DE4338691B4 - Hair treatment agents - Google Patents

Abstract

in der R¹ für einen überwiegend ungesättigten aliphatischen Kohlenwasserstoffrest mit 16 bis 18 Kohlenstoffatomen, R² für Wasserstoff oder R¹, n für Zahlen von 1 bis 10 und X für Wasserstoff, ein Alkali- oder Erdalkalimetall oder Ammonium steht und
(b) Alkyl- und/oder Alkenyloligoglykoside der Formel (II) enthalten, R³-O-[G]_p (II)in der R³ für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für eine Zahl im Bereich von 1 bis 10 steht.Hair treatment preparations, characterized in that they
(a) have a content of alkyl and / or alkenyl ether phosphates of the formula (I),

in which R ^{1 is} a predominantly unsaturated aliphatic hydrocarbon radical having 16 to 18 carbon atoms, R ^{2 is} hydrogen or R ¹ , n is a number from 1 to 10 and X is hydrogen, an alkali or alkaline earth metal or ammonium and
(b) alkyl and / or alkenyl oligoglycosides of the formula (II), R ³ -O- [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 in the range of 1 to 10.

Description

Field of the invention

The This invention relates to hair treatment compositions containing alkyl and / or alkenyl ether phosphates and the use of alkyl and / or alkenyl ether phosphates for the preparation of these agents.

damage the hair structure are the result of frequent bleaching, permanent wave, dyeing, strong UV exposure, washing the hair with degreasing surfactants as well as the result of normal aging. The hair becomes brittle and loses its splendor. Furthermore, when combing the hair finds an electrostatic Charge instead, while the roughened hair surface Reason to There are tangles and knots of the hair and in this way the combing difficult. Hair treatment or care products with a combability-improving The effect has therefore gained considerable importance in the cosmetics market. such Means can for example in the form of a rinse, an aerosol foam or in the form of emulsions (cream rinses) after shampooing spread in still wet hair and either after a few minutes of exposure rinsed or left on the hair.

When Active ingredients for improving the hair structure have become cationic monomeric and polymeric surfactants, in particular quaternary ammonium compounds such as distearyldimethylammonium chloride (DSDMAC) or cationized guar alone or in combination with various waxy additives, such as hydrocarbons, fatty alcohols or fatty acid esters proven [Perfume. Kosm. 56, 157 (1975)].

From Disadvantage here is that the mentioned cationic surfactants insufficient biodegradability and, when entering surface waters, over time operability aquatic communities. It therefore exists Marktbedüfnis, the cationic surfactants against other ecotoxicologically less problematic Substances that have at least the same, preferably but should be distinguished improved effectiveness.

From the German patent application DE 35 27 974 A1 (Wella), for example, aminous esters of betaines with fatty alcohols or fatty alcohol polyglycol ethers are known for use in acidic hair care products. Although the betaine esters have a high ecotoxicological compatibility, they are unsatisfactory with regard to improved combability, antistatic properties, handling and rinsing behavior, and are also not resistant to hydrolysis in the acidic range.

In the GB 2 192 194 A (Procter & Gamble) are also proposed hair shampoos containing alkyl phosphates in addition to monoglyceride sulfates, siloxanes and consistency. Because of the content of anionic surfactants with sulfate structure, these mixtures are of course not usable in the acidic range.

The The object of the invention was therefore to provide new hair treatment to develop, which are free from the disadvantages described.

Description of the invention

• (a) einen Gehalt an Alkyl- und/oder Alkenyletherphosphaten der Formel (I) aufweisen,
  
  in der R¹ für einen überwiegend ungesättigten aliphatischen Kohlenwasserstoffrest mit 16 bis 18 Kohlenstoffatomen, R² für Wasserstoff oder R¹, n für Zahlen von 1 bis 10 und X für Wasserstoff, ein Alkali- oder Erdalkalimetall oder Ammonium steht und
• (b) Alkyl- und/oder Alkenyloligoglykoside der Formel (II) enthalten, R³-O-[G]_p (II)in der R³ für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für eine Zahl im Bereich von 1 bis 10 steht.

The invention relates to nitrogen-free hair treatment compositions, which are characterized in that they

• (a) have a content of alkyl and / or alkenyl ether phosphates of the formula (I),
  
  in which R ^{1 is} a predominantly unsaturated aliphatic hydrocarbon radical having 16 to 18 carbon atoms, R ^{2 is} hydrogen or R ¹ , n is a number from 1 to 10 and X is hydrogen, an alkali or alkaline earth metal or ammonium and
• (b) alkyl and / or alkenyl oligoglycosides of the formula (II), R ³ -O- [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 in the range of 1 to 10.

Surprisingly was found that the according to the invention and / or alkenyl ether phosphates derived from substantially unsaturated Fatty alcohols and especially derived from technical oleyl alcohol, excellent and opposite cationic surfactant-containing products of the prior art improved anti-vivifying properties for both dry and wet hair feature. This behavior is all the more surprising than that Ether phosphates in contrast to conventional Finishing agents are neither high molecular weight nor cationically charged. The alkyl and / or alkyl ether phosphates can be combined with other, especially nonionic surfactants combine easily and are also resistant to hydrolysis in the acidic range.

Alkyl and / or alkenyl ether phosphates

alkyl phosphates and alkyl ether phosphates have long been known anionic Surfactants, but predominantly because of their good foam and wetting properties used for the production of washing and textile pretreatment agents were. At this point, for example, to the review article by R. S. Cooper et al. in J.Am.Oil.ChemSoc. 41, 337 (1964), H. Distler et al. in tens. Deterg. 12, 263 (1975), K. Henning in soap-oil-grease waxes 102, 221 (1976) and A.J. O'Lennick et al. in Soap Cosm. Chem. Spec. 7, 26 (1986).

From the EP 0 392 665 B1 (Kao) skin cleansing compositions are also known which have a content of alkyl ether phosphates. According to the embodiments, however, only saturated alkyl phosphates, preferably lauryl phosphates are used.

to Production of the alkyl and / or to be used in the context of the invention Alkenyl ether phosphates are started from the corresponding fatty alcohols from, in a conventional manner with ethylene oxide to the corresponding Polyglycol ethers are implemented. These in turn can preferably esterified with phosphorus pentoxide to give the corresponding ether phosphates become.

at the alkyl and / or alkenyl ether phosphates to be used in the context of the invention these are preferably compounds of the formula (I) which of predominantly unsaturated Fatty alcohols having 16 to 18 carbon atoms and iodine numbers in the range from 45 to 125 derive. Typical examples are oleyl ether phosphates in the form of their sodium, magnesium and / or ammonium salts, on Base of technical oleyl alcohol with an iodine number in the range be prepared from 55 to 98 and the one Ethoxylierungsgrad in the range of 1 to 5, preferably 2 to 4.

Farther preference is given to those ether phosphates in which the ratio of Mono to diester in the range of 1: 2 to 10: 1, preferably 1 : 2 to 2: 1 and a share of Triesters below of 15% by weight.

The Hair treatment agent according to the invention can the alkyl and / or alkenyl ether phosphates in amounts of 10 to 95, preferably 25 to 75 wt .-% - related on the solids content of the funds - included.

anionic and nonionic surfactants

The Hair treatment agent according to the invention can contain further anionic and / or nonionic surfactants.

Typical examples of anionic surfactants are alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, amide soaps, Ethercarboxylic acids, Isethi onates, sarcosinates, taurides and alkyl oligoglucoside sulfates. If the anionic surfactants contain polyglycol ether chains, they may have a conventional, but preferably a narrow homolog distribution.

typical examples for nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol, Fettsäureamidpolygylcolether, Fatty amine polyglycol ethers, alkoxylated triglycerides, alk (en) yloligoglycosides, fatty acid glucamides, polyol Sugar esters, sorbitan esters and polysorbates. Unless the nonionic Surfactants contain polyglycol ether chains, they can be a conventional, but preferably have a narrow homolog distribution.

The Alkyl and / or alkenyl ether phosphates and the anionic and / or nonionic surfactants can in the weight ratio of 1: 1 to 1: 5, preferably 1: 2 to 1: 4 are used.

In a preferred embodiment of the invention, nonionic surfactants used are fatty alcohol polyglycol ethers, optionally in admixture with the corresponding fatty alcohols, which contain 12 to 18 carbon atoms in the fatty radical and 10 to 30 ethylene oxide units in the polyether chain. A typical example is the use of a mixture of cetylstearyl alcohol and its adduct of average 20 mol of ethylene oxide, sold under the trade designation 1000 Ni Emulgade ^®. From a performance standpoint mixtures are, for example, alkyl ether phosphates and Emulgade ^® 1000 or equivalent emulsifiers in a weight ratio of 1: 1 to 1: 5 preferred.

Alkyl and / or alkenyl oligoglycosides

In the preparations according to the invention, the alkyl and / or alkenyl ether phosphates are used together with alkyl and alkenyl oligoglycosides which follow the formula (I), R ³ -O- [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 in the range of 1 to 10. Alkyl and / or alkenyl oligoglycosides are known substances which can be obtained by the relevant processes of preparative organic chemistry. Representatives of the extensive literature are here on the writings EP 0 301 298 A1 and WO 90/03977 A1.

The Alkyl- and / or alkenyloligoglycosides can be derived from aldoses or Ketoses of 5 or 6 carbon atoms, preferably glucose derived. 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 degree), d. H. the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p in a given compound must always be integer and here especially the values p = 1 to 6 can assume, the value p is for a certain one Alkyl oligoglycoside an analytically determined arithmetic size, the usually represents a fractional number. Preferably, alkyl and / or Alkenyloligoglykoside used with a mean Oligomemerisierungsgrad p of 1.1 to 3.0. From an application point of view, those are alkyl and / or alkenyl oligoglycosides preferred, the degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6.

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, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides of the chain length C ₈ -C ₁₀ (DP = 1 to 3) which are obtained as a feedstock in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and in a proportion of less than 6% by weight C ₁₂ - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C _9/11 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, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and technical mixtures thereof as above can be obtained described. Preference is given to alkyl oligoglucosides based on hydrogenated C _12/14 coconut alcohol having a DP of 1 to 3.

typically, can the alkyl and / or alkenyl ether phosphates and the alkyl and / or Alkenyl oligoglycosides in a weight ratio of 1: 1 to 1: 2 used become.

Fatty acid N-alkyl polyhydroxyalkylamides

in der R⁴CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R⁵ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht.In a further embodiment of the invention, the alkyl and / or alkenyl ether phosphates are used together with fatty acid N-alkylpolyhydroxyalkylamides which follow the formula (III),

in R ⁴ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{5 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.

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. For the methods for their preparation, see the US patents US 1,985,424 A. . US 2 016 962 A and US 2 703 798 A and International Patent Application WO 92/06984 A1. An overview of this topic by H.Kelkenberg can be found in Tens. Surf.Det. 25, 8 (1988).

Preferably, the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars having 5 or 6 carbon atoms, especially glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (IV):

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (IV) in which R ^{5 is} hydrogen or an amine group and R ⁴ CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, Isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or whose technical mixtures. Particular preference is given to 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 C _12/14 coconut fatty acid or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

typically, can the alkyl and / or alkenyl ether phosphates and the fatty acid alkyl polyhydroxyalkylamides in weight ratio 1: 1 to 1: 2 are used.

Hair treatment agents

The Hair treatment agent according to the invention preferably have a pH in the range of 2 to 11, preferably 4 to 7 on.

Although the agents may also be marketed as acidic solutions or suspensions of the alkyl and / or alkenyl ether phosphates in water, they preferably contain further ingredients customary in cosmetic compositions, such as, for example, fatty alcohols, fatty acid esters, nonionic and / or anionic surfactants, preservatives, vitamins, waxes, protein hydrolysates and nonionic and / or cationic polymers.

In a preferred embodiment of the invention, 1% by weight of the alkenyl ether phosphate and 6% by weight of a microemulsion are emulsified cold in 93% by weight of water. The microemulsion itself was prepared by the PIT process from 3 wt .-% cetearyl alcohol (Lanette ^® O, Henkel KGaA, Dusseldorf / FRG), Ceterylalkohol 12 EO (Eumulgin ^® B1, Henkel KGaA, Dusseldorf / FRG and 20 wt .-% 1,3- (2-ethylhexyl) cyclohexane (Cetiol ^® S, Henkel KGaA, Dusseldorf / FRG) was prepared.

commercial applicability

The Hair treatment agent according to the invention improve combability both wet and dry hair, put the static Charging down, can be easily rinse, are also in the acidic area stable to hydrolysis, have a favorable viscosity and give the hair shine and a pleasant soft touch. moreover are the alkyl and / or alkenyl ether phosphates contained therein readily biodegradable, toxicologically and dermatologically safe and with the usual Ingredients of such agents fully compatible.

One Another object of the invention therefore relates to the use the alkyl and / or alkenyl ether phosphates of the formula (I) for the preparation of hair treatment products, such as hair shampoos, hair conditioners, Hair care emulsions, hair treatments, aerosol foams, hair lotions, hair dye, hair bleach and hair Well agent.

The The following examples are intended to explain the subject matter of the invention in more detail, without to restrict him to it.

I. Recipes

• a1) Oleyl-2,9EO-phosphate. Ratio mono / diphosphate = 1: 1; Purity based on oleyl alcohol: about 85% by weight;
• b1) Plantaren 1200. ^® C _12/16 -Kokosalkyloligoglucosid;
• b2) Emulgade ^® 1000 Ni. Mixture of Cetearyl Alcohol / Cetearyl Alcohol 20EO (1: 1).
• b3) Texapon.RTM ^® N25. C _12/14 coconut fatty alcohol 2EO sulfate sodium salt;
• c1) Dehyquart ^® A. 2-Hydroxycetyl-2-hydroxyethyldimethylammonium;
• c2) Dehyquart ^® E. Dimethyl-N- (2-hydroxyethyl) -N- (2-hydroxyhexadecyl) ammonium chloride

All Starting materials are products of the company Henkel KGaA, Düsseldorf / FRG. All formulations contained 0.15% by weight of formalin for preservation (37 wt .-% strength) and added with water to 100 wt .-%. The recipes R1 to R3 are according to the invention, the formulations R4 to R6 are for comparison.

II. Recipes

Tab.1: Inventive and comparative formulations Percentages as wt .-%

III. Dry and wet combability studies

a) dry combability

The dry combing was examined under the authorization of electrostatic charging. It was set a relative humidity of 20%. The Conditioning time was 12 h at 30 ° C. The measurement took place over the Charge tap on a double Faraday cage after execution of 10 combs. The error in the measurements was on average 2.5%, the statistical Safety was at least 99.9%. The results of combing are shown in Tab.2.

b) wet combability

The wet combing was on brown hair (Alkinco # 6634, strands length 12 cm, strand mass 1 g). After the zero measurement, the strands were with 100 ml of the formulations A to J or U, V and W soaked. To for a period of 5 minutes, the tresses were immersed in running water for 1 minute (1 l / min, 38 ° C) rinsed out. The strands were measured again and compared with the zero measurement. Of the Error in the measurements averaged 2%, the statistical safety was at least 99%. The results are also shown in Tab.2.

A detailed Description of the measuring methods is in J. Soc. Cosm. Chem., 24, 782 (1973).

Tab.2: dry and wet combability

Legend:

• R

  = Recipe

  in front.

  = before

  to.

  = after

  Diff.

  = Difference

The Examples show that the Use of oleyl-2,9EO-phosphate-Na salt over typical cationic ones Surfactants of the market to improve the wet and dry combability leads.

IV. Viscosity

The viscosity of the formulations was determined by the Brookfield method at 20 ° C, 10 rpm, spindle 3 and 4, respectively. The results are summarized in Table 2: Table 2: Viscosities

The Examples show that the Composition according to the invention via a advantageously higher viscosity feature.

Claims (6)

Hair treatment preparations, characterized in that they contain (a) a content of alkyl and / or alkenyl ether phosphates of the formula (I),

in which R ^{1 is} a predominantly unsaturated aliphatic hydrocarbon radical having 16 to 18 carbon atoms, R ^{2 is} hydrogen or R ¹ , n is a number from 1 to 10 and X is hydrogen, an alkali or alkaline earth metal or ammonium and (b) alkyl and / or alkenyl oligoglycosides of the formula (II), R ³ -O- [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 in the range of 1 to 10. Hair treatment preparations, characterized in that they contain (a) a content of alkyl and / or alkenyl ether phosphates of the formula (I),

in which R ^{1 is} a predominantly unsaturated aliphatic hydrocarbon radical having 16 to 18 carbon atoms, R ^{2 is} hydrogen or R ¹ , n is a number from 1 to 10 and X is hydrogen, an alkali or alkaline earth metal or ammonium and (b) fatty acid N-alkylpolyhydroxyalkylamides of the formula (III),

in R ⁴ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{5 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands. Hair treatment composition according to at least one of claims 1 to 2, characterized in that technical alkyl and / or alkenyl ether phosphates of the formula (I) included, which are predominantly unsaturated Fatty alcohols having 16 to 18 carbon atoms and iodine numbers in the range from 45 to 125 derive. Hair treatment composition according to claims 1 to 3, characterized in that technical alkyl and / or alkenyl phosphates of the formula (I), where the proportion of triesters is below 15% by weight. Hair treatment composition according to claims 1 to 4, characterized in that the alkyl and / or Alkenyl ether in amounts of 10 to 95 wt .-% - related on the solids content of the funds - included. Hair treatment composition according to claims 1 to 5, characterized in that the alkyl and / or Alkenyl ether phosphates and the anionic and / or nonionic Surfactants in the weight ratio 1 : 1 to 1: 5 included.