EP0633924A1 - Detergent pour surfaces dures, notamment en verre. - Google Patents

Detergent pour surfaces dures, notamment en verre.

Info

Publication number
EP0633924A1
EP0633924A1 EP93908848A EP93908848A EP0633924A1 EP 0633924 A1 EP0633924 A1 EP 0633924A1 EP 93908848 A EP93908848 A EP 93908848A EP 93908848 A EP93908848 A EP 93908848A EP 0633924 A1 EP0633924 A1 EP 0633924A1
Authority
EP
European Patent Office
Prior art keywords
weight
cleaning agent
agent according
water
mixtures
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
EP93908848A
Other languages
German (de)
English (en)
Other versions
EP0633924B1 (fr
Inventor
Heinz-Dieter Soldanski
Bernd-Dieter Holdt
Juergen Noglich
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6455409&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0633924(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0633924A1 publication Critical patent/EP0633924A1/fr
Application granted granted Critical
Publication of EP0633924B1 publication Critical patent/EP0633924B1/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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear
    • 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
    • C11D3/2068—Ethers
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/43—Solvents

Definitions

  • the present invention relates to cleaning agents which can be used in undiluted form for cleaning hard surfaces, in particular glass, a method for cleaning hard surfaces and corresponding cleaning agent concentrates.
  • the cleaning agents for hard surfaces which are customary today are generally aqueous preparations which contain, as essential active substances, surface-active substances, organic solvents and, if appropriate, complexing agents for the hardness constituents of the water, abrasive substances and cleaning alkalis.
  • Detergents which are primarily intended for cleaning glass and ceramic surfaces, are often formulated as solutions of the active ingredients in a mixture of water and water-miscible organic solvents, primarily lower alcohols and glycol ethers. Examples of such agents can be found in German Offenlegungsschrift 2220 540, US Pat. Nos. 3,839,234 and 3,882,038 and in EP Patent Applications 344,847 and 393,772.
  • the cleaning agents In addition to the obvious requirement for high cleaning performance, there is also the requirement for the simplest and most convenient application of the agents. In most cases, it is expected that the agents will deliver the desired effect even with a single application without further measures. Here arises especially in An ⁇ application on smooth surfaces, in particular those which can reflect such as glass or ceramic specularly 'difficulties by one, that means that clean well, generally do not dry without leaving streaks, while such means substantially without Dry visible residues, have only a limited cleaning effect. In order to achieve a sufficient cleaning effect with an acceptable residue behavior, especially against greasy soiling, it is necessary to clean the in addition to organic solvents, large amounts of more or less volatile alkalis are added.
  • ammonia and alkanolamines have been used here.
  • higher concentrations of ammonia or A in not only cause a noticeable odor nuisance, but also a corresponding increase in the pH value in the cleaning agent solution, with the result that more sensitive surfaces, such as lacquered surfaces, are significantly attacked by these cleaning agents.
  • the present invention offers a solution to this problem in the form of an aqueous cleaning agent, the anionic surfactant, water-miscible organic solvent from the group of alcohols, ether alcohols and their mixtures, alkali from the group ammonia, alkanolamine with up to 9 carbon atoms and their Mixtures, and also contains a carboxylic acid with up to 6 carbon atoms or a mixture of such carboxylic acids, the equivalent ratio of amine and / or ammonia to carboxylic acid being between 1: 0.9 and 1: 0.1.
  • the detergent preferably also contains nonionic surfactant.
  • the cleaning agent according to the invention has a much weaker odor than such a agent which contains the same amount of alkali without carboxylic acid addition.
  • the high cleaning performance is practically only slightly reduced by the addition of the carboxylic acid.
  • ammonium or amine salts are formed by the addition of the carboxylic acid, the agent according to the invention exhibits excellent residue behavior. Greasy residues, as can often be observed with agents rich in alkanolamine, are largely avoided by the addition of carboxylic acid. In this way, the gloss of the surfaces is maintained without the need for rinsing or polishing.
  • Suitable surfactants for the agents according to the invention are surfactants, in particular from the classes of anionic and non- ionic surfactants. Mixtures of anionic and nonionic surfactants are preferably used. The amount of anionic surfactant is in the ready-agent is preferably between 0.05 and "0.3 wt .-%, in particular 0.08 to 0.2 wt .-%, based on the finished composition.
  • the concentration is correspondingly higher and can preferably be up to 3% by weight
  • non-ionic surfactants are used in addition to anionic surfactants, their concentration in the ready-to-use agents is preferably not more than 0.15% by weight % and in particular between 0.02 and 0.08% by weight, and is correspondingly higher in concentrations, preferably up to about 1% by weight.
  • Suitable anionic surfactants are preferably alkylbenzenesulfonates with 9 to 16 carbon atoms in the alkyl part, in particular with about 12 carbon atoms in the alkyl part, alkanesulfonates with 12 to 20 carbon atoms in the alkyl part, monoalkyl sulfates with 12 to 18 carbon atoms in the alkyl part , Alkyl ether sulfates with 12 to 18 carbon atoms in the alkyl part and 2 to 6 ethylene oxide units (E0) in the ether part and sulfosuccinic acid esters with 8 to 16 carbon atoms in the alcohol residues.
  • the anionic surfactants are preferably used as sodium salts, but can also be used in the form of ammonium or A salts.
  • surfactants examples include sodium lauryl ether sulfate with 2 E0, sodium coconut alkyl sulfate, sodium sec-alkane sulfonate with about 15 carbon atoms and sodium dioctyl sulfosuccinate. Fatty alkyl sulfates with 12 to 14 carbon atoms have proven to be particularly suitable.
  • nonionic surfactants especially ethoxylated long-chain alcohols with 12 to 18 carbon atoms in the alkyl part and 5 to 15 ethylene oxide units (EO), ethoxylated alkylphenols with 8 to 10 carbon atoms in the alkyl part and 8 to 14 ethylene oxide units, ethoxylated fatty acid - A ide with 12 to 18 carbon atoms in the fatty acid part and 2 to 8 ethylene oxide units, long-chain amine oxides with 14 to 20 carbon atoms and long-chain alkyl polyglycosides with 8 to 14 carbon atoms in the alkyl part and 1 to 3 glycoside units .
  • EO ethylene oxide units
  • alkylphenols with 8 to 10 carbon atoms in the alkyl part and 8 to 14 ethylene oxide units
  • ethoxylated fatty acid - A ide with 12 to 18 carbon atoms in the fatty acid part and 2 to 8 ethylene oxide units
  • long-chain amine oxides with 14 to 20 carbon
  • surfactants examples include oleyl-cetyl alcohol with 10 E0, nonylphenol with 10 E0, lauric acid diethane. nolamide, coconut alkyl dimethylamine oxide and coconut alkyl polyglucoside with an average of 1.4 glucose units.
  • the alkyl polyglycosides are particularly preferred as nonionic surfactants, and of these the representatives with 8 to 10 carbon atoms in the alkyl part and up to 2 glucose units.
  • a particularly preferred combination of anionic surfactant and nonionic surfactant is the combination of Fe alkyl sulfate with alkyl polyglucoside, in which an optimum of wetting and spreading behavior appears to be present.
  • the agents according to the invention can also contain smaller amounts of amphoteric surfactants (betaine surfactants).
  • betaine surfactants are long-chain compounds which contain both a quaternary ammonium group or an amine group and one anionic group, especially a carboxylate or sulfonate group. Examples of such ten ⁇ sides are N-cocoalkyl-N.N-dimethylammoniumacetobeta n and N- (cocoacylamidopropyl) -N, N-dimethylammoniumacetobetaine.
  • the organic solvents used in the cleaning agents according to the invention are water-miscible lower alcohols and / or ether alcohols, but preferably mixtures of alcohols and ether alcohols.
  • the amount of organic solvent in ready-to-use cleaning agents is preferably 0.5 to 15% by weight, in particular 3 to 10% by weight, based on the finished cleaning agent. In concentrates, the organic solvent content can be correspondingly higher and preferably up to 50% by weight.
  • ethanol isopropanol and n-propanol are used as alcohols, of which in turn ethanol is particularly preferred.
  • Sufficiently water-soluble compounds with up to 10 carbon atoms in the molecule are suitable as ether alcohols.
  • ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, Diethylene glycol monobutyl ether, propylene glycol non-tertiary butyl ether and propylene glycol onoethyl ether.
  • Ethylene glycol monobutyl ether and propylene glycol onobutyl ether are particularly preferred in the context of the invention.
  • the weight ratio of the two is preferably between 1: 2 and 4: 1.
  • the volatile alkali content is essential for the good cleaning performance of the agents according to the invention.
  • ammonia and / or alkanolamines which can contain up to 9 carbon atoms in the molecule, are used.
  • the preferred alkanolamines are the ethanolamines and the monoethanol in them.
  • the ammonia and / or alkanolamine content in the ready-to-use cleaning agent is preferably 0.1 to 3% by weight, in particular 0.2 to 1.5% by weight .-%. In cleaning agent concentrates, the content is correspondingly higher and can be, for example, 1 to 10% by weight.
  • the cleaning agent according to the invention preferably contains ammonia and ethanolamine, in particular monoethanolamine, side by side.
  • ammonia and ethanolamine in particular monoethanolamine, side by side.
  • a particularly high fat removal effect appears to occur here with a weight ratio of ammonia to monoethanolamine of between approximately 1: 2 and approximately 1:10.
  • carboxylic acid is of crucial importance for the special properties of the agents according to the invention, the equivalence ratio of amine and / or ammonia to carboxylic acid being between 1: 0.9 and 1: 0.1.
  • Carboxylic acids with up to 6 carbon atoms are suitable according to the invention, which may be mono-, di- or polycarbonic acids.
  • the content of carboxylic acid in ready-to-use cleaning agents is preferably between 0.05 and 3% by weight, in particular between 0.05 and 1% by weight.
  • the concentration in concentrates is correspondingly higher and can be, for example, 1 to 10% by weight.
  • the addition of the carboxylic acid is a part of the converted otherwise free "present ammonia or alkanolamine in the salt form.
  • the pH drops significantly and can be reset to values at which damage to sensitive surfaces no longer occurs.
  • the pH Values in the ready-to-use agent are set from about 9 to about 10.
  • the agents have almost the same cleaning performance as corresponding agents without the addition of acid, agents without the addition of acid with correspondingly less amine or ammonia are set to such low pH values, have significantly poorer, unacceptable cleaning results.
  • carboxylic acids examples include acetic acid, glycolic acid, lactic acid, citric acid, succinic acid and adipic acid, of which acetic acid, citric acid and lactic acid are preferably used.
  • Acetic acid is particularly preferably used.
  • the agents according to the invention can contain auxiliaries and additives as are customary in such agents. These include, in particular, dyes, perfume oils, preservatives, complexing agents for alkaline earth metal ions and viscosity regulators.
  • auxiliaries and additives include, in particular, dyes, perfume oils, preservatives, complexing agents for alkaline earth metal ions and viscosity regulators.
  • the amount of such additives is usually not more than 2% by weight in the ready-to-use cleaning agent. The lower limit of use depends on the type of additive and can be up to 0.001% by weight and below, for example in the case of dyes.
  • the amount of auxiliaries is preferably between 0.01 and 1% by weight. In concentrates, the amount can be correspondingly larger, for example up to 10% by weight. Otherwise, the agents according to the invention consist of water, the water content in concentrates should be at least 10% by weight.
  • a ready-to-use cleaning agent therefore preferably has the following composition: 0.05 to 0.3% by weight of anionic surfactant,
  • nonionic surfactant 0 to 0.15% by weight of nonionic surfactant
  • Concentrates that have to be diluted to the application concentration beforehand with water are preferably composed as follows:
  • anionic surfactant 0 to 1% by weight of nonionic surfactant, 10 to 50% by weight of water-miscible organic solvent,
  • the agents according to the invention are used in such a way that the ready-to-use agent is applied in amounts of, for example, about 1.5 to 5 g / ⁇ .2 to the surface to be cleaned and immediately afterwards these surfaces are wiped with an absorbent soft object and it cleans them.
  • the agents are preferably applied with the aid of suitable spraying devices in order to achieve a distribution which is as uniform as possible.
  • sponges or cloths are suitable for wiping. Treatment of larger areas can be rinsed out with water from time to time. A further treatment of the surfaces is not necessary, since the cleaning solutions dry practically free of fog and do not leave streaks even on critical high-gloss surfaces. Examples
  • Agents 1 to 9 were mixed directly from the raw materials as dilute aqueous solutions, the perfume first being predissolved in the organic solvents. The carboxylic acid was added last.
  • the light remission was measured on white PVC sheets (40 x 554 mm) which were provided with test soiling after standardized treatment in the Gardener tester.
  • the test dirt had the following composition

Landscapes

  • 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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Surface Treatment Of Glass (AREA)
EP93908848A 1992-03-30 1993-03-22 Utilisation de detergents pour surfaces dures, notamment en verre Expired - Lifetime EP0633924B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4210364 1992-03-30
DE4210364A DE4210364B4 (de) 1992-03-30 1992-03-30 Reinigungsmittel für harte Oberflächen, insbesondere Glas
PCT/EP1993/000689 WO1993020176A1 (fr) 1992-03-30 1993-03-22 Detergent pour surfaces dures, notamment en verre

Publications (2)

Publication Number Publication Date
EP0633924A1 true EP0633924A1 (fr) 1995-01-18
EP0633924B1 EP0633924B1 (fr) 1996-06-19

Family

ID=6455409

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93908848A Expired - Lifetime EP0633924B1 (fr) 1992-03-30 1993-03-22 Utilisation de detergents pour surfaces dures, notamment en verre

Country Status (9)

Country Link
EP (1) EP0633924B1 (fr)
JP (1) JPH07505182A (fr)
AT (1) ATE139561T1 (fr)
CA (1) CA2133468A1 (fr)
DE (2) DE4210364B4 (fr)
DK (1) DK0633924T3 (fr)
ES (1) ES2088671T3 (fr)
GR (1) GR3020378T3 (fr)
WO (1) WO1993020176A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5531933A (en) * 1993-12-30 1996-07-02 The Procter & Gamble Company Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders
AU675833B2 (en) * 1994-03-23 1997-02-20 Amway Corporation Concentrated all-purpose light duty liquid cleaning composition and method of use
US5534198A (en) * 1994-08-02 1996-07-09 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity
EP0842251B1 (fr) 1996-02-14 2005-10-26 Stepan Company Produit de nettoyage pour surfaces dures, contenant un hydrotrope et laissant peu de residus
GB9911818D0 (en) † 1999-05-21 1999-07-21 Reckitt & Colman Inc Improvements in or relating to organic compositions
DE10258831A1 (de) * 2002-12-17 2004-07-08 Henkel Kgaa Reinigungsmittel für harte Oberflächen
DE102010007321B4 (de) * 2010-02-08 2017-11-09 Chemische Werke Kluthe Gmbh Wässrige Reinigungslösung, insbesondere zur Entfernung von Lackanhaftungen, sowie Konzentratzusammensetzung zur Bereitstellung einer wässrigen Reinigungslösung
CN105283530A (zh) * 2013-05-24 2016-01-27 宝洁公司 浓缩型表面活性剂组合物
US11937602B2 (en) 2017-09-26 2024-03-26 Ecolab Usa Inc. Solid acid/anionic antimicrobial and virucidal compositions and uses thereof
AU2020408331B2 (en) 2019-12-16 2023-12-14 Ecolab Usa Inc. Anionic surfactant impact on virucidal efficacy
WO2022241180A1 (fr) 2021-05-14 2022-11-17 Ecolab Usa Inc. Retraitement d'instrument par neutralisation

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839234A (en) * 1973-01-26 1974-10-01 C Roscoe Multi-purpose cleaning concentrate
DE3642564A1 (de) * 1985-12-12 1987-07-09 Lion Corp Fluessiges wasch- und reinigungsmittel
DE3713998A1 (de) * 1987-04-27 1988-11-10 Henkel Kgaa Reinigungsmittel fuer harte oberflaechen
US4943392A (en) * 1988-06-03 1990-07-24 The Procter & Gamble Company Containing butoxy-propanol with low secondary isomer content
AU4702289A (en) * 1989-01-19 1990-07-26 Sterling Drug Inc. Hard surface cleaning composition
DE3910974A1 (de) * 1989-04-05 1990-10-11 Henkel Kgaa Fluessigwaschmittel
GB8909157D0 (en) * 1989-04-21 1989-06-07 Procter & Gamble Hard-surface cleaning compositions
DE3943070A1 (de) * 1989-12-27 1991-07-04 Henkel Kgaa Fluessiges reinigungsmittel fuer harte oberflaechen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9320176A1 *

Also Published As

Publication number Publication date
EP0633924B1 (fr) 1996-06-19
GR3020378T3 (en) 1996-09-30
WO1993020176A1 (fr) 1993-10-14
JPH07505182A (ja) 1995-06-08
CA2133468A1 (fr) 1993-10-14
ATE139561T1 (de) 1996-07-15
DK0633924T3 (da) 1996-10-21
ES2088671T3 (es) 1996-08-16
DE59303027D1 (de) 1996-07-25
DE4210364A1 (de) 1993-10-07
DE4210364B4 (de) 2006-05-18

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