DE19548068C1 - Process for the production of light colored, low viscosity surfactant concentrates - Google Patents

Description

Field of the Invention

The invention relates to a method for producing light-colored, low-viscosity surfactant concentrates by mixing sugar surfactants and betaines in the gel phase.

State of the art

Alkyl oligoglycosides, especially alkyl oligoglucosides, are nonionic surfactants which, owing to their excellent detergent properties and high ecotoxicological compatibility gaining importance. Manufacture and use of these fabrics have been in lately a number of review articles have been presented, of which the publications are representative by H.Hensen in Skin Care Forum, 1, (Oct. 1992), D.Balzer and N.Ripke in Soap-Oil-Fat-Waxes 118, 894 (1992) and B.Brancq in soap-oil-fat waxes 118, 905 (1992). Similarly advantageous properties of a second group of sugar surfactants, the fatty acid N-alkylpolyhydroxyalkylamides, in particular the fatty acid-N-alkylglucamides, are known.

In some ways, however, the use of sugar surfactants is problematic. So you can for example, no pumpable aqueous concentrates with a solids content above 40 Manufacture wt .-%, without it in the course of the concentration to a partial decomposition of the Sugar component is coming. The glycosides and glucamides have this property with the common to most anionic surfactants which are above an active substance content of about 35 % By weight form a viscous gel phase. The sugar surfactants also show a tendency in the course storage at low temperatures crystallize, making their further use significant difficult.

The common use of sugar surfactants of the types mentioned together with amphoteric or zwitterionic surfactants of the betaine type in surface-active agents is from the prior art Technology basically known.  

Mixtures of - albeit short-chain - alkyl glucosides and alkyl amido are disclosed for the first time betainen or imidazolinium betainen in an article by G.Proserpio et al. at Rivista Italiana 56 567 (1974). In EP-A 0 075 994 (Procter & Gamble) combinations of alkyl glucosides with Amine oxides, unsaturated soaps, water-soluble builders and selected anionic surfactants disclosed. The mixtures can also contain amphoteric surfactants, for example betaines of the 6 - (- N-dodecylbenzyl-N, N-dimethyl-ammonium) contain hexanoate. From US 4,668,422 (Henkel Corp.) are liquid soaps and bubble baths containing alkyl glucosides, betaines and amine oxides known. EP-A 0 250 181 (Helene Curtis) relates to liquid detergents containing alkyl glucoside, anionic surfactants and selected amphoteric surfactants with betaine structure. In EP-A 0 341 071 (Unilever) surfactant combinations are disclosed, containing alkyl glucosides, alkyl sulfates, Be taine and / or amine oxides and optionally alkanolamides. Containing manual dishwashing detergents Alkyl glucosides, fatty alcohol sulfates, fatty alcohol ether sulfates and betaines are from EP-A 0 513 138, DE-A1 42 34 487 and DE-A1 43 11 114 (all handles) are known. In EP-A 0 453 238 (Uni lever) mild shampoos based on alkyl glucosides, anionic surfactants and betaines wrote. Finally, EP-A 0 508 507 (Berol Nobel) relates to liquid detergents containing Alkyl glucosides, on ionic surfactants and selected amphoteric surfactants with betaine structure. All however, these documents have dilute aqueous surfactant mixtures or agents and no concentrations came to the object. Finally, Japanese Patent Application Laid-Open JP-A2 Hei 02/187 499 detergents suggested that contain alkyl polyglucosides and betaines.

The use of the fatty acid N-alkylpolyhydroxyalkylamides is also the subject of a large number of Publications. For example, from European patent application EP-A1 0 285 768 (Huls) known as thickeners. In French patent application FR-A1 580 491 (Henkel) are aqueous detergent mixtures based on sulfates and / or sulfonates, nonionic surfactants and optionally described soaps, the fatty acid N-alkylglucamides as foam regulators contain. Mixtures of short and long chain glucamides are described in the German patent DE-C1 44 00 632 (Henkel). In German Offenlegungsschrift DE-A1 43 09 567 (Henkel) is also concerned with the use of glucamides with longer alkyl residues than pseudoceramides in Skin care products and combinations of glucamides with protein hydrolyzates and cationic Surfactants in hair care products have been reported.

Subject of the international patent applications WO 92/06153; WO 92/06156; WO 92/06157; WHERE 92/06158; WO 92/06159 and WO 92/06160 (Procter & Gamble) are mixtures of fatty acid N- alkyl glucamides with ionic surfactants, surfactants with sulfate and / or sulfonate structure, ethers carboxylic acids, ether sulfates, methyl ester sulfonates and nonionic surfactants. The usage These substances in a wide variety of detergents, dishwashing detergents and cleaning agents are used in the internatio  nalen patent applications WO 92/06152; WO 92/06154; WO 92/06155; WO 92/06161; WO 92/06162; WO 92/06164; WO 92/06170; WO 92/06171 and WO 92/06172 (Procter & Gamble).

There is a need in the market for concentrated surfactant mixtures based on alkyl and / or Alkenyl oligoglucosides, which have a solids content above 30% by weight and preferably of about 40 to 60 wt .-% are flowable and pumpable and a significantly reduced crystallization gung, d. H. have improved storage stability. Since such surfactant compounds predominantly in Hand dishwashing detergents and hair shampoos are used for skin cosmetics or derma Tological tolerance is also extremely important.

The surfactant concentrates represent a particularly advantageous form of trade for manufacturers and users because they have been minimized in terms of their water content and thus lower costs Cause transport and storage. Nevertheless, it is desirable that the surfactant concentrates be used in the final formulations, which are naturally highly diluted and have a solids content of 20 to 30 % By weight, have a sufficiently high viscosity or can be used without problems allow known additives to thicken.

The complex object of the invention has therefore been to produce light-colored, pumpable aqueous Surfactant concentrates with good skin cosmetic tolerance based on alkyl glycosides or To provide fatty acid glucamides and betaines, which are characterized by high storage stability distinguish, a viscosity according to Brookfield of maximum 10,000 mPas and a solids content have from 40 to 60 wt .-%.

Description of the invention

The invention relates to a process for the preparation of light-colored, low-viscosity surfactant concentrates with a solids content of 40 to 60 wt .-%, in which one

• (a1) alkyl and / or alkenyl oligoglycosides and / or
• (a2) fatty acid N-alkyl polyhydroxyalkylamides and
• (b) Betaine surfactants

mixed in the weight ratio a: b from 90: 10 to 10: 90, with the proviso that the concentrated Feedstocks are present in the gel phase.  

Surprisingly, it was found that it was not necessary for the production of the desired concentrates is required of low viscosity, d. H. dilute aqueous feedstocks and this to concentrate later. Rather, it was found that when con centered feedstocks that are in the gel phase and are therefore not low-viscosity themselves, Products that are low viscosity, light colored and stable in storage.

Alkyl and / or alkenyl oligoglycosides

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

R¹O- [G] _p (I)

in the R¹ for an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G for a sugar radical with 5 or 6 carbon atoms and p represents numbers from 1 to 10. You can go to the one relevant methods of preparative organic chemistry can be obtained. Representing that For extensive literature, see EP-A1-0 301 298 and WO 90/03977. The Alkyl and / or alkenyl oligoglycosides can differ from aldoses or ketoses with 5 or 6 carbon atoms, preferably derived from glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (1) gives the degree of oligomerization (DP degree), d. H. the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p must always be an integer in a given connection and here can assume the values p = 1 to 6, the value p is for a certain one Alkyl oligoglycoside is an analytically calculated value, usually a fraction represents. Alkyl and / or alkenyl oligoglycosides with a medium oligomer are preferred Degree of p from 1.1 to 3.0 used. From an application point of view, these are alkyl and / or alkenyl oligoglycosides preferred, the degree of oligomerization of which is less than 1.7 and in particular 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, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained 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 occur as a preliminary in the distillative separation of technical C₈-C₁₈ coconut oil alcohol 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 radical R 1 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 their technical mixtures described above, which can be obtained as described above. Alkyl oligo glucosides 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-alkylpolyhydroxyalkylamides are nonionic surfactants which follow the formula (II)

in the R²CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R³ for an alkyl or Hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched poly hydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups. Both Fatty acid N-alkylpolyhydroxyalkylamides are known substances that are commonly known 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 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 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 reduie sugar with 5 or 6 carbon atoms, especially from glucose. The preferred Fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid re-N-alkylglucamides as represented by the formula (III) are represented:

Preferred fatty acid N-alkylpolyhydroxyalkylamides are glucamides of the formula (III) in which R³ is hydrogen or an alkyl group and R²CO is the acyl radical of capric 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. Fatty acid N-alkylglucamides 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.

Betaine surfactants

Betaines are known surfactants, which are predominantly by carboxyalkylation, preferably Carboxymethylation of amine compounds are produced. Preferably the Starting materials with halogen carboxylic acids or their salts, especially with sodium chloroacetate condensed, forming one mole of salt per mole of betaine. The addition of unsaturated carboxylic acids such as acrylic acid possible. To the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants is based on the contribution of U.Ploog in Seifen-Öle-Fette-Wwachs, 198, 373 (1982). Further overviews of 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). Examples of suitable betaines are the carboxyalkylation products of secondary and especially tertiary amines, which follow the formula (IV),

in the R⁴ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R⁵ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R⁶ for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X for an alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, Hexyld imethylamin, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C alkyldimethylamine myristyldimethylamine Cetyld imethylamin, stearyldimethylamine, and coconut amine _12/14, Stearylethylmethyl, imethylamin Oleyld, C _16/18 tallow alkyl dimethylamine and technical mixtures. Carboxyalkylation products of amidoamines which follow the formula (V) are also suitable,

in which R⁷CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R⁵, R⁶, n and X have the meanings 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, palm oleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid, arachinic acid , Behenic acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-di-ethylaminopropylamine, which are condensed with sodium chloroacetate. Be preferred is the use of a condensation product of C _8/18 coconut fatty acid N, N-dimethylamino propylamide with sodium chloroacetate. Furthermore, suitable starting materials for the betaines to be used in accordance with the invention are also imidazolines which follow the formula (VI)

in which R⁸ is an alkyl radical having 5 to 21 carbon atoms, R⁹ is a hydroxyl group, an OCOR⁸ or NHCOR⁸ radical and m 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 polyvalent amines such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine. The corresponding carboxyalkylation 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 again C _12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

Surfactant concentrates

The preparation of the surfactant concentrates is based on highly concentrated gel form aqueous starting materials. This means that the alkyl and / or alkenyl oligoglycosides and / or the fatty acid N-alkyl polyhydroxyalkylamides in the form of aqueous gels with a sugar surfactant content in the range of 45 to 60 and preferably 45 to 55% by weight. The betaine surfactants are used in the Usually with a non-aqueous content in the range of 45 to 60, preferably 48 to 54 wt .-% and a betaine content in the range from 25 to 40, preferably 28 to 35,% by weight. The production the surfactant concentrates are made in a purely mechanical way by mixing the gel-like form materials, if necessary at elevated temperature and strong shear. In a preferred out The betaines are implemented in a known manner, for example by implementation  of suitable tertiary amines with aqueous sodium chloroacetate solution at about 90 ° C and the crude betaines are mixed with the aqueous glucoside or glucamide pastes without cooling. Here the betainization is carried out with just the amount of water as a solvent that in the Mixing product with the sugar surfactants sets the desired solids content. In sum means this is that the betainization is carried out with an unusually low amount of solvent can be.

Flow improver

To improve the flowability, small amounts of polyols can be added to the concentrates, than there are:

• - glycerin;
• Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol;
• - Technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10, such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
• Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, Pentaerythritol and dipentaerythritol;
• - Hydroxycarboxylic acids such as glycolic acid, tartaric acid and citric acid;
• - Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as wise methyl and butyl glucoside;
• Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol,
• - Sugar with 5 to 12 carbon atoms, such as glucose or sucrose;
• - aminosugars, such as glucamine.

The concentrates are preferably used in amounts of 0.5 to 5, in particular 1 to 3,% by weight, based on the Concentrates - polyols, especially glycerin. As another fluidity improver the surfactant concentrates can contain small amounts, i.e. H. 0.5 to 3 and preferably 1 to 2% by weight - based on the concentrates - contain free fatty acids. Typical examples 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, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and eruca acid and their technical mixtures, the z. B. in the pressure splitting of natural fats and Oils in the reduction of aldehydes from Roelen's oxosynthesis or the dimerization of unsaturated fatty acids.  

Industrial applicability

The surfactant concentrates according to the invention are characterized by a low viscosity and Yield point. They are light colored, color and storage stable. They are therefore suitable for the production of a A large number of surface-active agents, such as, for example, washing, rinsing and cleaning agents which they contain in amounts of 0.5 to 50 and preferably 2 to 35% by weight, based on the composition can be hold.

Examples

The surfactant feedstocks described in Table 1 were used below. The Surfactant ingredients were mixed at 40 ° C, with surfactant concentrates that in Table 2 reproduced composition resulted.

Table 1

Input materials (quantities as% by weight)

Table 2

Surfactant concentrates (quantities as% by weight)

Claims (10)

1. Process for the preparation of light-colored, low-viscosity surfactant concentrates with a solids content of 40 to 60 wt .-%, in which

• (a1) alkyl and / or alkenyl oligoglycosides and / or
• (a2) fatty acid N-alkyl polyhydroxyalkylamides and
• (b) Betaine surfactants

mixed in the weight ratio a: b from 90: 10 to 10: 90, with the proviso that the concentrated feedstocks in the gel phase. 2. The method according to claim 1, characterized in that one uses as component (a1) alkyl and alkenyl oligoglycosides of the formula (I), R¹O- [G] _p (I) in the R¹ for an alkyl and / or alkenyl radical with 4th up 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 as component (a2), in which R²CO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R³ for hydrogen, 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. 4. Process according to claims 1 to 3, characterized in that betaine surfactants of the formula (IV) are used as component (b), in the R⁴ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R⁵ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R⁶ for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X for an alkali and / or earth alkali metal or ammonium. 5. Process according to claims 1 to 4, characterized in that betaine surfactants of the formula (V) are used as component (b), in which R⁷CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R⁵, R⁶, n and X have the meanings given above. 6. Process according to claims 1 to 5, characterized in that alkyl and / or Alkenyl oligoglycosides and / or fatty acid N-alkylpolyhydroxyalkylamides in the form of aqueous gels with a sugar surfactant content in the range of 45 to 60 wt .-%. 7. The method according to claims 1 to 6, characterized in that betaines in the form aqueous gels with a non-aqueous content in the range of 45 to 60 and a betaine content in the range from 25 to 40% by weight. 8. The method according to claims 1 to 7, characterized in that the concentrates 0.5 to 5 wt .-% - based on the concentrates - glycerin added. 9. The method according to claims 1 to 8, characterized in that the concentrate 0.5 up to 3% by weight, based on the concentrates, of fatty acids.