WO1994021771A1

WO1994021771A1 - Detergent mixtures

Info

Publication number: WO1994021771A1
Application number: PCT/EP1994/000807
Authority: WO
Inventors: Hermann Hensen; Holger Tesmann; Jörg KAHRE; Reinhard Müller; Wolfhard Scholz
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1993-03-24
Filing date: 1994-03-15
Publication date: 1994-09-29
Also published as: DE4309567A1; EP0690907A1; JPH08508055A

Abstract

Detergent mixtures containing polyhydroxy fatty acid amides of formula (I) in which R1CO stands for an aliphatic acyl group with 6-22 carbon atoms, R2 for hydrogen , an alkyl group or an hydroxyalkyl group with 1-4 carbon atoms and [Z] for a linear or a branched polyhydroxyalkyl group with 3-10 carbon atoms and 3-10 hydroxyl groups, protein hydrolyzates with an average molecular weight in the range of 1000-6000 and monomer cationic surfactants, enhance the springiness of the hair and can be used in hair-setting agents.

Description

Detergent

Field of the Invention

The invention relates to detergent mixtures containing polyhydroxyfatty acid amides, protein hydrolyzates and optionally monomeric cationic surfactants, a process for improving the bounce of hair, in which the detergent mixtures are used, hair fixatives which contain the detergent mixtures and their use for the preparation of hair fixatives.

State of the art

Washed hair is difficult and reluctant to style due to the degreasing and removal of all dirt particles. The electrostatic charging of the hair makes it difficult to create a durable hairstyle and to maintain it. It depends on the quality of the shapo and the level of ambient humidity and is particularly noticeable in winter when the heating air is warm and dry. To improve the combability of washed and terry hair, for conditioning and hair stabilizers are therefore used to stabilize them against external influences.

Commercial liquid hair fixers are solutions of film formers in water and / or alcohol. In addition, plasticizers are used to make the film on the hair more flexible. Cationic surfactants improve the combability of the hair and reduce the electrostatic charge. The addition of perfume oils rounds off the finished product, while dyes are dispensable, but are often used for aesthetic reasons. Polymeric substances, such as, for example, polyvinylpyrrolidone and / or polyvinyl acetate, are customarily suitable as film formers. In view of the constantly increasing importance of ecotoxicological properties of surface-active agents that come into contact with human skin or hair, there is a sustained need for products that are not only environmentally friendly, not only in total, but also in relation to their individual substances are.

The object of the invention was therefore to develop new hair fixatives with well dermatologically compatible and easily biodegradable film formers. Another task was to provide products that have improved rinsability or brushability. Description of the invention

The invention relates to detergent mixtures containing

a) polyhydroxy fatty acid amides of the formula (I)

R2

I.

R1_CO-N- [Z] (I)

in the R ^ -CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ^ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 is up to 10 hydroxyl groups,

b) protein hydrolyzates with an average molecular weight in the range from 1000 to 10,000 and, if appropriate

c) monomeric cationic surfactants.

Surprisingly, it was found that detergent mixtures containing polyhydroxy fatty acid amides, protein hydrolyzates and optionally cationic surfactants are able to improve the bounce of hair in a way that has not been possible to date using conventional mixtures of polymers and cationic surfactants. The products are easy to wash out, brush out easily and are characterized by excellent dermatological and ecological Tolerance out. The invention also includes the knowledge that mixtures of polyhydroxy fatty acid amides and protein hydrolyzates can act as film formers, a property that is otherwise only known from highly polymeric systems.

Polydroxy fatty acid amides

The polyhydroxy fatty acid amides 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 preparation, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798, as well as International Patent Application No. 92/06984.

The detergent mixtures according to the invention preferably contain polyhydroxy fatty acid amides of the formula (I) in which R ^ -CO represents an acyl radical having 12 to 22 carbon atoms, R ^{2 represents} hydrogen or a methyl group, and [Z] represents a reduced glucose radical. The preferred polyhydroxy fatty acid amides are therefore fatty acid N-alkylglucamides, as represented by the formula (II): R ² OH OH OH

I I I I

R ¹ CO-N-CH ₂ -CH-CH-CH-CH-CH2θH (II)

OH

The polyhydroxy fatty acid amides used are preferably fatty acid-N-alkylglucamides of the formula (II) in which R ^{2 represents} hydrogen or a methyl group and R * CO represents the acyl residue of lauric acid, myristic acid, palmitic acid, palmoleic 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 their technical mixtures. Particularly preferred are fatty acid N-alkylglucamides of the formula (II) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or Ci2 / i4 coconut fatty acid ^Dzw «a corresponding derivative.

Protein hydrolyzates

Protein hydrolyzates are substances which are usually produced by breaking down animal protein, preferably bovine collagen. In alkaline hydrolysis there is an unspecific opening of the peptide bonds, which follows the rules of statistics. Since the carboxy groups of the peptides are present as a salt during the hydrolysis, while the amino groups are unprotected and can be split off in part, a hydrolyzate results in which the polypeptides have a higher number of carboxy than amino groups. Also the acidic hydrolysis leads to unspecific opening of the peptide bonds. In contrast to alkaline hydrolysis, in the acidic degradation, however, the amino groups are in the form of salts and the carboxy groups are in free form, but these have a considerably higher stability than the unprotected amino groups. Depending on the hydrolysis process, the products therefore show strong structural differences [cf. YES . Oil. Chem. Soc., J59, 217 (1982); Soap-Oil-Fat-Waxes 108, 177 (1982)].

For the purposes of the invention, preference is given to using protein hydrolysates which have been prepared by enzymatic means. Enzymes acting specifically on the peptide bond are allowed to attack. The products have a high degree of homogeneity and in particular an improved dermatological compatibility compared to the other hydrolysates. The average molecular weight can be set via the reaction conditions and - as with the alkaline or acidic hydrolysates - can be in the range from 1,000 to 10,000, preferably 2,000 to 6,000.

In addition to animal protein, protein hydrolysates which are obtained by enzymatic degradation of vegetable protein are preferably used. Typical examples are hydrolyzates of soy protein, almond protein, wheat protein and / or potato protein. Compared to animal products, the protein hydrolysates mentioned also have the advantage of improved dermatological tolerance.

The detergent mixtures can the polyhydroxy fatty acid amides and the protein hydrolyzates in a weight ratio of 1: 5 to 5 : 1, preferably 1: 3 to 3: 1 - based on the mixtures.

Monomeric cationic surfactants

Suitable monomeric cationic surfactants are, for example, quaternary ammonium compounds (QAC) of the formula (III)

R5

1 ⁺ [R3-NR ⁴ ] x- (III)

I.

R6

in the R ^ for an optionally hydroxy-substituted alkyl and / or alkenyl radical having 6 to 22 carbon atoms, R ^ for R3 or an alkyl radical with 1 to 5 carbon atoms and R5 and R *> independently of one another for alkyl radicals with 1 to 5 carbon atoms and X represents halogen, phosphate, alkyl sulfate or alkyl phosphate.

The QAC are known substances that can be obtained using the relevant methods of preparative organic chemistry. One method for their preparation is, for example, to guaternate tertiary amines with methyl chloride or dimethyl sulfate.

Typical examples of QACs suitable for the purposes of the invention are stearyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride (Dehyquart ( ^R ) A, Henkel), dicetyldimethylammonium chloride, 2-hydroxycetyl-2-hydroxyethyldimethylammonium chloride (Dehyquart ( ^R ) E, Hen¬ kel) or oxyethylammonium phosphate (Dehyquart ( ^R ) SP, Henkel). Those QAVs are preferably used in which R ^{3 is} for one optionally hydroxy-substituted alkyl radical with 16 to 18 carbon atoms, R ⁴ for R ³ , a methyl or hydroxyethyl group, R ^ and R *> for a methyl group and X for chloride or methyl sulfate.

Another group in the sense of the invention of suitable monomeric cationic surfactants is represented by the esterquats of the formula (IV)

R8

1 ⁺ [R ⁷ CO- [EO] _x -OCH2CH2- ^N - ^CH 2 ^H 2 ⁰ - [ ^EO ] χ-COR ⁷ ] Y "(IV)

I CH2CH2θ- [EO] _z H

in the R ⁷ CO for an aliphatic, optionally hydroxy-substituted acyl radical having 12 to 22 carbon atoms and 0 or 1 double bond, R ^ for a methyl group or a polyethylene glycol ether chain with 1 to 5 ethylene oxide units, x, y and z for 0 or in Sum of numbers from 1 to 5 and Y stands for halogen, alkyl sulfate or alkyl phosphate.

Ester quats are technical mixtures of optionally ethoxylated mono- and difatty acid triethanolamine esters which are quaternized with ethylene oxide, alkyl halides, dialkyl sulfates or dialkyl phosphates. They are also known substances. Esterquats are preferably used which are derived from tallow, coconut and / or palm fatty acids with an iodine number in the range 0 to 40 and have a degree of esterification of 1.5 to 1.9. The degree of ethoxylation can be 0 or 1 to 5, preferably 1 to 3. Esterquats of the formula (IV) in which ^{RO represents} a methyl group or a polyethylene glycol chain having 1 to 3 ethylene oxide units and Y represents chloride or methyl sulfate are particularly suitable for reasons of application technology. A methylquaternized dimethyl fatty acid triethanolamine ester (Dehyquart ( ^R ) AU36, Pulcra / Barcelona) is particularly preferred.

The polyhydroxy fatty acid amides and the monomeric cationic surfactants can be present in the detergent mixtures in a weight ratio of 1:10 to 10 s 1, preferably 1: 1 to 7: 1, based on the mixtures.

The detergent mixtures according to the invention can be prepared by simple stirring, if appropriate at a slightly elevated temperature (30 to 40 ° C.). This is a purely mechanical process, there is no chemical reaction. Anhydrous or highly concentrated starting materials can be used for the production, which are then diluted with water to the desired application concentration. However, it is also possible to mix dilute solutions.

Another object of the invention relates to a method for setting hair, in which one contains hair in a manner known per se with detergent mixtures a) polyhydroxy fatty acid amides of the formula (I)

R ²

I _R l_CO-N- [Z] (I)

in the R ¹ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ² for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups,

b) protein hydrolyzates with an average molecular weight in the range from 500 to 5000 and, if appropriate

c) monomeric cationic surfactants,

treated.

Advantageously, the detergent mixture, depending on the fullness of the hair and the length of the hair, is applied in an amount of, for example, 15 to 25 ml to the washed and terry hair and is evenly distributed. It is advisable to comb through the hair to ensure an even distribution of the hair fixative. The hair is then rolled up on water wave curlers and air dried, preferably under a drying hood. However, it is also possible to do without rolling up and shaping the hair with a blow dryer brush and drying it at the same time ("blow drying").

Another object of the invention relates to hair fixatives containing

a) polyhydroxy fatty acid amides of the formula (I)

R ²

I

in the R * CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ² for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups,

c) monomeric cationic surfactants.

The hair fixatives are preferably in the form of liquid aqueous and / or alcoholic, in particular ethanolic, solutions with an active substance content of about 5 to 30, preferably 10 to 20,% by weight, based on the solution. As further additives, they can, for example, film-forming polymers, such as polyvinyl pyrrolidone and / or polyvinyl acetate, dyes, perfumes, UV adsorbers, thickeners. In addition to the liquid form of supply, the agents according to the invention can also be used as foams ("foam stabilizer").

Industrial applicability

Detergent mixtures containing polyhydroxy fatty acid amides, protein hydrolyzates and optionally monomeric cationic surfactants show film-forming and conditioning properties. They give the hair hold, fullness, manageability, firmness and bounce.

Another object of the invention therefore relates to the use of detergent mixtures containing

a) polyhydroxy fatty acid amides of the formula (I)

_R 2

I R1-C0-N- [Z] (I)

in the R ^ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ² for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. b) protein hydrolyzates with an average molecular weight in the range from 1,000 to 10,000 and, if appropriate

c) monomeric cationic surfactants

for the production of hair fixatives, in which they can be present in amounts of 10 to 95, preferably 30 to 80% by weight, based on the composition.

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

Examples

I. Substances used

^A ) Ci2 / i4 coconut fatty acid N-methylglucamide

B) Soy protein hydrolyzate, CF Grünau, Illertissen / FRG Average molecular weight approx. 4800

C) Ethyl alcohol, cosmetic, 96% by weight

D) Dehyquart ( ^R ) SP, Henkel KGaA, Düsseldorf / FRG oxyethylammonium phosphate

II. Recipes

Tab. 1: Recipes used

Recipe components (% by weight) *

A B C D

A 6.0 3.8 30.0 1.0

B 6.0 - 30.0 1.0

*) ad 100 distilled water III. Application engineering examples

To measure the bounce, strands of hair of the "European dark" code 6634 from Alkinco (12 cm long, approx. 1 g in weight) were treated with 250 mg of water or setting agent per formulation A or B per strand. The application was made on damp hair. The recipe A was according to the invention, the recipe B was used for comparison; in both cases the strengthening agents were adjusted to pH = 6.6. After the treatment, the strands were applied to hair curlers (diameter 48 mm) without rinsing and dried at 40 ° C. for 2 hours. The vibration behavior of the curls was determined in the uncombed or combed state at 15% relative air humidity. The mean values of the 10-fold determination regarding frequency, damping, O-amplitude, stretching force and stretching work are summarized in Tables 2 and 3.

Tab. 2: Examples according to the invention

E.g. Z damping O-amplitude StK StA s-1 mN

Min. Max. Min. Max. S-1 s-1 mN mN

la 2.86 0.89 0.97 3.88 3.78 11.01 0.46 lb 4.35 1.75 1.99 7.78 8.71 30.05 1.00

lc 2.96 1.22 1.18 4.19 3.94 11.12 0.43 id 4.09 1.59 1.89 9.15 8.72 30.99 0.89

Legend: F frequency

StK - stretching force StA = stretching work Min = Minimum Max = Maximum a) Water wave, curls not combed b) Test recipe A, curls not combed c) Water wave, curls combed d) Test recipe A, curls combed

Tab. 3: Comparative tests

Example J_ Damping O-Amplitude StK StA s-1 mN mJ

Min. Max. Min. Max. Ε-1 s-1 mN mN

Via 2.72 0.08 0.90 4.17 3.43 9.12 0.33

Vlb 4.28 2.10 2.39 6.78 7.88 39.00 1.29

VIc 2.91 1.21 1.29 5.09 4.62 10.16 0.35

Vld 3.25 1.27 1.40 4.41 4.67 21.00 0.75

Legend: a) water wave, curls not combed b) test formulation B, curls not combed c) water wave, curls combed d) test formulation B, curls combed

The examples and comparative examples show that formulations which contain polyhydroxyfatty acid amides and protein hydrolyzates as nonionic surfactants, in comparison to mere water treatment (water wave) and formulations which contain polyhydroxyfatty acid amides as nonionic surfactants alone, improve the jumping power, expressed by higher stretching work , Oscillation frequencies and initial amplitudes. Together with the increased vibration, an increased friction in the hair bandage and thus also an increased damping is observed. It makes no difference whether combed curls or combed curls are considered. With the former, the effect is particularly clear, since the strongly bonded strand bandage must be made to vibrate.

Table 4 shows the vibration behavior of curls. The measured values represent the damping of the maxima, the O-amplitude of the maxima and the stretching work of the combed-out curls at 15% relative air humidity.

Tab. 4: Vibration behavior of curls

Ex. R damping O-amplitude stretching s-1 mN mJ

2 A 1.89 8.88 0.91

V2 B 1.43 4.70 0.75

Legend: R «= recipe

Claims

1. Detergent mixtures containing

a) polyhydroxy fatty acid amides of the formula (I)

R ²

I.

R1_C0-N- [Z) (I)

in the R CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ² for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups,

b) protein hydrolyzates with an average molecular weight in the range from 1,000 to 10,000 and optionally

c) monomeric cationic surfactants.

2. Detergent mixtures according to claim 1, characterized gekennzeich¬ net that they contain polyhydroxy fatty acid amides of formula (I) in which R CO for an acyl radical having 12 to 22 carbon atoms, R ² for hydrogen or a methyl group, and [Z] for there is a reduced glucose residue.

3. Detergent mixtures according to claims 1 and 2, characterized in that they contain protein hydrolyzates. which have an average molecular weight in the range from 2000 to 6000.

4. Detergent mixtures according to claims 1 to 3, characterized in that they contain protein hydrolyzates which are produced by enzymatic degradation of vegetable proteins.

5. Detergent mixtures according to claims 1 to 4, characterized in that they contain quaternary ammonium compounds of the formula (III) as monomeric cationic surfactants,

R5

1+

[R3-NR ⁴ ] x- (III)

I.

R ^β

in which R ^{3 represents} an optionally hydroxy-substituted alkyl and / or alkenyl residue with 6 to 22 carbon atoms, R for R ³ or an alkyl radical with 1 to 5 carbon atoms and R 1 and R *> independently of one another for alkyl radicals with 1 to 5 carbon atoms and X represents halogen, alkyl sulfate or alkyl phosphate.

6. Detergent mixtures according to Claims 1 to 4, characterized in that they contain Esterquatε of the formula (IV) as monomeric cationic surfactants. R8 l ⁺ [R ⁷ CO- [EO] _x -OCH ₂ CH2- ^N - ^CH 2 ^H 2 ⁰ - [ ^EO ] χ- ^COR7 ] ^{γ "} (* ⁾

I CH ₂ CH ₂ 0- [EO] _z H

in the R ⁷ CO for an aliphatic, optionally hydroxy-substituted acyl radical with 12 to 22 carbon atoms with 0 or 1 double bond, R8 for a methyl group or a polyethylene glycol ether chain with 1 to 5 ethylene oxide units, x, y and z for 0 or in total represents numbers from 1 to 5 and Y represents halogen, alkyl sulfate or alkyl phosphate.

7. Detergenεgemische according to claims 1 to 6, characterized in that they contain the polyhydroxy fatty acid amides and the protein hydrolysates in the ratio 1: 5 to 5: 1 by weight - based on the mixtures.

8. Detergent mixtures according to claims 1 to 7, characterized in that they contain the polyhydroxy fatty acid amides and the monomeric cationic surfactants in a weight ratio of 1:10 to 10: 1, based on the mixture.

9. A method for fixing hair, in which hair is contained in a manner known per se with detergent mixtures

a) polyhydroxy fatty acid amides of the formula (I) R ²

I Rl-CO-N- [Z] (I)

in the RlCO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ² for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups,

b) protein hydrolysates with an average molecular weight in the range from 500 to 5000 and optionally

c) monomeric cationic surfactants,

treated.

10. Hair fixative containing

a) polyhydroxy fatty acid amides of the formula (I)

R ²

I.

_R l_CO-N- [Z] (I)

in the RlCO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ² for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or mixed branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups,

b) protein hydrolysates with an average molecular weight in the range from 1000 to 6000 and, if appropriate

c) monomeric cationic surfactants.

11. Use of detergent mixtures containing

a) polyhydroxy fatty acid amides of the formula (I)

R2

I R1_C0-N- [Z] (I)

c) monomeric cationic surfactants

for the manufacture of hair fixatives.