DK155912B - HAIR CONDITIONING SHAMPOO - Google Patents

Description

The present invention relates to a hair conditioning sham poo of the kind set forth in the preamble of the claim.

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After washing with hair detergents, shower and bath preparations based on synthetic, anionic surfactants, the hair is often in a cosmetically unsatisfactory condition. While wet, it is difficult to make it through, and it feels heavy. After drying, the washed hair tends to be electrostatically charged, which results in the well-known phenomenon of newly washed hair, namely that it is too "alive". In addition, newly-washed hair often has a shiny appearance. For these reasons, it is known to apply conditioners to the hair after washing or rinsing with shampoo treatment of the hair. The present compositions are mostly rinse agents or cream-like lotions containing cationic surfactants. It is also known that certain substances can be added to ordinary shampoos to obtain some conditioning effect when washing the hair. Substances of that type include e.g. water-soluble proteins or protein degradation products; 2Q polycationic polymers e.g. aminopolycarbamide resins of the type described in DE Publication No. 21 50 899, polycationic cellulose derivatives of the type disclosed in the US; 25 No. 4,292,212. Many other water-soluble polymers containing cationic or quaternary ammonium groups have been proposed for this purpose.

A disadvantage common to all known hair conditioning additives lies in their at least partially diminished 3Q action when used in anionic hair washing preparations. Products with a particularly strong effect often show excessive adsorption to the hair and, as a result, reduce the elasticity, structure and shape of the dried hair.

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Accordingly, the object of the present invention is to provide a shampoo composition based on the well-known highly foaming anionic detergent which, through the presence of suitable hair revitalizing additives, allows the hair to be easily penetrated in the wet state and also provide the dry hair with satisfactory cosmetic properties, including especially elasticity, structure, cutting and shape.

It has now been found that the hair-care properties of anionic detergent-based shampoo can be particularly effectively improved 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. Accordingly, the present invention relates to a hair conditioner shampoo of the kind set forth in the preamble, which shampoo is characterized by the characterizing part of the claim.

3 = (The trimethylamino-2-hydroxypropyl guar chloride is a cationic guar derivative known from U.S. Patent No. 3,589,978. The products described therein contain, as their basic unit, two mannose units linked by a glucoside bond and a galactose unit attached to a On average, each of the hexose rings carries three free hydroxyl groups, these free hydroxyl groups are reacted with reactive quaternary ammonium compounds to form the cationic polymers. The cationic polymer used in the shampoo of the invention is under trade. "Cos-media® Guar C 261".

The easily soluble, water-soluble 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 halogen = hydrogen group in the molecule are known from DE Patent No. 2,363,871.

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It is apparent from said patent that for the preparation of the curable polycondensation products for use in the shampoo of the invention, it is necessary to assume 5 polyamines having a content of alkylene oxide groups obtained in a known manner by reacting polyamines, especially polyalkylene polyamines, with mono- and / or polyfunctional derivatives of polyalkylene oxides. These mono- and / or polyfunctional derivatives of polyalkylene oxides may contain, as reaction-capable groups, chlorohydrin groups, glycidyl groups, halogen or other groups capable of forming anions such as e.g. sulfuric acid groups, alkylsulfonic acid groups, etc. The polyalkylene oxide groups present in the polyalkylene oxide derivatives may have varying molecular sizes, in which case the starting material is generally selected such that there are 3-70 available alkylene oxide groups. As an alkylene oxide, ethylene oxide is the first consideration, but other cyclic oxides such as e.g. propylene oxide as well as similar mixtures. The polyalkylene oxide chains may also be disconnected, e.g.

by insertion of a dicarboxylic acid group or diisocyanate group.

Compounds which can be used as a second reaction component include those containing in the molecule more than 1 epoxide and / or halo group such as epichlorohydrin, dichlorohydrin or bifunctional reaction products of these compounds with glycols, diglycols, polyalkylene oxides, glycerol, dicarboxylic acids, polycarboxylic acids, multivalent phenolic acids, etc.

The preparation of certain curable polycondensation products for use in the shampoo of the invention can be accomplished by a particularly simple process by reacting a polyalkylene glycol, e.g. a polyoxyethylene glycol having a molecular weight of 1000 or 600, with epichlorohydrin to form a bis-chlorohydrin ether and then further reacting this product with a sufficient amount of polyamine, 4 ·

DK 155912 B

° e.g. dipropylene triamine, diethylene triamine or triethylene tetraamine to provide in the reaction mixture a ratio of available chlorine atoms to available aminohydrocarbon atoms in the range of 4: 5 to 7: 5. With this production process, the intermediate polyglycolamine formed is not isolated, but directly reacted with additional polyglycol bis-chlorohydrin ether to form the desired polycondensation product. The reaction between the polyamines containing polyalkylene oxide groups with the compounds containing more than 1 epoxide and / or halohydrin group in the molecule can be carried out in the presence of organic solvents or preferably in the presence of water. To accelerate the reaction, suitable acid-binding compounds such as alkali metal hydroxide, sodium carbonate, magnesium carbonate or triethanolamine may also be included.

The reaction is carried out at temperatures between 50 and 100 ° C for a period of time sufficient to give a definite increase in the viscosity of the reaction product. The reaction is terminated, if necessary, by adjusting the pH to more than 6 as soon as the desired degree of polycondensation is reached, at which point the reaction product is still easily soluble.

Among the cationic polycondensation products disclosed in U.S. Pat. No. 2,363,871, the polycondensation product prepared as the product F described below is particularly suitable for use in the preparation of the hair conditioning shampoo of the invention.

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Product F

In a heatable and coolable container with stirring, reflux condenser and thermometer, place 180 kg of liquid polygly-35 O

col 600. At approx. At 30 ° C, 2.7 kg of tin tetrachloride is slowly allowed to flow under stirring. After heating to 68-70 ° C, 56 kg of epichlorohydrin is added with still stirring and any cooling so rapidly that the temperature of the mixture remains 5.

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between 68 and 70 ° C. Stir further at a temperature of approx. 70 ° C for 1 hour. The total amount of the crude poly-glycol bis-chlorohydrin ether obtained is approx. 239 kg.

5 80 kg of the crude chlorohydrin ether obtained are placed in a stirring vessel which can hold approx. 600 liters which can be heated and cooled, equipped with a thermometer and reflux condenser, and with stirring 13.2 kg of dipropylenetriamine, 50 kg of water and 28 kg of 40% sodium hydroxide are added. Then heat for 45 minutes under reflux.

Then, the remaining amount of crude chlorhydrin ether of polyglycol 600 is added in the first container with stirring, and after addition of an additional 30 kg of water, boil for an additional 20-30 minutes. The pH of the viscous reaction product decreases during this time to approx. 7.2.

It then cools vigorously. The pH is adjusted during cooling by adding approx. 38 kg 10% aqueous hydrochloric acid to 5.5-6. Approx. 500 kg of a pale yellow colored, slightly cloudy, high viscous liquid.

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A product of this type is commercially available, e.g. under the designation "Polyquart H®".

The esterification products of ethylene oxide adducts of glycerol 25 and 4 to 20 moles of ethylene oxide with 1 to 2 moles of a C 6 -C 8 g fatty acid are known from DE disclosure no. 20 24 051. Of the esterification products mentioned therein, a partial residues obtained by adding 7.4 moles of ethylene oxide to 1 mole of glycerol, followed by the esterification of 1 mole of the resulting adduct with 1 mole of C 6 -C 18 g coconut oil fatty acid particularly suitable for use in the hair conditioning shampoos of the invention. A product of this composition is commercially available, for example, under the designation "Cetiol HE®".

Polyvinylpyrrolidones are commercially available e.g. under the designations "Kollidon®" and "Luviskol®". Polyvinylpyrrolidones having an average molecular weight of approx. 40.0Q0 corresponding to a KT value of approx. 30. are particularly suitable for the manufacture of

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The concentration of the aforementioned mixture of essential conditioners in the finished shampoo may range from 1.7 to 14% by weight, and a range from 2-8% by weight is preferred.

The ratio of the various essential conditioning agents mentioned above may be approx. 1 part of the guardiate to 0.5-4 parts of "Polyquart®H" to 0.5-4 parts of "Cetiol®HE" to 0.15-0.5 parts of PVP.

The hair-conditioning shampoos of the invention contain 10 contain, as anionic detergents, alkali metal, magnesium, ammonium and / or alkanolammonium salts of alkyl = sulfuric acid semisters containing from 8-18 and preferably from 12-16 carbon atoms in the alkyl radical or alkyl polyglycol ether sulfuric acid semesters containing from 8-18 and preferably -15 shows from 12-16 carbon atoms in the alkyl radical and from 1-6 gly- - · colether groups in the molecule. Other suitable anionic detergents are primary and secondary linear alkanesulphonates containing from 10-18 carbon atoms, alkenesulphonates and hydroxyalkanesulphonates of the type obtained by the sulphonation of olefins containing from 10-18 carbon atoms, fatty acid alkylolamide polysuglycolic acid sulphate acid sulphate acid sulphate sulphate containing from 8-18 carbon atoms in the alkyl group or dialkyl esters containing from 6-10 carbon atoms in the alkyl groups, 25 alkyl polyglycol ether carboxylates containing from 8-18 carbon atoms in the alkyl group and 2-6 polyglycol ether groups in the molecule, acyl sarcosines, acyl taurides and acyl isothionates containing 8 in the acyl group.

The concentration of anionic surfactants in the sham-3Q poo can vary from 5 to 50% by weight. A preferred range is approx. 8 to approx. 30% by weight.

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Preferred surfactants are sodium lauryl ether sulfate and fatty alcohol sulfates in a ratio of 2: 1 to 1: 1 1 by weight. The fatty alcohol sulfate preferably contains an alcohol moiety having 10-14 carbon atoms, preferably 5 12-14 carbon atoms. The ratio of the total amount of anionic surfactant present in the mixture of essential conditioners can range from .10: 1 to 1: 1, preferably from 2.5: 1 to 1.5: 1.

The hair-conditioning shampoos of the invention may des-1Q without containing standard additives and adjuvants such as e.g. thickeners of the fatty acid alkylolamide type; of the ethylene glycol distearate type, pH stabilizers such as alkali or ammonium phosphates or citrates, preservatives such as formaldehyde or p-hydroxybenzoic acid esters, dyes, fragrances and known hair cosmetically active agents such as anti-dandruff or sebostatic agents.

The hair conditioning shampoos of the composition according to the invention are characterized by an unexpectedly pronounced improvement in the hair conditioning properties of hair washed therewith. The so-called ability to permeate the hair in the wet state after washing with the conditioning shampoos of the invention is e.g. substantially improved in comparison to that obtained with shampoos containing only one of the conditioning components, e.g.

"Cosmedia guar ® C 261". This is all the more surprising since the other essential constituents in themselves have little or no effect on the ability to penetrate the wet hair. Similar surprising synergistic effects can be found by examining the parameters gloss, grip and antistatic properties, the so-called "conditioning effect".

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DK 155912B

Also, the grip (elasticity) and gloss of the dry hair are improved by the shampoos of the invention to a greater extent than with conventional shampoos which, e.g. contains only one of the components required in accordance with the invention. Finally, the tendency of the hair to become electrostatically charged after drying is greatly diminished by the use of the conditioning shampoo of the invention. The hair has less tendency to become '' alive '', can be more easily penetrated and beyaxe for longer periods of time.

The hair cosmetic effects obtained with a hair conditioning shampoo according to the invention are shown in the following examples when compared to conventional shampoos.

examples

Shampoo compositions of the invention (Nos. 1-3). are compared, respectively, to analogous shampoo preparations containing none (# 10) or only a portion (# 4-9) of the necessary components of the invention shampoos.

The shampoo preparations examined are listed in Table 1.

Example 1 20 Determination of wet hair permeability (laboratory test).

The ability to penetrate wet hair bley is determined by measuring the resistance to penetration, ie. the force needed to pull a comb through a hairpin. A modified tensile tester was used. (type 1402 manufactured by Zwick Company from Einsingen iiber Ulm / Danube). The sample arrangement is described in "JRiechstoffen, Aromen, Cosmetika, no. 12/1977", page 325, columns 2 and 3.

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Standard hair locks were used which had previously been damaged by bleaching and permanent wavering under defined conditions. The shampoos listed in Table 1 were washed in hand-warmed water and rinsed with 5 pure water.

In order to reduce errors, resistance to re-salvage was determined 15 times with each of the shampoos to be tested and the average values calculated- The average values for resilience to penetration 10 are given as a percentage relative to the blind value- The blind value was determined after hair washing with an aqueous one. solution of sodium lauryl ether sulfate and rinsing with pure water.

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Example 2.

Testing of hair cosmetic properties (salon experiment).

5 The testing and determination of the hair cosmetic properties was carried out in comparison experiments, where for each comparison a group of 10 subjects with varying hair quality were used using the so-called half-side test. The trial was conducted by a trained hairdresser.

10 The half-page trial is used for comparative studies of a hair treatment preparation and a standard trial of subjects. In the present studies, by default, hair shampoo # 1 according to the invention was used in Example 1. The comparison results set forth in Table 2 are a measure of the extent to which hair shampoo # 4 ID differs from the shampoo rating assessment. 1.

Procedure and assessment.

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The subjects' hair was moistened and split into two halves. The standard shampoo was applied to the left half of five subjects' head hair in an amount of 5 g, and the comparator shampoo was applied to the right half in the corresponding 25 volumes in each case (prewash). In the other five subjects, the standard shampoo (# 1) was applied to the right half and the comparison shampoo to the left half. Both sides were washed the same way and rinsed with water. For the subsequent washing, the shampoos were again added to the same half in quantities of 2.5 g, rubbed to form a foam and rinsed thoroughly with clear water.

During and after washing, the criteria set out in the following Table 2 were determined separately by the hairdresser for each of the two two sides. The determination was performed using the score values (1 s excellent, 2 = good, 3 = moderate, 4 = poor).

From the point values determined for each of the ten subjects, the average values were calculated for each of the two shampoos included in the comparison experiment.

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From the average values of the standard product, the average values of the comparison product were subtracted. The following Table 2 shows the difference thus obtained in the average values from each of the comparison experiments.

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Result: The comparison shampoos were all judged to be inferior in their hair cosmetic properties than the standard shampoo (shampoo # 1 according to the invention).

10 T A B E L 2.

Comparison with shampoo # 1 (pairwise difference) 15 r π r! Salon Experiment 1 ..... 4 5 6 7 .8. 9 10 i___________ 20 Wet has

The ability of ± 0 -i 2 -0.6 -0.4 -1.0 -0.4 -0.6 -1.2 penetration ·

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Gloss ± 0 -0.5 -0.3 -0.2 -0.5 -0.4 | ± 0; -0.5

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Claims (1)

DK 155912B Patent claim. Hair conditioning shampoo comprising a water-soluble anionic detergent and standard additives and adjuvants and further comprising one or more of the conditioning agents a polycationic quartz derivative, a curable cationic poly-condensation product, a hydrophilic fatty acid ester and a water-soluble polyvinyl pyrrole in don, by comprising 5-50% by weight of a soluble anionic alkali metal, magnesium, ammonium or C2-C3 alkanolammonium detergent salt selected from C8-C18 alkyl alkylsulates c8 "cie" alkyl polyglycol ether sulfates with 1-6 glycol ether groups in the molecule, C -alkylsulfosuccinates, C0-C8-8 alkylpolyglycol ether carboxylates with 2-6 polyglycol ether groups in the molecule, C8-C8 acylsar-cosines, Cg-Cjg acyl taurides and Cg-Cjg acyl isothionate are 1.7-20 wt% of conditioning agents consisting of a) 0.1 - 4% by weight of 3- (trimethylamino) -2-hydroxypropyl guar chloride, b) 0.5-5% by weight of a water-soluble, curable poly-condensation product formed by reaction of a water-soluble polyamine containing reactive amino groups and having from 4 to 6 carbon atoms with an ether of poly-C2-3 alkylene glycol having terminated halohydrin or hydroxy 1 groups followed by reaction with either epichlorohydrin or with further reaction product of the polyamine and ether , c) 1-4% by weight of an esterification product formed by reacting from 1 to 2 moles of Cg-C C g fatty acid with adducts obtained by reacting 4-20 moles of ethylene oxide with 1 mole of glycerol, and 35 d) 0.1 - 1 weight of polyvinyl pyrrolidone having an average molecular weight of 10,000 - 70,000, the weight ratio of (a): (b): is (c): (d): / of 1: 0.5-4: 0.5 -4: 0.15-0.5, and the weight ratio of the anionic detergent to the conditioning mixture is from 10: 1 to 1: 1, the remainder being water and additives and / or excipients. 5 10 15 20 25 30 35