WO1994014944A1

WO1994014944A1 - Neutral liquid cleaning agents (ii)

Info

Publication number: WO1994014944A1
Application number: PCT/EP1993/003492
Authority: WO
Inventors: Birgit Skodell; Rainer Osberghaus; Karl-Heinz Rogmann; Heiko Faubel; Herta Tuchermann
Original assignee: Henkel-Ecolab Gmbh & Co. Ohg
Priority date: 1992-12-22
Filing date: 1993-12-10
Publication date: 1994-07-07
Also published as: DE4243477A1

Abstract

The water-based cleaning agents proposed have a pH between 5 and 9 in the undiluted state and contain, in addition to 1 to 25 % by wt. of non-ionic or anionic surfactant, 0.1 to 12 % by wt. of a monoalkyl diethylene glycol ether with 1 to 4 C-atoms in the alkyl group. The agents are intended for use above all in the undiluted state for cleaning hard surfaces and in the diluted state for cleaning textile floor coverings.

Description

"Neutral liquid detergent (II)"

The invention described below is in the field of aqueous cleaning agents which are intended for use in the household and commercial.

For cleaning objects of all kinds, aqueous surfactant solutions, which can optionally contain further active ingredients and additives, are predominantly used. For example, liquid general-purpose cleaners have found widespread use in households and businesses, with the aid of which surfaces made of metal, painted wood, plastic, ceramic products and glass can be cleaned without problems. These cleaning agents, which mostly contain anionic or nonionic surfactants as essential active substances, can be used both in concentrated form and in more or less diluted form. In addition, liquid cleaning agents are also used to clean textiles, in particular textile floor coverings. The application here is preferably in dilute form or in the form of foam.

Whereas in the past liquid cleaning agents usually had a more alkaline pH value, which promoted dirt removal, or had a relatively strongly acidic pH value if lime deposits were to be dissolved, there has recently been a tendency towards neutral cleaning agents developed, from which one promises greater protection of the material and better skin tolerance. Reference is made here, by way of example only, to German laid-open specification 2220540 and American patents 3,463,735, 3,882,038 and 3,939,090. Until now, these advantages of neutral cleaning agents have generally had to be bought with certain disadvantages, of which only the lower cleaning power and the lower network capacity compared to alkaline agents should be mentioned here.

In this context, the object of the present invention was to provide a neutral liquid cleaning agent which is improved compared to the prior art. itte! to develop. In connection with the present invention, the neutral range is the range between pH values 5 and 9, in particular between 6 and 8.

The solution according to the invention consists of an aqueous cleaning agent which, in the undiluted state, has a pH of the above range and which is characterized in that it contains 1 to 25% by weight of surfactant from the classes of the nonionic and / or the synthetic anionic surfactants and 0.1 to 12% by weight of a monoalkyldiethylene glycol ether with 1 to 4 carbon atoms in the alkyl part or a mixture of several of these ethers. Cleaning agents in which the content of these ethers is 3 to 7% by weight are particularly preferred.

The cleaning agents according to the invention are distinguished in particular by the fact that, when used on solid surfaces, they do not run together to form drops and larger stains when drying, but instead dry evenly and thereby leave practically no optically disturbing residues on the surfaces. At the same time, the agents have an extraordinarily high cleaning performance both in the undiluted and in the diluted state. It is also surprising that the agents according to the invention are stable against microbial attack, so that the addition of conventional preservatives can be dispensed with. In addition, it was found that the agents according to the invention can be stored even at unusually low temperatures without the occurrence of segregation and without the need for special anti-freeze agents. The good storage stability is also given when larger quantities of perfume oils are incorporated into the agents. Overall, the agents represent a significant improvement over the prior art.

The synthetic anionic surfactants which may be present in the agents according to the invention are, above all, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are alkylbenzene sulfonates with a Cg-Ci5-alkyl radical and olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained from Ci2-Ci8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are the alkanesulfonates which are obtainable from Ci2-Ci8-Al anen by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of α-sulfofatty acids, e.g. B. the α-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Suitable sulfate-type surfactants are the sulfuric acid monoesters of long-chain primary alcohols of natural or synthetic origin, ie of fatty alcohols, such as, for. B. coconut fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the Cio- ^ O- ^ ⁰³ ^ ^0- or secondary alcohols of this chain length. The sulfuric acid monoesters of the aliphatic long-chain primary alcohols or ethoxylated secondary alcohols ethoxylated with 1 to 6 mol of ethylene oxide (EO) are also suitable. Also suitable are sulfated fatty acid alkanolamides, sulfated fatty acid onoglycerides, long-chain sulfosuccinic acid esters and the salts of long-chain ether carboxylic acids which can be obtained, for example, by reacting long-chain alcohols ethoxylated with 1-10 mol EO with chloroacetic acid. The anionic surfactants are preferably used as alkali salts, in particular sodium salts, but ammonium salts or the salts of alkanols with 2 to 6 carbon atoms can also be used. In the context of the present invention, particularly preferred anionic surfactants are the alkane sulfonates, the olefin sulfonates and the fatty alcohol sulfates.

The synthetic anionic surfactants are contained in the agents according to the invention in concentrations of up to 25% by weight. At least 1% by weight is preferably present. Agents which are intended for undiluted use preferably contain 1 to 5% by weight of the anionic surfactants, while agents which are preferably or exclusively used in the diluted state usually contain relatively large amounts of these surfactants, preferably 1 to 11 % By weight.

Suitable nonionic surfactants are primarily the adducts of 3 to 20 moles of ethylene oxide (EO) with primary CIO-C2θ alcohols, such as z. B. on coconut or tallow alcohols, on oleyl alcohol, on oxo alcohols or on secondary alcohols of this chain length. In addition to the water-soluble nonionic surfactants included here, the incompletely water-soluble, low ethoxylated fatty alcohol polyglycol ethers with 3 to 7 ethylene glycol ether residues in the molecule may also be of interest, especially if they are used together with water-soluble nonionic or anionic surfactants. The corresponding ethoxylation products of other long-chain compounds, for example the fatty acids and the fatty acid amides with 12 to 18 carbon atoms and the alkylphenols with 8 to 16 carbon atoms in the alkyl part, are also suitable. In all of these products, propylene oxide (PO) can also be added instead of part of the ethylene oxide. Other suitable nonionic surfactants are also the water-soluble addition products containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups of ethylene oxide on polypropylene glycol, alkylene diamine polypropylene glycol and on alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic residue . Also suitable as nonionic surfactants are mono- and diethanolamides of fatty acids and long-chain amine oxides or sulfoxides, for example the compounds N-coconut alkyl-N, N-dimethylamine oxide, N-tallow alkyl-N, N-dihydroxyethylamine oxide, and also the water-soluble alkyl glycosides, the latter is hydrophobically linked via C8-C20-alkyl radical with a mostly oligomeric hydrophilic glycoside radical, for example Ci2-Ci4-fatty alcohol + 1.6 glucose. In the agents according to the invention, preferred nonionic surfactants are ethoxylates of fatty alcohols or oxoalcohols with 5 to 15 mol E0, fatty acid ethanolamides and alkyl polyglucosides.

The nonionic surfactants can be used in the compositions according to the invention in quantities of up to 25% by weight, with the proviso that the sum of anionic and nonionic surfactants in the compositions is 1 to 25% by weight. In the compositions which are used undiluted, the content of nonionic surfactants is preferably between 1 and ...% by weight, while in the compositions which are preferably or exclusively used in the diluted state, the content of these surfactants is higher is and is preferably 1 to 15 wt .-%. In many cases, a mixture of anionic and nonionic surfactants is used, as synergies gisms, especially with regard to the cleaning effect. In these cases, a weight ratio of anionic to nonionic surfactant such as 7: 1 to 1: 1, in particular 5: 1 to 2: 1, is preferred.

In addition to synthetic anionic and / or nonionic surfactants, the agents according to the invention can also contain amphoteric surfactants and in particular beefs in large quantities if this is desired in order to achieve particular effects. The a photere tensides are long-chain compounds whose hydrophilic part consists of a cationically charged center (usually a tertiary amino or a quaternary ammonium group) and an anionically charged center (usually a carboxylate or a sulfonate group ) consists. Examples of such surfactants are N-cocoalkyl-N, N-dimethylaminoacetate and N-dodecyl-N, N-dimethyl-3-aminopropanesulfonate. The soaps are the alkali or ammonium salts of the fatty acids with 12 to 18 carbon atoms in the chain. Examples are Cio-Ciβ-coconut fatty acid sodium salt, Cι§-Ci8-tallow alkyl ammonium salt and myristic acid potassium salt.

The content of amphoteric surfactants and / or soaps depends on the desired effect and can be up to 10% by weight with the amphoteric surfactants and up to 25% by weight with the soaps, based on the total agent. If these surfactants are contained in the compositions, their concentration is at least 0.1% by weight, preferably 0.3% by weight, while the upper limits are preferably 5 or 15% by weight. High levels of soap are provided in particular in those agents which, for example, are intended to leave a nourishing matt glossy soap film when used on floor coverings and which are therefore also referred to as wiping agents. High levels of amphoteric surfactants and / or soaps generally simultaneously result in a lower level of anionic and / or nonionic surfactants, so that the total level of surfactants in the concentrated agents used in dilute solution preferably does not exceed 15% by weight. , in particular not more than 10% by weight.

Another essential component of the agents according to the invention are the monoalkyl diethylene glycol ethers with 1 to 4 carbon atoms in the alkyl part, which contained in the agents individually or in a mixture. In conjunction with the anionic and / or nonionic surfactants, these ethers are apparently responsible for the special effects of the neutral cleaning agents according to the invention. Methyl, ethyl and n-butyldiethylene glycol ether are particularly preferred. It is noteworthy that relatively low levels of ether are sufficient for the effects described. The minimum content is about 0.1% by weight; the agents preferably contain no more than 12% by weight. A particularly preferred range is between 3 and 7% by weight, based on the total aqueous agent.

In addition to the constituents already mentioned, the agents according to the invention can contain further active ingredients and additives, for example cleaning salts, solvents, viscosity regulators, solubilizers, dyes and perfume oils, provided that the advantageous effects of the agents according to the invention are not impaired thereby.

The cleaning-active salts, which can be present in the compositions in amounts of up to 10% by weight, are water-soluble salts, in particular alkali salts, of inorganic or organic acids which serve to tolerate the cleaning action and the material compatibility improve and, if necessary, suppress the effects of water hardness. Examples include sodium citrate, sodium triphosphate, monopotassium phosphate, potassium pyrophosphate, potassium carbonate and sodium hydrogen carbonate.

The solvents, which in addition to the above-mentioned monoalkyldiethylene glycol ethers can be present in amounts of up to 10% by weight, are completely water-miscible solvents from the group of alcohols having 2 to 4 carbon atoms and the lower monoglycol monoalkyl - ethers with up to 8 carbon atoms, for example ethanol, isopropanol and ethanediol. These solvents, as well as any other solubilizers that may be included, serve to make the agents according to the invention single-phase even when active ingredients that are not very water-soluble are used. The solubilizers, which are also referred to as hydrotropes, are mostly salts of non-surfactant sulfonic acids, for example sodium xylene sulfonate, or compounds that strongly influence the structure of water, such as urea.

In the simplest case, the agents can be produced by mixing all the components together in any order. If little water-soluble active ingredients are incorporated, it is often advisable to first mix them with the solvents and then add them to the aqueous solution of the surfactants. The presence of the diglycol ethers has an advantageous effect in the stabilization of poorly water-soluble compounds in the compositions. If necessary, the pH is adjusted to the desired value in the neutral range (pH 5 to pH 9) with the aid of alkali or acids.

The agents according to the invention can be used both undiluted and after more or less strong dilution with water. One and the same agent can be used both in the undiluted state to remove heavy soiling, mostly point-by-point, and also used for surface cleaning in the diluted state. As a rule, however, agents which are intended for undiluted use throughout are less concentrated than agents for which a dilution step with water is usually initially provided prior to the actual use. Agents for undiluted use therefore usually contain more than 80% by weight, preferably more than 90% by weight of water, while the agents which are diluted, depending on the degree of dilution provided, can also have water contents below 30% by weight. Their water content is preferably between about 40% by weight and about 80% by weight, depending on the intended degree of dilution, which can preferably be 1: 3 to 1: 500, in particular 1: 5 to 1:50.

The actual cleaning process then consists in impregnating an absorbent object, for example a cloth or a sponge, with the optionally diluted cleaning agent and wiping the surface to be treated evenly therewith. In this process, the dirt is detached from the surface and picked up by the rag or sponge, in order to then be released onto this medium when the rag or sponge is rinsed out with water or dilute cleaning agent solution. There the agents dry extremely evenly and streak-free on almost all surfaces, as a rule, rinsing with water and other post-treatments such as polishing can be dispensed with. While the diluted cleaning agent solutions can also be used for cleaning textile coverings, for example using the spray extraction process, the main focus of the application is on cleaning hard surfaces such as floors, plastic surfaces, painted wood, glass panes and tiles.

Examples

Cleaner based on non-ionic surfactant

Cleaners 1 and 2 were produced from the components listed in Table 1 by intensive mixing. Unless otherwise stated, the numbers in this and the later tables represent percentages by weight, based on the finished product, and are always calculated as pure active substance. In all cases the perfume was mixed in as the last component. Agent 2 according to the invention was then compared with agent 2 not according to the invention in terms of residue behavior when cleaning solid surfaces and in terms of storage-stable incorporation of the perfume oil.

The residue behavior of the agents was checked by running each 100 ml of a 1% solution of the agent down a black tile wall and allowing it to dry. After drying completely, the residue was assessed visually using a rating scale from -5 to 0:

-5 very strong veil, not polishable

-4 strong veils, difficult to polish

-3 medium veils, difficult to polish

-2 fogging, polishable

-1 little veil, easy to polish

0 no veil or impairment in gloss

The stability of the perfume in the compositions was checked in a storage test in an alternating climate (12 hours at 0 ° C, 12 hours at 40 ° C). Here, too, the assessment was made visually, according to the following scale:

1. Very good dispersibility; The perfume oil droplets are evenly distributed in the solution and no longer separate even during the storage test.

2. good dispersibility; only a part of the perfume separates as droplets only at the end of the storage test.

3. Medium dispersibility; some of the perfume droplets separate after 4 weeks of storage. 4. Poor dispersibility; the entire perfume separates after 4 weeks of storage.

Table 1

Examples 1 2

The advantages of the agent 2 according to the invention over the agent 1 not according to the invention are clear from the test results.

Cleaner based on anionic surfactant

Cleaners of this type (3-4) were produced from the raw materials listed in Table 2 by intensive mixing. In all cases, the perfume was the last to be added to the mixture. The agents were tested using the same criteria and methods as in Examples 1 and 2.

From the test results, the advantages of the agent 4 according to the invention over the comparative example 3 can also be seen very clearly here.

Soap cleaner

The soap cleaners according to Examples 5 to 6 were prepared by mixing the components shown in Table 3. The agent 6 according to the invention was then compared with the agent 5 not according to the invention with regard to its cleaning power and its low-temperature stability.

The cleaning effect was determined with the aid of a Gardner washability and abrasion test device, as is the case in the quality standards for wiping agents from the Industrial Association of Cleaning and Care Agents. V. is described (Seifen-Öle-Fette, Wachsen, 108, pages 526 - 528 (1982)). With this method, a white PVC film is coated with a soot and grease soiling and, under standardized conditions, with a machine thinned (1: 500) detergent soaked sponge. The cleaning performance is measured by photoelectric determination of the reflectance.

To assess the cold stability, the samples were stored at 0 - 3 ° C for 12 weeks. During this time, the samples were removed from the freezer weekly and assessed visually after reaching room temperature. Visible signs of instability were flocculation, sedimentation, flooding and changes in viscosity. The evaluation was carried out on the following scale:

0 uniform, homogeneous sample

1 slight flooding or sediment after 12 weeks

2 suspensions or sediment after 3 weeks

3 medium suspension or sediment after 3 weeks

4 heavy swellings or sediment after 3 weeks

5 very strong floods or sediment after 3 weeks

Table 3

Examples 5 6

In this case too, the test results clearly show the advantages of the inventive agent 6 compared to the comparative example.

Claims

1. Aqueous cleaning agent which, when undiluted, has a pH in the range between 5 and 9 and which has 1 to 25% by weight of surfactant from the classes of nonionic and synthetic anionic surfactants and 0.1 to 12% by weight. % of a monoalkyl diethylene glycol ether having 1 to 4 carbon atoms in the alkyl part or a mixture of several of these ethers.

2. Cleaning agent according to claim 1, containing 3 to 7 wt .-% of a monoalkyldiethylene glycol ether having 1 to 4 carbon atoms in the alkyl part or a mixture of several of these ethers.

3. Cleaning agent according to one of claims 1 or 2, containing monoalkyldiethylene glycol ether from the group methyldiethylene glycol ether, ethyldiethylene glycol ether, n-butyldiethylene glycol ether and mixtures thereof.

4. Cleaning agent according to one of claims 1 to 3, which has a pH between 6 and 8 in the undiluted state.

5. Cleaning agent according to one of claims 1 to 4, which contains 0.1 to 25 wt .-% soap as a further active ingredient.

6. Cleaning agent according to one of claims 1 to 5, which contains 0.1 to 10% by weight of amphoteric surfactant as a further active ingredient.

7. Cleaning agent according to one of claims 1 to 6, which contains further auxiliaries and additives from the group of cleaning-active salts, solvents, solubilizers, dyes, perfume oils and mixtures thereof.

8. Use of a cleaning agent according to one of claims 1 to 7 in the undiluted state for cleaning hard surfaces.

9. Use of a cleaning agent according to one of claims 1 to 7 after dilution with water in a weight ratio of 1: 3 to 1: 500, preferably 1: 5 to 1: 50, for cleaning textile coverings or hard surfaces.