EP1446470B1 - Compositions detergentes abrasives liquides - Google Patents

Compositions detergentes abrasives liquides Download PDF

Info

Publication number
EP1446470B1
EP1446470B1 EP02777294A EP02777294A EP1446470B1 EP 1446470 B1 EP1446470 B1 EP 1446470B1 EP 02777294 A EP02777294 A EP 02777294A EP 02777294 A EP02777294 A EP 02777294A EP 1446470 B1 EP1446470 B1 EP 1446470B1
Authority
EP
European Patent Office
Prior art keywords
composition according
cleaning composition
abrasive
amount
cleaning
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02777294A
Other languages
German (de)
English (en)
Other versions
EP1446470A1 (fr
Inventor
Nancy Iris Unilever de Argentina SA BEJARANO
Diego Unilever de Argentina SA PRIETO
José Daniel Unilever de Argentina SA SIVEIRO
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
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 Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP02777294A priority Critical patent/EP1446470B1/fr
Publication of EP1446470A1 publication Critical patent/EP1446470A1/fr
Application granted granted Critical
Publication of EP1446470B1 publication Critical patent/EP1446470B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
    • 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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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

Definitions

  • the invention relates to aqueous liquid compositions that comprise an abrasive and a polymeric thickening agent and that are suitable for hard surface cleaning.
  • Liquid abrasive cleaning compositions for hard surfaces are well known in the art and used for cleaning hard surfaces generally encountered in homes and institutions, particularly in kitchens, bathrooms, toilets and the like.
  • Such compositions typically comprise a solid abrasive, and optionally a detergent surfactant, in an aqueous medium.
  • the solid abrasive is kept suspended in the liquid medium. This can be done, either with a combination of detergent surfactants, particularly anionic and nonionic surfactants, which together form a lamellar phase and thereby cause thickening of the liquid, or with a thickening polymer to give the liquid the required viscosity properties, or by a combination of both methods.
  • liquid abrasive cleaning compositions in which the suspending properties of the liquid are provided by the use of thickening polymers in most cases still contain a certain amount of detergent surfactant to improve the cleaning properties of the composition and provide for the desired foaming of the composition in use.
  • Liquid abrasive cleaning compositions that contain thickening polycarboxylates and only a minimal amount of surfactant are described in WO 01/05931.
  • nonionic surfactants are long chain aliphatic alcohol ethoxylates and amine oxides.
  • Typical abrasive materials include minerals such as calcite and dolomite or other materials of relatively high density and sufficient hardness.
  • a thickening mixture comprising a gum-type polymer (polysaccharide) and an acrylic type polymer in a ratio and amount determined by the sigmoid curves of log (viscosity) versus log (concentration) of each polymer.
  • the preferred polysaccharide is xanthan gum.
  • the combination of polymers is said to give synergistic thickening properties.
  • the thickening mixtures are disclosed to be suitable for a large variety of applications, including liquid abrasive cleaners.
  • a well-known problem with liquid abrasive cleaners is their tendency to leave residues of solid abrasive on the cleaned surface, which are difficult to rinse away and remain visible as a white hue.
  • abrasives content are quoted in the patent literature, ranging from less than 1% to 80% or higher, for the normal liquid abrasive cleaner well known to the consumer the practical abrasive content is generally at least 20% and ranges up to 50%. Lower abrasive contents have been described as a way to solve the rinsing problem.
  • compositions described in WO 97/41204 comprise 0.1-10% abrasive, up to 20% of PAS and/or LES, up to 30% of ethoxylated alcohol nonionic surfactant, 1-30% of a co-surfactant being glycerol or mono- or polyethylene glycol or mono- or polypropylene glycol, 0.6-10% of a perfume or a water-insoluble hydrocarbon having 6-18 carbon atoms, and some other components.
  • abrasive up to 20% of PAS and/or LES, up to 30% of ethoxylated alcohol nonionic surfactant, 1-30% of a co-surfactant being glycerol or mono- or polyethylene glycol or mono- or polypropylene glycol, 0.6-10% of a perfume or a water-insoluble hydrocarbon having 6-18 carbon atoms, and some other components.
  • a co-surfactant being glycerol or mono- or polyethylene glycol or mono- or polypropylene glycol
  • EP 336651 describes such compositions, containing a wide range of organic solvents with examples as diverse as 2-butoxyethanol, pine oil and limonene.
  • the compositions all require colloidal aluminium oxide thickener to obtain a stable suspension. They preferably contain 20-40%, particularly 30% abrasive.
  • a similar composition is described in EP 335471, comprising 1.8-4.5% of a grease-removal solvent and 10-60% of an insoluble abrasive.
  • anionic surfactants is mentioned for the surfactant system, the preferred ones being fatty acid soap and PAS.
  • composition comprising 2-10% of surfactant and 1-10% of a non- or sparingly water-soluble solvent.
  • the surfactant is preferably a mixture of LAS and LES in a 1:1 to 4:1 ratio.
  • the amount of abrasive is quoted to be 5-50%, but the examples all show 30%.
  • Japanese patent application no. 01/040600 describes cleaning compositions for cars and windows comprising surfactant, alcohol, an abrasive and a combination of a film-forming resin (preferably a polyvinyl alcohol resin) and a cellulose derivative. On top of that it may contain a thickener, which may be methylcellulose. The resin is supposed to dry out to form a film on the surface to be cleaned which traps dirt and abrasive.
  • a film-forming resin preferably a polyvinyl alcohol resin
  • a cellulose derivative On top of that it may contain a thickener, which may be methylcellulose.
  • the resin is supposed to dry out to form a film on the surface to be cleaned which traps dirt and abrasive.
  • the resin is present in an amount of at least 10% of the composition and the cellulose derivative in an amount of at least 0.6%, preferably at least 0.8%.
  • compositions comprising a thickening system consisting of hydroxypropyl cellulose or hydroxyethyl cellulose and an acrylic copolymer comprising monomeric groups possessing surfactant properties which are prepared by reacting an unsaturated acid with a nonionic surfactant.
  • the compositions do not contain an abrasive.
  • US 4,830,783 discloses contact lens cleaning fluids comprising an inorganic polishing compound with an average particle size preferably below 10 ⁇ m, a surfactant and a thickening agent.
  • an inorganic polishing compound with an average particle size preferably below 10 ⁇ m
  • a surfactant and a thickening agent.
  • a large list of possible polymeric and clay thickening agents is given, among which polyacrylic acid and some cellulose derivatives, without any particular preference.
  • Japanese patent application no. 60/108499 describes liquid abrasive cleaning compositions comprising a surfactant, a thickener, an insoluble abrasive and a hydrocarbon solvent.
  • the list of generally named thickeners includes polyacrylic acid, carboxycellulose and hydroxyethyl cellulose. The examples all use the clay mineral hectorite as the thickener. Similar compositions are described in DE 19918265 in which various cellulose ethers and anionic methacrylic acid/ethyl acrylate copolymers are mentioned as possible thickening agents.
  • liquid abrasive cleaning compositions comprising between 10% and 50% inorganic abrasive in combination with a mixture of thickening polymers, in amounts as defined in claim 1, comprising a nonionic cellulose ether and an alkali swellable or soluble (meth)acrylate polymer which has molecular weight of at least 100,000, provide excellent cleaning on a large variety of soils, including tough and strongly adhering soils, are easily rinsed away and have a non-gritty and smooth feel.
  • the invention also provides a process for cleaning hard surfaces comprising the steps of applying to the surface a composition according to the invention followed by removing the soil and the composition from the surface.
  • the invention provides an aqueous liquid abrasive cleaning composition according to claim 1.
  • the nonionic cellulose ether is a cellulose derivative in which some of the cellulose hydroxy groups are replaced by methoxy or ethoxy groups and/or hydroxyethoxy or hydroxypropoxy groups.
  • Such cellulose derivatives which are well known in the art, are e.g. methyl-cellulose, ethyl-cellulose, hydroxyethyl-cellulose, hydroxypropyl-cellulose, hydroxyethyl-methyl- and ethyl-cellulose and hydroxypropyl-methylcellulose.
  • Preferred are those cellulose ethers that are soluble in cold water and give increased viscosity at alkaline pH. Methyl-celluloses and their derivatives are particularly preferred, more particularly hydroxypropyl-methylcellulose.
  • those cellulose ethers are preferred which give a viscosity in 2% by weight solution in water of at least 10,000 mPa.s (BrookfieldTM, 20rpm, at 20°C), more preferably at least 20,000 mPa.s, most preferably between 30,000 and 55,000 mPa.s.
  • Suitable cellulose ethers are methyl-hydroxypropyl-cellulose PMC40 US, marketed by Samsung Fine Chemicals and Culminal MHPC 45000 PFR, marketed by Hercules Inc.
  • the cellulose ether is used in an amount of at least 0.01%, preferably at least 0.05%. An amount of more than 1% is not required; preferably the amount is at most 0.5%, more preferably at most 0.3%.
  • the amount is chosen such that the composition with cellulose ether but without the (meth)acrylate polymer has a viscosity of at most 200 mPa.s, preferably at most 100 mPa.s, more preferably at most 50mPa.s, most preferably at most 25 mPa.s (Equipment: HaakeTM VT 550; measurement conditions: Rotor MV II, 21 sec -1 shear rate and 25°C).
  • the other polymer in the double polymeric thickening system is an alkali-swellable or alkali-soluble (meth)acrylate polymer.
  • (meth)acrylate polymer is defined as homo- and copolymers of acrylate and/or methacrylate monomers and optionally other vinylic monomers.
  • it includes polyacrylate, polymethacrylate, copolymers of acrylate and methacrylate and copolymers of acrylate and/or methacrylate with other vinylic monomers such as maleic anhydride and styrene.
  • the carboxylate groups in the polymer are preferably partly esterified.
  • the polymer may also be cross-linked and/or hydrophobically modified. However, the polymer contains sufficient free carboxylic acid/carboxylate groups to make it alkali-swellable or alkali-soluble.
  • the polymers have a molecular weight of at least 100,000, preferably at least 500,000.
  • alkali-swellable or -soluble copolymers of methacrylic acid and ethyl acrylate and optionally other comonomers such as are exemplified in the ASE- and HASE-type AlcogumTM L and SL series polymers, marketed by National Starch & Chemical Company.
  • Alcogum L15 which is a medium cross-linked methacrylic acid/ethyl acrylate copolymer of molecular weight between 500,000 and 1000,000, is a particular example of a suitable polymer, as are Alcogum L11 and SL117.
  • (Meth)acrylate polymers suitable for the invention have in 1% (by weight of dry solids) solution in water at 20°C and pH 8 a viscosity of at least 500 mPa.s and at most 50,000 mPa.s (BroookfieldTM, 10rpm), preferably at least 1000 and at most 30,000.
  • the (meth)acrylate polymer is used in an amount of at least 0.1%, preferably at least 0.2%, more preferably at least 0.4%. Amounts of more than 4% are not required to obtain sufficient viscosity. Generally the amount is at most 2%, preferably at most 1%.
  • the two components of the double polymeric thickening system are generally used in a (meth)acrylate polymer/cellulose ether ratio of between 20:1 and 1:1, preferably between 10:1 and 2:1, more preferably between 7:1 and 2:1.
  • the liquid abrasive cleaning compositions according to the invention have such fluid flow characteristics that they are stable suspensions when not in use, but thin enough to be poured from the packaging container and spread on the soiled surface without appearing thin and watery.
  • the components and amounts of the thickening system are chosen in such a way that the composition has a viscosity between 300 and 5000 mPa.s, preferably 300-3000 mPa.s, more preferably 500-2500, most preferably 900-1800 mPa.s. (Equipment: HaakeTM VT 550; measurement conditions: Rotor MV II, 21 sec -1 shear rate and 25°C).
  • An inorganic abrasive is an essential component of the composition.
  • the amount of abrasive in the cleaning compositions according to the invention is preferably at least 15%, more preferably at least 20%, but preferably does not exceed 45% or even 40%.
  • Preferred abrasives have a Moh hardness of below 6, but above 1, preferably at least 2, although abrasives with higher hardness than 6 can be employed for specialist applications.
  • Suitable inorganic abrasives can be selected from water-soluble and water-insoluble materials. Soluble abrasives are present in an amount exceeding their solubility in water and the 10-50% amount of abrasive material then refers to the amount present as insoluble material. Examples of such materials are to be found among alkali metal carbonates, phosphates, sulphates, borates and chlorides, such as Na bicarbonate, Na borate, Na tripolyphosphate, K sulphate, water-free Ca sulphate. Suitable water-insoluble abrasives are zeolites, silica's, silicates, carbonates and aluminas.
  • Water-insoluble abrasives are preferred and preferred examples are: Ca carbonate (e.g. as calcite), mixtures of Ca and Mg carbonates (e.g. as dolomite), alumina, hydrated alumina, feldspar, talc and silica. Calcite and dolomite are particularly preferred due to their low cost and good abrasive properties.
  • Preferred weight average particle sizes for the abrasives fall in the range 1-500 microns, with values of 5-100 microns being particularly preferred.
  • compositions according to the invention preferably have pH between 5 and 14, more preferably at least 7.
  • An alkaline pH improves the cleaning properties, particularly on fatty soils and pH values between 8 and 13 are very suitable.
  • an alkaline pH is required for alkali metal and alkaline earth metal carbonates and bicarbonate abrasives.
  • the compositions according to the invention preferably contain one or more detergent surfactants. They may be chosen from a wide range of anionic, nonionic, zwitterionic and amphoteric surfactants well known in the art. For liquid abrasive cleaning compositions anionic and/or nonionic surfactants are most often chosen as the principle surfactant and for the purposes of the present invention nonionic surfactants are particularly preferred.
  • Synthetic anionic surfactants may be chosen from the alkali metal, alkaline earth metal, ammonium or alkanolammonium salts of the well known organic sulphuric acid esters and sulphonic acids having in the molecular structure a branched or straight chain alkyl group containing 8-22 C atoms or an alkylaryl group containing 6-20 C atoms in the alkyl part.
  • anionic surfactants are water-soluble salts of:
  • a suitable class of nonionic surfactants can be broadly described as compounds produced by the condensation of simple alkylene oxides, which are hydrophilic in nature, with an aliphatic or alkyl-aromatic hydrophobic compound having a reactive hydrogen atom.
  • the length of the hydrophilic or polyoxyalkylene chain that is attached to any particular hydrophobic group can be readily adjusted to yield a compound having the desired balance between hydrophilic and hydrophobic elements. This enables the choice of nonionic surfactants with the right HLB.
  • Particular examples include:
  • nonionic surfactants are:
  • Amphoteric or zwitterionic surfactants may be used as additional surfactants.
  • Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 6 to 20 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance sodium 3-dodecylamino-propionate, sodium 3-dodecylaminopropane-sulphonate and sodium N-2-hydroxy-dodecyl-N-methyltaurate.
  • Suitable zwitterionic surfactants can be found among derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic group of from 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance 3-(N,N-dimethyl-N-hexadecylammonium)-propane-1-sulphonate betaine, 3-(dodecylmethyl-sulphonium)-propane-1-sulphonate betaine and 3-(cetylmethyl-phosphonium)-ethanesulphonate betaine.
  • anionic water-solubilising group for instance 3-(N,N-dimethyl-N-hexadecylammonium)-propane-1-sulphonate betaine, 3-(dodecylmethyl-sulphonium)-propane-1-sulphonate betaine and 3-(cetylmethyl-phosphonium)-
  • surfactants are compounds commonly used as surface-active agents given in the well-known textbooks: “Surface Active Agents” Vol.1, by Schwartz & Perry, Interscience 1949; Vol.2 by Schwartz, Perry & Berch, Interscience 1958; in the current edition of "McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in “Tenside-Taschenbuch", H. Stache, 2nd Edn. Carl Hauser Verlag, 1981.
  • the total amount of surfactant is usually 0 - 4%, preferably, 0.1 - 2%, more preferably 0.2 - 1%.
  • the total surfactant in the composition according to the invention consists primarily or entirely of nonionic surfactant. Ethoxylated aliphatic alcohols are particularly preferred nonionic surfactants.
  • An organic solvent may optionally be present in the compositions according to the invention.
  • Various hydrocarbons e.g. mineral oil derived or terpenoid
  • alcohols e.g. mineral oil derived or terpenoid
  • polyols and polyol ethers have been described as suitable solvents for use in liquid abrasive cleaning compositions.
  • Preferred are mono- and diethylene glycol mono-ethers and mono- and di-propylene glycol mono-ethers.
  • Mono- and di-propylene glycol mono-(C 1 -C 5 )alkyl ethers are particularly suitable. When present the amount is kept below 5%, preferably below 2%, more preferably below 1%, but preferably at least 0.1%.
  • compositions according to the invention may further comprise well-known optional components to further enhance their properties in use, such as builders, antifoams, preservatives, antimicrobials, etc. They may also comprise components to enhance their consumer appeal such as colorants, pigments and perfume. They may contain bleaching agents provided that the other components in the composition are stable in their presence
  • the invention also provides a process for cleaning hard surfaces comprising the steps of applying to the surface a composition according to the invention, followed by removing the soil and the composition from the surface.
  • the composition may be appplied to the surface straight from the container and the surface thereafter cleaned by loosening the soil from the surface with a wet wipe, cloth, sponge or similar implement rubbing the composition over the surface.
  • the composition is first applied to a wipe, cloth or sponge which may be prewetted with water, wherafter the soil is loosened from the surface by rubbing the implement with the composition over the surface.
  • the treatment is completed by removing the soil and the composition from the surface, either with an implement or by rinsing the surface with water.
  • Stable liquid abrasive cleaning compositions having excellent cleaning properties on a variety of soils were prepared having the compositions given in the table below:
  • Example 1 Example 2 C 9 -C 11 Ethoxylated fatty alcohol 6OE 0.600 0.600 Sodium hydroxide 0.125 0.106 Alcogum L15 0.70 0.55 Calcium Carbonate (Omyacarb A30) 30.00 30.0 PMC 40US * 0.140 0.220 1.2 benzothiazolin-3-one 0.016 0.016 Dipropylene glycol n-butyl ether 0.60 - Water To 100% * Hydroxypropyl-methyl-cellulose supplied by Samsung Fine Chemicals.
  • the PCM 40US was premixed with sufficient water to obtain a thick, but pourable liquid mix. To the remainder of the water Alcogum, sodium hydroxide, abrasive, surfactant, the PCM 40US premix and the solvent (Example 1) were added, preferably in that order. Thereafter preservative and/or perfume was added, if desired.
  • the final mixture of Example 1 had a viscosity of 1250 mPa.s at 21 sec -1 (Haake VT550, rotor MVII).
  • the same composition, but without added PCM 40US has a viscosity of 500 mPa.s, whereas the same mixture with PCM 40US but without Alcogum has a viscosity of less than 50 mPa.s.
  • the sensory properties of the product according to example 1 were compared with those of a commercial product containing 20% calcite, 4.7% anionic/2.1% nonionic self-structuring surfactant mixture, 1% butyl digol solvent and 0.03% Acusol 820 polycarboxylate.
  • a panel of 20 consumers judged both products on creaminess and consistency using a scale of 1-5.
  • the average rating on creaminess of example 1 was 3.8 versus 2.0 for the commercial product; the average rating on consistency for example 1 was 3.7, versus 2.3 for the commercial product.
  • the product according to example 1 was often commented on as having a silky feel

Landscapes

  • 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)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des compositions détergentes abrasives liquides aqueuses. Ces compositions contiennent 10 à 50 % d'un abrasif inorganique, ainsi qu'un système épaississant polymère double comprenant un éther de cellulose non ionique et un polymère (méth)acrylique qui gonfle ou se dissout dans les alcalis.

Claims (13)

  1. Composition aqueuse détergente abrasive liquide comprenant un abrasif inorganique et un épaississant polymérique caractérisé en ce qu'elle comprend :
    - 10 à 50 % d'abrasif inorganique;
    - un double système épaississant polymérique comprenant un éther de cellulose non ionique en quantité de 0,01 à 1 % et un polymère (méth)-acrylate capable de gonfler ou soluble en milieu alcalin ayant une masse moléculaire au moins égale à 100 000 en une quantité de 0,1 à 4 %,
    et dans laquelle la composition a une viscosité entre 300 et 5000 mPa.s.
  2. Composition détergente selon la revendication 1 caractérisée en ce que la quantité de dérivé cellulosique est de 0,05 à 0,5 %.
  3. Composition détergente selon les revendications 1 à 2 caractérisée en ce que l'éther de cellulose est une méthylcellulose ou un dérivé de celle-ci.
  4. Composition détergente selon la revendication 3 caractérisée en ce que l'éther de cellulose est une méthylhydroxypropylcellulose.
  5. Composition détergente selon les revendications 1 à 4 caractérisée en ce que les éthers de celluloses choisis donnent une viscosité en solution à 2 % dans l'eau au moins égale à 10 000 mPa.s.
  6. Composition détergente selon les revendications 1 à 5 caractérisée en ce que la quantité de polymère (méth)acrylate capable de gonfler ou soluble en milieu alcalin est de 0,2 à 2 %.
  7. Composition détergente selon les revendications 1 à 6 caractérisée en ce qu'un polymère (méth)-acrylate choisi possède, en solution à 1 % dans l'eau à 20°C et pH 8, une viscosité entre 500 et 50 000 mPas.
  8. Composition détergente selon la revendication 6 ou 7 caractérisée en ce que le polymère (méth)-acrylate est un copolymère d'acide méthacrylique et d'acrylate d'éthyle et de manière facultative d'autres comonomères.
  9. Composition détergente selon les revendications 1 à 8 caractérisée en ce que les deux composants du double système épaississant polymérique sont utilisés dans un rapport polymère (méth)acrylate/éther de cellulose entre 20/1 et 1/1.
  10. Composition détergente selon les revendications 1 à 9 caractérisée en ce que l'abrasif est choisi dans le groupe comprenant le carbonate de calcium, les mélanges de carbonates de calcium et de magnésium, la zéolite, l'alumine, l'hydrate d'alumine, le feldspath, le talc et la silice et possède une taille de particule de 5 à 100 µm.
  11. Composition détergente selon les revendications 1 à 10 caractérisée en ce qu'elle contient un surfactant en quantité jusqu'à 4 %.
  12. Composition détergente selon la revendication 11 caractérisée en ce qu'elle contient un surfactant non ionique en quantité de 0,1 à 4 %.
  13. Procédé de nettoyage de surfaces dures comprenant les étapes consistant à appliquer sur la surface une composition selon l'une quelconque des revendications 1 à 12 et à éliminer de la surface la salissure et la composition.
EP02777294A 2001-11-06 2002-10-08 Compositions detergentes abrasives liquides Expired - Lifetime EP1446470B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02777294A EP1446470B1 (fr) 2001-11-06 2002-10-08 Compositions detergentes abrasives liquides

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP01204217 2001-11-06
EP01204217 2001-11-06
EP02777294A EP1446470B1 (fr) 2001-11-06 2002-10-08 Compositions detergentes abrasives liquides
PCT/EP2002/011268 WO2003040284A1 (fr) 2001-11-06 2002-10-08 Compositions detergentes abrasives liquides

Publications (2)

Publication Number Publication Date
EP1446470A1 EP1446470A1 (fr) 2004-08-18
EP1446470B1 true EP1446470B1 (fr) 2006-02-08

Family

ID=8181188

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02777294A Expired - Lifetime EP1446470B1 (fr) 2001-11-06 2002-10-08 Compositions detergentes abrasives liquides

Country Status (7)

Country Link
EP (1) EP1446470B1 (fr)
AR (1) AR037206A1 (fr)
AT (1) ATE317424T1 (fr)
DE (1) DE60209135T2 (fr)
HU (1) HUP0401706A2 (fr)
WO (1) WO2003040284A1 (fr)
ZA (1) ZA200402658B (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070117736A1 (en) * 2005-11-22 2007-05-24 Figger David L Sprayable high viscosity thixotropic surface cleaners
US20100197557A1 (en) * 2007-07-31 2010-08-05 The Dial Corporation Shear-thinning, dispensable liquid abrasive cleanser with improved soil removal, rinseability and phase stability
EP2719752B1 (fr) * 2012-10-15 2016-03-16 The Procter and Gamble Company Composition détergente liquide avec des particules abrasives
US10266793B2 (en) 2016-09-30 2019-04-23 Novaflux, Inc. Compositions for cleaning and decontamination
EP3441447A1 (fr) * 2017-08-09 2019-02-13 Henkel AG & Co. KGaA Éther de cellulose non ionique en tant que renforçateur d'élimination de salissures lors du nettoyage de surfaces dures
JP2021520442A (ja) 2018-04-03 2021-08-19 ノバフラックス インコーポレイテッド 高吸収性ポリマーを備える洗浄組成物
US11918677B2 (en) 2019-10-03 2024-03-05 Protegera, Inc. Oral cavity cleaning composition method and apparatus

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4830783A (en) * 1979-06-25 1989-05-16 Polymer Technology, Corp Abravise-containing contact lens cleaning materials
JPS60108499A (ja) * 1983-11-18 1985-06-13 ライオン株式会社 研磨材含有液体洗浄剤組成物
US5057241A (en) * 1988-11-16 1991-10-15 S. C. Johnson & Son, Inc. Dual polymer self-sealing detergent compositions and methods
DE19918265A1 (de) * 1999-04-22 2000-10-26 Henkel Kgaa Abrasivstoffhaltiges Reinigungsmittel mit Mikrokapseln

Also Published As

Publication number Publication date
HUP0401706A2 (hu) 2004-12-28
WO2003040284A1 (fr) 2003-05-15
AR037206A1 (es) 2004-10-27
ATE317424T1 (de) 2006-02-15
DE60209135D1 (de) 2006-04-20
ZA200402658B (en) 2005-04-05
DE60209135T2 (de) 2006-07-13
EP1446470A1 (fr) 2004-08-18

Similar Documents

Publication Publication Date Title
CA1315636C (fr) Compositions de nettoyage pour surfaces dures
EP2447349A1 (fr) Composition liquide de nettoyage d'une surface dure
CZ299089B6 (cs) Cisticí prostredek pro tvrdé povrchy
EP0699226B2 (fr) Compositions nettoyantes pour surfaces dures, comprenant des polymeres
EP3015540B1 (fr) Nettoyants de surfaces dures comprenant des tensioactifs non ioniques alcoxylés éthoxylés
WO2004046292A1 (fr) Detergent ayant une composition amelioree
EP1446470B1 (fr) Compositions detergentes abrasives liquides
CA2066623C (fr) Detersifs liquides des polymeres deflocucants
CA1160134A (fr) Detergent a teneur d'abrasif
AU2004242124B2 (en) Bathroom cleaning composition
AU647912B2 (en) Linear viscoelastic aqueous liquid detergent composition, especially for automatic dishwashers
AU8019498A (en) Abrasive cleaning composition
EP1607472A1 (fr) Compositions nettoyantes liquides aqueuses
JP2002003890A (ja) 洗浄剤組成物
WO2002090477A2 (fr) Compositions de nettoyage liquides contenant des agents abrasifs
IE921274A1 (en) Viscoelastic aqueous liquid detergent compositions,¹especially for automatic dishwashers of improved¹dispensability
WO2000020544A1 (fr) Composition abrasive non liquide
EP0574236A2 (fr) Composition aqueuse contenant un polymère non-réticulé pour augmenter la viscosité
WO2015101448A1 (fr) Composition nettoyante pour surfaces dures

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040326

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

17Q First examination report despatched

Effective date: 20050324

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER N.V.

Owner name: UNILEVER PLC

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20060208

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060208

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060208

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060208

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060208

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060208

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060208

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060208

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60209135

Country of ref document: DE

Date of ref document: 20060420

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060508

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060508

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060519

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060710

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: UNILEVER PLC

Owner name: UNILEVER N.V.

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061031

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20061031

Year of fee payment: 5

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20061109

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070501

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20061008

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20070629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061008

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061031

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060208

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060509

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060208

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060208

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061008

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060208

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071008