WO1997001322A1

WO1997001322A1 - Hair care products with at least one conditioner

Info

Publication number: WO1997001322A1
Application number: PCT/EP1996/002481
Authority: WO
Inventors: Mustafa Akram; Herbert Deutz; Astrid Kleen
Original assignee: Hans Schwarzkopf Gmbh
Priority date: 1995-06-26
Filing date: 1996-06-07
Publication date: 1997-01-16
Also published as: AU6301396A

Abstract

The invention pertains to hair care products with components that are standard in cosmetics ans with at least one conditioner. The aim of the invention is to provide hair care products which have standard cosmetics components and at least one conditioner and which enable the condition of the hair to be improved from the inside out during the treatment. The conditioner used should penetrate into the treated hair and be stable in the pH range of 2 to 12. This should then result in a distinctly measurable stabilization of hair structure, particularly where there has been damage to the hair. The aim of the invention is achieved with the hair care products as per claims 1 to 25, containing as conditioner(s) the compounds of formula (I) indicated therein.

Description

Hair treatment agent with at least one conditioner

The invention relates to preparations for hair treatment with constituents customary in cosmetics with at least one care substance

The hair treatment agents according to the invention include all hair cleansing agents (shampoos), hair shaping agents (permanent wave preparations), hair setting agents (hair waxes, gels, varnishes, liquid strengthening agents, sprays, foams) and hair care agents (hair lotions, pomades, rinses, and cures) ), as described for example in the book "Cosmetics" by Wilfried Umbach, Georg Thieme Verlag Stuttgart, New York, 1988 on pages 223 to 280

Studies have shown that 70 percent of women wash their hair several times a week, 8 percent of them daily. This care behavior leads to the so-called "all-purpose shampoos" being replaced by diverse, need-based and gentler recipes likewise the need for additional care products, because mechanical stresses such as combing, blow-drying or rubbing on the clothes put a strain on the hair. In addition, chemical treatments such as perms or color changes have an additional burden. A hair becomes long until it is 20 cm long has reached an average of 400 times washed, blow-dried and brushed under the micros- kop ^'st ungeschadigtes hair similar to a pine cone surrounded by a geschlos¬ Senen cuticle For damaged hair, this layer is no longer included ge The scales are available from and break partially out The light falling on it is no longer reflected rt, the hair looks dull and lackluster Hair treatments alleviate worse problems, but often make the hair "heavy" and often hide the image of "too much of a good thing" due to their valuable ingredients. They also only work on the surface of the hair and can therefore do so do not regenerate completely

Therefore, there is an urgent task to develop hair treatment agents with care substances that improve the condition of the hair from the inside during the hair treatment by penetrating the care substances used into the hair to be treated. This is intended to bring about a regeneration or structural stabilization of the hair that is not remains exclusively limited to the hair surface

The object of the invention is achieved by the hair treatment agents mentioned in claims 1 to 25. The care substances of the general formula (I) according to the invention are intended to penetrate the hair to be treated and to be stable in the pH range from 2 to 12 Combability and improved grip, above all a clearly measurable and permanent structural stabilization of the hair, in particular in damaged areas, can be achieved

ORIGINAL DOCUMENTS The hair treatment compositions of the invention can, in addition to at least one compound of the general formula (I) in amounts of 0.01 to 10% by weight, additionally tiyptophan or another amino acid from the series glycine, alanine, leucine, isoleucine, norleucine, phenylalanine, arginine, histidine, proline , Hydroxyproline, cystine, cysteine, methionine, aspartic acid, glutamic acid and cysteic acid and / or mixtures thereof in amounts of 0.01 to 5% by weight.

In a special embodiment, typhophane can additionally be present up to the same amount by weight of the compounds of the general formula (I) contained.

Preferred care substances of the invention according to the general formula (I) are given in Table I.

Table I:

In addition to at least one care substance of the general formula (I), the hair treatment compositions of the invention can additionally contain one or more care substances, such as panthenol, tocopherol, wheat proteins, lecithins, keratin and silk hydrolyzates, Contain phospholipids, ceramides, pseudoceramides, phytosterols. These additional care substances can be present in the hair treatment product in quantities of 0.01 to 10% by weight

Proteins and especially wheat proteins include in the Rompp Chemie Lexikon, 9th edition, vol. 5 on pages 3650 to 3657 and vol. 6 on pages 5029 to 5030. in the Rompp Chemie Lexikon, 9 edition, vol. 6 on pages 4637 to 4639. Structure and properties of phyto-sterols are described, for example, in Parfumerie & Kosmetik, 75th year (1994) on pages 755 to 758, and lecithins and their properties are for example from SA Riethmayer in SOFW, 121 volume (1995) discussed on pages 367 to 72. Ceramides and pseudoceramides are dealt with in the Rompp Chemie Lexikon, 9th edition, vol. 1 on page 623 with references

Hair cleaners (shampoos) with care substances are described in the documents DE 33 36 609, US 38 16 616 and US 42 920 212. These are care substances that accumulate in the cuticle area and consequently can only influence the hair from the outside. The active substances can do this Do not restructure hair from the inside

The hair cleansing agents according to the invention with one or more compound (s) of the general formula (I) as a care substance restructure the hair from the inside. Thermoanalytical measurements on treated hair prove that the structure of the damaged hair is improved by treating a hair cleansing agent according to the invention

The hair cleansing agents according to the invention can, as water-soluble anionic, washing-active substances, preferably alkali metal, magnesium, ammonium and / or C ₂ - to C ₃ - to alkanolammonium salts of alkyl sulfuric acid hemiesters with 8 to 18 and preferably 12 to 16 carbon atoms in the Alkyl group or of alkyl polyglycol ether sulfuric acid hemiesters with 8 to 18 and preferably 12 to 16 carbon atoms in the alkyl group and 1 to 6 glycol ether groups in the molecule. Other suitable anionic detergent substances are primary and secondary linear alkanesulfonates with 10 to 18 carbon atoms, alkenesulfonates and hydroxyalkanesulfonates Cg - to Cjg- fatty acid alkylolamide polyglycol ether sulfates, Cg to C \ g fatty acid monoglyceride sulfates, sulfosuccinic acid monoalkyl esters with 8 to 18 carbon atoms in the alkyl group or - dialkyl esters with 6 to 10 carbon atoms in the alkyl groups, alkylpolyglycol 18 carbons with men in the alkyl group and 2 to 6 polyglycol ether groups in the molecule as well as acyl sarcosines, acyl taurides and acyl isethionates with 8 to 18 carbon atoms in the acyl group In general, the concentration of the anionic surface-active substances in the shampoo can be about 5 to about 50% by weight and preferably about 8 to about 40% by weight. In addition, the hair cleansing agents according to the invention can contain standard additives and build-up substances, for example thickeners from the type Cg to C _j g-fatty realkylolamide, opacifying agents, for example of the type of ethylene glycol distearate, pH-stability catalysts such as alkali or ammonium phosphates or -zitrate, preservatives, such as p-

Hydroxybenzoic acid esters, dyes, fragrances and known hair cosmetic substances, such as agents against dandruff or oily hair (see "Cosmetics" by Wilfried Umbach, Georg Thieme Verlag Stuttgart, New York, 1988, pages 223 to 237).

The hair cleaners according to the invention with contents of 0.1 to 5% by weight of care substance (s) of the general formula (I) are distinguished by an unexpectedly intensive improvement in the properties of the hair washed with them. For example, the inner structure of the hair is significantly improved compared to shampoos with previously used care substances. This is very surprising because the other recipe ingredients themselves have no effects on the inner hair structure.

The following Examples 1 and 2 describe a hair cleanser (shampoo) according to the invention:

example 1

Hair shampoo

Laureth sulfate 22% 63.64%

Citric acid approx. 0.20%

Na benzoate 0.50% salicylic acid 0.20%

Perfume 0.50%

NaCl approx.2.50%

L-serine 1.00%

Water ad 100.00%

Example 2 Hair shampoo

Laureth sulfate 22% 63.64%

Citric acid approx. 0.20%

Na benzoate 0.50%

Salicylic acid 0.20%

Perfume 0.50% NaCl approx.2.50%

Threonine 0.50%

D / L serine 0.50%

Water ad 100.00%

Shampoo produced according to Example 1 or Example 2 was used to wash the hair on the head of women with hair damaged by permanent wave treatment. Comparative shampoos with the same composition, but without the addition of serine, were also used. Special investigations have shown that only the attacked hair treated with shampoos according to Example 1 and Example 2 has received clearly measurable structural improvements. Thus, a "repair effect" was found on the damaged hair.

The physical, chemical and morphological properties of hair are negatively influenced by various types of action. For example, the hair is affected by cosmetic treatments, such as repeated bleaching, perming and dyeing, but also by frequent washing of the hair with degreasing surfactants, by climatic influences, such as differences in humidity and temperature, or by the intensive action of sunlight and by mechanical treatment such as brushing, combing and terry towels, especially in the area of the ends of the hair, subject to severe wear and tear, while the hair at the hairline has a healthy, undamaged structure. The mostly different hair structure between the hairline and the hair tips is a big problem with the permanent wave treatment of the hair. If the permanent wave agent is adjusted in its wave effectiveness to the stressed and damaged hair tips, then you get an insufficient permanent deformation of the hair at the hairline. If, on the other hand, you adapt the permanent wave agent in its wave effectiveness to the healthy, undamaged structure of the hair at the hairline, the hair at the damaged hair tip can be damaged so much that it can lead to a severely restricted curl up to breaking off the hair.

In the case of permanent wave treatment of the hair with keratin-reducing shaping agents, the procedure is generally such that the hair which has been washed and wiped off with a towel is divided into strands, these strands are individually wound onto permanent wave curlers and then moistened with the shaping agent. After the shaping process has ended, the hair is rinsed with water, then fixed by oxidation, then the curlers are removed and, if appropriate, the fixative is applied again, the hair is rinsed again with water and, if appropriate, aftertreated with a treatment preparation.

Today thioglycolic acid or its salts or esters are used almost exclusively as reducing agents. Show the corresponding, slightly alkaline preparations Although the desired reduction performance, it can damage the treated hair, which manifests itself, for example, in the increasing breakage of the hair

There have been a number of proposals to develop improved preparations, but these have not given satisfactory results

The use of other reducing agents either led to inadequate forming performance, as in the case of the system, or was associated with a number of further problems. The use of thioglycerol, which shows good forming performance, is toxicologically problematic, for example

Other compounds that are sufficient in terms of their activity, such as, for example, thio-glycolamides, are described as very unstable against oxidizing agents or as extremely malodorous and have a sensitizing effect. Other unsuccessful solution options are described, for example, in European Patent Application 261387, Japanese Patent Application 57/62217 and German Offenlegungsschrift 38 33 681 discloses information on this problem can also be found in the "Handbook of Cosmetics and Fragrances" by H Janistyn, Dr Alfred Huthig Verlag Heidelberg, 2nd Edition, 1973, in Volume III on pages 353 and following remove

The hair is known to be mechanically and chemically damaged after a permanent wave shaping treatment, so that aftertreatment with a hair treatment agent is necessary in order to give the hair a natural feel and shine again

EP-PS 0 014 479 describes an agent for the treatment of hair before winding on permanent wave curlers, which has a content of a methylpolysiloxane and / or paraffin or isoparaffin, a cationic compound and an ampholytic compound. However, this agent is in relation to the protection of the damaged hair tips during the permanent waving process and thus on the uniformity of the permanent waving is not fully satisfactory

EP-OS 0 260 641 discloses an emulsion-like hair treatment agent with hair-fixing properties containing a hair-fixing polymer, a silicone oil, a non-ionic surfactant and ethanol. US Pat. No. 4,954,335 discloses clear, non-emulsion-like ones Hair conditioning agents are described which contain, among other things, a combination of non-ionic surfactant, ethanol and a volatile silicone oil. Thickeners in the form of polyacrylic acid derivatives can be added to the agents, but they necessarily contain quaternary ammonium compounds and an amidoamine compound with a conditioning effect from the PCTΛVO 89/04164 is a hair conditioning agent containing thickener, a non-volatile polydiorganosiloxane in Form of an oil-in-water emulsion and a non-ionic surfactant known A care and protective effect of the agents during a permanent wave treatment is not described

The object was therefore to provide a hair treatment agent which protects the hair from severe damage during or after the permanent wave process. It has been found that by adding at least one of the compounds according to claim 1 to the base curl or by means of a post-treatment agent which contains at least one of the compounds of the general formula (I) according to claim 1 as a care component, the object is achieved in an outstanding manner

This may contain 0.1 to 10% by weight, preferably 0.8 to 5% by weight, of a care substance of the general formula (I) in the one-component or two-component corrugating agent system

The invention is illustrated by the following examples

Example 3 Two-component hair styling agent

Component A

95.6 g ammonium thioglycolate (70% aqueous solution)

4.4 g thioglycolic acid (98% -ιg) 100.0 g

The pH of component A is 6 0

Component B

1.5 g ammonium bicarbonate

0.6 g ammonia (25% aqueous solution)

1.5 g glycerol-polyethylene glycol ricinoleate (Cremophor EL from BASF, Ludwigshafen)

1.0 g poly (dimethyldiallylammonium chloride)

1.0 g cocobetaine

0.8 g perfume oil

0.5 g vinyl pyrrolidone styrene mixed polymer (Antara 430 from GAF Corp New York USA)

1.0 g L-serine

92.1 g water 100.0 g

The pH of component B is 8 5 Before use, 14 g of component A and 66 g of component B are mixed with one another. The pH of the hair styling agent thus obtained is 7.3 The washed and terry hair is wound on rollers with a diameter of 6 millimeters and then moistened evenly with the hair shaping agent described above. After an exposure time of 18 minutes, the hair is rinsed thoroughly with water and then oxidatively treated with 80 g of a 3 percent aqueous hydrogen peroxide solution. After removing the curlers, the hair is again with

Rinsed water, put to the water wave and then dried. The treated like this

Hair has an even and lively frizzy.

In comparative studies in which a component B was used without the addition of care products (that is to say according to the prior art), the structure of the hair was improved only with a component B which contained L-serine.

Example 4

One-component hair styling agent

Thioglycolic acid 6.0%

Ammonium carbonate 3.0%

Texapon K 1296 * 3.0%

Copherol 1250 ** 2.0%

L-lysine 2.0%

Ammonia ad pH-8

Water ad 100.0%

* Sodium lauryl sulfate (96% active substance, CTFA name: sodium lauryl sulfate) (HENKEL), ** D-α-tocopheryl acetate (approx. 92% active substance; CTFA name: tocopheryl acetate) (HENKEL)

Example 5

Single component hair styling agent

Thiolactic acid 6.0%

Ammonium carbonate 3.0%

Texapon SB *** 7.5%

Copherol 1250 2.0%

L-lysine 1.0%

L-serine 1.0%

Ammonia ad pH 7.5

Water ad 100.0%

*** Disodium salt of a sulfosuccinic acid half-ester based on an alkyl polyglycol ether (approx. 40% active substance; CTFA name: Disodium Laurethsulfosuccinate) (HENKEL) The one-component hair styling agents according to Examples 4 and 5 were used in the usual way for permanent waving treatment. When comparing with waving agents according to Examples 4 and 5, but without serine or serine / lysine addition, the hair-protecting or hair-improving effect of the waving agents according to the invention was clearly evident approved

Means for setting the hair are described in DE 40 34 315. There, an agent for setting the hair is claimed which contains a combination of a partially or completely neutralized amphoteric polymer and a nonionic polymer. This results in good hair strengthening and good hairstyle durability. However, it is not possible to improve the structure of damaged hair with such a product

Surprisingly, the hair fixatives according to the invention, which contain one or more compounds of the general formula (I) in amounts of 0.01 to 10% by weight as a care substance, improve not only good and stable hair but also an improvement in the damaged structure of the hair

The hair fixatives according to the invention can be hair waxes, hair gels, liquid hair fixes, hair sprays or hair foams

Nonionic polymers such as polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate or terpolymers of vinylpyrrolidone, vinyl acetate and vinyl propionate can be used as film formers in the hair setting agent according to the invention

Particularly preferred is the use of copolymers of vinylpyrrolidone and vinyl acetate, which are sold, for example, by the company BASF, Ludwigshafen / FRG under the name LUVISKOL VA, and terpolymers of vinylpyrrolidone, vinyl acetate and vinyl propionate, which are sold by the company BASF, Ludwigshafen / FRG the name LUVISKOL VAP

A liquid hair-strengthening composition according to the invention preferably has a pH of 7 to 9.5 and can be in the form of an alcoholic or aqueous-alcoholic solution

Suitable alcohols are, in particular, the lower alcohols with 1 to 4 carbon atoms usually used for cosmetic purposes, such as ethanol and isopropanol, for example. These alcohols can be used in the agent according to the invention in an amount of 10 to 98% by weight, preferably in an amount of 20 to 90% by weight Of course, further hair cosmetic additives, such as perfume oils, herbal extracts, bactericidal or fungicidal substances, solubilizers for perfume oils, plasticizers such as phthalic acid esters or alkyl citrates, or hydrophobicizing substances such as silicone oils, can of course also be contained in the agent according to the invention, provided such additives appear useful and expedient .

The agent according to the invention for setting the hair can also be in the form of an aerosol hair spray or aerosol hair lacquer or a non-aerosol hair spray or non-aerosol hair lacquer sprayable with the aid of a suitable spray device (for example a spray pump).

If the agent according to the invention is in the form of an aerosol hairspray or aerosol hair lacquer, it additionally contains 2 to 80% by weight of a propellant and is filled into a pressure vessel. Easily volatile chlorofluorocarbons, such as, for example, are suitable as blowing agents. B. difluorochloromethane, trichloromonofluoromethane and tetrafluor dichloroethane or lower alkanes, such as. B. n-butane, i-butane and propane, or dimethyl ether, and furthermore, at the pressures under consideration, gaseous blowing agents, such as N ₂ , N ₂ O and CO ₂ , and mixtures of the above-mentioned compounds , suitable. Among the blowing agents mentioned above, dimethyl ether and mixtures of lower alkanes with dimethyl ether are preferred, the use of dimethyl ether as blowing agent being particularly preferred.

More about hair fixers can be found in the book Cosmetics; Development, production and use of cosmetic products, published by Wilfried Umbach, Georg Thieme Verlag.

The means for setting the hair according to the present invention bring about an improvement in the hair structure with, at the same time, excellent setting. This was not to be expected from the content of compounds of the general formula (I).

The following examples are intended to explain hair setting agents according to the invention in more detail

Example 6

mousse

PVP / VA copolymer 8.00 g

Propane 5.00 g

Butane 5.00 g

Polyquaternium- 16 3.00 g

Cetrimonium bromide 0.20 g

Laureth-4 0.10 g

Isoamyl p-methoxycinnamate 0.10 g

L-serine 1.00 g

Perfume 0.10 g

Water ad 100 g

Example 7

Hairspray (aerosol)

PVP / VA copolymer 10.00 g

Cyclomethicone 0.10 g

Isopropyl myristate 0.05 g

D, L-tyrosine 0.30 g

L-serine 0.20 g

Perfume 0.05 g

Water 4.00 g

Dimethyl ether 60.00 g

Alcohol ad 100.00 g

Example 8

Hair lacquer (aerosol)

Octylacrylamide acrylate / butylaminoethyl methane acrylate copolymer 5.00 g

Aminomethyl propanol 1.00 g

Cyclomethicone 0.10 g

Isopropyl myristate 0.05 g

Perfume 0.05 g

Water 6.00 g

D, L-serine 0.40 g

Dimethyl ether 60.00 g

Alcohol ad 100.00 g Example 9 Hairspray (Pump)

PVP / VA copolymer 10.00 g

Cyclomethicone 0.10 g

Isopropyl myristate 0.05 g

D, L-phosphoserine 0.35 g

Perfume 0.05 g

Water 5.00 g alcohol to 100.00 g

When the hair-setting preparations according to Examples 6 to 9 were used as intended, a structure-stabilizing effect on the treated hair could be clearly demonstrated by measurement. In these investigations, too, the same hair-setting preparations were used as comparison material, but without the addition of care products according to the invention. The specified effects were found only in hair setting products of the invention.

The present invention also relates to cosmetic hair care products in the form of hair washers, hair pomades, hair rinses, hair treatments, spray preparations, etc. with 0.01 to 10% by weight of the compounds of the general formula (I).

It is common to treat human hair regularly with hair care products. This occurs in particular after bleaching, dyeing, tinting and perming the hair in order to give it a natural feel and bounce. It is also important to protect the hair against various harmful environmental influences with such a conditioning treatment.

Compositions are usually used for this purpose which contain cationic surface-active substances, in particular quaternary ammonium compounds and / or film-forming polymers, in particular those of a cationic type, and / or protein hydrolyzates as conditioning agents. These active ingredients are not only added to aftertreatment agents, but can also be used in so-called conditioning shampoos, which likewise improves the appearance, feel and shine of the hair.

However, since the compositions mentioned are not or only insufficiently able to regenerate damaged hair from "inside", there is still a great need for the new and further development of corresponding products. The invention solves this need in that it provides hair care products based on conventional carrier materials, ie solutions, emulsions, dispersions, lotions, aerosol spray compositions, etc., from conventional combinations of active substances, as described, for example, in documents DE 43 24 962 and DE 4234413, exist and additionally contain at least one of the compounds of the general formula (I) as a care substance.

Thermal analysis measurements show that damaged hair receives a measurable structural improvement by treatment with hair treatment compositions of this invention.

The following Examples 10 to 14 describe hair care compositions according to the invention.

Example 10

Foam balm

Alcohol 20.00 g

Isobutane 10.00 g

PVP / VA copolymer 4.00 g

Amodimethicone 2.00 g

Trideceth-12 2.00 g

Cetrimonium chloride 0.50 g

L-serine methyl ester 0.50 g

Distearyldimonium chloride 0.50 g

Perfume 0.10 g

Water ad 100.00 g

Example 1 1

hair conditioner

Dehyquart F 30 3.5 g

Cutina MD 0.5 g

Plantaren 1200 2.0 g

Lameform TGI 1.0 g

Cetiol V 1.0 g

Nutrilan Keratin W 1.3 g

D, L-tyrosine 0.5 g

D, L-serine 0.5 g

Water 89.7 g Example 12

hair conditioner

Dehyquart F 30 3.5 g

Cutina MD 0.5 g

Emulgin B 2 2.0 g

Lameform TGI 1.0 g

Cetiol SN 1.0 g

Gluadin Almond 1.1 g

L-threonine 0.5 g

L-serine 0.5 g

Water 91.7 g

Example 13

hair conditioner

Dehyquart F 30 3.5 g

Cutina MD 0.5 g

Emulgin B 2 2.0 g

Lameform TGI 1.0 g

Cetiol SN 1.0 g

Gluadin Almond ι, i g

Promois Silk 1000 0.5 g

Lowenol S-216 0.5 g

L-serine 0.5 g

Water 91.2 g

Example 14

hair conditioner

Dehyquart F 30 3.5 g

Cutina MD 0.5 g

Emulgin B 2 2.0 g

Lameform TGI 1.0 g

Cetiol SN 1.0 g

Gluadin Almond ι, i g

Phospholipid EFA 0.2 g

Panthenol 0.5 g

L-serine 0.5 g

Water 91.5 g The hair care products according to Examples 10 to 14 were used in the usual way for hair care treatment. When comparing with hair care products according to Examples 10 to 14, but without the addition of care substances or care substance combinations according to the invention, the hair-protecting or hair-improving effect of the

Hair care products according to the invention confirmed.

Veruleichs measurements to prove the height of the invention

To demonstrate the level of the invention, some comparative studies are listed below as examples. The method of thermal differential calorimetry (DSC) was used as the measurement method, which will be briefly explained here

Thermoanalytical investigations are particularly suitable for the characterization of two-phase systems, which also include human hair as fiber keratins with their crystalline α-helix component and amorphous matrix component. On the one hand, glass transitions and aging behavior of the amorphous matrix can be examined, on the other hand, the melting behavior of the crystalline, helical phase provides important insights. Thermal analysis was first described in 1899 (WC Roberts-Austen, Proc. Inst. Mech. Eng., London 1899, page 35ff), first differential thermal analysis (DTA) on protein fibers was carried out in the late 1950s (F. Schwenker, JH Dusenbury, text Res. J. 1963, 30, page 800ff; WD Felix, MA Mcdowall, H. Eyring, ibid. 1963, 33, page 465ff). In the following years, different thermoanalytical measuring methods, such as DTA, HP-DTA (high pressure, high pressure DTA) and DSC (differential scanning calorimetry, dynamic differential calorimetry), were applied to keratin fibers (G. Ebert, FH Müller, Proc. Int. Woll Text. Res. Conf., Cirtel, Paris 1965, 4, page 487ff; G. Ebert, J. Wendorff, Kolloid-Zeitschrfit and Zeitschrift. Für Polymer 1967, 216/217, page 277ff; M. Spei, R Holzem, Colloid and Polymer Sei. 1987, 265, page 965ff; M. Spei, R. Holzem, Mell. Text. 1987, 68, page 923ff .; AR Haly, JW Snaith, Text. Res. J. 1967, 37 , Page 898ff .; JS Crighton, ER Hole, Proc. 7th Int. Wool Text. Res. Conf. 1985, Vol. I, page 283; JS Crighton, WM Findon, Proc. 6th Int. Wool Text. Res. Conf. , Pretoria 1980, Vol. V, page 235ff), for example to investigate the phenomenon of supercontact, α-ß phase transitions of the helices or denaturation processes. Recently, in particular at the German Wool Research Institute in Aachen (FJ Wortmann, H. Deutz, J. Appl. Polym. Sei. 1993, 48, page 137ff), the HP-DSC method has been used to investigate keratin fibers that solve the problems with pyrolytic effects, as they occur in conventional DSC, and problems with data acquisition and interpretation, such as those contained in the DTA, rule out. DSC measurements are carried out on keratins that are mixed with water in commercially available, pressure-resistant measuring capsules are included. In the keratin-water system, high water pressure develops in the encapsulated steel crucibles when heated above 100 ° C, from which the HP-DSC analysis is derived. The serious difference between the HP-DSC thermograms of human hair and normal DSC thermograms is that the endothermic peaks, which reflect the transition point and enthalpy of transformation, shifted here by approximately 90 ° C. to lower temperatures are. This is due to the fact that the water after diffusion into the hair fiber by weakening and splitting hydrogen bonds and salt bonds reduces the protein stability and thus lowers the "gluing temperature" of the keratins. If only hydrogen bonds and salt bridges are released by the supercontracting agent, such as water, the thermal effect is reversible (supercontact). However, the process becomes irreversible as soon as covalent bonds, such as disulfide bridges, are also broken. This happens when you heat human hair fibers in pressure-resistant capsules with water to over 150 ° C. The irreversible transformation, interpreted as the transition of the α-helical regions in the proteins into a disordered state, results in endothermic peaks, the peak position representing the transformation or melting point and the peak area the transformation or melting enthalpy.

Using dynamic differential calorimetry (DSC), structural and chemical states and changes in fiber keratins and in particular in human hair can thus be recorded. Under precisely defined experimental conditions, the calorimetrically detectable processes can be recorded on human hair using thermograms and their peak positions, structures and areas as indicators for influencing order-disorder transitions by changing internal and / or external parameters, e.g. by cosmetic treatment of the hair. That From the endothermic peaks recorded in the thermogram of human hair, statements about the strength or damage of the human hair fiber can be made based on the peak position (transition point) and peak area (conversion enthalpy).

Extensive investigations regarding the influence of the cystine content on the denaturation of the α-helices in keratins have shown, for example, that the melting temperature (transition temperature) of the keratin increases linearly with the cystine content. The increased stability of the matrix area due to the higher degree of crosslinking of the increased proportion of disulfide bridges in the matrix leads to the fact that conversion of the helices embedded in this matrix is made more difficult and thus results in an increase in the melting temperature. Conversely, a reduction in melting point and especially melting enthalpy can be caused by permanent wave or bleaching or dyeing treated human hair can be observed (H. Deutz, doctoral thesis, RWTH Aachen 1993).

The care substance (s) contained in the hair treatment compositions according to the invention, such as e.g. Serine penetrate the hair and, due to their polar character, form additional hydrogen bonds and salt bonds in the matrix, which in turn leads to increased stability against deformation and thus causes a general structural stabilization of the hair. This can be seen in thermoanalytical studies on the human hair treated with hair treatment agents according to the invention by a shift in the transformation or melting point of the human hair fibers to higher temperatures.

Table III shows the result of comparative tests using DSC (dry heating), in which damaged human hair is compared to the same hair samples, but treated on the one hand with tap water for 20 minutes and on the other hand with a 1% aqueous L-serine solution for 20 minutes.

Table ED

Peak maximum [° C] human hair, stressed 223.1 ° C human hair, stressed, treated with tap water 223.7 ° C

Human hair, damaged, treated with 1% L-serine solution 227.2 ° C

The measurement results clearly show that the addition of 1% by weight of L-serine as a care substance can significantly stabilize the structure of the stressed human hair treated with this solution. This result can be applied in the broadest sense to all hair cosmetic products that are based on water.

Furthermore, the structural stabilization caused by the hair treatment agents according to the invention is demonstrated by the so-called fatigue test. After conditioning at 21 ° C and 65% RH, the human hair to be examined is individually clamped on a platform at the upper end and provided with a weight (30 to 40 g) at the lower end so that it lies straight on the floor. The platform rises and falls vertically, so that the hair fibers are alternately loaded and relieved. Typically, 100,000 cycles are performed at a frequency of 1 cycle / second and the survival rate is determined. The stability of the fibers relative to one another is determined from this survival rate. Fatigue test studies at the Textile Research Institute (Princeton NJ 08542) on human hair samples treated as follows:

Sample 1 untreated human hair lock Sample 2 permanently waved and then treated with 1% aqueous L-serine solution for 20 minutes human hair lock

Sample 3 permanent wavy strand of human hair

As a result of the research, there was a decreasing stability in the order

Sample 1> Sample 2> Sample 3 found.

The following further comparative studies are also intended to prove the level of the invention

A half-side comparison of human hair showed a hair rinse that cannot be rinsed out, a hair rinse or a heated hair rinse (hot oil) against the corresponding hair treatment agent with 0.2% by weight D / L-serine or 0.2% by weight L-lysine - Hydrochloride as care product tested for wet and dry combability and grip The results for the hair treatment products with care product in comparison to the corresponding hair treatment products without care product are shown in Table IV

Table IV: Half-side comparison of combability and grip

s = significantly better s ++ = highly significantly better

t + = positive trend

Tension-elongation measurements were also carried out on human hair, each in triplicate using a permanent wave preparation according to Example 3, but containing 2% by weight D / L-serine or 2% by weight L-lysine hydrochloride as a care substance. Compared to human hair, treated with the appropriate permanent wave preparation without a care substance, significantly higher strengths were achieved. Table V shows the tensile strength required in each case, which results from the tensile / stretch tests.

Table V:

The results show that an unexpected and significant increase in tear strength of more than 20% is achieved in this test by adding the respective care substance.

Claims

claims

1. hair treatment composition with ingredients customary in cosmetics with at least one care substance, characterized in that one or more compounds of the general formula (I) are contained as care substance,

wherein R1 is a hydroxy group, a (C1-C3) alkoxy group or a group of the general formula (II)

represents in which R5 can be a hydroxy group, a (CH2) 3-NH2 group or a 4-hydroxyphenyl group and R ^ can be hydrogen or a (C1-C3) alkyl group, R ² can be hydrogen or a (C1 -C3) alkyl group, R3 is hydrogen or a methyl group and R ^{4 is} a hydroxy group, a (CH2) 3-NH2 group, a 4-hydroxyphenyl group or a H2PO3 group and their physiologically tolerable salts of inorganic and / or organic bases insofar as the compounds of the general formula (I) or (II) are in the acid form and the general formula (I) or (II) comprise the D and L isomers and D / L mixtures (racemates).

2. Hair treatment composition according to claim 1, characterized in that 0.01 to 10% by weight of at least one compound of the general formula (I) is contained as care substance.

3. Hair treatment composition according to claim 1, characterized in that it contains 0.01 to 10% by weight of a compound of the general formula (I) in which R 1 = OH, R ² = H, R ³ = H and R ⁴ = OH (= Serine) means contains.

4. Hair treatment composition according to claim 1 or 2, characterized in that it contains as a care substance a compound of general formula (I), wherein Rl = OH, R ² = H, R3 = CH3 and R ⁴ = OH (= threonine) .

5. Hair treatment composition according to claim 1 or 2, characterized in that it contains as a care substance a compound of general formula (I), wherein Rl = OH, R ² = H, R ³ = H and R ⁴ = 4-hydroxyphenyl (= tyrosine) mean contains.

6. Hair treatment composition according to claim 1 or 2, characterized in that it is a ° care substance a compound of general formula (I), wherein R ¹ = OH, R ² = H, R ³ = H and R ⁴ = (CH2) 3NH2 ( = Lysine) means contains.

7. Hair treatment composition according to claim 1 or 2, characterized in that it contains as a care substance a compound of general formula (I), wherein Rl = OCH3, R ² - H, R3 = H _j 0 and R ⁴ = OH (= serine methyl ester ) mean contains.

8. Hair treatment composition according to claim 1 or 2, characterized in that it is a care substance a compound of general formula (I), wherein R ¹ = OCH3, R ² = H, R ³ = CH3 and R ⁴ = OH (= threonine methyl ester ) mean contains.

! 5 9. Hair treatment composition according to claim 1 or 2, characterized in that it is a care substance a compound of general formula (I), wherein Rl = OH, R ² = H, R ³ = H and R ⁴ = OPO (OH) ₂ ( = Phosphoserine) mean contains.

10. Hair treatment composition according to claim 1 or 2, characterized in that it contains as a care substance a compound of general formula (I), wherein Rl = OH, R ² = H, R ³ = CH3 and R ⁴ = OPO (OH) 2 ( = Phospho-threonine), contains.

11. Hair treatment composition according to claim 1 or 2, characterized in that it as

Care substance the serine dimer of the general formulas (I) and (II), wherein Rl = general

Formula (II) with R ⁵ = OH and R ⁶ = H, R ² = H, R ³ = H and R ⁴ = OH, contains. 25th

12. Hair treatment composition according to claim 1 or 2, characterized in that it contains a combination of 5 to 95 wt .-% serine and 5 to 95 wt .-% threonine as a care substance.

30 13. Hair treatment composition according to claim 1 or 2, characterized in that it contains a combination of 5 to 95 wt .-% serine and 5 to 95 wt .-% lysine as a care substance.

14. Hair treatment composition according to claim 1 or 2, characterized in that it contains a combination of 5 to 95% by weight of serine and 5 to 95% by weight of tyrosine as care substance.

35

15. Hair treatment composition according to claim 1 or 2, characterized in that it contains a combination of 5 to 95 wt .-% threonine and 5 to 95 wt .-% lysine as a care substance.

16. Hair treatment composition according to one of claims 1 to 15, characterized in that in addition to the care substance or mixture according to the general formula (I) one or more of the amino acids from the series tryptophan, glycine, alanine, valine, leucine,

Isoleucine, norleucine, phenylalanine, arginine, histidine, proline, hydroxyproline, cystine, cysteine,

Methionine, aspartic acid, glutamic acid and cysteic acid is / are and / or one or more care substances such as panthenol, tocopherol, wheat proteins, lecithins, keratin hydrolysates, silk hydrolyzates, phospholipid EFA, ceramides and pseudoceramides are / are contained

17 hair treatment composition according to one of claims 1 to 16, characterized in that compounds of the general formula (I) are contained as care substance in the L-form

18 hair treatment composition according to one of claims 1 to 17, characterized in that the pH of the composition is in the range of about 2 0 to 12 5

19 hair treatment agent according to one of claims 1 to 18, characterized in that it contains 0 01 to 10% by weight of serine, 0 1 to 5% by weight of panthenol and 0 1 to 5% by weight of phospholipid EFA as a care substance combination

20 hair treatment composition according to one of claims 1 to 18, characterized in that it contains 0 01 to 10% by weight of serine, 0.1 to 5% by weight of keratin hydrolysate and 0 1 to 8% by weight of soy lecithin as a care substance combination

21 hair treatment composition according to one of claims 1 to 20, characterized in that an aqueous preparation in the form of cream, emulsion, gel, wax, foam aerosol, or else a powdered preparation is contained as a cosmetic carrier

22 hair treatment composition according to one of claims 1 to 21, characterized in that it is an agent for cleaning the hair (hair shampoo)

23 hair treatment composition according to one of claims 1 to 21, characterized in that it is a means for setting / styling the hair (hair wax, hair gel, liquid conditioner, hair spray, hair foam)

24 hair treatment agent according to one of claims 1 to 21, characterized in that it is a means for carrying out the reducing step for permanent deformation of the hair (permanent wave preparation)

25. Hair treatment agent according to one of claims 1 to 21, characterized in that it is an agent for hair care (hair tonic, hair rinsing, hair treatment, hair pomades)