GB1560189A

GB1560189A - Use of fine-particulate water-insoluble alkali metal aluminium silicates in hair washing agents for the purpose of reducing the tendency of the hair to become greasy after washing

Info

Publication number: GB1560189A
Application number: GB7397/78A
Authority: GB
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1977-04-02
Filing date: 1978-02-24
Publication date: 1980-01-30
Also published as: FR2385393B1; NL7802659A; IT7821753A0; DK108478A; BE865564A; DK146953B; CA1091159A; FR2385393A1; ATA228078A; JPS53124629A; CH637539A5; AU523476B2; DE2714954C3; DK146953C; AU3464178A; JPS6159282B2; IT1095553B; SE7802784L; DE2714954B2; SE443085B

Abstract

Finely divided, synthetic, crystallised, water-insoluble alkali metal aluminium silicates containing bound water are used. The alkali metal aluminium silicates correspond to the formula (Cat2O)x.Al2O3.(SiO2)y, in which Cat denotes an alkali metal ion, x denotes a number from 0.7-1.5 and y denotes a number from 0.8-6. These silicates have a particle size of 1-12 mu and a calcium binding ability of 100-200 mg of CaO/g of anhydrous active substance. The proportion is 2-30% by weight relative to the total weight of the hair cleaning composition.

Description

(54) USE OF FINE-PARTICULATE WATER-INSOLUBLE ALKALI METAL ALUMINIUM SILICATES IN HAIR WASHING AGENTS FOR THE PURPOSE OF REDUCING THE TENDENCY OF THE HAIR TO BECOME GREASY AFTER WASHING (71) We, HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN, a German company of 67, Henkelstrasse, 4000 Dusseldorf-Holthausen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The invention relates to the use of fine-particulate water-insoluble alkali metal aluminium silicates in hair washing agents for the purpose of reducing the tendency of the hair to become greasy after washing.

Hair washing agents in a liquid or solid form primarily serve to wash hair in a satisfactory manner. However, in addition to the required cleanliness of the hair, it is also considered desirable for further advantageous properties to be imparted to the hair treated with the hair washing agents. In addition to improving the fullness and feel, improving the wet combability and prolonging the durability of the coiffure, these further properties particularly include the delaying of the tendency of the hair to become greasy after washing, in order to retain the aesthetic appearance of the hair over a longer period of time. Attempts have already been made to meet these requirements by adding a wide variety of products, even in the form of after-treatment agents, although, hitherto, it has not been possible to find a satisfactory solution to this complicated problem.

It has now been found that all the requirements, particularly the requirement with respect to reducing the tendency of the hair to become greasy after washing, can be largely met by using, as a corresponding effective substance in hair washing agents, a quantity of from 2 to 30 percent by weight, preferably of from 5 to 25 percent by weight, relative to the total hair washing agent, of fine-particulate water-insoluble alkali metal aluminium silicates of the general formula (Cat2 O)x . A1203 . (SiO2)y in which Cat represents an alkali metal ion, preferably a sodium ion,xrepresents a number of from 0.7 to 1.5, y represents a number of from 0.8 to 6, preferably 1.3 to 4, which alkali metal aluminium silicates have a primary particle size of from 1 to 12 u, preferably of from 2 to 8 ,u, and a calcium binding capacity of 100 to 200 mg CaO/g of anhydrous active substance.

The alkali metal aluminium silicates, to be used in accordance with the invention, can be produced synthetically in a simple manner, for example by reaction of water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed with one another, or a component in a solid state may be reacted with the other components present in the form of an aqueous solution. The desired aluminium silicates are also obtained by mixing the two components present in a solid state, in the presence of water. Alkali metal aluminium silicates can also be produced from A1(OH)3, Awl 203 or SiO2 by reaction with alkali metal silicate solutions or aluminate solutions. Finally, substances of this type are also formed from the melt, although, owing to the high melting temperatures required and the necessity of converting the melt into finely distributed products, this method appears to be less interesting from an economic viewpoint.

The alkali metal aluminium silicates produced by precipitation, or converted to an aqueous suspension in a finely distributed state by other methods, may be converted from the amorphous state into the aged or the crystalline state by heating to temperatures of from 50 to 200"C. The amorphous or crystalline alkali metal aluminium silicate, present in an aqueous suspension, can be separated from the remaining aqueous solution by filtration and can be dried at temperatures of, for example, 50 to 800"C. The product contains a greater or smaller quantity of bound water according to the drying conditions. Anhydrous products are obtained at 800"C. The use of anhydrous or substantially anhydrous alkali metal aluminium silicates of course, only of importance for the production of dry shampoos and the conventional hydrous shampoo formulations may be based on wet filter cakes or flowable suspensions of alkali metal aluminium silicates.

The precipitation conditions can contribute to the formation of the required small particle sizes of from 1 to 12 ,u, the intermixed aluminate and silicate solutions, which may also be introduced simultaneously into the reaction vessel, being subjected to high shearing forces by, for example, intensively agitating the suspension. When crystallised alkali metal aluminium silicates are produced (these are preferably used in accordance with the invention), the formation of large, possibly interpenetrating crystals is thus prevented by slow agitation of the crystallising compound.

Nevertheless, undesired aglomeration of crystal particles can occur during drying, so that it is advisable to remove these secondary particles in a suitable manner by, for example, air separators. Alkali metal aluminium silicates obtained in a coarser state, and which have been ground to the desired grain size, can also be used. By way of example, mills and/or air separators, or combinations thereof, are suitable for this purpose.

In addition to the amorphous and sharp-edge alkali metal aluminium silicates of the specified composition, and in accordance with the invention, those products may also be used in which the alkali metal aluminium silicate crystallites have rounded corners and edges.

These products are, in particular, synthetically produced crystalline alkaline aluminium silicates of the composition.

0.7 - 1.1 Cat2 O . A1203 . 1.3 - 3.3 SiO2 in which Cat is an alkali metal cation, preferably a sodium cation.

If it is desired to produce the alkali metal aluminium silicates with rounded corners and edges, it is advantageous to start with a preparation whose molar composition lies preferably in the range 2.5 - 6.0 Cat2 O. A1203 - 0.5 - 5.0 SiO2. 60 - 200 H2O wherein Cat2 has the meaning given above and, in particular, signifies the sodium ion. This preparation is crystallized in a conventional manner. Advantageously, this is effected by heating the preparation for at least 2 hour to 70 to 1200C, preferably to 80 to 950C, under agitation. The crystalline product is isolated in a simple manner by separating the liquid phase. If required, it is advisable to rewash the products with water, and to dry them, before further processing. Even when working with a preparation whose composition differs only slightly from that stated above, one still obtains products having rounded corners and edges, particularly when the difference only relates to one of the four concentration parameters given above.

Furthermore. in accordance with the invention, fine-particulate water-insoluble alkali metal aluminium silicates may also be used which have been precipitated and aged or crystallised in the presence of water-soluble inorganic or organic dispersing agents. Products of this type are obtainable in a technically simpler manner, since the intermixed aluminate and silicate solutions no longer have to be subjected to high shearing forces, thus dispersing with the considerable expenditure of energy required for this purpose, as well as the grinding and air-separating of the dry product. Suitable water-soluble organic dispersing agents are surfactants, non-surfactant-like aromatic sulphonic acids and compounds having a complexforming capacity for calcium. The said dispersing agents may be introduced into the reaction mixture in an optional manner before or during precipitation, and, for example, they may be introduced in the form of a solution or they may be dissolved in the aluminate solution and/or silicate solution. Particularly satisfactory effects are obtained when the dispersing agent is dissolved in the silicate solution. The quantity of dispersing agent should be at least 0.05 percent by weight, preferably 0.1 to 5 percent by weight, relative to the starting solution. The product of precipitation is heated to temperatures of from 50 to 200"C for 2 to 24 hours for the purpose of ageing or crystallisation. Some of the large number of dispersing agents which may be used, and which do not in any way impair the use of the products in hair washing agents, will be mentioned below, such as sodium lauryl ether sulphate, sodium polyacrylate, hydroxyethane diphosphonate, amino-trismethylene phosphonate, and others.

As already mentioned above, liquid suspensions of alkali metal aluminium silicates may also be used as starting materials in the production of liquid hair washing agents. Stable liquid suspensions of this type essentially comprise A) finely distributed compounds, preferably containing bound water, of the general formula given above.

(Cat2 O)x . A12O3 . (SiO2)y, in which Cat, x andy have the meanings already given, and B) the product of ethoxylation of a saturated alcohol, having 16 to 18 carbon atoms, with 1 to 8 mol of ethylene oxide per mol of alcohol, and water. Preferably, the product of ethoxylation is a product 2 to 7, particularly 2 to 6 mol of ethylene oxide per mol of alcohol; it is particularly advantageous to use derivatives of straight chain alcohols. Alternatively, however, derivatives of branched chain alcohols may be used, particularly of alcohols produced by oxosynthesis.

The products of ethoxylation used to stabilise the suspension are not generally chemically uniform compounds, but are usually mixtures in which adducts of differing degrees of ethoxylation are present side-by-side in statistical distribution, including the "zero" degree of ethoxylation which exists in the non-ethoxylated starting material generally present in a small quantity. The products of ethoxylation used are virtually water-insoluble compounds, and their turbidity point, determined in an aqueous butyldiglycol solution in accordance with DIN 53917, generally lies in the range of from approximately 55 to 85"C. Typical products, which are preferably used, are saturated products of fatty alcohol ethoxylation which are derived from stearic fatty acids and which, with a degree of ethoxylation of 2,4,5 or 7 mol of ethylene oxide per mol of fatty alcohol, have turbidity points of 58, 71, 77 and 83"C respectively.

The Cl6-s alcohol component is also generally a technical mixture in which alcohols having a larger and/or smaller number of carbon atoms, generally in subordinate quantities of, for example, up to 15%, may also be present.

The quantity of the product of ethoxylation to be used essentially depends upon the desired degree of stabilisation of the suspension. In general, the concentration of the special products of ethoxylation in the suspensions lies at approximately 0.5 percent by weight, and in excess thereof, relative to the total weight of the aqueous suspension, and lies preferably in the range of from approximately 1 to 4 percent by weight. Alternatively, the concentration of products of ethoxylation can be higher. Thus, concentrations of, for example, 6 percent by weight and in excess thereof may also be advantageous. However, advantageously, the concentration is approximately 1.3 to 3 percent by weight in most cases. The aqueous suspensions of alkali metal aluminium silicates which may be used essentially comprise at least 20 percent by weight of component A), at least approximately 0.5 percent by weight of component B), and water. Preferred concentrations of the suspensions of alkali metal aluminium silicates lie in the range between approximately 25 and 40 percent by weight, particularly between approximately 28 and 38 percent by weight, relative to the weight of the suspension.

The suspensions can be produced by simply mixing their constituents, wherein the alkali metal aluminium silicates may, for example, be used as such or already in a wet state or in aqueous suspensions, optionally from production. It is particularly advantageous to introduce the alkaline aluminium silicates, still wet from manufacture, for example in the form of filter cakes, into a dispersion, preferably heated to, for example, 70"C, of the product of ethoxylation in water. However, it will be appreciated that alkali metal aluminium silicates which have already been dried, that is they have been freed from adhering water, and which optionally still contain bound water, may be used.

Compounds of the general formula 0.7 - 1.1 Na2O . A1203. > 2.4 - 3.3 SiO2 constitute a special variant with respect to their crystal structure, of the alkali metal aluminium silicates to be used in accordance with the invention. The possibility of their use in hair washing agents for reducing the tendency of the hair to become greasy after washing does not differ from that of the other alkali metal aluminium silicates which have been mentioned.

Compounds of the formula 0.7 - 1.1 - Na2O . AI2O . > 3.3 - 5.3 SiO2 constitute a further variant of the fine-particulate, water-insoluble alkali metal aluminium silicates to be used in accordance with the invention. If it is desired to produce products of this type, it is advantageous to commence with a preparation whose molar composition lies preferably in the range 2.5 - 4.5 Na2O; A1203; 3.5 - 6.5 SiO2; 50 - 110 H2O This preparation is crystallised in a conventional manner. Advantageously, this is effected by heating the preparation for at least t hour to 100 to 200"C, preferably to 130 to 1600C, under vigorous agitation. The crystalline product is isolated in a simple manner by separation of the liquid phase. If required, it is advisable to wash the products with water before further processing and to dry them at temperatures of 20 to 200"C. The products thus obtained still contain bound water. When the products are produced in the manner described, one obtains very fine crystallites which agglomerate to form spherical particles, possibly to form hollow balls having a diameter of approximately 1 to 4 .

Furthermore, alkali metal aluminium silicates suitable for use, in accordance with the invention, in hair washing agents are those which can be produced from calcinated (destructured) kaolin by hydrothermal treatment with aqueous alkali hydroxide. The formula 0.7-1.1 Cat2 O . A12O3 . 1.3-2.4 SiO2 . 0.5-5.0 H20 corresponds to the products, Cat signifying an alkali cation, particularly a sodium cation. The production of the alkali metal aluminium silicates from calcinated kaolin leads, without any special technical expense, directly to a very fine-particulate product. The kaolin, previously calcinated at 500 to 800"C, is hydrothermally treated with aqueous alkali hydroxide at 50 to 100"C. The crystallisation reaction thereby taking place is generally concluded after 0.5 to 3 hours.

Commercially available, elutriated kaolins predominantly comprise the clay mineral kaolinite of the approximate composition A1203 .2 2 SiO2 . 2H20 and which has a layer structure. In order to obtain the alkali metal aluminium silicates, to be used in accordance with the invention, therefrom by hydrothermal treatment with alkali hydroxide, it is first necessary to destructure the kaolin, this being effected to best advantage by heating the kaolin to temperatures of 500 to 800"C for two to four hours. The X-ray amorphous anhydrous metakaolin is thereby produced from the kaolin. In addition to destructuring the kaolin by calcination, the kaolin can also be destructured by mechanical treatment (grinding) or by acid treatment.

The kaolins usable as starting materials are light-coloured powders of great purity; of course, their iron content of 2000 to 10,000 ppm Fe is substantially higher than the values of from 20 to 100 ppm Fe in the alkali metal aluminium silicates produced by precipitation from alkali metal silicate and alkali metal aluminate solutions. This higher iron content in the alkali metal aluminium silicates produced from kaolin is not disadvantageous when used in hair washing agents, since, in this case, the iron is firmly embedded in the form of iron oxide in the alkali metal aluminium silicate lattice and is not dissolved out. A sodium aluminium silicate having a cubic, faujasite-like structure is produced during the hydrothermal action of sodium hydroxide on destructured kaolin.

Alkali metal aluminium silicates, usable in accordance with the invention, may also be produced from calcined (destructured) kaolin by hydrothermal treatment with aqueous alkali metal hydroxide with the addition of silicon dioxide or a compound producing silicon dioxide. The mixture of alkali metal aluminium silicates of differing crystal structure generally obtained thereby comprises very fine-particulate crystal particles having a diameter of less than 20,u, and 100% of which usually comprise particles having a diameter of less than 1 O,u. In practice, this conversion of the destructured kaolin is effected preferably with soda lye and water glass. A sodium aluminium silicate J is thereby produced which is known by several names in the literature, for example, molecular sieve 13 X or zeolite NaX (see O.

Grubner, P. Jiru and M. Ralek, "Molecular Sieves", Berlin 1968, pages 32, 85 to 89), when the preparation is preferably not agitated during the hydrothermal treatment, at all events when only low shearing energies are used and the temperature preferably remains at 10 to 20"C below the boiling temperature (approximately 103"C). The sodium aluminium silicate J has a cubic crystal structure similar to that of natural faujasite. The conversion reaction may be influenced particularly by agitating the preparation, by elevated temperature (boiling heat at normal pressure or in an autoclave) and greater quantities of silicate, that is by a molar preparation ratio SiO2:Na20 of at least 1, particularly 0.1 to 1.45, such that sodium aluminium silicate F is produced in addition to, or instead of, sodium aluminium silicate J.

Sodium aluminium silicate F is designated "zeolite P" or "type B" in the literature (see D.W.

Breck, "Zeolite Molecular Sieves". New York, 1974, page 72). Sodium aluminium silicate F has a structure similar to the natural zeolites gismondine and garronite and is present in the form of crystallites having an extremely spherical appearance. In general, the conditions for producing the sodium aluminium silicate F and for producing mixtures of J and F are less critical than those for a pure crystal type A.

The fine-particulate water-soluble alkali metal aluminium silicates, to be used in accordance with the invention, may be made up in the form of solid or liquid hair washing agents, for example in the form of shampoo tablets, a pulverulent dry shampoo, optionally in aerosol form, or as a conventional liquid shampoo. The liquid shampoo constitutes the preferred embodiment.

In addition to the alkali metal aluminium silicates present in a quantity of from 2 to 30 percent by weight, preferably from 5 to 25 percent by weight, relative to the total shampoo, the liquid shampoos, preferably used, primarily contain a quantity of from 4 to 30 percent by weight, preferably from 5 to 20 percent by weight, relative to the total shampoo, of washing active substances. Suitable washing active substances for use are primarily anion-active surfactants such as alkyl sulphates, alkyl aryl sulphonates, alkyl ether sulphates, alkyl aryl ether sulphates, olefin sulphonates, fatty acid alkylolamide sulphates, sarcosides, condensation products of albumen fatty acid, alkyl polyglycol ether carboxylic acids, sulphated monoglycerides of longer chain fatty acids, alkyl sulphosuccinates, and others. Alternatively, however, nonionic surfactants such as fatty alcohol polyglycol other, fatty acid polyglycol ester, oxethylated amines or oxethylated amides, and tertiary amine oxides or ampholytes such as betaines and sulphobetaines, alkyl amino carboxylic acids, and imidazoline derivatives, may be used as washing active substances. If antistatic properties are also to be imparted to the hair treated with the hair washing agents in accordance with the invention, the shampoos may also incorporate a quantity of from 0.2 to 1 percent by weight, relative to the total shampoo, of cation-active washing active substances in the form of quaternary ammonium compounds. The hair washing agents may also contain further conventional additives such as thickening agents, foam improvers and foam stabilisers, means for adjusting the pH value, opacifiers, agents for imparting lustre, perfume oils, dissolving intermediaries for perfume oils, preservatives, anti-dandruff agents, dyes and other auxiliary agents.

The following Examples are intended to further explain the subject of the invention, but without limiting the invention to these Examples.

Examples The production of the alkali metal aluminium silicates to be used will be described in the first instance, no protection being claimed for this.

This silicate solution was added to the aluminate solution under vigorous agitation in a vessel having a capacity of 15 litres. Agitation was effected at 3000 r.p.m. by means of an agitator having a dispersing disc. The two solutions were at room temperature. An X-ray amorphous sodium aluminium silicate was formed as a primary product of precipitation under exothermic reaction. After agitating for 10 minutes, the suspension of the product of precipitation was transferred to a crystalliser and, for the purpose of crystallisation, remained in the crystallizer for 6 hours 90"C under agitation (250 r.p.m). The filtration residue was dried after drawing off the lye from the crystal sludge and washing it with deionized water until the water flowing off had a pH value of approximately 10. Instead of the dried sodium aluminium silicates, the suspension of the crystallization product or of the crystal sludge was also used to produce the hair washing agents. The water contents were determined by heating the pre-dried products to 800"C for 1 hour. The sodium aluminium silicates were washed or neutralized to a pH value of approximately 10 and were then dried and were subsequently ground in a ball mill. The grain size distribution was determined by means of a sedimentation balance Conditions for producing the sodium aluminium silicate A: Precipitation: 2.985 kg of aluminate solution of the composition: 17.7 %Na2O 15.8 % A12O3 , 66.6%H2O 0.15 kg of caustic soda 9.420 kg of water 2.445 kg of a 25.8 % sodium silicate solution of the composition 1 Na2O . 6.0 SiO2 freshly prepared from commercially available water glass and slightly alkali-soluble silicic acid Crystallization: 6 hours at 900C Drying: 24 hours at 1000C Composition: 0.9 Na20 . 1 A1203 . 2.04 SiO2 . 4.3 H20 ( 21.6 % H2O) Degree of crystallization: fully crystalline.

Calcium binding capacity: 170 mg Ca/g active substance.

The particle size distribution, determined by sedimentation analysis, resulted in a maximum particle size of3 to 6 .

Conditions for producing the sodium aluminium silicate B: Precipitation: 7.63 kg of an aluminate solution of the composition 13.2 % Na20 ; 8.0 % Al2O3 ; 78.8 % H2O; 2.37 kg of a sodium silicate solution of the composition 8.0 % Na2O; 26.9% Si02 ; 65.1 %H20; Preparation ratio in mol: 3.24 Na2O ; 1.0 Al203 ; 1.78 SiO2 70.3 H2O; Crystallization: 6 hours at 900C Drying: 24 hours at 100 C; Composition of the dried product: 099 Na2O . 1.00 A1203 . 1.83 SiO2 4.0 H20; (20.9%H2O) Crystalline form: Cubic with greatly rounded corners and edges; Average particle diameter: 5.4 Calcium binding capacity: 172 mg/g of active substance.

Conditions for producing the sodium aluminium silicate C: Precipitation: 12.15 kg of an aluminate solution of the composition 14.5 % Na2O ; 5.4 % A1203 80.1 %H20 2.87 kg of a sodium silicate solution of the composition 8.0 % Na2O ; 26.9 % SiO2 65.1 %H20; Preparation ratio in mol: 5.0 Na2O ; 1.0 Al203 ; 2.0 SiO2 ; 100 H20 Crystallization: 1 hour at 900C Drying: Hot atomization of a suspension of the washed product (pH 10) at 2950C ; 46 % content of solid substances in the suspension Composition of the dried product: 0.96 Na20 . 1 A1203 . 1.96 SiO2 .4 H2O; Crystalline form: Cubic with greatly rounded corners and edges water content 20.5 % Average particle diameter: 5.4 p Calcium binding capacity: 172 mg CaO/g of active substance.

Conditions for producing the potassium aluminium silicate D: The sodium aluminium silicate C was produced in the first instance. After the mother lye had been drawn off, and the crystalline mass had been washed to the pH value 10 with demineralised water, the filtration residue was suspended in 6.1 1 of a 25 % KCl solution. The suspension was heated for a short time to 80 to 900C, and was then cooled, filtered off again and washed.

Drying: 24 hours at 1000C; Composition of the dried product: 0.35 Na2O . 0.66 K20 . 1.0 Al2O3 1.96 SiO2 . 4.3 H2O; (water content 20.3 %) Conditions for producing the sodium aluminium silicate E: Precipitation: 0.76 kg of aluminate solution of the composition: 36.0 %Na2O, 59.0% Al2O3 5.0 %water.

0.94 kg of caustic soda; 0.94 kg of water; 3.94 kg of a commercially available sodium silicate solution of the composition: 8.0%Na2O, 26.9%SiO2,65.1%H2O; Crystallization: 12 hours at 900C; Drying: 12 hours at 100 C; Composition: 0.9 Na2O . A1203 . 3.1 SiO2 . 5 H2O; Degree of crystallization: Fully crystalline.

Maximum particle size was 3 to 6 u Calcium binding capacity: 110 mg CaO/g active substance.

Conditions for producing the sodium aluminium silicate F: Precipitation: 10.0 kg of an aluminate solution of the composition: 0.84 kg NaA1O2 + 0.17 kg NaOH + 1.83 kg H2O; 7.16 kg of a sodium silicate solution of the composition 8.0 % Na2O , 269 % SiO2 65.1 %H2O; Crystallization: 4 hours at 150 C; Drying: Hot atomization of a 30 % suspension of the washed product (pH 10); Composition of the dried product: 0.98 Na20 . 1 A1203 . 4.12 SiO2 4.9 H2O; The particles were of spherical shape ; the average diameter of the balls was 3 to 6 eel.

Calcium binding capacity: 132 mg CaO/g active substance at 500C.

Conditions for producing the sodium aluminium silicate G: Precipitation: 7.31 kg of aluminate (14.8 % Na2O 9.2%Al203 ,76.0 % H2O) ; 2.69 kg of silicate (8.0 % Na2O,26.9 % SiO2, 65.1 %H20); Preparation ratio in mol: 3.17 Na2O, 1.0 A1203 , 1.82 SiO2, 62.5 H20 Crystallization: 6 hours at 900C; Composition of the dried product: 1.11 Na2O .1 A1203 . 1.89 SiO2 3.1 H2O (= 16.4%H20); Crystalline structure Mixed structural type in the ratio 1:1; Crystalline form: Rounded crystallites Average particle diameter; 5.6 p.

Calcium binding capacity: 105 mg CaO/g of active substance at 500C.

Conditions for producing the sodium aluminium silicate H produced from kaolin: 1. Destructuring kaolin In order to activate the natural kaolin, samples of 1 kg were heated to 700 C in a fire-clay crucible for 3 hours. The crystalline kaolin A1203 2 SiO2.

Preparation: 1.65 kg of calcined kaolin 13.35 kg of 10 % NaOH , mixed at room temperature Crystallization: 2 hours at 1000C; Drying: 2 hours at 1600C in a vacuum drying cabinet; Composition: 0.88 Na20 . 1 A1203 .2.14 SiO2 - 3.5H20 (=18.1%H20); Crystalline structure: Mixed structural type like Na aluminium silicate G, although in the ratio 8 : 2.

Average particle diameter: 7.0 .

Calcium binding capacity: 126 mg CaO/g active substance.

Conditions for producing the sodium aluminium silicate J produced from kaolin: The destructuring of the kaolin and the hydro-thermal treatment was effected in the same manner as in the case of the sodium aluminium silicate H.

Preparation: 2.6 kg of calcined kaolin 7.5 kg of 50 % NaOH, 7.5 kg of water glass, 51.5 kg of deionized water mixed at room temperature Crystallization: 24 hours at 1000C ,without agitation Drying: 2 hours at 160 C in a vacuum drying cabinet; Composition: 0.93 Na2O . 1 A1203 . 3.60 SiO2 6.8H20 (=24.6%H20); Crystalline structure: Sodium aluminium silicate J) in accordance with above definition cubic crystallites Average particle diameter: 8.0 ; Calcium binding capacity: 105 mg CaO/g active substance.

The following hair washing agents were produced: Example 1: Liquid shampoo Sodium lauryl ether sulphate 28% washing active substance 40.0 parts by weight Sodium aluminium silicate A 10.0 parts by weight Sodium chloride 5.0 parts by weight Perfume 0.5 parts by weight Water 44.5 parts by weight Example 2: Liquid shampoo Mixture of sulphated esters of sulphosuccinic acid and fatty alcohol ether, 28% washing active substance 30.0 parts by weight Fatty alcohol polyglycol ether 5.0 parts by weight Coconut fatty acid diethanolamide 5.0 parts by weight Sodium aluminium silicate E 10.0 parts by weight Perfume 0.5 parts by weight Water 49.5 parts by weight Example 3: Liquid shampoo Oleylcetyl alcohol + approximately 5 mol of ethylene oxide 10.0 parts by weight Coconut fatty amine derivative with betaine structure approximately 30% washing active substance 20.0 parts by weight Sodium aluminium silicate B 25.0 parts by weight Perfume 0.5 parts by weight Water 44.5 parts by weight Example 4: Liquid shampoo Sodium lauryl ether sulphate approximately 28% washing active substance 30.0 parts by weight Methylcellulose, 2% solution 40.0 Coconut fatty acid diethanolamide 3.0 Potassium aluminium silicate D 15.0 Perfume 0.5 " Water 11.5 " Example 5: Liquid shampoo Oleylcetyl alcohol + approximately 5 mol of ethylene oxide 10.0 parts by weight Fatty alcohol polyglycol ether 15.0 Cetyl trimethyl ammonium chloride, 25% solution 2.0 Oleic acid diethanolamide 5.0 Sodium aluminium silicate C 5.0 Perfume 0.5 " Water 62.5 " Example 6: Liquid shampoo Sodium lauryl sulphate, 25 to 28% of washing active substance 12.0 parts by weight Sodium lauryl ether sulphate, 28% washing active sub stance 12.0 Lauric acid isopropanolamide 90% 1.0 Coconut fatty acid monoethanolamide 95% 1.0 Ethylene glycol stearate 2.0 Fatty alcohol polyglycol ether 1.0 Sodium aluminium silicate E 12.0 Perfume 0.5 " Water 58.5 Example 7: Liquid shampoo Sodium lauryl sulphate 90% 15.0 parts by weight Hydroxyethyl cellulose 2% solution 35.0 Coconut fatty acid diethanolamlde 2.0 Sodium aluminium silicate G 5.0 Perfume 0.5 " Water 42.5 Example 8: Liquid shampoo Sodium lauryl sulphate 28 to 30% washing active substance 10.0 parts by weight Sodium lauryl ether sulphate 28% washing active substance 10.0 parts by weight Mixture of fatty alcohol ether sulphonates and additive of components impairing lustre 20.0 Coconut fatty acid diethanolamide 5.0 Sodium aluminium silicate F 12.0 " Perfume 0.5 " Water 42.5 " Example 9: Liquid shampoo Sodium lauryl ether sulphate 28% washing active substance 30.0 parts by weight Hydroxyethyl cellulose 2% solution 30.0 Oleic acid diethanolamide 2.0 Zinc pyridinthion 2.0 Sodium aluminium silicate H 8.0 Perfume 1.0 " Water 27.0 Example 10: Liquid shampoo Oleylcetyl alcohol + approximately 5 mol of ethylene oxide 10.0 parts by weight Oleylcetyl alcohol + approximately 10 mol of ethylene oxide 5.0 Coconut fatty amine derivative with betaine structure 30% washing active substance 10.0 Sodium chloride 2.0 Sodium aluminium silicate I 5.0 Perfume 0.5 " Water 67.5 Example 11: Liquid shampoo Coconut fatty amine derivative with betaine structure 30% washing active substance 20.0 parts by weight Oxyethylalkylammonium phosphate 50% 2.0 Oleylcetyl alcohol + approximately 5 mol of ethylene oxide 10.0 Sodium aluminium silicate D 15.0 Perfume 0.5 " Water 52.5 " Example 12: Dry shampoo Pyrogenic silicic acid powder Aerosil (Reg. Trade Mk.) 200 2.3 parts by weight Rice starch 70.0 parts by weight Sodium aluminium silicate A 15.0 Talc 12.0 " Isopropylmyristate 0.2 Perfume 0.5 Exampie 13: Shampoo in tablet form Sodium-alkyl-C12-Clg-sulphate, powder 40.0 parts by weight Sodium lauryl sulphate, granulate 1.0 Sodium sulphate 33.0 Sodium aluminium silicate B 25.0 Perfume 1.0 The shampoos given in the above Examples 1 to 5 were tested over a period of 6 weeks on 25 test persons having greasy hair. The hair was washed once per week. The assessment was made by trained personnel. The tendency of the hair to become greasy after washing was considerably delayed even after the first wash, so that the weekly washing of the hair was sufficient to give the hair a good appearance for a period of one week. The hair of all the test persons had an improved feel after 6 weeks and was considerably fuller and its lustre was substantially improved. The tendency of the hair to become greasy after washing was considerably delayed, so that all the test persons who previously had to wash their hair at least twice per week now did not have to wash their hair for a week and in excess thereof.

Furthermore, all the shampoos of Examples 1 to 11 were used to make a single comparative washing test on test persons having greasy hair. For this purpose, a conventional shampoo was used on one half of the head, and a shampoo in accordance with the invention was used on the other half. The hair was appraised by a hairdresser after one week. It was shown that the hair treated with the conventional shampoo had reached the previous unsightly, greasy state, while the hair treated with the shampoo in accordance with the invention still had an attractive appearance and a soft and full "feel".

WHAT WE CLAIM IS: 1. A method of improving the feel and handle of hair and of reducing the tendency of hair to become greasy after washing which comprises washing the hair with the aid of a hair washing agent which contains a quantity of from 2 to 30 percent by weight, relative to the total agent, of a fine-particulate water-soluble alkali metal aluminium silicate of the general formula (Cat2O)x . A12O3 . (SiO2)y, in which Cat represents an alkal metal ion, preferably a sodium ion, x represents a number of from 0.7 to 1.5, y represents a number of from 0.8 to 6, which aluminium silicates have a particle size of 1 to 12,a preferably 2 to 8,u and a calcium binding capacity of from 100 - 200 mg CaO/g of anhydrous active substance.

2. A method as claimed in claim 1 in which the agent contains from 5 to 25 percent by weight of the alkali metal aluminium silicate, and in whichy represents a number of from 1.3 to 4.

3. A method as claimed in claim 1 or 2, in which the alkali metal aluminium silicate has rounded corners and edges and corresponds to the general formula 0.7 - 1.1 Cat2O . A1203 . 1.3 - 3.3 SiO2 wherein Cat has the meaning given in claim 1.

4. A method as claimed in claim 1 or 2, in which the alkali metal aluminium silicate corresponds to the general formula 0.7 - 1.1 Na2O . A1203 . > 2.4 - 3.3 SiO2 5. A method as claimed in claim 1 or 2 in which the alkali metal aluminium silicate used corresponds to the general formula 0.7 - 1.1 Na2O . A1203 . > 3.3 - 5.3 SiO2 6. A method as claimed in claim 1 in which the alkali metal aluminium silicate is produced from calcinated kaolin, and corresponds to the general formula 0.7-1.1 Cat2O . A12O3 . 1.3-2.4 SiO2 .0.5-5.0 H20 wherein Cat has the meaning given in claim 1.

7. A method as claimed in any of claims 1 to 6, in which the hair washing agent is in the form af a stable liquid suspension which contains, in addition to the alkali metal aluminium silicate, the product of ethoxylation of a saturated alcohol having 16 to 18 carbon atoms, with 1 to 8 mol of ethylene oxide, preferably 2 to 7 mol of ethylene oxide, particularly 2 to 6 mol of ethylene oxide, per mol of alcohol, and water.

8. A method as claimed in any of claims 1 to 7, in which the hair washing agent additionally contains 4 to 30 percent by weight of washing active substances in the form of anionic, nonionic or amphoteric surfactants.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. Exampie 13: Shampoo in tablet form Sodium-alkyl-C12-Clg-sulphate, powder 40.0 parts by weight Sodium lauryl sulphate, granulate 1.0 Sodium sulphate 33.0 Sodium aluminium silicate B 25.0 Perfume 1.0 The shampoos given in the above Examples 1 to 5 were tested over a period of 6 weeks on 25 test persons having greasy hair. The hair was washed once per week. The assessment was made by trained personnel. The tendency of the hair to become greasy after washing was considerably delayed even after the first wash, so that the weekly washing of the hair was sufficient to give the hair a good appearance for a period of one week. The hair of all the test persons had an improved feel after 6 weeks and was considerably fuller and its lustre was substantially improved. The tendency of the hair to become greasy after washing was considerably delayed, so that all the test persons who previously had to wash their hair at least twice per week now did not have to wash their hair for a week and in excess thereof. Furthermore, all the shampoos of Examples 1 to 11 were used to make a single comparative washing test on test persons having greasy hair. For this purpose, a conventional shampoo was used on one half of the head, and a shampoo in accordance with the invention was used on the other half. The hair was appraised by a hairdresser after one week. It was shown that the hair treated with the conventional shampoo had reached the previous unsightly, greasy state, while the hair treated with the shampoo in accordance with the invention still had an attractive appearance and a soft and full "feel". WHAT WE CLAIM IS:

1. A method of improving the feel and handle of hair and of reducing the tendency of hair to become greasy after washing which comprises washing the hair with the aid of a hair washing agent which contains a quantity of from 2 to 30 percent by weight, relative to the total agent, of a fine-particulate water-soluble alkali metal aluminium silicate of the general formula (Cat2O)x . A12O3 . (SiO2)y, in which Cat represents an alkal metal ion, preferably a sodium ion, x represents a number of from 0.7 to 1.5, y represents a number of from 0.8 to 6, which aluminium silicates have a particle size of 1 to 12,a preferably 2 to 8,u and a calcium binding capacity of from 100 - 200 mg CaO/g of anhydrous active substance.

4. A method as claimed in claim 1 or 2, in which the alkali metal aluminium silicate corresponds to the general formula 0.7 - 1.1 Na2O . A1203 . > 2.4 - 3.3 SiO2

5. A method as claimed in claim 1 or 2 in which the alkali metal aluminium silicate used corresponds to the general formula 0.7 - 1.1 Na2O . A1203 . > 3.3 - 5.3 SiO2

6. A method as claimed in claim 1 in which the alkali metal aluminium silicate is produced from calcinated kaolin, and corresponds to the general formula 0.7-1.1 Cat2O . A12O3 . 1.3-2.4 SiO2 .0.5-5.0 H20 wherein Cat has the meaning given in claim 1.

9. A method as claimed in claim 8 in which the hair washing agent contains 0.2 to 1

percent by weight of cationic surfactants.

10. A method as claimed in claim 8 or 9 in which the hair washing agent contains 5 to 20 percent by weight of washing active substance in the form of anionic, nonionic or amphoteric surfactants.

11. A method as claimed in claim 1 substantially as hereinbefore described in any one of the Examples.