WO1999006518A1

WO1999006518A1 - Thickened aqueous tenside solutions

Info

Publication number: WO1999006518A1
Application number: PCT/EP1998/004605
Authority: WO
Inventors: Hans-Christian Raths; Norman Milstein; Werner Seipel
Original assignee: Cognis Deutschland Gmbh
Priority date: 1997-07-30
Filing date: 1998-07-22
Publication date: 1999-02-11
Also published as: AU8807698A

Abstract

The invention relates to thickened aqueous tenside solutions, characterised in that they contain organic thickeners in the form of fatty acid alkylene glycols of formula (I): R1COO(AlkO)nH, wherein R<1>CO is a linear or branched, aliphatic, saturated and/or unsaturated acyl radical with 6 to 22 carbon atoms, Alk is CH2CH2, CHCH3CH2 and/or CH2CHCH3 and n is a number between 0.5 and 5.

Description

Thickened aqueous surfactant solutions

Field of the Invention

The invention relates to aqueous surfactant solutions which contain fatty acid alkylene glycols as thickeners, the use of fatty acid alkylene glycols as thickeners in aqueous surfactant solutions and processes for the production of fatty acid propylene glycols and for the production of fatty acid ethylene propylene glycols.

State of the art

Aqueous surfactant solutions, in particular those which are used in the field of personal care as hair shampoos, bubble baths, shower baths, hand wash pastes and the like, usually contain anionic surfactants, such as, for example, alkyl ether sulfates. In order to stabilize these clear or disperse systems and to improve their handling for the user, thickeners are usually added to these surfactant solutions. A large number of inorganic and organic compounds which are used to increase the viscosity of solutions containing anionic surfactants are already known to the person skilled in the art. Water-soluble electrolyte salts, usually table salt, are generally used as inorganic thickeners. Examples of organic thickeners are fatty acid alkanolamides, polyethylene glycol difatty acid esters and a number of water-soluble polymers. In most cases it is at most possible to use large amounts to adjust the desired viscosity of the surfactant solution simply by using inorganic electrolyte salts. It is therefore generally the way to use organic thickeners in addition to the inorganic salts, but some of them have a number of disadvantages. Thus, the surfactant solutions thickened with polyethylene glycol fatty acid diester often have inadequate viscosity stability during storage, while water-soluble polymers have an undesirable slimy flow behavior with a tendency to string in the thickened surfactant solutions. In the German patent applications DE-A 3730179 and DE-A 3817415 it is therefore proposed to use adducts of ethylene oxide and / or propylene oxide, possibly with a restricted homolog distribution, with saturated and / or unsaturated fatty alcohols to thicken surfactant solutions. These products no longer have the above disadvantages. However, there is a need for further organic thickeners with an increased thickening effect, which in particular make it possible to use low levels of organic and inorganic thickeners for a given viscosity of the surfactant solution to be set.

Description of the invention

The present invention therefore relates to thickened aqueous surfactant solutions which are characterized in that they are fatty acid alkylene glycols of the formula (I) as organic thickeners,

RiCOO (AlkO) _n H (I)

in which R ¹ CO represents a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, Alk represents CH2CH2, CHCH3CH2 and / or CH2CHCH3 and n represents numbers from 0.5 to 5.

It has now surprisingly been found that fatty acid alkylene glycols have excellent thickening properties and are free from the disadvantages described at the outset. In the context of the present application, the term “thickened” is to be understood such that the thickened surfactant solutions have at least one viscosity which is at least 5 times, preferably 10 times, higher than the non-thickened surfactant solutions. The terms “thickener” and “thickener” are also used "used synonymously.

Fatty acid alkylene glycols

The fatty acid alkylene glycols are addition products of ethylene oxide or of ethylene oxide and propylene oxide onto fatty acids of the formula R COOH, in which R ¹ CO is as defined above. Typical examples are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, and technical mixtures which are obtained, for example, in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or as a monomer fraction in the dimerization of unsaturated fatty acids. Technical fatty acids with 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty acids, are preferred. Particularly preferred are ethoxylated or ethoxylated and propoxylated fatty acids which have n numbers between 1 and 2 as the degree of alkoxylation. It can it is exclusively propoxylated or ethoxylated and propoxylated fatty acids, and the mixed alkoxylated can be either random or block compounds.

method

The ethoxylated and / or propoxylated fatty acids, which are also referred to as fatty acid alkylene glycols, are known compounds. They can be prepared, for example, in accordance with German Offenlegungsschrift DE-A-2024050 by reacting carboxylic acids with alkylene oxides in the presence of armines as catalysts. According to this process, however, the low alkoxylated compounds are obtained in yields well below 90% of theory. According to this process, the ethoxylation is carried out in the presence of alkanolamines as catalyst and gives significantly higher yields. For the exclusively propoxylated fatty acids and for the ethoxylated and propoxylated fatty acids, however, no process is known which, in particular for the low-propoxylated and ethoxylated / propoxylated fatty acids, gives good yields of over 90% of theory. In the context of the present invention it was found that this can be achieved if the propoxylation or propoxylation / ethoxylation of the fatty acids is carried out in the presence of alkanolamines. Another object of the present invention therefore relates to a process for the preparation of fatty acid propylene glycols of the formula (II),

RiCOO (PO) "H (II)

in which R ¹ CO is as defined in formula (I), PO stands for CHCH3CH2 and / or CH2CHCH3 and n stands for numbers from 0.5 to 5 and fatty acid ethylene propylene glycols of the formula (III),

RiCOO (EO) χ (PO) y (EO) _z H (III)

in which R ¹ CO is as defined in formula (I), EO is CH2CH2, PO is CHCH3CH2 and / or CH2CHCH3 and x = 0-5, y = 0.1-5 and z = 0-5, the sum of x and z is greater than 0 and the sum of x, y and z is in the range from 0.5 to 5, by propoxylation or propoxylation / ethoxylation of fatty acids, which is characterized in that the propoxylation or ethoxylation / propoxylation reaction in the presence of alkanolamines as catalysts.

Typical examples of alkanolamines which can be used as basic catalysts are monoethanolamine, diethanolamine and preferably triethanolamine. The alkanolamines are usually used in amounts of 0.1 to 5, preferably 0.5 to 3.0,% by weight, based on the fatty acids. The propoxylation and / or ethoxylation propoxylation reaction can be carried out in a manner known per se be performed. The fatty acid and the catalyst are usually placed in a stirred autoclave, which is freed of traces of water by alternating evacuation and nitrogen flushing before the reaction. The fatty acid is then reacted with the propylene oxide or with the ethylene oxide / propylene oxide mixture in a molar ratio of 1: 0.5 to 1: 1.5, which can be metered into portions of the pressure vessel after heating by means of a siphon. The fatty acids are preferably reacted with one mole to 2 moles of propylene oxide or with one to 2 moles of the ethylene oxide / propylene oxide mixture. The reaction can be carried out at temperatures in the range from 80 to 180 ° C., preferably 100 to 120 ° C. and autogenous pressures in the range from 1 to 5, preferably 2 to 3 bar. After the end of the reaction, it is advisable to stir at the reaction temperature for a certain time to complete the conversion (15 to 90 min). The autoclave is then cooled, decompressed and, if desired, acids such as lactic acid or phosphoric acid are added to the product in order to neutralize the basic catalyst.

Surfactant solutions

The fatty acid alkylene glycols of the type described are usually present in the thickened aqueous surfactant solutions according to the invention in amounts of 0.2 to 5% by weight, based on the surfactant solution. Furthermore, the surfactant solutions also contain 3 to 30% by weight of ionic surfactants and optionally up to 10% by weight of water-soluble inorganic and / or organic electrolyte salts. The rest of 100% by weight of the surfactant solution is water.

Anionic, zwitterionic and cationic surfactants can be present as ionic surfactants. Suitable ionic surfactants are distinguished by a lipophilic, preferably linear alkyl or alkylene group having 8 to 18 carbon atoms and a ionic group, preferably terminally bonded to it, dissociating in water. The anionic group can be, for example, a sulfate, sulfonate, phosphate or carboxylate group, the cationic group can be, for example, a quaternary ammonium group. Typical examples of anionic surfactants are soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates,

Sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, Glycerol ether, Hydroxymischethersulfate, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N Acylamino acids, such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) 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 cationic surfactants are quaternary ammonium compounds and ester quats, especially quaternized fatty acids retrialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example 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. Alkyl sulfates, fatty alcohol ether sulfates, alkane sulfonates and / or ether carboxylic acids, in particular fatty alcohol ether sulfates, are preferably present as anionic surfactants.

Suitable inorganic electrolyte salts are all water-soluble alkali, ammonium and / or alkaline earth metal salts such as fluorides, chlorides, bromides, sulfates, phosphates and nitrates, provided that they are soluble in water at 20 ° C in an amount of at least 1% by weight. The chlorides or sulfates of an alkali metal, ammonium or magnesium are preferably used. Sodium chloride (table salt) and magnesium chloride are particularly preferred. All water-soluble alkali, ammonium and alkaline earth salts of mono-, di- and tricarboxylic acids are particularly suitable as organic electrolyte salts. Preference is given to carboxylic acids which have a molar mass of less than 200 g / mol.

Industrial applicability

The increase in viscosity of aqueous solutions of the type described with a comparatively low content of organic thickeners and of inorganic thickening electrolyte salts is of particularly high technical interest. By using the fatty acid alkylene glycols described, the thickening effect of the inorganic electrolyte salts is increased in a synergistic manner, so that the amount of inorganic electrolyte salts used can be reduced for a given viscosity setting. Another object of the present invention therefore relates to the use of the fatty acid alkylene glycols of the formula (I) as organic thickeners for aqueous surfactant solutions.

Auxiliaries and additives

The thickened surfactant solutions of the invention, such as, for example, hair shampoos, hair lotions, foam baths, creams, lotions or ointments, can furthermore contain oil bodies, emulsifiers, superfatting agents, pearlescent waxes, stabilizers, consistency enhancers, thickening agents, polymers, silicone compounds, biogenic active substances, antidandruff agents as further auxiliaries and additives Film maker Preservatives, hydrotropes, solubilizers, UV light protection filters, insect repellents, self-tanners, perfume oils, dyes and the like contain.

Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C6-C22 fatty acids with linear C6-C22 fatty alcohols, esters of branched C6-Ci3-carboxylic acids with linear C6-C ₂ come as oil bodies, for example 2-fatty alcohols, esters of linear C6-C22 fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimerediol or trimer triol) and / or Guerbet alcohols, triglycerides Basis C6-Cιo fatty acids, liquid mono- / di-triglyceride mixtures based on Cβ-Cis fatty acids, esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C2-Ci2-dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary Alcohols, substituted cyclohexanes, linear C6-C22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C6-C22 alcohols (e.g. Finsolv® TN), dialkyl ethers, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons.

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

(1) adducts of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group;

(2) C-i2 / i8 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;

(3) glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;

(4) alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs;

(5) adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;

(6) polyol and especially polyglycerol esters such as e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate. Mixtures of compounds from several of these classes of substances are also suitable;

(7) adducts of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;

(8) partial esters based on linear, branched, unsaturated or saturated C6 / 22 fatty acids, ricinoleic acid as well as 12-hydroxystearic acid and glycerin, polyglycerin, pentaerythritol, dipenta- erythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (eg cellulose);

(9) mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;

(10) wool wax alcohols;

(11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

(12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol and

(13) Polyalkylene glycols.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are mixtures of homologs, the middle of which Degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. Ci2 / i8 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 20 24 051 as refatting agents for cosmetic preparations.

C & 7i8 alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylamino propyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxyl -3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a Cs / iβ-alkyl or -acyl group, have at least one free amino group in the molecule and at least one -COOH- or -SO3H- Contain group and are able to form internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each have about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and Ci2 / ιβ-acylsarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

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

Pearlescent waxes, for example, are: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

Mainly fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides come into consideration as consistency agents. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred. 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 (eg Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylic amides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylol propane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides as well as electrolytes such as sodium chloride and ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is obtained from Amerchol under the name Polymer JR 400®. is, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinyl pyrrolidone / vinyl imidazole polymers, such as Luviquat® (BASF), condensation products of polyglycols and amines, quaternized colagen polypeptides such as lauryldimonium hydroxypropyl hydrolyzed collagen ( ®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merviron), poly 550, described for example in FR-A 2252840 and its crosslinked water-soluble polymers, cationic chitin derivatives such as, for example, quaternized chitosan, optionally microcrystalline, condensation products of dihaloalkylene, such as dibromobutane with bisdialkylamines, such as bis-dimethylamino-1,3-propane, cationic guar Gu m, such as Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers such as Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol .

Anionic, zwitterionic, amphoteric and nonionic polymers include, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleateV isobomylacrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, polyols, acrylamide and non-crosslinked acrylamide and acrylamide vinyl chloride Acrylate copolymers, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / vinylcaprolactam terpolymer and optionally derivatized cellulose ether.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds, which can be both liquid and resinous at room temperature. Typical examples of fats are glycerides, beeswax, camamauba wax, candelilla wax, montan wax, paraffin wax or microwaxes, if appropriate in combination with hydrophilic waxes, for example cetylstearyl alcohol or partial glycerides. Metal salts of fatty acids such as magnesium, aluminum and / or zinc stearate can be used as stabilizers. Biogenic active substances are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamins. Climbazole, octopirox and zinc pyrethione can be used as antidandruff agents. 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, collagen, hyaluronic acid or their salts and similar compounds. Montmorillonites, clay minerals, pemulene and alkyl-modified carbopol types (Goodrich) can serve as swelling agents for aqueous phases.

UV light protection filters are organic substances which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, e.g. To give off heat again. UVB filters can be oil-soluble or water-soluble. As oil-soluble substances e.g. to call:

3-benzylidene camphor and its derivatives, e.g. 3- (4-methylbenzylidene) camphor;

4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;

• esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, isopentyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3-phenylcinnamate (octocrylene);

• esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomethyl salicylic acid;

• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;

• Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate;

Triazine derivatives, e.g. 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine and octyltriazone.

Propane-1,3-dione, e.g. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione;

Possible water-soluble substances are:

• 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;

• Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;

Sulfonic acid derivatives of 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione or 1-phenyl-3-, are particularly suitable as typical UV-A filters. (4'-isopropylphenyl) propane-1,3-dione. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble pigments, namely finely dispersed metal oxides or salts, such as, for example, titanium dioxide, zinc oxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc), barium sulfate and zinc stearate are also suitable for this purpose. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape have, however, it is also possible to use those particles which have an ellipsoidal shape or shape which differs in some other way from the spherical shape. In addition to the two aforementioned groups of primary light stabilizers, secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples are superoxide dismutase, tocopherols (vitamin E) and ascorbic acid (vitamin C). Further suitable UV light protection filters can be found in the overview by P.Finkel in SÖFW-Journal 122, 543 (1996).

Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior. Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. Typical examples are

• glycerin;

Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;

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;

• Lower alkyl glucosides, in particular those with 1 to 8 carbons in the alkyl radical, such as 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.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid. N, N-diethyl-m-touluamide, 1, 2-pentanediol or Insect repellent 3535 are suitable as insect repellents, and dihydroxyacetone is suitable as a self-tanner.

Perfume oils include mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, mountain pine), resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, such as civet and castoreum, are also suitable. Typical synthetic Fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propylate pylate allylpropionate, The ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, oc-isomethylionone and methyl cedryl ketone , the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balsams. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Essential oils of lower volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Bergamot oil, dihydro myrcenol, lilial, lyral, citronellol, phenylethyl alcohol, oc-hexyl cinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin oil, allyl oil oil, orangol oil, orangol oil, orangol oil, are preferred , Muscatel sage oil, ß-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramate alone or in mixtures, used.

The dyes which can be used are those substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes" by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106. 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. The agents can be produced by customary cold or hot processes; the phase inversion temperature method is preferably used.

Examples

Example 1. 200 g (1 mol) of technical lauric acid were placed in a 1 liter stirred autoclave and 6 g of triethanolamine (corresponding to 3% by weight based on lauric acid) were added. The autoclave was alternately evacuated and pressurized with nitrogen three times to remove traces of water that could lead to the formation of polyethylene glycol. After the reaction mixture had been charged with nitrogen for the last time, the autoclave was closed and heated to 100 ° C. and 44 g (1 mol) of propylene oxide were added in portions at a maximum pressure of 5 bar. After completion of the reaction, recognizable by the fact that the pressure dropped again to a value of 1.2 bar and then remained constant, stirring was continued for 30 minutes and the reaction mixture was then cooled and let down. The basic catalyst was neutralized by adding an appropriate amount of lactic acid. The characteristics of the lauric acid + 1PO adduct are (quantities as% by weight):

Free fatty acid 6.1

Fatty acid + 1 PO 90.0

Fatty acid + 2PO 1.8

Diester 2.1

Application example for thickenability. A 10% by weight aqueous solution of sodium laureth sulfate was mixed with 2% by weight of the lauric acid propoxylate prepared according to Example 1 with stirring and thickened by adding 1.25% by weight sodium chloride. A viscosity (Brookfield, spindle 1, room temperature, 20 rpm) of 8140 mPas was established. Even after storing the sample for 4 weeks at 40 ° C, the viscosity remained constant. For comparison, the same fatty alcohol sulfate solution as in the application example was mixed with 3% by weight of the nonionic thickener Laureth-2 and thickened with 1.5% by weight sodium chloride. A viscosity of 8500 mPas was established. The comparative example shows that, with the viscosity to be set approximately the same, smaller amounts of the organic thickener according to the invention (lauric acid + 1 PO) and of thickening sodium chloride are used.

Claims

claims

1. Thickened aqueous surfactant solutions, characterized in that they contain fatty acid alkylene glycols of the formula (I) as organic thickeners,

RiCOO (AlkO) "H (I)

2. Thickened aqueous surfactant solutions according to claim 1, characterized in that they contain fatty acid alkylene glycols of the formula (I) as organic thickeners, in which n stands for numbers between 1 and 2.

3. Thickened aqueous surfactant solutions according to claim 1 or 2, characterized in that they contain, as organic thickeners, fatty acid alkylene glycols of the formula (I) in which R ¹ CO represents an acyl radical having 12 to 18 carbon atoms.

4. Thickened aqueous surfactant solutions according to one of claims 1 to 3, characterized in that they contain the fatty acid alkylene glycols of the formula (I) as organic thickeners in amounts of 0.2 to 5% by weight, based on the surfactant solution.

5. Thickened aqueous surfactant solutions according to one of claims 1 to 4, characterized in that the surfactant solutions contain 3 to 30% by weight of ionic surfactants and 0 to 10% by weight of water-soluble inorganic and / or organic electrolyte salts, based on the surfactant solution.

6. Thickened aqueous surfactant solutions according to claim 5, characterized in that contain alkyl sulfates, fatty alcohol ether sulfates, alkane sulfonates and / or ether carboxylic acids as ionic surfactants.

7. Use of fatty acid alkylene glycols of the formula (I) with the meanings given in claim 1 as organic thickeners for aqueous surfactant solutions.

. Process for the preparation of fatty acid propylene glycols of the formula (II),

R ¹ COO (EO) χ (PO) y (EO) _z H (III)

in which R ¹ CO is as defined in formula (I), EO is CH2CH2, PO is CHCH3CH2 and / or CH2CHCH3 and x = 0-5, y = 0.1-5 and z = 0-5, the sum of x and z greater than 0 and the sum of x, y and z is in the range from 0.5 to 5, by propoxylation or propoxylation / ethoxylation of fatty acids, characterized in that the propoxylation or ethoxylation / propoxylation reaction in the presence of alkanolamines as Performs catalysts.

9. The method according to claim 8, characterized in that the fatty acids are reacted with 1 to 2 moles of propylene oxide or with 1 to 2 moles of a mixture of ethylene oxide and propylene oxide.

10. The method according to any one of claims 8 or 9, characterized in that the alkanolamines in amounts of 0.1 to 5 wt.% - Based on the fatty acids - used.