DE19500799A1 - Aqueous electrolyte salt-free surfactant formulations - Google Patents

Abstract

The proposal is for novel electrolytic salt-free tenside formulations containing (a) sugar tensides, (b) fatty alcohol ether sulphates and (c) polyol esters. The formulations are of low viscosity when highly concentrated but highly viscous when diluted.

Description

Field of the Invention

The invention relates to electrolyte salt-free surfactant formulations with sugar surfactants, fatty alcohol ether sulfates and polyol esters, a process for their manufacture and the use of polyol esters as viscosity regulators goals.

State of the art

Production of a variety of surface active products ten such as cleaning agents, but in particular Even hair shampoos or shower baths are usually two very different demands on the viscosity ver bound:

• 1. The surfactant raw materials are usually considered highly concentrated trated aqueous pastes used, which are easy to handle ben and should therefore be as low viscosity as possible.  
• 2. When diluted with water, the concentrates are formed the finished surfactant formulations, which in turn again have to have a significantly higher viscosity.

For the production of skin-friendly care products and skin and hair cleansing have been in the past unit sugar surfactants - such as alkyl oligoglucosides or fatty acid N-alkyl glucamides and fatty alcohol ether sulfates proven to be particularly suitable alone or in combination. The prior art is accordingly extensive on these surfactants or surfactant mixtures with regard to ih uses in the field of cosmetics.

So are mixtures of long chain alkyl oligoglucosides and Coconut fatty alcohol + 3EO ether sulfate salts already from the Euro European patent EP-H 0070074 (Procter & Gamble) knows. In international patent application WO 91/04313 (Henkel Corp.) proposes to increase the viscosity of aq anionic surfactant solutions through the addition of electrolyte salt and lower alkyl oligoglucosides. According to the Leh ren of the two European patent applications EP-A 0490041 (Hüls) and EP-A 0453238 (Unilever) are suitable mixtures of alkyl oligoglucosides and fatty alcohol ether sulfates for Manufacture of hair shampoos and bath gels. According to the teaching international patent application WO 93/00417 (Henkel) can be aqueous surfactant mixtures based on alkyl oligoglucosides and fatty alcohol ether sulfates by the addition of electrolyte salts and nonionic polymers. In DE-A 41 21 612 (Henkel) dilute aqueous anion surfactant formulations described by small additions a ternary combination of alkyl oligoglucosides, electro  lytic salts and polyol ether esters are thickened. Finally are from DE-A 41 39 935 (Kao) liquid body cleaning medium known, the alkyl polyglucosides, oil bodies as in for example monoglycerides and anionic surfactants as in for example, may contain ether sulfates.

It corresponds to everyday experience that the viscosity of a aqueous solution containing dissolved substances in the Rule increases. The object of the invention is therefore in it existed to provide formulations that a just opposite viscosity and thinning behavior show.

Description of the invention

The invention relates to aqueous electrolyte salt-free Containing surfactant formulations

• a) sugar surfactants,
• b) fatty alcohol ether sulfates and
• c) polyol esters.

Surprisingly, it was found that concentrated aqueous Systems of sugar surfactants, such as alkyl and / or alkenyl oligoglycosides and / or fatty acid N-alkyl poly droxyalkylamides, and fatty alcohol ether sulfates, through the Zu set of polyol esters can be liquefied. If you dilute it Formulations with water, on the other hand, find an advantageous one Increase in viscosity instead. To the usual Verdic You can do without electrolyte salts.  

Alkyl and / or alkenyl oligoglycosides

Examples of suitable sugar surfactants are alkyl and Al kenyloligoglycosides, which are known substances which follow the general 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 two fonts EP-A1 0301298 and WO 90/03977.

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 I 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. Preferably alkyl and / or alkenyl oligoglycosides with a medium oligome  degree of risk p from 1.1 to 3.0 is used. From application From a technical point of view, such alkyl and / or alkenyl oligo preferred glycosides whose degree of oligomerization is less than 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, capronalcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxo synthesis. Alkyl oligoglucosides of the chain length C₈-C₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation by distillation of technical C₈-C₁₈ coconut oil 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, 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

Other sugar surfactants are fatty acid N-alkyl poly droxyalkylamides of the formula (II) into consideration

in the R²CO 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.

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 1 985 424, US 2 016 962 and US 2 703 798 and Inter refer to national patent application WO 92/06984. An over A view of this topic from 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 fat  acid-N-alkylglucamides as represented by the formula (III) are reproduced:

Preferably used as fatty acid-N-alkylpolyhydroxyalkyl amides are glucamides of the formula (III) in which R³ is hydrogen or an amine group and R²CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, nyristic 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 European patent application EP-A1 0285768 (Huls) For example, their use as a thickener is known. In French Offenlegungsschrift FR-A 1580491 (Henkel) aqueous detergent mixtures based on sulfates and /  or sulfonates, nonionic surfactants and optionally soaps wrote the fatty acid N-alkylglucamides as foam regulators gates included.

Subject of the international patent applications WO 92/6153; 6156; 6157; 6158; 6159 and 6160 (Procter & Gamble) are Wed. mixtures of fatty acid N-alkyl glucamides with anionic Surfactants, surfactants with sulfate and / or sulfonate structure, Ether carboxylic acids, ether sulfates, methyl ester sulfonates and nonionic surfactants. The use of these substances in the different detergents, dishwashing and cleaning agents in international patent applications WO 92/6152; 6154; 6155; 6161; 6162; 6164; 6170; 6171 and 6172 (Procter & Gamble).

Fatty alcohol ether sulfates

Fatty alcohol ether sulfates ("ether sulfates") hire known ones ionic surfactants, which are commercially available through SO₃- or CSA- Sulfation of fatty alcohol polyglycol ethers and subsequent ones Neutralization can be made.

For the purposes of the invention, ether sulfates come into consideration which follow formula (IV),

R⁴O- (CH₂CH₂O) _m SO₃X (IV)

in the R⁴ for a linear or branched alkyl and / or Alkenyl radical with 6 to 22 carbon atoms, m for numbers from  1 to 10 and X for an alkali and / or alkaline earth metal, Am monium, alkylammonium, alkanolammonium or glucammonium stands.

Typical examples are the sulfates of addition products from an average of 1 to 10 and in particular 2 to 5 moles Ethylene oxide on capro alcohol, caprylic alcohol, 2-ethylhexylal alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, my ristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol hol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, Petro selinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol hol and erucyl alcohol and their technical mixtures, in Form of their sodium and / or magnesium salts. The ether sulfates can both a conventional and a have narrow homolog distribution.

It is particularly preferred to use ether sulfates based on adducts of an average of 2 to 3 moles of ethylene oxide with technical C _12/14 or C _12/18 coconut fatty _alcohol fractions in the form of their sodium and / or magnesium salts.

Components (a) and (b) can have a weight ratio of 5: 1 to 1: 5, preferably 2: 1 to 1: 2 - based on the Active substance content - can be used.

Polyol ester

Polyol esters are to be understood as substances which by Um setting of polyols with 2 to 12 hydroxyl groups with fat acids with 6 to 22 carbon atoms can be obtained.  

Examples of suitable polyol components include a. Glycerin; Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol; technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as techni special diglycerol mixtures with a diglycerol content of 40 to 50% by weight; Methyl compounds, such as especially trimethylol ethane, trimethylolpropane, trimethylolbutane, pentaerythritol and Dipentaerythritol; Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical such as Me thyl and butyl glucoside; Sugar alcohols with 5 to 12 coals atoms of matter such as sorbitol or mannitol, sugar with 5 to 12 carbon atoms such as glucose or Sucrose; Aminosugars such as glucamine.

Examples of suitable fatty acid components 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, elai dic acid, petroselinic acid, linoleic acid, linolenic acid, Elaeo stearic acid, arachic acid, gadoleic acid, behenic acid and Erucic acid and its technical mixtures, the z. B. at the pressure splitting of natural fats and oils, in which Reduction of aldehydes from Roelen's oxo synthesis or the dimerization of unsaturated fatty acids.

The polyol esters are full, preferably but partial esters. In preferred embodiments of the Invention are used as polyol esters of partial glycerides, Sorbitan and / or oligoglycerols with saturated fatty acids used with 12 to 18 carbon atoms. Typical example le are technical lauric acid, palmitic acid, stearic acid  re, coconut fatty acid mono / diglycerides and the sorbitan mono, sesqui, di and / or triesters of the fatty acids mentioned. These substances are known commercial products products.

The viscosity regulators are usually used in quantities of 5 to 15, preferably 8 to 12 wt .-% - based on the sum me the solids content of components (a) and (b) - ein puts. The concentrated formulations can be one Solids content of 25 to 50, preferably 30 to 40% by weight and the diluted solutions have a solids content of 10 to 25, preferably 15 to 20 wt .-% have.

Industrial applicability

For the purposes of the present invention, the addition of Polyol esters, preferably partial glyceride fatty acid esters and / or sorbitan fatty acid esters in concentrated aqueous sy stemen containing sugar surfactants and ether sulfates partly low viscosity. Will these solutions come with what diluted, on the other hand, takes place especially in the absence of Electrolyte salts instead of a desired build-up of viscosity.

Another object of the invention therefore relates to the Ver Use of polyol esters as viscosity regulators for elec trolyte salt-free aqueous surfactant formulations based on Sugar surfactants and fatty alcohol ether sulfates.

The mixtures according to the invention are suitable for the manufacture position of foaming cleaning agents, preferably in  Area of hair and body care. In these funds can the formulations in amounts of 1 to 50, preferably 4 to 35 wt .-% - based on the agent - be included.

Auxiliaries and additives

The hair and body cleansing agents can be additives and additives substances included. These include, in particular, others with the other ingredients compatible surfactants. Typical examples are monoglyceride sulfates, mono- and / or dialkyl sulfosuccina te, fatty acid isethionates, fatty acid sarcosinates, fatty acid dew ride, ether carboxylic acids, alkyl amido betaines or protein fat acid condensates.

Furthermore, emulsifiers, over greasing agents, other thickeners, biogenic agents fe, film formers, preservatives, colors and fragrances be included.

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 ricinoleate 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.  

Suitable thickeners are, for example, polysaccha ride, especially xanthan gum, guar guar, agar agar, algi nate and tylosen, 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 or alkyl oligoglucoside and electrolytes 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, guaternized 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 sorbine 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% by weight, based on the composition carry.

Examples

The viscosity of various concentrated and diluted Surfactant formulations (pH 5.5) were at 25 ° C and one Shear rate of D = 1 / s determined. The results are summarized in Table I. Understand the percentages weight% (all formulations with water ad 100 % By weight).

The following surfactants and polyol esters were used:

A = C _12/16 cocoalkyl oligoglucoside (Plantaren (R) APG 1200)
B = C _12/14 coconut fatty alcohol + 2EO ether sulfate Na / Mg salt (Texapon® NSO)
C1 = glycerol monolaurate (Monomuls® 90-L12)
C2 = sorbitan monolaurate (Dehymuls® SML)

Table 1

Viscosities of surfactant formulations

The examples and comparative examples show that conc trated mixtures of alkyl oligoglucosides and alkyl ethers sulfates due to the addition of polyol esters with low viscosity are an advantage while the same dilute solutions have high viscosity. The addition of electrolyte Salt as a thickener surprisingly causes an addition collapse of viscosity.

Claims (10)

1. Electrolyte salt-free aqueous surfactant formulations, containing ent

• a) sugar surfactants,
• b) fatty alcohol ether sulfates and
• c) polyol esters.

2. Process for the preparation of aqueous, electrolyte salt free, highly concentrated low viscosity and in dilute ter form containing highly viscous surfactant formulations Sugar surfactants and fatty alcohol ether sulfates, thereby ge indicates that they are polyol esters as viscosity regulators adds. 3. The method according to claim 2, characterized in that one uses alkyl and / or alkenyl oligoglycosides of the formula (I), R¹O- [G] _p in the R¹ for an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G for a sugar residue with 5 or 6 carbon atoms and p represents numbers from 1 to 10. 4. The method according to claim 2, characterized in that one uses fatty acid-N-alkylpolyhydroxyalkylamides of the formula (II), 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 . 5. Process according to claims 2 to 4, characterized in that fatty alcohol ether sulfates of the formula (IV) are used, R⁴O- (CH₂CH₂O) _m SO₃X (IV) in the R⁴ for a linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms, m represents numbers from 1 to 10 and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. 6. The method according to claims 2 to 5, characterized records that components (a) and (b) in Ge weight ratio 5: 1 to 1: 5 - based on the Ak active substance content - used. 7. The method according to claims 2 to 6, characterized records that as viscosity regulators (component c) esters of partial glycerides, sorbitan and / or oligo  glycerols with saturated fatty acids with 12 to 18 Koh len atoms used. 8. The method according to claims 2 to 7, characterized records that the viscosity regulators in quantities from 5 to 15% by weight based on the total of the solid content of components (a) and (b) - used. 9. The method according to claims 2 to 8, characterized records that the concentrated formulations one Solids content of 25 to 50 wt .-% and the diluted Solutions a solids content of 10 to 25% by weight exhibit. 10. Use of polyol esters as viscosity regulators for electrolyte salt-free aqueous surfactant formulations Based on sugar surfactants and fatty alcohol ether sulfates.