DE19727656A1 - Hair treatment compositions containing quaternized monoesteramines - Google Patents

Abstract

The invention relates to a hair treatment product, containing a quaternary monoester amine of formula (I), wherein R<1> means C5-C21-alkyl, C5-C21-alkenyl, R<2>, R<3> and R<4> can be the same or different and mean C1-C6-alkyl, wherein two of the radicals R<2>, R<3> or R<4> can together form a five or six-membered heterocyclic ring with the inclusion of an oxygen, sulfur phosphorus or nitrogen atom, A means a group of formulae C2H4 or C3H7, n is a figure between 1 and 8, and X is an anion.

Description

By frequent bleaching, perming and dyeing, strong UV exposure, but also by frequent washing of hair with degreasing surfactants and normal Aging causes damage to the hair structure. The hair becomes brittle and loses its shine. Furthermore, the hair is electrostatically charged when combing on, and the roughened hair surface causes matting as well Knots of the hair. This makes the combing difficult. Hair treatment agent with a combability-improving and caring The effect has therefore gained considerable importance.

For example, such funds often take the form of a clear one Hair conditioner, an aerosol foam or in emulsion form as so-called cream rinses after shampooing in still-wet hair and spread depending on the type of hair treatment, either after a few minutes of exposure rinsed with water or left on the hair.

Hair cleaning and care in two steps is time consuming, so many Consumers hair products with cleansing and nourishing effects at the same time, to be favoured.

For the preparation of conditioning shampoos are a number of nourishing Active ingredients available.

As active ingredients for improving the hair structure are mainly cationic, in particular quaternary ammonium compounds, such as Cetyltrimethylammonium chloride or distearyldimethylammonium chloride alone or in combination with various waxy additives, such as  Hydrocarbons, fatty alcohols and fatty acids used (Par Cosm 56,157 (1975)).

The disadvantage here, however, that the cationic surfactants mentioned a have insufficient biodegradability and thus at entry in Surface waters over time the functioning aquatic Communities.

According to EP-A-0 309 052 the use of quaternized Fatty acid alkanolamine esters as textile softeners and hair conditioners known. EP-A-0 284 036 also discloses the use of cationic surfactants with ester structure for cosmetic applications. EP-A-0 252 441 Esterification products of etheramines, which are then quaternized and EP-A-0 299 787 describes the use of esterquats as textile softeners.

Furthermore, DE-A-3 527 974 discloses esters of betaine with fatty alcohols or fatty alcohol polyglycol ethers for use in acid hair care products known. Although the betaine esters have a high ecotoxicological compatibility However, in terms of combability improvement, antistatic, and grip Flushing unsatisfactory and also in the acidic area not hydrolysis.

The application properties of the known for the Haaravivage Products are not satisfactory. Accordingly, there is a constant Interest in new cationic surfactants that have the disadvantages described above do not have.

From DE-A-19 60 7 824, DE-A-19 616 482, US-A-4 228 044 and US-A-4 239 660 are already known quaternary monoesteramines, which inter alia Laundry softeners and cosmetic bases can be used. The Use of these compounds in hair treatment compositions is not mentioned there.  

The invention relates to hair treatment compositions containing a quaternized monoesteramine of the formula

R ¹ -CO (OA) _n -N ^⊕ R ² R ³ R ⁴ X ^⊖

in which R ^{1 is} C ₅ -C ₂₁ alkyl, C ₅ -C ₂₁ alkenyl, R ² , R ³ and R ⁴ , which may be identical or different, are C ₁ -C ₆ alkyl, where two of the radicals R ² , R ³ or R ⁴ together with the inclusion of an oxygen, sulfur, phosphorus or nitrogen atom can also form a five- or six-membered heterocyclic ring, A is a group of the formulas C ₂ H ₄ or C ₃ H ₆ , n a Number from 1 to 8 and X represents an anion.

R ^{1 is} alkyl or alkenyl groups each having 7 to 17 C atoms, for example caproic, caprylic, capric, lauryl, myristyl, palmityl, stearyl, behenyl, oleyl, elaidinyl , Petroselinyl, Arachinyl, Erucaalkyl radicals. The alkyl or alkenyl groups under the meaning of R ¹ may be branched or unbranched. As usual in the field of fatty chemistry, the radical R ¹ -CO- can be derived from naturally occurring fatty acid mixtures, for example fatty acid mixtures which are based on palm oil, palm kernel oil, coconut oil or beef tallow.

A radical R ² , R ³ or R ⁴ is preferably methyl and the other two substituents are then preferably propyl or butyl. X is an anion, for example chloride, methyl or ethyl carbonate, methyl or ethyl phosphate, methyl or ethyl sulfate. n is preferably 1.

The preparation of the quaternized monoesteramines to be used according to the invention is carried out by methods known per se, for example by reacting an alkanolamine compound of the formula

H (OA) _n -NR ² R ³

with a carboxylic acid of the formula

R ¹ CO-OH

esterified to Carbonsäurealkanolaminester compound and quaternized with the addition of the radical R ⁴ .

The reaction of alkanolamine compound and carboxylic acid to ester compound can be in substance, that is in the absence of organic or other Solvents are carried out. The temperature of the esterification reaction is 100 to 200 ° C, preferably 130 to 200 ° C. Alkanolamine and carboxylic acid be in a molar ratio of 0.8 to 1.2 moles of carboxylic acid, preferably 1 to 1.05 mol of carboxylic acid, used per mole of alkanolamine. To speed up the Esterification reaction can be used esterification catalysts. Preference is given to acidic catalysts, namely hydrogen halide acids such as Hydrochloric acid; Phosphoric acids such as hypophosphorous acid or orthophosphoric acid; Sulfuric acid and sulfonic acids such as methanesulfonic acid, paratoluene sulfonic acid or dodecylbenzenesulfonic acid. Preference is given to phosphoric acids and sulfonic acids. The amount of acidic catalyst is generally 0.05 to 0.5 wt .-%, based on the weight of the alkanolamine used. Depending on Reaction temperature and type of reaction components is the reaction depressurized or run under the onset of pressure. It is preferred while the reaction of an inert gas atmosphere, for example, nitrogen atmosphere, too hold. It is further preferred to add the reaction water from the reaction mixture remove, for example by means of an inert gas stream and / or vacuum. The Reaction time is generally in the range of 5 to 15 hours.

The quaternization reaction can be carried out solvent-free or in the presence of a solvent, preferably in water as solvent, wherein a temperature of 40 to 150 ° C, preferably 50 to 100 ° C, is advantageous. Alkyl halide as alkylating agent is preferably used in such an amount that a pressure of not more than 10 bar, preferably from 2 to 8 bar. Alkylating agents such as dimethyl sulfate are preferably used in an amount of 0.8 to 1 mol, preferably 1 mol, per mol of ester amine. These quaternized monoesteramines can be prepared free of solvents. They are relatively low viscous at room temperature and are characterized by improved biodegradability and favorable Aquatox values. The compounds preferred in the context of this invention in which one radical R ² , R ³ or R ^{4 is} methyl and the other two radicals propyl or butyl have the advantage that it is possible to prepare highly concentrated aqueous formulations having an active substance content of more than 90 Wt .-%, but they are low viscosity and therefore easy to handle. Surprisingly, it has been found that these quaternized monoester amines significantly improve the dry and wet combability of hair and almost completely suppress the electrostatic charge during dry combing. The products give the hair a soft feel and are easy to rinse off again. In addition, can be eliminated with these quaternized monoesteramines damage to the hair, delay the refatting of the hair and improve the Haaravivage and the hair shine. These compounds can be incorporated into all common types of hair treatment products, such as hair shampoos or hair conditioners. The content of quaternized monoester amines in such hair treatment compositions is generally from 0.1 to 25, preferably 1 to 10 wt .-%, based on the hair treatment agent.

In addition to the quaternized monoester amines, the inventive Hair treatment agent the usual ingredients in such products in the conventional amounts such as conventional anionic, cationic, zwitterionic or nonionic surfactants and conventional auxiliaries and additives.

Suitable anionic surfactants are, in particular, the alkali metal salts, ammonium salts and amine salts of the following compounds:
Alkyl sulfates, alkyl ether sulfates, alkylamide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, α-olefin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, Alkylpolyglycerin carboxylates, alkyl phosphates, alkyl ether phosphates, alkyl sarcosinates, Alkylpolypeptidate, Alkylamidopolypeptidate, Alkylethionate, alkyltaurates ,
Fatty acids, such as oleic acid, ricinoleic acid, palmitic acid, stearic acid, coconut oil acid salt or hydrogenated coconut oil acid salts, compounds of the general formula

A- (OCH ₂ -CH ₂ ) _n -OCH ₂ -CO ₂ H

where n is an integer between 5 and 15. The alkyl radical of all this Compounds contains 12 to 18 carbon atoms.

Cationic surfactants are especially long quaternary ammonium compounds Chain, alkylpyridinium salts, fatty amines of polyethers and imidazoline derivatives.

Nonionic surfactants are in particular polyethoxylated or polypropoxylated Ethers or polyglycerol ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerinated fatty acid esters, polyethoxylated esters of fatty acids and of Sorbitol, polyethoxylated or polyglycerinated fatty amides.

Amphoteric surfactants are in particular alkylamino mono- and dipropionates, betaines, such as N-alkylbetaines, N-alkylsulfobetaines, N-alkylamidobetaines, Cycloimidinium compounds, such as alkylimidazolines, asparagine derivatives, wherein the Alkyl group in these surfactants preferably 1 to 22 carbon atoms.

Auxiliaries and additives are, in particular, emulsifiers, superfatting agents, Thickeners, biogenic agents, film formers, preservatives, Pearlescing agents, dyes, perfume oil, foam inhibitors, enzymes.  

Hair treatment agents may include nonionic emulsifiers such as oxyethylenated or polyglycerinated fatty alcohols, e.g. B. oleic alcohol with 10 to 30 moles of ethylene oxide, Stearyl alcohol with 10 to 15 or 20 moles of ethylene oxide, oleic alcohol, polyglycerinated with 4 moles of glycerine and the synthetic fatty alcohols with 9 to 15 carbon atoms, polyoxyethylenated with from 5 to 10 moles of ethylene oxide, sorbitan esters, monoglycerides, Polysorbates, polyethyleneglycol monololdifatty acid esters, highly ethoxylated Fatty acid esters and high molecular weight silicone compounds, such. B. Dimethyl polysiloxane and phosphoric acid ester in an amount of 1 to 25 wt .-% contain. The hair treatment agents may also include ionic emulsifiers, such as optionally oxyethylated alkyl sulfate, e.g. Sodium lauryl sulfate, Ammonium lauryl sulfate, sodium cetyl stearyl sulfate, triethanolamine stearyl sulfate, Monoethanolamine lauryl sulfate, sodium lauryl ether sulfate and Monoethanolaminlaurylethersulfat contain, these emulsifiers in Concentrations between 0.5 and 15 wt .-% are present.

As Überfettungsmittel substances such as polyethoxylated Lanolin derivatives, lecithin derivatives and fatty acid alkanolamides are used, the latter also serving as foam stabilizers.

As a thickener are preferably hydrogenated castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5 wt .-% and especially in amounts of from 0.5 to 2% by weight, for example sodium, potassium, Aluminum, magnesium and titanium stearates or the sodium and / or potassium Salts of behenic acid, as well as polysaccharides, in particular xanthan gum, guar Guar, agar-agar, alginates and tyloses, carboxymethylcellulose and Hydroxyethylcellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone as well Electrolytes such as saline and ammonium chloride used.

Among biogenic agents are, for example, plant extracts, protein hydrolysates and vitamin complexes.  

Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate Copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives and similar compounds.

Suitable preservatives are, for example, phenoxyethanol, Formaldehyde solution, parabens, pentadiol or sorbic acid. As pearlescing agents, for example, glycol distearic esters such as Ethylene glycol distearate, but also fatty acid monoglycol esters.

Dyes which are suitable and approved for cosmetic purposes Substances are used, as for example in the publication "Cosmetic colorants" of the color commission of the Germans Research Community, published by Verlag Chemie, Weinheim, 1984, page 81-106 are compiled. These dyes are commonly used in Concentrations of 0.001 to 0.1% by weight, based on the total mixture, used.

The agents according to the invention can be used as foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, Microcrystalline waxes and their mixtures with silanated silica. With Advantage may also be used mixtures of different foam inhibitors, z. As those of silicone oil, paraffin oil or waxes. Preferably Foam inhibitors to a granular, water-soluble or dispersible Vehicle bound.

The desired viscosity of the hair treatment agent can be achieved by adding Water and / or organic solvents or by adding a combination be adjusted from organic solvents and thickeners. In principle, all monovalent or polyvalent ones come as organic solvents  Alcohols into consideration. Alcohols having 1 to 4 carbon atoms are preferred Methanol, ethanol, propanol, isopropanol, butanol, glycerol and mixtures of used the said alcohols. Further preferred alcohols are Polyethylene glycols with a molecular weight below 2000. In particular a use of polyethylene glycol with a molecular weight between 200 and 600 and in amounts up to 45 wt .-% and of polyethylene glycol with a molecular weight between 400 and 600 in amounts of 5 to 25 wt .-% prefers. An advantageous mixture consists of ethanol and polyethylene glycol in the Ratio 0.5: 1 to 1.2: 1, wherein the hair treatment agent 8 according to the invention may contain up to 12% by weight of such a mixture. Further suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.

As enzymes are such proteases, lipases, amylases or mixtures thereof Question. Their proportion can be 0.2 to 1 wt .-%. The enzymes can on Carrier substances are adsorbed and / or embedded in enveloping substances.

To bind traces of heavy metals, the salts of Polyphosphoric acid, such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and Diethylentriaminpentamethylenphosphonsäure (DTPMP) can be used.

Suitable salts or setting agents are, for example, sodium sulfate, sodium carbonate or sodium silicate. Typical examples of further additives include sodium borate, starch, Sucrose, polydextrose, stilbene compounds, methyl cellulose, toluenesulfonate, Cumene sulfonate, soaps and silicones.

The total proportion of auxiliaries and additives may be 1 to 50, preferably 5 to 40 wt .-%, based on the hair treatment agent according to the invention.  

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

Examples Cream Conditioner I

AL = L <A Quaternized monoesteramine I 2.50% Hostaphat® KL 340 N 1.50% Cetylstearylalcohol 3.00% Hydrocarbon compound 1.00% AL = L CB = 2 <B @ water 89.20% Genamin® KSL 2.50% preservative q.s. C @ Perfume 0.30% dye q.s. AL = L CB = 2 <D @ Citric acid (→ pH 4.0) q.s.

Cream conditioner II

AL = L <A Quaternized monoesteramine I 2.50% Hostacerin® T-3 1.00% cetyl alcohol 1.50% jojoba oil 1.50% AL = L CB = 2 <B @ water 92.70% Pantheol 0.50% preservative q.s. AL = L CB = 2 <C @ Perfume 0.30% dye q.s. AL = L CB = 2 <D @ Citric acid (→ pH 4.0) q.s.

Cream conditioner III

AL = L <A Quaternized monoesteramine I 1.00% Hostaphat® KL 340 N 1.50% cetyl alcohol 3.00% AL = L CB = 2 <B @ water 94.20% preservative q.s. AL = L CB = 2 <C @ Perfume 0.30% dye q.s. AL = L CB = 2 <D @ Citric acid (→ pH 4.0) q.s.

Cream conditioner IV

AL = L <A Quaternized monoesteramine I 1.00% Hostacerin® T-3 1.50% cetyl alcohol 3.00% AL = L CB = 2 <B @ water 94.20% preservative q.s. AL = L CB = 2 <C @ Perfume 0.30% dye q.s. AL = L CB = 2 <D @ Citric acid (→ pH 4.0) q.s.

Cream conditioner V

AL = L <A Quaternized monoesteramine II 1.00% Genamin® KDMP 1.00% Hostaphat® KL 340 N 1.50% cetyl alcohol 3.00% AL = L CB = 2 <B @ water 93.20% preservative q.s. AL = L CB = 2 <C @ Perfume 0.30% dye q.s. AL = L CB = 2 <D @ Citric acid (→ pH 4.0) q.s.

Cream conditioner VI

AL = L <A Quaternized monoesteramine III 1.00% Hostacerin® T-3 1.50% cetyl alcohol 3.00% AL = L CB = 2 <B @ water 94.20% preservative q.s. AL = L CB = 2 <C @ Perfume 0.30% dye q.s. AL = L CB = 2 <D @ Citric acid (→ pH 4.0) q.s.

Cream conditioner VII

AL = L <A Quaternized monoesteramine IV 1.00% Genamin® EQ 1.00% Hostacerin® T-3 1.50% cetyl alcohol 3.00% AL = L CB = 2 <B @ water 93.20% preservative q.s. AL = L CB = 2 <C @ Perfume 0.30% dye q.s. AL = L CB = 2 <D @ Citric acid (→ pH 4.0) q.s.

Cream conditioner VIII

AL = L <A Quaternized monoesteramine IV 1.00% Hostacerin® DGSB 1.50% cetyl alcohol 3.00% AL = L CB = 2 <B @ water 94.20% preservative q.s. AL = L CB = 2 <C @ perfume oil 0.30% dye q.s. AL = L CB = 2 <D @ Citric acid (→ pH 4.0) q.s.

The preparation of the hair treatment compositions I to VIII was carried out as follows:
IA is melted at 75 ° C
II B is heated separately to 75 ° C
III II added with stirring I and cold stirring
IV at about 40 ° C, the components of C in III stir
V adjust the pH value with D.

The quaternized monoesteramines I to IV of Examples I to VIII have the following constitution:

R ¹ -COO-CH ₂ -N ^⊕ R ³ R ⁴ R ⁵ X ^⊖

I: R ¹ = C ₁₁ H ₂₃ alkyl, R ³ = CH ₃ , R ⁴ and R ⁵ = C ₃ H ₇ , X = chloride
II: R ¹ = C ₁₇ H ₃₅ alkyl, R ³ = CH ₃ , R ⁴ and R ⁵ = C ₄ H ₉ , X = methosulfate
III: R ¹ = C ₂₁ H ₄₃ -alkyl, R ³ = CH ₃ , R ⁴ and R ⁵ = C ₄ H ₉ , X = methosulfate
IV: R ¹ = C ₁₇ H ₃₅ alkyl, R ³ = CH ₃ , R ⁴ and R ⁵ = C ₃ H ₇ , X = chloride.

Chemical name of the commercial products used

Genamin EQ (Hoechst AG): N, N-bis (β-stearoylethyl) dimethylammonium chloride
Hostacerin T-3 (Hoechst AG): Cetaereth-3
Genamine KDMP (Hoechst AG): Behentrimethylammonium chloride
Hostaphat KL 340 N (Hoechst AG): trilaureth-4-phosphate
Hostacerin DGSB (Hoechst AG): diglycerol-di-stearate-oxyethylate
Genamine KSL (Hoechst AG): stearyl pentaethoxy ammonium lactate
Testing for foaming power, wetting power, washing action and skin compatibility.

For the determination of the foaming power was for those named in Table 1 Test substances foam height (in mm) according to Ross-Miles at the concentrations  1.0%, 0.1%, 0.03%, 0.006% and 0.002% at the temperature 37 ° C, the Water hardness 15 ° dH, pH 7 determined after 30 s and 5 min. The foam (Foam volume in ml) at the concentration 1 g / l, the temperature 37 ° C, the Water hardness 15 ° dH, pH 7 determined after 30 s and 5 min.

The network capacity was determined by determining the grid time in s at a concentration 0.1%, a temperature of 37 ° C, a water hardness of 15 ° dH and pH 7 measured.

The washing effect of the test substances 1-6, (Table 1) was determined by determination
The remission values in the Linitest at concentrations of 4 g / l, a temperature of 40 ° C, in drinking water at pH 9-9.5 and a washing time of 30 min examined.

Skin compatibility was determined by means of zein tests.

Table 1 test substances

1 behenoyl-ethoxy-dibutylmethylammonium methosulfate
2 stearoyl-ethoxy-dibutylmethylammonium methosulfate
3 stearoyl-ethoxy-dibutylmethylammonium chloride
4 lauroylethoxy dipropylmethylammonium chloride
5 Caproyl-ethoxy-dipropylmethyl-ammonium chloride
6 lauroyl EO dipropylmethylammonium chloride

foaming power

Table 2

Ross-Miles foam (mm foam height)

Table 3

Blowing foam (ml foam height)

Table 4

Network assets (S)

Table 5

Washing performance (Linitest, dR in%)

Table 6

Zein test (mg N / 100 ml sample)

Claims (3)

A hair treatment composition containing a quaternized monoesteramine of the formula
R ¹ -CO (OA) _n -N ^⊕ R ² R ³ R ⁴ X ^⊖
wherein R ¹ C ₅ -C ₂₁ alkyl, C ₅ -C ₂₁ alkenyl, R ² , R ³ and R ⁴ , which may be identical or different, C ₁ -C ₆ alkyl, wherein two of the radicals R ² R ³ or R ⁴ together with the inclusion of an oxygen, sulfur, phosphorus or nitrogen atom can also form a five- or six-membered heterocyclic ring, A is a group of the formulas C ₂ H ₄ or C ₃ H ₇ , n is a number from 1 to 8 and X represents an anion. 2. hair treatment composition according to claim 1 containing a quaternized monoester amine according to claim 1, wherein R ^{1 is} C ₇ -C ₁₇ alkyl or alkenyl, R ^{2 is} methyl, R ³ and R ^{4 is} propyl or butyl, n = 1, A is -CH ₂ CH ₂ - and X is a chloride, methyl or ethyl carbonate, methyl or ethyl phosphate, methyl or ethyl sulfate anion. 3. hair treatment composition according to claim 1, containing 0.1 to 25, preferably 0.1 to 5 wt .-% of the quaternized monoester amine.