Aluminium-magnesium-hydroxy-carboxylic acid-compound containing gel composition.

The present invention relates to a novel gel composition consisting of a powdery aluminum-magnesium compound with a layer structure, a polar additive and an organic, lipophilic compound which is liquid at room temperature, and to its production and use in cosmetics as a rheological additive and anti-settling agent .

Good applicability, stability and reproducibility in the manufacture of cosmetic preparations depend primarily on the rheological properties of their components. Most cosmetic preparations contain gels that have their own rheology and thus have a decisive influence on the properties of the finished products. An important property of cosmetic gels is thixotropy. When the shear force treatment is increased, the viscosity drops significantly, ie an apparently solid substance becomes liquid for a certain time, because the original solid gel structure slowly re-forms when the shear force treatment wears off. This effect has great benefits in cosmetic preparations such as. B. antiperspirants, creams, nail polishes but also in paints, inks and soaps.

Cosmetic gels generally consist of a swellable clay mineral that forms a gel of high viscosity when absorbed by liquid.

During gel formation, the layer structure of the clay mineral is expanded by organic liquids. For the absorption of organic liquids such. B. Oils, fats and waxes, the clay mineral must be constructed accordingly, ie it must be organophilic or lipophilic or be chemically modified accordingly.

The known gel compositions contain clay minerals with a layer structure, e.g. B. from the series of bentonites or montmorillonites whose composition corresponds to the formula:<chemistry id="chem0001" num="0001"><img file="EP0318642A2_D0001.tif" /></chemistry>in which X = Al, Fe (3), Mn (3) or Cr (3); Y = Mg, Fe (2), Mn (2), Ni, Zn or Li and Z = K, Na or Ca.

Such a silicate shows a strong hydrophilicity and can absorb a large amount of water and swell strongly between its lattice planes and form aqueous gels with high viscosity.

Furthermore, it is known that an ionophilic or lipophilic material can be produced from such hydrophilic substances by ion exchange. Here. B. Na + ions exchanged for positive quaternary ammonium ions with long-chain, organic residues (see Jordan, JW, Jour. Phys. And Colloid Chem. 53, 294, (1949) and Jordan JW and co-workers, Kolloid Z., 137, 40 ( 1954) or European patent application 0 204 240 and DE OS 31 45 449 etc. Materials produced in this way are called "organically modified". These organically modified clay minerals show a good swelling effect in oils, fats and waxes and form viscous gels with them using mechanical energy, suitable additives and at a suitable temperature. Furthermore, a gel composition is known which contains an organically modified or unmodified clay mineral of the montmorillonite series, a surface-active agent and an organic solvent (Basic materials and methods of pharmaceutical preparation, 1960, page 715 v. F. Gstirner). However, the gelling ability of this montmorillonite is very low, so that large amounts of the expensive montmorillonite have to be used, but pigments which have been added are very easy to precipitate and the desired viscosity of the gel preparation was not readily obtainable.

Other gel compositions contain 10% organically modified montmorillonite, 86.7% mineral oil and 3.3% wetting agent, which is also known as a polar additive (HP Fiedler, Lexicon of auxiliary substances, EDITIO Cantor Aulendorf, p. 167).

A particular disadvantage of the known gel preparations is that the high percentages of the organic polar additives such as methanol, ethanol, acetone etc. and the quaternary ammonium salts introduced by the ion exchange have a skin-irritating effect and may even trigger allergies. In addition, the impurities in the montmorillonite minerals and the various organic additives give a yellow to brown color and an unpleasant smell of the wetting agents. In cosmetics in particular, this is perceived as particularly annoying and unaesthetic.

The object of the present invention was therefore to find new gel compositions which contain swellable, yellowing compounds with a layer structure and these compounds do not have the disadvantages of the known organoclay mentioned at the outset. Another object was to drastically reduce the amount of polar additive contained in the known gel compositions and to find suitable organic compounds which are liquid at room temperature and in which the gel formation and swelling of the aluminum-magnesium-hydroxy compound are optimal is guaranteed.

The object is achieved with a gel composition according to claim 1. With this gel composition, the disadvantages mentioned at the beginning can be eliminated.

The new aluminum-magnesium-hydroxy compounds have a layer structure and show very good gel formation in organic liquids. The composition and the preparation of these Al / Mg hydroxides are described in a not yet published application.

According to the earlier application, the compounds have the general formula<chemistry id="chem0002" num="0002"><img file="EP0318642A2_D0002.tif" /></chemistry>in which R represents the radical RCOO- of a monocarboxylic acid with 2 to 22 carbon atoms and the indices x, y and z meet the following conditions:<ul id="ul0001" list-style="none"><li>3 ≦ x ≦ 9</li><li>4 ≦ y ≦ 13</li><li>3 ≦ z ≦ 5</li><li>and 3x + 2y = 3₅</li></ul>Compounds in which x = 5, y = 10 and z = 4 are particularly suitable. As monocarboxylic acids, technical mixtures of aliphatic monocarboxylic acids having 16 to 18 carbon atoms are advantageously incorporated into the new compounds.

The compounds are prepared by reacting the aqueous suspension of a compound of the formula<chemistry id="chem0003" num="0003"><img file="EP0318642A2_D0003.tif" /></chemistry>in which x, y have the meaning just given and for z applies 3 ≦ z 5 5, where 3x + 2y = 35, with the aqueous suspension of an alkali salt of a monocarboxylic acid, the RCOO radical containing 2 to 22 carbon atoms, with stirring at temperatures between 20 C and 100 ° C, preferably between 20 C and 60 ° C. It is preferred to work under the action of shear forces on the aqueous suspensions. Under these process conditions, the reaction is in many cases complete after 2 hours.

The reaction product can be separated from the aqueous suspension by one of the known processes, but preferably by filtration. The filter cake must be washed with water to remove the adhering alkali sulfate until there is no SO in the wash water with barium chloride₄²- is demonstrable. The filter cake is dried at temperatures between 60 to 130 ° C., but preferably at 80 to 110 ° C., for example in a tray dryer. Other drying devices can also be used.

In another drying variant, the sulfate-free filter cake is resuspended in water and spray-dried, the entry temperature T_E= 250 to 350 ° C. preferably 270 to 300 ° C, and the outlet temperature T_A= 80 C to 130 C, preferably 90 to 110 ° C.

According to other process variants, the aqueous suspension of the compound<chemistry id="chem0004" num="0004"><img file="EP0318642A2_D0004.tif" /></chemistry>the alkali salt of a monocarboxylic acid is added in solid form, all other process characteristics remaining the same.

The Al, Mg compounds used as starting material in the process are already known from the prior art, for example from DE 34 08 463 C2. The monocarboxylic acids are commercially available compounds. The alkali salts can be prepared according to examples.

The compounds are solid, white and odorless, crystalline substances. Their structure is characterized by means of X-ray diffraction and scanning electron microscopy. The X-ray diffractometer recordings proved that the compounds are crystalline. The layer or lamella structure is shown in the enclosed SEM image. Figure 1 shows the SEM image of the product from Example 10.

Compared to an organically modified hectorite or sodium bentonite, both of which are commercially available, the compounds according to the unpublished application show a significantly higher degree of whiteness.

The degree of whiteness is a measure of the color of the substances and is measured, for example, with the Tricolor LFM 3 color measuring device from Dr. Long measured against an enamel white standard. Table 1 shows the degree of whiteness of the products from Examples 6 to 17 below, and the degree of whiteness of two commercial products. This table clearly shows that the new compounds have a significantly higher degree of whiteness, ie are almost white, while the commercial products are colored.<tables id="tabl0001" num="0001"><img file="EP0318642A2_D0005.tif" /></tables>

The following tests show the effectiveness of the new product as an anti-settling agent even in a concentration of 2%:

Formulations as described in Table 2 were prepared and the settling curve determined by means of a turbidity measurement using an Eppendorf photometer:

The absorbance of the solvent paraffin oil is set to 0 in a 300 ml beaker, ie 100% permeability. In the same beaker, the products from the individual examples are now compared with commercially available Na bentonite and an org. modif. Hectorite in a 2% concentration in paraffin oil, homogeneously suspended by stirring and then at 100 rpm for 3 minutes. touched. The stirrer is switched off and the decrease in absorbance is followed by a recorder. The extinction value, which is obtained immediately after switching off the stirrer, is assumed to be 0% permeability.

From Table 2 it can easily be seen that the products produced settle much more heavily than the comparative products, which is an advantage with pigment colors.<tables id="tabl0002" num="0002"><img file="EP0318642A2_D0006.tif" /></tables>

For this purpose, the settling volume is determined separately after various times in a 100 ml measuring cylinder. To do this, the formulation is shaken 20 times vertically and 20 times horizontally and then left to stand. The sedimentation volume provides information on the easy dispersibility of the organic products according to unpublished application in this solvent under low shear forces.

In contrast to the sedimentation tests from Tables 2/3, the products were here after the unpublished application (2%) with a substance insoluble in this solvent (e.g. aluminum chlorohydrate with a grain size of 90% in the range between 10 and 75 µm) in 15 % concentration suspended in the respective solvent. It can also be seen that the suspended products are more difficult to settle when the substances from Examples 6 to 11 are added.<tables id="tabl0003" num="0003"><img file="EP0318642A2_D0007.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0318642A2_D0008.tif" /></tables>

The subject of the earlier application is explained in more detail using the examples below.

Example 1: Production of

<chemistry id="chem0005" num="0005"><img file="EP0318642A2_D0009.tif" /></chemistry>

In an open stirred kettle, 4,743 g of aluminum hydroxide paste with 6.74% Al₂0₃ submitted, diluted with 8 995 g of water and then 2 924.8 g of aluminum sulfate solution with 21.54% SO₄ and 4.21% AI stirred. Allow to stand overnight so that any C0₂ -Gas can escape. 1,336.7 g of MgO with a 60.3% Mg content are added with stirring, with a slight heating. The mixture is left to stir for a further 2 hours and the suspension can then be used for further processing.

Analysis: 2.46% Al, 4.47% Mg, 3.5% SO₄

Example 2: Preparation of sodium caprylate C.

7

H

15

COONa

800 g of caprylic acid are suspended in 7 liters of water and heated to 80 ° C. with stirring. A solution of 221.8 g of NaOH in 500 g of water is then slowly added and the mixture is allowed to cool to room temperature. The aqueous solution is slowly evaporated and the residue is dried at 105 ° C. in a drying cabinet.

Yield: 877 g (95% of theory) of white powder

Example 3: Preparation of sodium myristate C.

13

H

27

COONa

800 g myristic acid are suspended in 3 l of water and heated to 80 ° C. with stirring. A solution of 140.2 g of NaOH in 350 ml of water is then slowly added and the mixture is allowed to cool to room temperature. The sodium myristate precipitates, which is filtered off via a suction filter. It is carefully dried to constant weight in a drying cabinet.

Finishing: 820 g (89% of theory) of white powder

Example 4: Preparation of sodium palmitate C.

15

H

31

COONa

800 g of palmitic acid are suspended in 9 l of water and heated to 80 ° C. with stirring. A solution of 124.8 g of NaOH in 350 ml of water is then added and the mixture is allowed to cool to room temperature. It is filtered off and the residue is dried at 105 ° C. in a drying cabinet

Yield: 814 g (94% of theory) of white powder

Example 5: Preparation of sodium behenate C.

2

, H

43

COONa

700 g of behenic acid are suspended in 9,000 ml of water and heated to 80 ° C. Then a solution of 83 g of NaOH in 350 ml of dist. Add water. The sodium behenate precipitates immediately. The mixture is allowed to cool to room temperature and the precipitate is filtered off through a suction filter. The mixture is washed with 3 × 200 ml of ethanol each time and the residue is dried in a drying cabinet at 65 ° C.

Yield: 708 g (95% of theory) of white powder

Example 6: Preparation of

<chemistry id="chem0006" num="0006"><img file="EP0318642A2_D0010.tif" /></chemistry>119.6 g of Na acetate are suspended in 1,076 g of water by means of a stirrer and added to 2,000 g of Al, Mg hydroxysulfate suspension, as prepared in Example 1. The mixture is heated at 80 C for 3 hours to complete the reaction, allowed to cool and then the insoluble Al, Mg-hydroxy-acetate is filtered off. Wash with water until no more sulfate with BaCI &lt;t2 solution than BaSO₄ is detectable. The filter cake is then dried in the drying cabinet at 105 ° C. to constant weight.

Yield: 395 g (95% of theory)

Description: white, odorless, crystalline powder ID:<ul id="ul0002" list-style="none"><li>11.5% AI i. Tr. (Theory 11.8%)</li><li>20.9% Mg i. Tr. (Theory 21.3%)</li><li>8.3% / C i. Tr. (Theory 8.4%)<img file="EP0318642A2_D0011.tif" /></li></ul>

Example 7: Preparation of Al-Mg-hydroxy-caprylate

<chemistry id="chem0007" num="0007"><img file="EP0318642A2_D0012.tif" /></chemistry>242.3 g of Na caprylate (from Example 2) are suspended in 2 181 g of water by stirring and added to 2 000 g of Al, Mg-hydroxysulfate suspension, as prepared in Example 1. The mixture is heated at 60 ° C. for 1 hour to complete the reaction, allowed to cool and then the insoluble Al, Mg-hydroxy-caprylate is filtered off. Wash with water until no more sulfate with BaCl₂- Solution as BaSO₄ is detectable. The filter cake is then dried in the drying cabinet at 105 ° C. to constant weight.

Yield: 517 g (96% of theory)

Description: white, odorless, crystalline powder ID:<ul id="ul0003" list-style="none"><li>9.0% AI. i. Tr. (Theory 9.1%)</li><li>16.2% Mg i. Tr. (Theory 16.4%)</li><li>25.0% C i. Tr. (Theory 26.0%)<img file="EP0318642A2_D0013.tif" /></li></ul>

Example 8: Preparation of Al-Mg-hydroxymristat

<chemistry id="chem0008" num="0008"><img file="EP0318642A2_D0014.tif" /></chemistry>182.5 g of sodium myristate (from Example 3) are suspended in 1,643 g of water by stirring and added to 1,000 g of Al, Mg-hydroxysulfate suspension, as prepared in Example 1. The mixture is heated at 60 ° C. for 1 hour to complete the reaction, allowed to cool and then the insoluble Al, Mg-hydroxymyristate is filtered off. Wash with water until no more sulfate with BaCl₂ Solution as BaSO₄ is detectable. The filter cake is then dried in the drying cabinet at 105 ° C. to constant weight.

Yield: 321 g (97% of theory)

Description: white, odorless, crystalline powder ID:<ul id="ul0004" list-style="none"><li>7.3% AI i. Tr. (Theory 7.4%)</li><li>13.2% Mg i. Tr. (Theory 13.4%)</li><li>36.3% C i. Tr. (Theory 37.0%)<img file="EP0318642A2_D0015.tif" /></li></ul>

Example 9: Preparation of Al-Mg-hydroxypalmitate

<chemistry id="chem0009" num="0009"><img file="EP0318642A2_D0016.tif" /></chemistry>405.9 g of Na palmitate (from Example 4) are suspended in 3,653 g of water by stirring and added to 2,000 g of Al, Mg-hydroxysulfate suspension, as prepared in Example 1. The mixture is heated at 60 ° C. for 1 hour to complete the reaction, allowed to cool and then the insoluble Al, Mg-hydroxypalmitate is filtered off. Wash with water until no more sulfate with BaCl₂- Solution as BaSO₄ is detectable. The filter cake is then dried in the drying cabinet at 105 ° C. to constant weight.

Yield: 660 g (94% of theory)

Description: white, odorless, crystalline powder ID:<ul id="ul0005" list-style="none"><li>6.8% AI i. Tr. (Theory 7.0%)</li><li>12.4% Mg i. Tr .. (theory 12.6%)</li><li>39.4% C i. Tr. (Theory 39.9%)<img file="EP0318642A2_D0017.tif" /></li></ul>

Example 10: Preparation of Al-Mg-hydroxystearate

<chemistry id="chem0010" num="0010"><img file="EP0318642A2_D0018.tif" /></chemistry>446.8 g of Na stearate are suspended in 4,021 g of water by stirring and added to 2,000 g of Al, Mg-hydroxysulfate suspension, as prepared in Example 1. The mixture is heated at 60 ° C. for 1 hour to complete the reaction, allowed to cool and then the insoluble Al, Mg-hydroxystearate is filtered off. Then wash with water until no more sulfate with BaCl₂- Solution as BaSO₄. is detectable. The filter cake is then dried in the drying cabinet at 105 ° C to constant weight

Yield: 738 g (98% of theory)

Description: white, odorless, crystalline powder ID:<ul id="ul0006" list-style="none"><li>6.5% AI i. Tr. (Theory 6.6%)</li><li>11.7% Mg i. Tr. (Theory 11.9%)</li><li>42.2% C i. Tr. (Theory 42.4%)</li></ul>

X-ray image for example 10:<img file="EP0318642A2_D0019.tif" /><tables id="tabl0005" num="0005"><img file="EP0318642A2_D0020.tif" /></tables>

Thermal analysis for example 10:<img file="EP0318642A2_D0021.tif" />

Example 11: Preparation of Al-Mg-Hydroxy-behenate

<chemistry id="chem0011" num="0011"><img file="EP0318642A2_D0022.tif" /></chemistry>528.6 g of Na-behenate (from Example 5) are suspended in 4,758 g of water by stirring and added to 2,000 g of Al, Mg-hydroxysulfate suspension, as prepared in Example 1. The mixture is heated at 60 ° C. for 1 hour to complete the reaction, allowed to cool and then the insoluble Al, Mg-hydroxy-behenate is filtered off. Wash with water until no more sulfate with BaCl₂ Solution as BaS0₄ is detectable. The filter cake is then dried in the drying cabinet at 105 C to constant weight.

Yield: 767 g (95% of theory)

Description: white, odorless, crystalline powder ID:<ul id="ul0007" list-style="none"><li>5.8% AI i. Tr. (Theory 6.0%)</li><li>10.5% Mg i. Tr. (Theory 10.7%)</li><li>46.2% C i. Tr. (Theory 46.7%)<img file="EP0318642A2_D0023.tif" /></li></ul>

Example 12: Preparation of Al-Mg-hydroxystearate

<tables id="tabl0006" num="0006"><img file="EP0318642A2_D0024.tif" /></tables>

In an open stirred kettle, 578.2 g of aluminum hydroxide paste with 12.73% Al₂O₃ submitted, diluted with 3 151.4 g of water and then 796 g of aluminum sulfate solution which 4.22% Al and 21.62% SO₄ contains, stirred. Allow to stand overnight so that any C0 present₂ -Gas can escape and then adds 474 g of MgO (commercially available) with 99% MgO content with stirring. This causes a slight warming.

Analysis of the suspension: 1.40% Al, 5.60% Mg, 3.46% SO₄

986 g of Na stearate suspended in 7,000 g of water are added to 4,469 g of the above suspension with stirring. The mixture is heated to 60 ° C. for one hour, allowed to cool and then the insoluble Al, Mg-hydroxystearate is filtered off. Wash with water until no more sulfate can be detected. The filter cake is resuspended in 10 kg of water and spray dried. The inlet temperature is 270 C and the outlet temperature is 100 C.

Eliminations: 1,606 g (97% of theory)

Description: white, odorless, crystalline powder ID:<ul id="ul0008" list-style="none"><li>3.7% AI i. Tr. (Theory 3.9%)</li><li>15.3% Mg i. Tr. (Theory 15.4%)</li><li>40.8% C i. Tr. (Theory 41.5%)</li></ul>

Example 13: Preparation of Al-Mg-hydroxystearate

<chemistry id="chem0012" num="0012"><img file="EP0318642A2_D0025.tif" /></chemistry>

In an open stirred kettle 1,581 g of aluminum hydroxide paste with 12.3% Al₂O₃ submitted, diluted with 3,000 g of water and then 975 g of aluminum sulfate solution (solid aluminum sulfate commercially available), which 4.21% AI and 21.54% SO₄ contains, stirred. Allow to stand overnight so that any CO₂ -Gas can escape and then adds 446 g of 99% MgO MgO with stirring. This causes a slight warming.

Analysis of the suspension: 2.41% Al, 4.40% Mg, 3.45% SO₄

984 g of sodium stearate suspended in 7,000 g of water are added to 4,470 g of the above suspension with stirring. The mixture is heated to 60 ° C. for one hour, allowed to cool and then the insoluble Al, Mg-hydroxystearate is filtered off. Wash with water until no more sulfate can be detected. The filter cake is resuspended in 10 kg of water and spray dried. The inlet temperature is 275 C and the outlet temperature is 100 C.

Yield: 1 556 g (95% of theory)

Description: white, odorless, crystalline powder ID:<ul id="ul0009" list-style="none"><li>6.5% AI i. Tr. (Theory 6.6%)</li><li>11.7% Mg i. Tr. (Theory 11.9%)</li><li>42.0% C i. Tr. (Theory 42.4%)</li><li>Density: 1.19 g / ml</li></ul>

Example 14: Preparation of Al-Mg-hydroxystearate

<chemistry id="chem0013" num="0013"><img file="EP0318642A2_D0026.tif" /></chemistry>

In an open stirred kettle, 2,086 g of aluminum hydroxide paste with 12.73% Al₂O₃ submitted, diluted with 1 825 g of water and then 824 g of aluminum sulfate solution, which 4.22% Al and 21.62% SO₄ contains, stirred. Allow to stand overnight so that any C0 present₂-Gas can escape and then adds 264 g of 99% MgO MgO with stirring. This causes a slight warming.

Analysis of the suspension: 3.4% Al, 3.2% Mg, 3.7% SO₄

1,054 g of sodium stearate suspended in 7,000 g of water are added to 4,469 g of the above suspension with stirring. The mixture is heated to 60 ° C. for one hour, allowed to cool and then the insoluble Al-Mg-hydroxystearate is filtered off. Wash with water until no more sulfate can be detected. The filter cake is resuspended in 10 kg of water and spray dried. The inlet temperature is 270 C and the outlet temperature is 100 C.

Yield: 1,668 g (96% of theory)

Description: white, odorless, crystalline powder ID:<ul id="ul0010" list-style="none"><li>9.2% AI i. Tr. (Theory 9.3%)</li><li>8.1% Mg i. Tr. (Theory 8.4%)</li><li>41.9% C i. Tr. (Theory 42.3%)</li></ul>

Example 15: Preparation of Al-Mg-hydroxystearate

<chemistry id="chem0014" num="0014"><img file="EP0318642A2_D0027.tif" /></chemistry>

In an open stirred tank, 2 881 g of aluminum hydroxide paste with 12.73% A1₂0₃ submitted, diluted with 1 126 g of water and then 839 g of aluminum sulfate solution, which 4.22% and 21.62% SO₄ contains, stirred. Allow to stand overnight so that any C0 present₂ -Gas can escape and then adds 154 g of MgO (commercially available) with 99% MgO content with stirring. This causes a slight warming.

Analysis of the suspension: 4.32% Al, 4.87% Mg, 3.85% S0₄.

1,098 g of sodium stearate suspended in 7,000 g of water are added to 4,469 g of the above suspension with stirring. The mixture is heated to 60 ° C. for one hour, allowed to cool and then the insoluble Al, Mg-hydroxystearate is filtered off. Wash with water until no more sulfate can be detected. The filter cake is resuspended in 10 kg of water and spray dried. The inlet temperature is 270 C and the outlet temperature is 100 C.

Yield: 1,685 (94% of theory)

Description: white, odorless, crystalline powder ID:<ul id="ul0011" list-style="none"><li>12.0% AI i. Tr. (Theory 12.1%)</li><li>4.7 g Mg i. Tr. (Theory 4.9%)</li><li>42.4% C i. Tr. (Theory 42.7%)</li></ul>

Example 16: Preparation of Al-Mg-hydroxystearate

<chemistry id="chem0015" num="0015"><img file="EP0318642A2_D0028.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP0318642A2_D0029.tif" /></chemistry>

In a 200 l stirred kettle, 11.1 kg of aluminum hydroxide paste with 12.3% Al₂O₃ submitted, diluted with 30 kg of water and then 6.8 kg of aluminum sulfate solution, which 4.2% AI and 21.5% SO₄ contains, stirred. The mixture is stirred for 3 hours and then 3.1 kg of MgO with 99% MgO content are added. This causes a slight warming. After stirring for a further 3 hours, 7.2 kg of sodium stearate and 49 kg of water are added. The mixture is stirred for a further 2 hours and then the suspension is treated with high shear forces in order to obtain a homogeneous paste. After further stirring (approx. 1 hour), the insoluble Al, Mg-hydroxystearate is filtered off using a filter press. Wash with water until no more sulfate can be detected. The filter cake is suspended in 70 kg of water and spray dried. The inlet temperature is 280 C and the outlet temperature is 90 C.

Yield: 10.5 kg (92% of theory)

Description: white, odorless, crystalline powder ID:<ul id="ul0012" list-style="none"><li>6.5% AI i. Tr. (Theory 6.6%)</li><li>11.8% Mg i. Tr. (Theory 11.9%)</li><li>42.1% C i. Tr. (Theory 42.4%)</li></ul>

Example 17: Preparation of Al-Mg-hydroxypalmitate stearate

<chemistry id="chem0017" num="0017"><img file="EP0318642A2_D0030.tif" /></chemistry>

101 g of Na palmitate (from Example 4) and 335 g of Na stearate are suspended in 3,930 g of water with stirring and added to 2,000 g of Al-Mg-hydroxysulfate suspension, as prepared in Example 1. The mixture is homogenized with a Turrax and stirred for 3 hours at room temperature. It is filtered off and washed with dist. Water sulfate free. The filter cake is dried at 95 C in a drying cabinet to constant weight.

Yield: 693 g (95% of theory)

Description: white, odorless, crystalline powder ID:<ul id="ul0013" list-style="none"><li>6.6 AI i. Tr. (Theory 6.7%)</li><li>11.5 mg i. Tr. (Theory 12.0%)</li><li>41.4 C i. Tr. (Theory 41.8%)</li></ul>

The concentration of the aluminum-magnesium-hydroxy compound in the new gel composition is advantageously 5 to 25% by weight, based on the gel composition, preferably 10 to 20% by weight.

The organic compound which is liquid at room temperature and in which the gel formation takes place can be selected from the group:<ul id="ul0014" list-style="none"><li>a) vegetable and animal fats, oils and waxes (e.g. castor oil, jojoba oil, wool waxes),</li><li>b) paraffinic hydrocarbons (with a boiling range between 170 - 550 C)</li><li>c) the silicone oils (e.g. Dimethicone, Cyclomethicone tetramer and pentamer),</li><li>d) the aliphatic and aromatic esters (e.g. isopropyl myristate, isopropyl palmitate, di-octyl adipate)</li><li>e) the higher alcohols and ethers</li></ul>(e.g. polyethylene glycol, octadodecanol).

Mixtures of compounds from a group can also be combined with one another if they are compatible with one another.

The concentration of the organic lipophilic compound should be between 95 and 75% by weight, based on the gel composition; it is preferably between 90 and 80%.

According to a particularly favorable embodiment, the new gel compositions also contain a polar additive in amounts of up to 20% by weight, based on the aluminum-magnesium hydroxide compound. In many cases, amounts of up to 1% by weight are sufficient. It is worth mentioning at this point that the addition of the additive can even be dispensed with.

Mixtures of water / methanol and / or water / ethanol can be used as the polar additive. Acetone, propylene carbonate and polyoxyethylene (4) lauryl alcohol are also suitable.

The new gel compositions are prepared in such a way that the powdery aluminum-magnesium-hydroxy compound, the polar additive and the lipophilic compound which is liquid at room temperature are heated to 120 ° C. to 130 ° C. in a suitable mixer using high shear forces. The gel obtained has a vaseline-like consistency and is transparent to white. It is an optimal rheological additive and anti-settling agent for cosmetics.

The preparation and the physical properties of the gels according to the invention, such as viscosity, color, odor, stability, thixotropy and settling behavior, are described in detail in the examples below.

The consistency of highly viscous gels is determined using the micropenetration method. The measurement was carried out with the penetrometer from the company Sommer &amp; Runge in Berlin with a 5 g drop rod, which penetrates the gel to be measured for 5 seconds after unlocking. The penetration depth is given in 0.1 mm data.

Figure 2 shows a decrease in the viscosity of the gels with an increase in the amount of polar additive to a minimum and subsequent increase.

Examples 18-24: Preparation of mineral oil gels with various polar additives

20 g of the aluminum-magnesium-hydroxystearate powder from Example 17 are suspended in paraffin oil (type Pioneer 2 660, hochviscos, from Hansen &amp; Rosenthal in Hamburg) in a 400 ml beaker and heated to 90 with the aid of a hotplate Degree C heated up. Then the polar additive is added and the mixture is heated to about 120 ° C. with stirring until the suspension begins to foam slightly. The foaming is due to traces of water. The suspension is then treated with high shear forces (e.g. IKA Laboratory Turrax) without further cooling for about 30 seconds until a thickening is formed. The suspension is then cooled in a desiccator under vacuum and with gentle stirring.

The result is a colorless, transparent gel with different viscosities.<tables id="tabl0007" num="0007"><img file="EP0318642A2_D0031.tif" /></tables>

Example 25-28: Preparation of mineral oil gels with Al-Mg-hydroxystearates of different compositions

30 g of the aluminum-magnesium-hydroxystearate powder from Examples 12-15 are suspended in 170 g of paraffin oil (type Pioneer 2 660, highly viscous from Hansen &amp; Rosenthal in Hamburg) in a 400 ml beaker and placed under with the help of a heating plate Stirring heated to 90 degrees C. Then 0.1 g of polyoxyethylene- (4) -lauryl alcohol (0.5% based on the powder used) is added and the mixture is heated to about 120 ° C. with stirring until the suspension begins to foam slightly. The foaming is due to traces of water. The suspension is then treated with high shear forces (e.g. IKA Laboratory Turrax) without further cooling for approx. 30 seconds until a thickening forms. The suspension is then cooled in a desiccator under vacuum and with gentle stirring.

The result is transparent gels of different viscosity and stability.<tables id="tabl0008" num="0008"><img file="EP0318642A2_D0032.tif" /></tables>

Examples 29-32: Preparation of mineral oil gels with different powder concentrations

Aluminum-magnesium-hydroxystearate powder from Example 16 are suspended in paraffin oil (type Pioneer 2 660, hochviscos, from Hansen &amp; Rosenthal in Hamburg) in a 400 ml beaker and heated to 90 ° C. with stirring using a heating plate. Then 0.1 g of polyoxyethylene (4) lauric alcohol (0.5% based on the powder used) is added and the mixture is heated to about 120 ° C. with stirring until the suspension begins to foam slightly. The foaming is due to traces of water. The suspension is then treated with high shear forces (e.g. IKA Laboratory Turrax) without further cooling for approx. 30 seconds until a thickening forms. The suspension is then cooled in a desiccator under vacuum and with gentle stirring.

The result is colorless, transparent gels of different viscosities.<tables id="tabl0009" num="0009"><img file="EP0318642A2_D0033.tif" /></tables>

Examples 33-40: Preparation of gels with different organic liquids

30 g of the aluminum-magnesium-hydroxypalmitate-stearate powder from Example 17 are suspended in 170 g of an organic liquid in a 400 ml beaker and heated to 90 ° C. with stirring using a hot plate. Then 0.1 g of polyoxyethylene- (4) -lauryl alcohol (0.5% based on the powder used) is added and the mixture is heated to about 120 ° C. with stirring until the suspension begins to foam slightly. The foaming is due to traces of water. The suspension is then treated with high shear forces (e.g. IKA Laboratory Turrax) without further cooling for approx. 30 seconds until a thickening forms. The suspension is then cooled in a desiccator under vacuum and with gentle stirring.<tables id="tabl0010" num="0010"><img file="EP0318642A2_D0034.tif" /></tables>

Example 41: Preparation of gel with mineral oil

400 g of powder from Example 17 are suspended in a laboratory mixer (type Unimix from Hagen &amp; Rinau, Bremen) with a maximum content of 5 kg at room temperature in 3,600 g paraffin oil (type Pioneer 2 660, highly viscous from Hansen &amp; Rosenthal in Hamburg). 0.5% polyoxyethylene (4) lauric alcohol was added and the mixture was heated to 120 ° C. with gentle stirring. The heating is switched off and the suspension is treated with high shear forces (Turrax) for 10 minutes. The temperature rises to approx. 130 Degree C, which is held for about 20 minutes. The mixture is then cooled under vacuum (approx. 0.6 bar) to room temperature within 2 hours.

The yield of colorless, transparent gel is quantitative.

Physical Properties

The experiments on Examples 25 to 28 show that gels are obtained even with changing Al: Mg ratios, but which have deviations from the ratio of 5:10 instabilities.<tables id="tabl0011" num="0011"><img file="EP0318642A2_D0035.tif" /></tables>

Table 10 below gives an overview of the increase (measured via micropenetration at 25 degrees C) of the gels from Examples 29 to 32 with different powder proportions. The stability increases with increasing powder content.<tables id="tabl0012" num="0012"><img file="EP0318642A2_D0036.tif" /></tables>

In order to obtain a clear comparison of the consistency, the micropenetration of petrolatum was determined to be 103 (0.1 mm). The lower the value, the higher the viscosity of the material. This comparison shows that the gels from the examples of the present application have a consistency comparable to that of petroleum jelly.<tables id="tabl0013" num="0013"><img file="EP0318642A2_D0037.tif" /></tables>

An important characteristic of gels used in cosmetics is color. For the production of absolutely white cream, e.g. B. sunscreen, white or colorless gels are advantageous. Table 12 below shows a color comparison with commercially available gels. This shows the clear superiority of the gels according to the invention.<tables id="tabl0014" num="0014"><img file="EP0318642A2_D0038.tif" /></tables>

In cosmetics, the formulations of finished products are subject to additional difficulties in perfuming if the products used have a strong inherent odor. Table 13 below shows a comparison with commercially available products. This also shows the superiority of the gels described by the invention.<tables id="tabl0015" num="0015"><img file="EP0318642A2_D0039.tif" /></tables>

A comparison of the stabilities shows that the gels described in the invention are more stable than commercially available gels.<tables id="tabl0016" num="0016"><img file="EP0318642A2_D0040.tif" /></tables>

An important property of swellable bentonites is the extremely thixotropic and thickening behavior.

Table 15 below shows the viscosity as a function of the shear rate as a function of the temperature on the gel from Example 41 measured with the Rheomat 115 from Contraves in Stuttgart (measuring body DIN 125):<tables id="tabl0017" num="0017"><img file="EP0318642A2_D0041.tif" /></tables>

Table 15 shows the decrease in viscosity with increasing shear rate and temperature. Table 16 below shows the viscosity as a function of the increase and subsequent decrease in the shear rate of the gel from Example 26 at different temperatures. Table 16 clearly shows the thixotropic behavior due to the different viscosities in the start and end values.<tables id="tabl0018" num="0018"><img file="EP0318642A2_D0042.tif" /></tables>

As already described at the beginning, the thixotropic properties of gels are extremely important for cosmetics. A comparison with commercially available gels is shown in Table 17 below. The viscosity was measured as a function of the increase and decrease in the shear rate at 20 ° C. of the gel from Example 31 and the bentonite gel with mineral oil.<tables id="tabl0019" num="0019"><img file="EP0318642A2_D0043.tif" /></tables>

When the two gel qualities are compared with one another, the gel according to the invention shows a higher thixotropic behavior, which is shown by the greater difference between the initial and final values.

Use of the gel composition in cosmetic compositions

In order to demonstrate the advantages in using the gels described by the invention compared to conventional gels, several finished formulations were produced and tested.

1. Manufacture of thermostable W / 0) sun creams:

A problem in the manufacture of sunscreen, which has not yet been optimally solved, is the instability of the viscosity of creams at higher temperatures up to 60 degrees C, as can occur in the sun on the beach or in displays. At these temperatures, a conventional cream is liquid and can no longer be applied well. It runs away like water. If the gel produced in Example 18 is incorporated into a cream in a concentration of up to 15%, the viscosity at 60 ° C. is still so high that the cream can be applied well. In addition, the long-term stability start is improved.

The following cream formulations were tested for comparison:<tables id="tabl0020" num="0020"><img file="EP0318642A2_D0044.tif" /></tables>

The cream is produced by melting the oil phase at 80 ° C and adding the water at 80 ° C while stirring. The mixture is stirred for about 5 minutes and then cooled to about 35 degrees C. Then the perfume oil and the preservative are added. The consistency of the creams is again determined via the micropenetration. From the enclosed fig. 3rd it can be seen that the creams usually produced on the basis of hydrocarbon become liquid at over 40 degrees C (dashed line), while formulation A with the gel from Example 18 still has a semi-solid consistency at temperatures above 70 degrees C. Another problem with the production of suspensions in cosmetics is the rapid sedimentation of the insoluble components. For example, with antiperspirant aerosols consisting of propellant gas, silicone oil and the insoluble active ingredient aluminum chlorohydrate, the active ingredient should remain homogeneously distributed in the suspension for a long time after shaking. If this is not the case, the active substance concentrations would vary depending on the duration. The same problem also occurs with the suspension roll-ons. The gels from Examples 33 to 35 are ideally suited for the above use.

For a comparison with and without a rheological additive, the following aerosol formulations were prepared and the settling behavior was checked. For this purpose, the volume of sedimentation is determined after different times. The aerosol glass bottle is shaken 20 times vertically and 20 times horizontally and then left to stand. The total volume of the suspension is 100%. The sedimentation volume is the total volume minus the excess propellant gas after the corresponding times, stated in%.<tables id="tabl0021" num="0021"><img file="EP0318642A2_D0045.tif" /></tables>

Manufacturing:

The products, with the exception of the blowing agent, are mixed homogeneously, filled into spray cans and mixed with the hydrocarbon propellant.<tables id="tabl0022" num="0022"><img file="EP0318642A2_D0046.tif" /></tables>

The components gel, isopropyl myristate, ethanol, aluminum chlorohydrate and perfume oil are stirred into the cyclomethicone (pentamer) in the following order. Figures 4 and 5 show the settling curves for the formulations. The difference to formulation without rheological additive and thus the advantage of the gels described in the invention can be clearly seen. Another problem with ready-to-use cosmetics is that of lipsticks and lip-gloss preparations in changing storage temperatures, e.g. B. night day and the sensitivity of the consistency to temperatures above 40 degrees C, for example in summer. In addition, the pigment pigments sediment in the molten state during production.

To study the above parameters, the formulations below were made in the laboratory:<tables id="tabl0023" num="0023"><img file="EP0318642A2_D0047.tif" /></tables>

Production of lipsticks according to formulations A, B, C according to Table 21:

The components (apart from pigment trituration, BHT, propylparaben and perfume oil) are melted at 90 degrees C with stirring, then cooled to approx. 70 degrees C under vacuum and the pigment trituration is added. Then add the remaining components and fill.

To investigate the changing storage temperatures, the above formulations were stored at + 5 degrees C for one night and then at 40 degrees C for 8 hours. The visual comparison of the samples clearly shows oiling of formulation A, while formulations B and C were perfect. In order to observe a possible sedimentation of color pigments in the molten state, the remelted formulations A to C were filled at 80 ° C in 80 ° C glass tubes with an internal diameter of 1 cm and a length of 10 cm and allowed to cool at room temperature. Here there is a slight difference in the color intensity of the upper to the lower part in formulation A, while no difference was visible in formulations B and C.

Production of stable water in silicone formulations:

A problem that has not yet been solved in cosmetics to date is the production of stable water in silicone oil formulations. Usually the products oil out after a short time or are immediately unstable at higher temperatures. As shown in Table 22, this problem can also be solved with the gels according to the invention. The stabilities of a cream made from the gel of Example 34 and a cream made from pentameric cyclomethicone are compared.

The cream is produced by melting the oil phase at 80 degrees C and adding the 80th

Grade C hot water with stirring. Then you cool down.<tables id="tabl0024" num="0024"><img file="EP0318642A2_D0048.tif" /></tables>

The comparison of the stabilities was carried out by storage at room temperature and 1 week at 60 degrees C. Formulation B shows slight inhomogeneities after 4 weeks of storage at room temperature and marked separation at 60 ° C., while formulation A with the gel from Example 34 was absolutely stable.