DE19512411A1 - Process for the production of viscous sugar surfactants - Google Patents

Abstract

Aqueous solutions or pastes of: (a) alkyl and/or alkenyl oligoglycosides and/or (b) fatty acid N-alkyl polyhydroxyalkyl glucamides can be thickened by the addition of highly ethoxylated trimethylol propane fatty acid esters. The products are suitable, for example, for the production of hair treatment agents.

Description

Field of the Invention

The invention relates to a method for producing thickened ter solutions or pastes of sugar surfactants using of highly ethoxylated trimethylolpropane fatty acid esters, aq hair treatment compositions containing sugar surfactants and mentioned thickeners and the use of the esters as a thickener for sugar surfactants.

State of the art

An important aspect in the production of surfaces active agents, such as hair shampoos or Hand dishwashing detergent is that the detergent is a must not have too high a viscosity, so that a pump ability is still given. On the other hand, those in the Usually aqueous products also have a sufficiently high viscosity have, so that the consumer simply dose the funds can.

In contrast to a large number of other surfactants Sugar surfactants such as alkyl glucoside or fat  acid glucamides - because of their excellent application technical and dermatological properties for the above mentioned uses are particularly suitable - by Zu known additives such as table salt, alkanolamides and thicken the like difficult.

In the past, attempts have therefore not been successful applies, new and improved thickeners for the Ver Thickening of a variety of surfactant systems supply.

For example, in the European patent application EP-A 0343463 (Henkel) as a nitrogen-free thickener low ethoxylated fatty alcohol polyglycol ethers with concentrated ter homolog distribution proposed. From the German Pa tent registration DE-A 32 39 564 (Th. Goldschmidt) are low oxylated, from PCT patent application WO 93/10072 (Henkel) highly ethoxylated glycerin fatty acid esters for the same Known purpose. Finally, from the patent US 5192462 (Croda) the use of highly ethoxylated pen Taerythritol fatty acid esters for thickening surfactant Systems known.

In practice, however, it has been found that the thickening Effect of the substances mentioned is not sufficient and / or is not preserved over a longer period of time; in addition, milky cloudy products are often obtained.

The object of the invention was therefore a Ver drive to thicken aqueous sugar surfactants  to provide that free of the disadvantages described is.

Description of the invention

The invention relates to a method for producing viscous sugar surfactant, which is characterized in that aqueous solutions or pastes of

• (a) alkyl and / or alkenyl oligoglycosides and / or
• (b) Fatty acid N-alkyl polyhydroxyalkyl glucamides

by adding highly ethoxylated trimethylolpropane fatty acid Reestern thickened.

Surprisingly, it was found that the addition of high Comparison of ethoxylated trimethylolpropane fatty acid esters to products of the prior art to a higher viscosity action leads. The products are also permanently thickened and are clear.

Alkyl and / or alkenyl oligoglycosides

Alkyl and alkenyl oligoglycosides are known substances which follow the formula (I)

R¹O- [G] _p (I)

in R¹ for an alkyl and / or alkenyl radical with 4 to 22nd Carbon atoms, G for a sugar residue with 5 or 6 Koh lenstoffatomen and p stands for numbers from 1 to 10, and the according to the relevant procedures of preparative organic Chemistry can be obtained. Representing the order extensive literature is here on the writings WO 90/03977 and EP-A1 0301298.

The alkyl and / or alkenyl oligoglycosides can differ from Aldoses or ketoses with 5 or 6 carbon atoms derive preferably the glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkene nyloligoglucoside.

The index number p in the general formula (I) gives the oli Degree of gomerization (DP degree), d. H. the distribution of mono and Oligoglycosides and stands for a number between 1 and 10. Whilst p is always an integer in a given connection must be and assume here the values p = 1 to 6 is the value p for a particular alkyl oligoglycoside an analytically calculated quantity, most of the time represents a fractional number. Alkyl and / or Alkenyl oligoglycosides with a medium oligo Degree of merit p used from 1.1 to 3.0. From use From an nutritional point of view, such alkyl and / or alkenyl oligoglycosides preferred, their degree of oligomerization is smaller is 1.7 and is in particular between 1.2 and 1.4.

The alkyl or alkenyl radical R 1 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic 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 the chain length C₈-C₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C₈-C₁₈ coconut fatty alcohol by distillation and can be contaminated with a proportion of less than 6% by weight of C₁₂ alcohol and Alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3).

The alkyl or alkenyl group R¹ can also be derived from primary alcohols with 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, petro selinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and their 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.

Fatty acid N-alkyl polyhydroxyalkylamides

Fatty acid N-alkyl polyhydroxyalkylamides follow the formula (II),

in the R²CO for an aliphatic acyl radical with 6 to 22 Carbon atoms, R³ for hydrogen, an alkyl or Hy droxyalkyl radical with 1 to 4 carbon atoms and [Z] for egg NEN linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups.

The fatty acid N-alkylpolyhydroxyalkylamides are are known substances, usually through reductive Amination of a reducing sugar with ammonia, a Alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a Fatty acid chloride can be obtained. With regard to the Processes for their production are based on the US patents US 1985424, US 2016962 and US 2703798 and the Internationa le Patent application WO 92/06984 referenced. An overview of this topic by H. Kelkenberg can be found in Tens. Surf. Det. 25, 8 (1988).

The fatty acid N-alkylpolyhydroxyal is preferably derived kylamides of reducing sugars with 5 or 6 carbon atoms, especially from glucose. The preferred Fatty acid N-alkyl polyhydroxyalkylamides are therefore fatty Acid-N-alkylglucamides as represented by the formula (III) are reproduced:

The fatty acid N-alkylpolyhydroxyalkyl amides used are preferably glucamides of the formula (III) in which R³ is hydrogen or an alkyl group and R²CO 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, petrose linic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkyl glucamides of the formula (III) 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.

Also the use of the fatty acid N-alkyl polyhydroxyalkyl amide has been the subject of numerous publications. From the European patent application EP-A1 0 285 768 (Hüls) their use as a thickener is known, for example. In French patent application FR-A 1 580 491 (Henkel) are aqueous detergent mixtures based on Sul faten and / or sulfonates, non-ionic surfactants and optionally fen described the fatty acid N-alkylglucamide as a foam regulators included.

Highly ethoxylated trimethylolpropane fatty acid esters

Highly ethoxylated trimethylolpropane fatty acid esters known substances, which according to the relevant procedures of  preparative organic chemistry can be obtained. On Process for their production consists, for example, in Trimethylolpropane in the presence of an alkaline catalyst to ethoxylate and the reaction product with fatty acids to esterify. However, it is also possible to start with the Tri To produce methylolpropane fatty acid esters and the ethoxylie to be carried out subsequently. In the presence of selected th catalysts such as calcined or hydro phobicized hydrotalcite finds an insertion of the Ethy lenoxide building blocks in the ester group.

The fatty acid component of the trimethylolpropane fatty acid ester can differ from saturated and / or unsaturated fatty acids with 6 to 22 carbon atoms. Typical examples are esters based on caproic acid, caprylic acid, 2-ethyl hexanoic acid, capric acid, lauric acid, isotridecanoic acid, my ristic acid, palmitic acid, palmoleic acid, stearic acid, Isostearic acid, oleic acid, elaidic acid, petroselinic acid, Li nolic acid, linolenic acid, elaeostearic acid, arachic acid, Gadoleic acid, behenic acid and erucic acid and their techni cal mixtures z. B. in the pressure splitting of natural Chen fats and oils, in the reduction of aldehydes from the Roelen's oxosynthesis or the dimerization of unsaturated fatty acids.

Trimethylolpropane esters based on branched fatty acids with 8 to 18 carbon atoms, such as for example trimethylolpropane-2-ethylhexanoate and esp special trimethylolpropanisostearate. With the esters it can are full or partial esters, preferably lies the degree of esterification at 2 to 3. In a particularly before  preferred embodiment of the method according to the invention the trimethylolpropane triisostearate used.

The degree of ethoxylation of trimethylolpropane fatty acid esters can be 100 to 150, preferably 110 to 120. Here ter is understood to be one mole of the ester, for example with a degree of ethoxylation of 100, 100 moles of ethyl lenoxide is eliminated. Ethoxylation is a reaction that follows statistical laws. However, it will only after the Performed ester formation, ester and free hydroxyl occur groups in competition so that the distribution of EO groups the functions are no longer even; This is however irrelevant to the thickening effect of the agents. Trimethylolpropane triisostearates with a Degree of ethoxylation from 120 to 130 used.

The thickeners are usually used in amounts of 0.5 to 15, preferably 5 to 10 wt .-% - based on the solid substance content of the aqueous solutions or pastes - used. The aqueous solutions or pastes can contain a solid, d. H. essentially (sugar) surfactant content from 5 to 60 and preferably have 10 to 50 wt .-%.

Industrial applicability

The addition of highly ethoxylated trimethylolpropane fatty acid esters to aqueous sugar surfactant solutions or pastes leads to a significant and permanent increase in viscosity. This effect can be used, for example, for the manufacturer  easy and economical dosage of hair treatment products make use of.

Hair treatment products

Accordingly, another object of the invention relates aqueous hair treatment agent based on sugar surfactant, ent tend

• (a) alkyl and / or alkenyl oligoglycosides and / or
• (b) fatty acid N-alkyl polyhydroxyalkylamides as well

Highly ethoxylated trimethylol propane fat as thickener acid ester.

The hair treatment products can be used in minor amounts other surfactants compatible with the other ingredients contain. Typical examples are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, Fatty acid taurides, ether carboxylic acids, alkyl amido betaines or Protein fatty acid condensates.

The hair treatment agents, such as hair shampoos, Hair lotions or bubble baths can be used as additional aids and Additives emulsifiers, superfatting agents, thickeners medium, biogenic agents, film formers, preservatives tel, dyes and fragrances.  

Both known W / O- and O / W- come as emulsifiers Emulsifiers such as hardened and ethoxylated Castor oil, polyglycerol fatty acid ester or polyglycerol poly ricinoleates or polyhydroxystearates in question.

Substances such as, for example, can be used as superfatting agents polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides ver be used, the latter at the same time as foam stabilizers serve.

Other suitable co-thickeners are, for example, Polysac charide, especially xanthan gum, guar guar, agar agar, Al ginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and - diesters of fatty acids, polyacrylates, polyvinyl alcohol and Polyvinylpyrrolidone, surfactants such as fatty alcohol ethoxylates with narrow homolog distribution and electro lyte such as table salt and ammonium chloride.

Among the biogenic active substances are, for example, plant ex to understand tracts and vitamin complexes.

Common film formers are, for example, chitosan, mi crocrystalline chitosan, quaternized chitosan, polyvinyl pyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, Po polymers of the acrylic acid series, quaternary cellulose derivatives, Collagen, hyaluronic acid or its salts and similar compounds fertilize.  

Phenoxy, for example, are suitable as preservatives ethanol, formaldehyde solution, parabens, pentanediol or Sorbic acid.

As a pearlescent agent, for example, glycol distearin acid esters such as ethylene glycol distearate, but also fatty acid monoglycol ester.

Suitable dyes are those suitable for cosmetic purposes and approved substances, such as those used in for example in the publication "Cosmetic Colorants" of Dye Commission of the German Research Foundation, published by Verlag Chemie, Weinheim, 1984, pp. 81-106 are put together. These dyes are commonly used in concentrations of 0.001 to 0.1% by weight, based on the whole mixture, used.

The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40 wt .-% - based on the means - be carry.

A final object of the invention finally relates to Use of highly ethoxylated trimethylolpropane fatty acid esters as thickeners for aqueous solutions or pastes of sugar surfactants.

The following examples are intended to be the subject of the invention explain in more detail without restricting it.

Examples I. Substances used

• A1) C₈-C₁₆ alkyl oligoglucoside (Plantaren® APG 2000)
• A2) Coconut fatty acid N-methylglucamide
• B1) Trimethylolpropane triisostearate + 120 EO
• B2) Pentaerythritol tetraisostearate + 150 EO
• B3) Glycerol tristearate + 150 EO
• B4) Polyglycerol poly-12-hydroxystearate
• B5) tetraglycerol triisostearate
• B6) Sorbitan tristearate
• B7) Polymer Antil® 411 S (Th. Goldschmidt) / common salt (1: 1)

The thickener B1 is according to the invention, the thickener B2 to B7 are used for comparison.

II. Viscosity measurements

There were 10% by weight aqueous solutions of the sugar Surfactants A1 and A2 prepared, adjusted to pH = 6 and with 5 to 10% by weight of the thickeners B1 to B6 are added. After homogenizing the mixtures, the viscosity became 20 ° C in a Brookfield RVT viscometer (spindle 2, 10 rpm) certainly. The results are summarized in Table 1 (Percentages as% by weight).  

Table 1

Viscosity measurements

Furthermore, aqueous hair treatment agent formulations stanchions containing

16% by weight alkyl oligoglucoside (Plantaren® APG 2000)
13% by weight ether sulfate (Texapon® NSO)
9% by weight protein fatty acid condensate (Lamepon® S
5% by weight protein hydrolyzate (Nutrilan® Keratin W)

and 3 to 5% by weight of thickener (water ad 100% by weight) produced and assessed in its viscosity according to Brookfield Splits. The results are summarized in Table 2:

Table 2

Hair treatment products

Claims (11)

1. Process for the production of viscous sugar surfactants, characterized in that aqueous solutions or Pa sten of

• (a) alkyl and / or alkenyl oligoglycosides and / or
• (b) Fatty acid N-alkyl polyhydroxyalkyl glucamides

by adding highly ethoxylated trimethylolpropane fatty acid esters thickened. 2. The method according to claim 1, characterized in that one uses alkyl and / or alkenyl oligoglycosides of the formula (I), R¹O- [G] _p (I) in the R¹ for an alkyl and / or alkenyl radical having 4 to 22 carbon atoms , G stands for a sugar residue with 5 or 6 carbon atoms and p stands for numbers from 1 to 10. 3. Process according to claims 1 and 2, characterized in that fatty acid-N-alkylpolyhydroxyalkylamides of the formula (II) are used, in which R²CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R³ is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups . 4. The method according to claims 1 to 3, characterized records that as a thickener trimethylol propane fatty acid ester uses, its fatty acid component from branched fatty acids with 8 to 18 carbons derives atoms. 5. The method according to claims 1 to 4, characterized records that as a thickener trimethylol propane fatty acid ester uses an esterification have degrees of 2 to 3. 6. The method according to claims 1 to 5, characterized records that as a thickener trimethylol propane fatty acid ester uses an ethoxylie degree of 100 to 150. 7. The method according to claims 1 to 6, characterized records that the thickeners in amounts of 0.5 to 15 wt .-% - based on the solids content of the aqueous solutions or pastes - used.   8. Aqueous hair surfactants containing sugar surfactant

• (a) alkyl and / or alkenyl oligoglycosides and / or
• (b) fatty acid N-alkyl polyhydroxyalkylamides as well

highly ethoxylated trimethylolpro as thickener pan fatty acid esters. 9. Use of highly ethoxylated trimethylol propane fat acid esters as thickeners for aqueous solutions or pastes of sugar surfactants.