EP1137750A1

EP1137750A1 - General purpose cleaners

Info

Publication number: EP1137750A1
Application number: EP99962184A
Authority: EP
Inventors: Rita Köster; Ansgar Behler; Karl-Heinz Schmid; Michael Neuss
Original assignee: Cognis Deutschland GmbH and Co KG
Current assignee: BASF Personal Care and Nutrition GmbH
Priority date: 1998-12-09
Filing date: 1999-11-30
Publication date: 2001-10-04
Also published as: DE19856727A1; US6660706B1; WO2000034425A1

Abstract

The invention relates to general purpose cleaners containing alkoxylated carboxylic acid esters, especially such as those produced by reacting carboxylic acid esters and alkylene oxides in the presence of calcinated hydrotalcites; and betaines and/or amine oxides as co-tensides. The invention also relates to the use of a tenside mixture containing alkoxylated carboxylic acid esters and betaines and/or amine oxides for producing general purpose cleaners of this type.

Description

"All-purpose cleaner"

The present invention relates to general-purpose cleaners containing alkoxylated carboxylic acid esters, in particular those which have been prepared by reacting carboxylic acid esters and alkylene oxides in the presence of calcined hydrotalcites, and containing betaines and / or amine oxides as co-surfactants. Another object of the invention relates to the use of a surfactant mixture containing alkoxylated carboxylic acid esters and betaines and / or amine oxides for the production of such all-purpose cleaners.

Agents for cleaning hard, non-textile surfaces that occur in the household and commercial sector, with the exception of dishes, are commonly referred to as all-purpose cleaners (AZR). Low-foaming AZR are those that develop a small volume of foam when used manually, which decreases significantly further within a few minutes. Means of this kind have been known for a long time and are established on the market. These are essentially aqueous surfactant solutions of various types with or without the addition of builders, hydrotropes or solvents. To prove the effectiveness at the beginning of the cleaning work, the consumer wants a certain amount of foam in the application solution, but the foam should collapse quickly so that once cleaned surfaces do not have to be wiped down. For this purpose, agents of the type mentioned are usually formulated with low-foaming nonionic surfactants, for example mixed ethers or alcohol alkoxylates, in particular oxo alcohol ethoxylates.

Low-foaming all-purpose cleaners are known from German published patent application DE-A-43 26 112, which contain fatty acid alkyl ester alkoxylates in addition to the strongly foaming alkyl polyglycosides. All-purpose cleaners of this type have a high cleaning power and a distinctly low foaming power.

However, the agents of the prior art are often not sufficiently tolerated by the skin, so that despite a large number of products on the market, both the manufacturers of the products and the customers have a constant need for milder preparations. stands, which must nevertheless at least reach the level of known products with regard to foam and cleaning behavior. The object of the invention was therefore to take these needs into account.

The invention relates to all-purpose cleaners containing

(a) alkoxylated carboxylic acid esters of the formula (I),

R'CCOAU _n OR ² (I)

II o

in which R'CO is an aliphatic acyl radical, AlkO is CH ₂ CH ₂ O, CHCH ₃ CH ₂ O and / or CH CHCH ₃ O, n is a number from 1 to 20 and R ^{2 is} an aliphatic alkyl radical, and

(b) betaines and / or amine oxides.

Surprisingly, it has been found that the compositions according to the invention are also highly concentrated, flowable and slightly foaming, can be excellently diluted in water without passing through a gel phase and are largely irritating to the skin irrespective of the concentration and have excellent cleaning properties, in particular excellent fat-dissolving properties.

Alkoxylated carboxylic acid esters

Alkoxylated carboxylic acid esters, which are mandatory as component a) in the all-purpose cleaners according to the invention, are known from the prior art. For example, such alkoxylated carboxylic acid esters are accessible by esterification of alkoxylated carboxylic acids with alcohols. For the purposes of the present invention, however, the compounds are preferably prepared by reacting carboxylic acid esters with alkylene oxides using catalysts, in particular using calcined hydrotalcite in accordance with German Offenlegungsschrift DE-A-39 14 131, which provide compounds with a restricted homolog distribution. Preferably according to the Invention are alkoxylated carboxylic acid esters of the general formula (I) in which R ^! CO for an aliphatic acyl radical with 6 to 22 carbon atoms, AlkO for a CH ₂ CH ₂ O, CHCH ₃ CH ₂ O and / or CH ₂ -CHCH ₃ O radical, n on average for numbers from 3 to 20 and R for is an aliphatic alkyl radical having 1 to 22 carbon atoms.

Preferred acyl radicals are derived from carboxylic acids having 6 to 22 carbon atoms of natural or synthetic origin, in particular from straight-chain saturated and / or unsaturated fatty acids, including technical mixtures thereof, as are obtainable by fat cleavage from animal and / or vegetable fats and oils, for example Coconut oil, palm kernel oil, palm oil, soybean oil, sunflower oil, rape oil, cottonseed oil, fish oil, beef tallow and lard. Examples of such carboxylic acids are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, araenachic acid, elaachene acidic acid, elaeostolic acid and / or erucic acid. In particular, R * CO stands for a straight-chain, even-numbered acyl radical having 8 to 18 carbon atoms.

Preferred alkyl radicals R are derived from primary, aliphatic monofunctional alcohols having 1 to 22 carbon atoms, which can be saturated and / or unsaturated. Examples of suitable monoalcohols are methanol, ethanol, propanol, butanol, pentanol and the hydrogenation products of the above-mentioned carboxylic acids with 6 to 22 carbon atoms.

• y _t atoms. In particular, R represents a methyl radical.

AlkO is preferably a CH CH O radical.

Alkoxylated carboxylic acid esters of the formula (I) are particularly suitable in which R, 1 / CO for a straight-chain, even-numbered acyl radical having 8 to 18 carbon atoms, AlkO for a CH ₂ CH ₂ O radical, n on average for numbers from 5 to 15 and R ^{2 represents} a methyl radical. Examples of such compounds are methyl carboxylates alkoxylated on average with 5, 1, 9, 10 or 11 mol of ethylene oxide. If particularly low-viscosity all-purpose cleaners are desired, the use of alkoxylated carboxylic esters derived from short-chain carboxylic acids, especially those with 8 to 10 carbon atoms, is recommended. In contrast, high cleaning performance is obtained with alkoxylated carboxylic acid esters, which are derived from longer-chain carboxylic acids, in particular those with 12 to 18 carbon atoms.

Component b) is mandatory in the all-purpose cleaners according to the invention. According to one embodiment, betaines are contained as component b).

Betaine

Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds. The starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine. The addition of unsaturated carboxylic acids, such as acrylic acid, is also possible. Regarding the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants, reference is made to the contribution by U.Ploog in Seifen-Öle-Fette-Wwachs, 198, 373 (1982). Further overviews on this topic can be found for example by A. O'Lennick et al. in HAPPI, Nov. 70 (1986), S. Holzman et al. in tens. Det. 23: 309 (1986), R.Bilbo et al. in Soap Cosm. Chem. Spec. Apr. 46 (1990) and P.Ellis et al. in Euro Cosm. 1, 14 (1994).

In accordance with one embodiment, betaines are present which are carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (II)

R ⁴ R ³ -N- (CH ₂ ) mCOOX (II) in which R ³ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ⁴ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ⁵ for alkyl radicals with 1 to 4 carbon atoms, m for numbers from 1 to 6 and X for a Alkali and / or alkaline earth metal or ammonium ion. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecyl methylamine, dodecyl dimethylamine, Dodecylethylmethylamin, Cι _/ ι ₄ -Kokosalkyldimethyl- amine, cetyldimethylamine, stearyldimethylamine amine myristyldimethylamine, Stearylethylmethyl-, oleyldimethylamine, _C16 / ι tallow alkyl dimethyl amine, and their technical mixtures.

According to a further embodiment, carboxyalkylation products of amidoamines which follow the formula (III) are also suitable as betaines,

R ⁴ R ⁶ CO-NH- (CH ₂ ) ₀ -N- (CH ₂ ) _m COOX (III)

I.

R ⁵

in which R ⁶ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, o represents numbers from 1 to 3 and R ⁴ , R ⁵ , m and X have the meanings of the formula (II) given above . Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, galenic acid, arachene acid and erucic acid and their technical mixtures with NN-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-di-ethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.

Also suitable as starting materials for the betaines to be used in accordance with the invention are also imidazolines which follow the formula (IV)

in which R ^{7 is} an alkyl radical having 5 to 21 carbon atoms, R ^{8 is} a hydroxyl group, an OCOR ⁷ or ΝHCOR ⁷ radical and p is 2 or 3. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine. The corresponding Carboxyalkylie- addition products are mixtures of different open-chain betaines. Typical examples are condensation products of the above mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or C ₁ turn _/ ι ₄ coconut oil fatty acid, which are subsequently betainized with sodium chloroacetate.

Amine oxides

Finally, the agents according to the invention can contain, as component (b), amine oxides in a mixture or instead of the betaines. They are prepared from tertiary fatty amines, which usually have either one long and two short or two long and one short alkyl radical, and are oxidized in the presence of hydrogen peroxide. The amine oxides which are suitable for the purposes of the invention follow the formula (V)

_R ιo

R ⁹ -N-> O (V)

R ¹¹

in which R ^{9 represents} a linear or branched alkyl radical having 12 to 18 carbon atoms and R ¹⁰ and R ¹¹ independently of one another R ⁹ or an optionally hydroxyl-substituted alkyl radical having 1 to 4 carbon atoms. Amine oxides are of the formula (V) used, in which R ⁹ and R ¹⁰ is C _{12 /} ι ₄ - or C _{1 /} ι -Kokosalkylreste _8, and R ¹ 'represents a methyl or a hydroxyethyl radical. Amine oxides are also preferred of formula (V) in which R is a C ₁₂ / ι ₄ - or C _12/18 - is cocoalkyl and R ¹⁰ and R ^{1 'has} the meaning of a methyl or hydroxyethyl group have.

In the all-purpose cleaners according to the invention, components a) and b) can be present in a weight ratio of 10:90 to 90:10, preferably 30:70 to 70:30. In particular, the weight ratio of a): b) is in the range from 60:40 to 90:10. The ratio of betaines and amine oxides to one another in component b) is less critical and can therefore vary within wide ranges.

The all-purpose cleaners according to the invention may additionally contain anionic surfactants as component c). Typical examples of anionic surfactants which can be considered as component (c) are soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, alkyl ether sulfates, hydroxyl ether sulfate (ether) sulfate (ether) sulfate (mon) sulfate ethersulfates - mischethersulfate, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates , Protein fatty acid condensates (especially vegetable products based on wheat), fatty acid polyglycol ester sulfates and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Alkali soaps, alkyl sulfates, alkyl benzene sulfonates, alkyl ether sulfates, monoglyceride sulfates, fatty acid polyglycol ester sulfates and / or sulfosuccinates and in particular alkyl sulfates and / or alkyl ether sulfates are preferably contained as anionic surfactants.

Fatty alcohol sulfates and fatty alcohol ether sulfates (component c) are known anionic surfactants which are produced on an industrial scale by SO ₃ - or chlorosulfonic acid (CSA) sulfation of primary alcohols or their addition products with ethylene oxide and subsequent neutralization. For the purposes of the invention, fatty alcohol (ether) sulfates are suitable which follow the formula (VI) RO- (CH ₂ CH ₂ O) _a SO ₃ Y (VI)

in which R represents a linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms, a for 0 or numbers from 1 to 10 and Y for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of fatty alcohol sulfates are the sulfates of capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl alcohol alcohol, elaidyl alcohol, elaidyl alcohol Brassidyl alcohol and their technical mixtures, in the form of their sodium and / or magnesium salts. Typical examples of fatty alcohol ether sulfates are the sulfation products of the adducts of an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with the abovementioned alcohols. It is particularly preferred to use coconut fatty alcohol ether sulfate and fatty alcohol ether sulfates based on adducts of an average of 2 to 3 moles of ethylene oxide with technical C _{12 /} ι ₄ - or Cι _{2 /} ι ₈ - coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.

In addition to the alkoxylated carboxylic acid esters described under a), the all-purpose cleaners according to the invention can optionally contain further nonionic surfactants as component d). Typical examples of further nonionic surfactants that can be considered as component d) are mixed ethers, hydroxy mixed ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, alk (en) yl oligoglycosides, fatty acid-N-alkylglucose amides especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Preferred further nonionic surfactants are fatty alcohol polyglycol ethers, alkyl oligoglucosides, fatty acid N-alkyl glucamides, hydroxy mixed ethers and / or mixed ethers.

In a preferred embodiment of the invention, alkyl and alkenyl oligoglycosides which follow the formula (VII) are used as further nonionic surfactants (component d), R ¹² O- [G] _q (VII)

in which R ^{12 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and q represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry.

The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number q in the general formula (VII) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While q in a given compound must always be an integer, especially here can assume the values q = 1 to 6, the value q for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization q of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ¹² can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -Cιo (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation by distillation of technical C ₈ -C ₈ coconut fatty alcohol and with a proportion of less than 6% by weight of C ₁₂ alcohol may be contaminated and alkyl oligoglucosides based on technical C _/ π-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹² can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and the like technical mixtures which can be obtained as described above. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Another group of preferred further nonionic surfactants are fatty acid N-alkyl polyhydroxyalkylamides which follow the formula (VIII)

R ¹³ R ¹⁴ CO-N- [Z] (VIII)

in which R ¹⁴ CO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹³ for an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their production, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO 92/06984. An overview of this topic by H.Kelkenberg can be found in Tens.Surf.Deterg. 25, 8 (1988).

The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (IX):

R ¹⁵ OH OH OH

R ¹⁶ CO-N-CH _2- CH-CH-CH-CH-CH ₂ OH (IX)

I.

OH

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (IX) in which R ^{15 represents} an alkyl group and R ¹⁶ CO represents the acyl radical of the Capron acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Particularly preferred are fatty acid-N-alkyl glucamides of formula (IX), the _/ ι by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C ₁ ₄ coconut oil fatty acid or a corresponding derivative is obtained. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

Fatty alcohol polyglycol ethers are particularly preferred as further nonionic surfactants. The fatty alcohol polyglycol ethers are addition products of alkylene oxides with 2 to 4 carbon atoms (ethylene oxide, propylene oxide and / or butylene oxide) onto fatty alcohols with 6 to 22 carbon atoms. According to one embodiment, the fatty alcohol polyglycol ethers are adducts of addition of first ethylene oxide and, if appropriate, subsequently propylene oxide and / or butylene oxide with fatty alcohols. In this embodiment, particularly suitable fatty alcohol polyethylene glycol / polypropylene or polybutylene glycol ethers are those of the formula (X),

R ¹⁷ O (CH ₂ CH ₂ O) _r [MO] _s H (X)

in which R ^{17 represents} an alkyl and / or alkylene radical having 8 to 22 carbon atoms, MO represents a propylene oxide and / or a butylene oxide radical, r represents a number from 1 to 15 and s represents 0 or a number of 1 to 10 stands.

Fatty alcohol polyethylene glycol / polypropylene or polybutylene glycol ethers of the formula (X) can be prepared, for example, according to the European patent application EP-A2- 161 537 or the German patent applications DE-AI 39 28 602 and DE-AI-39 28 600.

Particularly suitable representatives are those of the formula (X) in which R is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 18 carbon atoms, r is a number from 3 to 10 and s is 0. These are addition products from 3 to 10 moles of ethylene oxide with fatty alcohols. Suitable fatty alcohols are alcohols based on fats and oils such as capron, capryl, lauryl, myristyl and stearyl alcohol and their technical mixtures, such as those obtained in the high pressure hydrogenation of technical methyl esters based on fats and oils. Also suitable are monofunctional, branched alcohols, so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are produced by the oxo process, and so-called Guerbet alcohols, which are branched in the 2-position with an alkyl group. Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol. Such oxo alcohols and Guerbet alcohols are also included in the context of the invention under the term fatty alcohols.

Further suitable compounds of the formula (X) are those in which R ^{17 is} an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 18 carbon atoms, r is a number from 2 to 7 and s is a number from 3 to 7 stands. These are addition products of monofunctional alcohols alkoxylated with 2 to 7 moles of ethylene oxide and then with 3 to 7 moles of propylene oxide and / or butylene oxide of the type already described.

According to a further preferred embodiment, fatty alcohol polyglycol ethers are included, which are addition products of initially propylene oxide and then optionally ethylene oxide. Accordingly, they are fatty alcohol polypropylene glycol / polyethylene glycol ethers, which preferably follow the formula (XI)

R ¹⁸ O [CH ₂ (CH ₃ ) CHO] _u (CH ₂ CH ₂ O) _w H (XI)

in which R ^{18 is} an alkyl and / or alkylene radical having 8 to 22 carbon atoms, u is a number from 1 to 10 and w is a number from 0 to 15.

Such compounds are described, for example, in German Offenlegungsschrift DE-Al-43 23 252. Particularly preferred representatives of the compounds of the formula (XI) are those in which R ^{18 is} an aliphatic, saturated, straight-chain or branched Alkyl radical with 8 to 18 carbon atoms, u stands for a number from 1 to 5 and w stands for a number from 1 to 6. These are preferably addition products of 1 to 5 mol of propylene oxide and of 1 to 6 mol of ethylene oxide with monofunctional alcohols, of the type already described.

Other particularly preferred nonionic surfactants are so-called mixed ethers. The mixed ethers are addition products of ethylene oxide and / or propylene oxide with fatty alcohols, which are end-capped by subsequent reaction with an alkyl chloride in the presence of bases. Particularly suitable mixed ethers are those which have been end-capped with an alkyl halide having 1 to 8 carbon atoms, in particular having 1 to 4 carbon atoms, of the fatty alcohol polyglycol ethers of the formula (X) and / or (XI). Typical examples are mixed ethers based on a technical respectively. on the 5th to 10th

Moles of ethylene oxide have been added and which have been end-capped with a methyl group or with a butyl group, for example Dehypo 'LS-54, LS-104, LT-54, LS-104, LS -531, Henkel KGaA, Duesseldorf / FRG.

Further particularly preferred nonionic surfactants are so-called hydroxy mixed ethers which have been prepared by reacting 1, 2 epoxyalkanes with mono-, di- and / or polyhydric alcohols which were alkoxylated. Preferred hydroxy mixed ethers follow the formula (XII),

R ¹⁹ O [CH ₂ CH (CH3) O] _J (CH2CHR ²⁰ O) _k [CH ₂ CH (OH) R ²¹ ], (XII)

in which R ^{19 represents} an alkyl and / or alkylene radical having 4 to 18 C atoms, R represents hydrogen or a methyl or ethyl radical, R ^{21 represents} an alkyl radical having 2 to 22 C atoms, j represents 0 or a number of 1 to 10, k is a number from 1 to 30 and 1 is the number 1, 2 or 3. Hydroxy mixed ethers of the formula (XII) are known from the literature and are described, for example, in the international application WO 96/12001. They are produced by reacting 1, 2-epoxyalkanes (R CHOCH) with mono-, di- and / or trihydric alcohols which have been alkoxylated. Preferred hydroxy mixed ethers for the purposes of the invention are those derived from alkoxylates of monohydric alcohols (1 = 1) of the formula R ¹⁹ -OH. Suitable examples of alcohols have already been described in connection with the fatty alcohol polyglycol ethers.

The alcohols are used in the form of their alkoxylates, which are prepared in a known manner by reacting the alcohols with ethylene oxide, propylene oxide and / or butylene oxide. Alkoxylates of alcohols are preferably used which contain 10 to 25 moles of ethylene oxide (R ²⁰ = hydrogen, j = 0, k = 10 to 25) or 1 to 3 moles of propylene oxide and then 10 to 25 moles of ethylene oxide (R ²⁰ = hydrogen , j = 1 to 3, k = 10 to 25) have been alkoxylated.

Very particularly suitable hydroxy mixed ethers of the formula (XII) are those in which R ¹⁹ for a saturated straight-chain alkyl radical having 8 to 14 C atoms, R ²⁰ for hydrogen, R ²¹ for a saturated straight-chain alkyl radical having 8 to 12 C atoms, j stands for 0 or for numbers from 1 to 3 and k for numbers from 10 to 25 and 1 for the number 1. Such hydroxy mixed ethers are described in detail in DE-Al-3723 323.

If desired, the all-purpose cleaners according to the invention can contain further amphoteric or zwitterionic surfactants as further component e), for example aminopropionates, aminoglycinates and sulfobetaines. From this group, particular preference is given to the aminoglycinates which have been described in detail, for example, in EP-B-0689 582.

The all-purpose cleaners according to the invention advantageously contain in amounts of

1 to 80% by weight, preferably 5 to 25% by weight, alkoxylated carboxylic acid esters (component a);

1 to 20% by weight, preferably 3 to 10% by weight, betaines and / or amine oxides (component b); 0 to 70 wt.%, Preferably 0 to 50 wt.%, Anionic surfactants (component c);

0 to 80 wt.%, Preferably 10 to 75 wt.%, Further nonionic surfactants (component

Φ;

0 to 20% by weight, preferably 0 to 10% by weight, further amphoteric or zitterionic surfactants (component e)

- Based on the surfactant mixture in the all-purpose cleaner, the weight data being calculated as the active substance and with the proviso that the weight data add up to 100% by weight.

The all-purpose cleaners according to the invention contain components a) and b), preferably in combination with d) and, if appropriate, in a mixture with c) and / or e) in amounts of 3 to 20, preferably 5 to 15% by weight, calculated as active substance and related to all-purpose cleaner. The 100% by weight of the rest are auxiliaries and water.

The agents according to the invention can contain, for example, solubilizers, such as ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol or preferably butyl diglycol, foam regulators, such as soap, soluble builders, such as, for example, citric acid or sodium citrate, EDTA or NTA, and abrasives, as auxiliaries. In many cases an additional bactericidal action is desired, which is why the agents can contain cationic surfactants or biocides, for example glucoprotamine. The agents according to the invention can be both alkaline (pH greater than 7.5) and acidic (pH less than 6.5).

Another object of the present invention relates to the use of mixtures of alkoxylated carboxylic acid esters and betaines and / or amine oxides as a skin-friendly surfactant mixture for the production of all-purpose cleaners. Examples

The test method described below according to "Seifen-Öle-Fette-Wwachs", 112, 371, (1986) was used to test the cleaning ability and provides very reproducible results. The cleaning agent to be tested was then placed in the form of a 1% by weight aqueous solution (10 g / 1) on an artificially soiled plastic surface. A mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling for the dilute use of the cleaning agent. 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 water, squeezed out and moved mechanically on the dirt-coated test surface to which 10 ml of the 1% detergent solution to be tested had been applied. After 10 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed.

5 test persons visually assessed the whiteness of the cleaned plastic surface, the cleaning ability being better the lighter the plastic surface looked. The results are summarized in Table 1; Examples 1-4 according to the invention and VI are a standardized comparative example. The rating "better than standard" was given if at least 4 out of 5 test persons visually rated the plastic surface as lighter.

Table 1: Cleaning performance of all-purpose cleaners on plastic surfaces (figures in% by weight of active substance)

Claims

Patent claims

1. Containing all-purpose cleaner

a) alkoxylated carboxylic acid esters of the formula (I),

R ¹ C (OAlk) _ll OR ² (I)

II o

b) betaines and / or amine oxides.

2. All-purpose cleaner according to claim 1, characterized in that alkoxylated carboxylic acid esters of the formula (I) are contained in which R ^ O for an aliphatic acyl radical having 8 to 18 carbon atoms, AlkO for a CH ₂ CH ₂ O radical, n on average for Numbers from 5 to 15 and R stands for a methyl radical.

3. All-purpose cleaner according to one of claims 1 or 2, characterized in that betaines of formula (II),

R ⁴ R ³ -N- (CH ₂ ) mCOOX (II)

R ⁵

in which R represents alkyl and / or alkenyl radicals having 6 to 22 carbon atoms, R represents hydrogen or alkyl radicals having 1 to 4 carbon atoms, R ^{5 represents} alkyl radicals having 1 to 4 carbon atoms, m represents numbers from 1 to 6 and X represents an alkali and / or alkaline earth metal or ammonium ion is included.

4. All-purpose cleaner according to one of claims 1 or 2, characterized in that betaines of formula (III),

R ⁴ R ⁶ CO-NH- (CH ₂ ) ₀ -N- (CH ₂ ) _m COOX (III)

R ⁵

in which R ⁶ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, o represents numbers from 1 to 3 and R ⁴ , R ⁵ , m and X have the meanings of the formula (II) given above , are included.

5. All-purpose cleaner according to one of claims 1 to 4, characterized in that amine oxides of the formula (V),

_R ιo

R ⁹ -N-> O (V)

A ^» in which R ^{9 is} a linear or branched alkyl radical having 12 to 18 carbon atoms and R ¹⁰ and R ¹¹ independently of one another are R ⁹ or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms.

6. All-purpose cleaner according to one of claims 1 to 5, characterized in that it contains the components a) and b) in a weight ratio of 30:70 to 70:30.

7. All-purpose cleaner according to one of claims 1 to 6, characterized in that they contain anionic surfactants as component c), preferably alkyl sulfates and / or alkyl ether sulfates.

8. All-purpose cleaner according to one of claims 1 to 7, characterized in that it additionally as component d) other nonionic surfactants, in particular selected from the group of fatty alcohol polyglycol ethers, alkyl oligoglucosides, fatty acid N-alkyl glucamides, hydroxy mixed ethers and / or mixed ethers.

9. All-purpose cleaner according to one of claims 1 to 8, characterized in that it contains further amphoteric or zwitterionic surfactants, in particular aminoglycinates, as component e).

10. All-purpose cleaner according to one of claims 1 to 9, characterized in that it

1 to 20% by weight, preferably 3 to 10% by weight, betaines and / or amine oxides (component b);

0 to 70 wt.%, Preferably 0 to 50 wt.%, Anionic surfactants (component c); 0 to 80% by weight, preferably 10 to 75% by weight, of further nonionic surfactants (component d);

0 to 20 wt.%, Preferably 0 to 10 wt.%, Contain further amphoteric or zitterionic surfactants (component e) - based on the surfactant mixture.

11. Use of mixtures of alkoxylated carboxylic acid esters and betaines and / or amine oxides as a skin-friendly surfactant mixture for the production of all-purpose cleaners.