EP0702711B1 - Giessfähige flüssige wässrige reinigungsmittelkonzentrate ii - Google Patents

Giessfähige flüssige wässrige reinigungsmittelkonzentrate ii Download PDF

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Publication number
EP0702711B1
EP0702711B1 EP94919605A EP94919605A EP0702711B1 EP 0702711 B1 EP0702711 B1 EP 0702711B1 EP 94919605 A EP94919605 A EP 94919605A EP 94919605 A EP94919605 A EP 94919605A EP 0702711 B1 EP0702711 B1 EP 0702711B1
Authority
EP
European Patent Office
Prior art keywords
weight
contain
alkyl
cleaning concentrates
amphoteric surfactants
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
EP94919605A
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German (de)
English (en)
French (fr)
Other versions
EP0702711A1 (de
Inventor
Rainer Jeschke
Eva Kiewert
Katica Bocarac
Rainer Hofmann
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0702711A1 publication Critical patent/EP0702711A1/de
Application granted granted Critical
Publication of EP0702711B1 publication Critical patent/EP0702711B1/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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the invention relates to pourable liquid aqueous detergent concentrates which can be used undiluted as abrasives and in dilute form as general-purpose detergents.
  • Such agents are known and are based on the use of water-soluble abrasive components which have an abrasive function in concentrated media, but which practically dissolve in dilute media and can be easily removed from the substrate by simply rinsing with water after use.
  • Stable pastes are known from US Pat. No. 4,179,414, which consist of approximately 50 to 65% by weight sodium bicarbonate, approximately 50 to 35% by weight water and approximately 5 to 20% by weight sodium chloride and approximately 10 to 30% by weight C. 12 -C 16 fatty acid diethanolamide, both based on the water content, consist of an abrasive effect in concentrated form and clean hard surfaces in a diluted form. No information is given on the particle size of the sodium bicarbonate.
  • Liquid agents are known from EP 0 193 375 A2, which can contain 1.5 to 30% by weight of surfactants and 6 to 45% by weight of sodium bicarbonate with an average diameter of 10 to 500 ⁇ m. The rest is water.
  • aqueous agents which contain 1.5 to 40% by weight of surfactants, 2.0 to 65% by weight of mostly undissolved potassium sulfate with the same particle size as above, preferably 20-300 ⁇ m, and optionally contain 0.5 to 10 wt .-% sodium chloride.
  • liquid abrasives with water-soluble abrasives are known which contain about 1.5 to 30% by weight of surfactants, about 45 to about 75% by weight of sodium bicarbonate with a small mean particle size of expressly less than 80 ⁇ m and can contain more than 10% by weight of water.
  • DE 42 27 863.5 discloses liquid detergent concentrates with water-soluble abrasives, which consist of about 2 to 30% by weight of a slightly foaming agent Mixture of surfactants and about 50 - 65 wt .-% sodium bicarbonate with an average particle size of about 200 microns exist.
  • Almost all known pourable liquid aqueous cleaning agents with water-soluble abrasive components contain a carrier phase consisting of a combination of anionic surfactants of the sulfonate and / or sulfate type and nonionic surfactants.
  • a low-foaming carrier phase composed of particularly skin-mild surfactants, which makes it possible to use both coarse sodium bicarbonate with an average particle size of about 200 ⁇ 100 ⁇ m, which is characterized by a particularly good abrasive cleaning performance, and finer sodium bicarbonate with an average one Particle size distribution of about 65 ⁇ 40 ⁇ m, which is characterized by a particularly creamy soft consistency, to be dispersed in a stable manner.
  • This carrier phase consists essentially of alkyl polyglycol ethers with a narrow homolog distribution, amphoteric surfactants and soaps.
  • This may optionally contain anionic surfactants of the sulfate or sulfonate type, but the cleaning concentrates according to the invention are preferably free of anionic surfactants of the sulfate or sulfonate type.
  • bicarbonate sodium bicarbonate
  • inorganic salts e.g. Sodium sulfate, sodium carbonate, sodium chloride, but sodium bicarbonate (hereinafter referred to as bicarbonate) primarily fulfills the requirements for a technically feasible product (compare WO 91/8282, p. 12 f).
  • alkyl polyglycol ethers those with a narrowed homolog distribution of the attached ethylene oxide, such as are known from "A. Behler et al, Seifen- ⁇ le-Fett-Vachse, 116 , 60-68, (1990) and DE 38 17 415, are used which thicken act and are furthermore distinguished by the fact that they are particularly mild on the skin and are readily biodegradable, including, for example, the alkyl polyglycol ethers with a narrow homolog distribution with 8 to 18, preferably 9 to 16 carbon atoms in the alkyl radical and 2 to 8, preferably 2 to 5, ethylene oxide units (EO) in the molecule These are contained in the cleaning agent concentrates according to the invention in an amount of 1 to 20% by weight, preferably 2 to 15% by weight.
  • EO ethylene oxide units
  • amphoteric surfactants to which 0.5 to 10, preferably 1 to 5% by weight of quaternary ammonium compounds consisting of an alkyl radical with 7 to 18 carbon atoms and a hydrophilic head group.
  • N- (3-N'-C 8 -C 18 -Acylaminopropyl) -N, N-dimethylammonium acetate and N-alkyl-N, N-dimethylammonium acetate are preferably used.
  • the individual surfactant classes of the surfactant mixture can be represented by one or more of their compounds.
  • the alkyl polyglycol ethers can be derived from technical alcohol mixtures, such as those obtained by high-pressure hydrogenation of methyl esters based on vegetable or animal raw materials or by hydrogenation of aldehydes from ROELEN's oxo synthesis.
  • C 8 -C 18 -alkyl polyglycol ethers with normal distribution of the ethylene oxide units can also be present in an amount of 1 to 20% by weight, such as the products sold under the trade name Dehydol.
  • 8 -C 18 fatty acid mono- and dialkanolamides, that sold under the trade name Comperlan 100 C 8 -C 18 fatty acid monoethanolamide be contained in an amount of 0.1 to 4 wt .-% optionally C, for example.
  • the flow properties and the stability of the dispersion can be increased by adding up to 5% by weight, preferably 0.5 to 3% by weight, of a polyalkylene glycol of the general formula H- (OC (H) R 1 -CH 2 ) n - OH, where R 1 is hydrogen or a methyl group and n is an integer from 4 to 40 and / or by adding up to 5% by weight, preferably 0.2 to 3% by weight, of alkyl polyglycosides of the general formula R 2 O- [Z] x , where R 2 is a linear or branched alkyl - or alkenyl group having 6 to 22 carbon atoms, Z represents a sugar residue from the group of aldopentoses or aldohexoses, for example glucose, mannose and xylose, and x on average has a number from 1.3 to 1.8.
  • Suitable polyalkylene glycols are the polyethylene glycols sold under the trade names Polydiol 600 and Polydiol 1000 with average molecular weights of 600 and 1000, respectively.
  • Suitable alkyl polyglycosides are, for example, C 8 -C 10 alkyl polyglucosides, which are sold under the Plantaren 225 trade name.
  • Preferred cleaning agent concentrates further contain an inorganic material stabilizing the carrier phase in an amount of 0.2 to 5% by weight, preferably 0.5 to 3% by weight.
  • stabilizing inorganic materials are understood to be those substances which contribute to the stabilization and viscosity regulation of the cleaning agent concentrates according to the invention.
  • the inorganic material is preferably selected from the group of phyllosilicates, aluminum oxide hydrates and precipitated silicas. Suitable layered silicates are e.g. Montmorillonite, calcium silicate and magnesium silicate.
  • the inorganic materials do not impair the desired properties of the detergent concentrates, e.g. easy rinsing after concentrated use.
  • Particularly preferred cleaning agent concentrates contain 0.1 to 3% by weight, preferably 0.2 to 2% by weight, of polymers selected from the group of the polysaccharides, the modified cellulose molecules and the synthetic polycarboxylates.
  • suitable polysaccharides are xanthan gum or locust bean gum.
  • Modified cellulose molecules are taken to mean cellulose substituted with groups such as carboxymethyl, hydroxyethyl, hydroxypropyl or methyl.
  • Suitable synthetic polycarboxylates are homopolymers or copolymers of acrylic acid, methacrylic acid, maleic acid or their alkali salts and C 1 -C 4 -alkyl esters, which are optionally crosslinked by means of compounds such as diallyl sucrose, preferably the molecular weights of the polycarboxylates are above 100,000.
  • agents according to the invention can contain customary components such as inorganic or organic builders, for example in the form of low molecular weight dicarboxylic acids or sodium chloride, known solubilizers such as hydrotropes and solvents, preservatives, other antimicrobially active substances, dyes and fragrances.
  • customary components such as inorganic or organic builders, for example in the form of low molecular weight dicarboxylic acids or sodium chloride, known solubilizers such as hydrotropes and solvents, preservatives, other antimicrobially active substances, dyes and fragrances.
  • Sodium bicarbonate forms a buffer at pH 8.7, so that the pH of the agents according to the invention is generally between 8.0 and 9.0.
  • the cleaning agents according to the invention were prepared by mixing the constituents with stirring using a commercially available paddle stirrer in the following sequence: Approx. 6% of the total amount of bicarbonate was dissolved in water at about 40 ° C, then the fatty acid was added in a molten form. After a homogeneous mixture was present, the mixture was cooled to 25 ° C. and then the remaining constituents were added.
  • the cleaning agent to be tested was placed on an artificially soiled plastic surface.
  • a mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling for the dilute use of the cleaning agent.
  • the test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater.
  • a plastic sponge was soaked in each case with 10 ml of the cleaning agent solution to be tested and wheezily moved on the test surface, which was also coated with 10 ml of the cleaning agent solution to be tested. After ten wiping movements with a plastic sponge, the cleaned test area was kept under running water and the loose dirt was removed.
  • the cleaning effect ie the whiteness of the plastic surface cleaned in this way, was determined using a Microcolor color difference measuring device from Dr. Measured for a long time.
  • the clean white plastic surface served as the white standard. Since the measurement of the clean surface was set to 100% and the soiled area was displayed with 0, the read values for the cleaned plastic areas are to be equated with the percentage cleaning ability (% RV).
  • test product was placed in a large lumen beaker. Then, from a height of 30 cm, the amount of tap water was allowed to flow in freely, which, together with the amount of product presented, gave the recommended application solution of the product.
  • Foam decay % Foam height start-foam height after 3 min. Foam height beginning ⁇ 100
  • An agent with a foam breakdown of more than 50% was defined as a low-foam cleaner.
  • Table 3 The examples listed in Table 3 are intended to show that the carrier phase is able to stabilize different amounts of sodium bicarbonate and sodium bicarbonate with different particle size distributions.

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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)
  • Cosmetics (AREA)
EP94919605A 1993-06-11 1994-06-03 Giessfähige flüssige wässrige reinigungsmittelkonzentrate ii Expired - Lifetime EP0702711B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4319287A DE4319287A1 (de) 1993-06-11 1993-06-11 Gießfähige flüssige wäßrige Reinigungsmittelkonzentrate
DE4319287 1993-06-11
PCT/EP1994/001816 WO1994029418A1 (de) 1993-06-11 1994-06-03 Giessfähige flüssige wässrige reinigungsmittelkonzentrate ii

Publications (2)

Publication Number Publication Date
EP0702711A1 EP0702711A1 (de) 1996-03-27
EP0702711B1 true EP0702711B1 (de) 1997-03-12

Family

ID=6490066

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94919605A Expired - Lifetime EP0702711B1 (de) 1993-06-11 1994-06-03 Giessfähige flüssige wässrige reinigungsmittelkonzentrate ii

Country Status (15)

Country Link
US (1) US5756442A (cs)
EP (1) EP0702711B1 (cs)
KR (1) KR960702862A (cs)
CN (1) CN1065269C (cs)
AT (1) ATE150078T1 (cs)
CA (1) CA2164985A1 (cs)
CZ (1) CZ285195B6 (cs)
DE (2) DE4319287A1 (cs)
DK (1) DK0702711T3 (cs)
ES (1) ES2098964T3 (cs)
GR (1) GR3023775T3 (cs)
HU (1) HU218019B (cs)
PL (1) PL175463B1 (cs)
SK (1) SK280903B6 (cs)
WO (1) WO1994029418A1 (cs)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997004889A1 (en) * 1995-07-27 1997-02-13 Henkel Corporation Process for cleaning paint residues from surfaces
WO1998006802A1 (en) * 1996-08-13 1998-02-19 Ppg Industries, Inc. Abrasive cleaning of fluid delivery systems
DE19646520A1 (de) * 1996-11-12 1998-05-14 Henkel Kgaa Geschirrspülmittel mit verstärkter Reinigungswirkung
ID22436A (id) * 1996-12-31 1999-10-14 Reckitt & Colman Plc Komposisi pembersih yang kesat
DE10157541A1 (de) * 2001-11-23 2003-06-12 Beiersdorf Ag Hautreinigungszubereitung
US7666963B2 (en) * 2005-07-21 2010-02-23 Akzo Nobel N.V. Hybrid copolymers
NO20073834L (no) * 2006-07-21 2008-01-22 Akzo Nobel Chemicals Int Bv Sulfonerte podede kopolymerer
NO20073821L (no) * 2006-07-21 2008-01-22 Akzo Nobel Chemicals Int Bv Podede kopolymerer med lav molekylvekt
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
WO2011025624A1 (en) 2009-07-31 2011-03-03 Akzo Nobel N.V. Graft copolymers
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
CN103945828A (zh) 2011-11-04 2014-07-23 阿克佐诺贝尔化学国际公司 混杂树枝状共聚物、其组合物及其制备方法
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
WO2015074692A1 (en) * 2013-11-20 2015-05-28 Rhodia Operations Fabric softener composition
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
EP4349943A1 (en) * 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition

Family Cites Families (14)

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Publication number Priority date Publication date Assignee Title
GB1534680A (en) * 1977-10-14 1978-12-06 Colgate Palmolive Co Cleaning compositions
US4179414A (en) * 1978-10-23 1979-12-18 Mobil Oil Corporation Fatty acid diethanol amide-containing general purpose cleaner in paste form
US4396525A (en) * 1981-09-14 1983-08-02 Lever Brothers Company Phosphate free liquid scouring composition
DE3320727A1 (de) * 1983-06-09 1984-12-13 Henkel KGaA, 4000 Düsseldorf Verwendung von fettsaeurecyanamiden als tenside zum reinigen von harten oberflaechen
GB8504862D0 (en) * 1985-02-26 1985-03-27 Unilever Plc Liquid detergent composition
US4820436A (en) * 1985-06-22 1989-04-11 Henkel Kommanditgesellschaft Auf Aktien Detergents for low laundering temperatures
DE3726912A1 (de) * 1987-08-13 1989-02-23 Henkel Kgaa Fluessige mittel zum reinigen harter oberflaechen
AU611541B2 (en) * 1988-03-21 1991-06-13 Unilever Plc Liquid detergent composition
DE3817415A1 (de) * 1988-05-21 1989-11-30 Henkel Kgaa Verdickte waessrige tensidloesungen
GB8926643D0 (en) * 1989-11-24 1990-01-17 Unilever Plc Cleaning composition
DE4102744A1 (de) * 1991-01-30 1992-08-06 Henkel Kgaa Schwachschaeumendes scheuerpulver
DE4209923A1 (de) * 1992-03-27 1993-09-30 Henkel Kgaa Flüssige Reinigungsmittel für harte Oberflächen
DE4227863A1 (de) * 1992-08-22 1994-02-24 Henkel Kgaa Gießfähige flüssige wäßrige Reinigungsmittelkonzentrate
EP0592947A1 (en) * 1992-10-12 1994-04-20 ALBRIGHT & WILSON UK LIMITED Cleaning preparations

Also Published As

Publication number Publication date
CZ285195B6 (cs) 1999-06-16
EP0702711A1 (de) 1996-03-27
CN1065269C (zh) 2001-05-02
DK0702711T3 (da) 1997-10-13
CZ326195A3 (en) 1996-07-17
SK154095A3 (en) 1997-06-04
SK280903B6 (sk) 2000-09-12
PL311964A1 (en) 1996-03-18
HU9503533D0 (en) 1996-02-28
KR960702862A (ko) 1996-05-23
HUT72473A (en) 1996-04-29
GR3023775T3 (en) 1997-09-30
US5756442A (en) 1998-05-26
HU218019B (hu) 2000-05-28
WO1994029418A1 (de) 1994-12-22
CN1124976A (zh) 1996-06-19
DE59402087D1 (de) 1997-04-17
ATE150078T1 (de) 1997-03-15
DE4319287A1 (de) 1994-12-15
PL175463B1 (pl) 1998-12-31
CA2164985A1 (en) 1994-12-22
ES2098964T3 (es) 1997-05-01

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