DE19527596A1 - Aqueous mixture of surfactants - Google Patents

Abstract

Claimed are aqueous surfactant mixtures with improved cleaning performance and containing (A) 0.01 to 6 % by wt., relative to the complete agent, of C11-C14 alcohol, (B) 1.0 to 30 % by wt., relative to the complete agent, of C8-C18 alcohol alcoxylate, (C) 1.0 to 50 % by wt., relative to the complete agent, of C8-C20 alcohol sulphate and (D) 14 to 97.99 % by wt. of water. Such agents have high performance and are kind to the skin.

Description

The present invention relates to a surfactant mixture, the nonionic surfactant, anioni contains surfactant and medium chain alcohols, and the use of these Surfactant mixture as an aqueous hand dishwashing liquid.

Liquid cleaning agents usually consist of aqueous solutions of synthetic anionic and / or nonionic surfactants and conventional additives. you will be especially for cleaning hard surfaces, e.g. B. of glass, ceramic materials, Plastics, painted and polished surfaces are used. An important Field of application for liquid detergents is the manual rinsing of food and Cookware. The dishes are usually cleaned at slightly elevated temperatures from about 25 to 45 ° C in very dilute liquors. It is from Consumers generally rate the cleaning power of an agent the better the stronger and the longer the cleaning liquor foams. Because of the contact of the hands with the cleaning liquor over a longer period of time when washing manually Dishes and the ease of use of the product are of particular importance. From these The expert provides reasons for the selection of the components and the addition composition of an agent for the manual cleaning of dishes others Considerations than with liquid cleaning agents for other hard surfaces.

Hand dishwashing detergents usually contain high levels of anioni as an active ingredient tensides. The anionic surfactants are both the top performers for rinsing process, as well as the components that make the greatest contribution to foam formation However, the anionic surfactants have a disadvantageous effect on human skin from, which is also degreased during the rinsing process and thereby attacked. To do that To reduce the problem of skin irritation, the anionic surfactants in Ge  Dishwashing detergents partly replaced by non-ionic surfactants. With the use of not However, ionic surfactants are often associated with poor cleaning performance.

German patent application 21 63 195 describes liquid surfactant concentrates for the Textile and dishwashing based on anionic surface-active substances discloses those to improve the solubility and shelf life of the conc occurred and to strengthen the cleaning effect C₈-C₁ Verstärkung fatty alcohols are added. Because of the high content of anionic surfactants, the ease with which they are used However, medium unsatisfactory.

By J. Krüßmann et al. (J. Chem. Tech. Biotechnol., 50, pp. 399-409 (1991)) was the Influence of medium chain alcohols and their ethoxylates with low ethoxylie degrees of cleaning effect of detergents containing ethoxylates and certain dishwashing detergents for machine cleaning and anionic Surfactants examined and found that an addition of decanol a performance-enhancing effect. Decanol is with the because of its vapor pressure Operating temperatures of hand dishwashing detergents for use in these detergents are not suitable.

The object of the present invention is the cleaning performance of Surfactant mixtures, in particular hand dishwashing detergents, which are anionic and contain nonionic surfactants.

The present invention relates to aqueous surfactant mixtures containing

• (A) 0.01 to 6 wt .-%, based on the finished agent, C₁₁-C₁₄ alcohol,
• (B) 1.0 to 30 wt .-%, based on the finished agent, C₈-C₁₈ alcohol alkoxylate
• (C) 1.0 to 50 wt .-%, based on the finished agent, C₈-C₂₀ alcohol sulfate and
• (D) 14 to 97.99 wt% water.

Surprisingly, it was found that the cleaning performance of the inventor surfactant mixtures according to the invention, the anionic and nonionic surfactants, in particular C₈-C₁₈ alcohol alkoxylates and C₈-C₂₀ alcohol sulfates contain, by Addition of medium chain alcohols can be increased. This Surfactant mixtures are particularly suitable as hand dishwashing detergents.  

Another object of the present invention is accordingly the use of Surfactant mixtures in aqueous hand dishwashing detergents.

Undecanol and dodecanol are preferred as component (A). Be a cut with 12 to 14 obtained from fatty alcohols by distillation is particularly preferred C atoms used. When choosing alcohols, factors such as boiling point and Processability are taken into account. The alcohols are preferably used in quantities from 0.1 to 6% by weight, based on the finished composition.

The C₈-C₁₈ alcohol alkoxylates of component (B) are compounds of the formula I. or II:

R¹O- (CH₂CH₂O) _m -H (I),

wherein R¹ is a saturated or unsaturated, straight-chain or branched C₈-C₁₈ alkyl group and m stands for numbers from 1 to 10,

wherein R² and p can have the same meaning as R¹ and m in formula I and n for Numbers from 0.5 to 2 stands.

The compounds can by ethoxylation or ethoxylation and propoxylation can be obtained from linear or branched C₈-C₁₈ alcohols. As alkoxylates in particular the ethoxylates and the mixed ethoxylates / propoxylates used. Suitable C₈-C₁₈ alcohols are, for example, those from natural occurring fats, especially from vegetable-based fats, are available. Fatty alcohols such as B. octanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, Stearyl alcohol, behenyl alcohol, oleyl alcohol, elaidyl alcohol, ricinoyl alcohol, linoleyl alcohol hol, linolenyl alcohol and those available from the naturally occurring fats Mixtures such as coconut fatty alcohol, palm and palm kernel fatty alcohol or peanut fat alcohol. It can also C₈-C₁₈ alcohols, for example in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis, or the so-called Ziegler  Alcohols are used. C₁₀-C₁₄ fatty alcohol ethoxylates are particularly preferred used. The weight fraction of the alkoxylate unit is preferably between 30 and 90%, especially between 35 and 75%.

The C₈-C₂₂ alkyl sulfates of component (C) are also known anionic surfactants with the formula (V),

R⁶O-SO₃X (V),

in the R⁶ for a saturated or unsaturated C₈-C₂₂ alkyl group and X for an alkali or alkaline earth metal or a quaternary ammonium ion.

The C₈-C₂₂ alkyl sulfates can be obtained by sulfating primary or branched C₈-₂₂ alcohols. The primary C₈-C₂₂ alkyl sulfates are preferably derived from the so-called fatty alcohols, such as. B. caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures. Sulfates of technical _grade C _12/14 or C _12/18 coconut _fatty alcohol _{cuts are} preferably used in the form of their sodium or magnesium salts. As branched C₈-C₂₂ alkyl sulfates, the 2,3-alkyl sulfates should be mentioned in particular.

Other nonionic surfactants that can be used include, for example, alkylphenol polyglycol ethers, C₆-C₂₂-alkyl polyglycosides, C₆-C₂₂-carboxylic acid polyglycol esters, C₆-₂₂-carboxamide poly glycol ether, C₆-C₂₂ amine polyglycol ether, mixed ether, alkoxylated triglycerides, C₆-C₂₂-Car bonic acid-N-alkylpolyhydroxyalkylamides, polyol-C₆-C₂₂-carboxylic acid esters, sugar esters, Sorbitan esters, polysorbates and any mixtures of the above are used will.

As further nonionic surfactants are preferably C₆-C₂₂-alkyl polyglycosides, fatty acid N-alkylpolyhydroxyalkylamides and fatty acid alkanolamides are used.

C₆-C₂₂-alkyl glycosides are known substances that are made using the relevant processes of preparative organic chemistry can be obtained. Representing that  extensive literature is here on the documents EP-A1-0 301 298 and WO 90/3977 referred. The C₆-C₂₂ alkyl glycosides follow the formula III,

R³O [G] _x (III),

in the R³ for a linear or branched, saturated or unsaturated alkyl radical 6 to 22 carbon atoms, [G] for a glycosidic sugar and x for a number of 1 to 10.

The index number x in the general formula III indicates the degree of oligomerization (DP degree) on, d. H. the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x must always be an integer in a given connection and here especially can assume the values x = 1 to 6, is the value x for a particular one Alkylglycoside is an analytically calculated quantity, usually one represents fractional number. Alkyl glycosides with a medium Degree of oligomerization x used from 1.1 to 3.0. From an application perspective those alkyl glycosides are preferred whose degree of oligomerization is less than 1.8 and is in particular between 1.2 and 1.7. As glycosidic sugar units preferably glucose and xylose used.

The alkyl or alkenyl radical R³ is preferably derived from primary alcohols with 8 to 18, in particular 8 to 14 carbon atoms. Typical examples are caprylic alcohol, Caprinal alcohol and undecyl alcohol and their technical mixtures, such as those as in the course of the hydrogenation of technical fatty acid methyl esters or in the course the hydrogenation of aldehydes from Roelen's oxosynthesis.

The alkyl or alkenyl radical R³ is preferably derived from lauryl alcohol, myristyl alcohol, Cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol and Behe are also available to name nyl alcohol, erucyl alcohol and their technical mixtures.

The fatty acid N-alkylpolyhydroxyalkylamides are known substances that usually by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fat  acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained. With regard to the processes for their production, reference is made to the US patents US 1,985,424, US 2,016,962 and US 2,703,798 and the international patent application Referred to WO 92/06984. An overview of this topic by H. Kelkenberg can be found in tens. Surf. Det. 25, 8 (1988).

The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing agents Sugars with 5 or 6 carbon atoms, especially from glucose. The preferred Fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (IV):

Preferably used as fatty acid N-alkylpolyhydroxyalkylamides are glucamides of the formula (IV) in which R⁵ is hydrogen or an amino group and R⁴CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myrstic 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. Fatty acid N-alkylglucamides of the formula (IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C _12/14 coconut fatty acid or a corresponding derivative are particularly preferred. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

Fatty acid alkanolamides can be used as further nonionic surfactants, e.g. B. C _12/18 fatty acid _{monoethanolamide} or addition products from 4 to 20, preferably from 4 to 10 moles of alkylene oxide, preferably ethylene oxide to C₁₀-C₂₀-, preferably C₁₂-C₁₈ alkanols, but also the addition products of ethylene oxide to propylene glycols, which under the Pluronics® names are known, and addition products of 1 to 7 mol of ethylene oxide with 1 to 5 mol of propylene oxide reacted with C₁₂-C₁₈ alkanols. Fatty alkyl amine oxides are also suitable.

The anionic surfactants can in the agent according to the invention in an amount of 1 to 50 wt .-%, preferably 10 to 35 wt .-%, based on the finished agent, may be included.

Suitable further anionic surfactants are e.g. B. C₈-C₂₂-alkylbenzenesulfonates, alkanesul fonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfo nates, sulfo fatty acids, fatty alcohol ether sulfates, glycerin ether sulfates, hydroxy mixed ethers sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfo succinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, Ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, Fatty acid aurides, acyl glutamates, acyl lactylates, acyl tartrates, alkyl oligoglucoside sulfates and Alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, you can have a conventional, but also a narrow homolog distribution sen. Preferred further anionic surfactants are the C₈-C₂₂ alkyl ether sulfates.

The C₈-C₂₂ alkyl ether sulfates that can be used in the sense of this invention follow Formula VI,

R⁷O- (CH₂CH₂O) _n -SO₃Y (VI)

in the R⁷ for a saturated or unsaturated C₈-C₂₂ alkyl group, n for numbers of 0.5 to 5 and Y represent an alkali or alkaline earth metal or a quaternary ammonium ion.

These substances are also known chemical compounds that by sulfation of primary or branched C₈-C₂₂ alcohols, preferably of Fatty alcohol polyglycol ethers can be obtained. Also C₈-C₂₂ alkyl ether sulfates narrow homolog distribution (NRE = narrow range ethoxylates) as they for example in international patent application WO 91/05764 and in D.L.'s Overview Smith in J. Am. Oil. Chem. Soc. 68, 629 (1991), can be used.

Typical examples are the sulfation products of adducts of 0.5 to 10 mol of ethyl lenoxide (conventional or narrow homolog distribution) to 1 mol caprylal each alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, Ste aryl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleylal  alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures. Prefers are sulfates of adducts of 1 to 7 moles of ethylene oxide with saturated coconut oil alcohols in Form of their sodium, potassium and / or magnesium salts and ammonium salts, such as Monoi sopropanolammonium salts. For example, fatty alcohol ether sulfates can be used be, which are derived from corresponding fatty alcohol polyglycol ethers, which in turn prepared in the presence of calcined or, in particular, hydrophobicized hydrotalcite and therefore have a particularly advantageous narrow homolog distribution point.

Soaps, d. H. Alkali or ammonium salts of saturated or unsaturated C₆-C₂₂ fatty acid ren, are because of their foam-suppressing properties in the invention preferably not included.

The feature "not included" should not mean that very small Amounts of soap may not be included; Amounts of up to 2% by weight on the entire average, are still tolerable in the sense of the invention.

As further surfactants, amphoteric and zwitterionic surfactants are used. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, Aminoglycinates, imidazolinium betaines and sulfobetaines. The amphoteric and zwitterionic surfactants can be present in an amount of up to 10% by weight, preferably 0.1 to 5 % By weight, based on the finished composition, may be present.

Betaine compounds of the formula VI are preferably used as amphoteric surfactants

are used in the R⁶, optionally by heteroatoms or heteroatoms groups interrupted alkyl radical with 8 to 25, preferably 10 to 21 Carbon atoms and R⁷ and R⁸ identical or different alkyl radicals with 1 to 3  Mean carbon atoms. C₁₉-C₁₈-Alkyldimethylcarboxymethylbetain are preferred and C₁₁-C₁₇ alkylamidopropyldimethylcarboxymethyl betaine.

The total surfactant content in these compositions is preferably above 15% by weight on the entire average, with an upper limit of 75% by weight, in particular 50 % By weight.

The agents according to the invention can also contain solvents, par form, dyes and opacifiers, as well as skin protection components such as them e.g. B. are known from EP-A1 522 756. To adjust the viscosity of the agent substances such as gelatin or casein can be used without the To impair the performance of the agent according to the invention. Are products with an improved cold behavior desired, the agent according to the invention Hydrotropes can also be added.

The solvents to be added if necessary are low molecular weight Alkanols with 1 to 4 carbon atoms in the molecule, preferably around ethanol and isopro panol. As further solubilizers, for example for dyes and perfume oils, can optionally, for example alkanolamines, polyols such as ethylene glycol, propylene glycol, Glycerol and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical are used.

Preferred thickeners include urea, sodium chloride and Ammonium chloride, polysaccharides and the like, which are also used in combination can be. Examples of preservatives are sodium benzoate, To name formaldehyde and sodium sulfite. The agents according to the invention can also Contain common disinfectants.

The pH of the agents according to the invention is preferably between 5.0 and 7.5.

Examples

In the following examples, all data in% by weight relate to the total ge importance of the recipe.

example 1

15% by weight of C _12/14 fatty alcohol ether (3EO) sulfate Na salt
8% by weight of C _12/14 fatty alcohol sulfate Na salt
10% by weight decanol + 8 EO
2% by weight dodecanol
3% by weight coconut monoethanolamide
9% by weight ethanol
Balance to 100% water by weight.

Example 2

20% by weight of C _12/14 fatty alcohol ether (3EO) sulfate Na salt
8% by weight of C _12/14 fatty alcohol sulfate Na salt
10% by weight octanol + 1 PO + 8 EO
2% by weight dodecanol
2% by weight lauryldimethylamine oxide
7 wt% ethanol
Balance to 100% water by weight.

Example 3

12 wt .-% C _12/14 fatty alcohol sulfate NH₄ salt
18% by weight undecanol + 9 EO
2% by weight dodecanol
3% by weight of C _12/14 alkyl polyglucoside with a DP of 1.4
4 wt% ethanol
Balance to 100% water by weight.

Example 4

13 wt .-% C _12/14 fatty alcohol sulfate NH₄ salt
18% by weight undecanol + 9 EO
2% by weight dodecanol
3% by weight coco amidopropyl betaine
3% by weight ethanol
3% by weight PEG 400
Balance to 100% water by weight.

Example 5

13 wt .-% C _12/14 fatty alcohol sulfate NH₄ salt
10% by weight undecanol + 9 EO
2% by weight dodecanol
8% by weight of C₁₂-N-methylglucamide
3% by weight ethanol
3% by weight PEG 400
Balance to 100% water by weight.

Example 6

13 wt .-% C _12/14 fatty alcohol sulfate NH₄ salt
18% by weight undecanol + 9 EO
2% by weight dodecanol
3% by weight coco amidopropyl betaine
3% by weight PEG 400
Balance to 100% water by weight.

Example 7

29% by weight C _12/14 fatty alcohol ether (1,2EO) sulfate Mg salt (NRE)
10% by weight of C _12/14 fatty alcohol sulfate Mg salt
18% by weight C _10/14 fatty alcohol + 1.2 PO + 8 EO
4% by weight dodecanol
3% by weight of C _12/14 alkyl polyglucoside with a DP of 1.5
12 wt .-% C₄-alkyl polyglucoside with a DP of 1.5
8% by weight PEG 200
10 wt% ethanol
Balance to 100% water by weight.

Determination of the cleaning power of C₁₁-C₁₄ alcohol-containing Surfactant mixtures

Different amounts of the surfactant mixture shown in Table 1 were used Dodecanol added. The rinsing capacity was then mechanized Plate test (c = 0.5 g / l) on a grease stain and on a mixed stain tested (rinsing power without the addition of dodecanol 100%). The results are in Table 2 reproduced.

Table 1

Table 2

The test results clearly show that the addition of decanol to a surfactant schung containing C₈-C₁₈ alcohol alkoxylate and C₈-C₂₀ alcohol sulfate to an improvement rinsing capacity.

Claims (8)

1. Aqueous surfactant mixture containing

• (A) 0.01 to 6 wt .-%, based on the finished agent, C₁₁-C₁₄ alcohol,
• (B) 1.0 to 30 wt .-%, based on the finished agent, C₈-C₁₈ alcohol alkoxylate
• (C) 1.0 to 50 wt .-%, based on the finished agent, C₈-C₂₀ alcohol sulfate and
• (D) 14 to 97.99 wt% water.

2. Aqueous surfactant mixture according to claim 1, characterized in that as Alcohol undecanol, dodecanol or mixtures of the foregoing are used will. 3. Aqueous surfactant mixture according to claim 1 or 2, characterized in that that as further nonionic surfactants C₆-C₂₂-alkyl polyglycosides, C₆-C₂₂-fatty acid N-alkylpolyhydroxyalkylamides, fatty acid alkanolamides or any mixtures of the foregoing. 4. Aqueous surfactant mixture according to one of claims 1 to 3, characterized records that as a further anionic surfactant C₆-C₂₂-alkyl ether sulfate with a Degree of ethoxylation from 0.5 to 5 can be used. 5. Aqueous surfactant mixture according to one of claims 1 to 4, characterized records that it is free of alkali or ammonium salts saturated or unsaturated is C₆-C₂₂ fatty acids. 6. Aqueous surfactant mixture according to one of claims 1 to 5, characterized records that it contains amphoteric and zwitterionic surfactants in an amount of 0.1 up to 10 wt .-%, based on the finished agent contains. 7. Aqueous surfactant mixture according to one of claims 1 to 6, characterized records that the total surfactant content over 15 wt .-%, based on the finished Medium, lies.   8. Use of the surfactant mixtures according to one of claims 1 to 7 as a hand Dishwashing liquid.