WO1993020176A1

WO1993020176A1 - Detergent for hard surfaces, in particular glass

Info

Publication number: WO1993020176A1
Application number: PCT/EP1993/000689
Authority: WO
Inventors: Heinz-Dieter Soldanski; Bernd-Dieter Holdt; Jürgen Noglich
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1992-03-30
Filing date: 1993-03-22
Publication date: 1993-10-14
Also published as: DE4210364B4; CA2133468A1; ATE139561T1; EP0633924B1; DE59303027D1; DK0633924T3; EP0633924A1; JPH07505182A; ES2088671T3; DE4210364A1; GR3020378T3

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.

Description

"Detergent for hard surfaces, especially glass"

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.

When using 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. In particular, ammonia and alkanolamines have been used here. However, 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. There was therefore still a need for cleaning agents which did not have the disadvantages mentioned with high cleaning performance.

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. In contrast, the high cleaning performance is practically only slightly reduced by the addition of the carboxylic acid. Although 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.

A description of the individual components of the agent now follows:

a) surfactants

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. In concentrated compositions, which before If the application still has to be diluted, the concentration is correspondingly higher and can preferably be up to 3% by weight If 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.

Examples of such surfactants are 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.

As 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 . Examples of such surfactants are 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. In addition to the addition products of ethylene oxide and fatty alcohols, 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.

In addition to nonionic and / or anionic surfactants, the agents according to the invention can also contain smaller amounts of amphoteric surfactants (betaine surfactants). These 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.

Water-miscible organic solvent

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.

In particular, 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. Examples of such 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.

If alcohol and ether alcohol are used side by side, the weight ratio of the two is preferably between 1: 2 and 4: 1.

c) Volatile alkali

In addition to the organic solvent content, the volatile alkali content is essential for the good cleaning performance of the agents according to the invention. As such, 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. 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.

d) carboxylic acid

The content of 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. Depending on the equivalent weight of amino and carboxylic acid, 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. Thus, the pH drops significantly and can be reset to values at which damage to sensitive surfaces no longer occurs. Preferably, the pH Values in the ready-to-use agent are set from about 9 to about 10. Despite this decrease in the pH, 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.

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 preferably used.

Other usual auxiliary substances

In addition to components a) to d), 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. 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,

0 to 0.15% by weight of nonionic surfactant,

0.5 to 15% by weight of water-miscible organic solvent,

0.1 to 3% by weight of ammonia and / or alkanolamine,

0.05 to 3% by weight carboxylic acid,

0 to 2% by weight of other customary auxiliaries to 100% by weight of water.

Concentrates that have to be diluted to the application concentration beforehand with water are preferably composed as follows:

0.3 to 3% by weight of anionic surfactant, 0 to 1% by weight of nonionic surfactant, 10 to 50% by weight of water-miscible organic solvent,

1 to 10% by weight of ammonia and / or alkanolamine 1 to 10% by weight of carboxylic acid,

0 to 10% by weight of other customary auxiliaries and 100% by weight, at least 10% by weight of water.

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 / π.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. First and foremost, 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.

Two different methods were used to test the cleaning effect under extreme conditions:

a) 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

7% fine carbon black 57% myritol ( ^R ) (fatty acid triglyceride) 36% white spirit

and was evenly applied at 0.3 g per plate. After a drying time of 1 to 1.5 hours, the plates which had been soiled in groups of several were used for the test. The cleaning process consisted of 20 strokes with a polyester sponge under standardized load (800 g), using 6 g of detergent. After rinsing under running water, measurements were taken. The results of these tests are given in the following table as% light emission compared to the untreated plate (100%) (RV values).

Highly polished sheets of stainless steel (40 x 554 mm) were evenly coated with 0.4 g of a mixture of vegetable oil and white spirit (1: 1) and stored in the air for 15 hours at 80 ° C after the solvent had evaporated. The sheets were then cleaned as indicated under a), while the cleaning effect was assessed visually in comparison to an unpurified and an unpolluted sheet. The following evaluation grades were used:

1 = fat completely removed

2 = fat largely removed

3 = fat partially removed

4 = only a small part of the fat removed

5 = fat almost unchanged

The results are also shown in the table.

It is clear from the results that almost the same cleaning result can be achieved with the examples 2, 3 and 7 according to the invention as with the agents which have no added acid at the same alkali concentration (1,6). At the same time, the significantly improved cleaning performance compared to agents without added alkali or with only a minor addition of alkali (4, 5, 8, 9) can be seen (the pH value in agents 4 and 8 is explained by traces of alkali in the surfactant raw materials) .

Detergents and their effects in weight%

Claims

1. Aqueous cleaning agent for hard surfaces, containing 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 a carboxylic acid 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.

2. Cleaning agent according to claim 1, which additionally contains nonionic surfactant.

3. Cleaning agent according to one of claims 1 or 2, wherein the carboxylic acid is selected from the group acetic acid, citric acid, lactic acid and mixtures thereof.

4. Cleaning agent according to one of claims 1 or 2, which contains ammonia together with an ethanolamine from the group of mono-, di- and triethanolamine and mixtures thereof, preferably with monoethanolamine.

5. Cleaning agent according to one of claims 1 or 2, the water-miscible organic solvent contains a mixture of lower alcohol having 2 or 3 carbon atoms and glycol ether from the group ethylene glycol monobutyl ether, propylene glycol monobutyl ether and mixtures thereof.

6. Cleaning agent according to one of claims 1 or 2, in which the anionic surfactant is selected from the group consisting of alkane sulfonates, alkyl ether sulfates, alkyl sulfates and mixtures thereof.

7. Cleaning agent according to claim 2, wherein the nonionic surfactant is selected from the group of ethoxylates of long-chain alcohols, the alkyl polyglycosides and mixtures thereof.

8. Cleaning agent according to claim 7, containing a surfactant combination of fatty alcohol sulfate and alkyl polyglucoside.

9. Ready-to-use cleaning agent according to claim 1, containing

% By weight of anionic surfactant,% by weight of nonionic surfactant,% by weight of water-miscible organic solvent,% by weight of ammonia and / or alkanolamine,% by weight of carboxylic acid,% by weight of other customary auxiliaries

% By weight of water.

10. detergent concentrate according to claim 1, containing

0.3 to 3% by weight of anionic surfactant,

0 to 1% by weight of nonionic surfactant, 10 to 50% by weight of water-miscible organic solvent,

1 to 10% by weight of ammonia and / or alkanolamine 1 to 10% by weight of carboxylic acid, 0 to 10% by weight of other customary auxiliaries and 100% by weight, at least 10% by weight of water.

11. A method for cleaning hard surfaces, in particular glass, in which a cleaning agent according to claim 9 in amounts of 1.5 to 5 g per π) is applied to the surface to be cleaned, preferably by spraying, and this surface is then wiped with an absorbent soft object is cleaned.