WO2001035909A1

WO2001035909A1 - Anti-grease hair treatment preparation

Info

Publication number: WO2001035909A1
Application number: PCT/EP2000/010998
Authority: WO
Inventors: Manuela Ehlert; Ulrich Bernecker; Detlef Hollenberg
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-11-17
Filing date: 2000-11-08
Publication date: 2001-05-25
Also published as: DE19955239A1

Abstract

Zwitterionic polymerizates comprising free carboxyl groups and quaternary ammonium groups are suited as constituents in hair treatment preparations for reducing the greasy appearance of hair. Aqueous hair treatment preparations as well as those that are rinsed out of the hair after use, and the zwitterionic polymerizates with carboxyl groups and quaternary ammonium groups contain a surfactant in quantities of 1-10 wt. % and 1-30 wt. %, they improve the fullness of hair and they reduce the straggly or greasy appearance of the hairstyle.

Description

"Anti fat hair products'

The invention relates to the use of zwitterionic polymers as a component in hair care products for reducing the greasy appearance of the hair. Oily hair is perceived by most people in Central Europe and North America as a cosmetic problem. This manifests itself essentially in the fact that the hair looks streaky and appears to be less voluminous. Greasy hair is difficult to style because the fibers adhere to one another over large areas. So far, greasy-looking hair has been treated with agents that counteract excessive sebum production. Frequent washing and wearing shorter hairstyles have also been recommended to reduce the problems of oily hair. From SÖFW-Journal, 120th volume, 6/1994, page 340-344 it is known that the regreasing of the hair can also be slowed down with an abietic acid-protein condensate.

The previous methods for reducing the greasy appearance of the hair are partly not useful for cosmetic use because they represent too much interference in the physiology of the scalp, but partly they are also very ineffective or have serious disadvantages.

Shampoos containing zwitterionic polymers were also known from EP 283 817 B1 and GB 2 104 091 A1, but no degreasing action of these polymers was disclosed there.

It has now surprisingly been found that water-soluble, zwitterionic polymers in hair care products, for. B. in hair rinses or hair shampoos, slow down the re-greasing of the hair very clearly.

The invention therefore relates to a process for reducing the greasy appearance of the hair by treating the hair with a hair care product in the form of an aqueous preparation which contains a zwitterionic polymer with free carboxyl groups and quaternary ammonium groups dissolved therein. All hair cosmetic preparations which are used in the form of aqueous preparations on the hair can be used as hair care products. Such preparations are e.g. B. hair rinses, hair shampoos, oxidizing dye developers, permanent wave fixatives, hair fixatives, water wave lotions, and other aqueous hair cosmetics. It is particularly surprising here that the effect of the zwitterionic polymers is also imparted by preparations which are rinsed out of the hair after use (rinse-off preparations). A particularly preferred embodiment of the method therefore consists in rinsing the hair with water after the treatment with the hair care product and after a contact time. Such preferred hair treatment agents are, in particular, hair rinses, hair treatments and shampoos.

Numerous zwitterionic polymers with free carboxyl groups and quaternary ammonium groups are known. What is important for the purposes of the present invention, however, is water solubility which enables a clear solution of at least 0.5% by weight of the polymers in water at 20 ° C.

Suitable zwitterionic polymers can be obtained either by polymerizing zwitterionic monomers or by copolymerizing cationic monomers with quaternary ammonium groups, unsaturated carboxylic acids and, if appropriate, neutral monomers.

A particularly preferred group of zwitterionic polymers consists essentially of monomers with quaternary ammonium groups of the formula I,

R'-CH = CR ² -CO-Z- (C _n -H _2n ) -N ⁽⁺⁾ (CH ₃ ) ₃ A ^Θ (I)

in which R ¹ and R ^{2 are} hydrogen or methyl groups, Z is an oxygen atom or an NH group. n = 2 to 5 and A ^(" 'is a chloride, bromide, methoxysulfate or ethoxysulfate anion. Monomers with free carboxyl groups of formula II,

R ³ -CH = CR ⁴ -COOH (II)

in which R ³ and R ^{4 are} hydrogen or methyl groups and monomers with ester groups of the formula III,

R ⁵ -CH = CR ⁶ -COOR ⁷ (III) in which R ⁵ and R are hydrogen or methyl groups and R ^{7 is} an alkyl group with 1-4

C atoms is together.

Suitable monomers of formula I are e.g. B .:

Methacrylamidopropyl trimethylammonium chloride or acrylic acid trimethylammonioethyl ester chloride.

Suitable monomers of formula II are e.g. B. acrylic acid, methacrylic acid or crotonic acid and suitable monomers of formula III are such. B. ethyl acrylate, butyl methacrylate or

Methyl methacrylate.

The term "consisting essentially of" is intended to express that minor

Fractions of up to 5 mol% of other neutral monomers or non-quaternized cationic

Monomers can be contained in the preferably suitable zwitterionic polymers without the effect of delaying the regreasing of the hair suffering. Particularly good effects, especially in delaying the regreasing of the hair, have been found in such

Compositions observed made from zwitterionic polymers

30-40 mol% of monomers of the formula I,

20-30 mol% of monomers of the formula II and

Contain 40-50 mol% of monomers of the formula III.

The effect of the zwitterionic polymers is achieved not only from aqueous solutions, but from typical aqueous hair-cosmic preparations, such as those used for. B. for the purposes of hair remediation, antistatic treatment, shampooing, setting and for other hair cosmetic tasks. A surfactant content

Fabrics are not detrimental to the retoiling effect of hair. Another object of the invention is therefore an aqueous hair care product for reducing the greasy appearance of the hair, which 1-20% by weight of a zwitterionic polymer, which essentially consists of

30-40 mol% of a monomer of the formula I,

20-30 mol% of a monomer of formula II and

40-50 mol% of a monomer of the formula III,

such as

Contains 1-30% by weight of anionic, ampholytic, zwitterionic, cationic or nonionic surfactants or a mixture thereof.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

Ether carboxylic acids of the formula RO- (CH ₂ -CH O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group,

Sulphosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms. Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula R- (OCH -CH) -OSO H, in which R is a preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12 is

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide on fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one in the molecule

Wear a -COO or -SO group. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammonium glycinate, and 2-alkyl -3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C ₈ -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO H group in the molecule and are used for Are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N- alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-

Alkyltaurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-cocoalkylaminopropionate and the cocoacylaminoethylaminopropionate.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

Addition products of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group , C ₁₂ . ₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol, C 8-22 alkyl mono- and oligoglycosides and their ethoxylated analogues,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened

Castor oil,

Addition products of ethylene oxide with sorbitan fatty acid esters

Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethyla monium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention. Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines such as the ^{stearylamidopropyldimethylamine} available under the name Tego Amid ^® S 18, are notable for their good biodegradability.

Also very readily biodegradable quaternary Esterverbindungen, so-called "esterquats", such as the Diacyloxyethyl- marketed under the trademark Stepantex ^® are dimethyl-methosulfates and methyl hydroxyalkyldialkoyloxyalkyl- methosulfates.

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to CTFA nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds with alkyl or acyl groups used as surfactants can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different chain lengths depending on the respective raw material are obtained.

Another object of the invention is an aqueous hair care product in the form of a

Hair conditioner, that

1-10% by weight of a zwitterionic polymer

1-5% by weight of a cationic surfactant and, if appropriate

Contains 0.05-1% by weight of a cationic polymer. The cationic surfactants counteract the static chargeability of the hair in such preparations, which makes combing easier and the fit of the hairstyle improved. The cationic polymers are characterized by a lasting improvement in the combability of wet hair and the detangling ability of dry hair. In this way, hair that has been damaged or damaged in the structure by numerous dyeing or permanent wave processes is noticeably softened. The hair rinses according to the invention are therefore also suitable as hair treatment preparations for greasy hair or hair prone to re-greasing, in particular after dyeing and permanent wave applications.

Suitable cationic polymers are synthetic polymers or natural polysaccharide or protein derivatives that contain a cationic grouping z. B. contain a tertiary amino group or a quaternary ammonium group in the chain or on the chain. Examples of such suitable cationic polymers are e.g. B.

- Quaternized cellulose derivatives, such as z. B. are sold under the trade name Celquat ^® L200 or Polymer JR 400, polysiloxanes with quaternary ammonium groups,

Dimethyl-diallylammonium chloride polymers and their copolymers with acrylamide, such as z. B. are commercially available under the trademark Merquat ^® 550, dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, quaternized with dimethyl sulfate, such as those used for. B. are commercially available under the trademark Gafquat ^® 755, vinylimidazolinium methoxychloride-vinylpyrrolidone copolymers (Luviquat FC550)

Poly- (N- (3- (dimethylammonium) propyl) -N - (3-ethyleneoxyethylene-dimethylammonium) propyl) urea dichloride (Mirapol AI 5)

An important factor for a satisfactory effect is a water solubility of the cationic polymers of at least 0.5 g / 1 at 25 ° C. Another object of the invention is an aqueous hair care product in the form of a

Hair shampoos, that

1-10% by weight of the zwitterionic polymer

5-35% by weight of a water-soluble anionic surfactant and optionally

Contains 0.05-0.5% by weight of a cationic polymer.

Preferred anionic surfactants are alkyl polyglycol ether sulfates with 10-16 C atoms in the alkyl group and 1-12 glycol ether groups in the form of their alkali metal, magnesium or ammonium salts or also alkyl sulfates with 10-16 C atoms in the alkyl group in the form of their mono-, di - Or contain triethanolammonium salts or their isopropanolammonium salts.

Other auxiliaries and additives that can be contained in the inventive hair conditioners and shampoos are, for. B.

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed glow, dextrans, cellulose derivatives, e.g. As methyl cellulose, hydroxyalkyl cellulose and carboxy methyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol,

Structurants such as glucose and maleic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin,

Egg lecithin and cephaline, as well as silicone oils,

Protein hydrolyzates, especially elastin, collagen, keratin, milk protein,

Soy protein and wheat protein hydrolyzates, their condensation products with

Fatty acids and quaternized protein hydrolyzates,

Perfume oils

Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol

Glycerin and diethylene glycol,

Dyes for coloring the preparations,

Anti-dandruff agents such as Piroctone Olamine and Zink Omadine, salicylic acid other substances for adjusting the pH value,

Active ingredients such as panthenol, pantothenic acid, niacinamide, allantoin,

Pyrrolidone carboxylic acids and their salts, plant extracts and vitamins,

Cholesterol,

Light stabilizers,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,

Fats and waxes such as whale, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,

fatty acid,

Complexing agents such as EDTA, NTA and phosphonic acids,

Swelling and penetration substances such as glycerin, propylene glycol monoethyl ether,

Guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers like latex,

Pearlescent agents such as ethylene glycol mono- and distearate,

Blowing agents such as propane-butane mixtures, NO, dimethyl ether, CO and air,

Antioxidants, as well

Preservatives such as B. p-hydroxybenzoic acid ester, phenoxyethanol and

Sodium benzoate.

The following examples are intended to explain the subject of the invention in more detail:

Examples

Hair rinses of the following composition were produced:

Polymer S is a zwitterionic polymer made from methacrylamidopropyl trimethylammonium chloride, sodium acrylate and ethyl acrylate in a molar ratio of 3: 2: 4 (22% aqueous solution, pH = 7). Commercial name: Amphopolymer SCI 6060-3 (Cognis Deutschland GmbH) 12

Hair shampoos of the following composition were produced:

The following commercial products were used:

Dehyquart A: Cetyltrimethylammonium chloride 25% by weight in water (Henkel KGaA)

Celquat ^® L 200: cellulose derivative, quaternized (Polyquaternium-4) (National Starch & Chemical)

Euxyl ^® K 400: methyldibromoglutaronitrile (20% by weight) in phenoxyethanol. (Schülke & Mayr)

Cremophor ^® RH 40: hydraulic castor oil oxethylate (40 mol EO). (BASF) Natrosol ^® 250 HR: hydroxyethyl cellulose (Hercules) Luviskol ^® K 30: Polyvinylpyrrolidone (K-value 27-33). (BASF) Texapon ^® N50: alkyl (Cι _2/14 ) polyglycol ether (2EO) sulfate, Na salt, 28% by weight in water (Henkel KGaA)

Dehyton ^® G: N- (2-hydroxyethyl) -N-kokosalkylamidoethylcarboxymethyl- glycinate. Na salt. (Henkel KGaA) Polymer JR ^® 400: hydroxyethyl cellulose quaternized (Polyquaternium -10).

(Amerchol) Euperlan ^® PK900: Pearlescent concentrate based on PEG-3 distearate, Na Laurethsulfa

Water (solids content 35-38% by weight in water).

Checking the greasiness of strands of hair

2 g heavy, 18 cm long hair strands of type 6634 (from Alkinco) were used. These were pre-cleaned (30min., 25 ° C) with a 12% alkyl ether sulfate solution (Texapon ^® NSO, pH = 6.5), rinsed (5min., 25 ° C) and dried (40 ° C, 20% relative humidity).

The pre-cleaned hair strands were measured for their volume using the silhouette method.

Then the strands were combed 20 times and measured again.

Treatment with hair rinsing agents 1 and IV (comparison without active ingredient) or 2 and 2 V was then carried out. 2 g were applied to each strand and after an exposure time of 5

Minutes rinsed with water (1 min, 25 ° C).

Then the strands were dried (40 ° C, 20% relative humidity), in the dried

Condition combed and measured again. After that, the strands were covered with a

Sebum comb 'combed 100 times and measured again.

^* T_) he sebum comb contains a reservoir made of cellulose filling material and fiber tines

Fiber post material. It is used for the defined application of sebum (synthetic skin fat according to Bey), which is contained in the reservoir as a 5% solution in isopropanol and at

Combing is applied to the strand of hair.

(The fuller the hair, the larger the shadow area of the streak, the greasier the hair appears, the smaller the shadow area of the strand). Results

The results listed in the following table are mean values from 10 measurements each.

The experiment shows that the zwitterionic polymer S in hair conditioner (1) improves the fullness of the hair. He also shows that a defined supply of sebum leads to a smaller decrease in the fullness of the hair than in the case of hair treated with formulation IV (without zwitterionic polymer).

In the case of shampoo (2), there is initially no improvement in the fullness, but the regreasing of the hair (with a defined supply of sebum) is significantly reduced.

Claims

claims

1. A method for reducing the greasy appearance of the hair by treating the hair with a hair care product, characterized in that an aqueous preparation containing a zwitterionic polymer with free carboxyl groups and quaternary ammonium groups is used as the hair care product.

2. The method according to claim 1, characterized in that the zwitterionic polymer consists essentially of monomers with quaternary ammonium groups of the formula I,

(I) R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ⁽⁺⁾ (CH ₃ ) ₃ A ( ^: -)

in which R 'and R ^{2 are} hydrogen or methyl groups, Z is an oxygen atom or an NH group, n = 2 to 5 and A ^{w is} a chloride, bromide, methoxysulfate or ethoxysulfate anion, monomers with free carboxyl groups of the formula II,

(II) R ³ -CH = CR ⁴ -COOH

(III) R ⁵ -CH = CR ⁶ -COOR ⁷

in which R and R are hydrogen or methyl groups and R is an alkyl group with 1-4 C atoms.

3. The method according to claim 1 or 2, characterized in that the hair is rinsed with water after treatment with the hair care product and after an exposure time.

4. The method according to any one of claims 1-3, characterized in that the zwitterionic polymer from

30-40 mol% of the monomer of formula I 20-30 mol% of the monomer of formula II and 40-50 mol% of the monomer of formula III

is composed.

5. Use of zwitterionic polymers, which essentially consist of

(A) monomers with quaternary ammonium groups of the formula I,

(I) R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ⁽⁺⁾ (CH ₃ ) ₃ A ^ω

1 ^* ) in which R and R are hydrogen or methyl groups, Z is an oxygen atom or an NH group, n = 2 to 5 and A ^{(_) is} a chloride, bromide, methoxysulfate or ethoxysulfate anion,

(B) monomers with free carboxyl groups of the formula II,

(II) R ³ -CH = CR ⁴ -COOH

in which R ³ and R ^{4 are} hydrogen or methyl groups and

(C) monomers with ester groups of the formula III,

(III) R ⁵ -CH = CR ⁶ -COOR ⁷

in which R ³ and R ^{6 are} hydrogen or methyl groups and R ^{7 is} an alkyl group with 1-4 C atoms, as a component in aqueous hair products to reduce the greasy appearance of the hair. Aqueous hair care product for reducing the greasy appearance of the hair, characterized by a content of

1-10% by weight of a zwitterionic polymer, which essentially consists of

30-40 mol% of a monomer of the formula I,

(I) R ^! -CH = CH ² -CO-Z- (C _n H _2n ) -N ⁽⁺⁾ (CH ₃ ) ₃ A ^H

in which R and R are hydrogen or methyl groups, Z is an oxygen atom or an NH group, n = 2 to 5 and A ^{(_) is} a chloride, bromide, methoxysulfate or ethoxysulfate anion,

20-30 mol% of a monomer of the formula II,

(II) R ³ -CH = CR ⁴ -COOH

in which R ³ and R ^{4 are} hydrogen or methyl groups and

40-50 mol% of a monomer of the formula III,

(III) R ⁵ -CH = CR ⁶ -COO R ⁷

in which R and R are hydrogen or methyl groups and R is an alkyl group with 1-4 C atoms, and

1-30% by weight of anionic, ampholytic, zwitterionic, cationic or nonionic surfactants or a mixture thereof.

7. Aqueous Haaφflegemittel according to claim 6 in the form of a hair conditioner, the 1-10 wt.% Of a zwitterionic polymer

1-5% by weight of a cationic surfactant and, if appropriate

Contains 0.05-1% by weight of a cationic polymer.

8. Aqueous Haaφflegemittel according to claim 6 in the form of a hair shampoo, the 1-10 wt.% Of the zwitterionic polymer

5-35% by weight of a water-soluble anionic surfactant and optionally

Contains 0.05-0.5% by weight of a cationic polymer.