EP0863972A1

EP0863972A1 - Aqueous surfactant mixture

Info

Publication number: EP0863972A1
Application number: EP96927564A
Authority: EP
Inventors: Axel Böhmer; Udo Hees
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1995-07-28
Filing date: 1996-07-20
Publication date: 1998-09-16
Also published as: WO1997005223A1; DE19527596A1

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

"Aqueous surfactant mixture"

The present invention relates to a surfactant mixture which contains nonionic surfactant, anionic surfactant and alcohols of medium chain length, and to the use of this surfactant mixture as an aqueous hand dishwashing detergent.

Liquid cleaning agents usually consist of aqueous solutions of synthetic anionic and / or nonionic surfactants and conventional additives. They are especially used for cleaning hard surfaces, e.g. of glass, ceramic materials, plastics, painted and polished surfaces. An important area of application for liquid detergents is the manual washing of dishes and cookware. The dishes are usually cleaned at slightly elevated temperatures of around 25 to 45 ° C in very dilute liquors. In general, the cleaning power of an agent is assessed by the consumer as 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, the skin-friendliness of the agent is of particular importance when washing dishes. For these reasons, the expert makes different considerations when selecting the components and the composition of an agent for the manual cleaning of dishes than with liquid detergents for other hard surfaces.

Hand dishwashing detergents usually contain a high proportion of anionic surfactants as an active ingredient. The anionic surfactants are both the performers for the rinsing process and the components which make the greatest contribution to the formation of foam. However, the anionic surfactants have a disadvantageous effect on human skin, which also degreases during the rinsing process and is attacked as a result becomes. In order to reduce the problem of skin irritation, the anionic surfactants in dishwashing detergents are partially replaced by nonionic surfactants. However, the use of non-ionic surfactants is often associated with poorer cleaning performance.

German patent application 21 63 195 discloses liquid surfactant concentrates for cleaning textiles and dishes based on anionic surface-active substances which are used to improve the solubility and storage stability of the concentra occur and C ₈ -C ₁₄ fatty alcohols are added to enhance the cleaning effect. However, the skin-friendliness of these agents is unsatisfactory because of the high content of anionic surfactants.

By J. Krüßmann et al. (J. Chem. Tech. Biotechnol., 50, pp. 399-409 (1991)), the influence of alcohols of medium chain length and their ethoxylates with low degrees of ethoxylation on the cleaning action of detergents containing ethoxylates and certain dishwashing detergents for machine washing Cleaning and investigating anionic surfactants and found that the addition of decanol brings about a performance-increasing effect. Because of its vapor pressure at the operating temperatures of hand dishwashing detergents, decanol is not suitable for use in these detergents.

The present invention is based on the object of improving the cleaning performance of surfactant mixtures, in particular hand dishwashing detergents which contain anionic and nonionic surfactants.

The present invention relates to aqueous surfactant mixtures containing

(A) 0.01 to 6 wt .-%, based on the finished agent, Cn-Cι ₄ alcohol,

(B) 1, 0 to 30 wt .-%, based on the finished agent, C ₈ -C ₈ alcohol alkoxylate

(C) 1.0 to 50 wt .-%, based on the finished agent, C ₈ -C ₂ o-alcohol sulfate and

(D) 14 to 97.99 wt% water.

Surprisingly, it was found that the cleaning performance of erfindungsgemä¬ SEN surfactant, the anionic and nonionic surfactants, in particular C ₈ -Cι ₈ - alcohol alkoxylates and C ₈ -C ₂ o-alcohol sulfates which contain, by addition of alcohols mittle¬ rer chain length increase can . These surfactant mixtures are particularly suitable as hand dishwashing detergents.

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

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

The C ₈ -C ₈ alcohol alkoxylates of component (B) are compounds of the formulas I or II:

R ¹ O- (CH ₂ CH ₂ O) _m -H (I),

in which R ^{1 represents} a saturated or unsaturated, straight-chain or branched C ₈ -C ₈ -alkyl group and m represents numbers from 1 to 10,

CH ₃

IR ² O- (CHCH ₂ O) _n - (CH ₂ CH ₂ 0) _p -H (II),

wherein R ² and p can have the same meaning as R ¹ and m in formula I and n stands for numbers from 0.5 to 2.

The compounds can be obtained by ethoxylation or ethoxylation and propoxylation of linear or branched C ₈ -C 16 alcohols. In particular, the ethoxylates and the mixed ethoxylates / propoxylates are used as alkoxylates. Suitable C ₈ -C ₈ alcohols are, for example, the so-called fatty alcohols obtainable from naturally occurring fats, in particular from vegetable-based fats, such as octanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, elaidyl alcohol, Ricinoyl alcohol, linoleyl alcohol, linolenyl alcohol and their mixtures available from the naturally occurring fats, such as coconut oil alcohol, palm and palm kernel oil alcohol or peanut oil alcohol. It is also possible to use C ₈ -C ₈ alcohols which are obtained, for example, in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis, or the so-called Ziegler alcohols. C ₁ -C ₁₄ -fatty alcohol ethoxylates are particularly preferably used. The proportion by weight of the alkoxylate unit is preferably between 30 and 90%, in particular between 35 and 75%.

The C ₈ -C ₂₂ alkyl sulfates of component (C) are also known anionic surfactants with the formula (V),

in which R ^{6 represents} a saturated or unsaturated Cβ-Ca alkyl group and X represents an alkali or alkaline earth metal or a quaternary ammonium ion.

The C ₈ -C ₂₂ alkyl sulfates can be obtained by sulfating primary or branched Cβ-C _∑∑ alcohols. The primary C ₈ -C-> 2-alkyl sulfates are preferably derived from the so-called fatty alcohols, such as, for example, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, arachyl alcohol, arachyl alcohol and erucyl alcohol and their technical mixtures. Sulphates of technical C 1 - / _{4 4} - or Ci-yiβ coconut fatty alcohol cuts are preferably used in the form of their sodium or magnesium salts. The 2,3-alkyl sulfates in particular should be mentioned as branched Cβ-C∑∑ alkyl sulfates.

Other nonionic surfactants that can be used include, for example, alkylphenol polyglycol ethers, Cβ-C ₂₂ alkyl polyglycosides, Ce-C _{∑∑ carboxylic} acid _polyglycol esters, C-rC-sr carboxylic acid amide polyglycol ethers, C6-C ₂₂ amine polyglycol ethers, mixed ethers, alkoxylated triglycerides, C ₆ -C ₂₂ - Bonic acid-N-alkyl polyhydroxyalkylamides, polyol-C _for rC- ₂₂ carboxylic acid esters, sugar esters, sorbitan esters, polysorbates and any mixtures of the above are used.

As a further non-ionic surfactants preferably _C6-C22 alkyl polyglycosides, fatty acid N-alkyl polyhydroxyalkyl amides and fatty acid used.

C-rC ₂₂ alkyl glycosides are known substances which can be obtained by the relevant methods of preparative organic chemistry. As a representative of the extensive literature, reference is made to the documents EP-A 1-0 301 298 and WO 90/3977. The Cβ-Ca alkyl glycosides follow the formula III,

R ³ O [G] _x (III), in which R ^{3 is} a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms, [G] is a glycosidic sugar and x is a number from 1 to 10.

The index number x in the general formula III indicates the degree of oligomerization (DP degree), i.e. 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 compound and here can take on the values x = 1 to 6, the value x is for a certain alkyl glycoside an analytically calculated quantity, which usually represents a fractional number. Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl glycosides are preferred whose degree of oligomerization is less than 1.8 and in particular between 1.2 and 1.7. Glucose and xylose are preferably used as glycosidic sugar units.

The alkyl or alkenyl radical R ³ is preferably derived from primary alcohols having 8 to 18, in particular 8 to 14, carbon atoms. Typical examples are caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.

The alkyl or alkenyl radical R ³ 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, gadoieyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures are also to be mentioned.

The fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, 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. Det. 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 (IV):

R ⁵ OH OH OH

I I I I

R ⁴ CO-N-CH ₂ -CH-CH-CH-CH-CH ₂ OH (IV)

I OH

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (IV) in which R ^{s is} hydrogen or an amino group and R ⁴ CO is the acyl radical of 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, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Particularly preferred are fatty acid N-alkyl glucamides of formula (IV), the amine by reductive amination of glucose with Methyl¬ and subsequent acylation with lauric acid or C _{_2/4} ι coconut oil fatty acid or a corresponding derivative is obtained. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

Fatty acid alkanolamides can be used as further nonionic surfactants, e.g.

Ci ₂ / ιs fatty acid monoethanolamide or addition products of 4 to 20, preferably 4 to 10, mol of alkylene oxide, preferably ethylene oxide, at Cio-C _∑ o-, preferably C ₁₂ -

Cis alkanols, but also the addition products of ethylene oxide with propylene glycols

® are known under the name Pluronics, and addition products of 1 to 7 moles

Ethylene oxide with 1 to 5 moles of propylene oxide converted C ₂ -C ₈ alkanols. Fatty alkyl amine oxides are also suitable.

The anionic surfactants can be present in the agent according to the invention in an amount of 1 to 50% by weight, preferably 10 to 35% by weight, based on the finished agent.

Suitable further anionic surfactants are e.g. B. C ₈ -C ₂₂ alkyl benzene sulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates te, sulfo fatty acids, fatty alcohol ether sulfates, glycerin ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, fatty acids, fatty acid salic acid sulfate sulfate, ether carbonsate sulfate , Fatty acid taurides, acyl glutamates, acyl lactylates, acyl tartrates, alkyl oligoglucoside sulfates and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but also a narrow homolog distribution. Preferred further anionic surfactants are the C ₈ -C ₂₂ alkyl ether sulfates.

The C ₈ -C ₂ alkyl ether sulfates which can be used for the purposes of this invention follow the formula VI,

R ⁷ O- (CH2CH ₂ O) π-SO ₃ Y (VI)

in which R ^{7 is} a saturated or unsaturated C ₈ -C ₂ r alkyl group, n is a number from 0.5 to 5 and Y is an alkali or alkaline earth metal or a quaternary ammonium ion.

These substances are known chemical compounds which may be obtained by sulfation of holpolyglykolethern primary or branched Cβ-C _Σ rAlkoholen, preferably fatty alcohol. Also Cβ-C- ₂₂ alkyl ether sulfates with a narrow homolog distribution (NRE = narrow range ethoxylates), as described, for example, in international patent application WO 91/05764 and in the review by DL 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 ethylene oxide (conventional or narrow homolog distribution) with 1 mol of caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl , Arachyl alcohol, Gadoieyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures. Sulfates of adducts of 1 to 7 moles of ethylene oxide with saturated coconut oil alcohols in the form of their sodium, potassium and / or magnesium salts and ammonium salts, such as monoisopropanolammonium salts, are preferred. For example, fatty alcohol ether sulfates can be used which are derived from corresponding fatty alcohol polyglycol ethers which in turn are prepared in the presence of calcined or, in particular, hydrophobicized hydrotalcite have been and therefore have a particularly advantageous narrow homolog distribution.

Soaps, i.e. Alkali or ammonium salts of saturated or unsaturated C6-C22 fatty acids are preferably not contained in the agents according to the invention because of their foam-suppressing properties.

The feature "not included" is not intended to mean that very small amounts of soap cannot be included; Quantities of up to 2% by weight, based on the total agent, are still tolerable in the sense of the invention.

Amphoteric and zwitterionic surfactants can also be used as further surfactants in the agent according to the invention. 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 agent.

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

R ⁷ I

R ⁶ _ N ⁺ - CH2COO ^" (VI)

I.

R ⁸

are used in which R ^{6 is} an alkyl radical with 8 to 25, preferably 10 to 21 carbon atoms and R ⁷ and R ⁸ , which are optionally interrupted by heteroatoms or heteroatom groups, and R ⁷ and R ^{8 are} identical or different alkyl radicals with 1 to 3 carbon atoms. C ₁ -C ₈ -alkyldimethylcarboxymethylbetaine and CιrCιτ-alkylamidopropyldimethylcarboxymethylbetaine are preferred.

The total surfactant content in these compositions is preferably above 15% by weight, based on the total composition, an upper limit being 75% by weight, in particular 50% by weight. As further constituents, the agents according to the invention can also contain solvents, perfumes, dyes and opacifiers, as well as skin protection components, as are known, for example, from EP-A1 522 756. Substances such as gelatin or casein can be used to adjust the viscosity of the compositions without impairing the performance of the compositions according to the invention. If products with improved cold behavior are desired, hydrotropes can also be added to the agent according to the invention.

The solvents to be added if necessary are low molecular weight alkanols with 1 to 4 carbon atoms in the molecule, preferably ethanol and isopropanol. Optional further solubilizers, for example for dyes and perfume oils, can be alkanolamines, polyols such as ethylene glycol, propylene glycol, glycerol and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical.

The preferred thickeners include urea, sodium chloride and ammonium chloride, polysaccharides and the like, which can also be used in combination. Examples of preservatives which can be mentioned are sodium benzoate, formaldehyde and sodium sulfite. The agents according to the invention can also contain conventional 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 weight of the formulation.

Example 1 :

15% by weight of C ^* i2 / 14 fatty alcohol ether (3EO) sulfate Na salt

8% by weight Ci2 / 14 fatty alcohol sulfate Na salt 10% by weight decanol + 8EO

2% by weight dodecanol

3% by weight coconut monoethanolamide

9% by weight ethanol

Balance to 100% water by weight

Example 2:

20% by weight Ci2 / 14 fatty alcohol ether (3EO) sulfate Na salt 8% by weight C * i2 / 14 fatty alcohol sulfate Na salt

10% by weight octanol + 1PO + 8EO 2% by weight dodecanol

2% by weight lauryldimethylamine oxide

7 wt% ethanol

Balance to 100% water by weight

Example 3:

12% by weight Ci2 / 14 fatty alcohol sulfate NH4 salt 18% by weight undecanol + 9EO

2% by weight dodecanol

3% by weight Ci2 / 14-alkyl polyglucoside with a DP of 1.4

4 wt% ethanol

Balance to 100% water by weight Example 4:

13% by weight Ci2 / 14 fatty alcohol sulfate NH4 salt 18% by weight undecanol + 9EO

2% by weight dodecanol

3% by weight cocosamidopropylbetaine 3% by weight ethanol

3% by weight of PEG 400 balance to 100% by weight of water

Example 5:

13% by weight Ci2 / 14 fatty alcohol sulfate NH4 salt 10% by weight undecanol + 9EO

2% by weight dodecanol

8% by weight of C-12-N-methylglucamide

3% by weight ethanol 3% by weight PEG 400

Balance to 100% water by weight

Example 6:

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 of Ci2 / 14 fatty alcohol ether (1,2EO) sulfate-Mg salt (NRE) 10% by weight of Ci2 / 14-fatty alcohol sulfate-Mg salt 18% by weight of CIO / 14-fatty alcohol + 1.2 PO + 8 EO

4% by weight dodecanol

3% by weight of Ci2 / 14-alkyl polyglucoside with a DP of 1.5 12% by weight of 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 Cleansing Ability of Cn-Cn-Alcohol-Containing Surfactant Mixtures:

Different amounts of Dode canol were added to the surfactant mixture shown in Table 1. The rinsing capacity was then tested in a mechanized plate test (c = 0.5 g / l) on grease and mixed soiling (rinsing capacity without the addition of dodecanol 100%). The results are shown in Table 2.

Table 1

"based on active substance

Table 2

The test results clearly show that the addition of decanol to a surfactant mixture which contains C ₈ -C ₈ alcohol alkoxylate and C ₈ -C ₂ o alcohol sulfate leads to an improvement in the rinsing capacity.

Claims

claims

1. Aqueous surfactant mixture containing

(A) 0.01 to 6 wt .-%, based on the finished agent, Cn-Cι ₄ - alcohol,

(B) 1.0 to 30 wt .-%, based on the finished agent, C ₈ -C ₈ alcohol alkoxylate

(D) 14 to 97.99 wt% water.

2. Aqueous surfactant mixture according to claim 1, characterized in that undecanol, dodecanol or mixtures of the foregoing are used as alcohol.

3. Aqueous surfactant mixture according to claim 1 or 2, characterized in that Ce-C∑∑-alkyl polyglycosides, C ₆ -C ₂₂ fatty acid-N-alkyl polyhydroxyalkylamides, fatty acid alkanolamides or any mixtures of the above are used as further nonionic surfactants.

4. Aqueous surfactant mixture according to one of claims 1 to 3, characterized gekenn¬ characterized in that C-rC _∑∑ alkyl _ether sulfate with a degree of ethoxylation of 0.5 to 5 are used as a further anionic surfactant.

5. Aqueous surfactant mixture according to one of claims 1 to 4, characterized gekenn¬ characterized in that it is free of alkali or ammonium salts of saturated or unsaturated C6-C22 fatty acids.

6. Aqueous surfactant mixture according to one of claims 1 to 5, characterized gekenn¬ characterized in that it contains amphoteric and zwitterionic surfactants in an amount of 0.1 to 10 wt .-%, based on the finished agent.

7. Aqueous surfactant mixture according to one of claims 1 to 6, characterized gekenn¬ characterized in that the total surfactant content is above 15 wt .-%, based on the finished agent.

8. Use of the surfactant mixtures according to one of claims 1 to 7 as hand dishwashing detergent.