MXPA97006112A - Use of 4-ter-butil-1-ciclohexanol as an antioxide - Google Patents

Abstract

The present invention relates to the use of 4-tert-butyl-1-cyclohexanol as an antioxidant in soaps, shampoos and other cosmetics, as well as in cleaning products for general use.

Description

USE OF 4-TER-BUTIL-l-CICLOHEXANOL AS AN ANTIOXIDANT TECHNICAL AND TECHNICAL FIELD BACKGROUND The present invention relates to perfumery and cosmetics. It is related, more particularly, to the use of 4-tert-butyl-1-cyclohexanol as an antioxidant. 4-tert-Butyl-l-cyclohexanol is a well-known ingredient in perfumery, but it is not used regularly in perfumery as a result of its not too elegant canthoracic note. In fact, it develops an odor of woody-patchouli, canforaceous type. It is also known that this compound is very stable even in very aggressive media, characteristic of soaps, detergents or bleaching products. However, to our knowledge, it has never been suggested to use this compound as a stabilizing agent against oxidation in cleaning products or cosmetics. DESCRIPTION OF THE INVENTION Now we have discovered that 4-tert-butyl-1-cyclohexanol proves to be very efficient as an antioxidant, especially when used in detergent and cosmetic media containing fatty materials that are easily oxidized with their exposure to air and / or light, and whose oxidation products develop unpleasant odors, particularly of the rancid type.

REF: 25287 It is known, for example, that certain types of soaps develop stale, spicy and fruity scents after only a few weeks of air storage. Now, we have observed that the occurrence of such bad odors could be prevented entirely, or at least prevented by much longer storage periods, if 4-tert-butyl-1-cyclohexanol was added to these soaps. Similar effects were observed in shampoos, or even in bath gels or shower-bath gels. In a general way, this compound is revealed as an efficient stabilizing agent against oxidation in all cosmetic and skin or hair cleaning products comprising materials that are susceptible to being oxidized by exposure to air and / or light and, as a result, of developing unpleasant odors. In this context, one can quote, in addition to the consumer products mentioned above, creams and cosmetic milks. It has also been established that this compound could be useful as an antioxidant in other cleaning products or detergents, particularly general purpose detergents or multipurpose cleaners for hard surfaces, dish washing products and others, when they comprise fatty materials susceptible to be oxidized with exposure to air or light. To achieve the desired effects according to the invention, 4-tert-butyl-1-cyclohexanol can be added to soap, shampoo or other base type, either independently or in admixture with other ingredients commonly used in perfumery, especially co-ingredients , solvents or usual adjuvants of perfumery. A more detailed description of the latter is superfluous in the present. Its nature will depend especially on the perfuming effect that one wishes to achieve, as well as on the type of product that is going to be perfumed, and the expert person is able to select such ingredients based on his general knowledge in the technique, and taking inspiration from reference textbooks such as S. Arctander's book, Perfume and Flavor Chemicals, Montclair, NJ (1969), or more recent versions of it, among 'others. The concentrations in which the aforementioned compound can be added to the various products to impart their anti-oxidation effect vary over a wide range of values. Beneficial effects can already be observed at concentrations of the order of 0.005 or 0.001% by weight, relative to the weight of the finished product, ie soap, shampoo, shower gel or other.

However, it is preferred, according to the invention, to use this compound in concentrations of, or above, 0.005% by weight, relative to the weight of the finished product. More preferably, such products will contain in the order of 0.05 to 0.5% by weight of 4-tert-butyl-1-cyclohexanol. As apparent from the examples presented below, 4-tert-butyl-1-cyclohexanol is found to be a more efficient antioxidant than other agents commonly used for this purpose, such as BHT (2,6-di-tert-butyl). -p-cresol; Bayer origin), a- or? -tocopherol, ascorbic, citric or tartaric acids, and their salts and esters, or even any mixture of two or more of these products. It is obvious that 4-tert-butyl-1-cyclohexanol can also be used in admixture with these antioxidants. We observed in particular that excellent results could be obtained when 4-tert-butyl-1-cyclohexanol was used in combination with tocopherols (a or o), citric acid, ascorbic acid, or tartaric acid, or even their esters. As mentioned above, 4-tert-butyl-1-cyclohexanol can be used as an antioxidant in perfumery or cosmetic compositions, in compositions for cleansing the skin or hair, or even in multi-purpose cleaning compositions, and The invention also relates to such compositions. The nature of the base compositions to which this product is added is very insubstantial here, all the soap, cosmetic or detergent bases currently used in the corresponding industries or known in the art are suitable for preparing compositions according to the invention, in where 4-tert-butyl-l-cyclohexanol is incorporated as an antioxidant. Examples of such base compositions presented below are cited for illustrative purposes only, and it is clear that other current bases of similar type, containing materials susceptible to being oxidized, can be used instead of those given herein as examples. In particular, cosmetic compositions and for cleaning the skin or hair containing 0.05 to 0.5% by weight of this compound, relative to the weight of the composition, are preferred according to the invention. Soaps, shampoos or even gels for bath or shower bath are embodiments of such compositions according to the invention, and the same applies to creams or nutritional or beauty milks, or others. On the other hand, it is to be noted that it is a known fact that, in certain media where hyysis readily occurs, the addition thereto of 4-tert-butyl-1-cyclohexanol acetate may be equivalent to adding 4-tert-butyl -1-cyclohexanol, the acetate is capable of being partially or fully hyyzed to form this corresponding alcohol. It is therefore obvious that the invention also relates to any composition or product of the type mentioned above that contains, or to which is added, 4-tert-butyl-1-cyclohexanol acetate, and the pH of which is susceptible to causing the formation therefrom of the corresponding 4-tert-butyl-1-cyclohexanol, in an amount sufficient for the latter to impart its antioxidant effect to the composition or product. When used in perfumery compositions, which can themselves be added to the products mentioned above to impart to them certain fragrances, 4-tert-butyl-1-cyclohexanol can integrate from 5 to 50% by weight of the composition of perfumery The invention will now be described in more detail by way of the following examples, wherein the temperatures are indicated in degrees Celsius.

MODES OF THE INVENTION EXAMPLE 1 Stabilization of a semi-synthetic type soap A basic soap was prepared by mixing the following ingredients according to current methods. Ingredients% by weight Sodium cocoyl methionate11 51. 0 Sodium dodecylbenzenesulfonate2 '2. . 0 Sodium Isethionate3 '5. 0 Stearic acid 25. 0 Sodium salt of fatty acids of 12 to 18 carbon atoms 17.0 Total 100.0 1) origin: PPG Industries, USA 2) origin: Chem. Werke Hüls, Germany 3) origin: Witco Chem. Comp., USA To this composition of The ingredients listed in the following table, in the amounts indicated, were added to prepare samples of stabilized soap bases.

TABLE 1 Sample Ingredients% by weight, relative to the base A B C D E TenoxMR l) GT II 0.07 - 0. 05 IrganoxMR 2) PS-800 0.05 0. 05 0. 05 Citric acid * 0.2 0.2 0. twenty . 2 BHT 0.07 0. 07 - TurpinalMR 3) SL 0. 1 __ 4-tert-butyl-l-cyclohexanol 0.1 0.2 * 50% in water 1) a-tocopherol; origin: Eastman Chemicals 2) dilaurylthiopropionate; origin: Ciba-Geigy AG 3) etidronic acid; origin: Henkel Soaps with these stabilized bases were molded in the conventional manner. The soaps A to E thus obtained were stored in glass containers at 40 ° C, and then subjected to an evaluation by a panel of expert perfumers, on a blind examination. The panel judged that soaps A to C developed a fatty, buttery and rancid odor, which could not be found in soap D, nor in soap E, which, additionally, presented a slightly floral fragrance. EXAMPLE 2 Stabilization of solid soaps A stabilizing mixture was prepared by means of 1 g of 4-tert-butyl-1-cyclohexanol, 0.5 g of Tenox® 1) GT II and 0.5 g of Irganox® 2) PS-800. By means of the base composition described in Example 1, perfumed soap bases were then prepared, adding the ingredients indicated below, in the quoted amounts: TABLE II Sample Ingredients% by weight, based on the weight of the base composition A B C D E Hediona ™ 1.). 0.05 0.05 0.05 0.05 0.05 Rosewood essential oil 0.1 - - - Bergamot essential oil - 0.1 Benzoin essential oil * - - 0.1 Cedar essential oil. - - 0.1 Geranium essential oil - - - - 0.1 * to 20% in dipropylene glycol 1) methyl dihydrojasmonate; origin: Firmenich S.A., Geneva, Switzerland Soaps A to E were molded with these soap bases.

At the same time, the soaps A 'to E' were obtained from these bases A to E, but to which 0.3% of the stabilizing mixture mentioned above had been added. These ten soaps were then stored at 40 ° C for one month, and then evaluated in a blind trial and two times two, ie, A and A ', B and B', etc ..., by a panel of experts The result of these evaluations showed that the soaps A 'to E' had a good smell, without any fat, rancid notes, while soaps A to E developed fragrances in which unpleasant rancid notes were clearly detected. EXAMPLE 3 Stabilization of solid soaps A standard soap base was prepared in a conventional manner, by mixing the following ingredients: Ingredients% by weight Sodium salts of beef tallow fatty acids 60.0 Sodium salts of coconut oil fatty acids 26.0 Water 14.0 Total 100.0 To this soap base was added after 1.5 to 2% by weight of one of the perfuming compositions A or B, which contained the following ingredients, to prepare scented soap bases: Ingredients Composition A Composition B (Parts by weight) Fenetilol 3500 3500 Citronelol 2000 2000 Iralia ™ 1 '300 300 Geraniol 600 600 Diphenil ether 200 200 Benzyl Acetate 800 800 Phenylethyl acetate 400 400 3-Methyl-5-phenyl-l-pentanol2) 400 400 Dorinia SA3) 100 100 Vert of lilas4 '200 200 50% * of 15-Pentadec- (11, 12) -olid 5) 50 50 4-tert-butyl-l-cyclohexanol 1000 Total 9000 10000 * in dipropylene glycol 1) methylionone; Origin: Firmenich SA; Geneva, Switzerland 2) origin: Firmenich SA; Geneva, Switzerland 3) origin: Firmenich SA; Geneva, Switzerland 4) (2, 2-dimethoxyethyl) benzene; origin: Givaudan-Roure Vernier, Switzerland 5) origin: Firmenich SA; Geneva, Switzerland The soaps A and B were conveniently molded with the perfumed soap bases by means of compositions A, B respectively. After storage for one month at 40 ° C, the two soaps were evaluated by a panel of expert perfumers, on a blind examination. In the opinion of the latter, soap B developed a floral, rose, herbal, musky smell, while soap A had fat, rancid, clearly detectable notes, which made its smell clearly less pleasant than that of soap B EXAMPLE 4 Preparation of a liquid shampoo A liquid shampoo, proposed for cleaning the body and hair, was prepared by mixing the following ingredients, according to the usual techniques: 1 Ingredients% by weight TexaponMR 1! N28 25.0 MedialanMR 2) LD 7.0 Demineralised water 64.4 NaCl 1.5 Citric acid 0.5 KathonMR 3) CG 0.1 ComperlandMR 4) KD 1.5 Total 100.0 1) Sodium ether sulphate; origin: Henkel 2) lauryl sarcosinate; origin: Hoechst 3) conservative; Origin: Rohm & Haas 4) cocoic acid diethanolamide; origin: Henkel To this fragrance-free shampoo base, 0.1% by weight of 4-tert-butyl-1-cyclohexanol, 0.05% by weight of Tenox ™ Gil, 0.05% by weight of Irganox ** PS-800 and 0.1% by weight were added. weight of citric acid, to obtain a stabilized shampoo. Separate plastic containers were filled with this stabilized shampoo, and with the base shampoo. After storing them for one month at 40 ° C, the two shampoos were evaluated by a panel of experts, on a blind examination. The latter indicated a marked preference for stabilized shampoo, which did not present traces of oily notes, while the shampoo base had a well-marked fatty and pungent odor. EXAMPLE 5 Stability test To test the antioxidant effect of 4-tert-butyl-1-cyclohexanol in perfuming compositions susceptible to oxidation by air, it was added to a mixture of orange terpenes (containing 95% by weight of limonene), 0.1% by weight of the cyclohexanol mentioned above, 0.05% by weight of Irganox® PS-800 and 0.05% by weight of Tenox® GT II. The mixture of terpenes independently, and the mixture of terpenes with the stabilizing compounds mentioned above, were subjected to a Rancimat type test (see for example, M. W. Láubli, Lebensmttelchemie 4J3, page 134). To do this, the two mixtures were heated to 110 ° C, under air, while the conductivity was mediated. It was thus observed that the conductivity of the unstabilized terpene mixture indicated its oxidation after 2 hours of heating, while the mixture of terpenes containing the stabilizing agents only began to show oxidation after 5.5 hours of heating in air.

EXAMPLE 6 Stabilization of a multipurpose cleaner A multipurpose cleaner was prepared by mixing the following ingredients, according to the usual methods of the art. Ingredients% by weight Water 74.7 Sodium carbonate 3.0 Sodium citrate 2.0 Sodium cumolsulfonate 1 '1.0 Marlon ™ 2) A375 10.0 Tergitol ™ 3) 15-S-9 3.0 Perfume41 0.3 Total 100.0 1) origin: Hüls AG, Germany 2) dodecylbenzene sulfonate sodium; origin: Hüls AG, Germany 3) ethoxylated secondary alcohol of 11 to 15 carbon atoms; origin: Union Carbide, USA 4) Blue Water, No. 114338; origin: Firmenich SA, Geneva, Switzerland To this perfumed base composition, then 0.1% by weight of sweet almond oil was added, to obtain a general purpose cleanser base. A novel cleaning composition according to the invention was then prepared with the latter, via the addition of 0.2% by weight of 4-tert-butyl-1-cyclohexanol. The general purpose cleaner base and the novel general purpose cleaner were then stored in plastic bottles under ultraviolet light for 8 hours. At the end of this storage period, both bottles were evaluated, in a blind examination, by a panel of experts, who indicated that the product containing 4-tert-butyl-l-cyclohexanol did not present traces of any fat note, while that the detergent base had a rancid odor of almond oil.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following:

Claims (10)

1. RE-VINDICATIONS 1. Use of 4-tert-butyl-l-cyclohexanol, characterized because it is like an antioxidant.
2. 2. Use according to claim 1, characterized in that it is for the preparation of a perfumery or cosmetic composition, a skin or hair cleaning composition, or a multipurpose cleaning composition.
3. 3. Use according to claim 1 or 2, characterized in that the 4-tert-butyl-1-cyclohexanol is in combination with a- or β-tocopherol, ascorbic acid, citric acid, tartaric acid, or an unsupported ester. of these acids.
4. 4. Perfumery composition, characterized in that it comprises, as an antioxidant, 4-tert-butyl-1-cyclohexanol, in a concentration of between 5 and 50% by weight, based on the weight of the composition.
5. 5. Cosmetic composition or cleaning composition for skin or hair, or for cleaning surfaces, characterized in that it comprises as an antioxidant 4-tert-butyl-1-cyclohexanol, in a concentration of at least 0.05% by weight, relative to the weight of the composition.
6. Composition according to claim 5, characterized in that the concentration of 4-tert-butyl-1-cyclohexanol is between 0.05% and 0.5% by weight, relative to the weight of the composition.
7. 7. Composition according to any of claims 4 to 6, characterized in that the 4-tert-butyl-1-cyclohexanol is in combination with a- or β-tocopherol, ascorbic acid, citric acid, tartaric acid, or an ester of one of these acids.
8. 8. Soap, bath gel or shower gel, or shampoo, characterized in that it comprises about 0.05 to 0.5% by weight of 4-tert-butyl-1-cyclohexanol.
9. 9. Soap, bath gel or shower gel, or shampoo, according to claim 8, characterized in that 4-tert-butyl-1-cyclohexanol is in combination with a- or β-tocopherol, ascorbic acid, citric acid, tartaric acid, or an ester of one of these acids.
10. 10. Multi-purpose cleaner, characterized in that it comprises about 0.05 to 0.5% by weight of 4-tert-butyl-1-cyclohexanol. USE OF 4-TER-BUTIL-1-CYCLOHEXANOL AS AN ANTIOXIDANT SUMMARY OF THE INVENTION The present invention describes the use of 4-tert-butyl-1-cyclohexanol as an antioxidant in soaps, shampoos and other cosmetics, as well as in products of general purpose cleaning.