FR2979803A1 - VANILLIN COMPOSITIONS IN LIQUID FORM - Google Patents

Abstract

The present invention relates to a vanillin composition in liquid form comprising vanillin, ethyl vanillin and at least one solvent, wherein the amount of solvent is at least 40% by weight based on the total weight of said composition.

Description

The present invention relates to vanillin compositions in liquid form and to the process for their preparation. The present invention also relates to the uses of said compositions, in particular in the pharmaceutical or food field. Vanillin is a widely used product in many fields of application as aroma and / or fragrance.

Thus, vanillin is widely consumed in the food and feed industry but it also has applications in other areas such as for example, pharmacy or perfumery. It follows that it is a consumer product. Vanillin is currently available on the market in the form of a crystalline powder. The disadvantages that result are the presence of fines that cause problems of dusting and flowability, during storage and handling of said powder. Currently, it is desired to have in many applications, ingredients in a liquid form. Indeed, besides this form solves the problem of dusting and flowability, a liquid presentation has many advantages, particularly ease of dosing and easier handling. Moreover, it is known that it is difficult to develop liquid compositions of sufficiently concentrated vanillin and further having good stability over time, namely stable liquid compositions over time, especially at room temperature, without crystallization. The problem is therefore to find a new formulation of vanillin that satisfies the following requirements: - be in the form of a liquid product that can be poured or pumped at room temperature of the order of 15 ° C at 25 ° C; and / or - to be mechanically stable, that is to say, not to separate in phases during a variation of temperatures in a zone lying between 0 ° C. and 50 ° C., nor to crystallize during prolonged storage ; and / or - be chemically stable; and / or - have an ease of implementation resulting in a simple dilution during use; and / or - be in the form of a transparent solution; and / or - present a color that does not evolve or little; and / or - possess a bacterial stability and not constitute a favorable ground for a development of bacteria under optimal temperature conditions; and / or - meet the organoleptic requirements in the case of a food use; and / or - be in accordance with the legislation of the relevant field of application; and / or - be easy to manufacture so as not to burden the selling price. The present invention aims to provide a new liquid formulation of vanillin meeting the above requirements. The present invention therefore aims to provide a stable liquid vanillin composition over time at room temperature.

The present invention therefore aims to provide a liquid vanillin composition having no crystallization or demixing over time. Thus, the present invention relates to a vanillin composition in liquid form comprising vanillin, ethyl vanillin and at least one solvent, wherein the amount of solvent is at least 40% by weight based on the total weight of said composition. In the context of the present invention, the amount of solvent is calculated by weight relative to the total weight of the composition, namely relative to the total weight of vanillin, ethyl vanillin and solvent. The compositions of the invention have the advantage of being sufficiently concentrated and therefore of presenting an appropriate aroma force, without the appearance of crystallization phenomena generating instability. According to one embodiment, the amount of solvent is at least 50%, preferably at least 60%, by weight relative to the total weight of said composition.

An advantageous composition according to the present invention is characterized in that the amount of solvent represents from 40% to 90% by weight relative to the total weight of said composition. Another advantageous composition according to the present invention is characterized in that the amount of solvent represents from 60% to 80% by weight relative to the total weight of said composition.

According to one embodiment, in the compositions of the invention, the mass ratio vanillin / ethyl vanillin is from 80/20 to 40/60, and preferably from 80/20 to 45/55. Thus, according to one embodiment, in the compositions of the invention, the amount of vanillin is from 40% to 80% by weight relative to the total weight of solids and the amount of ethylvanillin is from 20% to 60% by weight relative to the total weight of dry matter. In the context of the present invention, the term "total weight of solids" means the total weight of ethylvanillin and vanillin. It is therefore the weight of the composition without the solvent. According to an advantageous embodiment, in the compositions according to the invention, the amount of vanillin is from 45% to 80% by weight relative to the total weight of solids and the amount of ethylvanillin is from 20% to 55% by weight. % by weight relative to the total weight of dry matter. According to an advantageous embodiment, in the compositions according to the invention, the amount of vanillin is from 60% to 75% by weight relative to the total weight of solids and the amount of ethylvanillin is from 25% to 40% by weight relative to the total weight of dry matter. In the context of the present invention, the solvent present in the vanillin composition according to the invention is liquid at ambient temperature, that is to say generally in a temperature range of between 10 ° C. and 30 ° C. preferably between 10 ° C and 25 ° C, very preferably between 16 ° C and 22 ° C. It is chosen to be chemically inert to vanillin and ethylvanillin. According to the present invention, the solvent used is an aqueous or organic solvent, or a mixture of solvents. Among the organic solvents, a polar, apolar, protic or aprotic organic solvent is preferably chosen. As solvents which can be used in the compositions of the invention, it is preferable to use a polar, apolar, protic or aprotic organic solvent or a mixture of said solvents. As solvents, there may be mentioned in particular the following solvents: - water or glucose syrup; alcohols or diols, preferably aliphatic or arylaliphatic and more preferably, methanol, ethanol, propanol, isopropanol, butanol, beta-phenylethyl alcohol, ethylene glycol, diethylene glycol, monopropylene glycol, glycerol; preferably aliphatic ether-oxides and, more particularly, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, di-tert-butyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; alkyl or arylalkyl esters of carboxylic, aliphatic, cycloaliphatic or aromatic acids, and more preferably, ethyl acetate, butyl acetate, benzyl salicylate, methyl laurate, benzoate methyl, ethyl citrate and glyceryl triacetate (or triacetin); and - their mixtures. According to an advantageous embodiment, the solvent is selected from the group consisting of water, glyceryl triacetate (or triacetin), ethanol, monopropylene glycol, glycerol and mixtures thereof. According to one embodiment, when the solvent is water, it is preferably used in a mixture with another solvent advantageously chosen from the solvents described above. The water / ethanol and water / monopropylene glycol solvent mixtures are preferred. The amount of water present in a solvent mixture is such that it represents from 2% to 30% by weight based on the total weight of the composition. The choice of the solvent is made according to the intended field of application. Thus, in the case of the use of the compositions of the invention in the food field, it is imperative that the solvent used is not toxic and tolerated by the legislations of this field. The compositions of the invention may also comprise an antioxidant, especially ascorbic acid. According to one embodiment, the present invention relates to a composition as defined above comprising ascorbic acid at, for example, from 0.01% to 1%, preferably from 0.01% to 0.5% by weight. weight relative to the total weight of said composition. The presence of such an antioxidant makes it possible to limit the phenomena of parasitic staining. In fact, solutions of vanillin and ethyl vanillin mixtures in a solvent, as well as solutions of vanillin in a solvent and solutions of ethyl vanillin in a solvent, develop a yellow coloration.

This coloration may be limited by the use of a food antioxidant such as ascorbic acid. The compositions of the invention may also comprise a food coloring, in particular a caramel. The addition of a food coloring such as caramel also allows the color to be stabilized at a higher brown level. The method for obtaining the vanillin-based compositions according to the invention is described below. The present invention also relates to a process for preparing the compositions as defined above, comprising mixing vanillin, ethyl vanillin and the solvent with stirring. According to one embodiment of the invention, vanillin and ethyl vanillin are preferably introduced into the solvent which is kept stirring. Preferably, the process of the invention is carried out at ambient temperature of between 15 ° C. and 30 ° C., but it may also comprise a step of heating the mixture obtained in order to obtain a liquid that is recovered. According to one embodiment, the mixture is brought to a temperature preferably lower than or equal to 50 ° C, preferably between 20 ° C and 50 ° C, and even more preferably between 20 ° C and 30 ° C. The mixture is stirred with stirring until a homogeneous solution is obtained. Generally, the duration varies between 10 minutes and 3 hours. Then, the composition is obtained in liquid form that is conditioned according to the needs of use. The present invention also relates to a food composition comprising a vanillin composition according to the present invention. The present invention also relates to the use of the vanillin composition according to the present invention as a flavor, as a perfume, as an odor-masking agent or as a perfume base. The compositions of the invention can be used in many fields of application, inter alia, in the food and pharmaceutical field, and in the perfume industry. More particularly, the present invention relates to the use of the vanillin composition as defined above as a flavor in the field of food and feed, pharmacy, and as a perfume in the cosmetics industry, perfumery and detergency.

According to another embodiment, the vanillin composition as defined above can be used as odor masking agent, in particular in the pharmaceutical industry. According to another embodiment, the vanillin composition as defined above can be used in the field of cosmetics for the preparation of creams, milks and blushes and other products, as perfume base in perfumery and in the field of cosmetics. detergency, especially in soap. A preferred field of application of compositions of the invention is that of biscuit and pastry, and more particularly: - dry biscuit, including sweet biscuits of conventional type, small butter, cookies, snack or shortbread; - industrial pastry, including champagne boudoirs, cat tongues, sponge biscuits, genoa bread, sponge cake, madeleines, pound cake, cakes, almond pastry, petits fours.

The basic elements present in the mixtures intended for the aforementioned industries are the proteins (gluten) and the starch which are most often brought by the wheat flour. For the preparation of various types of biscuits and cakes, ingredients such as sucrose, salt, eggs, milk, fatty substances, possibly chemical yeasts (sodium bicarbonate or other artificial yeasts) or organic yeasts and flours are added to the flour. various cereals etc ... The incorporation of the vanillin composition according to the invention is carried out during manufacture, depending on the desired product and is conducted according to conventional techniques of the field in question (see in particular JL KIGER and JC KIGER - Modern Techniques of Biscuits, Bakery and Industrial Bakery, DUNOD, Paris, 1968, Volume 2, pp. 231 and following). In a preferential manner, the composition of the invention is introduced into the fatty substances that are involved in the preparation of the dough. As an indication, it will be specified that the composition of the invention is introduced in an amount of 0.05 to 1.5 g per kg of dough.

The vanillin compositions of the invention are quite suitable for use in the field of chocolate and whatever the form of implementation: chocolate plates, couverture chocolates, filling for chocolates. They can be introduced during conching, that is to say the mixing of the cocoa paste with the various ingredients, including flavorings, or after conching, by use in cocoa butter.

In this field of application, the vanillin compositions of the invention are used according to the type of chocolate, at a rate of 0.05 g to 1 g per 1 kg of finished product, the highest contents being found in chocolate. for cover. Another use of the compositions of the invention is the manufacture of sweets of all kinds: sugared almonds, caramels, nougats, boiled sweets, melting sweets and others. They are introduced preferably in the liquid phase. The amount of vanillin introduced depends on the more or less pronounced taste that is sought. Thus, the use doses of the compositions of the invention may vary between 0.001% and 0.2%. The compositions of the invention are well suited for uses in the dairy industry and more particularly in flavored and gelled milks, desserts, yogurts, ice creams and ice creams. The aromatization is by simple addition of the compositions of the invention in one of the mixing stages required during the preparation of the product. The contents of said compositions to be used are generally low, of the order of 0.2 g per 1 kg of finished product. Another application of the compositions of the invention in the food field is the preparation of vanillin sugar, that is to say the impregnation of the sugar with these, in a content of about 7 g expressed by compared to 1 kg of finished product. The compositions of the invention may also be used in various drinks and include, among others, grenadine and chocolate drinks. It is common to use vanillin for the denaturation of butter. For this purpose, the vanillin compositions of the invention can be used at a rate of 6 g per ton of butter. Another field of application of the compositions of the invention is the animal feed, especially for the preparation of feed meal for calves and pigs. The recommended content is about 0.2 g per kg of flour to be aromatized. The compositions of the invention may find other applications as a masking agent, for the pharmaceutical industry (masking the drug odor) or for other industrial products (of the rubber, plastic, rubber, etc. type). . They are quite suitable in completely different fields such as cosmetics, the perfume industry or detergents.

They can be used in cosmetics such as creams, milks, blushes and other products and also, as perfume ingredients, in perfume compositions, substances and scented products. By "perfuming compositions" are meant mixtures of various ingredients such as solvents, solid or liquid carriers, fixatives, various odorous compounds, etc., in which the compositions of the invention are incorporated, which are used to provide various types of finished products, the desired fragrance. Fragrance bases are preferred examples of perfume compositions in which the compositions of the invention may be advantageously used at a level of from 0.1% to 2.5% by weight. The bases for perfume can be used for the preparation of many scented products such as, for example, toilet waters, perfumes, aftershave lotions; toilet and hygiene products such as bath or shower gels, deodorant or antiperspirant products, whether in the form of sticks or lotions, talcs or powders of any kind; hair products such as shampoos and hair products of all types. Another example of implementation of the compositions of the invention is the field of soap. They can be used at a content of 0.3% to 0.75% of the total mass to be perfumed. Generally, vanillin is combined in this application with benzoin resinoid and sodium hyposulphite (2%). The vanillin compositions according to the invention can find many other applications, in particular in air fresheners or any maintenance product.

It will not be departing from the scope of the invention, to add in the compositions of the invention, additives required at the level of the intended application. The following are examples illustrating the present invention, without being limiting in nature. EXAMPLES In the examples, the percentages mentioned are expressed by weight. MPG: monopropylene glycol (or 1,2-propanediol) Example 1 - Preparation of a vanillin composition according to the invention The preparation is carried out at ambient temperature by mixing the various constituents. A vanillin / ethyl vanillin / MPG mixture consisting of 20% by weight of vanillin, 20% by weight of ethyl vanillin and 60% by weight of MPG (mixture according to the 20/20/60 mass ratio) is prepared according to the following procedure: In a 2L calorimeter reactor, 792.45 g of MPG are charged at 22 ° C. Vanillin and ethyl vanillin are poured in 5 minutes with stirring. Stir at 22 ° C for 2h at 300 rpm. A liquid vanillin composition according to the invention is thus obtained. The same protocol is applied for the preparation of liquid vanillin compositions according to the invention (compositions 4 to 8 in Table 1) and for the preparation of vanillin compositions not in accordance with the invention (compositions 1, 2 and 3 in Table 1), adapting only the amounts of solvent, vanillin and ethyl vanillin. The vanillin / ethyl vanillin / solvent mass proportions for each of the compositions 1 to 8 are shown in Table 1. EXAMPLE 2 - Stability of the Vanillin Compositions of the Invention Several liquid vanillin compositions according to the invention were prepared and the stability of these solutions were evaluated, in particular to control the absence of crystallization or demixing over a period of 3 months. These liquid compositions are all prepared by mixing the solvent, ethyl vanillin and vanillin according to the protocol of Example 1. The stability of each of the liquid compositions is evaluated for a period of 3 months under the following conditions: At room temperature (normal conditions of use); and at 4 ° C. (conditions which may be encountered during transport, for example in the hold). The results obtained are given below in Table 1.

Table 1 C Vanillin Ethylvinillin MPG Ethanol Triacetin Behavior at t. ambient Behavior at 4 ° C / 3 months o (% w / w) (% w / w) (% w / w) (% w / w) (% w / w) m P o s ti on 1 53.4 26.6 Insoluble Insoluble 2 40 0 60 Insoluble Insoluble 3 0 40 60 Insoluble Insoluble 4 20 20 60 Liquid Liquid 5 33 17 50 Liquid Liquid 5 10 10 80 Liquid Liquid 7 25 25 50 Liquid Liquid 8 12.5 12.5 75 Liquid Liquid It has therefore been found that the compositions according to the invention (4 to 8) are stable over time, both at room temperature and at 4 ° C.

In contrast, a composition comprising only 20% by weight of solvent is not stable over time and crystallizes at room temperature and at 4 ° C. Similarly, a composition containing a single compound selected from vanillin and ethyl vanillin is also not stable over time and crystallizes at room temperature and at 4 ° C. although said composition contains a quantity of dry matter (vanillin or ethylvanillin) identical to that of the compositions according to the invention (see compositions 2 and 3 against composition 4 which contain 40% by weight of dry material (s)). Example 3 - Staining The color number of the vanillin / ethyl vanillin / MPG composition was measured according to the 20/20/60 mass ratio (prepared in Example 1), stored in a transparent bottle at room temperature, at room temperature. light, over time. Ascorbic acid (antioxidant) was added to the composition. The results are collated in Table 2 below. Table 2: Evolution of the vanillin / ethylvanillin composition color index as a function of time and the presence of antioxidant Duration (days) 30 60 90 Without antioxidant 2.5 13 20 500 ppm of antioxidant 2.5 The color number is determined on a Minolta colorimeter by "yellow index" test according to the standardized method DIN 6167 (measurement of yellow index according to the standardized method). DIN 6167). The color number is lower as the composition is insensitive to light. These results demonstrate the beneficial effect of ascorbic acid addition on staining: the coloring of the liquid vanillin composition varies little over time when it contains an antioxidant. Example 4 - Applications Example 4.1. Preparation of a milk drink To a 5% sweetened semi-skimmed milk by the addition of 50 g of sugar (sucrose) to 950 g of semi-skimmed milk, 0.6 g of the liquid aroma which is the object of the invention are added. invention (composition of Example 1). After homogenization, the preparation is assessed by olfaction by the retro-nasal route by a panel of evaluators.

The 0.06% flavored milk of the composition of the invention has a vanilla flavor similar to vanillin. Example 4.2. Preparation of a cake 250 parts of fat and 0.5 parts of liquid flavor of the invention (composition of Example 1) are mixed with 250 parts of sugar until an ointment is obtained. 250 parts of egg are added to the mixture. The mixture is beaten until a homogeneous mixture. 250 parts of flour and 2 parts of salt are also added. The mixture is beaten until a homogeneous paste. The cake is baked for 30 minutes at 150 ° C. The cake is evaluated after one day at room temperature by olfaction by the retro-nasal route by a panel of evaluators. The cake flavored with 0.05% of the composition of the invention has a vanilla flavor, similar to vanillin.

Claims (14)

REVENDICATIONS1. A vanillin composition in liquid form comprising vanillin, ethyl vanillin and at least one solvent, wherein the amount of solvent is at least 40% by weight based on the total weight of said composition. 2. The composition of claim 1 wherein the amount of solvent is from 40% to 90%, preferably 60% to 80%, by weight based on the total weight of said composition. 3. Composition according to any one of claims 1 or 2, wherein the mass ratio vanillin / ethyl vanillin is between 80/20 to 40/60. 15 4. Composition according to any one of claims 1 to 3, wherein the mass ratio vanillin / ethyl vanillin is 80/20 to 45/55. 5. A composition according to any one of claims 1 to 4, wherein the solvent is an aqueous solvent or a polar, apolar, protic or aprotic organic solvent or a mixture of solvents. 6. Composition according to any one of claims 1 to 5, wherein the solvent is selected from the group consisting of: - water or glucose syrup; Monohydric alcohols or diols, preferably aliphatic or arylaliphatic and more preferably, methanol, ethanol, propanol, isopropanol, butanol, beta-phenylethyl alcohol, ethylene glycol, diethylene glycol, monopropylene glycol, glycerol; preferably aliphatic ether-oxides and, more particularly, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, di-tert-butyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; alkyl or arylalkyl esters of carboxylic, aliphatic, cycloaliphatic or aromatic acids, and more preferably, ethyl acetate, butyl acetate, benzyl salicylate, methyl laurate, methyl benzoate, ethyl citrate and glyceryl triacetate; and their mixtures. The composition according to any one of claims 1 to 6, wherein the solvent is selected from the group consisting of water, glyceryl triacetate, ethanol, monopropylene glycol, glycerol and mixtures thereof. 8. Composition according to any one of claims 1 to 7, further comprising an antioxidant. 9. Composition according to any one of claims 1 to 8, further comprising a food coloring. A process for preparing a vanillin composition according to any one of claims 1 to 9, comprising mixing vanillin, ethyl vanillin and the solvent with stirring. 11. Food composition comprising the vanillin composition according to any one of claims 1 to 9. 12. Use of the vanillin composition according to any one of claims 1 to 9, as aroma in the field of food and feed, pharmacy, and as perfume, in the cosmetics industry, perfumery and detergency. 13. Use of the vanillin composition according to any one of claims 1 to 9, as odor masking agent, especially in the pharmaceutical industry. 14. Use of the vanillin composition according to any one of claims 1 to 9, in the field of cosmetics for the preparation of creams, milks and blushes and other products, as perfume base in perfumery and in the field of cosmetics. detergency, especially in soap.