FI81003B - SHAMPOO. - Google Patents

Description

1 81003

This invention relates to hair conditioner shampoos and whole body wash preparations.

When hair is washed with shampoos, shower or bath detergents based on synthetic anionic surfactants, they often look cosmetically nasty. When hair is wet, it is difficult to comb and it looks lifeless. After drying, washed hair tends to develop a static charge, resulting in the well-known "flying" of freshly washed hair. In addition to this, freshly washed hair often looks unpolished. For these reasons, it is known to apply conditioner to hair after washing or shampooing. These preparations are most often lotions or ointment-like lotions containing cationic surfactants. It is also known that some substances can be added to ordinary shampoos to achieve a certain therapeutic effect after washing the hair. Substances of this type include, for example, water-soluble proteins or protein degradation results, polycationic polymers, e.g. aminopolyurea resins of the type described in DE-OS No. 21 50 899, polycationic cellulose derivatives which are US-PS No. 3,816,616 or polycationic guar derivatives of the type described in U.S. Pat. No. 4,292,212. Several other water-soluble polymers containing cationic or quaternary ammonium groups have been proposed for this purpose.

One downside common to all known hair care additives is that their effectiveness is at least partially reduced when used in anionic hair wash products. Products with a particularly strong effect often adsorb too much on the hair and as a result reduce the elasticity, thickness and retention of the hair in dry hair.

It is therefore an object of the present invention to provide a shampoo recipe based on well-known, highly foaming anionic detergents which, thanks to the presence of suitable hair revitalizing additives, makes hair easy to comb wet and also gives dry 2 81003 hair good cosmetic properties such as particularly good elasticity. fullness, splendor and beautiful hairstyle.

It has been found that the hair care properties of a shampoo based on anionic detergents can be improved particularly effectively by adding to the shampoo a combination of a polycationic guar derivative, a curable cationic polycondensation product, a hydrophilic fatty acid ester and a water-soluble polyvinylpyrrolidone. The present invention therefore relates to a hair conditioner shampoo containing in an aqueous medium 5 to 50% by weight of a water-soluble, anionic, alkali metal, magnesium, ammonium or C 2 -C 3 alkanolammonium detergent salt which is C 1 -C 18 alkyl sulphate, C 1 -C 18 alkyl polyglycol ether sulfate having 1 to 6 glycol ether groups in the molecule, C 6 -C 18 alkane sulfonate, C 6 -C 6 olefin sulfonate, C 8 -C 6 fatty acid alkylolamide amide polyglycol ether sulfate, C 8 -C 6 g alkylsulfosuccinate, C8-C18 dialkyl sulfosuccinate, C8-C18 alkyl polyglycol ether carboxylate having 2-6 polyglycol ether groups in the molecule, C8-C18 acyl sarcosinate, C8-C18 acyl ion and C8-C8 acyl azuride or 1.7-14% by weight of a conditioner mixture consisting of a) 0.1-4% by weight of 3- (trimethylamino) -2-hydroxypropyl guar chloride, b) 0.5-5% by weight of easily water a soluble, curable polycondensation product having a by reacting a water-soluble polyamine having reactive amino groups and 4 to 6 carbon atoms with an ether of poly-C2-C3-alkylene glycol having halohydrin and hydroxyl end groups, followed by reaction with either epichlorohydrin or an additional reaction of said polyamine and said ether ) 1-4% by weight of an esterification product formed by reacting 1-2 moles of C8-C18 fatty acid with the addition product obtained by reacting 4-20 moles of ethylene oxide and 1 mole of glycerol, and d) 0.1-1% by weight of % of polyvinylpyrrolidone having an average molecular weight of 10,000 to 70,000 and characterized in that the weight ratio a): b): c): d) is 1: 0.5-4: 0.5-4: 0.15- 0.5 and the weight ratio of anionic detergent to conditioner mixture is 10: 1-1: 1.

388100 3- (Trimethylamino) -2-hydroxypropyl guar chloride is a cationic guar derivative known from US-PS No. 3,589,978. The substances described therein contain as their basic unit two mannose units attached by a glucoside bond and one galactose unit attached to one hydroxyl group of the mannose units. On average, each hexose ring has three free hydroxyl groups. These three free hydroxyl groups are reacted with reactive quaternary ammonium compounds to give cationic polymers. The cationic polymer used in the shampoo of the invention is commercially available under the name "Cosmedia-Guar C 261".

Easily water-soluble, curable polycondensation products of water-soluble polyamines containing reactive amino groups and polyalkylene oxide radicals and epichlorohydrin or compounds containing more than one epoxide and / or halohydrin group in the molecule are known from DE-PS No. 2 363.

As stated in this patent, the curable polycondensation products used in the compositions according to the invention are obtained only from polyamines containing polyalkylene oxide groups obtained by a known method by reacting polyamines, in particular polyalkylene polyamines, with a mono- and / or polyfunctional derivative of polyalkylene oxides. These mono- and / or polyfunctional derivatives of polyalkylene oxides may contain, as reactive groups, chlorohydrin groups, glycidyl groups, halogen atoms or other groups capable of forming anions such as sulfuric acid groups, -70 alkylene oxide groups are available. Of the alkylene oxides, 4 81003 ethylene oxide will be considered first, but other oxides, such as, for example, propylene oxide and the like, are also useful. Polyalkylene oxide chains can also be interrupted by the incorporation of a dicarboxylic acid or diisocyanate.

Compounds suitable as a second reaction component are those having more than one epoxy and / or halohydrin group in the molecule, such as epichlorohydrin, dichlorohydrin or bifunctional reaction products of these compounds with glycols, diglycols, polyalkylene oxides, glycerol, dicarboxyl.

The preparation of some of the curable polycondensation products used in the mixtures according to the invention can be effected by a particularly simple method by reacting a polyalkylene glycol, e.g. a polyoxyethylene glycol having a molecular weight of 1000 or 600, with epichlorohydrin,. . to form a bichlorohydrin ether and further reacting this product with a sufficiently large amount of polyamine, e.g. dipropylene triamine, diethylenetriamine or triethylenetetraamine, to form a ratio of 4 to 5 available chlorine atoms and available amino hydrocarbon groups in the reaction mixture. . In this production method, the intermediate polyglycol polyamine is not isolated, but is immediately reacted immediately with polyglycol bischlorohydrin ether to form the desired polycondensation product. Reactions of polyamines containing polyalkylene oxide groups with compounds containing more than one epoxy and / or halohydrin group in the molecule can be carried out in the presence of organic solvents or, preferably, water. To accelerate the reaction, suitable acid-binding groups such as inorganic bases, sodium carbonate, magnesium carbonate or triethanolamine may also be included in the mixture.

li 5 81003

The reaction is carried out at a temperature of 50 to 100 ° C for such a time that the viscosity of the reaction product clearly increases. The reaction is stopped when the desired degree of polymerization has been reached, at which point the reaction product continues to dissolve well, adjusting the pH to less than 6, if necessary.

Product F

180 kg of liquid polyglycol 600 was placed in a heated and cooled mixing vessel with a reflux condenser and a thermometer. While stirring, 2.7 kg of tin tetrachloride was slowly added thereto at about 30 ° C. After raising the temperature to 68-78 ° C, 56 kg of epichlorohydrin were added with constant stirring and cooled, if necessary, so rapidly that the temperature of the mixture was maintained between 68-70 ° C. Stirring was continued for one hour at about 70 ° C. The total amount of crude polyglycol-bischlorohydrin ether obtained was 239 kg.

A second 600 liter stirred vessel equipped with a thermometer and reflux condenser was charged with 80 kg of the crude chlorohydrin ether obtained and combined with stirring 13.2 kg of dipropylene triamine, 50 kg of water and 28 kg of NaOH solution. The vessel was kept at boiling point for 45 minutes by heating and refluxing. The crude hydrochloride ether of the polyglycol 600 remaining in the first vessel was then added with stirring and the mixture was kept boiling for another 20-30 minutes after the addition of another 30 kg of water. During this time, the pH of the viscous reaction product drops to about 7.2, after which the mixture is vigorously cooled. During cooling, the pH is adjusted to 5.5-6 by adding about 38 kg of 10% HCl solution. About 400 kg of a yellowish, cloudy and very viscous liquid are recovered.

6 81003

One such type of material that is commercially available is, for example, called Polyquart I®.

The esterification products of the addition products of glycerol and 4-20 moles of ethylene oxide as well as 1-2 moles of C8-C18 fatty acid are known from DE-AS No. 20 24 051. Of the esterification products mentioned therein, a partial ester obtained by adding 7.4 moles of ethylene oxide to one mole of glycerol followed by esterification of 1 mole of the obtained adduct with 1 mole of C8-C18 coconut oil fatty acid is particularly preferred for use in this invention. in the manufacture of hair conditioner shampoos. One product with this combination is, for example, the commercially available Cetiol HE®.

Polyvinylpyrrolidones having an average molecular weight of about 10,000 to 70,000 are commercially available, e.g., under the names Kollidor® and Luviskol®. Polyvinylpyrrolidones with an average molecular weight of about 40,000 and corresponding to a K value of about 30 are particularly suitable for the preparation of the hair conditioner shampoos of the invention.

The concentration of the mixture of the above-mentioned main conditioners in the final shampoo may vary between 1.7 and 14% by weight and the preferred concentration between 2 and 8% by weight.

The proportions of the main therapeutic agents mentioned above can vary widely. Usually the ratio is about 1 part guar derivative: 0.5-4 parts Polyquart® H: 0.5-4 parts Cetiol® HE: 0.15-0.5 parts PVP.

It is preferred that the hair conditioner shampoos of the invention contain, as water-soluble anionic detergents, alkyl sulfuric acid semi-esters containing 8-18 and primarily 12-16 carbon atoms alkali metal, magnesium, ammonium and / or C2-C3 alkylammonium esters, or alkyl polyglycol glycol containing 8 to 18003 and mainly 12 to 16 carbon atoms in the alkyl radical and 1 to 6 g of a glycol ether group in the molecule, the corresponding salts. Other suitable anlonic detergents include primary and secondary linear alkane sulfonates containing from 10 to 18 carbon atoms, alkene sulfonates and hydroxyalkanesulfonate of the type obtained by sulfonation of olefins containing from 10 to 18 carbon atoms, C8-C18-fatty acid fatty acid , C8-C18 fatty acid monoglyceride sulphates, sulphomeric resin monoalkyl esters containing 8 to 18 carbon atoms in the alkyl group or dialkyl esters containing 6 to 10 carbon atoms in alkyl groups, alkyl polyglycol ether ether carboxylates containing 8 to 18 carbon atoms in the polyglycyl group and 2 to 18 carbon atoms in the alkyl group and acyl sarcosines, acyl taurides and acyl isothionates containing 8 to 18 carbon atoms in the acyl group.

The concentration of anionic surfactants in the shampoo is usually from about 5% to about 50% by weight; the preferred amount is from about 8% to about 30% by weight.

The preferred anionic surfactant is a mixture of sodium lauryl polyglycol ether sulfate and fatty alcohol sulfate in a weight ratio of about 2: 1 to 1: 1. The fatty alcohol sulfate preferably contains an alcohol moiety having about 10-14 C atoms, primarily 12-14 C atoms. The ratio of the total amount of anionic surfactants to the mixture of main therapeutic agents can range from about 10: 1 to 1: 1, mainly from 2.5: 1 to 1.5: 1.

The hair conditioner shampoos of the invention may further contain standard additives and hair lotions such as thickeners of the C8-C18 fatty acid alkylolamide, opacifiers, e.g. ethylene glycol distearate type, ammonium nitrate or alkali stabilizing agents such as 81003, preservatives such as formaldehyde or p-hydroxybenzoic acid esters, colorants, fragrances and known hair cosmetics such as anti-dandruff and hair oil control agents.

The hair conditioner shampoos having the composition of the invention are characterized by an unexpectedly clear improvement in the hair care effect when the hair is washed with these shampoos. For example, the so-called hair care shampoos according to the invention wet hair combability is clearly improved over shampoos containing only one of the conditioner components, e.g., Cosmedia-Quai®: 261. This is all the more surprising since the other main ingredients have little or no effect on wet combability per se. Similar surprising synergistic effects can be observed when looking at the parameters of shine, antistatic properties and the "feel" of the hair, i.e. the so-called Treatment effects.

The feeling (i.e., elasticity of the hair) and shine in dry hair have also been improved to a much greater extent when using the shampoos according to the invention than with conventional shampoos which contain e.g. only one of the components required according to the invention. Finally, the tendency of the hair to develop an electrostatic charge after drying is considerably reduced when using the therapeutic shampoo according to the invention. Hair has a lower tendency to "fly", can be combed more easily and the hairstyle stays in them longer.

The cosmetic effects on the hair obtained with the hair conditioner shampoo according to the invention have been demonstrated in the following examples by comparison with conventional shampoos.

eXAMPLES

The shampoo recipes according to the invention (Nos. 1 to 3) are tested by comparison with analogous shampoo recipes which do not contain any (No. 10) or only part (Nos. 4 to 9) of the necessary ingredients present in the shampoos according to the invention.

The shampoo recipes tested for their effectiveness are shown in Table 1.

Example 1 Determination of profitability when wet (laboratory test).

When wet, profitability was determined by measuring the combing resistance, i.e. force, which was required to pull the comb through the hair follicle. A modified tensile tester (type 1402, manufactured by Zwick Company of Einsingen iiber Ulm / To hub) was used. The design of the test is described in "Riech-stoffe, Aromen, Kosmetika", No. 12/1977, page 325, columns 2 and 3.

I used standard hair strands that had been pre-damaged by bleaching and permanent curling under specified conditions. They were washed with the shampoos shown in Table 1 in hand-warm water and rinsed with clean water.

To minimize the error, the combing resistance was determined 15 times with each shampoo tested and averaged. Average hairstyle resistance values are expressed as a percentage of the blind test value. The value of the blank test was determined after shampooing with an aqueous solution containing 10% by weight of sodium lauryl ether diethylene oxysulfate and rinsing with pure water.

10 81 003 so. force, which was required to pull the comb through the hair follicle. A modified tensile tester (type 14 02, manufactured by Zwick Company of Einsingen iiber Ulm / Danube) was used. The design of the test is described in "Riechstoffe, Aromen, Kosmetika", No. 12/1977, page 325, columns 2 and 3.

Standard hair strands that had been previously spoiled by bleaching and permanent curling under specified conditions were used. They were washed with the shampoos shown in Table 1 in hand-warm water and rinsed with clean water.

To minimize the error, the combing resistance was determined 15 times with each shampoo tested and averaged. Average hairstyle resistance values are expressed as a percentage of the blind test value. The value of the blank was determined after shampooing with an aqueous solution containing 10% by weight of sodium lauryl ether diethylene oxysulfate and rinsing with pure water.

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Example 2

Hair cosmetics testing (hair salon test)

Testing and analysis of the cosmetic properties of the hair was performed on ten test subjects, which differed in their hair quality and using the so-called second half test. The test was performed by a trained hairdresser. Such a second hemisphere test is used in a comparative test of two therapeutic products, or in a comparative test of one therapeutic product and one standard product on a test subject. In the tests in question, hair shampoo No. 1 according to the invention was used as a standard. The reference values given in Table 2 are a measure of the extent to which hair shampoos 4 to 10 differ from the evaluation of shampoo 1.

Method and evaluation method

The test subjects' hair was soaked and a split was made in the middle. Standard shampoo was applied to the left half of the head for five test subjects and reference shampoo to the right half, the same amount of 5 g in each case (prewash). For the other 5 test subjects, the other half of the head was treated with the same product. Both halves were shampooed in the same manner and rinsed with water. For the actual wash, shampoos were placed again on the same side of the head in an amount of 2.5 c, rubbed to form a foam and rinsed very well with very clean water.

During and after the wash, the hairdresser evaluates each side separately according to the criteria in Table 2 below. The review was done by giving

A AA A

grades (1 = excellent, 2 = good, 3 = moderate, 4 = poor). Averages of the grades given to 10 test subjects for the same product were calculated. The averages of the standard product were subtracted from the averages of the reference product. Table 2 below shows the pairwise differences thus obtained from the evaluation means for 10 test subjects.

i3 81 003

Result: The reference shampoos were all rated inferior to the cosmetic properties of the hair than the standard shampoo (shampoo No. 1 according to the invention).

Table 2

Reference shampoo with No. 1 „. (Double difference)

Tests in the salon 1456789 10 Wet hair

Profitability + 0 -1/2 -0.6 -0.4 -1.0 -0.4 -0.6 -1.2 "Feel" + 0 -0.9 -0.8 -0.3 -0 .8 -0.5 -0.8 -0.8

Dry hair

Antistatic + 0 -0.5 -0.3 -0.5 -0.6 -0.1 -0.3 -0.6 in the mouth

Feel + 0 -0.5 -0.4 -0.6 -0.3 -0.5 -0.3 -0.6 (elasticity)

Gloss + 0 -0.5 -0.3 -0.2 -0.5 -0.4 +0 -0.5

Claims (5)

14 81003 A hair conditioner shampoo containing, in an aqueous medium, 5 to 50% by weight of a water-soluble, anionic, alkali metal, magnesium, ammonium or C 1 -C 6 alkanolammonium detergent salt which is a C 1 -C 6 alkyl sulfate, a C 8 -C 18 alkyl sulfate alkyl polyglycol ether sulfate having 1 to 6 glycol ether groups in the molecule, C 1 -C 18 alkanesulfonate, C 10 -C 18 olefinsulfonate C 8 -C 18 fatty acid alkyl sulfide g-dialkyl sulfosuccinate, C8-C8-alkyl polyglycol ether carboxylate having 2 to 6 polyglycol ether groups in the molecule, C8-C18-acyl sarcosinate, C8-C8-acyl tauride or C8-C8-acyl isethionate, and 1,8-C8-acyl isethionate, and -14% by weight of a conditioner mixture consisting of a) 0.1-4% by weight of 3- (trimethylamino) -2-hydroxypropyl guar chloride, b) 0.5-5% by weight of easily water-soluble , a curable polycondensation product obtained by giving a water - soluble, reactive and a polyamine having 4 to 6 carbon atoms is reacted with an ether of a poly-C2-C3-alkylene glycol having halohydrin and hydroxyl end groups, followed by reaction with either epichlorohydrin or a further reaction product of said polyamine and said ether, c) 4% by weight of an esterification product formed by reacting 1-2 moles of C8-C18 fatty acid with the addition product obtained by reacting 4-20 moles of ethylene oxide and 1 mole of glycerol, and d) 0.1-1% by weight -% polyvinylpyrrolidone with an average molecular weight of 10,000 to 70,000, characterized in that the weight ratio a): b): c): d) is 1: 0.5-4: 0.5-4: 0.15-0 , 5 and the weight ratio of anionic detergent to conditioner mixture is 10: 1 to 1: 1. Shampoo according to claim 1, characterized in that 2-8% by weight of said conditioner mixture is present. 15 81 003 Shampoo according to claim 2, characterized in that said anionic detergent is present in an amount of 8-30% by weight. Shampoo according to claim 3, characterized in that the weight ratio of said detergent to said mixture is 2.5: 1 to 1.5: 1. Shampoo according to any one of claims 1 to 4, characterized in that said anionic detergent is a mixture of said C 6 -C 18 alkyl polyglycol ether sulphate and C 6 -C 6 alkyl sulphate in a weight ratio of 2: 1 to 1: 1.