EP0437462A1

EP0437462A1 - Use of amphoteric and zwitterionic cellulose ethers in hair care products

Info

Publication number: EP0437462A1
Application number: EP89910861A
Authority: EP
Inventors: Reinhard Müller; Brigitte Hase; Konrad Engelskirchen; Karl Giede; Klaus-Dieter Wisotzki
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1988-10-04
Filing date: 1989-09-25
Publication date: 1991-07-24
Also published as: WO1990003779A1; ES2045328T3; GR3006129T3; DE3833658A1; DE58901987D1; EP0365845B1; KR900701243A; EP0365845A1; ATE79017T1

Abstract

Amphoteric and zwitterionic, water-soluble cellulose ethers which contain on average per anhydroglucose unit at least 0.1 amino and/or ammonium groups and at least 0.1 carboxyl groups and, where appropriate, additionally a number which is at least necessary for their solubility in water of alkyl or hydroxyalkyl groups which are bonded in the manner of an ether and have 1-4 C atoms, are suitable as additives for improving combability to agents for cleaning and caring for the hair. The agents preferably contain 0.01 - 5% by weight of the amphoteric and zwitterionic cellulose ethers and 0.1 - 25% by weight of a surface-active substance.

Description

"Use of amphoteric and zwitterionic cellulose ethers in

Hair care products "

The invention relates to the use of amphoteric and zwitterionic cellulose ethers in compositions for cleaning and care of the hair and hair care compositions which contain such polymers as additives which improve and combability.

After washing with shampoos, shower and bath preparations based on synthetic surfactants, but especially after cosmetic treatments such as dyeing and shaping, the main hair shows a cosmetically unsatisfactory condition. It is difficult to comb when wet, feels dull when dry and looks lackluster. It tends to become static, which causes the known "flying" of freshly washed hair.

It is therefore known to allow conditioning preparations to act on the hair after washing, dyeing or perming the hair. Cationic surfactants are usually present as active ingredients in such preparations. It is also known to determine conventional shampoos based on anionic surfactants or on the basis of mixtures of surfactants of different ionicity. Add substances to achieve a certain conditioning effect at the same time as washing the hair. Such substances are e.g. B. water-soluble proteins or protein degradation products, polycationic polymers or also zwitterionic synthetic polymers, such as those used for. B. are described in DE OS 21 50 557 or DE OS 28 17 369. The known polymeric cationic conditioning agents, however, have numerous shortcomings. Products with good water solubility and sufficient compatibility with anionic wash raw materials are usually too weakly effective, which makes a high dosage necessary. Other, limited water-soluble products are too strong a noun, they absorb almost completely on the hair, lead to accumulation when the hair is treated several times and thereby reduce the fullness and fit of the dried hair.

/

The zwitterionic polymers known for hair treatment and hair setting agents have the disadvantage, particularly in formulations with anionic surfactants, that the hair-activating and hair-fixing properties are gradually lost in the course of longer storage times.

It was therefore an object to find water-soluble polymers which, when used as an additive in aqueous compositions for cleaning and care of the hair, in particular in compositions for washing and rinsing the hair, have a good avivating, combability-improving effect and do not have the disadvantages mentioned - or to a much lesser extent - have.

The invention relates to the use of amphoteric and zwitterionic, water-soluble cellulose ethers which, on average, contain at least 0.1 amino and / or ammonium groups and at least 0.1 carboxyl groups per anhydrogiucose unit in an arrangement of the formulas I and II

(CH) - ⁽⁺⁾ NR ¹ R ² R ³ -CH, COO ^{(_ :)}

2 mn 2n 1 2 wherein m = 2-4, n = 1-3, x = 0-3 and R and R alkyl groups with

1-4 carbon atoms, R ^{3 is} a group - (CH - R ^ ² or - (CH.) -

(+) 1 2 4 4

^J NR RR, in which R is an alkyl group with 1-4 C atoms or a group —C H. COO, and optionally additionally a number of ether-linked alkyl or hydroxyalkyl groups with 1-4 that are at least necessary for their water solubility

C atoms contain, as a combable additive to improve

Cleaning and care of the hair.

Groupings of the formula I result from the reaction of dialkylaminoalkyl groups introduced primarily into the celluloses with the aminoalkylating and / or carboxylalkylating agents. Depending on the composition of the products, additional cations and anions may be present for charge balancing, preferably e.g. Sodium ions or protons and chloride or sulfate ions.

The full water solubility of the cellulose ethers is preferably adjusted solely via the number of ionic groups of the formulas I and II, and it is therefore preferred that they contain an average of a total of 0.5 ionic groups in the arrangement of the formulas I and II per anhydroglucose unit. Those cellulose ethers which contain 0.2-0.6 amino and / or ammonium groups and 0.4-0.8 carboxyl groups in an arrangement of the formulas I and II are particularly preferred. It is preferred that m = 2, n = 1, R ¹ and R ² = ethyl and R ³ = (CH ₂ ) ₂ -N (C ₂ H ₅ ) ₂ or (CH ₂ ) ₂ - ⁽⁺⁾ N (C ₂ H ₅ ) ₂ CH ₂ COθ ^" .

The cellulose ethers to be used according to the invention are readily soluble in water and in aqueous solutions of anionic, cationic, ampholytic, zwitterionic and nonionic surfactants and retain their combability-improving, hair-activating and hair-fixing properties in aqueous solutions of such surfactants even over prolonged storage times at. On the basis of the properties mentioned, they are suitable according to the invention using cellulose ether as a setting and hair-activating component in aqueous preparations for cleaning and care of the hair. Such preparations can e.g. B. Hair shampoos, hair rinsing agents, hair setting agents, hair blow-drying agents and aqueous colorants, permanent waving agents or permanent waving fixing agents.

The amphoteric cellulose ethers to be used according to the invention

^• 3 i

(= - (CH. -NR R) are known from the literature or can be prepared by processes known from the literature, 2 m. Their preparation is described, for example, in US Pat. No. 2,591,748. The production of particularly preferred amphoteric cellulose ethers is described also described in more detail in Example 1 .1 to 1.4 The preparation takes place essentially by passing a carboxyalkyl cellulose through

1 2 reaction with a compound of formula X- (CH_) -NR R, 2 'm

1 2 wherein X = chlorine or bromine and R and R have the meaning given for formula I, alkylated. Is preferred

Carboxymethyl cellulose used.

Notwithstanding this. However, the process can also first be carried out using an alkali cellulose with a compound of the formula X- (CH_) -

1 2 ^{2 m}

NR R and simultaneously or subsequently with z. B. Alkylate sodium chloroacetate. Zwitterionische groups of the

3 f-1

Formula I, in which R is a group -CH.-COO ^1, is formed.

The introduction of groups of the formula C H_ -COO, where n = 2 or 3, z. B. by adding esters or. Amides of acrylic acid or methacrylic acid and subsequent hydrolysis of the ester or amide groups achieved.

The alkyl or hydroxyalkyl ether groups with 1 to 4 carbon atoms that may be required to achieve good water solubility are introduced in a conventional manner by etherification with alkyl halides with 1 to 4 carbon atoms or by etherification with diaikyl sulfate, eg. B. Dimethyl sulfate, or by the addition of epoxyalkanes such as ethylene oxide or propylene oxide or glycid according to procedures known from the literature. The alkyl and hydroxyalkyl groups can be introduced before, simultaneously with or after the introduction of the cationic and / or anionic groups.

The zwitterionic polymers to be used according to the invention with quaternary ammonium groups of the formula I (x = 1-3, R =

Alkyl groups with 1 to 4 carbon atoms) can be obtained by alkylation

3 1 2 of the corresponding amphoteric polymers (R = - (CH_) -NR R)

4 H ^m with compounds of the formula R -X and, SO _ü , where

4 R is an alkyl group with 1 to 4 carbon atoms and X = chlorine or

Is bromine. But you can also use the alkali cellulose

1 2 a compound of the formula X- (CH_) -NR R and then

4 ^m n with compounds of the formulas RX or R _? S0 _Ü alkylate and r-1 ^{l μ} only introduce the -C H_ -COO group, n 2n "^

The amphoteric and zwitterionic cellulose ethers to be used according to the invention are preferably added to the agents for cleaning and caring for the hair in amounts of 0.01-5% by weight. The amphoteric and zwitterionic cellulose ethers work particularly well as additives to agents for washing or rinsing the hair, which are characterized by a content of surface-active substances, generally in an amount of 0.1-25% by weight. A preferred embodiment of the invention is e.g. an aqueous-based hair shampoo which contains 0.1-5% by weight of the amphoteric or zwitterionic cellulose ether and 5-25% by weight of at least one anionic surfactant.

All anionic surface-active substances suitable for use on the human body are suitable as anionic surfactants in hair treatment compositions according to the invention. These are characterized by a water-solubilizing, anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having 10 to 22 carbon atoms. In addition, the molecule may contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are the sodium, potassium, ammonium, mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, of linear fatty acids with 10 to 22 carbon atoms (soaps), Ether carboxylic acids of the formula R ⁵ -0- (CH ₂ -CH ₂ 0) -CH ₂ -COOH in which R is a linear alkyl group having 10 to 22 carbon atoms and x = 0 or 1 to 12,

Acyisarcosines 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, sulfosuccinic acid and dialkyl esters with 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkyl 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 form! R ⁶ -0 (CH ₂ -CH ₂ 0) _χ -OS0 ₃ H, in which R ^{6 is} a preferably linear alkyl group with 10 to 18 carbon atoms and x = O or 1 to 12.

Alkyl sulfate and alkyl polyglycol ether sulfates having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule are preferred.

In addition to the anionic surfactants mentioned, the hair shampoo formulations according to the invention can contain all auxiliaries and additives known for this purpose in the usual amounts. These are especially non-ionic, amphoteric and zwitterionic surfactants. Nonionic surfactants are primarily the adducts of 2 to 20 moles of ethylene oxide with preferably linear alcohols with 12 to 18 C atoms, with alkylphenols with 8 to 15 C atoms in the alkyl group, with fatty acids with 12 to 18 C atoms, on fatty acid partial glycerides, on fatty acid sorbitan partial esters, on fatty acid alkanolamides and on methyl glucoside fatty acid esters. Further suitable nonionic surfactants are alkyl (oligo) glucosides, alkyl amine oxide surfactants and fatty acid alkanolamides. Amphoteric surfactants are, for example, alkyl (Cp-C.) Trimethylammonio-glycinate or acyl- (C ₀ -C ₁₀ ) -aminopropyltrimethylammonio-glycinate.

O I ö

A particularly preferred embodiment of the invention are means for rinsing the hair, e.g. after a shampoo treatment or after a dyeing or bleaching treatment. Such products usually contain 0.1-10% by weight of a cationic surfactant to reduce the antistatic chargeability of the hair. The combability of the hair and the fullness of the dry hairstyle is further improved by the addition according to the invention of 0.1-1% by weight of an amphoteric or zwitterionic water-soluble cellulose ether. A content of 0.5-5% by weight of a cationic surfactant of the general formula IV is particularly useful

R ⁸ (IV) R ⁷ N ⁽⁺⁾ R ¹⁰ A ^(" >

R ⁹

In which R is an alkyl or hydroxyalkyl group with 8-22 carbon atoms

11 11 men, a group R -CONH (CH_) -, in which R is an alkyl group

8 ~ pe with 7 - 21 C atoms and y is a number from 2 - 4, R and R are an alkyl group with 1 - 4 C atoms or a group of the formula

- (C H_ O) H, in which m is a number from 2 - 4 and z is a number of m 2m z _1Q

1-10 and R is a benzyl group or one of those for R, 8 9 (-)

R and R has the meanings indicated, and A is a chloride,

Bromide, hydrogen sulfate, hydrogen phosphate, methoxysulfate or

Is ethoxysulfate anion.

Suitable cationic surfactants are e.g. Cetyltrimethylammonium chloride, lauryldimethyibenzylammonium chloride, stearyitrimethylammonium chloride, distearyldimethyammonium chloride, tallow alkyl tris (oligooxyethyI) ammonium phosphate, 2-hydroxyhexadecyl-2-hydroxyethyl-2-methyl-hydroxyethyl-2-dimethyl-hydroxyl-2-methyl-dimethyl-hydroxyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-ethyl

To improve the hair-activating effect, it is also expedient that the hair rinses according to the invention additionally contain a fatty substance, e.g. contain a cosmetic oil, fat or wax component, a paraffin oil or paraffin wax, wool wax or a wool wax derivative. Particularly fatty alcohols are fatty alcohols with 14-22 carbon atoms, e.g. Cetyl and / or stearyl alcohol as well as fatty acid monoglycerides and / or fatty acid diglycerides of fatty acids with 16-22 C atoms, e.g. of palmitin and / or stearic acid. Such fatty substances are preferably present in amounts of 1-10% by weight, based on the entire preparation.

In addition to the components mentioned, the hair rinsing agents according to the invention may also contain minor auxiliaries and additives, which are customary in hair rinsing agents, in up to about 5% by weight. Such auxiliaries and additives are e.g. lower polyols, 1, 2-propylene glycol or glycerin, water-soluble non-ionic thickeners such as e.g. Hydroxyethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl starch and

Hydroxypropyl guar, also preservatives, fragrances, dyes, light stabilizers and hair cosmetic agents such as vitamins, plant extracts, balms, anti-dandruff agents (e.g. Zn- or Mg-pyridinthione) or sebostatics. The following examples are intended to explain the subject matter of the invention in more detail without restricting it thereto.

EXAMPLES

Production examples of amphoteric cellulose ethers

Example 1 .1

688 g of acetone (suspending agent) were placed in a stirring beaker and 95.5 g (0.4 mol of anhydrogiucose units) of sodium carboxymethylcellulose (CMC, viscosity 1% in water: 1250 mPas (20 ° C.) , Degree of carboxymethylation: DS = 0.73, water content 7.6% by weight) suspended with stirring using a Pendraulic stirrer. After stirring under nitrogen for five minutes, 40 g (0.5 mol) of 50% strength aqueous sodium hydroxide solution were added dropwise over the course of five minutes. After a further five minutes, 86 g (0.25 mol) of a 50% aqueous 2-chloroethyldiethylamine hydrochloride solution (CDA) were added dropwise. After stirring for five minutes, the mixture was transferred to a 2-1 flask and heated to reflux for four hours while passing nitrogen over it. The crude product was filtered off with suction and washed with 80% aqueous acetone until no more chloride was detectable. The yield was 11 g. The product had the following key figure:

Degree of substitution based on nitrogen-containing groups (MS _* .): 0, 39 (determined by nitrogen determination)

Example 1 .2

A further product was produced by the process described under 1.1.

Starting product: CMC, viscosity 1% in water: 550 mPas (20 ° C), DS _C = 0.70

Molar ratio CMC: NaOH: CDA = 1: 1: 0.50

The reaction product had the following key figure: S _N : 0, 21 Example 1.3

Another product was produced by the process described under 1.

Starting product: CMC, viscosity 1% in water: 2000 mPas (20 ° C), DS _C : 0.92

Molar ratio CMC: NaOH: CDA = 1: 1, 25: 0.625

The reaction product had the following key figures:

MS _N : 0.22

Example 1.4

516 g of acetone were placed in a stirring beaker and, after nitrogen had been passed in, 34.4 g (0.2 mol) of cellulose powder (water content 5.8%) were suspended therein with stirring using a hydraulic stirrer. After stirring under nitrogen for five minutes, 32 g (0.4 mol) of 50% strength aqueous sodium hydroxide solution were added dropwise over the course of five minutes. After a further five minutes, 68.8 g (0.2 mol) of a 50% aqueous 2-chloroethyldiethyla in hydrochloride solution were added dropwise. After stirring for five minutes, the mixture was transferred to a 2 liter flask and refluxed for one hour with nitrogen bubbling. Then 36 g (0.45 mol) of 50% aqueous sodium hydroxide solution and then 26.6 g (0.225 mol) of 80% aqueous chloroacetic acid solution were added dropwise and the reaction clay mixture was heated under reflux under nitrogen for a further three hours. The crude product was filtered off with suction and washed with 80% aqueous acetone until chloride was no longer detectable. The yield was 54.1 g. The product had the following key figures:

MS _N : 0.56

DS _C : 0.86 water content: 6.4% by weight.

2. Examples of use 2.1 Shampoos Example 2.1.1

Texapon ALS 33.3 wt.

Dehyton K ² 16.7% by weight

Cellulose ether

Example 1.1 0.5% by weight

Cooking salt 0.5% by weight

Water 49.0% by weight

Example 2.1.2

3 Texapon N 25 21.5% by weight

Suifosuccinate S 2 ⁴ 30.0% by weight

Cellulose ether

Example 1.2 0.5% by weight

^Table salt 0.5% by weight

Water 47.5% by weight

Example 2.1.3

Texapon N 25 26.8% by weight

Alkyl glucoside (Hl-Be 94-0) ⁶ 12.3% by weight

Cellulose ether

Example 1.1 0.5% by weight

Cooking salt 0.5% by weight

Water 59.9% by weight Example 2.1.5

3

Texapon N 25 21.4% by weight

Comperlan KD 6.0% by weight

Cellulose ether

Example 1.2 0.5% by weight

Cooking salt 0.5% by weight

Water 71.6% by weight

Example 2.1.6

Texapon NSW ⁸ 56.0% by weight

Dehyton K ² 10.0% by weight cellulose ether

Example 1.4 0.5% by weight

Cooking salt 0.5% by weight

Water 33.0% by weight

The hair washed with the listed shampoos shows good wet combability and dry combability and no electrostatic charge when combing after drying.

2.2 rinses

Example 2.2.1

9

Dehyquart A 3.0% by weight

Stenol 1618 ¹⁰ 3.0% by weight

Culminal MHPC 3000 ¹¹ 0.6% by weight

Cellulose ether

Example 1.1 0.5% by weight

Water 92.9% by weight

Example 2.2.2 g

Dehyquart A 3.0% by weight

Stenol 1618 ¹⁰ 3.0% by weight

Culminal MHPC 3000 ¹¹ 0.6% by weight

Genami n DSAC ¹² 1.0% by weight Cellulose ether

Example 1.2 0.5% by weight

Water 91.9% by weight

Example 2.2.3

13 Dehyquart E 3.0% by weight

Stenol 1618 ¹⁰ 3.0 Cew .-% o

Culminal MHPC 3000 ¹¹ 0.6% by weight

Genamin DSAC ¹² 1.0% by weight Ceilulpseether

Example 1.3 0.5% by weight

Water 91.9% by weight

Example 2.2.4

Dehyquart SP ¹⁴ 3.0% by weight

Stenol 1618 ¹⁰ 3.0% by weight

Culminal MHPC 3000 ¹¹ 0.6% by weight

Genamin DSAC ¹² 1.0 Cew .-% cellulose ether

Example 1.4 0.5% by weight

Water 91.9% by weight

The rinsing agents listed give the wet and dry hair very good combability and a pleasant feel. When combing dry hair with a hard rubber comb, there is no electrostatic charge.

1 ammonium lauryl sulfate (30% AS)

2 cocoalkylamidopropyldimethylglycine (30% AS)

3 FattyIkohoI-C ₁₂ _ ₁₄ + 2EO-suIfat, Na salt (28% AS)

4 fatty alcohol C ₂ + 2EO-sulfosuccinic acid monoesters, di-Na salt (30%)

5 coconut fatty acid monoethanolamide 4-carboxylate, Na salt (ether carboxylic acid) (30% AS)

6 R.O (Z) with Z = glucose, x = 1, 4 and R. =

I Λ 1 n-alkyl (C- ₂ _ ₁₄ ) (60.8% AS) coconut fatty acid diethanolamide fatty alcohol C ₁₂ _ ₁₄ + 2EO sulfate, Na salt (28% AS) cetyltrimethylammonium chloride (25% AS) fatty alcohol C ₁₆ _ _lg methylhydroxypropyl cellulose (used as a 3% solution in water) dimethyldistearylammonium chloride N- (2-hydroxyhexadecyl-1) -N, N-dimethyl-N-2-hydroxyethylammonium chloride (28% AS) (H- (O-CH ₂ -CH ₂ -) ₁₀ ) ₃ (CH ₃ - (CH ₂ ) _{li 6} -CH ₂ -) N ⁺ H ^ - (50% AS) (% AS means:% by weight dissolved in water)

Claims

PATENT CLAIMS

1. Use of amphoteric and zwitterionic, water-soluble cellulose ethers which average at least 0.1 amino and / or ammonium groups and at least 0.1 carboxyl groups per anhydroglucose unit in an arrangement of formulas 1 and II.

I x II

1 2 wherein m = 2-4, n = 1-3, x = 0-3 and R and R are alkyl groups with 1-4 C atoms, R is a group - (CH_) -NR ^ ² or

- (CH-) - ^{f +)} NR ¹ R ² R ⁴ , wherein R ^{4 is} an alkyl group with 1-4 ^m (-)

C atoms or a group -C n H 2_n COO, and optionally additionally contain at least a number of ether-like alkyl or hydroxyalkyl groups with 1-4 C atoms, which are required for their water solubility, as a combability-improving additive for cleaning and care of the hair .

2. Use according to claim 1, characterized in that the cellulose ethers contain a total of at least 0.5 ionic ^ groups per anhydroglucose unit in the arrangement according to formula 1 and II.

3. Use according to claim 1, characterized in that the cellulose ethers per anhydroglucose unit an average of 0.2-0.6 amino and / or ammonium groups and 0.4-0.8 Car¬ boxyl groups in the arrangement according to formula 1 and II, with m or

4. Use according to one of claims 1 or 2, characterized ge indicates that the agent for cleaning and care of the hair 0.01 - 5 wt .-% of the amphoteric or zwitterionic cellulose ether and 0.1 - 25 wt .-% of a surface-active Contain substance.

5. Agent for rinsing the hair, characterized in that it contains 0.1-10% by weight of a cationic surfactant and 0.1-1% by weight of an amphoteric or zwitterionic, water-soluble cellulose ether according to claim 1.

6. Means for rinsing the hair according to claim 4, characterized in that it additionally 1 - 10 wt .-% of a Fett¬ substance from the group of fatty alcohols with 14 - 22 carbon atoms or fatty acid monoglycerides and / or fatty acid diglycerides of fatty acids with Contains 16 - 22 carbon atoms.