CA2107120A1 - Cosmetic preparations for the hair - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The invention concerns the use of combinations of active substances, consist-ing of (a) a cationic derivative of a protein hydrolyzate and (b) a carbohydrate and/or (c) a cationic, anionic or ampholytic polymer, in hair-cleaning and hair-care agents, thus improving the qualities of the hair, in particular its brittleness and its ease of combing when dry.

Description

PATENT .:
210 712 0 Dockcl D 9410 PCT/US

Certificate of Mailina bv ExPress Mail I h~r~by c~rtify that this paper is b~ing d~posited with th~ United S~a~es Postal Se~ice ~Express Mail Post Oflice to Address~s" s~rvice undor 37 CFR 1.10 on the dat~ indicat~d below and is addressed to ths Commissioner of Patents and Trademarks, Washington, DC 20231.
Dat~ of Depos~:
"Express Mail" Mailing Label Number (Typed or printed name of person mailing paper) . ~ :
. ''''', '' (Signature of person mailing paper) [What follows be/ow after this bracketed note, except for the edge line numbers and bottom page numbers, is a translation into English of the German lang-uage original speclfication for PCT Application No. PCT/EP92/00S86 filed on March 18, 1992. mis translation, except for the claims, should be used as the equiva/ent of the originai specification for the U.S. National Stage of this PCT :`
application. For the claims, a separatèly provided iranslation of the claims as last presented in the Intemational S~age should be used.~
~ ~;
COSMET:IC PREPARATIONS FOR THE HAIR :
:

This invention relates to cosmetic preparations for the hair containing a special combination of active substances.~
Nowadays human hair is treated in many~different ways with hair-cosmetic i~ -preparations ~ncludlng for~example the washing :of~hair with shampoos :and shower ; ..
5 ~ ~` preparations and the: bleaching7 dyeing :and~ shaplng of hair with `wave ~preparations~
tinting ~preparations ~and styling preparations. ~Almost every form of hair treatment can ~ : :
result ln unwanted~damage to:;(he~halr structure.~ Such damage is reflected inter alia n ~poor~wet and dry combability ;n ~increased electrostatic charging in~ reduced maxi~
mum~tensile s~rength~and breaking elongation of ~he hair and in the poor appearance .
0~ of ha;r~styles. ~

-"21~712 ~
One known mclhod of ovcrcoming these drawbacks is lo subject the hair to after~reatmen~ wi~h suitable aclive subslances, generally cationic surfactant~s, which may optionally be combined wilh other subslances However, this approach is unsatisfactory in many respects.
s Thus, it is known that cationic surfactants are only suitable for the treatmenl of non-greasy hair. By contrast, their use on greasy hair is problematical because they impose an additional burden on the hair and intensify the natural refatting process.
In addition, the quaternary ammonium compounds typically used as cationic surfactants show inadequate biode~radability so that their use should be avoided or re-duced on ecological grounds.
Another unsatisfactory aspect is that any treatment with cationic surfactants generally has to be carried out in a separate step, normally by rinsing, because cationic surfactants often cannot be incorporated in preparations containing anionic surfactants, such as shampoos for example.
Another group of substances used to prevent unwanted darnage to hair are the protein hydrolyzates.
DE 35 28 168 describes synergistic mixtures of protein hydrolyzates and mono-, di- and oligo-saccharides which are distinguished by good film-forming properties as required for the treatment of unwanted damage to hair. Unfortunately, mixtures of known protein hydrolyzates and saccharides have the disadvantage that the so-called Maillard reaction can take place durin~ storage at room temperature. This results in degradation of the active substance and turns the preparations brown in color. This brown coloration is generally not accepted by the consumer so that it has to be masked by addition of increased quantities of dyes.
., .
Accordingly, there is still a need for hair cosmetic preparations which are dis-tinguished by a reducbon in unwanted damage to the hair. ~ .
It has now surprisingly been found that hair cosmetic preparations containing : ~ .
a~cationically derivatized protein hydrolyzate (A) and a carbohydrate (B) and/or a cati-anic, amonic or ampholytic polymer (C) have a far less unfavorable influence on the :
hair.~ The use of these combinations of active substances increases the tensile strength of ~hair and also provides for better style retention and improved volume. In addition, .. : ~:
no~ Maillard reaction occurs in the combinations (A)+(B) and (A)+(B)+(C).

' , ' ~ ,.. . ! ' . . . , ., ' ' ,i ' " ' -- 21~71~0 Accordingly, Ihc present invention relates to preparations containing typical constitucnts for the washing and care of hair, charactcrized in that they contain a com-bination of active substances consisting of (A) a cationically derivatized protein hy-drolyzate and (B) a carbohydrate and/or (C) a cationic, anionic or ampholytic polymer.
Cationically derivatized protein hydrolyzates (A) are n~ixtures of substances which ma~y be o~tained, for example, by reaction of alkali-, acid- or enzyme-hydro-lyzed proteins with glyciclyl trialkyl ammonium salts or 3-halo-2-hydroxypropyl trial-kyl arnmonium salts.
Proteins used as starting materials for the protein hydrolyzates may be of both animal and vegetable origin. Typical starting materials are, for example, keratin, col-lagen, elastin, soya protein, milk protein, wheat protein, silk protein and almond pro-tein.
Mixtures having molecular weights in the range from about 100 to about 50,000 Daltons are formed by the hydrolysis. Typical average molecular weights are in the range from about 500 to about 1000 Dalton.
Further particulars of cationic derivatization can be found inter alia in Japanese patent application 77173485 (Chemical Abstracts, AbsLract 90:174508v).
The cationically derivatized protein hydrolyzates advantageously contain one or two long alkyl chains containing 8 to 22 carbon atoms and, accordingly, two or one short alkyl chain containing 1 to 4 carbon atoms. Compounds containing one long .
alkyl chain are preferred. ;
Preferred compounds (A) correspond to formula (I): i R' ..
R3-N+-CH2-CH-CH2-(NH-CH-C)"-oH (I), ~ ~
~ . , R2 OH ; R O ~:
in which R represents the side chains of the amino acids of the protein, R' and R2 in- -dependently of one another represent alkyl chains containrng 1 to 4 carbon atoms and : 30 R3 represents an alkyl shain containing 8 to 22 carbon atoms.
A; commercially available product is Lamequat(~L (Chemische Fabrik Grunau).
It~has the following structure: -:
~1~7120 CH
3 .
CH,-(CH~ N+-CH2-CH-CH2-(NH-CH-C)n-OH, s CH3 OH R O
in which R represents the side chains of the amino acids of collagcn. Its CTFA name is Lauryldimonium Hydroxypropylamino Hydrolyzed Animal Protein. This product is a particularly preferred component (A).
According to the invention, both monosaccharides and oligosaccharides, such as for example cane sugar, lactose and raffinose, may be used as the carbohydrates (B). The use of monosaccharides is preferred. Preferred rnonosaccharides are com-pounds containing 5 or 6 carbon atoms.
Suitable pentoses and hexoses are, for example, ribose, arabinose, xylose, lyx-ose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose and fructose.
Arabinose, glucose, galactose and fructose are preferred carbohydrates, glucose being particularly preferred.
In addition, derivatives of these pentoses and hexoses, such as the correspond-ing onic and uronic acids ~sugar acids), sugar alcohols and glycosides, may also be used in accordance with the invention. Preferred sugar acids are gluconic acid, glucuronic acid, sugar acid, mannosugar acid and mucic acid. Preferred sugar alcohols are sorbitol, mannitol and dulcitol. Preferred glycosides are the methyl glucosides.
Quaternized carbohydrates may also be used as component (B) in accordance with the invention. The commercial product Glucquat(i~)100 (CTFA name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride) is a preferred quatemized car-bohydrate.
Since the carbohydrates used are normally obtained from natural raw materials, such as starch, the carbohydrates generally have the configurations corresponding to these~ raw materials (for example D-glucose, D-fructvse and D-galactose).
The following are examples of calionic polymers (C) suitable for use in ac-` ~ 30 ~ cordance with the invention: ~
Suitable cationic polymers (C) are, for example:
Quaternized~cellulose denvatives of the type commercially available under the names of Celquat~ and Polymer JR~. The compounds Celquat H 100, Cel-..
4 ~ ~
.
: ': ..

- .

~107120 :
qual L 200 and Polymer JR(I) 400 are preferred qualernized ccllulosc deriva-lives.
- Copolymers of vinyl pyrrolidone with quaterni~ed derivatives of dialkyl amino-acrylate and methacrylate, for example vinyl pyrrolidone/dimethyl aminometh-acrylate copolymers qua~ernized with dielhyl sulfate. Compounds such as these are commercially available under the names of Gafquat~ 734 and Gaf-quat(~ 755.
- Vinyl pyrrolidone/methoimidazolinium chloride copolymers of the type com-mercially available under the name of Luviquat(~.
o - Polymeric dimethyl diallyl ammonium salts and copolymers thereof with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names of Merquat~) 100 ~poly(dimethyl diallyl ammonium chloride) ~ and Merquat(~) 550 (dimethyl diallyl ammonium chloride/acrylamide copolymer) are examples of such cationic polymers.
Examples of anionic polymers suitable for the purposes of the invention are:
- Polyacrylic and polymothacrylic acids, salts thereof, copolymers thereof with esters and amides of (meth)acrylic acid and derivatives thereof obtained by ~rosslinking with polyfunchonal agents. Compounds of this type are commer-cially available, for example, under the names of Carbopol~ 934, Carbopol~
934P, Carbopol(~ 940, Carbopol(~) 950, Carbopol~) 980 and Hostacerin~9 PN
73.
- Polyoxycarboxylic acids, such as polyketocarboxylic and polyaldehydocarbox-ylic acids and salts thereof, such as for example ~POC~) HS 5060 and POC~
AS 5060.
25 - Polymers and ~copolymers of crotonic acid with esters and amides of (methj-acrylic acid,~such as vinyl acelatelcrotonic acid and vinyl acetate/ vinyl propio-nate/crotonic acid copolymers. Compoonds of this type are commercially available as Luviset~) CA-66 and Luviset(~ CAP.
ln the context of the invention, ampholytlc polymers are understood to be am-~ photeric polymers,~.e.~ polymers which contain ~both free amino; groups and free COl)H~or SO3H groups ~n the moiecole and which are capable of forming inner salts, zwitterionic polymers containing quaternary ammonium groups and -COO- or -SO3 :: : : : -` :

~: : ~ .',' ' . ':

groups in Ihe molecule and polymers containing -COOH or SO3H groups and quater-nary ammonium groups.
One example of an ampholytic polymer suitable for use in accordance with the invention is the acrylic resin commercially available as Amphomer(~) which is a co-s polymer of tert-bulyl aminoethyl methacrylate, N-(1,1,3,3-telramelhylbutyl)-acrylamide and two or more monomers from the group consisting of acrylic acid, methacrylic acid and simple esters thereof.
Other ampholytic polymers suitable for use in accordance with the invention are the cornpounds mentioned in GB-A-2,104,091, EP-A-47 714, EP-A-217 274, EP-A-283 817 and DE-A-28 17 369.
Preferred ampholytic polymers are polymers consisting essentially of (a) monomers containing quaternary ammonium groups corresponding to general formula (II): ~ :
R4-CH=CR5-Co-Z-(CnH~n)-N(+)R6R7Rg A(-) (II), in which R~ and R5 independently of one another represent l1ydrogen or a ~ -methyl group and R6, R7 and R8 independently of one another represent C,~
alkyl groups, Z is an NH group or an oxygen atom, n is an integer of 2 to 5 and A(-) is the anion of an organic or inorganic acid; -and 20 (b) monomeric carboxylic acids corresponding to general formula (III):
~ R9-CH=CR'0-CooH (III) ;
in which R9 and R! mdependently of one another represent hydrogen or methyl groups.
These compounds may be used in accordance with the invention both directly and in salt form, i.e. after neutralization of the polymers, for example with an aLkali :: -metal hydroxlde. Full particulars of the production of these polymers can be found ;
in DE-A-39 29 973. Polymers in which monomers of type (a), where R6, R7 and R8 are~ methyl groups, Z is an NH group and A( ) is a halide, methoxysulfate or ethoxysul-fate ion, are most particularly preferred~ Acrylamidopropyl trimethyl ammonium 30 ~ ~ chlonde~ ls a parbcularly preferled monomer (a). Acrylic acid is preferably used as ~ -monomer (b)~ for the polymers mentioned~
The active substances (A) are present in a quantity of 0.1 to 10 % by weight, based on thc preparation as a whole. Concenlrations of 0.5 to 5 % by weighl are pre-fcrrcd.
The aclivc substanccs (B) are also present in a quantity of 0.1 to 10 % by weight, based on the preparation as a whole. Concentrations of 0.5 to 5 % by weight s are preferred.
I~ has been found that a parlicularly advantageous effect is obtained when com-pounds (A) and (B) are present in a ratio by weight of 0.5:1 to 2:1. Preparations in .
which componenls (A) and (B) are present in substantially equal parts by weight are particularly preferred. :.
o The active substances (C) are preferably present in the preparations according to the invention in a quantity of 0.1 to 5 % by weight and, more preferably, in a quantity of 0.2 to 2 % by weight, based on the preparation as a whole.
Although the combinations of active substance (A) and active substanc.e (B) .
or active substance (A) and aclive substance (C) have a surprisingly strong effect on :
the structure and proper~ies of ~he hair, ii has been found that a further unexpectedly :
marked increase in effect occurs where all three active substances are combined. . .
In one preferred embodiment, therefore, the preparations according to the in-vention contain both active substance (B) and active substance (C) in addition to ac-tive substance (A). Combinations of (A), (B) and (C), in which (C) is an ampholytic polymer, are most particularly preferred.
The preparations according to the invention may be used both in hair treatment . . .
processes in which the preparation is rinsed out from the hair after use and in hair . . - .
treatment processes where the preparation remains in the halr. : .
Preparations which are normally rinsed from the hair after use are, for exam- . -25 ple, shampoosj wave preparations and coloring preparations. Products which normally remain in the hair are, for example, hair setting preparations, hair tonics and blow-wave preparations. In addition to the compulsory components, any other auxiliaries and addltives typical of the application in question may be present, depending on the type and prèparation.
: 30 ~ In the case of shampoos. such auxiliaries and additives besides water as the base are anionic, nonionic and ~witterionic surfactants, pearlescers, perfumes, pH regu-I ators, dyes, preservatives, optionally alkoxylated fatty acids and fatty alcohols and , .

:

- 2107~20 viscosily regulalors.
Hair rinses, which arc also water-based in most cascs, generally contain quater-nary ammonium compounds, lower alcohols, solubilizers, active principles, such as panthenol for example, nonionic polymers, YiSCoSi~y regulators and perfume oils.s In addition to water, hair setling preparations generally contain lower alcohols, surfactants, preterably nonionic surractants, stabilizers, cationic and/or anionic poly-mers, pH regula~ors and - in the case of setting foams - propellants.
Hair coloring preparations normally contain substantive dyes and/or oxidation dye precursors (modifiers, developer components), surfactants~ fatty alcohols and pH
regulators.
In addition to a reducing agent (thioglycolic acid, thiolactic acid), wave prepa-rations generally contain pH regulators, surfactants, complexing agents, solubilizers, fatty alcohols and perfume oils. The corresponding fixing solutions contain oxidizing agents, such as hydrogen peroxide and potassium bromate, instead of the reducingagent.
E x a m p l e s 1. Determination oî hair properties Four shampoos were tested, their compositions being set out in Table 1 below.
a) Elongation measurements on treated hair Alkinco type 6621 hair tresses (tress length: 12 cm) were used for the measurements.
The tresses were treated for 20 minutes with the test shampoo, then rinsed for aboul 30 seconds and dried with a blow dryer for about 1.5 hours at 38 C. The tresses were then ultrableached for 20 minutes (composition of the ultrableach: 6 2s by weight of hydrogen peroxide, 15 ~o by weight of ammonium peroxydisulfate, conc ammonia ad pH 9.4, remainder water) and rinsed with water for about I minute. The . :
wet tresses were then sharnpooed, rinsed :and dried as described above. The tresses .
were then cold-waved (wave solution: 7 % by weight thioglycolic açid,;conc. ammonia ad~pH 9.0, remainder water), rinsed with water (38 C) for about 1 minute and treated .
30~ with~a fixing solutlon (2 % by~weight hydrogen peroxide, citric acid ad pH 4.0, re-mainder water), shampooed, rinsed and dried as described above. The cycle of ultra- .;
; bleaching, rinsing, shampooing, rinsing, drying, cold waving, rinsing, fixing, rinsing, :

' - ' :, .

21~7~20 .

Table 1: Test shampoos Component 1 2 3 4 Texapon~N25' 43 43 43 43 Dehylon(~)K-IS2 10 10 10 10 Euperlan(~PK 810 IS3 5 5 5 5 Akypo(~RLM 100 NV4 5 5 5 5 :. .
Edenor KPK C12-18 + 9.2 EOs Preservative 0.3 0.3 0.3 0.3 Sodium chloride 1.2 0.25 0.19 0.19 Perfume oil, dyes l.l l.l 1.1 1.1 Lamequat~L6 - 3 3 3 :
D glucose - 3 3 3 Polymer JR(~4007 - - 0.2 Polymer Pl acc. to DE 39 29 9738 Citric acid ad pH 7.2 7.2 7.2 7.0 .
Water ~ ad 100 Viscosity ~mPas] 93009700 8500 9200 .
Sodium lauryl ether sulfate; CTFA name: Sodium Laureth Sulfate (about 28 % active substance in water) (HENKEL) : ;

2 Fatty acid amide derivative, betaine structure, corresponding to the formulaR-CONH-(CH,)3-N+(CH3)2-CH2-COO; CFTA name: Cocoarnidopropyl Be-taine (about 30 % active substance in water) (HENKEL) . .

3 Mixture of fatty alcohol ether sulfates with pearlescing substances; CTFA
name: Clycol Distearate (and) Sodium Laureth Sulfate (and) Cocoarnide MEA (and) Laureth-9 (about 37 5'c active substance, including about 13 %
anionic surfactant, in water) (HENKEL) .
: 4 C12 14 fatty alcohol + 10 EO acetic acid sodium salt; CTFA name: Sodium Laureth-ll Carboxyiate (22 % active substance) (CHEM-Y) 5 ~ ~ Coconut palm kernel oil fatty acid (C~2~l8) -t 9.2 ethylene oxide (HENKEL) ~ ~ 9 "~
. .

:

2107~2 0 ``
6 Cationic prolein hydrolyzate corresponding to tlle formula:
CH3 ~ -, CH3-(CH2)"-N+-CH2-CH-CH2-(NH-CH-C)"-OH, ':

(R = side chains of the aminoacids of collagen); CTFA name: Lauryldimon- i -ium Hydroxypropylamino Hydrolyzed Animal Protein (about 35 % dry mat-ter) ~CHEMISCHE FABRIK GRUNAU) .
0 7 Quaternized hydroxyethyl cellulose (Union Carbide) 8 Polymer of acrylamidopropyl trimethyl ammonium chloride and acrylic acid in a molar ratio of 3:1, neutralized with NaOH (20 % active substance in i:
water).

~s shampooing, rinsing and drying was then repeated another two times. For the dry mea~
surement, the tresses were heated in air at 38 C. For the wet measurements, the .
tresses were stored in water until just before the measurement. - -The following values were determined:
Maximum breaking s~ress ~tensile force at which the hair breaks) . .:
15 % Elongation value (tensile force at which the hair is elongated by 15 %) Breaking elongation (~o elongation at which the hair breaks) : . ``:
Brittleness Particulars of the measuring process can be found in the literature (Arztl. , . -Kosmetologie 15, 347 - 355 (1985) and Parf~merie & Kosmetik 72, 74 - 81 (19gl)).Brittleness is determined as the percentage of hairs which show a break at 20 % elongation and less.
Wet meaeurement Shampoo 1 2 3 4 Maximum breaking stress ~mN~ ~ 380 462 390 511 :~ -15~ % longation value [mNl ; ~ ~ ~ 268 307 290 304 30~

:

2107~20 Drv measuremcnt Shampoo 1 2 3 4 Maximum brcaking stless [mN] 477 446 461 501 15 % Elongalion value [mN] 432 401 403 418 Breaking Elongatioll [%1 21 28 28 42 s Britlleness [~c] 68 52 52 30 b) Determination of the dry combing work The dry combing work was determined on brown hair (Alkinco 6634, tress length 12 cm, tress weight 1 g) in the form of a comparison of paired mean values.
10 To determine the zero value, the tresses were rinsed with water (1 l/min, 38 C~ for 1.5 minutes and combed out. The tresses were then dried wilh a blow dryer for 40minutes at 45 C. After conditioning for 12 hours at 30 C/40 % relative air humidi-ty, the combing work was determined. The tresses were then treated with 100 g ofthe formulation for 5 minutes and then rinsed, dried and conditioned as described above. The dry combing work was then determined. Particulars of the measuring process can be found in ihe literature (Arztl. Kosmetologie 20, 498-502 (1990)). ~`
The following combing work values were measured:
':~
Shampoo Drv Combin~ Workt mJb/a. %
Before After 6.5 6.5 100 2 5.1 7.6 150 3 5.~ 9.7 175 4 7.6 10.9 144 :
. . .

' ' ~.
: ~ .
,.
.-:: 1 1 :
.. ..
~' -: ~. .
.

2~ ~7120 2. Application Ex~mples a) Hair se~ting foam % by weight Eumulgin OS9 O.S -s Luviset CA-66' 4.5 AMP-95"
Gafquat 75512 O.S
D glucose 0.2 Lamequat~L 0.2 Ammonia (2~% solution) 0.1 Perfume oil û. 13 Ethanol S.0 Drivosol~3.5'3 7.0 Water ad 100 : , . ' -9 Oleyl alcohol ~ S ethylene oxide; CTFA name: O]eth-S (HENKEL) ' Vinyl acetate/crotonic acid copolymer (90:10) (BASF) " 2-Amino-2-methyl propanol (9S % active substance, remainder water) (ANGUS CHEMIE~
12 Dimethylaminoethyl methacrylate/vinyl pyrrolidone copolymer quaternized : - `.
with diethyl sulfate; CTFA name: Polyquaternium 11 (about 19 % active sub- ; . .
stance in water) (GAF) ~ -13 ~ Propane/~sobutane/butane/dimethyl ether mixture (24:72:3:1) (HULS) ` : : , , .`,'.
..
......
.
~: ~ : . :;., : ~ ... . .

2~07120 b) Rinse Cremophor(~RH 4014 1.s Dehyquart~SP'5 1.0 Luviskol~)K 3016 1.0 Panthenol 1.0 D glucose 2.0 Lamequat(8)L 1.0 Polymer Pl acc. to DE 39 29 973 3.0 Hydroxyethyl cellulose 1.8 Ethanol (96%) 12.0 Water ad 100 .. __ . . !
4 Hydro~enated castor oil reacted with 45 moles of ethylene oxide per mole of !, castor oil (BASF) IS Oxyethyl alkylammonium phosphate; CTFA name: Quaternium-52 (S0 %
active substance in water) (HENKIEL) 16 Polyvinyi pyrrolidone (95% active sobstance, remainder water) (BASF).

~ , '' , .
. . .
- .

' ', : . .

.. .. ~ .-., . . ~ ... ~... . . . . . . ... . .. ... .. .. ... ... .. .. . .

Claims (5)

Article 34 Amendment

1. Preparations containing typical constituents for the cleaning and care of hair, characterized in that they contain a combination of active substances consisting of (A) a cationically derivatized protein hydrolyzate, (B) a carbohydrate selected from - monosaccharides, - oligosaccharides, - onic and uronic acids (sugar acids), - sugar alcohols and - glycosides and (C) a cationic, anionic or ampholytic polymer.

2. Preparations as claimed in claim 1, characterized in that (A) is a compound corresponding to formula (I):

(I), in which R represents the side chains of the aminoacids of the protein, R1 and R2 inde-pendently of one another represent alkyl chains containing 1 to 4 carbon atoms and R3 represents an alkyl chain containing 8 to 22 carbon atoms.

3. Preparations as claimed in claim 2, characterized in that (A) is a compound of formula (I) in which R1 and R2 are methyl groups and R3 is a lauryl group.

4. Preparations as claimed in any of claims 1 to 3, characterized in that a carbo-hydrate containing 5 or 6 carbon atoms is present as active substance (B).

5. Preparations as claimed in claim 4, characterized in that glucose is present as the carbohydrate.