CA2133468A1 - Cleaning compositions for hard surfaces, more particularly glass - Google Patents
Cleaning compositions for hard surfaces, more particularly glassInfo
- Publication number
- CA2133468A1 CA2133468A1 CA002133468A CA2133468A CA2133468A1 CA 2133468 A1 CA2133468 A1 CA 2133468A1 CA 002133468 A CA002133468 A CA 002133468A CA 2133468 A CA2133468 A CA 2133468A CA 2133468 A1 CA2133468 A1 CA 2133468A1
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- CA
- Canada
- Prior art keywords
- weight
- cleaning composition
- water
- cleaning
- group
- 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.)
- Abandoned
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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
- C11D3/16—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
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)
Abstract
Aqueous detergents contain an anionic surface-actif agent, alcohol or etheric alcohol as water-miscible organic solvent, ammonia or alkanolamine as alkali and a carboxylic acid having up to 6 C
atoms. The equivalent ratio between alkali and carboxylic acid lies between 1 : 0.9 and 1 : 0.1. These new detergents are characterized by a high cleaning power, the absence of residues and gentle treatment of materials.
atoms. The equivalent ratio between alkali and carboxylic acid lies between 1 : 0.9 and 1 : 0.1. These new detergents are characterized by a high cleaning power, the absence of residues and gentle treatment of materials.
Description
-2133`168 Clea~i~g compo~ition~ for h~rd ~urf~c~, more p~rticularly glass This invention relates to cleaning compositions which may be used in undiluted form for cleaning hard surfaces, more particularly glass, to a process for cleaning hard surfaces and to corresponding cleaning concentrates.
The compositions typically used at present for cleaning hard surfaces are generally water-based prepara-~ tions essentially containing surfactants, organic sol-vents and optionally complexing agents for the hardn~ss constituents of water, abrasives and alkalis with a cleaning effect. Cleaning compositions intended above all for cleaning glass and ceramic surfaces are often formulated as solutions of the active substances in a mixture of water and water-miscible organic solvents, primarily lower alcohols and glycol ethers. Examples of such compositions can be found in DE-OS 22 20 540, in US-PSS 3,839,234 and 3,882,038 and in ~uropean patent applicatio~ 344 847 and 393 772.
- In the practical application of the cleaning compo-sitionsj there is a demand for easy and convenient use besides the obvious demand for high cleaning performance.
The compositions are generally expectPd to develop the required effect after only one application and no other measures. Difficulties arise above all when the composi-tions are applied to smooth surfaces, more particularly to smooth surfaces which, like glass or ceramics, are capable of reflecting like mirrors, insofar as composi-tions which have a good cleaning effect generally do not dry without leaving streaks whereas compositions which dry with hardly any visible residues only develop a limited cleaning effect. In order to achieve an adequate -2~33~58 W0 93/20176 2 pcT/Ep93/oo68s cleaning effect, particularly against greasy soils, for acceptable drying behavior, relatively large quantities of more or less volatile alkalis also have to be added to the cleaning compositions in addition to organic sol-vents. Ammonia and alkanolamines in particular have beenused for this purpose. Unfortunately, relatively high concentrations of ammonia or amine, apart from causing significant odor-emission problems, produce a correspond-ing increase in the pH value of the cleaning solution with the result that relatively sensitive surfaces, such as paint surfaces for example, are clearly attacked by ~ the cleaning compositions. Accordingly, there is a still a need for cleaning compositions which, despite their high cleaning performance, are not attended by any of the disadvantages mentioned above.
The present invention provides a solution to this problem in the form of a water-based cleaning composition containing anionic surfactant, water-miscible organic solvent from the group of alcohols, ether alcohols and mixtures thereof, alkali from the group ammonia, alkanol-amine containing up to 9 carbon atoms and mixtures thereof and a carboxylic acid containing up to 6 carbon atoms or a mixture of such carboxylic acids, the equiva-lent ratio of amine and/or ammonia to carboxylic acid 25being between 1:0.9 and 1:0.1. In addition, the cleaning - composition preferably also contains nonionic surfactant.
The cleaning composition according to the invention has a very much weaker odor than cleaning compositions containing the same quantity of alkali with no addition of carboxylic acid. By contrast, the high cleaning performance is hardly affected by the addition of the carboxylic acid. Although ammonium or amine salts are formed by the addition of the carboxylic acid, the composition according to the invention shows excellent drying behavior. The greasy residues which are often 21~3~S8 W0 93~20176 3 PC~/EP93/00689 observed in the case of high-alkanolamine compositions are largely avoided by the addition of the carboxylic acid. In this way, the surfaces retain their shine without any need for subsequent rinsing or polishing.
The individual components of the composition are described in the following:
a) Surfactants Suitable surface-active substances for the composi-tions according to the invention are surfactants/ more particularly from the classes of anionic and nonionic ~ surfactants. Mixtures of anionic and nonionic surfac-tants are preferably used. In the ready-to-use composi-tion, the quantity o~ anionic surfactant is preferably between 0.05 and 0.3% by weight and more preferably between 0.08 and 0.2% by weight, based on the final compositionO In concentrated compositions which have to be diluted before use, the concentration is correspond-ingly higher and may advantageously be up to 3% by weight. Where nonionic surfactants are used in addition to anionic surfactants, their concentration in the ready-to-use composition is preferably not more than 0.15% by weight and, more preferably, is between 0.02 and 0.08% by weight. In concentrates, it is correspondingly higher, preferably up to about 1% by weight.
Preferred anionic surfactants are alkyl benzenesul-fonates containing 9 to 16 carbon atoms in the alkyl component, more particularly about 12 carbon atoms in the alkyl component, alkanesulfonates containing 12 to 20 carbon atoms in the alkyl component, monoalkylsulfates containing 12 to 18 carbon atoms in the alkyl component, alkyl ether sulfates containing 12 to 18 carbon atoms in the alkyl component and 2 to 6 ethylene oxide units (E0) in the ether component and also sulfosuccinic acid esters containing 8 to 16 carbon atoms in the alcohol compo-nents. The anionic surfactants are preferably used assodium salts although they may also be used in the form of ammonium or amine salts.
Examples of such surfactants are sodium lauryl ether - 5 sulfate containing 2 EO, sodium coconut oil alkylsulfate, sodium sec.alkanesulfonate containing approximately 15 carbon atoms and sodium dioctyl sulfosuccinate. Fatty alkylsulfates containing 12 to 14 carbon atoms have proved to be particularly suitable.
Suitable nonionic surfactants are, above all, ethoxylated long-chain alcohols containing 12 to 18 carbon atoms in the alkyl component and 5 to 15 ethylene oxide units (EO), ethoxylated alkylphenols containing 8 to 10 carbon atoms in the alkyl component and 8 to 14 ethylene oxide units, ethoxylated fatty acid amides containing 12 to 18 carbon atoms in the fatty acid component and 2 to 8 ethylene oxide units, long-chain amine oxides containing 14 to 20 carbon atoms and long-chain alkyl polyglycosides containing 8 to 14 carbon atoms in the alkyl component and 1 to 3 glycoside units.
Examples of such surfactants are oleyl cetyl alcohol containing 10 EO, nonylphenol containing 10 EO, lauric acid diethanolamide, coconut oil alkyl dimethylamine oxide and coconut oil alkyl polyglucoside containing on average 1.4 glucose units. Besides the adducts of ethylene oxide and fatty alcohols, particularly preferred nonionic surfactants are the alkyl polyglycosides of which representatives containing 8 to 10 carbon atoms in the alkyl component and up to 2 glucose units are partic-ularly preferred.
A particularly preferred combination of anionicsurfactant and nonionic surfactant is the combination of fatty alkylsulfate with alkyl polyglucoside where an optimum of wetting and spreading behavior appears to be present.
~133468 '~
W0 93~20176 5 PCT/EP93/00689 In addition to nonionic and~or anionic surfactants, the compositions according to the invention may also contain relatively small quantities of amphoteric sur~ac-tants (betaine surfactants). These surfactants are long-5 chain compounds which contain both a quaternary ammoniumgroup or an aminic group and an anionic group, more particularly a carboxylate or sulfonate group. Examples of such surfactants are N-coconut oil alkyl N,N-dimethyl-ammonium acetobetaine and N-(coconut oil acylamidopro-pyl)-N,N-dimethylammonium acetobetaine.
b) Water-misaible organic solvent Water-miscible lower alcohols and/or ether alcohols, but preferably mixtures of alcohols and ether alcohols, are used as organic solvents in the cleaning compositions according to the invention. The quantity of organic solvent in the ready-to-use cleaning compositions is preferably 0.5 to 15% by weight and more preferably 3 to 10% by weight, based on the final cleaning composition.
In concentrates, the content of organic solvent may be correspondingly higher and is preferably up to 50% by weight.
The alcohols used are, in particular, ethanol, - isopropanol and n-propanol, of which ethanol is particu-larly preferred. Suitable ether alcohols are sufficient-ly water-soluble compounds containing up to 10 carbon atoms in the molecule. Examples of such ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monotert.butyl ether and propylene glycol monoethyl ether. Ethylene glycol monobutyl ether and propylene glycol monobutyl ether are particularly preferred for the purposes of the invention.
If alcohol and ether alcohol are used alangside one another, the ratio by weight between the two is preferab-Wo 93/20176 6 PCT/EP93/0068s ly from 1:2 to 4:1.
c) Volatile alkali In addition to the content of organic solvent, the content of volatile alkali is es~ential to the high cleaning performance of the compositions according to th~
invention. Ammonia and/or alkanolamines which may contain up to 9 carbon atoms in the molecule are used as the volatile alkali. Preferred alkanolamines are the ethanolamines, of which monoethanolamine is preferred.
The content of ammonia and/or alkanolamine in the ready-to-use cleaning composition is preferably 0.1 to 3% by weight and more preferably 0.2 to 1.5% by weight. In concentrated cleaning compositions, the content is correspondingly higher and may amount for example to between l and 10% by weight.
The cleaning composition according to the invention preferably contains ammonia and ethanolamine, more particularly monoethanolamine, alongside one another. A
particularly good fat-removing effect appears to occur when the ratio by weight of ammonia to monoethanolamine is about 1:2 to about l:10.
d) Carboxylic acid The content of carboxylic acid is crucially impor-tant to the particular properties of the cleaning compo-sitions according to the invention, the equivalent ratio of amine and/or ammonia to carboxylic acid being between l:0.9 and 1:0.1. Carboxylic acids containing up to 6 carbon atoms, which may be mono-, di- or polycarboxylic acids, are suitable for the purposes of the invention.
Depending on the equivalent weight of amine and car-boxylic acid, the content of carboxylic acid in ready-to-use cleaning compositions is preferably between 0.05 and 3% by weight and more preferably between 0.05 and 1% by 213~8 weight. In concentrates, the content is correspondingly higher and may amount, for example, to between l and 10%
by weight. Through the addition of the carboxylic acid, part of the otherwise free ammonia or alkanolamine is converted into the salt form. The pH value thus falls appreciably and may be returned to values where damage to sensitive surfaces no longer occurs. pH values of about 9 to about 10 are preferably adjusted in the ready-to-use composition. Despite this reduction in the pH value, the compositions show substantially the same cleaning effect as corresponding compositions with no addition of acid.
- Compositions which are adjusted to such low pH values with correspondingly less amine or ammonia without any addition of acid show much poorer and unacceptable cleaning results.
Examples of suitable carboxylic acids are 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 preferred.
'' e) Other typical auxiliaries In addition to components a) to d), the compositions according to ths invention may contain auxiliaries and additives of the type typically encountered in cleaning compositions. These include in particular dyes, perfume oils, preservatives, complexing agents for alkaline earth metal ions and viscosity regulators. The quantity of such additives is typically not more than 2% by weight in the cleaning composition according to the invention. The lower limit depends upon the type of additive and, in the case of dyes for example, may be up to 0.001% by weight or lower. The quantity of auxiliaries is preferably between 0.01 and 1% by weight. In concentrates, the quantity may be correspondingly larger, for example up to 213~8 Wo 93/20176 8 PCT/EP93/00689 10% by weight. For the rest, the compositions a~cording to the invention consist of water, the water content in concentrates having to be at least 10% by weight.
Accordingly, a ready-to-use cleaning composition preferably has the following composition:
0.05 to 0.3 % by weight anionic surfactant, 0 to 0.15% by weight nonionic surfactant, 0.5 to 15 % by weight water-miscible organic solvent, 0.1 to 3 ~ by weight ammonia and/or alkanolamine, 0.05 to 3 % by weight carboxylic acid, - 0 to 2 % by weight other typical auxiliaries, up to 100 % by weight water.
Concentrates which have to be diluted with water beforehand to the in-use concentration preferably have the following composition:
0.3 to 3% by weight anionic surfactant, 0 to 1% by weight nonionic surfactant, 10 to 50% by weight water-miscible organic solvent, - 1 to 10% by weight ammonia and/or alkanolamine, 1 to 10~ by weight carboxylic acid, 0 to 10% by weight other typical auxiliaries and balance to 100% by weight at least 10% by weight water.
The compositions according to the invention are used by applying the ready-to-use composition to the surface to be cleaned in quantities of, for example, about 1.5 to 5 g/m2 and wiping the surfaces immediately afterwards with a soft absorbent article and thus cleaning them.
The compositions are preferably applied by means of suitable sprays to ensure uniform distribution. Sponges or cloths are particularly suitable for wiping; in the treatment of relatively large surfaces, they may be 2133~8 WO 93/20176 9 PCT/~P93/00689 periodically rinsed out with water. There is no need for any further treatment of the surfaces because the clean-ing solutions dry with hardly any streaks and do not leave any streaks behind, even on critical high-shine surfaces.
- Examples Compositions 1 to 9 were directly mixed from the raw materials in the form of dilute aqueous solutions, the perfume initially being predissolved in the organic solvents. The carboxylic acid was added last of all.
To test the cleaning effect under extreme condi-tions, two different methods were used:
a) On white PVC plates (40 x 554 mm3 coated with a test soil, light reflectance was measured in a Gardener apparatus after standardized treatment. The test soil had the following composition:
7% fine-particle soot 57% Myritol~ (fatty acid triglyceride) - 36% white spirit and was uniformly applied in quantities of 0.3 g per plate. After a drying time of 1 to 1.5 hours, the plates, of which several had been soiled at the same time, were used for the test. The cleaning phase consisted of 20 wipes with a polyester sponge under a standardized load (800 g), the cleaning composi-tion being used in a quantity of 6 g. After rinsing under running water, the plates were measured. The results of these tests are set out in the following Table as % light reflectance by comparison with an untreated plate (100%) (CP values).
21~68 ~O 93/20176 10 PCT/EP93/00689 b) Highly polished plates of stainless steel (40 x 554 D) were uniformly coated with 0.4 g of a mixture of vegetable oil and white spirit (1:1) and, after the solvent had evaporated, were stored in air for 15 hours at 80C. The plates were then cleaned in the same way as in a), the cleaning effect being ~isual-ly evaluated by comparison with a non-cleaned plate and an unsoiled plate. The following scoring system was used:
1 = fat completely removed - 2 = fat substantially removed 3 = fat partly removed 4 = fat only slightly removed 5 = fat almost unchanged.
The results are also set out in the Table.
It is clear from the results that Examples 2, 3 and 7 according to the invention give substantial-ly the same cleaning result as compositions which contain no addition of acid for the same alkali concentration (1,6). At the same time, the con-siderably improved cleaning performance in relation to compositions with no addition of alkali or with only a small of addition of alkali (4, 5, 8, 9) can be seen (the pH value in compositions 4 and 8 is ex-plained by traces of alkali in the surfactant raw materials).
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The compositions typically used at present for cleaning hard surfaces are generally water-based prepara-~ tions essentially containing surfactants, organic sol-vents and optionally complexing agents for the hardn~ss constituents of water, abrasives and alkalis with a cleaning effect. Cleaning compositions intended above all for cleaning glass and ceramic surfaces are often formulated as solutions of the active substances in a mixture of water and water-miscible organic solvents, primarily lower alcohols and glycol ethers. Examples of such compositions can be found in DE-OS 22 20 540, in US-PSS 3,839,234 and 3,882,038 and in ~uropean patent applicatio~ 344 847 and 393 772.
- In the practical application of the cleaning compo-sitionsj there is a demand for easy and convenient use besides the obvious demand for high cleaning performance.
The compositions are generally expectPd to develop the required effect after only one application and no other measures. Difficulties arise above all when the composi-tions are applied to smooth surfaces, more particularly to smooth surfaces which, like glass or ceramics, are capable of reflecting like mirrors, insofar as composi-tions which have a good cleaning effect generally do not dry without leaving streaks whereas compositions which dry with hardly any visible residues only develop a limited cleaning effect. In order to achieve an adequate -2~33~58 W0 93/20176 2 pcT/Ep93/oo68s cleaning effect, particularly against greasy soils, for acceptable drying behavior, relatively large quantities of more or less volatile alkalis also have to be added to the cleaning compositions in addition to organic sol-vents. Ammonia and alkanolamines in particular have beenused for this purpose. Unfortunately, relatively high concentrations of ammonia or amine, apart from causing significant odor-emission problems, produce a correspond-ing increase in the pH value of the cleaning solution with the result that relatively sensitive surfaces, such as paint surfaces for example, are clearly attacked by ~ the cleaning compositions. Accordingly, there is a still a need for cleaning compositions which, despite their high cleaning performance, are not attended by any of the disadvantages mentioned above.
The present invention provides a solution to this problem in the form of a water-based cleaning composition containing anionic surfactant, water-miscible organic solvent from the group of alcohols, ether alcohols and mixtures thereof, alkali from the group ammonia, alkanol-amine containing up to 9 carbon atoms and mixtures thereof and a carboxylic acid containing up to 6 carbon atoms or a mixture of such carboxylic acids, the equiva-lent ratio of amine and/or ammonia to carboxylic acid 25being between 1:0.9 and 1:0.1. In addition, the cleaning - composition preferably also contains nonionic surfactant.
The cleaning composition according to the invention has a very much weaker odor than cleaning compositions containing the same quantity of alkali with no addition of carboxylic acid. By contrast, the high cleaning performance is hardly affected by the addition of the carboxylic acid. Although ammonium or amine salts are formed by the addition of the carboxylic acid, the composition according to the invention shows excellent drying behavior. The greasy residues which are often 21~3~S8 W0 93~20176 3 PC~/EP93/00689 observed in the case of high-alkanolamine compositions are largely avoided by the addition of the carboxylic acid. In this way, the surfaces retain their shine without any need for subsequent rinsing or polishing.
The individual components of the composition are described in the following:
a) Surfactants Suitable surface-active substances for the composi-tions according to the invention are surfactants/ more particularly from the classes of anionic and nonionic ~ surfactants. Mixtures of anionic and nonionic surfac-tants are preferably used. In the ready-to-use composi-tion, the quantity o~ anionic surfactant is preferably between 0.05 and 0.3% by weight and more preferably between 0.08 and 0.2% by weight, based on the final compositionO In concentrated compositions which have to be diluted before use, the concentration is correspond-ingly higher and may advantageously be up to 3% by weight. Where nonionic surfactants are used in addition to anionic surfactants, their concentration in the ready-to-use composition is preferably not more than 0.15% by weight and, more preferably, is between 0.02 and 0.08% by weight. In concentrates, it is correspondingly higher, preferably up to about 1% by weight.
Preferred anionic surfactants are alkyl benzenesul-fonates containing 9 to 16 carbon atoms in the alkyl component, more particularly about 12 carbon atoms in the alkyl component, alkanesulfonates containing 12 to 20 carbon atoms in the alkyl component, monoalkylsulfates containing 12 to 18 carbon atoms in the alkyl component, alkyl ether sulfates containing 12 to 18 carbon atoms in the alkyl component and 2 to 6 ethylene oxide units (E0) in the ether component and also sulfosuccinic acid esters containing 8 to 16 carbon atoms in the alcohol compo-nents. The anionic surfactants are preferably used assodium salts although they may also be used in the form of ammonium or amine salts.
Examples of such surfactants are sodium lauryl ether - 5 sulfate containing 2 EO, sodium coconut oil alkylsulfate, sodium sec.alkanesulfonate containing approximately 15 carbon atoms and sodium dioctyl sulfosuccinate. Fatty alkylsulfates containing 12 to 14 carbon atoms have proved to be particularly suitable.
Suitable nonionic surfactants are, above all, ethoxylated long-chain alcohols containing 12 to 18 carbon atoms in the alkyl component and 5 to 15 ethylene oxide units (EO), ethoxylated alkylphenols containing 8 to 10 carbon atoms in the alkyl component and 8 to 14 ethylene oxide units, ethoxylated fatty acid amides containing 12 to 18 carbon atoms in the fatty acid component and 2 to 8 ethylene oxide units, long-chain amine oxides containing 14 to 20 carbon atoms and long-chain alkyl polyglycosides containing 8 to 14 carbon atoms in the alkyl component and 1 to 3 glycoside units.
Examples of such surfactants are oleyl cetyl alcohol containing 10 EO, nonylphenol containing 10 EO, lauric acid diethanolamide, coconut oil alkyl dimethylamine oxide and coconut oil alkyl polyglucoside containing on average 1.4 glucose units. Besides the adducts of ethylene oxide and fatty alcohols, particularly preferred nonionic surfactants are the alkyl polyglycosides of which representatives containing 8 to 10 carbon atoms in the alkyl component and up to 2 glucose units are partic-ularly preferred.
A particularly preferred combination of anionicsurfactant and nonionic surfactant is the combination of fatty alkylsulfate with alkyl polyglucoside where an optimum of wetting and spreading behavior appears to be present.
~133468 '~
W0 93~20176 5 PCT/EP93/00689 In addition to nonionic and~or anionic surfactants, the compositions according to the invention may also contain relatively small quantities of amphoteric sur~ac-tants (betaine surfactants). These surfactants are long-5 chain compounds which contain both a quaternary ammoniumgroup or an aminic group and an anionic group, more particularly a carboxylate or sulfonate group. Examples of such surfactants are N-coconut oil alkyl N,N-dimethyl-ammonium acetobetaine and N-(coconut oil acylamidopro-pyl)-N,N-dimethylammonium acetobetaine.
b) Water-misaible organic solvent Water-miscible lower alcohols and/or ether alcohols, but preferably mixtures of alcohols and ether alcohols, are used as organic solvents in the cleaning compositions according to the invention. The quantity of organic solvent in the ready-to-use cleaning compositions is preferably 0.5 to 15% by weight and more preferably 3 to 10% by weight, based on the final cleaning composition.
In concentrates, the content of organic solvent may be correspondingly higher and is preferably up to 50% by weight.
The alcohols used are, in particular, ethanol, - isopropanol and n-propanol, of which ethanol is particu-larly preferred. Suitable ether alcohols are sufficient-ly water-soluble compounds containing up to 10 carbon atoms in the molecule. Examples of such ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monotert.butyl ether and propylene glycol monoethyl ether. Ethylene glycol monobutyl ether and propylene glycol monobutyl ether are particularly preferred for the purposes of the invention.
If alcohol and ether alcohol are used alangside one another, the ratio by weight between the two is preferab-Wo 93/20176 6 PCT/EP93/0068s ly from 1:2 to 4:1.
c) Volatile alkali In addition to the content of organic solvent, the content of volatile alkali is es~ential to the high cleaning performance of the compositions according to th~
invention. Ammonia and/or alkanolamines which may contain up to 9 carbon atoms in the molecule are used as the volatile alkali. Preferred alkanolamines are the ethanolamines, of which monoethanolamine is preferred.
The content of ammonia and/or alkanolamine in the ready-to-use cleaning composition is preferably 0.1 to 3% by weight and more preferably 0.2 to 1.5% by weight. In concentrated cleaning compositions, the content is correspondingly higher and may amount for example to between l and 10% by weight.
The cleaning composition according to the invention preferably contains ammonia and ethanolamine, more particularly monoethanolamine, alongside one another. A
particularly good fat-removing effect appears to occur when the ratio by weight of ammonia to monoethanolamine is about 1:2 to about l:10.
d) Carboxylic acid The content of carboxylic acid is crucially impor-tant to the particular properties of the cleaning compo-sitions according to the invention, the equivalent ratio of amine and/or ammonia to carboxylic acid being between l:0.9 and 1:0.1. Carboxylic acids containing up to 6 carbon atoms, which may be mono-, di- or polycarboxylic acids, are suitable for the purposes of the invention.
Depending on the equivalent weight of amine and car-boxylic acid, the content of carboxylic acid in ready-to-use cleaning compositions is preferably between 0.05 and 3% by weight and more preferably between 0.05 and 1% by 213~8 weight. In concentrates, the content is correspondingly higher and may amount, for example, to between l and 10%
by weight. Through the addition of the carboxylic acid, part of the otherwise free ammonia or alkanolamine is converted into the salt form. The pH value thus falls appreciably and may be returned to values where damage to sensitive surfaces no longer occurs. pH values of about 9 to about 10 are preferably adjusted in the ready-to-use composition. Despite this reduction in the pH value, the compositions show substantially the same cleaning effect as corresponding compositions with no addition of acid.
- Compositions which are adjusted to such low pH values with correspondingly less amine or ammonia without any addition of acid show much poorer and unacceptable cleaning results.
Examples of suitable carboxylic acids are 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 preferred.
'' e) Other typical auxiliaries In addition to components a) to d), the compositions according to ths invention may contain auxiliaries and additives of the type typically encountered in cleaning compositions. These include in particular dyes, perfume oils, preservatives, complexing agents for alkaline earth metal ions and viscosity regulators. The quantity of such additives is typically not more than 2% by weight in the cleaning composition according to the invention. The lower limit depends upon the type of additive and, in the case of dyes for example, may be up to 0.001% by weight or lower. The quantity of auxiliaries is preferably between 0.01 and 1% by weight. In concentrates, the quantity may be correspondingly larger, for example up to 213~8 Wo 93/20176 8 PCT/EP93/00689 10% by weight. For the rest, the compositions a~cording to the invention consist of water, the water content in concentrates having to be at least 10% by weight.
Accordingly, a ready-to-use cleaning composition preferably has the following composition:
0.05 to 0.3 % by weight anionic surfactant, 0 to 0.15% by weight nonionic surfactant, 0.5 to 15 % by weight water-miscible organic solvent, 0.1 to 3 ~ by weight ammonia and/or alkanolamine, 0.05 to 3 % by weight carboxylic acid, - 0 to 2 % by weight other typical auxiliaries, up to 100 % by weight water.
Concentrates which have to be diluted with water beforehand to the in-use concentration preferably have the following composition:
0.3 to 3% by weight anionic surfactant, 0 to 1% by weight nonionic surfactant, 10 to 50% by weight water-miscible organic solvent, - 1 to 10% by weight ammonia and/or alkanolamine, 1 to 10~ by weight carboxylic acid, 0 to 10% by weight other typical auxiliaries and balance to 100% by weight at least 10% by weight water.
The compositions according to the invention are used by applying the ready-to-use composition to the surface to be cleaned in quantities of, for example, about 1.5 to 5 g/m2 and wiping the surfaces immediately afterwards with a soft absorbent article and thus cleaning them.
The compositions are preferably applied by means of suitable sprays to ensure uniform distribution. Sponges or cloths are particularly suitable for wiping; in the treatment of relatively large surfaces, they may be 2133~8 WO 93/20176 9 PCT/~P93/00689 periodically rinsed out with water. There is no need for any further treatment of the surfaces because the clean-ing solutions dry with hardly any streaks and do not leave any streaks behind, even on critical high-shine surfaces.
- Examples Compositions 1 to 9 were directly mixed from the raw materials in the form of dilute aqueous solutions, the perfume initially being predissolved in the organic solvents. The carboxylic acid was added last of all.
To test the cleaning effect under extreme condi-tions, two different methods were used:
a) On white PVC plates (40 x 554 mm3 coated with a test soil, light reflectance was measured in a Gardener apparatus after standardized treatment. The test soil had the following composition:
7% fine-particle soot 57% Myritol~ (fatty acid triglyceride) - 36% white spirit and was uniformly applied in quantities of 0.3 g per plate. After a drying time of 1 to 1.5 hours, the plates, of which several had been soiled at the same time, were used for the test. The cleaning phase consisted of 20 wipes with a polyester sponge under a standardized load (800 g), the cleaning composi-tion being used in a quantity of 6 g. After rinsing under running water, the plates were measured. The results of these tests are set out in the following Table as % light reflectance by comparison with an untreated plate (100%) (CP values).
21~68 ~O 93/20176 10 PCT/EP93/00689 b) Highly polished plates of stainless steel (40 x 554 D) were uniformly coated with 0.4 g of a mixture of vegetable oil and white spirit (1:1) and, after the solvent had evaporated, were stored in air for 15 hours at 80C. The plates were then cleaned in the same way as in a), the cleaning effect being ~isual-ly evaluated by comparison with a non-cleaned plate and an unsoiled plate. The following scoring system was used:
1 = fat completely removed - 2 = fat substantially removed 3 = fat partly removed 4 = fat only slightly removed 5 = fat almost unchanged.
The results are also set out in the Table.
It is clear from the results that Examples 2, 3 and 7 according to the invention give substantial-ly the same cleaning result as compositions which contain no addition of acid for the same alkali concentration (1,6). At the same time, the con-siderably improved cleaning performance in relation to compositions with no addition of alkali or with only a small of addition of alkali (4, 5, 8, 9) can be seen (the pH value in compositions 4 and 8 is ex-plained by traces of alkali in the surfactant raw materials).
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Claims (11)
PCT/EP93/00698(Replacement for page 12)
1. The use of a water-based composition for cleaning hard surfaces, this composition containing anionic surfactant, water-miscible organic solvent from the group consisting of alcohols, ether alcohols and mixtures thereof, alkali from the group consisting of ammonia, alkanolamines containing up to 9 carbon atoms and mix-tures thereof and a carboxylic acid containing up to 6 carbon atoms or a mixture of such carboxylic acids and the equivalent ratio of amine and/or ammonia to car-boxylic acid in the composition being between 1:0.9 and 1:0.1.
2. The use claimed in claim 1, in which the cleaning composition additionally contains nonionic surfactant.
3. The use claimed in claim 1 or 2, in which the carboxylic acid in the cleaning composition is selected from the group consisting of acetic acid, citric acid, lactic acid and mixtures thereof.
4. The use claimed in claim 1 or 2, in which the cleaning composition contains ammonia together with an ethanolamine from the group consisting of mono-, di- and triethanolamine and mixtures thereof, preferably mono-ethanolamine.
5. The use claimed in claim 1 or 2, in which the cleaning composition contains a mixture of lower alcohol containing 2 or 3 carbon atoms and glycol ether from the group consisting of ethylene glycol monobutyl ether, polyglycol monobutyl ether and mixtures thereof as the water-miscible organic solvent.
6. The use claimed in claim 1 or 2, in which the the anionic surfactant in the cleaning composition is selec-ted from the group consisting of alkanesulfonates, alkyl ether sulfates, alkylsulfates and mixtures thereof.
7. The use claimed in claim 2, in which the nonionic surfactant in the cleaning composition is selected from the group consisting of ethoxylates of long-chain alco-hols, alkyl polyglycosides and mixtures thereof.
8. The use claimed in claim 7, in which the cleaning composition contains a surfactant combination of fatty alcohol sulfate and alkyl polyglucoside.
9. The use claimed in claim 1, in which the cleaning composition contains the following active substances:
0.05 to 0.3 % by weight anionic surfactant, 0 to 0.15% by weight nonionic surfactant, 0.5 to 15 % by weight water-miscible organic solvent, 0.1 to 3 % by weight ammonia and/or alkanolamine, 0.05 to 3 % by weight carboxylic acid, 0 to 2 % by weight other typical auxiliaries, up to 100 % by weight water.
0.05 to 0.3 % by weight anionic surfactant, 0 to 0.15% by weight nonionic surfactant, 0.5 to 15 % by weight water-miscible organic solvent, 0.1 to 3 % by weight ammonia and/or alkanolamine, 0.05 to 3 % by weight carboxylic acid, 0 to 2 % by weight other typical auxiliaries, up to 100 % by weight water.
10. The use claimed in claim 1, in which the cleaning composition is initially prepared by diluting a con-centrate containing the following active substances:
0.3 to 3% by weight anionic surfactant, 0 to 1% by weight nonionic surfactant, to 50% by weight water-miscible organic solvent, 1 to 10% by weight ammonia and/or alkanolamine, 1 to 10% by weight carboxylic acid, 0 to 10% by weight other typical auxiliaries, and balance to 100% by weight at least 10% by weight water.
0.3 to 3% by weight anionic surfactant, 0 to 1% by weight nonionic surfactant, to 50% by weight water-miscible organic solvent, 1 to 10% by weight ammonia and/or alkanolamine, 1 to 10% by weight carboxylic acid, 0 to 10% by weight other typical auxiliaries, and balance to 100% by weight at least 10% by weight water.
11. The use claimed in any of claims 1 to 10 for clean-ing hard surfaces, more particularly glass, in which the cleaning composition is applied, preferably by spraying, to the surface to be cleaned in quantities of 1.5 to 5 g per m2 and the surface is subsequently cleaned by wiping with a moist and absorbent article.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4210364.9 | 1992-03-30 | ||
| DE4210364A DE4210364B4 (en) | 1992-03-30 | 1992-03-30 | Cleaning agents for hard surfaces, in particular glass |
| PCT/EP1993/000689 WO1993020176A1 (en) | 1992-03-30 | 1993-03-22 | Detergent for hard surfaces, in particular glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2133468A1 true CA2133468A1 (en) | 1993-10-14 |
Family
ID=6455409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002133468A Abandoned CA2133468A1 (en) | 1992-03-30 | 1993-03-22 | Cleaning compositions for hard surfaces, more particularly glass |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0633924B1 (en) |
| JP (1) | JPH07505182A (en) |
| AT (1) | ATE139561T1 (en) |
| CA (1) | CA2133468A1 (en) |
| DE (2) | DE4210364B4 (en) |
| DK (1) | DK0633924T3 (en) |
| ES (1) | ES2088671T3 (en) |
| GR (1) | GR3020378T3 (en) |
| WO (1) | WO1993020176A1 (en) |
Families Citing this family (9)
| 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 |
| WO1997030140A1 (en) | 1996-02-14 | 1997-08-21 | Stepan Company | Reduced residue hard surface cleaner comprising hydrotrope |
| GB9911818D0 (en) † | 1999-05-21 | 1999-07-21 | Reckitt & Colman Inc | Improvements in or relating to organic compositions |
| DE10258831A1 (en) * | 2002-12-17 | 2004-07-08 | Henkel Kgaa | Hard surface cleaner |
| DE102010007321B4 (en) * | 2010-02-08 | 2017-11-09 | Chemische Werke Kluthe Gmbh | Aqueous cleaning solution, in particular for the removal of paint deposits, and concentrate composition for providing an aqueous cleaning solution |
| WO2014190130A1 (en) * | 2013-05-24 | 2014-11-27 | The Procter & Gamble Company | Concentrated surfactant composition |
| CA3077050A1 (en) | 2017-09-26 | 2019-04-04 | Ecolab Usa Inc. | Acidic/anionic antimicrobial and virucidal compositions and uses thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3839234A (en) * | 1973-01-26 | 1974-10-01 | C Roscoe | Multi-purpose cleaning concentrate |
| DE3642564A1 (en) * | 1985-12-12 | 1987-07-09 | Lion Corp | Liquid detergent and cleaner |
| DE3713998A1 (en) * | 1987-04-27 | 1988-11-10 | Henkel Kgaa | CLEANER FOR HARD SURFACES |
| 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 (en) * | 1989-04-05 | 1990-10-11 | Henkel Kgaa | Liquid detergent |
| GB8909157D0 (en) * | 1989-04-21 | 1989-06-07 | Procter & Gamble | Hard-surface cleaning compositions |
| DE3943070A1 (en) * | 1989-12-27 | 1991-07-04 | Henkel Kgaa | LIQUID CLEANER FOR HARD SURFACES |
-
1992
- 1992-03-30 DE DE4210364A patent/DE4210364B4/en not_active Expired - Fee Related
-
1993
- 1993-03-22 DK DK93908848.0T patent/DK0633924T3/en active
- 1993-03-22 AT AT93908848T patent/ATE139561T1/en not_active IP Right Cessation
- 1993-03-22 CA CA002133468A patent/CA2133468A1/en not_active Abandoned
- 1993-03-22 ES ES93908848T patent/ES2088671T3/en not_active Expired - Lifetime
- 1993-03-22 WO PCT/EP1993/000689 patent/WO1993020176A1/en active IP Right Grant
- 1993-03-22 DE DE59303027T patent/DE59303027D1/en not_active Expired - Lifetime
- 1993-03-22 JP JP5517037A patent/JPH07505182A/en active Pending
- 1993-03-22 EP EP93908848A patent/EP0633924B1/en not_active Expired - Lifetime
-
1996
- 1996-06-27 GR GR960401749T patent/GR3020378T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE4210364B4 (en) | 2006-05-18 |
| EP0633924B1 (en) | 1996-06-19 |
| JPH07505182A (en) | 1995-06-08 |
| WO1993020176A1 (en) | 1993-10-14 |
| EP0633924A1 (en) | 1995-01-18 |
| ES2088671T3 (en) | 1996-08-16 |
| GR3020378T3 (en) | 1996-09-30 |
| DE59303027D1 (en) | 1996-07-25 |
| DE4210364A1 (en) | 1993-10-07 |
| DK0633924T3 (en) | 1996-10-21 |
| ATE139561T1 (en) | 1996-07-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |