyl alcohol.
  • Isopropanol may be commercially available from Merck/BDH Italia under its chemical name.
  • Suitable glycol ethers and/or derivatives thereof to be used herein include monoglycol ethers and/or derivatives thereof, polyglycol ethers and/or derivatives thereof and mixtures thereof. 14
  • Suitable monoglycol ethers and derivatives thereof to be used herein include n- buthoxypropanol (n-BP), water-soluble CELLOSOLVE® solvents or mixtures thereof.
  • Preferred Cellosolve® solvents include propoxy ethyl acetate salt (i.e., Propyl Cellosolve acetate salt®), ethanol-2-butoxy phosphate salt (i.e., Butyl Cellosolve phosphate salt®), 2-(Hexyloxy)ethanol (i.e., 2-hexyl Cellosolve®), 2- ethoxy ethanol (i.e., 2-ethyl Cellosolve®), 2-butoxyethanol (i.e., 2-buthyl Cellosolve®) or mixtures thereof.
  • Suitable polyglycol ethers and derivatives thereof to be used herein include n- butoxypropoxypropanol (n-BPP), butyl triglycol ether (BTGE), butyl diglycol ether (BDGE), water-soluble CARBITOL® solvents or mixtures thereof.
  • Preferred water-soluble CARBITOL® solvents are compounds of the 2-(2- alkoxyethoxy)ethanol class, 2-(2-alkoxyethoxy)propanol class and/or 2-(2- alkoxyethoxy)butanol class wherein the alkoxy group is derived from ethyl, propyl or butyl.
  • a preferred water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol®.
  • Preferred glycol ethers and/or derivatives thereof are 2-ethoxyethanol, 2- butoxyethanol, n-butoxypropoxypropanol, butyl carbitol® or mixtures thereof.
  • Suitable polyol solvents to be used herein are the polyols having at least 2 hydroxyl groups (-OH) like diols.
  • Suitable diols to be used herein include 2- ethyl-1 ,3-hexanediol, 2,2,4-trimethyl-1 ,3-pentanediol, methyl-2,4 pentanediol or mixture thereof.
  • the volatile organic compounds are present as they further contribute to the excellent overall cleaning performance of the present invention. Additionally, their addition in the compositions herein also enhances the sanitising properties of the compositions.
  • compositions according to the present invention typically comprise a surfactant or a mixture thereof.
  • the compositions herein comprise from up to 50% by weight of the total composition of a surfactant or a mixture thereof, 15
  • Suitable surfactants for use herein have the ability to not dry as tacky residues.
  • Such surfactants may be selected from those well known in the art including anionic, nonionic, zwitterionic, amphoteric and cationic surfactants and mixtures thereof.
  • Particularly suitable surfactants to be used herein are anionic surfactants.
  • Said anionic surfactants are preferred herein as they further contribute to the outstanding stain removal performance of the compositions of the present invention on various type of stains. Moreover they do not stick on carpet, thereby reducing resoiling.
  • Suitable anionic surfactants for use herein include sulfonate and sulfate surfactants.
  • anionic surfactants are well-known in the art and have found wide application in commercial detergents. These anionic surfactants include the C8-C22 alkyl benzene sulfonates (LAS), the C4-C22 alkyl sulfates (AS), unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy sulfates (AES) and the C10-C18 alkyl alkoxy carboxylates.
  • LAS C8-C22 alkyl benzene sulfonates
  • AS C4-C22 alkyl sulfates
  • unsaturated sulfates such as oleyl sulfate
  • C10-C18 alkyl alkoxy sulfates AES
  • C10-C18 alkyl alkoxy carboxylates C
  • the neutralising cation for the anionic synthetic sulfonates and/or sulfates is represented by conventional cations which are widely used in detergent technology such as sodium, potassium or alkanolammonium.
  • Preferred herein are the alkyl sulphate, especially coconut alkyl sulphate having from 6 to 18 carbon atoms in the alkyl chain, preferably from 8 to 15, or mixtures thereof.
  • anionic surfactants useful for detersive purposes can also be used herein. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C8-C22 primary or secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C8-C22 primary or secondary alkanesulfonates C8-C24 olefinsulfonates
  • sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrate
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C-
  • phosphates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below).
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
  • acyl sarcosinate or mixtures thereof, in its acid and/or salt form preferably long chain acyl sarcosinates having the following formula:
  • M is hydrogen or a cationic moiety and wherein R is an alkyl group of from 11 to 15 carbon atoms, preferably of from 11 to 13 carbon atoms.
  • M are hydrogen and alkali metal salts, especially sodium and potassium.
  • Said acyl sarcosinate surfactants are derived from natural fatty acids and the amino-acid sarcosine (N-methyl glycine). They are suitable to be used as aqueous solution of their salt or in their acidic form as powder. Being derivatives of natural fatty acids, said acyl sarcosinates are rapidly and completely biodegradable and have good skin compatibility.
  • particularly preferred long chain acyl sarcosinates to be used herein include C12 ac y' sarcosinate (i.e. an acyl sarcosinate according to the above formula wherein M is hydrogen and R is an alkyl group of 11 carbon atoms) and C1 acyl sarcosinate (i.e. an acyl sarcosinate according to the above formula wherein M is hydrogen and R is an alkyl group of 13 carbon 17
  • 2 acyl sarcosinate is commercially available, for example, as Hamposyl L-30® supplied by Hampshire.
  • C14 acyl sarcosinate is commercially available, for example, as Hamposyl M-30® supplied by Hampshire.
  • Particularly preferred anionic surfactants for use are the alkyl sulphate surfactants according to the formula R1 SO4M wherein R-
  • R1 is a straight or branched alkyl radical containing from 6 to 18 carbon atoms, more preferably from 6 to 12 and most preferably from 6 to 10.
  • M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium and the like) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • alkali metal cation e.g., sodium, potassium, lithium, calcium, magnesium and the like
  • ammonium or substituted ammonium e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and
  • amine oxide surfactants according to the formula R1 R2R3NO, wherein each of R1 , R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl groups of from 1 to 30 carbon atoms, preferably of from 1 to 20 carbon atoms, and mixtures thereof.
  • Particularly preferred amine oxide surfactants to be used according to the present invention are amine oxide surfactants having the following formula R-j R2R3NO wherein R1 is a saturated linear or branched alkyl group of from 1 to 30 carbon atoms, preferably of from 6 to 20 carbon atoms, more preferably of from 6 to 16 carbon atoms, and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched alkyl groups of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms, and more preferably are methyl groups.
  • Preferred amine oxide surfactants used herein are pure-cut amine oxide surfactants, i.e., a pure single amine oxide surfactant, e.g. C ⁇ N,N- dimethyl amine oxide, as opposed to mixtures of amine oxide surfactants of different chain lengths 18
  • Suitable amine oxide surfactants for use herein are for instance pure cut C8 amine oxide, pure cut C10 amine oxide, pure cut C14 amine oxide, natural blend C8-C10 amine oxides as well as natural blend C12-C16 amine oxides.
  • Such amine oxide surfactants may be commercially available from Hoechst or Stephan.
  • Suitable nonionic surfactant for use herein include any ethoxylated C ⁇ -C24 fatty alcohol nonionic surfactant, alkyl propoxylates and mixtures thereof, fatty acid C6-C24 alkanolamides, C ⁇ -C20 polyethylglycol ethers, polyethylene glycol with molecular weight 1000 to 80000 and glucose amides, alkyl pyrrolidones, betaines.
  • Suitable cationic surfactants for use herein include quaternary ammonium compounds of the formula R-
  • Zwitterionic surfactants are also suitable optional ingredients for use herein.
  • Suitable zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulphonium compounds in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 24 carbon atoms and another substituent contains, at least, an anionic water-solubilizing group.
  • Particularly preferred zwitterionic materials are the ethoxylated ammonium sulphonates and sulfates disclosed in U.S. Patents 3,925,262, Laughlin et al., issued December 9, 1975 and 3,929,678, Laughlin et al., issued December 30, 1975.
  • Preferred surfactants for use herein are the amine oxide surfactants and alkyl sulphate surfactants and mixture thereof and most preferred surfactants herein are alkyl sulphate surfactants.
  • optimum cleaning performance is delivered when combining the surfactant, preferably an alkyl sulphate, with the polymer preferably the polyamine polymer, at a weight ratio of the polymer to said surfactant of 1 :40 to 20:1 , preferably of 1 :20 to 10:1 , more preferably of 1 :10 to 5:1 and most preferably of 1 :6 to 1 :1. Also the total level of surfactant together with polymer is from 1 % to 20%, preferably from 2% to 10% 19
  • an advantage of the present invention is that excellent cleaning performance is provided with reduced total amount of cleaning agent, i.e. surfactant and/or polymer.
  • surfactants have the advantage of assisting the polymers herein when present, to form easily removable non-tacky residues upon drying on the surface of the carpet after having combined soils deposited thereto.
  • compositions herein may also comprise a hydroxy pyridine N-oxides or derivatives thereof according to the following formula:
  • X is nitrogen
  • Y is one of the following groups oxygen, -CHO, -OH, - (CH2)n-COOH, wherein n is an integer of from 0 to 20, preferably of from 0 to 10 and more preferably is 0, and wherein Y is preferably oxygen.
  • hydroxy pyridine N-oxides or derivatives thereof to be used herein is 2-hydroxy pyridine N-oxide.
  • Hydroxy pyridine N-oxides or derivatives thereof may be commercially available from Sigma.
  • compositions herein comprise up to 2% by weight of the total composition of a hydroxy pyridine N-oxide or derivatives thereof or mixtures thereof, preferably from 0.001 % to 1 % and more preferably from 0.001 % to 0.5%.
  • compositions herein may also comprise a chelating agent or mixtures thereof.
  • Suitable chelating agents are those known to those skilled in the art. 20
  • Suitable chelating agents include for examples phosphonate chelating agents, polyfunctionally-substituted aromatic chelating agents, amino carboxylate chelating agents, other chelating agents like ethylene diamine N,N'- disuccinic acid and mixtures thereof.
  • the compositions herein comprise up to 4% by weight of the total composition of a chelating agent or mixtures thereof, preferably from 0.001 % to 1%, and more preferably from 0.001 % to 0.5%.
  • Suitable phosphonate chelating agents to be used herein may include ethydronic acid, alkali metal ethane 1 -hydroxy diphosphonates as well as amino phosphonate compounds, including amino alkylene poly (alkylene phosphonate), alkali metal ethane 1 -hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene t amine penta methylene phosphonates.
  • the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
  • Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonates (DETPMP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®-
  • Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21 , 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy -3,5-disulfobenzene.
  • a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
  • Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987. to Hartman and Perkins.
  • Ethylenediamine N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
  • Suitable amino carboxylate chelating agents to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA), N-hydroxyethylethylenediamine triacetates, nitrilotri- acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa- acetates, ethanoldiglycines, propylene diamine tetracetic acid (PDTA) and 21
  • MGDA methyl glycine di-acetic acid
  • DTPA diethylene triamine penta acetic acid
  • Suitable chelating agents to be used herein include salicylic acid or derivatives thereof, or mixtures thereof according to the following formula:
  • X is carbon
  • Y is one of the following groups -CHO, -OH, -(CH2)n- COOH, and preferably is -(CH2)n-COOH
  • n is an integer of from 0 to 20, preferably of from 0 to 10 and more preferably is 0.
  • Salicylic acid and derivatives thereof may be used herein either in their acid form or in their salts form as for example sodium salts.
  • Salicylic acid is particularly preferred herein and may be commercially available from Rhone Poulenc.
  • compositions according to the present invention may further comprise propyl gallate up to a level of 1 % by weight of the total composition, preferably from 0.01 % to 0.1 %, and more preferably from 0.01 % to 0.06%. It has now been found that the addition of propyl gallate in the liquid preferred compositions herein comprising a peroxygen bleach contributes to deliver excellent chemical stability to said compositions.
  • compositions according to the present invention may further comprise a bleach activator or mixtures thereof, as another optional ingredient.
  • bleach activator it is meant herein a compound which reacts with hydrogen peroxide to form a peracid.
  • the peracid thus formed constitutes the activated bleach.
  • Suitable bleach activators to be used herein include those belonging to the class of esters, amides, imides, or anhydrides. Examples of suitable compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2 22
  • TAED tetracetyl ethylene diamine
  • NOBS n- nonanoyloxybenzenesulphonate
  • N-acyl caprolactam selected from the group consisting of substituted or unsubstituted benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam pentanoyl caprolactam or mixtures thereof.
  • a particular family of bleach activators of interest was disclosed in EP 624 154, and particularly preferred in that family is acetyl triethyl citrate (ATC).
  • Acetyl triethyl citrate has the advantage that it is environmentally friendly as it eventually degrades into citric acid and alcohol. Furthermore, acetyl triethyl citrate has a good hydrolytical stability in the composition upon storage and it is an efficient bleach activator.
  • compositions according to the present invention may comprise up to 30% by weight of the total composition of said bleach activator, or mixtures thereof, preferably from 1 % to 20%, and more preferably from 2% to 10%.
  • compositions according to the present invention may further comprise a builder system.
  • a builder system Any conventional builder system known in the art is suitable for use herein.
  • Suitable builders for use herein include derivatives of succinic acid of the formula R_CH(COOH)CH2(COOH) wherein R is C-
  • Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate, 2-tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water- soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
  • Suitable builders are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071. 23
  • fatty acid builders including saturated or unsaturated C10-I8 fatty acids, as well as the corresponding soaps.
  • Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • the preferred unsaturated fatty acid is oleic acid.
  • compositions herein may comprise from 0% to 10%, preferably from 1 % to 7% by weight of the total composition of a builder system.
  • the present invention also encompasses a method of cleaning and sanitising a carpet wherein a composition as described herein, is applied to said carpet, left to dry onto said carpet before being optionally removed from it.
  • the step of leaving the composition to dry onto the carpet can either be an "active drying step” or a "passive drying step”.
  • active drying step it is meant herein, performing an additional action to facilitate the evaporation of the volatile ingredients of the liquid composition as disclosed herein, preferably by means of application of hot air, infrared radiation and the like.
  • passive drying step it is meant herein, evaporation of the volatile ingredients of the liquid composition as disclosed herein without performing further action.
  • dry it is meant herein the stage where at least 40%, preferably at least 60% of the initial amount of composition dispensed onto the carpet is lost due to evaporation.
  • the step of applying a composition onto the carpets as described herein before does not need to be followed by a step where manual action is required other than vacuum cleaning.
  • the compositions herein allow excellent cleaning performance and sanitising performance without requiring any manual action like rubbing and/or brushing.
  • An advantage of the present invention is that the cleaning and sanitising action of the present compositions commence as soon as said compositions are applied onto said carpet.
  • compositions onto the carpet in the form of a spray of small droplets as defined herein By applying the composition onto the carpet in the form of a spray of small droplets as defined herein, a higher coverage can be achieved with the same amount of composition, as compared to applying the same composition but in the form of a spray of bigger droplets.
  • the present invention allows excellent cleaning and sanitising performance while requiring low amount of composition.
  • the composition is applied/sprayed onto the carpet in an amount of from 1 ml to 120 ml by square meter of carpet, preferably from 10 ml to 80, more preferably from 20 ml to 60 ml and most preferably from 30 ml to 50 ml.
  • it is by combining this feature with the particle size distribution of the composition herein when sprayed as defined herein on the carpet that optimum coverage of the carpet surface is obtained resulting in more faster drying time.
  • applying the composition on the carpet as mentioned herein further translates in limited wetting of the surface and thus in faster drying of the composition. In other words, the housewife has to wait less time between the step of applying the composition on the carpet and those of removing it by for example vacuum cleaning the carpet.
  • composition is left to dry on the carpet for less than 2 hour, preferably less than 1 hour, more preferably less than 40 minutes, even more preferably from 1 to 30 minutes and most preferably from 5 to 25 minutes.
  • the area to be cleaned by applying preferably spraying the compositions according to the present invention may be of any size. Indeed, a complete section or more preferably the whole carpet may be sprayed with the composition for the cleaning of carpets according to the present invention.
  • the container, and especially the spray dispenser head is typically maintained at a distance of from 1 cm to 40 cm from the carpet onto which the composition will be sprayed, preferably from 2 cm to 30 cm more preferably from 3 cm to 20 cm.
  • Sanitising properties of a composition may be measured by the bactericidal activity of said composition.
  • compositions for the cleaning of carpets according to the present invention provide excellent cleaning performance on various types of soils including diffuse soils (e.g., particulate and/or greasy soils) that tend to accumulate in the so called “high traffic areas” but also in delivering good cleaning performance on other types of stains or soils, i.e., on spot stains like bleachable stains (e.g., coffee, beverage, food) and/or enzymatic stains like blood.
  • diffuse soils e.g., particulate and/or greasy soils
  • bleachable stains e.g., coffee, beverage, food
  • enzymatic stains like blood.
  • pill stains any soils or stains of particulate nature that can be found on any carpet, e.g. clay, dirt, dust, mud, concrete and the like.
  • greasy/oily stains any soils or stains of greasy/oily nature that can be found on any carpet, e.g., make-up, lipstick, dirty motor oil and mineral oil, greasy food like mayonnaise and spaghetti sauce.
  • bleachable stains any soils or stains containing ingredients sensitive to bleach that can be found on any carpet, e.g., coffee or tea.
  • enzymatic stains any soils or stains of enzymatic nature that can be found on any carpet, e.g., grass.
  • the cleaning performance of a given composition on a soiled carpet may be evaluated by the following test method.
  • a liquid composition according to the present invention is first sprayed onto the stained portion of a carpet, left to act thereon from about 1 to about 10 minutes, preferably 5 minutes, after which the carpet is vacuum cleaned.
  • Typical soils used in this test may be grass, dirty motor oil, tea, coffee, dust and/or mayonnaise.
  • the cleaning performance may be evaluated by visual grading. 26
  • compositions are made by combining the listed ingredients in the listed proportions (weight % unless otherwise specified).
  • compositions 1 li III IV V VI Compositions 1 li III IV V VI
  • Salicylic Acid 0.5 0.01 ⁇ — 0.1 —
  • AMCP is acrylic/malic based copolymers (Sokalan CP5®)
  • Chelant* is a phosphonate chelant available under the trade name DEQUEST®
  • Na CnAS is sodium alkyl sulphate.
  • PA is an ethoxylated tetraethylenepentamine, average molecular weight about
  • compositions exemplified above are packaged in a container adapted to deliver a spray of droplets having a particle size distribution with a mean diameter D(v,0.9) of 200 to 400 microns, when measured with Malvern Mastersizer S longBed ® referenced herein before.
  • a suitable container used was an electrically driven sprayer.
  • compositions in the examples above deliver excellent cleaning performance on particulate soil, greasy/oily soil, and/or enzymatic as well as on other types of soils such as bleachable stains like coffee, tea and the like as well as excellent sanitising properties.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne une composition liquide appropriée pour le nettoyage et l'aseptisation de tapis, la composition comprenant un agent de blanchiment peroxyde et étant contenue dans un récipient adapté pour permettre l'application de la composition sur le tapis sous forme de pulvérisation de gouttelettes présentant une distribution granulométrique à diamètre moyen D(v,0,9) inférieur à 1500 micromètres. La présente invention possède d'excellentes caractéristiques de nettoyage et d'aseptisation de tapis, tout en réduisant la dégradation des couleurs des tapis.
EP99909160A 1998-04-08 1999-04-07 Compositions de nettoyage de tapis et procede de nettoyage de tapis Revoked EP0988362B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE29923546U DE29923546U1 (de) 1998-04-08 1999-04-07 Teppichreinigungs-Zusammensetzungen
EP99909160A EP0988362B1 (fr) 1998-04-08 1999-04-07 Compositions de nettoyage de tapis et procede de nettoyage de tapis

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP98870076 1998-04-08
EP98870076A EP0949325A1 (fr) 1998-04-08 1998-04-08 Compositions pour le nettoyage de tapis et méthode de nettoyage
EP99909160A EP0988362B1 (fr) 1998-04-08 1999-04-07 Compositions de nettoyage de tapis et procede de nettoyage de tapis
PCT/IB1999/000593 WO1999053006A1 (fr) 1998-04-08 1999-04-07 Compositions de nettoyage de tapis et procede de nettoyage de tapis

Publications (2)

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EP0988362A1 true EP0988362A1 (fr) 2000-03-29
EP0988362B1 EP0988362B1 (fr) 2002-12-11

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EP99909160A Revoked EP0988362B1 (fr) 1998-04-08 1999-04-07 Compositions de nettoyage de tapis et procede de nettoyage de tapis

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DE (1) DE29923546U1 (fr)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9953006A1 *

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EP0988362B1 (fr) 2002-12-11

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