WO1996008548A1 - Mild detergent mixtures - Google Patents

Abstract

The invention concerns novel detergent mixtures having improved dermatological tolerance and containing: (a) plant protein fatty acid condensates; and (b) further anionic, non-ionic, cationic and/or amphoteric or zwitterionic surfactants. The mixtures are suitable for preparing a plurality of surfactants.

Description

 Mild detergent mixtures

Field of the Invention

The invention relates to detergent mixtures with improved skin cosmetic compatibility, containing vegetable protein fatty acid condensates and other anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants, surface-active agents which contain these mixtures and the use of the mixtures for the production of surface-active agents.

State of the art

Acylation products of protein hydrolyzates, so-called protein fatty acid condensates, are anionic surfactants of the modified soap type which are used, for example, in aqueous cosmetic preparations (hair shampoo etc.) because of their good cleaning performance and special skin tolerance. With regard to the properties of this surfactant class, reference is made to the contributions by G. Schuster and H. Modde in Parf.Kos. 5, 337 (1964) and OJ Muscio et al. in J.Am. Oil.Chem.Soc. J> 9_ _# 217 (1982). Commercial protein fatty acid condensates based on animal proteins, such as collagen or keratin, have high foaming power and good dermatological compatibility as individual surfactants, but these advantageous properties are only retained to a limited extent in the resulting formulations when mixed with other surfactants . Another problem is that the formulations show too low a viscosity for many applications.

The object of the invention was therefore to provide new detergent mixtures based on protein fatty acid condensates, the performance and dermatological properties of which, particularly with regard to the tolerance to the eye mucosa, have been significantly improved.

Description of the invention

The invention relates to mild detergent mixtures containing

(a) vegetable protein fatty acid condensates and

(b) further anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants.

Surprisingly, it was found that vegetable protein fatty acid condensates have a significantly improved dermatological tolerance compared to products based on animals and, when mixed with other surfactants, in particular in a weight ratio of 25:75 to 75:25, if a synergistic improvement in the dermatological properties and the foaming power as well as in the recipes show an advantageous viscosity. The invention also includes the knowledge that detergent mixtures with particularly good dermatological compatibility can be obtained if highly acylated vegetable protein fatty acid condensates with a total nitrogen content of 1.8 to 4.1 and preferably 2.5 to 3.5 are used

Vegetable protein fatty acid condensates

As mentioned, protein fatty acid condensates are known substances. Almond and potato protein and, in particular, wheat and soy protein, which are cleaved by acidic, alkaline and / or enzymatic hydrolysis and then an average molecular weight, are usually used to produce the vegetable products have in the range of 600 to 4000, preferably 2000 to 3500. The hydrolyzate is then subjected to a Schotten-Baumann acylation, preferably using fatty acid chlorides.

The substances of component (a) to be used in accordance with the invention are formally acylation products of vegetable protein hydrolyzates with aliphatic fatty acids of the formula (I),

RlC0-0H (I)

in which R ^ CO represents an aliphatic acyl radical having 6 to 22, preferably 12 to 18 carbon atoms. How nice described, the fatty acyl radical is not introduced into the condensates via the fatty acids, but via the fatty acid chlorides. If it is explained in the following which fatty acids the protein fatty acid condensates can be derived from, then this is linked to the teaching of technical action to use the corresponding fatty acid chlorides for their production.

Examples of fatty acids from which the protein fatty acid recondensates can be formally derived are: caproic acid, caprylic acid, 2-ethylhexanoic acid, isononanoic 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, elasostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid as well as their technical mixtures, which are obtainable, for example, by pressure splitting of fats and oils or reduction of aldehydes from Roelen's oxosynthesis.

The protein fatty acid condensates can be used in the form of their alkali, alkaline earth and / or ammonium salts, preferably as sodium, magnesium and / or calcium salts.

Surfactants

Typical examples of anionic surfactants are alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, o-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, gly- cerine 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, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, acyl lactylates, acyl glutamates, acyl tartrates, alkyl oligoglucoside sulfates and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, fatty acid-N-protein hydrolysates, especially vegetable hydrolysates Soy or wheat base) polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates. If the nonionic tenides contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.

Mixtures of vegetable protein fatty acid condensates (a) with fatty alcohol ether sulfates (bl) and / or alkyl oligoglucosides (b2) in a weight ratio (a): (b) or (bl: b2) of 25:75 to 75:25 each are preferred. Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, in particular quaternized fatty acid trialkanolamine ester salts.

Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, amino glycinates, imidazolinium betaines and sulfobetaines.

The surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, relevant review articles include J. Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J. Falbe (ed.) , "Catalysts, surfactants and mineral oil additives", Thieme Verlag, Stuttgart, 1978, pp. 123-217.

The vegetable protein fatty acid condensates and the further surfactants can be used in a weight ratio of 1:99 to 99: 1, preferably 25:75 to 75:25 and in particular 40:60 to 60:40.

Industrial applicability

The detergent mixtures according to the invention are distinguished by a particularly advantageous foaming power and a dermatological compatibility, which is improved in a synergistic manner, and a sufficiently high viscosity, properties which are important in the development of a large number of surface-active agents: Further objects of the invention therefore relate to surface-active agents which contain these detergent mixtures and which are defined in more detail below:

o Powder-form universal detergents containing 10 to 30% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

Liquid universal detergents containing 10 to 70% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Liquid mild detergent containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o softening agents containing 10 to 50% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Hand dishwashing detergent, containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o rinse aid, containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Liquid detergents and disinfectants containing 10 to 30% by weight - based on the agent - of the invented detergent mixtures according to the invention and customary auxiliaries and additives.

Bar soaps of the combibar type, containing 1 to 2% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Syndet soaps containing 1 to 2% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Hair shampoos containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Hair rinses containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Hair colorants containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Hair waving compositions containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Bubble baths containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Textile and fiber auxiliaries containing 1 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Leather greasing agents containing 1 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Flotation auxiliaries containing 1 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Aids for dewatering of solids, containing 1 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

Auxiliaries and additives

Detergents, rinsing agents, cleaning agents and agents based on the detergent mixtures according to the invention can - in addition to the surfactants already mentioned - as further auxiliaries and additives, for example builders, salts, bleaching agents, bleach activators, optical brighteners, graying inhibitors Contain solubilizers and enzymes.

Common builders are sodium aluminum silicates (zeolites), phosphates, phosphonates, ethylenediaminetetraacetic acid, nitrilotriacetate, β-alanine diacetate, citric acid and / or polycarboxylates. Suitable salts or adjusting agents are, for example, sodium sulfate, sodium carbonate or sodium silicate (water glass). Typical individual examples of other additives are sodium borate, starch, sucrose, polydextrose, TAED, stilbene compounds, methyl cellulose, toluenesulfonate, cumene sulfonate, long-chain soaps, silicones, mixed ethers, lipases and proteases.

Hair shampoos, hair lotions or foam baths can contain emulsifiers such as alkoxylated fatty alcohols or sorbitan esters as further auxiliaries and additives, in addition to the surfactants already mentioned.

Substances such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.

Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides as well as electrolytes such as table salt and ammonium chloride.

Biogenic active substances are understood to mean, for example, plant extracts and vitamin complexes. Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives and similar compounds.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentadiol or sorbic acid.

Suitable pearlizing agents are, for example, glycol distearic acid esters such as ethylene glycol distearate, but also fatty acid monoglycol esters.

The dyes which can be used are those which are approved and suitable for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes" by the Dye Mission of the German Research Foundation, published by Chem e, Weinheim, 1984, pp. 81-106 are. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.

The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight, based on the composition.

Finally, the last aspect of the invention relates to the use of the detergent mixtures according to the invention for the production of liquid or solid surface-active agents in which they are used in amounts of 1 to 99 and preferably 10 up to 90 wt .-% - based on the solids content of the agents may be included.

Examples

I. Manufacturing examples

a) Hydrolysis of wheat protein. 9000 l of water were placed in a lδ-m ^ stirred kettle and 3 kg of sodium sulfite and 30 kg of activated carbon were added at 55 to 60 ° C. 1000 kg of wheat isolate were then added and the mixture was stirred to give a 10% by weight suspension. The pH of the reaction mixture was then adjusted to 9.5 by adding calcium oxide and 5 kg of Alcalase were added. The enzymatic degradation was carried out at 60 ° C. over a period of 2 h. After the end of the enzymatic hydrolysis step, the pH of the mixture was adjusted to 4.2 by adding hydrochloric acid. The reaction mixture was then heated to 80 ° C., a further 10 kg of activated carbon and 120 kg of filter aid (Perlite ( ^R ) P50) were added and the mixture was stirred for 30 minutes. The reaction product was then filtered through a filter press and the filtrate was adjusted to a pH of 11.5 with calcium oxide. After a residence time of 30 min at 90 ° C., the solution was filtered, sodium carbonate solution was added and the calcium salts which had precipitated out were again separated off using a filter press. The filtrate was concentrated in a falling stream evaporator to a content of 41% Brix and, after a storage period of 3 days, was finally filtered until bare. b) Production of wheat protein coconut fatty acid condensate.

1000 kg of wheat protein solution from (a) were adjusted to a pH of 9.5 by adding aqueous sodium hydroxide solution. The solution was heated to 50 ° C. and a total nitrogen content of 2.7 was established by adding Ci2 / i4 coconut fatty acid chloride. The hydrochloric acid released during the condensation was collected by adding further sodium hydroxide solution. The mixture was then stirred for two hours.

II. Dermatological tolerance

The dermatological compatibility of protein fatty acid condensates of vegetable or animal origin was assessed alone and in a mixture with surfactants by two methods.

(a) The test on the chorionallantoic membrane of the incubated chicken egg (HET-CAM) represents a model for the tolerance of a substance to the mucous membrane of the eye. The cytotoxicity is determined.

(b) The neutral red method is based on the determination of changes in the ability of cells to absorb the neutral red dye after exposure to the substance to be tested. The relative stimulus potential is determined.

For the implementation of dermatological in-vitro test methods cf. F. Bartnik et al in Seifen-Öle-Fette-Wwachs, 114, 41 (1988). The measurements were carried out against a standard (Ci2 / i8 coconut oil alcohol 8EO ether sulfate Na / Mg salt) in a 5% strength by weight aqueous solution. The results are summarized in Table 1 (percentages as% by weight)

Table 1 Results of HET-CAM and neutral red test

Ex. (A) (b) c (A) c (b) HET-CAM Neutral Red%% Test Test

% -rel% -rel

1 AI 100 7 33 2 AI Bl 50 50 33 50

VI Bl 100 100 100 V2 A2 100 71 66 V3 A2 Bl 50 50 135 130

Legend: AI = wheat protein coconut fatty acid condensate A2 = collagen coconut fatty acid condensate A3 = coconut fatty alcohol 8EO ether sulfate Na / Mg salt

The examples and comparative experiments show that the vegetable protein fatty acid condensate has an improved dermatological tolerance compared to a product based on animal collagen. Mixtures of animal protein fatty acid condensate and anionic surfactant behave additively with regard to the irritation potential; when the vegetable product is used, an unexpected synergistic improvement is observed. III. Application studies

Skin cosmetic preparations were formulated with wheat protein coconut fatty acid condensate (A) or a comparative product based on animal collagen (B) and examined for their viscosity (Brookfield, 20 ° C., spindle 3, 20 rpm). The trade names are explained in Table 2, the results are summarized in Table 3 (percentages as% by weight),

Table 2 Ingredients used (*)

Designation Herst. CTFA registration

Baysilon M 350 Bayer silicone resin

Carbopol 981 Goodrich polyacrylates

Cetiol LC Henkel Coco-Caprylate / Caprate OE Dicaprylether SN Cetylisononanoat 868 Octylstearate

Cutina CBS Henkel Mono / diglycerides

Lanette 0 Henkel cetearyl alcohol

(*) The designations given are registered trademarks. Table 3 Viscosity studies

Component example or comparative example

3 V4 V5

AI 2.0 A2 2.0 3.5

Cutina ( ^R ) CBS 7.0 7.0 8.0 Lanette ^(R ) 0 2.0 Cetiol ^(R) 868 7.0 7.0 Cetiol ^(R) SN 6.5 6.5 Cetiol ( ^R ) LC 10 .0 Cetiol ^(R) OE 5.0 Baysilon ( ^R ) M 350 0.5 0.5 0.5 Glyeerin (86%) 5.0 5.0 3.0 Carbopol ( ^R ) 10.0 10.0 NaOH (1% solution) 10.0 10.0 citric acid (10%) 7.0

Water ad 100

Viscosity [mPs] 15,200 10,000 10,000

Claims

claims 1. Mild detergent mixtures containing (a) vegetable protein fatty acid condensates and (b) further anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants. 2. Detergent mixtures according to claim 1, characterized in that they contain anionic surfactants which are selected from the group consisting of alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkylethersulfonates, glycerolethersulfonates, o-methyl ester sulfonates, sulfofatty acids, alkyl sulfates , Fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulf ten, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids, fatty acids and their carbonic acids, and their salts , Fatty acid taurides, acyl acylates, acyl glutamates, acyl tartrates, alkyl oligoglucoside sulfates, and alkyl (ether) phosphates. 3. Detergent mixtures as claimed in claim 1, characterized in that they contain nonionic surfactants which are selected from the group consisting of fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated mixed triglycerides ethers, alk (en) yl oligoglycosides, fatty acid N-alkyl glucides, protein hydrolyzates, polyol fatty acid esters, Sugar esters, sorbitan esters and polysorbates are formed. 4. Detergent mixtures according to claim 1, characterized in that they contain cationic surfactants which are selected from the group consisting of quaternary ammonium compounds and ester quats, in particular quaternized difatty acid trialkanolamine ester salts. 5. Detergent mixtures according to claim 1, characterized in that they contain amphoteric or zwitterionic surfactants which are selected from the group formed by alkyl betaines, alkyl amido betaines, aminopropionates, amino glycinates, imidazolinium betaines and sulfobetaines. 6. Detergent mixtures according to claims 1 to 5, characterized in that they contain the vegetable protein fatty acids recondensates and the other surfactants in a weight ratio of 99: 1 to 1:99. 7. Powdered universal detergent containing 10 to 30% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives. 8. Liquid universal detergents containing 10 to 70% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives. 9. Liquid mild detergent containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives. 10. Hand dishwashing detergent, containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives. 11. Rinse aid, containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives. 12. Liquid detergents and disinfectants containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives. 13. Bar soaps of the combibar type, containing 1 to 2% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives. 14. Syndet soaps containing 1 to 2% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives. 15. Hair shampoos containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives. 16. Hair rinses containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives. 17. Hair colorants containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives. 18. Hair waving compositions containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives. 19. Bubble baths containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention, and also conventional auxiliaries and additives. 20. Textile and fiber auxiliaries containing 1 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives. 21. Leather greasing agent, containing 1 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives. 22. Flotation auxiliaries containing 1 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives. 23. Aids for solids drainage, containing 1 to 30% by weight, based on the agent, of the inventive appropriate detergent mixtures and customary auxiliaries and additives. 24. Use of the detergent mixtures according to claim 1 for the manufacture of surface-active agents.