WO2001010999A1

WO2001010999A1 - Soap bars

Info

Publication number: WO2001010999A1
Application number: PCT/EP2000/007332
Authority: WO
Inventors: Hermann Hensen; Anke Eggers; Werner Seipel
Original assignee: Cognis Deutschland Gmbh
Priority date: 1999-08-06
Filing date: 2000-07-28
Publication date: 2001-02-15
Also published as: DE19937296A1

Abstract

Disclosed are novel soap bars containing: (a) between 1 and 60 % by weight of alkylated carboxylic acid ester; (b) 10 to 60 % by weight of fatty acid salts; (c) 0 to 40 % by weight of anionic, non-ionic or amphoteric co surfactants; (d) 0 to 10 % by weight of fatty acids and (e) 0 to 40 % by weight of water-soluble structurants, with the proviso that optionally water and normal additives and adjuvants can be added to said proportions to complete the quantities of 100 % by weight.

Description

bar soaps

Field of the Invention

The invention relates to new bar soaps which contain alkoxylated carboxylic acid esters and fatty acid salts as essential components.

State of the art

Modern bar soaps, especially toilet or fine soaps, are usually based on mixtures of beef tallow and coconut oil in a ratio of about 9: 1. This fat deposit is hydrolyzed by adding sodium hydroxide solution to the basic soap, which contains other additives such as. B. humectants, fillers and binders, superfatting agents, dyes and perfumes etc. are added. Usual fine soaps contain about 80% fatty acid salts, 10% water and ad 100% auxiliaries and additives. The large number of products offered to the consumer document the lively market interest and nevertheless make it clear that there is a constant need for consumers to further improve products, which are characterized in particular by improved dermatological compatibility, increased foaming capacity, higher creaminess, regreasing, rinsing ability , Skin feel and the like. Soap manufacturers, on the other hand, are looking for soap formulations which, for example, lead to pieces with higher breaking strength or allow the problem-free incorporation of certain surfactants, such as alkyl sulfates. An overview of this topic can be found, for example, in J.Am. Oil.Chem.Soc. 59: 442 (1982).

With regard to the production of bar soaps, a very large number of processes from the prior art can of course be looked back on. A distinction must essentially be made here between synthetic, "soap-free" soaps, so-called syndets, and in particular combinations of fatty acid salts and synthetic surfactants ("combibars"). To produce combi bars, it is proposed, for example, in EP-A 0176330 (Unilever) to combine fatty acid soaps with salts of isethionic acid. From the documents EP-A 0189332, EP-A 0472320 and EP-A 0508006 (Unilever) the use of fatty acid isethionates as a synthetic component of combibars is known. However, there is a constant need in the market for products with improved properties. In particular, bar soaps are desired which produce a more productive and creamy foam than the products of the prior art and which also have improved dermatological compatibility. The soaps should continue to impart an improved skin feel and have a lower tendency to swell and crack. The object of the present invention was therefore to provide bar soaps of the complex requirement profile described.

Description of the invention

The invention relates to bar soaps containing

(a) 1 to 60, preferably 5 to 15% by weight alkoxyated carboxylic acid esters,

(b) 10 to 60, preferably 20 to 50% by weight of fatty acid salts,

(c) 0 to 40, preferably 1 to 30% by weight of anionic, nonionic or amphoteric cosurfactants,

(d) 0 to 10, preferably 3 to 10% by weight of fatty acids and

(e) 0 to 40, preferably 1 to 30% by weight of water-soluble structuring agents,

with the proviso that the amounts given add up to 100% by weight with water and other conventional auxiliaries and additives.

Surprisingly, it was found that the bar soaps according to the invention not only produce a particularly stable and creamy foam, but also have improved dermatological compatibility, increased water retention on the skin (skin moisture) and a reduced tendency to swamp. The invention includes the knowledge that the combination of the alkoxyated carboxylic acid esters with other surfactants, in particular of the alkyl and / or alkenyl oligoglycoside type, fatty acid N-alkylpolyhydroxyalkylamides, monoglyceride (etfιer) sulfates, olefin suifonates, betaines and fatty acid polyglycol ester sulfates or mixtures thereof with bar soaps lead to further improved properties.

Alkoxyated carboxylic acid esters

Alkoxyated carboxylic acid esters which form component (a) are known from the prior art. For example, such alkoxyated carboxylic acid esters can be obtained by reacting alkoxylated carboxylic acids with alcohols. For the purposes of the present invention, however, the compounds are preferred by reacting carboxylic acid esters with alkylene oxides using tion of catalysts, in particular using calcined hydrotalcite according to German Offenlegungsschπft DE 3914131 A, which provide compounds with a restricted homolog distribution. According to this process, both carboxylic acid esters of monohydric alcohols and polyhydric alcohols can be alkoxylated. Alkoxylated carboxylic acid esters of the formula (I) are preferably used in accordance with the present invention,

in which R ¹ CO stands for an aliphatic acyl radical with 6 to 30 C atoms, AlkO for alkylene oxide, n for numbers from 1 to 30 and R ² for an aliphatic alkyl radical with 1 to 8 carbon atoms. AlkO stands for the alkylene oxides which correspond to the Carboxylic acid esters are reacted and include ethylene oxide, propylene oxide and / or butylene oxide, preferably ethylene oxide and / or propylene oxide, in particular ethylene oxide alone.

Particularly suitable are alkoxyated carboxylic acid esters of the formula (I) in which R ¹ CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and in particular 10 to 18 carbon atoms, AlkO for ethylene oxide and / or propylene oxide, n on average for numbers 5 to 20 and R ^{2 is} an aliphatic alkyl radical having 1 to 8, preferably 1 to 4 carbon atoms and in particular methyl

Preferred acyl radicals are derived from carboxylic acids with 6 to 22 carbon atoms of natural or synthetic origin, in particular from linear, saturated and / or unsaturated fatty acids, including technical mixtures thereof, as are obtainable by fat cleavage from deep and / or vegetable fats and oils, for example from coconut oil, palm kernel oil, palmol, soybean oil, sunflower oil, rubola, cotton seed oil, fish oil, beef tallow and lard , Elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and / or erucic acid

Particularly suitable are alkoxyated carboxylic acid esters of the formula (I) in which R ¹ CO is a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 10 to 18 carbon atoms, AlkO for ethylene oxide and / or propylene oxide, preferably ethylene oxide, n for numbers from 5 to 20 and R ^{2 represents} a methyl radical. Examples of such compounds are methyl acetate, alkoxylated with 5, 7, 9 or 11 mol ethylene oxide, methyl coconut fatty acid and tallow fatty acid methyl ester fatty acid salts

The fatty acid salts which form component (b) are the alkali metal salts of fatty acids having 6 to 22 and preferably 12 to 18 carbon atoms. Typical examples are the sodium or potassium salts of lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and their technical mixtures such as coconut fatty acid, palm kernel fatty acid, palm fatty acid and tallow fatty acid.

Alkyl and / or alkenyl olefin glycosides

Alkyl and alkenyl oligoglycosides, which may be included as optional surfactant component (d), are known nonionic surfactants which follow the formula (II),

R ³ 0- [G] _P (II)

in which R ^{3 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1 0301298 and WO 90/03977. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ³ 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 are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of the chain length Cβ-Cio (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical Cβ-Ciβ-coconut fatty alcohol by distillation and can be contaminated with a proportion of less than 6% by weight of C ₂ alcohol and alkyl oligoglucosides based on technical Cg / n oxo alcohols (DP = 1 to 3). The Alkyl or alkenyl radical R ³ 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, palmoley alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoieyl alcohol, behenyial alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as well as their technical mixtures. Alkyl oligoglucosides based on hydrogenated Ci2 / i4 coconut alcohol with a DP of 1 to 3 are preferred.

Fatty acid N-alkyl polyhydroxyalkylamides

Fatty acid N-alkylpolyhydroxyalkylamides, which may also be included as optional surfactant component (c2), are nonionic surfactants which follow the formula (III),

R ⁴

I

R ⁵ CO-N- [Z] (III)

in which R ⁵ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{4 is} 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. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their production, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO 92/06984. An overview of this topic by H.Kelkenberg can be found in Tens.Surf.Deterg. 25, 8 (1988). The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkyl polyhydroxyalkylamides are therefore fatty acid N-alkylglucamides, as represented by the formula (IV):

R ⁴ OH OH OH

I I I I

R ⁵ CO-N-CH ₂ -CH-CH-CH-CH-CH ₂ OH (IV)

I

OH

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (IV) in which R ^{5 represents} methyl group and R ³ CO represents the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid . Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or Ci2 i4 coconut fatty acid or a corresponding derivative are particularly preferred. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

Monoqlycerid (ether) sulfates

Monoglyceride sulfates and monoglyceride ether sulfates, which may be included as further anionic surfactants (component c3), are known substances which can be obtained by the relevant methods of preparative organic chemistry. The usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP-B1 0561825, EP-B1 0561999 (Henkel)]. If desired, the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE-A1 4204700 (Henkel)]. Overviews on the chemistry of monoglyceride sulfates are available, for example, from A.K. Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) and F.U. Ahmed J.Am.Oil. Soc. 67, 8 (1990). The monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula (V),

in which R ⁶ CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monogiyceride as well as their ethylene oxide adducts or their form of sulfuric acid with sulfuric acid trioxide. Monoglyceride sulfates of the formula (V) are preferably used, in which R ⁶ CO represents a linear acyl radical having 8 to 18 carbon atoms. The monoglyceride (ether) sulfates are preferably used as dry granules or powders, which can be obtained, for example, by drying aqueous pastes in a flash dryer. olefin

The stucco soaps according to the invention contain, as further anionic surfactants, olefin sulfonates (component c4) which are usually obtained by addition of SO3 onto olefins of the formula (VI),

where R ⁷ and R ⁸ independently of one another represent H or alkyl radicals having 1 to 20 carbon atoms, with the proviso that R ⁷ and R ⁸ together have at least 6 and preferably 10 to 16 carbon atoms With regard to preparation and use, reference is made to the review article J.Am .Oil. Soc. 55, 70 (1978)

Internal olefin sulfonates, but preferably α-olefin sulfonates, can be used, which result when R ⁷ or R ^{8 are} hydrogen. Typical examples of olefin sulfonates used are the sulfonation products which are obtained by treating SO3 with 1, 2-butene, 1 -, 2-, 3-hexene, 1-, 2-, 3-, 4-octene, 1-, 2-, 3-, 4-, 5-decene, 1-, 2-, 3-, 4-, 5-, 6- dodecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-tetradecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-hexadecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-octadecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-Eιcosen and 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 11-Docosen implemented. After sulfonation has taken place, neutralization is carried out, after which the olefin sulfonate is present in the mixture as an alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium, glucammonium, preferably sodium salt. Both olefin sulfonates in water-based paste, preferably at a pH of 7 to 10, and also as anhydrous products, preferably as granules, can be used, as can be obtained by conventional spray drying, drying in a thin layer ("flash dryer") DE 19710152 C1 (Henkel) or in a fluidized bed dryer ("sket system")

Betaine

Betaines, which can also be used as representatives of the amphoteric or zwitterionic surfactants, are known substances which are predominantly prepared by carboxyalkylation, preferably carboxymethylation, of amine compounds. The starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, where One mole of salt is formed per mole of betaine. The addition of unsaturated carboxylic acids, such as acrylic acid, is also possible. For the nomenclature and in particular to distinguish betaine and "real" amphoteric surfactants, see U.PIoog's contribution in soap-oil-fat-waxes , 198, 373 (1982). Further overviews on this subject can be found, for example, by A O'Lennick et al in HAPPI, Nov. 70 (1986), S Holzman et al in Tens. Surf.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 (component c5) are the carboxyalkylene products of secondary and in particular tertiary amines which follow the formula (VII),

I

R ³ -N- (CH ₂ ) _q COOX (VII)

I

R

in which R ⁹ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ¹⁰ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ¹¹ for alkyl radicals with 1 to 4 carbon atoms, q for numbers from 1 to 6 and X for a alkali and / or alkaline earth metal or ammonium Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, Removal cyldimethylamin, dodecylmethylamine dodecyldimethylamine Dodecylethylmethylamin, Ci2 _/ i4-Kokosal- kyldimethylamin, Myπstyldimethylamin, cetyldimethylamine, Stearyldimethylamm, Stearyiethyl-methyl-amine, Oleyldimethylamine Ci6 / 18-tallow alkyl dimethyl amine and their technical mixtures. Carboxyalkylation products of amidoamines which follow the formula (VIII) are also suitable,

I

R «CO-NH. (CH2) mN- (CH ₂ ) qCOOX (VIII)

I R "

in which R ¹² CO 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 R ¹⁰ , R ¹¹ , q and X have the meanings given above. Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, including caproic, caprylic acid, Capπnsaure, Lauπnsaure, Mynstinsaure, palmitic acid, Palmoleinsaure, Steannsaure, Isosteannsaure, oleic acid, Elaidiπsaure, petroselinic acid, linoleic acid, linolenic acid, Elaeosteaπnsaure, arachic acid, Gadolemsaure, behenic acid and erucic acid and technical mixtures thereof, with N, N-Dιmethylamιnoethylamιn, N, N-Dιmethylamιnopropylamιn, N, N-diethylaminoethylamine and NN-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of Cβ-coconut fatty acid-N-dimethyl-chloropropylamide

Fettsaurepolyqlvcoiestersulfate

The soaps according to the invention can contain fatty acid polyglycol ester sulfates (component c6) of the formula (IX) as further surfactants,

in which R ¹³ CO represents a linear or branched saturated or unsaturated acyl radical having 6 to 22 carbon atoms, w represents an average of 1 to 3 and AO represents a CH2CH2O-, CH ₂ CH (CH ₃ ) 0- and / or CH ( CH ₃ ) CH ₂ 0 radical and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, are known anionic surfactants and are prepared by sulfation of the corresponding fatty acid polyglycol esters. These in turn are according to the relevant preparative methods of Organic chemistry available For this purpose, ethylene oxide, propylene oxide or its mixture - in random or block distribution - is added to the corresponding fatty acids, this reaction being acid-catalyzed, but preferably in the presence of bases such as, for example, sodium methylate or calcined hydrotalcite. A degree of alkoxylation of 1 is desired , the intermediates can also be obtained by esterifying the fatty acids with a The alkylene glycol can be prepared. The sulfation of the fatty acid polyglycol esters can be carried out in a manner known per se with chlorosulfonic acid or preferably gaseous sulfuric oxide, the molar ratio between fatty acid polyglycol ester and sulfating agent in the range from 1 0.95 to 1 1, 2, preferably 1 1 to 1 1 , 1 and the reaction temperature can be 30 to 80 and preferably 50 to 60 ° C. It is also possible to undersulfate the fatty acid polyglycol esters, ie to use significantly less sulfating agents than would be stoichiometrically required for complete conversion. For example, if molar amounts of fatty acid polyglycol ester are selected Sulfating agents from 1 0.5 to 1 0.95 are obtained mixtures of fatty acid polyglycol ester sulfates and fatty acid polyglycol esters, which are also advantageous for a whole range of applications. In order to avoid hydrolysis, it is very important to use the neutralizers tion at a pH in the range from 5 to 9, preferably 7 to 8. Typical examples of suitable starting materials are the addition products of 1 to 3 moles of ethylene oxide and / or propylene oxide, but preferably the adducts with 1 mole of ethylene oxide or 1 mole of propylene oxide Capronic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotπdecansaure, myristic acid, palmitic acid, palmoleic acid, stearic acid, isosteanic acid, oleic acid, elaidic acid, petroselamic acid, linoleic acid, linoleic acid, acidic acid, mixtures, arenate acid, eric acid, acidic acid, mixtures of arenic acid, eric acid, acidic acid, mixtures of arenic acid, acidic acid, mixtures of arenic acid, acidic acid, acidic acid, acidic acid, acidic acid, acidic acid, acidic acid, acidic acid, organic acid which are then sulfated and neutralized as described above. Fatty acid polyglycol ester sulfates of the formula (IX) are preferably used in which R ¹³ CO for an acyl radical having 12 to 18 carbon atoms, w for an average of 1 or 2, AO for a CH2CH2θ group and X. stands for sodium or ammonium, such as, for example, lauric acid + 1 EO sulfate Na tπumsalz, Lauπnsaure + 1 EO sulfate ammonium salt, coconut fatty acid + 1 EO sulfate sodium salt, coconut fatty acid + 1 EO sulfate ammonium acid, tallow fatty acid + -1 EO sulfate sodium salt, tallow fatty acid + 1 EO sulfate sulfate as well as their mixtures fatty acids

Fatty acids which form optional component (d) are to be understood as aliphatic carboxylic acids of the formula (X)

R ¹ CO-OH (X)

in which R ¹ CO represents an aliphatic, linear or branched acyl radical having 6 to 22, preferably 12 to 18 carbon atoms and 0 and / or 1, 2 or 3 double bonds. 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, ginoleic acid and arachic acid, arachic acid, arachic acid Technical mixtures that occur, for example, in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids. Technical fatty acids with 12 to 18 carbon atoms, for example coconut, palm, palm kernel or tallow fatty acids, which correspond to the corresponding salts of component (b), are preferred.

Other auxiliaries and additives

The bar soaps can have water-soluble structurants as builders, such as starch, preferably untreated, partially hydrolyzed or acid-degraded wheat or corn starch or cellulose. As builders, they can also contain finely divided, water-insoluble alkali metal silicon silicates, the use of synthetic, bound water-containing crystalline sodium aluminum silicates, and in particular zeolite A, being particularly preferred here; Zeolite NaX and its mixtures with zeolite NaA can also be used. Suitable zeolites have a calcium binding capacity in the range from 100 to 200 mg CaO / g. NTA and / or EDTA can also be used as liquid builders. Suitable plasticizers are fatty alcohols, fatty acid partial glycerides or wax esters with 12 to 22 carbon atoms in each of the fat residues. Examples of suitable emulators are nonionic surfactants from at least one of the following groups:

> 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, with alkylphenols with 8 to 15 carbon atoms in the alkyl group and Alkylamines with 8 to 22 carbon atoms in the alkyl radical;

> Alkyl and / or alkenyl oligoglycosides with 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs; Anlaguπgsprodukte of 1 to 15 moles of ethylene oxide to castor oil and / or hardened castor oil;

> Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;

> Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;

> Partial esters of polyglycerin (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides with (e.g. / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;

> Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 1165574 PS and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.

> Mono-, di- and trialkylphosphates as well as mono-, di- and / or tri-PEG-alkylphosphates and their salts;

> Wool wax alcohols;

> Polysiioxane-polyalkyl-polyether copolymers or corresponding derivatives;

> Polyalkylene glycols as well

> Glycerine carbonate.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs whose average degree of alkoxylation is 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 2024051 PS as refatting agents for cosmetic preparations.

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 Lauroπ 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. Possible consistency agents are primarily fatty alcohols or hydroxyfatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycides, fatty acids or hydroxy fatty acids. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycine poly-12-hydroxystearates

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available under the name Polymer JR 400® from Amerchol, cationic starches, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as BASF Luviqu ), Condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®IJGrunau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as amidomethicones, copolymers of adipiethetic acid hydroxide and dimethylethylaxine (p / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemvιron), polyaminopolyamides, such as described in FR 2252840 A, and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chit osan, optionally microcrystalline, condensation products from dihaloalkyien, such as dibromobutane with bisdialkylamines, such as Bιs-Dιmethylamιno-1, 3-propane, cationic guar gum, 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 maleate / isobornylacrylate copolymers, methyl vinyl ether / malemic acid anhydride polymers and acrylamides and polyamides, polyamides, and polyamides, polyamides, and polyamides, polyamides, and polyamides, polyamides, and polyamides, polyamides, and polyamides, polyamides, and polyamides, u-amyl acrylate copolymers, πd / acrylate copolymers, octylacrylamιd / methyl methacrylate / tert-butylamιπo-ethyl methacrylate / 2-hydroxy-proyl-methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vmylpyrrolidone / dimethylaminoethylmethacrylate / optionally de-methylaminoethyl-methacrylate / de-methylated-methyl-methacrylate / de-methylated methacrylate / optionally in question

Suitable silicone compounds are, for example, dimethylpoysiloxanes, methylphenylpolysiloxanes, cyc cal silicones and ammo-, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds, which can be both liquid and resinous at room temperature Simethicones, which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable. A detailed overview of suitable volatile silicones can also be found by Todd et al in Cosm.Toil. 91, 27 (1976). Typical examples of fats are glycerides, natural waxes such as candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, walnut, lanolin (wool wax), burgundy fat , Ceresin, ozokerite (earth wax), petrolatum, paraffin waxes, micro waxes; chemically modified waxes (hard waxes), such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes, and synthetic waxes, such as polyalkylene waxes and polyethylene glycol waxes. In addition to fats, fat-like substances such as lecithins and phospholipids can also be used as additives. The person skilled in the art understands the term lecithins as those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often referred to in the art as phosphatidylcholines (PC) and follow the general formula

where R typically represents linear aliphatic hydrocarbon radicals with 15 to 17 carbon atoms and up to 4 cis double bonds. Examples of natural lecithins are the kephaiins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. In contrast, phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally classed as fats. In addition, sphingosines or sphingolipids are also suitable.

Cosmetic deodorants counteract, mask or eliminate body odors. Body odors arise from the action of skin bacteria on apocrine sweat, whereby unpleasant smelling breakdown products are formed. Accordingly, deodorants contain active ingredients which act as germ-inhibiting agents, enzyme inhibitors, odor absorbers or odor maskers.

In principle, all substances effective against gram-positive bacteria are suitable as germ-inhibiting agents, such as. B. 4-hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N ^' - (3,4 dichlorophenyl) urea, 2,4,4 ^' -Trichlor-2 ^' -hydroxydiphenylether (Triclosan), 4th -Chlor-3,5-dimethylphenol, 2,2 ^' - methylene-bis (6-bromo-4-chlorophenol), 3-methyl-4- (1-methylethyl) phenol, 2-benzyl-4-chlorophenol, 3- (4-chlorophenoxy) -1, 2-propanediol, 3-iodo-2-propynyl butyl carbamate, chlorhexidine, 3,4,4 ^' trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, famesol , Phenoxyethanol, glycerol monolaurate (GML), diglycerol monocaprinate (DMC), salicylic acid N-alkylamides such as B. salicylic acid-n-octylamide or salicylic acid-n-decylamide. Esterase inhibitors, for example, are suitable as enzyme inhibitors. These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG). The substances inhibit enzyme activity and thereby reduce odor. Other substances which can be considered as esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, such as, for example, glutaric acid, monoethyl glutarate, diethyl glutarate, adipic acid ester, Monoethyl adipate, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or tartaric acid diethyl ester and zinc glycinate.

Suitable odor absorbers are substances that absorb odor-forming compounds and can retain them to a large extent. They lower the partial pressure of the individual components and thus also reduce their speed of propagation. It is important that perfumes must remain unaffected. Odor absorbers are not effective against bacteria. They contain, for example, a complex zinc salt of ricinoleic acid or special, largely odorless fragrances, which are known to the person skilled in the art as "fixators", such as, for example, the main component. B. extracts of Labdanum or Styrax or certain abietic acid derivatives. Fragrance agents or perfume oils act as odor maskers and, in addition to their function as odor maskers, give the deodorants their respective fragrance. Perfume oils are, for example, mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and branches as well as resins and balms. 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, p-tert-butylcydohexyl acetate, linain acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allyl cyclohexyl propionate, styrallyl propionate and benzyl saiicylate. The ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones, for example, the ionones and methylcedryl 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 low 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, labdanum oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexyl cinnamaldehyde, geraniol, benzyl acetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, citro- nenoil, mandarin oil, orange oil, allylamylglycolate, cyclovertal, lavandin oil, muscatel sage oil, ß- damascone, geranium oil bourbon, cyclohexylsalicylate, vertofix coeur, iso-e-super, fixoiide NP, evemyl, iraldein gamma, phenylacetic acid, rose acetate, geranyl acetate acetate, geranyl acetate acetate, geranyl acetate acetate , Irotyl and Floramat used alone or in mixtures.

Antiperspirants (antiperspirants) reduce sweat formation by influencing the activity of the eccrine sweat glands and thus counteract armpit wetness and body odor. Aqueous or anhydrous formulations of antiperspirants typically contain the following ingredients:

astringent active ingredients,

> Oil components,

> nonionic emulators,

> Co-emulsifiers,

> Consistency generator,

> Auxiliaries such as B. thickeners or complexing agents and / or

> non-aqueous solvents such as As ethanol, propylene glycol and / or glycerin.

Salts of aluminum, zirconium or zinc are particularly suitable as astringent antiperspirant active ingredients. Such suitable antiperspirant active ingredients are e.g. Aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds e.g. B. with propylene glycol-1, 2nd Aluminum hydroxyallantoinate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and their complex compounds, for. B. with amino acids such as glycine.

In addition, oil-soluble and water-soluble auxiliaries customary in antiperspirants can be used in smaller quantities

Amounts may be included. Such oil soluble aids can e.g. his:

> anti-inflammatory, skin-protecting or fragrant essential oils,

> synthetic skin-protecting agents and / or

> Oil-soluble perfume oils.

Common water-soluble additives are e.g. Preservatives, water-soluble fragrances, pH adjusters, e.g. Buffer mixtures, water soluble thickeners, e.g. water-soluble natural or synthetic polymers such as e.g. Xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.

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, angeiica, celery, cardamom, costus, iris, Calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), needles and twigs (spruce, fir, pine, mountain pine), resins and balsams ( 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 methylphenylglycinate, allylcyclohexyl benzylatepylylpropylate, benzylate propylate pylate. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, α-isomethylionone and methylcedryl ketone the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineoi, 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, for example 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. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, Cyclovertal, lavandin oil, muscatel Sage oil, ß-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evemyl, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramate alone or in mixtures.

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.

Production of bar soap

The bar soaps according to the invention can be produced in the manner customary for such products take place, in particular through the combination of soap according to the invention with selected amounts of glucosides and / or glucamides, a particularly easily formable mass, which is plastic under heat and hard after cooling, and wherein the shaped products have a smooth surface. Customary processes for mixing or homogenizing, kneading, if appropriate piling, extruding, if appropriate pelleting, extruding, cutting and bar pressing are known to the person skilled in the art and can be used to produce the bar soaps according to the invention. The preparation is preferably carried out in the temperature range from 40 to 90 ° C., the meltable starting materials being placed in a heatable kneader or mixer and the non-melting components being stirred in. For homogenization, the mixture can then be passed through a sieve before the shaping follows. In a preferred embodiment of the invention, components (a) and optionally further surfactants (c) are used in anhydrous, granular form, as obtained after drying in a so-called flash dryer. Here, reference is made to the teaching of the German patent DE 19534371 C1 (Henkel).

Examples

The foam capacity and the creaminess of the foam were determined with the help of the rubbing foam method and, like the skin feeling, was assessed subjectively by a panel of 6 experienced test subjects on a scale from (+) = satisfactory to +++ (very good) the information is determined against a standard (V1). The results are summarized in Table 1. Preparations 1 to 6 are in accordance with the invention, the stucco soap based on isethionate V1 is used for comparison

Table 1

Bar soaps - compositions and properties (quantities as% by weight)

Claims

claims

1. Bar soaps containing

(a) 1 to 60% by weight alkoxylated carboxylic acid esters,

(b) 10 to 60% by weight of fatty acid salts,

(c) 0 to 40% by weight of anionic, nonionic or amphoteric cosurfactants,

(d) 0 to 10% by weight of fatty acids and

(e) 0 to 40% by weight of water-soluble structurants,

2. bar soaps according to claim 1, characterized in that they contain as component (a) alkoxyated carboxylic acid esters of the formula (I),

R CO (AlkO) _n OR2 (I)

in which R ¹ CO stands for an aliphatic acyl radical with 6 to 30 C atoms, AlkO for alkylene oxide, n for numbers from 1 to 30 and R ² for an aliphatic alkyl radical with 1 to 8 carbon atoms.

3. bar soaps according to claims 1 and / or 2, characterized in that they contain as component (a) alkoxylated carboxylic acid esters of the formula (I) in which R ¹ CO for a linear or branched, saturated or unsaturated acyl radical having 10 to 18 Carbon atoms, AlkO for ethylene oxide and / or propylene oxide, n for numbers from 5 to 20 and R ² for methyl.

4. bar soaps according to at least one of claims 1 to 3, characterized in that they contain as component (b) alkali metal salts of fatty acids having 6 to 22 carbon atoms.

5. bar soaps according to at least one of claims 1 to 4, characterized in that they contain as optional component (c) co-surfactants which are selected from the group formed by alkyl and / or alkenyl oligoglycosides, fatty acid-N- alkylpolyhydroxyalkylamides, monoglyceride (ether) sulfates, olefin sulfonates, betaines and fatty acid polyglycol ester sulfates and mixtures thereof.

6. bar soaps according to at least one of claims 1 to 5, characterized in that alkyl and / or alkenyl oligoglycosides of the formula (II) are contained, R ⁴ 0- [G] _P (II)

in which R ^{4 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10.

7. bar soaps according to at least one of claims 1 to 6, characterized in that they contain as optional component (d) fatty acids of formula (X),

R "CO-OH (X)

in which R ¹⁴ CO represents an aliphatic, linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.

8. bar soaps according to at least one of claims 1 to 7, characterized in that they contain starch as water-soluble structurants.

9. bar soaps according to at least one of claims 1 to 8, characterized in that they further contain builders, builders, emulsifiers, superfatting agents, cation polymers, silicone compounds, colorants and perfumes.

10. bar soaps according to at least one of claims 1 to 9, characterized in that they contain component (a) and optionally the other surfactants in practically anhydrous, granular form.