EP1337616B1 - Zusammensetzung zum reinigen von harten oberflächen - Google Patents

Zusammensetzung zum reinigen von harten oberflächen Download PDF

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Publication number
EP1337616B1
EP1337616B1 EP01993373A EP01993373A EP1337616B1 EP 1337616 B1 EP1337616 B1 EP 1337616B1 EP 01993373 A EP01993373 A EP 01993373A EP 01993373 A EP01993373 A EP 01993373A EP 1337616 B1 EP1337616 B1 EP 1337616B1
Authority
EP
European Patent Office
Prior art keywords
particles
composition according
cleaning composition
liquid
particle size
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
EP01993373A
Other languages
English (en)
French (fr)
Other versions
EP1337616A1 (de
Inventor
Paola Baggi
Helen Burgess
Cinzia Fontana
Takashi Inamura
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 EP01993373A priority Critical patent/EP1337616B1/de
Publication of EP1337616A1 publication Critical patent/EP1337616A1/de
Application granted granted Critical
Publication of EP1337616B1 publication Critical patent/EP1337616B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—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
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • 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

Definitions

  • the present invention relates to liquid compositions for cleaning hard surfaces. Particularly, the invention relates to clear liquid cleaning gels containing macroscopic solid particles.
  • Liquid abrasive cleaning compositions for hard surfaces are well known in the art. They generally have a milky white appearance. They have sufficient viscosity at low shear stress to keep the fine abrasive particles evenly dispersed in the liquid, while at the same time they behave as true liquids when being dispensed from a bottle.
  • the fine abrasive particles (powder) in these compositions generally have a particle size below 200 micron, in most cases below 100 micron.
  • Well know abrasives used in such compositions are silica, calcite, feldspar and similar inorganic materials as well as several organic polymer particles, all with a Mohs hardness of up to 6. Although many consumers extensively use such compositions, some do not appreciate the feel or appearance of these products, or fear that they might scratch their delicate surfaces.
  • Some liquid abrasive products on the market consist of a gel-like opaque liquid in which a variety of coarse and fine irregularly shaped abrasive polymer particles are dispersed varying in diameter between more than 1 mm at one end and hardly visible to the naked eye at the other end. Because of this the total product appearance is unattractive. Thus, there is a need for a new liquid hard surface cleaning product containing solid particles, which is visually appealing to the consumer and at the same time cleans effectively.
  • liquid crystal cleaning compositions which are transparent or slightly turbid and contain small amounts of abrasive particles.
  • the particles may be zeolites with a mean particle size of 8-10 ⁇ m, amorphous silica with a particle size of up to 300 ⁇ m or polyethylene powder with a particle size of up to 500 ⁇ m
  • WO00/65019 discloses liquid abrasive cleaning compositions containing a fine particulate abrasive and in addition thereto microcapsules containing various additional components such as perfume, silicone oil and the like. In view of the specified amount and particle size of the abrasive, the compositions are clearly not transparent or translucent.
  • WO00/36078 discloses pourable transparent laundry detergent compositions, containing at least 15% surfactant.
  • the compositions are thickened to be able to suspend macroscopic capsules containing ingredients that are desirably kept separate from the concentrated and highly alkaline detergent solution. Similar compositions, also for other applications, are disclosed in GB 1303810. The capsules do not have abrasive properties.
  • the invention provides liquid cleaning compositions for hard surfaces which are clear aqueous liquid gels comprising one or more detergent surfactants and macroscopic abrasive particles, which are dispersed in a stable fashion through the liquid.
  • the invention further provides a process for cleaning hard surfaces comprising the step of applying to the surface a clear aqueous liquid gel which comprises one or more detergent surfactants and macroscopic abrasive particles which are evenly dispersed through the liquid.
  • the cleaning compositions of the invention are clear aqueous liquid gels.
  • all components of the compositions with the exception of the abrasive particles, are clearly soluble in water.
  • the required viscosity to give the composition its gel consistency is obtained by the addition of suitable thickening agents that are able to give a clear solution.
  • suitable thickening agents include various vegetable or microbial polysaccharide gums, such as gum arabic, xanthan, alginates and the like, and synthetic polymers e.g. homopolymers of acrylic, methacrylic or maleic acid and copolymers thereof with each other and/or other monomers such as styrene, vinyl ethers etc.
  • a gel is considered to be clear if it transmits at least 50% of light at any one wavelength in the visible region i.e. between 400 and 800nm, preferably 550-700nm, measured in a 1cm cuvette in the absence of dyes and abrasive particles.
  • the transmittance is at least 70%, more preferably at least 90%.
  • Gels which are satisfactory for the purposes of the present invention generally have a viscosity of between 100 and 1000 mPas, preferably at least 250 mPas, more preferably 300-750 mPas at 21 sec -1 (measured with a Haake viscometer at 20°C).
  • the low shear rate viscosity is such that the gel is able to suspend the macroscopic particles.
  • the particles are macroscopic, i.e. clearly visible separately to the naked eye. This is in contrast to most abrasive powder particles which generally have average particle size well below 0.3mm and in the vast majority of cases at most 0.1mm (100 ⁇ m).
  • the particles according to the invention have an average particle size of from more than 0.5 to 2.5 mm, preferably at most 1.5mm, and all particles have a particle size within the range of plus or minus 70% of the average particle size, preferably within a range of ⁇ 50%, more preferably ⁇ 30%.
  • the abrasive particles are used in an amount of at least 0.1%, preferably 0.5%. In order to retain the transparent character of the total composition the maximum amount of particles is 20%, preferably 10%, more preferably 5%.
  • the particles may be made of abrasive materials known in the art.
  • they may consist of granules of one or more of the well known inorganic abrasives such as silica, silicates, calcite and the like.
  • They may consist of polymer granules, such as polyethylene, polypropylene, polycarbonate and the like. Particularly suitable are granules of a biodegradable polymer, such as the starch-derived plastics known in the art.
  • the abrasive particles may be made of softer materials such as hard waxes and fats, hard fatty acids, hard fatty acid soaps and the like. Such materials may also be mixed with fine particles of any of the known abrasives or with other materials, preferably solid materials, suitable for improving the cleaning process and thereafter formed into granules of the required size.
  • the visual appeal of the particles, and therefore the total composition, is further enhanced if the particles have a certain minimum sphericity, such that the ratio between the longest and the shortest diameter of a particle in any one direction is at most 3:1, preferably at most 2:1 or even 1.5:1.
  • Particularly preferred are particles with a round, preferably a smooth round shape.
  • Such particles may be made by prilling processes involving making a melt of the particle material, converting it into droplets, which are thereafter cooled in a gas (air) flow.
  • Various processes and suitable equipment therefore are known in the art and may be applied to the organic abrasives, provided they are sufficiently low melting.
  • High melting powders such as inorganic abrasive powders may be made into suitably shaped particles by various agglomeration processes known in the art, if necessary using an aglomeration binder.
  • the cleaning compositions according to the invention may consist of a colourless liquid and solid particles having their natural colour (in many cases white), the compositions are considerably more attractive to the consumer if the liquid and the particles have clearly different colours. They may have different shades of the same colour, e.g. dark blue particles in a light blue liquid, or preferably, the liquid and the particles have contrasting colours e.g. white particles in a blue, green or yellow liquid or vice versa, or coloured particles in a differently coloured liquid.
  • the pH of the cleaning compositions may vary within wide limits and will generally be between 2 and 14. Certain surfaces are acid-sensitive and for those a composition with pH of at least 3, preferably 3.5 or even 4 is advised. Improved cleaning of greasy soils is often obtained at alkaline pH i.e. above 7, preferably above 7.5. pH above 12 is generally not required.
  • compositions according to the invention comprise one or more surfactants which may be chosen from a wide range of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, examples of which are given below.
  • a suitable class of anionic surfactants are water-soluble salts of organic sulphuric acid esters and sulphonic acids having in the molecular structure an 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 organic hydrophobic compound which may be aliphatic or alkylaromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene chain that is attached to any particular hydrophobic group can be readily adjusted to yield a water-soluble 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:
  • Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 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 cationic surfactants can be found among quaternary ammonium salts having one or two alkyl or aralkyl groups of from 8 to 20 carbon atoms and two or three small aliphatic (e.g. methyl) groups, for instance cetyltrimethylammonium bromide.
  • 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 described 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.
  • Anionic and nonionic surfactants and combinations thereof are particularly preferred. In choosing the (combination of) surfactants care should be taken that they give a clear solution. Hydrotropes such as Na xylene- or cumene-sulfonate or others known in the art may be added if necessary.
  • the surfactants are generally present in an amount of at least 0.1%, but below 15%, preferably 0.5-10%, more preferably at least 1.0%.
  • compositions according to the invention may contain various optional components well known in the art which improve cleaning performance or consumer appeal.
  • the compositions may contain builders, chelating agents, electrolytes, organic solvents, active halogen or peroxy bleaching agents, pH regulating agents, anti-foams, antimicrobials, preservatives, perfumes, insect repellents, etc.
  • the process for cleaning a hard surface involves applying to the hard surface a suitable amount of the composition according to the invention, generally followed by rubbing the composition over the surface to be cleaned using a wipe or cloth.
  • the composition may be applied directly to the surface or, alternatively, the composition may be applied to the (preferably damp) wipe or cloth first and thereafter this is rubbed over the surface with the side on which the composition was applied facing the surface.
  • the abrasive particles are made of polymer or other relatively soft material the compositions according to the invention are very suitable for cleaning delicate surfaces which would otherwise easily be scratched.
  • a clear liquid blue coloured gel was prepared, according to the formula below, which contained fatty acid granules having a diameter of 0.8 mm ⁇ 20% dispersed therein.
  • a clear liquid green coloured gel was prepared, according to the formula below, which contained polyethylene granules having a diameter of 0.8 mm ⁇ 20% dispersed therein.
  • the product had a viscosity of 380 mPas at 21 sec -1 and 20°C and a pH of 11.
  • a mildly acidic (pH around 4.5) hydrogen peroxide containing clear hard surface cleaning gel was prepared according to the formula below.
  • Fatty acid prills containing 10% by weight (calculated on the prills) sodium bicarbonate and having a diameter of 1.0 mm ⁇ 20% were dispersed therein.
  • INGREDIENT TRADE NAME LEVEL in % Sequestrant Dequest 2046 0.10 Nonionic Lialet 111-5.5EO
  • Fatty acid (in solution) 0.30 Polyacrylate polymer Carbopol ETD2623 0.30 Hydrogen peroxide 3.00

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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)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (12)

  1. Klares wässeriges Gel als flüssige Abriebreinigungszusammensetzung für harte Oberflächen, umfassend ein oder mehrere oberflächenaktive Waschmittel und Abriebteilchen, dadurch gekennzeichnet, daß die Abriebteilchen, die in der Flüssigkeit dispergiert sind, makroskopisch mit einer durchschnittlichen Teilchengröße von mehr als 0,5 mm bis 2,5 mm sind, und daß alle Teilchen eine Teilchengröße im Bereich von plus oder minus 70 % der durchschnittlichen Teilchengröße aufweisen.
  2. Reinigungszusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die durchschnittliche Teilchengröße höchstens 1,5 mm beträgt.
  3. Reinigungszusammensetzung nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß alle Teilchen eine Teilchengröße im Bereich von ± 50 % der durchschnittlichen Teilchengröße aufweisen.
  4. Reinigungszusammensetzung nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Teilchen Kugelförmigkeit aufweisen, so daß das Verhältnis zwischen dem längsten und dem kürzesten Durchmesser eines Teilchens in irgendeine Richtung höchstens 3 : 1 beträgt.
  5. Reinigungszusammensetzung nach Anspruch 4, dadurch gekennzeichnet, daß die Teilchen eine glatte runde Form aufweisen.
  6. Reinigungszusammensetzung nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß sie eine Viskosität zwischen 100 und 1.000 mPas bei 21 s-1 aufweist.
  7. Reinigungszusammensetzung nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß die Flüssigkeit und die Teilchen unterschiedliche Farben aufweisen.
  8. Reinigungszusammensetzung nach Anspruch 7, dadurch gekennzeichnet, daß die Flüssigkeit und die Abriebteilchen kontrastierende Farben aufweisen.
  9. Reinigungszusammensetzung nach den Ansprüchen 1 bis 8, dadurch gekennzeichnet, daß sie zumindest 0,1 aber weniger als 15 % oberflächenaktives Mittel enthält.
  10. Reinigungszusammensetzung nach den Ansprüchen 1 bis 9, dadurch gekennzeichnet, daß das oberflächenaktive Mittel aus anionischen oberflächenaktiven Mitteln, nicht-ionischen oberflächenaktiven Mitteln und Gemischen hiervon ausgewählt ist.
  11. Reinigungszusammensetzung nach den Ansprüchen 1 bis 10, dadurch gekennzeichnet, daß sie 0,1 bis 20 % Abriebteilchen enthält
  12. Verfahren zur Reinigung einer harten Oberfläche, umfassend den Schritt der Auftragung einer Reinigungszusammensetzung nach einem der Ansprüche 1 bis 11 auf die Oberfläche.
EP01993373A 2000-11-03 2001-10-15 Zusammensetzung zum reinigen von harten oberflächen Expired - Lifetime EP1337616B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01993373A EP1337616B1 (de) 2000-11-03 2001-10-15 Zusammensetzung zum reinigen von harten oberflächen

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP00203831 2000-11-03
EP00203831 2000-11-03
PCT/EP2001/011881 WO2002038720A1 (en) 2000-11-03 2001-10-15 Composition for cleaning hard surfaces
EP01993373A EP1337616B1 (de) 2000-11-03 2001-10-15 Zusammensetzung zum reinigen von harten oberflächen

Publications (2)

Publication Number Publication Date
EP1337616A1 EP1337616A1 (de) 2003-08-27
EP1337616B1 true EP1337616B1 (de) 2004-12-22

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EP01993373A Expired - Lifetime EP1337616B1 (de) 2000-11-03 2001-10-15 Zusammensetzung zum reinigen von harten oberflächen

Country Status (15)

Country Link
EP (1) EP1337616B1 (de)
JP (1) JP4113429B2 (de)
AR (1) AR031192A1 (de)
AT (1) ATE285469T1 (de)
AU (2) AU2002220627B2 (de)
BR (1) BR0115088A (de)
CA (1) CA2424455C (de)
CZ (1) CZ299089B6 (de)
DE (1) DE60107979T2 (de)
ES (1) ES2230389T3 (de)
HU (1) HUP0303574A3 (de)
PL (1) PL196482B1 (de)
RU (1) RU2292386C2 (de)
WO (1) WO2002038720A1 (de)
ZA (1) ZA200302356B (de)

Families Citing this family (26)

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Publication number Priority date Publication date Assignee Title
GB2390097A (en) * 2002-06-28 2003-12-31 Reckitt Benckiser Nv Detergent gels containing coloured particles
AU2003258507A1 (en) * 2002-07-30 2004-02-23 Unilever Plc Abrasive hard surface cleaning compositions
GB2393908A (en) * 2002-10-12 2004-04-14 Reckitt Benckiser Inc Thickened, abrasive containing, liquid disinfectant
US20050176614A1 (en) 2002-10-16 2005-08-11 Heinz-Dieter Soldanski Transparent abrasive cleaning product, especially manual dishwashing liquid
DE10248313A1 (de) 2002-10-16 2004-05-06 Henkel Kgaa Transparentes abrasives Reinigungsmittel, insbesondere Handgeschirrspülmittel
US7799141B2 (en) 2003-06-27 2010-09-21 Lam Research Corporation Method and system for using a two-phases substrate cleaning compound
EP1786392B1 (de) 2004-07-21 2011-08-24 Colgate-Palmolive Company Strukturierte körperwaschlotion
ES2396144T3 (es) 2005-04-21 2013-02-19 Colgate-Palmolive Company Composición de detergente líquida
SG154438A1 (en) * 2005-12-30 2009-08-28 Lam Res Corp Cleaning compound and method and system for using the cleaning compound
CA2672566C (en) 2006-12-15 2013-10-08 Colgate-Palmolive Company Structured liquid detergent composition for suspending materials
EP2328998A1 (de) 2008-09-30 2011-06-08 The Procter & Gamble Company Flüssiges reinigungsmittel für feste oberflächen
ES2582573T3 (es) 2008-09-30 2016-09-13 The Procter & Gamble Company Composiciones limpiadoras líquidas de superficies duras
EP2336286A1 (de) * 2009-12-18 2011-06-22 The Procter & Gamble Company Zusammensetzung mit Mikrokapseln
CA2785485A1 (en) * 2009-12-22 2011-07-21 The Procter & Gamble Company Liquid cleaning and/or cleansing composition
ES2444618T3 (es) * 2009-12-22 2014-02-26 The Procter & Gamble Company Composición limpiadora y/o de lavado líquida
EP2561056A1 (de) 2010-04-21 2013-02-27 The Procter & Gamble Company Flüssigreinigung und/oder reinigungszusammensetzung
US9353337B2 (en) 2010-09-21 2016-05-31 The Procter & Gamble Company Liquid cleaning composition
US8445422B2 (en) 2010-09-21 2013-05-21 The Procter & Gamble Company Liquid cleaning composition
EP2431451A1 (de) * 2010-09-21 2012-03-21 The Procter & Gamble Company Flüssige Reinigungsmittelzusammensetzung mit Schleifpartikeln
JP6091045B2 (ja) * 2010-09-30 2017-03-08 小林製薬株式会社 研磨剤組成物
EP2537917A1 (de) 2011-06-20 2012-12-26 The Procter & Gamble Company Flüssige Reinigungsmittel mit Schleifpartikeln
CA2839953C (en) * 2011-06-20 2017-02-14 The Procter & Gamble Company Liquid cleaning and/or cleansing composition
EP2721136A1 (de) 2011-06-20 2014-04-23 The Procter and Gamble Company Flüssigreinigung und/oder reinigungszusammensetzung
US8852643B2 (en) 2011-06-20 2014-10-07 The Procter & Gamble Company Liquid cleaning and/or cleansing composition
ES2577147T3 (es) 2012-10-15 2016-07-13 The Procter & Gamble Company Composición detergente líquida con partículas abrasivas
RU2656334C1 (ru) * 2017-06-13 2018-06-05 Федеральное государственное бюджетное образовательное учреждение высшего образования "Тверской государственный университет" Способ механохимического удаления накипных отложений

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US5741770A (en) * 1989-09-22 1998-04-21 Colgate-Palmolive Co. Liquid crystal composition
US5723431A (en) * 1989-09-22 1998-03-03 Colgate-Palmolive Co. Liquid crystal compositions
US6362156B1 (en) * 1998-12-16 2002-03-26 Unilever Home & Personal Care, Usa, Division Of Conopco, Inc. Pourable transparent/translucent liquid detergent composition with suspended particles

Also Published As

Publication number Publication date
ZA200302356B (en) 2004-03-26
JP4113429B2 (ja) 2008-07-09
RU2292386C2 (ru) 2007-01-27
DE60107979D1 (de) 2005-01-27
ES2230389T3 (es) 2005-05-01
AU2062702A (en) 2002-05-21
CA2424455A1 (en) 2002-05-16
AR031192A1 (es) 2003-09-10
CZ299089B6 (cs) 2008-04-23
HUP0303574A2 (hu) 2004-03-29
AU2002220627B2 (en) 2006-06-01
HUP0303574A3 (en) 2005-11-28
PL196482B1 (pl) 2008-01-31
WO2002038720A1 (en) 2002-05-16
EP1337616A1 (de) 2003-08-27
CA2424455C (en) 2009-10-06
BR0115088A (pt) 2003-10-07
DE60107979T2 (de) 2005-05-19
JP2004514026A (ja) 2004-05-13
ATE285469T1 (de) 2005-01-15
PL361062A1 (en) 2004-09-20

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