EP0197480A2 - Manual cleaning process of objects with hard surfaces - Google Patents

Abstract

A liquid mixture of synthetic anionic surfactants of the sulphate and sulphonate type, where appropriate non-ionic surfactants or amphoteric surfactants with addition of a combination of a) highly polymeric water-soluble polyethylene glycols, b) one or more fat-dissolving solvents, especially terpene compounds, c) a builder and d) where appropriate a pH regulator, is used, where the pH of the liquid mixture is adjusted to 6.5 to 8 and where cleaning is carried out either with the concentrated mixture or with an aqueous mixture diluted to about 0.5 g/l to 5 g/l. The process is skin-friendly and is used for the manual cleaning of crockery and other hard surfaces.

Description

Commercial, liquid, manual dishwashing detergents, which can usually be used at slightly elevated temperatures, contain as active ingredients essentially mixtures of synthetic anionic surfactants in amounts of about 4 to 60% by weight and, if appropriate, z. B. as foam stabilizers, small amounts of nonionic surfactants, preferably alkanolamides, or amphoteric surfactants such as betaines, as well as solvents, solubilizers, hydrotropic substances, fragrances and dyes, preservatives, agents for viscosity adjustment, for pH adjustment and electrolytes. For skin protection reasons, the pH is around 5.5 to 8.0. Under certain circumstances, but this is not typical, they can still contain small amounts of builder substances or complexing agents such as hexametaphosphate or ethylenediaminetetraacetate for use in areas with highly iron-containing water. Such means are known for example from European patent 36 625.

Also common commercial all-purpose cleaning agents, ie agents for cleaning various hard surfaces in the household and in commercial premises, preferably contain combinations of anionic and nonionic surfactants in a total amount of about 5 to 15% by weight as well as cleaning-enhancing framework substances as active ingredients Amounts from about 0.5 to 5% by weight. Solvents, including terpene compounds, are usually used as further cleaning-enhancing constituents, and polyethylene glycols of the general formula HO- (CH ₂ -CH ₂ -O) _n -H are used to increase the cleaning performance as organic polymers, where n can vary between 4,800 and 64,600 ' , added. These agents are also made up with dyes and fragrances, electrolytes and viscosity regulators. Their pH is preferably in the range from 8.5 to 11, since the cleaning power, which must be used with these agents predominantly at room temperature, is generally better in an alkaline environment than in a neutral or acidic one. All-purpose cleaning agents of this type are, for example, also from the German patent specification. 27 09 690 and known from European Patent 9 193.

The addition of terpenes as solubilizers in liquid heavy-duty detergents is also known from British Patent 1,237,874.

As a rule, two cleaning compositions with different compositions are offered and used for two related but different cleaning sectors. In everyday household life, however, dishwashing detergents, which can be used manually, are also more frequently used for cleaning hard surfaces, in particular in the kitchen area, but the cleaning success can then not be optimal, as was explained above. It does not matter whether the dishes are used in a concentrated or diluted form. Also the reverse use of standard all-purpose cleaning agents .to manual dishwashing leads to unsatisfactory results.

There was therefore a need for a multigrade agent that combines high rinsing performance and skin-friendliness with the high emulsifying power of conventional all-purpose cleaning agents, that is, that has a cleaning performance at a neutral pH that normally only occurs with alkaline cleaning agents. The task was to find a single cleaning agent for all cleaning problems, in particular in the household, in connection with hard surfaces.

• a) hochpolymeren wasserlöslichen Polyethylenglykolen,
• b) wenigstens einem fettlösenden Lösungsmittel, insbesondere Terpenverbindungen,
• c) einer Gerüstsubstanz und
• d) gegebenenfalls einem pH-Wert-Regulator
  zusetzt, wobei der pH-Wert der flüssigen Mischung auf 6,5 bis 8 eingestellt wird und wobei das Reinigen mit der konzentrierten flüssigen Mischung oder deren auf etwa 0,5 g/I bis 5 g/I verdünnten wäßrigen Lösung durchgeführt wird.

The object was achieved by a method for the manual cleaning of objects with hard surfaces, in particular for the manual washing of dishes, using a liquid mixture, the synthetic anionic surfactants of the sulfate and / or sulfonate type, in particular mixtures of sulfate and sulfonate surfactants, and optionally contains nonionic surfactants or amphoteric surfactants in aqueous solution, characterized in that the liquid mixture is a combination of

• a) highly polymeric water-soluble polyethylene glycols,
• b) at least one fat-dissolving solvent, in particular terpene compounds,
• c) a framework and
• d) optionally a pH regulator
  is added, the pH of the liquid mixture being adjusted to 6.5 to 8 and the cleaning being carried out with the concentrated liquid mixture or its aqueous solution diluted to about 0.5 g / l to 5 g / l.

The invention preferably relates to a method for the manual cleaning of objects with hard surfaces, which is characterized in that the liquid mixture is a combination of a) 0.01 to 0.5, preferably 0.03 to 0.1 wt .-% a highly polymeric water-soluble polyethylene glycol of the formula HO (-CH ₂ -CH ₂ -O) _n H with n = 4,800 to 64,600, b) 0.5 to 5, preferably 1 to 2% by weight of one or more terpene compounds, c ) 0.1 to 1.5, preferably 0.5 to 1.0% by weight of a builder, and d) 0 to 5, preferably 0.5 to 3% by weight of agents for pH adjustment of 6, 5 to 8 adds.

If appropriate, 0 to 5, preferably 0.5 to 3% by weight of nonionic and / or amphoteric surfactants and other auxiliaries customary in liquid cleaning agents, in particular fragrances and colorants, solubilizers, hydrotropes, electrolytes and preservatives, can also be added to these agents.

The claimed agents are preferably prepared by presenting the calculated amount of water, running in the surfactant mixture or the individual surfactants in separate form without stirring at room temperature, then gently stirring without foaming until the streaks formed disappear, sprinkling the builders onto the liquid surface and also gently stirring , Stirring in a 2 to 5 percent by weight aqueous solution of the polyethylene glycol, stirring in the terpene compound and optionally sprinkling in or stirring in other customary auxiliaries and adjusting the pH to 6.5 to 8 by adding acid or alkali.

The claimed process results in improved dishwashing of greasy soiling and manual cleaning of heavily soiled hard surfaces as well as when using all-purpose cleaning agents with an otherwise common pH value of 8.5 to 11.

Suitable synthetic anionic surfactants, of which at least two different types are used together, as is customary in manual dishwashing detergents, are in particular those of the sulfonate and sulfate type.

The surfactants of the sulfonate type are primarily the alkylbenzenesulfonates with C _9-15 -alkyl groups and the surfactants of the sulfonate type, such as preferably the alkanesulfonates, which are obtained from C ₁₂ -C ₁₈ -alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or Neutralization or bisulfite addition to olefins, and the olefin sulfonates, which are mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline and acidic hydrolysis of the sulfonation products . Other useful surfactants are the esters of alpha sulfo fatty acids, e.g. B. alpha-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin, ie of fatty alcohols, such as, for. B. coconut fatty alcohols, Tallow fatty alcohols, oleyl alcohol, or the C ₁₀ -C ₂₀ oxo alcohols, and those of secondary alcohols of these chain lengths. In addition, the sulfuric acid monoesters of the aliphatic primary alcohols ethoxylated with 1 to 6 moles of ethylene oxide or ethoxylated secondary alcohols or alkylphenols are suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.

All of these anionic surfactants are preferably used in the form of the salts, in particular in the form of the sodium salts, but also as potassium or ammonium salts or as soluble salts of organic bases, such as mono-, di- or triethanolamine. Their amounts in the agents used in the process are 10 to 40, preferably 15 to 25 percent by weight.

Suitable nonionic surfactants which can optionally be added are addition products of 1 to 40, preferably 2 to 20, moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 18 to 20, preferably 10 to 16, carbon atoms in the alkyl radical from the group of the alcohols, alkylphenols, carboxylic acids, Carboxamides and carboxylic acid mono-, di- and -polyalkanolamides. The addition products of 8 to 20 moles of ethylene oxide with primary alcohols, such as, for. B. coconut or tallow fatty alcohols, on oleyl alcohol, on oxo alcohols of the corresponding chain lengths, or on corresponding secondary alcohols, and on mono- or dialkylphenols with 6 to 14 carbon atoms in the alkyl radicals. In addition to these water-soluble nonionics, non-fully or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether radicals in the molecule are also of interest, since they coexist with water-soluble anionic surfactants are used. Because of their good biodegradability, the ethoxylation products of primary aliphatic alkanols and alkenols are of particular practical interest.

Typical representatives of the nonionic surfactants with an average degree of ethoxylation of 2 to 7 are, for example, the compounds coconut fatty alcohol 3-EO (EO = ethylene oxide), tallow fatty alcohol 5-E0, oleyl / cetyl alcohol 5-EO (iodine number 30 to 50), Tallow fatty alcohol 7-E0, synthetic C ₁₂ -C ₁₆ fatty alcohol 6-E0, C ₁₁ -C ₁₅ oxo alcohol 3-E0, C ₁₄ / C ₁₅ oxo alcohol 7-E0, iC ₁₅ -C ₁₇ -Alkanediol-5-E0 (i = internal); sec-C ₁₁ -C ₁₅ alcohol-4-E0.

Exemplary representatives of the nonionic surfactants with an average degree of ethoxylation of 8 to 20, in particular 9 to 15, are the compounds coconut fatty alcohol-12-E0, synthetic C12 / C14 fatty alcohol-9-EO, oleyl / cetyl alcohol-10-E0 , Tallow fatty alcohol-14-E0, C ₁₁ -C ₁₅ -oxoalcohol-13-E0, C15-C18-oxoalcohol-15 E0, iC ₁₅ -C ₁₇ -alkanediol-9-E0, C ₁₄ / C ₁₅ -oxoalcohol-11- E0, sec-C ₁₁ -C ₁₅ alcohol-9-E0.

Furthermore, the non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, alkylenediamine-poly-propylene glycol and with alkylpolypropylene glycols having 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical . Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-coco-alkyl-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis (2,3- jihydroxypropylaminoxid), N-tallow alkyl-N, N-dihydroxy-ethylamine oxide.

The amounts of nonionic surfactants used are 0 to 5 percent by weight. However, preference is given to working without the addition of nonionic surfactants.

Suitable addable amphoteric surfactants are those which contain both acidic groups, such as, for. B. carboxyl; Sulfonic acid, sulfuric acid half-ester, phosphonic acid and phosphoric acid partial ester groups, as well as basic groups, such as. B. contain primary, secondary, tertiary and quaternary ammonium groups. Amphoteric compounds with quaternary ammonium groups belong to the type of betaines or zwitterionic surfactants. These are, in particular, derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C ₈ -C ₁₈ radical and another contains an anionic carboxy, sulfo or sulfato group which makes water soluble. Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propanesulfonate, 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hydroxypropanesulfonate, 3- ( N-hexadecyl-N, N-bis (2-hydroxyethyl) -ammonio) -2-hydroxypropyl sulfate, 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) -ammonio) propane sulfonate, N-tetradecyl -N, N-dimethyl-ammonioacetate, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonium acetate. C ₁₂ -C ₁₈ -Acylamido-propyldimethylammonium betaines are preferably used. The amounts of the amphoteric surfactants used are 0 to 5, preferably 0.5 to 3 percent by weight.

The framework substances in their entirety are alkaline inorganic or organic Compounds, in particular inorganic or organic complexing agents, which are preferably present in the form of their alkali or amine salts, in particular the potassium salts. The framework substances here also include the alkali metal hydroxides, of which the potassium hydroxide is preferably used.

The alkaline polyphosphates, in particular the tripolyphosphates and the pyrophosphates, are particularly suitable as inorganic complex-forming framework substances. They can be replaced in whole or in part by organic complexing agents. Further inorganic builder substances which can be used according to the invention are, for example, dicarbonates, carbonates, borates, silicates or orthophosphates of the alkalis.

The organic complexing agents of the aminopolycarboxylic acid type include, among others, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylene diamine triacetic acid and polyalkylene polyamine N-polycarboxylic acids. Examples of di- and polyphosphonic acids are: methylene diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, propane - 1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphonic acid, polyvinylphosphonic acid, copolymers of vinylphosphonic acid and acrylic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, ethane-1,2-dicarboxy-1,2-dihydroxydiphosphonic acid, phosphonosuccinic acid, 1-aminoethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid ), Methyl-amino- or ethylamino-di- (methylenephosphonic acid) and ethylenediamine-tetra- (methylenephosphonic acid). A wide variety of, mostly N- or P-free polycarboxylic acids have recently been proposed as builder substances in the literature, although in many cases, if not exclusively, they are carboxyl groups containing polymers. A large number of these polycarboxylic acids have a complexing ability for calcium. These include e.g. As citric acid, tartaric acid, benzothexacarboxylic acid, tetrahydrofuran tetracarboxylic acid, etc.

The terpene compounds include commercially available compounds on terpineols such as pine oil and terpene hydrocarbons such as limonene, preferably those with a lemon-like fragrance.

The water-soluble polyethylene glycols to be used according to the invention have a molecular weight of between approximately 200,000 and 4,000,000, preferably between approximately 500,000 and 1,000,000. They are produced in a known manner by subjecting ethylene glycols to a polycondensation process. They can also be seen as condensation polymers of ethylene oxide with ethylene glycol or water. They have the general formula HO (-CH ₂ -CH ₂ -O) _n H, where n can vary between 4,800 and 64,600 in the case of the polyethylene glycols used according to the invention. Such polymers are also commercially available and z. B. from Union Carbide Corporation (UCC) under the name "POLYOX ^(R) ".

To prepare the liquid detergents, known solubilizers can be incorporated, such as the water-soluble organic solvents, in particular low-molecular aliphatic alcohols having 1 to 4 carbon atoms, and also those with boiling points above 75 ° C., such as the ethers from the same or different types of polyhydric alcohols or the partial ethers from polyhydric alcohols. These include, for example, di or

Triethylene glycol polyglycerols and the partial ethers of ethylene glycol, P-ropylene glycol, butylene glycol or glycerol with aliphatic monohydric alcohols containing 1 to 4 carbon atoms in the molecule, but also the so-called hydrotropic substances of the lower alkyl aryl sulfonate type, which include, for example, toluene, xylene or cumene sulfonates. They can be in the form of their sodium and / or potassium and / or alkylamino salts.

Suitable water-soluble or water-emulsifiable organic solvents are also ketones, such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons.

To regulate the viscosity, it may be advisable to add higher polyglycol ethers with molecular weights up to about 600 or polyglycerol. It is also advisable to add electrolytes such as sodium chloride and / or urea to regulate the viscosity.

In addition, the cleaning agents can contain additives of colors and fragrances, preservatives and, if desired, antimicrobial agents of any kind.

For example, formaldehyde-amino alcohol condensation products can be used as antimicrobial agents. The products are obtained by reacting an aqueous solution of formaldehyde with amino alcohols, e.g. B. 2-aminoethanol, 1-aminoethanol, 1-amino-2-propanol, 2-aminoiso-butanol, 2 (2'-aminoethyl) aminoethanol.

Suitable pH-regulating agents are customary inorganic or organic acids or acidic salts, such as hydrochloric acid, sulfuric acid, bisulfates of alkalis, aminosulfonic acid, phosphoric acid or other acids of phosphorus, especially the anhydrous acids of phosphorus or their salts or their acidic acids solid compounds reacting with urea or other lower carboxamides, partial amides of phosphoric acids or anhydrous phosphoric acid, citric acid, tartaric acid, lactic acid and the like. Organic or inorganic compounds such as alkanolamines, namely mono-, di- or triethanolamine or ammonia, can also be added as basic substances. To set a weakly alkaline pH, alkaline builder substances and washing alkalis, such as. B. sodium tripolyphosphate, sodium carbonate and sodium bicarbonate, potassium carbonate and bicarbonate, sodium silicate and the sodium aiumosilicate.

Since alkali citrates and phosphates in particular have already been added as builders, there is often no need for additional pH regulation.

Examples

• Zum Nachweis des Reinigungseffektes der erfindungsgemäß eingesetzten Mittel beim manuellen Geschirrspülen wurde der sogenannte Tellertest durchgeführt. Die Methodik ist in der Zeitschrift "Fette, Seifen, Anstrichmittel", 74, (1972), Seiten 163 bis 165 beschrieben.

Plate test:

• The so-called plate test was carried out to demonstrate the cleaning effect of the agents used according to the invention in manual dishwashing. The methodology is described in the journal "Fette, Seifen, Anstrichmittel", 74, (1972), pages 163 to 165.

14 cm diameter plates were alternatively soiled with 2 g beef tallow (melting point 40 to 42 ° C, acid number 9 to 10) or with a mixed soiling of protein, fat and carbohydrates, for 15 hours at + 0 to + 5 ° C stored and rinsed at 45 ° C with tap water hardness 16 ° d. The test products were used with a dosage of 0.5 g / l water. The number of plates that are rinsed clean with 5 liters of wash liquor = number of plates serves as a measure of the cleaning effect.

Emulsifying power

• The fat emulsifying ability was also tested as follows:
  • The emulsion stability of olive oil in the detergent solutions was determined. For this purpose, 50 g of test solution (10 g of washing-up liquid / 40 g of water) with city water at 16 ° C. were prepared in a 400 ml beaker, covered with 50 g of olive oil (Olio Dante) at room temperature (20 to 30 ° C.) and with a propeller stirrer (Blade length 50 mm made of V2A steel) stirred at a speed of 1200 rpm for exactly 2 minutes. The impeller was roughly at the border of the two phases. The emulsion was then placed in a 250 ml graduated cylinder with a flat bottom (2 ml graduation, Industry standard) poured and the separated aqueous phase after 1 hour and after 4 hours determined. The less water was separated in the unit of time, the more stable the emulsion and thus the oil / fat carrying capacity of the cleaning agent solution.

Cleaning ability

• The following tests were carried out to demonstrate the all-purpose cleaning ability of the claimed combination of the compounds:
  • The surfactant combination to be tested for cleaning effect was applied to an artificially soiled plastic surface. Mixtures of carbon black, machine oil, triglyceride of saturated fatty acids and low-boiling aliphatic hydrocarbon (see below) were used as artificial soiling. The test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater.

A plastic sponge was soaked in each case with 12 ml of the cleaning agent solution to be tested and moved mechanically on the test surface. After 6 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, d. H. the whiteness of the plastic surface cleaned in this way was measured using a LF 90 photoelectric colorimeter (Dr. B. Lange). The clean, white plastic surface served as the white standard. Since the measurement of the clean surface was set to 100% and the soiled area was displayed with 0, the read values for the cleaned plastic areas are to be equated with the percentage cleaning ability (% RV). The% -RV values given are averages from quadruple determinations.

Soiling

Die Zusammensetzung der erfindungsgemäßen Reinigungsmittel ist in Tabelle 1 angegeben (Rezepturen 8 bis 14). Daneben finden sich Vergleichsversuche mit handelsüblichen manuell anwendbaren Geschirreinigungsmitteln (Rezepturen 1 bis 5) und handelsüblichen Allzweckreinigungsmitteln (Rezepturen 6 bis 7). Die Rezepturen wurden, falls erforderlich, mit Zitronensäure oder Natronlauge auf die angegebenen pH-Werte eingestellt. Die Rezepturen 8a, 8b und 14 a und b zeigen in ihren Ergebnissen, daß es auf die Kombination von Gerüstsubstanzen, Terpenverbindungen und Polyethylenglykolen ankommt und bei Weglassen eines dieser Bestandteile der gewünschte Erfolg nicht erzielt wird. Am Rezepturbeispiel 14 b wird deutlich, daß das Fett-Emulgiervermögen von Geschirreinigungsmitteln bereits durch den Polymerzusatz allein deutlich gesteigert wird. Diese Ergebnisse sind Tabelle 2 zu entnehmen. Aus ihr geht auch hervor, daß das Reinigungsvermögen der erfindungsgemäßen Mittel bereits bei neutralem pH-wert dem der alkalisch eingestellten handelsüblichen Allzweckreinigungsmittel entspricht, was für die Anwender noch den Vorteil der verbesserten Hautverträglichkeit mit sich bringt.

The composition of the cleaning agents according to the invention is given in Table 1 (formulations 8 to 14). In addition, there are comparative tests with commercially available, manual dishwashing detergents (recipes 1 to 5) and commercially available all-purpose cleaning agents (recipes 6 to 7). If necessary, the recipes were adjusted to the specified pH values with citric acid or sodium hydroxide solution. In their results, the formulations 8a, 8b and 14a and b show that the combination of builders, terpene compounds and polyethylene glycols is important and that if one of these components is left out, the desired success is not achieved. It is clear from recipe example 14 b that the fat-emulsifying power of dishwashing detergents is already significantly increased by the addition of polymer alone. These results are shown in Table 2. It also shows that the cleaning ability of the The agent according to the invention already corresponds to the alkaline, commercially available all-purpose cleaning agent at a neutral pH, which also brings the advantage of improved skin compatibility for the user.

Claims (8)

1.Method for the manual cleaning of objects with hard surfaces, in particular for the manual washing of dishes, using a liquid mixture, the synthetic anionic surfactants of the sulfate and / or sulfonate type, in particular mixtures of sulfate and sulfonate surfactants, and optionally nonionic surfactants or Contains amphoteric surfactants in aqueous solution, characterized in that a combination of the liquid mixture a) highly polymeric water-soluble polyethylene glycols, b) at least one fat-dissolving solvent, in particular terpene compounds, c) a framework and d) optionally a pH regulator
is added, the pH of the liquid mixture being adjusted to 6.5 to 8 and the cleaning being carried out with the concentrated liquid mixture or its aqueous solution diluted to about 0.5 g / l to 5 g / l. 2. The method according to claim 1, characterized in that the liquid mixture is a combination of a) 0.01 to 0.5, preferably 0.03 to 0.1 wt .-% of a highly polymeric water-soluble polyethylene glycol of the formula HO (-CH ₂ -CH ₂ -O) _n H with n = ₄₈₀₀ to 64,600, b) from 0.5 to 5, preferably 1 to 2 wt .-% of one or more terpene compounds, c) from 0.1 to 1.5, preferably 0.5 to 1.0% by weight of a builder, and d) 0 to 5, preferably 0.5 to 3% by weight of pH adjustment agents from 6.5 to 8 are added. 3. Process according to claims 1 and 2, characterized in that the mixture used contains no nonionic surfactant. 4. Process according to claims 1 and 2, characterized in that the mixture used additionally contains 5, preferably 0.5 to 3% by weight of amphoteric surfactants. 5. Process according to claims 1 to 4, characterized in that the mixture used additionally contains conventional auxiliaries, in particular fragrances and dyes, solubilizers, hydrotropes, electrolytes and preservatives. 6. The method according to claims 1 to 5, characterized in that the mixture used contains pine oil or limonene as terpene compounds. 7. Agent for carrying out the method according to claims 1 to 6, characterized in that it contains 10 to 40, preferably 15 to 25 wt .-% of a mixture of at least two different anionic surfactants, 0.01 to 0.5, preferably 0, 03 to 0.1% by weight of a water-soluble polyethylene glycol of the formula HO (-CH ₂ -CH ₂ -O) _n H with n = 4,800 to 64,600, 0.5 to 5, preferably 1 to 2% by weight one or more terpene compounds, 0.1 to 1.5, preferably 0.5 to 1.0% by weight of a builder, and 0 to 5, preferably 0.5 to 3% by weight of agents for pH adjustment of 6.5 to 8 contains. 8. A process for the preparation of the agents used according to claims 1 to 6 by presenting the calculated amount of water, running in the surfactant mixture or the individual surfactants in separate form without stirring at room temperature, then gentle stirring without foaming until the streaks formed disappear, sprinkling the framework substances onto the liquid surface and also gentle stirring, stirring in a 2 to 5 percent by weight aqueous solution of the polyethylene glycol, stirring in the terpene compound and optionally sprinkling and stirring in other customary auxiliaries and pH -Value adjustment to 6.5 to 8 by adding acid or alkali.