JPS6159282B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of finely divided water-insoluble alkali aluminum silicate in hair cleansers for the reduction of hair greasiness.

Liquid or solid hair cleansers primarily serve for easy cleaning of the hair. However, it is also desirable that the hair treated with this is endowed with further desirable properties in addition to the expected cleanliness. In addition to improved fullness and feel, these include improved wet styling, extended curl retention and, in particular, delayed greasiness of the hair in order to preserve its aesthetic appearance for a longer period of time. Already attempts have been made to meet these demands by adding a wide variety of products, optionally in the form of post-treatment agents, but hitherto no solution has been found that satisfies these diverse problems. Ta.

The inventors have now discovered a method which perfectly meets the overall requirements set forth, but in particular the need to reduce the fatty nature of hair. According to this, the corresponding effective substance in the hair cleansing agent has the following general formula (Na ₂ O) _x・Al ₂ O ₃・(SiO ₂ ) _y (wherein, water-soluble silicates and water-soluble aluminium in the presence of water, having a particle size of 1 to 12 μ, preferably 2 to 8 μ, and exhibiting a calcium binding strength of 100 to 200 mg CaO per g of anhydrous active substance. A finely divided water-insoluble alkali aluminum silicate prepared by precipitation from an acid salt is added to a hair cleansing agent in an amount of 2 to 30% by weight, preferably 5% by weight based on the total amount of the agent, in order to reduce the fatty nature of the hair. Use in amounts of ~25% by weight.

The alkali aluminum silicate used according to the invention is easily synthesized, for example, by reacting a water-soluble silicate and a water-soluble aluminate in the presence of water. For this purpose, the aqueous solutions of the starting materials are mixed with each other, or one component present in solid form is reacted with the other component present as an aqueous solution. The desired aluminum silicate can also be obtained by mixing both components present in solid form in the presence of water. Also Al(OH) ₃ ,
Alkali aluminum silicate can also be produced from Al ₂ O ₃ or SiO ₂ by reacting with an alkaline silicate solution or an aluminate solution. Furthermore, such materials can also be formed from melts, but this process is of little economic interest due to the high melting temperatures required and the necessity of forming the melt into a finely dispersed product. I think that the.

Alkali aluminum silicate produced by precipitation or otherwise finely dispersed in an aqueous suspension can be heated from an amorphous state to a crystalline state by heating to a temperature of 50 to 200°C. It can lead to a state. The amorphous or crystalline alkali aluminum silicate present in the aqueous suspension is separated off by filtering the remaining aqueous solution and drying, for example at a temperature of 50 DEG to 800 DEG C. Depending on the drying conditions, the product will contain some bound water. The anhydrous product is obtained at 800°C. Anhydrous or highly anhydrous alkali aluminum silicate is of course only of interest for the production of dry shampoos; in the case of conventional water-containing shampoo compositions one starts from a wet percake or a fluid suspension of alkali aluminum silicate. I can do it.

The precipitation conditions themselves may be conducive to forming the required small particle size of 1-12 microns. In this case, the mutually mixed aluminate and silicate solutions, which can be introduced simultaneously into the reaction vessel, are subjected to strong shearing forces, for example by stirring the suspension vigorously. When preparing crystallized alkali aluminum silicate, which is the preferred method of the present invention, the formation of large, possibly penetrating crystals is prevented by gentle stirring of the crystallizing mixture. .

Nevertheless, undesirable coagulation of crystal particles may occur, and it is advisable to remove these secondary particles in a suitable manner, for example by air sieving. Alkali aluminum silicate produced in coarse grain form and ground to the desired particle size is also used. Mills and/or air sieves or combinations thereof are suitable for this purpose.

In addition to the amorphous, sharp-edged alkali aluminum silicate of the above composition, also used in the present invention are products with rounded corners and sides of alkali aluminum silicate crystals. In particular, synthetically produced alkali _crystalline aluminum silicates _{of the} following composition _{0.7-1.1Na2O.Al2O3.1.3-3.3SiO2} come into consideration.

When it is desired to produce alkali aluminum silicate with rounded corners and sides, the molar composition is preferably in the range of 2.5 to 6.0Na ₂ O.Al ₂ O _3.0.5 to 5.0SiO _2.60 to 200H ₂ O. It is advantageous to start from Such a mixture can be crystallized by conventional methods. This mixes for at least 1/2 hour at 70~
This is advantageously carried out by heating to 120°C, preferably 80-95°C, with stirring. The crystalline product is easily isolated by separating the liquid phase. If appropriate, the product may be washed with water and dried before further processing. Even when operating with mixtures whose composition differs slightly from those mentioned above, products with rounded corners and sides are still obtained, especially when only one of the four concentration parameters mentioned above differs.

Furthermore, the present invention also uses finely divided water-insoluble alkali aluminum silicate which has been precipitated, aged or crystallized in the presence of a water-soluble inorganic or organic dispersant. Such products are relatively easily obtained industrially. Because the aluminate and silicate solutions mixed with each other no longer have to be subjected to strong shearing forces, the considerable energy consumption required for this is thus avoided, as well as the grinding and air sieving of the dry product. This is because it will be done. Suitable water-soluble organic dispersants include tenside, non-tenside-like aromatic sulfonic acids, and compounds that have complex bonding strength with calcium. The above-mentioned dispersants are optionally introduced into the reaction mixture before or during precipitation.
These may be provided as solutions or dissolved in aluminate and/or silicate solutions. Particularly good effects are achieved if the dispersant is dissolved in the silicate solution. The amount of dispersant is at least 0.05% by weight, preferably 0.1% by weight, based on the total precipitation mixture.
~5% by weight. For ripening or crystallization, the precipitation mixture is heated to a temperature of 50 to 200° C. for 1/2 to 24 hours. Among the large number of dispersants that can be used, a few may be mentioned which do not in any way interfere with the use of the products according to the invention in hair cleansers: for example sodium lauryl ether sulfate, sodium polyacrylate, hydroxyethane di phosphonate, amino-trimethylene phosphonate, etc.

As already mentioned above, when producing liquid hair cleansers it is also possible to start from a liquid suspension of alkali aluminum silicate. Such _a stable liquid suspension _essentially has the _above general formula ₍ Na ₂ O) .) from a compound containing finely dispersed, preferably bound water and (B) an ethoxylation product with 1 to 8 moles of ethylene oxide per mole of saturated alcohol having 16 to 18 carbon atoms and water. It is completed. 2 to 7, especially 2 to 7 per mole of alcohol
Ethoxylation products with 6 moles of ethylene oxide are preferred. In particular, it is preferable to use derivatives of linear alcohols. However, branched alcohols,
Derivatives of alcohols, especially those produced by oxo synthesis, may also be used.

The ethoxylation products used to stabilize suspensions are generally not chemically homogeneous compounds, but rather are usually adducts with different degrees of ethoxylation - zero degree of ethoxylation, i.e. ethoxyl often present in small amounts. Also includes starting products that have not been converted into
It is a mixture in which the particles are present in a statistically dispersed arrangement. The ethoxylation products used are virtually water-insoluble compounds and the cloud point determined in aqueous butyl diglycol solution according to DIN 53917 is usually approx.
In the range of 55-85℃. Typical, preferred products are saturated, bovine fatty acids with a cloud point of 58, 71, 77 or 83° C. at a degree of ethoxylation of 2, 4, 5 or 7 moles of ethylene oxide per mole of fatty alcohol. It is a fatty alcohol ethoxylation product derived from.

C _16-18 -Alcohol components are also often technical mixtures, in which alcohols with more and/or fewer C atoms - often e.g.
Non-problematic amounts of up to % can also be present.

The amount of ethoxylation product used depends on the desired degree of stabilization of the suspension. Generally, the concentration of the special ethoxylation product will be about 0.5% by weight or more, preferably in the range of about 1 to 4% by weight, based on the total weight of the aqueous suspension. The concentration of ethoxylated product may be higher than this. For example, a concentration of 6% by weight or more may be preferable depending on the case. However, in most cases the concentration will be between about 1.3 and 3% by weight. The aqueous suspensions of alkali aluminum silicates that can be used consist essentially of at least 20% by weight of component (A), at least about 0.5% by weight of component (B) and water. The preferred alkali aluminum silicate concentration of the suspension is about 25-40% by weight, especially about 28-38% by weight, based on the weight of the suspension.

Suspensions can be prepared by simply mixing the components, with the alkali aluminum silicate, for example, in neat or already wet form or in the form of an aqueous suspension. It can be used in the form that occurs during manufacture.
In particular, it is advantageous to introduce the still moist alkali aluminum silicate obtained during the preparation, for example as a percake, into the preferably warmed (for example to 70 DEG C.) aqueous dispersion of the ethoxylation product.
However, it is of course also possible to use an alkali aluminum silicate which has already been dried, ie freed of adhering water, and optionally still has bound water.

A special embodiment in terms of the crystal structure of the alkali aluminum silicates used according to the invention are compounds _of the following general formula: _{0.7-1.1Na2O.Al2O3 .} > _2.4-3.3SiO2 Fatification of hair It is no different from other alkali aluminum silicates in terms of how it is used in hair cleansers to reduce hair loss.

Yet another embodiment of the finely divided, water-insoluble alkali aluminum silicate used according to the invention is a compound of the formula:

_{0.7-1.1Na2O.Al2O3 . > 3.3-5.3SiO2} When it is desired to prepare such products, it is advantageous to start from a feedstock whose molar composition is preferably in the following range:

_2.5-4.5Na2O ; _Al2O3 ; _3.5-6.5SiO2 ; _50-110H2O This mixture is crystallized by _a conventional method. This is done by heating the mixture to 100-200°C, preferably 130-160°C, for at least 1/2 hour with vigorous stirring. The crystalline product is simply isolated by separating the liquid phase. Optionally, the product may be washed with water and dried at temperatures between 20 and 200°C before further processing. The product dried in this way still contains bound water. When the product is prepared as described above, very fine crystals are obtained which are formed into spherical particles, optionally spherical hollow bodies with a diameter of about 1 to 4 microns.

The finely divided water-insoluble alkali aluminum silicate used according to the invention is in solid and also in the form of liquid hair cleansers, for example as shampoo tablets, as powdered dry shampoo, optionally in aerosol form and in the usual liquid form. Commercialized as Shampoo. In this case, liquid shampoo is a preferred embodiment.

Besides the alkali aluminum silicate, which is present in an amount of 2 to 30% by weight, preferably 5 to 25% by weight, based on the total shampoo, the liquid shampoos that are preferably used first of all contain cleaning active substances in an amount of 4 to 30% by weight, based on the total shampoo. It is contained in an amount of 30% by weight, preferably 5-20% by weight. The cleaning active substances used are primarily anionically active tensides, such as alkyl sulfates, alkyl lauryl sulfonates, alkyl ether sulfates, alkyl lauryl ether sulfates, olefin sulfonates, fatty acid alkylolamide sulfates, sarcosides. ,
Protein-fatty acid condensation products, alkyl polyglycol ether carboxylic acids, sulfated monoglycerides of long-chain fatty acids, alkyl sulfosuccinates, etc. are considered. However, as cleaning active substances nonionic tensides such as fatty alcohol polyglycol ethers, fatty acid polyglycol esters, oxyethylated amines or oxyethylated amides,
It is also possible to use tertiary amino oxides or amphoteric compounds such as betaines and sulfobetaines, alkylaminocarboxylic acids, imidazoline derivatives. If the hair treated with the hair cleanser according to the invention is to be further provided with antistatic properties,
The shampoo can additionally be incorporated with cationically active detersive active substances in the form of quaternary ammonium compounds in amounts of 0.2 to 1% by weight, based on the total shampoo. Hair cleansers may also contain other customary additives, such as thickening agents, foam improvers and foam stabilizers, PH regulators, clouding agents, pearlescent agents, perfume oils, solubilizers for perfume oils, preservatives, anti-dandruff agents. It may contain colorants, colorants and other auxiliaries.

The following examples are intended to explain the subject matter of the present invention in detail, but are not intended to limit the subject matter thereof.

Example First, the production of the alkali aluminum silicate used will be described. No rights protection is required for this.

Add the silicate solution to the aluminate solution in a container of contents 15 with vigorous stirring. Stir at 3000 rpm using a stirrer with a dispersion disc. Both solutions are at room temperature. During the exothermic reaction, radiographically amorphous sodium aluminum silicate forms as the primary precipitation product. After stirring for 10 minutes, the suspension of the precipitated product was transferred into a crystallization vessel, where it was incubated at 90°C for 6 hours.
Leave to crystallize while stirring for an hour (250 rpm). After suctioning off the crystalline gruel from the lye and washing with deionized water until the discharged wash water has a PH value of about 10, the excess residue is dried. Instead of dried sodium aluminum silicate, suspensions or crystallized gruel of crystallized products are also used in the production of hair washes. The water content is determined by heating the pre-dried product to 800° C. for 1 hour. The washed or neutralized and then dried sodium aluminum silicate is subsequently ground in a ball mill until the pH value is approximately 10.
Particle size distribution is determined using a sedimentation balance.

Manufacturing conditions for sodium aluminum silicate A Precipitation: Aluminate solution with the following composition: 17.7% Na ₂ O, 15.8% Al ₂ O ₃ , 66.6% H ₂ O 2.985 Kg Caustic alkali 0.15 Kg Easily soluble in commercially available water glass and alkali 25.8% sodium silicate solution freshly prepared from silicic acid (composition: 1Na ₂ O・6.0SiO ₂ ) 2.445Kg Crystallization: 6 hours at 90℃ Drying: 24 hours at 100℃ Composition: 0.9Na ₂ O・1Al ₂ O ₃ .2.04SiO ₂・4.3H ₂ O(=
21.6% H ₂ O) Crystallinity: Fully crystalline Calcium binding strength: 170 mg Ca/g active substance The particle size distribution determined by sedimentation analysis showed a particle size maximum of 3-6 μ.

Manufacturing conditions for sodium aluminum silicate B Precipitation: Aluminate solution with the following composition: 13.2% Na ₂ O; 8.0% Al ₂ O ₃ ; 78.8% H ₂ O 7.63Kg 8.0% Na ₂ O; 26.9% SiO ₂ ; 65.1% Sodium silicate solution with composition H ₂ O 2.37Kg Mixing ratio (mol): 3.24Na ₂ O; 1.0Al ₂ O ₃ ;
1.78SiO ₂ ; 70.3H ₂ O Crystallization: Drying at 90°C for 6 hours: Drying at 100°C for 24 hours Product composition: 0.99Na ₂ O・1.00Al ₂ O ₃・
_1.83SiO2・_4.0H2O ; (=20.9% _H2O ) Crystal form: Cubic with strongly rounded corners and sides Average particle size: 5.4μ Calcium binding strength: 172mg/g Production of active substance sodium aluminum silicate C Precipitation conditions: Aluminate solution with a composition of 14.5% Na ₂ O; 5.4% Al ₂ O ₃ ; 80.1% H ₂ O 12.15 kg Silicic acid with a composition of 8.0% Na ₂ O; 26.9% SiO ₂ ; 65.1% H ₂ O Sodium solution 2.87Kg Mixing ratio (mol): 5.0Na ₂ O; 1.0Al ₂ O ₃ ;
2.0SiO ₂ ; 100H ₂ O Crystallization: Dry at 99℃ for 1 hour: Dry product suspension (PH10) at 295℃
Solids content of the heated spray suspension at 46% Composition of the dry product: 0.96Na ₂ O 1 Al ₂ O ₃
1.96SiO ₂ 4H ₂ O Crystal form: Cubic with strongly rounded corners and sides Water content
20.5% Average particle size: 5.4μ Calcium binding strength: 172mgCaO/Kg Active substance Sodium aluminum silicate E manufacturing conditions Precipitation: Aluminate solution with the following composition: 36.0% Na ₂ O; 59.0% Al ₂ O ₃ ; 5.0% water 0.76 Kg Caustic soda 0.94Kg Water 9.49Kg Commercially available sodium silicate solution with the following composition: 8.0% Na ₂ O; 26.9% SiO ₂ ; 65.1% H ₂ O 3.94 Kg Crystallization: Drying at 90°C for 12 hours: Drying at 100°C for 12 hours Composition: 0.9Na ₂ O・1Al ₂ O ₃・3.1SiO ₂・5H ₂ O Crystallinity: Perfect grain size The highest value is between 3 and 6μ Calcium binding strength: 110mgCaO/g Active substance Precipitation conditions for the production of sodium aluminum silicate F : _0.84KgNaAlO2 +0.17KgNaOH+ _1.83KgH2O
Aluminate solution with the following composition: 10.0Kg Sodium silicate solution with the following composition: 8.0% Na ₂ O, 26.9% SiO ₂ , 65.1% H ₂ O 7.16Kg Crystallization: Drying at 150°C for 4 hours: Washed product (PH10) Composition of spray-dried heated 30% suspension of product: 0.98Na ₂ O 1 Al ₂ O ₃
4.12SiO ₂ .4.9H ₂ O The particles have a spherical shape, and the diameter of the spheres is on average about 3-6μ.

Calcium binding strength: 132mgCaO/g active substance, 50
Precipitation conditions for sodium aluminum silicate G at °C: Aluminate 7.31Kg (14.8% Na ₂ O, 9.2
_{% Al2O3} , _76.0H2O ) Silicate 2.69Kg ( _8.0Na2O , 26.9% _SiO2 ,
65.1% _H2O ) Mixing ratio (mol): _3.17Na2O , _{1.0Al2O3 ,}
1.82SiO ₂ , 62.5H ₂ O Crystallization: Dry at 90°C for 6 hours Composition of product: 1.11Na ₂ O・1Al ₂ O ₃・
1.89SiO ₂・3.1H ₂ O (=16.4% H ₂ O) Crystal structure: 1:1 ratio mixed structure Crystal form: Rounded crystallites Average particle size: 5.6μ Calcium binding strength: 105mgCaO/g active substance , 50
The following hair cleansers were prepared at ℃: Example 1 Liquid shampoo sodium lauryl ether sulfate 28% cleaning active substance 40.0 parts by weight Sodium aluminum silicate A 10.0〃 Sodium chloride 5.0〃 Perfume oil 0.5〃 Water 44.5〃 Example 2 Liquid shampoo shampoo Mixture of sulfated esters of acids and alcohol ethers 28% cleaning active substances
30.0 parts by weight Fatty alcohol polyglycol ether 5.0〃 Coco oil acid diethanolamide 5.0〃 Sodium aluminum silicate E 10.0〃 Fragrance oil 0.5〃 Water 49.5〃 Example 3 Liquid shampoo oleyl cetyl alcohol + about 5 moles of ethylene oxide 10.0 parts by weight Coco coir with betaine structure Oil amine derivative cleaning active substance approx. 30% 20.0〃 Sodium aluminum silicate B 25.0〃 Fragrance oil 0.5〃 Water 44.5〃 Example 4 Liquid shampoo oleyl cetyl alcohol + approx. 5 moles of ethylene oxide 10.0 parts by weight fatty alcohol polyglycol ether 15.0〃 Cetyl trimethyl ammonium 25% chloride solution 2.0 parts by weight Oil acid diethanolamide 5.0〃 Sodium aluminum silicate C 5.0〃 Fragrance oil 0.5〃 Water 62.5〃 Example 5 Liquid shampoo sodium lauryl sulfate cleaning active substance 25-28%
12.0 parts by weight Sodium lauryl ether sulfate cleaning active substance
28% 12.0〃 90% Lauric acid isopropanolamide 1.0〃〃 95% Coco acid monoethanolamide 1.0〃 Ethylene glycol stearate 2.0〃 Fatty alcohol polyglycol ether 1.0〃 Sodium aluminum silicate E 12.0〃 Fragrance oil 0.5〃 Water 58.5〃 Example 6 Liquid shampoo 90% sodium lauryl sulfate 15.0 parts by weight Hydroxyethyl cellulose 2% solution 35.0〃 Coconut oil acid diethanolamide 2.0〃 Sodium aluminum silicate G 5.0〃 Fragrance oil 0.5〃 Water 42.5〃 Example 7 Liquid shampoo Sodium lauryl sulfate cleaning active substance 28~ 30%
10.0 parts by weight Sodium lauryl ether sulfate cleaning active substance
28% 10.0〃 Mixture of fatty alcohol ether sulfates Addition of pearl luster imparting ingredients 20.0〃 Coconut acid diethanolamide 5.0〃 Sodium aluminum silicate F 12.0〃 Fragrance oil 0.5〃 Water 42.5〃 Example 8 Coconut oil amine derivative with liquid shampoo betaine structure Cleaning active substance 30% 20.0 parts by weight 50% oxyethyl alkyl ammonium phosphate 2.0 oleyl cetyl alcohol + about 5 moles of ethylene oxide 10.0 sodium aluminum silicate D 15.0 fragrance oil 0.5 water 52.5 Example 9 Dry shampoo igneous silicic acid powder Aerosil 200 2.3 parts by weight Rice starch 70.0〃 Sodium aluminum silicate A 15.0〃 Talc 12.0〃 Isopropyl myristate 0.2〃 Fragrance oil 0.5〃 Example 10 Tablet-type shampoo alkyl C _12-18 - Sodium sulfate, powder
40.0 parts by weight Sodium lauryl sulfate, granules 1.0〃 Sodium sulfate 33.0〃 Sodium aluminum silicate B 25.0〃 Perfume oil 1.0〃 The shampoos of Examples 1 to 5 above were tested over a period of 6 weeks on 25 people with fatty hair. Tested. At that time, I washed my hair once a week. Judgments were made by trained personnel. Already after the first hair wash there is a strong retardation of fattening, so that washing once a week is sufficient to keep the hair comfortable for a week. After 6 weeks the hair of all those tested was found to have improved feel, being very full and with significantly improved shine. The greasiness of the hair is clearly delayed, and everyone tested can now get through more than a week with a single hair wash, whereas previously they had to wash their hair at least twice a week.

Additionally, a single comparative hair wash test was conducted on individuals with fatty hair using all of the shampoos of Examples 1-8. At this time, a conventional shampoo was applied to one half of the head, and a shampoo according to the invention was applied to the other half. A barber judged the hair after one week.
At that time, the hair treated with the ordinary shampoo was in its previous dirty and greasy state, but the hair treated with the shampoo according to the invention was still perfectly clean and felt silky and full. It has been shown.

Claims (1)

[Claims] 1 Represented by the general formula (Na ₂ O) _x・Al ₂ O ₃・(SiO ₂ ) _y (wherein, 1 to 12 μ and a calcium binding strength of 100 to 200 mg CaO per g of anhydrous active substance, produced by precipitation from water-soluble silicates and water-soluble aluminates in the presence of water. A method of using an insoluble alkali aluminum silicate in a hair cleansing agent in an amount of 2 to 30% by weight based on the total amount of the agent in order to reduce the fatty nature of the hair. 2. In the method of using a fine alkali aluminum silicate according to claim 1, it corresponds to the following general formula 0.7 _~1.1Na2O・_Al2O3・_1.3 ~ _3.3SiO2 and has rounded corners and sides. How to use the product. 3. A method of using a fine alkali aluminum silicate according to _claim 1, in which a product corresponding to the following general formula _{0.7-1.1Na2O.Al2O3 .} > _2.4-3.3SiO2 is used. 4. A method of using a fine alkali aluminum silicate according to _claim 1, in which a product corresponding to the following general formula _{0.7-1.1Na2O.Al2O3 .} > _3.3-5.3SiO2 is used. 5. In the method of using a fine alkali aluminum silicate according to any one of claims 1 to 4, in addition to the alkali aluminum silicate, a saturated alcohol having 16 to 18 C atoms; and an alcohol. process in the form of a stable liquid suspension containing the ethoxylation product with 1 to 8 mol of ethylene oxide, preferably 2 to 7 mol of ethylene oxide, especially 2 to 6 mol of ethylene oxide, and water per mole of ethylene oxide. . 6. The use of finely divided alkali aluminum silicate according to any one of claims 1 to 5, in addition to which 4 to 30 cleaning active substances in the form of anionic, nonionic or amphoteric tensides are used. Method for use in hair cleansers containing % by weight, preferably 5-20% by weight and optionally 0.2-1% by weight of cationically active tensides.