DD283930A5 - METHOD FOR PRODUCING TOPICAL COSMETIC AND PHARMACEUTICAL PREPARATION CONTAINING A FAT CONTENT AND FREE TOCOPHEROLS - Google Patents

Abstract

The invention relates to processes for the preparation of topical cosmetic and pharmaceutical preparations containing fatty substances and tocopherols, which is characterized by the addition of UV light filter substances and color stabilization ascorbic acid esters of fatty acids having 12 to 18 carbon atoms and citric acid esters of partial glycerides of fatty acids 12 to 20 carbon atoms. The free tocopherols are preferably present in amounts of 1 to 10 parts of the preparation and the ascorbic acid esters and citric acid esters in amounts of 0.1 to 10 times in each case based on the amount of tocopherol. {Preparations, pharmaceutical; topically cosmetically; Fat; free tocopherols; UV filter substances; Color stabilization; ascorbic acid; citric}

Description

Field of application of the invention

The present invention relates to processes for the preparation of topical cosmetic and pharmaceutical preparations containing fats and free tocopherols which can be used to care for the skin and hair.

Characteristic of the known state of the art

It is known that alpha-tocopherol acetate is added as a physiological active ingredient in skin and nutrient creams, oils, masks and bath preparations, especially for the treatment of aging skin, cosmetic and pharmaceutical preparations. Other tocopherol esters, such as tocopherol nicotinate, are used as active ingredient in medical hair lotions.

Tocopherols and their esters in such topical preparations are said to promote blood circulation in the skin, strengthen the connective tissue and regenerate cells, and bring about a better utilization of the oxygen in the tissue. The tocopherol esters described above are stable to oxygen and light, so that they are widely used today in topical cosmetic and pharmaceutical preparations.

In contrast, free tocopherols, such as the alpha-tocopherol, or mixed tocopherols from the alphabet, gamma and delta isomers to light and oxygen inconsistent substances, so that a use of the free tocopherols in cosmetic and pharmaceutical preparations is not yet possible because these are rapidly discolored under the influence of air and light, are therefore unsightly and can not be marketed in this form. The use of free tocopherols in the following compositions is known from the prior art: BE 899975 (Boots Lab., Corresponding to EP 147446) describes an emulsion-form topical composition against psoriasis which contains, inter alia, 0.02% ascorbyl palmitate, 0.9% % Citric acid and 0, T% alpha-tocopherol. DE-OS 3514724 (Jereb) relates to pharmaceutical ointments which contain, inter alia, 1.0 (% by weight of vitamin C and 0.3% by weight of alpha-tocopherol in a Vaseline or Eucerin base.

In "Food Chemistry", 23 (1987), pages 151 to 157, inter alia, the combination of D, L-alpha-tocopherol and ascorbyl palmitate for the preservation of canned meat tested and a synergistiicher antioxidant effect found (Table 3).

There also commercial antioxidants of the company. Hofmann La Roche are cited, z. Ronoxan® A and Ronoxan® D 20 containing such combination (Ronoxan® A = 25% ascorbyl palmitate, 5% DL-alpha-tocopherol, 0.8% citric acid, 1% mono- and diglycerides and dextrose; Ronoxan® D20 = 4.8% ascorbyl palmitate, 1.6% D, L-alpha-tocopherol, 0.8% citric acid, mono- and diglycerides and dextrose).

In addition, J. Am. Oil Che.n. Soc. 1986,63 (9), pages 1165 to 1169 that the pro-oxidative properties of alpha-tocopherol by combining with z. As ascorbyl palmitate or citric acid can be reduced or converted into an antioxidant effect.

In Chem. Abstr. 100: 66798f, a publication from Yukagaku 1983, 32 (12), pages 731 to 734 (Japanese), in which a synergistic, antioxidant effect of a combination of DL-alpha-tocopherol and monoacylglyceryl citrate (MGC) in lard and palm oil is described ,

Object of the invention

The present invention provides topical cosmetic and pharmaceutical preparations containing fats and free tocopherols which have very good color stability to light and air.

Explanation of the essence of the invention

Object of the present invention is to provide topical cosmetic and pharmaceutical preparations containing fats and free tocopherols, which have a very good color stability to light and air. According to the invention, this object is achieved by the use of free tocopherols in combination with ascorbic acid esters and MonO '/ di-glyceride citric acid esters as components of these topical compositions based on customary fat and oil components.

The invention therefore relates to topical cosmetic and pharmaceutical preparations with einom content of fatty substances and free tocopherols, which are characterized in that for color stabilization ascorbic acid esters of fatty acids having 12 to 18 carbon atoms and Citronensäuroester of partial glycerides of fatty acids having 12 to 20 carbon atoms are included. By means of the addition according to the invention of ascorbic acid esters and citric acid esters, it is possible to stabilize the free tocopherols in the topical cosmetic and pharmaceutical preparations to the extent that products are obtained whose color stability is comparable to the quality of corresponding commercial preparations containing tocopherol esters. For the purposes of this invention, free tocopherols are understood to mean either the pure D-alpha tocopherol, the D.L. alpha.-tocopherol, or the corresponding D-mixed tocopherol concentrates of natural origin, as obtained, for example, from edible oils. These are mixtures of the D-alpha, D-beta, D-gamma and D-delta homologs of tocopherol.

In the ascorbic acid esters of fatty acids having 12 to 18 carbon atoms according to the invention, the fatty acid moiety may consist of saturated and / or unsaturated aliphatic or cycloaliphatic !! Fatty acids exist. These are, for example, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, oleic acid, linoleic acid and linolenic acid or mixtures of these fatty acids, as obtained from animal or vegetable oleochemical starting materials.

Preferably, the ascorbic acid ester used is the ascorbyl palmitate.

In the case of the inventive citric acid esters of partial glycerides of fatty acids having 12 to 20 C atoms, the fatty acid fraction can consist of saturated and / or unsaturated aliphatic fatty acids. These are, for example, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, oleic acid, linoleic acid or linolenic acid or mixtures of these fatty acids, as obtained from animal or vegetable oleochemical starting materials, which may have been previously hydrogenated. The mono- / pi] citric acid citric acid esters are prepared, for example, by esterification of mono- / diglycerides with citric acid or by esterification of glycerol with citric acid and fatty acids. These citric acid esters usually have a citric acid content of 13 to 50% by weight, preferably 17 to 22% by weight, a content of free fatty acids of less than 3% by weight, a content of free glycerol of less than 2% by weight and a content of bound glycerol from 18 to 20% by weight. Such products are marketed under the name LAMEGIN ZE 30 (Grünau) and TEGIN C (Th. Goldschmidt). They are also often referred to by the name "Citrem".

The content of free tocopherols in the topical cosmetic and pharmaceutical preparations according to the invention is preferably 1 to 10% by weight. The content of the ascorbic acid ester and the citric acid ester is preferably 0.1 to 10% by weight, based on the amount of tocopherol used.

The topical preparations according to the invention may be added as further components ultraviolet radiation filter substances, ie UV-A radiation filters, UV-B radiation filters or UV-A / UV-B radiation filters. Suitable ultraviolet radiation filter substances are the para-aminobenzoic acid derivatives known to the person skilled in the art, benzimidazole derivatives, benzophenone derivatives, benzoxazole derivatives, camphor derivatives, coumarin derivatives, dibenzoylmethane derivatives, gallic acid derivatives, salicylic acid derivatives and cinnamic acid or paramethoxycinnamic acid derivatives. These are, for example, 4-aminobornzoic acid, 3- (4-trimethylammonium) -thienylidenebornan-2-one-methylsulfate, SSB-trimethylcyclohexylsalicylate, 2-hydroxy-4-methoxybenzophenione, 3-imidazol-4-yl-acrylic acid and its ethyl ester , 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 4-bis (hydroxypropyl) aminobenzoic acid ethyl ester, 4-bis (polyethoxy) aminobenzoic acid polyethoxyethyl ester, 4-dimethylaminobenzoic acid amylester, 4-aminobenzoic acid 1-glyceryl ester 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2-ethylhexyl salicylate, 3,3,5-trimethylcyclohexyl N-acetylanthranilic acid, potassium cinnamate, water-soluble 4-methoxycinnamic acid salts, 4-methoxycinnamic acid propyl, water-soluble salicylates, 4- Isoamyl methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, 2-ethoxyethyl 4-methoxycinnamate, trioleate 3,4-dihydroxy-5- (3 ', 4', 5'-trihydroxybenzoyloxy) benzoate, 2 -Hydroxy-4-methoxy-4'-methylbenzopher> on, 2-hydroxy-4-metho xybenzophenone-5-sulfonic acid and its sodium salt, 4-phenylbenzophenone-2'-carboxylic acid 2-ethylhexyl ester, 5-methyl-2-phenylbenzoxazole, 3,4-dimethoxy-phenylglyoxylic acid sodium, 1,3-bis (4 -methoxyphenyl) -propane-1,3-dione, 5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one, 3- (3'-sulfo-4'-methyl) benzylideneburnan-2 -on, 3- (4'-sulfo) benzyliden-bornan-2-one and salts, 3- (4'-methyl) -benzylidene-bornan-2-one, 3-benzyliden-bornan-2-one, 4- Hexyl methoxy-alpha-cyanocinnate, 1- (4'-isopropylphenyl) -3-phenylpropane-1,3-dione, 4-isopropylbenzyl salicylate, cyclohexyl 4-methoxycyclobutyl ester and 1- (4-tert-butylphenyl-3-yl ⁾ ( 4-methoxyphenyl) propane-1,3-dione. Preferred UV absorbers are the following products under the trade names Eusolex® (Merck, Darmstadt) and Parsol (Givaudan, Geneva):

1- (4-isopropylphenyl) -3-phenyl-1,3-propandior. {Eusolex 8020) 3- (4-Methylbenzylidene) -D, L-camphor (Eusu! .Jx 0300) 2-phenylbenzimidazole-5-sulfonic acid (Eusolex 232) 2-hydroxy-4-methoxybenzophenone (Eusolex 4360) benzaldazine (Eusolex 6553 ), which are used in concentrations of 1 to 10% by weight, based on the total weight.

embodiments

The topical cosmetic and pharmaceutical preparations according to the invention have been formulated in the following examples only for a lip balm (with sunscreen). However, it goes without saying for the person skilled in the art that other topical preparations in which a very good color stability is likewise given can be formulated in the same way. These topical formulations are furthermore especially bath preparations, skin and shampoo, skin care products, skin cleansers, insect repellents, foot care agents, acne agents, insect bites, shaving aids, hair care products and sunscreen preparations.

General manufacturing method of Lipponpllegostifte

On the water at 90 ° C, a mixture of 38 parts by weight of castor oil, 7.6 parts by weight of 2-octyl-dodecanol, 9.5 parts by weight Glycerinmonorinzinoleat, 5.7 parts by weight of Candellilla, 5 7 parts by weight of carnauba wax, 1.9 parts by weight of paraffin subliquidum, 1.9 parts by weight of cetyl alcohol, 1.9 parts by weight of beeswax, 2.8 parts by weight of microwax, 5 parts by weight Myristyl lactate and 5 parts by weight of myristyl myristate are heated and dissolved, then allowed to cool to 75 ° C and stirred into this melt (fat matrix) the substances listed in the following tables and poured this mass into molds.

Application test color stability

The lip balms prepared according to the above-described preparation processes using the composition described in Tables 1 to 3 were tested for 12 weeks at + 50 ° C. Tocopherol oxidation products could easily be recognized as intensively pale yellow to dark brown colored substances. The color change of the test samples compared to a tocopherol-free standard sample was evaluated as a measure of the stability of the tocopherols in the product.

The color changes were determined by an experienced application technician on a weekly basis according to the following color criteria:

1) color unchanged; without findings.

2) Color discolored from light yellow to dark brown; with findings.

The time in weeks to the observed color change was chosen as the evaluation criterion for the effect of the tested combinations (see Tables 1-6).

In Table 1 below, as examples 1 to 6, lip balm sticks were formulated and tested containing 5% D-alpha-tocopherol stabilized by additions of ascorbyl palmitate or citrem or by combination of ascorbyl palmitate and citrem.

It has been shown that maximum color stabilization is achieved when citrem and ascorbyl palmitate are used in combination (Examples 6 and 7). Examples 8 to 14 in Table 2 also describe lip balms containing D-alpha-tocopherol using light stabilizers, it also being possible here to show that a combination of citrem and ascorbyl palmitate leads to optimal color stabilization (see Examples 13 and 14).

In Table 3, in Examples 15 to 21, a lip balm was formulated and tested containing as active ingredient a D-mixed tocopherol. In Table 4, Examples 22-28 formulated and tested a lip balm to which sunscreen had been added. In these cases too, a combination of citrem and ascorbyl palmitate resulted in lip care sticks which have optimal color stability (see Examples 20/21 and 27/28).

In Tables 5 and 6, finally, by means of Comparative Examples 1 to 12, a lip balm containing D-alpha-tocopherol acetate as the active ingredient has been formulated and tested, as sold as a commercial product. These lip balms are color-stable without the addition of UV absorbers (Comparative Examples 1 to 5). However, adding a UV absorber added, the color stability of these pins is drastically reduced, and obtained in Comparative Examples 6 to 12 significantly worse values than the corresponding formulations of the invention, as described in Examples 13 and 14 and 27 of Tables -4 were found.

Table 1

Composition and color stabilization of a pen with D-alpha Tocophero! (without sunscreen)

Composition (parts by weight)

Example No.

 1 2

Fat matrix 95 - 1 95 - 0.01 95 - 0.02 95 - 0.05 95 - 4 91.5 91 D-alpha-tocopherol 5 · - 5 5 5 5 5 5 Citrem 0.5 0.5 0.5 Ascorbyipalmitat 1 2 8th 0.05 0.5 Application s test Color stabilized until .... weeks 12 12

= Citric acid esters of mono / diglycerides of fatty acids (manufactured by Fa. Grunau, Lamegin ZE 30) = Maximum Test duration 12 weeks at + 50 ⁰ C

NS OO OO

Table 2

Composition and color stabilization of a stick with D-alpha-tocopherol (with sunscreen)

composition Example no. - 0.01 10 - 0.02 11 - 0.05 12 - 7 13 14 (Parts by weight) 8 9 7 7 85 7 85 7 84.5 3 84.5 84 Fat matrix 85 85 3 3 5 3 5 3 5 5 5 D-alpha-tocopherol 5 5 0.5 0.5 0.5 Citrem 3 0.05 0.5 ascorbyl 2 2 2 1 7 7 Parsol ^R MCX ^x3 3 3 Parsol ^R 1789 ^xU x2 application test Color stabilized 7 12 until .... weeks

^Xl = sh. Table 1

= sh. Table 1

= 2-ethylhexyl p-methoxyl cinnamate (manufactured by Givaudan, Geneva)

= 4-tert-butyl-4'-methoxy-dibenzoylmethane (manufactured by Givaudan, Geneva)

Table 3

Composition and color stabilization of a pencil with D-mixed tocopherols {without sunscreen)

Composition (parts by weight)

Example no. 15

17

18

19

20

Fat matrix 95 - 1 95 - 0.01 95 - 0.02 95 - 0.05 94.5 94.5 94 D-Mi sch tocophe red 5 - 5 5 5 5 5 5 Citrem 0.5 0.5 0.5 ascorbyl 4 2 2 - 0.05 0.5 application test Color stabilized until ... weeks 4 7 12

= sh. Table 1 = sh .. Table 1 = 60 % D-gamma-tocopherol 60% D-delta-tocopherol 12% D-alpha-tocopherol 2% D-beta-tocopherol

M OO CO

Table 4

Composition and color deepening of a pencil with D-mixed tocopherols (with sunscreen)

composition Example no. - 7 23 - 0.01 21 - 0.02 25 - 0.05 • 26 27 28 (Parts by weight) 22 - 3 85 7 85 7 85 7 84.5 84.5 84 Fat matrix 83 5 3 5 3 5 3 5 5 5 x5 D-mi scli tocopherol 5 0.5 0.5 0.5 _n .. xi citrem 1 - 0.05 0.5 ascorbyl 2 2 2 7 7 7 Parsol ^R MCX ^x3 3 3 3 R xti Parsol 1789 application test Color stabilized 1 5 5 to ... weeks <

= sh. Table 1 = sh. Table 1 = sh. Table 2 = sh. Table 2 = sh. Table 3

Table 5

Composition and color stabilization of a stick with D-alpha-tocopherol acetate (without sunscreen)

Composition (parts by weight)

Comparative Example No.

 2 3

Fat matrix 95 - 95 - 0.01 95 - 0.02 95 - 0.05 94.5 - D-alpha-tocopherol acetate 5 - 5 5 5 5 Citrem 0.5 ascorbyl 12 12 12 12 application test 12 Color stabilized until ... weeks

= sh. Table 1 = sh. Table 1

ro oo ω

Table 6

Composition and color stabilization of a stick with D-alpha-tocopherol acetate (with sunscreen)

Composition (parts by weight)

Comparative Example no. 6 7 8

10

11

Fat matrix D-alpha-tocopherol

85

85

84.5

84.5

84

acetate 5 - 7 5 - 0.01 5 - 0.02 5 - 0.05 5 5 5 _., x1 Citrem - 3 7 7 7 0.5 C, 5 0.5 ascorbyl 3 3 3 - 0.05 0.5 Parso! ^R MCX ^x3 , 7 7 7 Parsol ^R 1789 ^x4 3 3 3 3 application test 2 2 12 Color stabilized until ... weeks 2 3 6 ^x1 = sh. Table 1 ^x2 = sh. Table 1 ^x3 = sh. Table 2 = sh. Table 2

IO OO CO

Claims (3)

1. A process for the preparation of topical cosmetic and pharmaceutical preparations containing fats and free tocopherols, characterized in that ascorbic acid esters of fatty acids having 12 to 18 carbon atoms and citric acid esters of partial glycerides of fatty acids having 12 to 20 carbon atoms added to the color stabilization , 2. The method according to claim 1, characterized in that free tocopherols in amounts of 1 to 10 wt .-% of the preparation and the ascorbic acid esters and citric acid esters in amounts of 0.1 to 10Gew .-%, based on the amount of tocopherol added. 3. The method according to claim 1 or 2, characterized in that in addition ultraviolet radiation filter substances are added.