EP2538802A1

EP2538802A1 - Method for preparing a composition including a compound containing vanillin and ethylvanillin, composition thus obtained and use thereof

Info

Publication number: EP2538802A1
Application number: EP11705518A
Authority: EP
Inventors: Jean-Claude Le-Thiesse; Kilani Lamiri
Original assignee: Rhodia Operations SAS
Current assignee: Rhodia Operations SAS
Priority date: 2010-02-24
Filing date: 2011-02-21
Publication date: 2013-01-02
Also published as: WO2011104208A1; JP2013520541A; SG183811A1; FR2956661A1; FR2956661B1; BR112012021066A2; US20130203863A1; CN102892306A

Abstract

The invention relates to a method for preparing a composition essentially including a compound containing vanillin and ethylvanillin. The method for preparing a composition essentially including a compound containing vanillin and ethylvanillin according to a vanillin/ethylvanillin molar ratio of 2 is characterized in that it includes an operation of co-granulating vanillin and ethylvanillin at a temperature of between 50°C and 57°C in the form of a powder and in amounts such that the vanillin/ethylvanillin molar ratio is at least equal to 2, and an operation of lowering the temperature of the composition thus obtained to room temperature.

Description

PROCESS FOR PREPARING A COMPOSITION COMPRISING

A COMPOUND BASED ON VANILLINE AND ETHYLVANILLINE,

COMPOSITION OBTAINED AND ITS APPLICATIONS

The present invention relates to a process for preparing a composition comprising essentially a vanillin and ethyl vanillin compound. Vanillin or 4-hydroxy-3-methoxybenzaldehyde is a widely used product in many fields of application as a flavor 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 very often associated with ethylvanillin or 3-ethoxy-4-hydroxybenzaldehyde because it is known that the presence of a small amount of ethyl vanillin makes it possible to exalt the vanishing properties and / or organoleptic properties of vanillin.

Thus, a potential user would like to have available a mixture of vanillin and ethylvanillin already made.

The problem that arises is that the preparation of said mixture carried out according to a conventional dry-blending technique of vanillin and ethyl vanillin powders leads to the production of a mixture which has the property of motter in a very important manner. This results in the impossibility of using such a mixture because of its presentation which is not in pulverulent form and very great difficulty in solubilizing the mass obtained.

In addition, prolonged storage leads to an aggravation of the caking phenomenon, resulting in a setting of the powder mass.

Thus, it is desirable to have a new presentation in solid form, based on vanillin and ethylvanillin having improved flowability properties and the absence of storage caking.

The Applicant has found according to the French patent application No. 08 05913 that a new compound obtained by co-crystallization of vanillin and ethylvanillin used in a molar ratio vanillin / ethyl vanillin of 2, had characteristics of its own, in particular as regards its flowability properties and its lack of caking.

Said compound is in the form of a white powder which has a melting point measured by differential scanning calorimetry of 60 ° C. ± 2 ° C. different from that of vanillin and ethylvanillin respectively of 81 ° C. ± 1 ° C. and 76 ° C ± 1 ° C.

It has an X-ray diffraction spectrum that is specific to it and that is different from that of vanillin and ethyl vanillin.

FIG. 1 represents three curves corresponding to the different X-ray diffraction spectra of the new vanillin and ethyl vanillin compound, vanillin and ethyl vanillin.

On the spectrum of the new compound vanillin and ethylvanillin, we note in particular the presence of lines at angles 2Θ (°) = 20.7 - 25.6 - 27.5 - 28.0; said lines being absent on the X-ray diffraction spectra of vanillin and ethyl vanillin.

Another feature of said compound is that its X-ray diffraction pattern does not undergo significant change during prolonged storage.

The evolution of its spectrum was followed as a function of the storage time at room temperature. Over a prolonged storage period (5 months), no change in the spectrum of the new compound is observed rigorously as shown in FIG. 2.

FIG. 2 shows the evolution of the X-ray diffraction spectrum of the new compound, as a function of the storage duration. It represents three curves corresponding to the different X-ray diffraction spectra of the compound of the invention obtained at time t = 0, then after storage for 2 months and 5 months.

The 3 curves obtained are normally superimposed. In order to better differentiate them, two of the 3 curves of FIG. 2 have a baseline voluntarily shifted with respect to the reference baseline, which is the X-ray diffraction spectrum at time t = 0. curve corresponding to the X-ray diffraction spectrum obtained after a storage of 2 months is shifted by 5,000 shots / sec and that obtained after a storage of 5 months is shifted by 10,000 shots / sec.

Figure 2 shows that there is no evolution of the compound of the invention after prolonged storage. There is no modification of the specific lines of the new vanillin / ethyl vanillin / ethylvanillin compound of vanillin / ethylvanillin molar ratio of 2

Another characteristic of said compound is that it is a not or very little hygroscopic compound such as vanillin and ethyl vanillin.

The hygroscopicity of said compound is determined by measuring its mass change after being held for 1 hour, at 40 ° C under air at 80% relative humidity.

Said compound adsorbs less than 0.5% by weight of water, its content is preferably between 0.1 and 0.3% by weight of water. Said compound remains perfectly solid.

Furthermore, this compound has good organoleptic properties and has a high aromatic power significantly higher than that of vanillin.

Thus, the compound as defined and which is hereinafter referred to as "new compound", has specific properties which result in a lower caking ability compared to a vanillin and ethyl vanillin composition obtained by simple dry mix.

The particular properties of the compound based on vanillin and ethyl vanillin as previously described are related to two parameters namely the molar ratio between vanillin and ethyl vanillin and the fact that there is a co-crystallization between vanillin and ethylvanillin in a specific crystalline form characterized by its melting point and its X-ray diffraction pattern.

One of the routes of access to said compound resides in a process which consists in effecting the melting of the mixture of vanillin and ethylvanillin implemented in a molar ratio of 2 and then cooling the molten mixture by lowering the temperature to 50 °. C ± 1 ° C, then the temperature is maintained until solidification of the mixture.

Cooling is advantageously carried out in the absence of any agitation.

For this purpose, the vanillin and ethylvanillin employed are charged in a molar ratio of 2, separately or in mixture, and the mixture is heated to a temperature which is chosen between 60 ° C. and 90 ° C. and which preferably between 70 ° C and 80 ° C.

It is desirable to carry out the preparation of this mixture under an inert gas atmosphere which is preferably nitrogen. The mixture is maintained at the chosen temperature until the melt is obtained.

The molten product is transferred into any container, for example a stainless steel tray, which will easily recover the product after solidification. This container is preheated between 70 and 80 ° C before receiving the molten mixture.

In a next step, the molten mixture is cooled to a temperature of 50 ° C. ± 1, by regulating the cooling temperature by any known means.

As mentioned above, the cooling is preferably carried out in the absence of any agitation.

The solidified mixture obtained can then be shaped according to various techniques, including grinding.

This process therefore makes it possible to obtain the new vanillin and ethyl vanillin compound, but it has the disadvantage of not being easily transferable on an industrial scale because the crystallization of the compound is rather slow. Indeed, said compound has a supercooling phenomenon, that is to say that when the product is melted and is cooled below its melting point, it crystallizes with difficulty and remains a long time in the liquid state . The time required for crystallization is more or less random and it is important to master the crystallization.

Thus, cooling to a temperature below 50 ° C. ± 1, for example 20 ° C., makes it possible to accelerate the solidification process of the molten mixture, but the crystallization is heterogeneous with the coexistence of different crystalline phases, some of which are unstable at ambient temperature or very hygroscopic. This results in an important caking storage of vanillin - ethylvanillin mixture crystallized under such conditions.

By way of comparative example, to illustrate the importance of the vanillin-ethyl vanillin molar ratio and the crystallization conditions of the melt, FIG. 3 represents the X-ray diffraction spectrum of an equimolar vanillin-ethyl vanillin mixture, melted at 70.degree. ° C, then crystallized by rapid cooling to 20 ° C.

This spectrum is different from that of vanillin, that of ethylvanillin and that of the new vanillin and ethyl vanillin / vanillin / ethylvanillin compound of 2, with specific lines especially at angles θ (°) = 7, 9 - 13.4 - 15.8 - 19.9 - 22.2 - 30.7. FIG. 4 shows the evolution of this spectrum over a storage period of 3 weeks at 22 ° C., proving that the phases thus crystallized are unstable and evolve rapidly, causing the caking of the product.

This product has a melting point of 48 ° C ± 1 and is very hygroscopic: in 1 hour at 40 ° C and under air at 80% relative humidity, it adsorbs more than 4% water by weight and becomes deliquescent.

Its properties are therefore very different from those of the new compound as described above and do not solve the clumping problems posed by vanillin-ethyl vanillin mixtures.

The objective of the present invention is to provide a method that is transposable on an industrial scale, making it possible to obtain essentially the new vanillin and ethyl vanillin compound of vanillin / ethyl vanillin molar ratio of 2.

Another object of the invention is that it leads to a composition comprising it which has the improved properties as mentioned above.

It has now been found and this is the object of the present invention, a process for the preparation of a composition essentially comprising a compound based on vanillin and ethyl vanillin in a vanillin / ethyl vanillin molar ratio of 2, characterized in that it comprises a co-granulation operation of vanillin and ethylvanillin implemented in powder form and in such quantities that the vanillin / ethyl vanillin molar ratio is at least equal to 2, conducted at a temperature between 50 ° C and 57 ° C, followed by an operation to bring the temperature of the resulting composition to room temperature.

In the present text, the expression "by composition essentially comprising a compound based on vanillin and ethyl vanillin" means a composition comprising at least 80% by weight of a mixture of the new vanillin / ethyl vanillin compound of the vanillin / ethyl vanillin molar ratio. 2 and vanillin: vanillin represents less than 20% by weight of said mixture.

By "new vanillin / ethyl vanillin compound" is meant the compound in anhydrous form and its hydrates.

"Co-granulation" is understood to mean an operation which consists, from vanillin and ethyl vanillin powders, of obtaining the novel compound of the invention in the form of granules.

By the term "granulation" is meant the shaping of a powder in the form of granules. According to the invention, it has been found that the new vanillin and ethyl vanillin compound is easily obtained by this co-granulation method.

The Applicant has found that the presence of an excess of vanillin can act as crystallization seeds and thus facilitate the crystallization of the new compound.

To ensure an excess of vanillin with respect to the molar ratio of 2, vanillin and ethyl vanillin are used in the following proportions:

from 65 to 72%, by weight of vanillin,

from 35 to 28% by weight of ethyl vanillin.

According to a preferred embodiment of the invention where a small excess of vanillin is preferred, the proportions are advantageously as follows:

from 67 to 70% by weight of vanillin,

30 to 33% by weight of ethyl vanillin.

According to the first step of the process of the invention, a homogeneous mixture of vanillin and ethyl vanillin powders is firstly made.

For this purpose, said powders are charged separately or in mixture in a mixer-granulator and subjected to stirring.

In a preferred manner, the stirring conditions are chosen so that there are no significant shears.

Thus, a slow stirring speed is preferred.

By way of indication, it may be specified that in the case of a mixer of plow plow type, the stirring conditions advantageously vary between 0.2 and 1 m / s at the end of the blades.

The mixture of powders is then heated to a temperature called in the rest of the text "co-granulation temperature".

This temperature is defined as being lower than the melting temperature of the new vanillin and ethyl vanillin compound which, measured by differential scanning calorimetry, is 60 ° C ± 2 ° C.

Thus, the co-granulation temperature is advantageously chosen between 50 and 57 ° C, preferably between 50 and 55 ° C.

According to the process of the invention, the mixture of vanillin and ethyl vanillin powders is brought from room temperature to the co-granulation temperature which is chosen as previously described.

By "ambient temperature" is generally meant a temperature of between 15 and 25 ° C. The temperature rise is preferably carried out progressively, for example 1 ° C. every 3 minutes.

Once the co-granulation temperature has been reached, the mixture is stirred at this temperature for a sufficient time in order to obtain the transformation of the reagents into the expected new compound.

The duration of this isothermal stage is determined as a function of the co-granulation temperature chosen.

The higher the co-granulation temperature is chosen, the shorter the duration of the plateau.

For example, for a co-granulation temperature advantageously chosen at 51 ° C., the duration of the plateau advantageously varies between 5 minutes and 1 hour and, preferably, between 20 minutes and 40 minutes. It should be noted that the upper limit is not critical but for reasons of productivity, a duration of at most 1 hour is preferably chosen.

For a temperature greater than or equal to 54 ° C, it turns out that it is no longer necessary to maintain an isothermal bearing. In other words, it is no longer necessary to keep the mixture stirring once the temperature reached.

It should be noted that the previously described operations are preferably conducted under an inert gas atmosphere, most often nitrogen.

In a next step, the composition obtained is cooled to a temperature below 40 ° C.

According to a preferred embodiment, the composition is allowed to cool with stirring and under an inert atmosphere to a temperature below 40 ° C, preferably to a temperature below 35 ° C. The lower limit of the cooling temperature is advantageously ambient temperature.

A composition comprising the new vanillin / ethyl vanillin compound is recovered.

The various operations of the process of the invention can be carried out in a mixer which is advantageously a mixer with plowshares or a ribbon mixer (s).

This mixer is advantageously provided with a double envelope in order to ensure the various heat transfers by circulating a coolant in the double jacket. The heat transfer fluid may be water maintained at a higher temperature, for example from 2 to 5 ° C., at the chosen co-granulation temperature or any other coolant, for example a silicone oil. In the case of cooling, the temperature of the coolant in this case the water is generally chosen at a lower temperature, for example 2 to 5 ° C at the chosen cooling temperature.

The composition obtained according to the process of the invention comprises at least 80% by weight, preferably at least 90% by weight of a mixture of the new vanillin / ethyl vanillin compound and vanillin.

The composition obtained comprises less than 20% by weight, preferably less than 10% by weight of other crystalline phases of the vanillin / ethyl vanillin phase diagram and possibly vanillin: this mixture is hereinafter referred to as "other crystalline phases". .

More specifically, the compositions obtained can comprise:

from 80 to 99% by weight of a mixture of the new vanillin / ethyl vanillin and vanillin compound,

from 1 to 20% by weight of other crystalline phases.

Preferred compositions of the invention include:

from 90 to 99% by weight of a mixture of the new vanillin / ethyl vanillin and vanillin compound,

from 1 to 10% by weight of other crystalline phases.

In the resulting mixture which comprises the new vanillin / ethyl vanillin compound and vanillin, the vanillin is less than 20% by weight, preferably less than 14% by weight of said mixture.

More specifically, the mixtures obtained can comprise:

from 80 to 94% by weight of the new vanillin / ethyl vanillin compound,

from 6 to 20% by weight of vanillin.

The preferred mixtures have the following composition:

from 86 to 94% by weight of the new vanillin / ethyl vanillin compound,

from 6 to 14% by weight of vanillin.

The composition obtained is in the form of granules whose size varies, for example, between 200 and 10,000 μιτι and preferably between 500 μιτι and 1 ΟΟΟμηη.

In order that the size of the particles is compatible with the intended application, a grinding operation can be envisaged.

It is conducted in such a way that the particle size expressed by the median diameter (dso) varies from 200 μιτι to 1,000 μιτι and is preferably between 500 μιτι and 800 μιτι. The median diameter is defined as being such that 50% by weight of the particles have a diameter greater than or less than the median diameter. The grinding operation can be carried out in conventional equipment such as a vane mill, a pin mill, a granulator.

The X-ray diffraction spectrum of the composition obtained has the lines at angles 2Θ (°) = 20.7 - 25.6 - 27.5 - 28.0 characteristics of the new compound of the invention.

With regard to its flowability properties, the composition of the invention has a flowability index after 24 hours of storage at 40 ° C. under air at 80% relative humidity under a normal stress of 2400 Pa varying between 0.degree. , 05 and 0.6.

According to a preferred variant of the process of the invention, it has been found that it is particularly advantageous to carry out the first step of mixing the powders under a moist nitrogen atmosphere, thus leading to a whiter product.

Thus, a small amount of water may be present in the nitrogen. It may represent from 1 to 5% by weight of nitrogen, preferably from 2 to 3% by weight of nitrogen.

The humidification of the nitrogen flow can be ensured by bubbling in the water.

According to a preferred embodiment of the process of the invention, the mixing of the powders is started under wet nitrogen, then the temperature is gradually increased and when the latter is greater than or equal to 44 ° C. and less than 49 ° C. dry nitrogen is introduced.

By "dry nitrogen" is meant a stream of nitrogen comprising less than 0.5 g, preferably less than 0.3 g of water per kg of nitrogen.

In a next step, the temperature of the composition obtained is brought to room temperature as previously described.

The composition obtained has an X-ray diffraction spectrum which comprises the characteristic lines as illustrated in FIG.

According to this embodiment under wet nitrogen, a whiter color composition is obtained and more quickly because the isothermal stage can be shortened. For example, following a rise in temperature under dry nitrogen, an isothermal plateau at 52 ° C for a duration of 2 hours is desirable. If the rise in temperature is carried out under wet nitrogen, an isothermal plateau at 52 ° C for a period of 30 minutes is sufficient.

The process of the invention is applicable to vanillin and ethyl vanillin produced by any chemical synthesis, regardless of the starting substrate. It is also suitable for the vanillin obtained according to the biochemical processes, in particular microbiological fermentation processes, in particular ferulic acid.

The invention does not exclude the use of one or more excipients with the composition of the invention

It should be noted that the choice of the excipient (s) must take into account the destination of the final product and thus have the property of edibility when it is used in the food industry.

The amount of excipient (s) can be very variable and it can represent from 0.1 to 90% of the weight of the final mixture.

It is advantageously chosen between 20 and 70% by weight.

Depending on the type of excipient retained, the quantity used and the destination of the final product, the excipient may be introduced, in whole or in part, at the end of the preparation of the composition of the invention or during the preparation of the composition of the the invention. In other words, the total amount of excipient (s) may be introduced during the preparation of the composition of the invention or added at the end of the preparation of the composition of the invention. It is also possible to split the quantities used during preparation or after preparation,

By way of example, it may be specified that from 5 to 50% by weight of an excipient can be added during the preparation of the composition of the invention and then again from 5 to 50% by weight of said excipient when the preparation of the composition of the invention is finished.

It is also possible to modulate the types of introduction according to the excipients, that is to say to introduce the total amount of an excipient for example during the preparation of the composition of the invention and to fractionate the quantity added from another excipient or vice versa.

According to a first variant, the excipient is added by dry mixing with the composition of the invention obtained.

According to another variant, the excipient may be incorporated in the process for obtaining the composition of the invention, for example during the step of co-granulation of the vanillin and ethyl vanillin mixture.

It goes without saying that the same excipient can be added, fractionated at these two stages of manufacture or that excipients of different types can also be introduced during or at the end of the preparation of the composition of the invention.

Examples of excipients which can be used which are given without limitation are given below. A first type of excipients are fatty substances.

As examples, there may be mentioned fatty acids optionally in the form of salts or esters.

The fatty acids used are generally long-chain saturated fatty acids, that is to say having a chain length of between about 9 and 21 carbon atoms such as, for example, capric acid, lauric acid , tridecyl acid, myristic acid, palmitic acid, stearic acid, behenic acid.

It is possible that said acids are in salified form and mention may in particular be made of calcium or magnesium stearate.

As fatty acid esters, mention may in particular be made of glyceryl stearate, isopropyl palmitate, cetyl palmitate and isopropyl myristate.

More specifically, esters of glycerol and of long-chain fatty acids such as glycerol monostearate, glycerol monopalmitostearate, glycerol palmitostearate, ethylene glycol palmitostearate, polyglycerol palmitostearate, palmitostearate of glycerol can be mentioned more specifically. polyglycol 1500 and 6000, glycerol monolinoleate; optionally mono- or diacetylated glycerol esters of long-chain fatty acids such as monoacetylated or diacetylated monoglycerides and mixtures thereof; the semisynthetic glycerides.

It is also possible to add a fatty alcohol whose carbon atom chain is between about 16 and 22 carbon atoms, such as, for example, myristyl alcohol, palmityl alcohol, stearyl alcohol.

It is also possible to use polyoxyethylenated fatty alcohols resulting from the condensation with ethylene oxide in a proportion of from 6 to 20 moles of ethylene oxide per mole, of linear or branched fatty alcohols having from 10 to 20 carbon atoms such as, for example, coconut alcohol, tridecanol or myristyl alcohol.

There may also be mentioned waxes such as microcrystalline waxes, white wax, carnauba wax, paraffin wax.

There may be mentioned sugars such as, for example, glucose, sucrose, fructose, galactose, ribose, maltose, sorbitol, mannitol, xylitol, lactitol, maltitol; inverted sugars: glucose syrups and sucroglycerides derived from fatty oils such as coconut oil palm oil, hydrogenated palm oil and hydrogenated soybean oil; sucroesters of fatty acids such as sucrose monopalmitate, sucrose monodistearate and sucrose distearate. As examples of other excipients, mention may be made of polysaccharides, and mention may be made, inter alia, of the following products and their mixtures:

starches derived in particular from wheat, maize, barley, rice, cassava or potato, native, pregelatinized or modified, and more particularly native corn starches rich in amylose, pregelatinized maize starches, modified corn starches, modified waxy maize starches, pregelatinized waxy maize starches, modified waxy maize starches, in particular OSSA / octenylsuccinate sodium starch,

starch hydrolysates,

- dextrins and maltodextrins resulting from the hydrolysis of a starch (wheat, maize) or starch (potato) as well as β-cyclodextrins,

cellulose, its ethers, especially methylcellulose, ethylcellulose, methylethylcellulose, hydroxypropylcellulose; or its esters, in particular carboxymethylcellulose or carboxyethylcellulose optionally in soded form,

gums such as carrageenan gum, Kappa or Iota carrageenan, pectin, guar gum, locust bean gum, and xanthan gum, alginates, gum arabic, acacia gum, agar -agar,

Preferably, a maltodextrin having a degree of hydrolysis measured by "equivalent dextrose" or D.E less than 20 and preferably between 5 and 19 and more preferably between 6 and 15 is chosen.

As other excipients, mention may be made of flour, especially wheat flour (native or pregel); starches, especially potato starch, Toloman starch, cornstarch, cornflour, sago or tapioca.

As excipients, it is also possible to use gelatin (preferably having a jelly strength measured with a 100, 175 and 250 Bloom gelometer). It can come either from the acid treatment of pork and ossein skins, or the alkaline treatment of cattle and bone skins.

It is also possible to add other excipients such as silica or for example an antioxidant such as vitamin E or an emulsifying agent including lecithin. In order to adjust the aromatic power of the mixture or to enhance its taste, the use of ethylmaltol and / or propenylguetol may be envisaged.

The invention does not exclude the addition of an additional amount of vanillin or ethyl vanillin.

The choice of excipients is made as mentioned above depending on the intended application.

The composition of the invention can be used in many fields of application, inter alia, in the food and pharmaceutical field, and in the perfume industry.

A preferred field of application for the implementation of the composition of the invention is that of biscuit and pastry, and more particularly:

- dry biscuits: sweet biscuits of the classic type, small butter, cakes, snacks, shortbread,

- industrial pastry: 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 the various types of cookies 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 composition according to the invention is carried out during manufacture, according to the desired product and is conducted according to the conventional techniques of the field in question (see in particular JL KIGER and JC KIGER - Modern Techniques of Biscuit, Pastry - Bakery industry and craft, 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 a guide, it will be specified that the composition of the invention is introduced in an amount of 0.005 to 0.2 g per kg of dough.

The composition of the invention is quite suitable for use in the field of chocolate and whatever the form of implementation. work: chocolates in plates, chocolates of cover, fodder for chocolates.

It 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 implementation in cocoa butter.

In this field of application, the composition of the invention is used according to the type of chocolate, at a rate of 0.0005 g to 0.1 g per 1 kg of finished product: the highest contents found in chocolate for cover.

Another use of the composition of the invention is the manufacture of sweets of all kinds: sugared almonds, caramels, nougats, boiled sweets, melting sweets and others.

The amount of composition of the invention introduced depends on the more or less pronounced taste that is sought. Thus, the use doses can vary between 0.001% and 0.2%.

The composition of the invention is well suited for uses in the dairy industry and more particularly in flavored and gelled milks, desserts, yogurt, ice cream and ice cream.

The aromatization is done by simple addition of the composition of the invention, in one of the mixing stages required during the preparation of the product.

The contents of said composition to be used are generally low of the order of 0.02 g per 1 kg of finished product.

Another application of the composition 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 relative to to 1 kg of finished product.

The composition of the invention may also be used in various drinks and include, among others, grenadine and chocolate drinks.

In particular, it can be used in instant beverage mixes dispensed by vending machines for beverages, flavored powdered drinks, chocolate powder or in instant preparations in the form of powder for the preparation of desserts of all kinds. , flans, pastry, pancakes, after dilution with water or milk.

It is common to use vanillin for denaturing butter. For this purpose, the composition of the invention may be implemented at a rate of 6 g per ton of butter. Another field of application of the composition 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 flavored.

The composition of the invention can 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 ...) .

It is quite suitable in completely different fields such as cosmetics, the perfume industry or detergency.

It 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 is incorporated the composition of the invention, which is used to provide various types of of finished products, the sought-after fragrance.

Fragrance bases are preferred examples of perfuming compositions in which the composition of the invention can be advantageously used in a proportion 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 composition of the invention is the field of soap. It can be used at a content of 0.3% to 0.75% of the total mass to be perfumed. Generally, it is associated in this application with benzoin resinoid and sodium hyposulphite (2%).

The composition according to the invention can find many other applications, in particular in air fresheners or any maintenance product. The physico-chemical characteristics of the compositions of the invention are determined according to the following methods:

1. Fusion point.

The melting point of the composition of the invention is measured by differential scanning calorimetry.

The measurement is carried out using a Mettler differential analyzer DSC822e under the following conditions:

- preparation of the sample at ambient temperature: weighing and introduction into a sample holder,

- sample holder: crimped aluminum capsule,

- test portion: 8.4 mg,

- rate of rise in temperature: 2 ° C / min,

- study range: 10 - 90 ° C.

We weigh the sample of the composition which is introduced into the capsule which is crimped and placed in the apparatus.

The temperature programming is started and the fusion profile is obtained on a thermogram.

The melting temperature is defined from a thermogram produced under the preceding operating conditions.

The onset temperature is selected: temperature corresponding to the maximum slope of the melting peak.

2. X-ray diffraction spectrum.

The X-ray diffraction spectrum of the composition of the invention is determined using the X'Pert Pro MPD PANalytical device equipped with an X 'Celerator detector, under the following conditions:

- Start Position [° 2Th.]: 1, 5124

- End Position [° 2Th.]: 49.9794

- Step Size [° 2Th.]: 0.0170

- Scan Step Time [s]: 41, 0051

- Anode Material: Cu

K-Alpha1 [?]: 1, 54060

- Generator Settings: 30 mA, 40 kV

3. Flowability property and caking index.

The composition of the invention has the characteristic of less motter storage which is evidenced by the determination of the flowability index of the powder. The flowability of powders is a technical concept well known to those skilled in the art. For further details, reference may be made in particular to "Standard Shear Testing Technique for Particulate Materials Using the Jenike Shear Cell", published by "The Institution of Chemical Engineers", 1989 (ISBN: 0 85295 232 5).

The flowability index is measured in the following manner.

The flowability of the powders is measured by shearing a sample in an annular cell (marketed by D. Schulze, Germany).

Precision of the powders is carried out under a normal stress of 5200 Pa.

The shear points required to plot the flow of the sample are obtained for 4 normal stresses lower than the stress of the precision, typically 480 Pa, 850 Pa, 2050 Pa and 3020 Pa.

From the Mohr circles in the "shear stress vs normal stress" diagram, two constraints are identified at the flow location that characterize the sample:

- the normal stress in the main direction; it is given by the end of the great circle of Mohr which passes by the point of precision,

- the cohesive force; it is given by the end of the small circle of Mohr which is tangent to the place of flow and passes by the origin.

The ratio between the normal stress in the principal direction and the cohesive force is a nondimensional number called "i, flowability index".

These measurements are carried out immediately after filling the annular cell, thus obtaining the instantaneous flowability index.

Another series of measurements is performed with a cell that has been stored for 24 hours at 40 ° C and 80% relative humidity under a normal stress of 2400 Pa.

This gives the caking index.

Examples illustrating the present invention are given below, without being limiting in nature.

In the examples, the percentages mentioned are expressed by weight. Example 1

In a plow-sided mixer equipped with a tank with a volume of 15 liters heated by double jacket, 2100 g of vanillin (VA) powder and 900 g of ethylvanillin (EVA), a VA mass ratio, are introduced. EVA = 70/30. The moisture of these powders is 0.1% by weight.

Stirring is put into operation at a speed of 20 rpm, ie a blade tip speed of 0.25 m / s. This stirring speed is kept constant during all phases of the process.

A circulation of wet nitrogen is established in the mixer with a flow rate of 200 l / h. The humidification of the nitrogen stream is ensured by bubbling in water maintained at 40 ° C. so as to obtain 25 g of water per kg of nitrogen. The feed line between the water bath and the mixer is maintained at 45 ° C so as to avoid any condensation in the pipes.

The temperature of the coolant circulating in the jacket is increased gradually so that the temperature of the powder mixture follows a ramp of + 0.3 ° C / min.

When the temperature of the product reaches 49.5 ° C, the water bath moistening the flow of nitrogen is short-circuited so as to supply the mixer with a circulation of dry nitrogen (less than 0.5 g of water / kg of nitrogen). At the same time, 15 g of Tixosil 365 silica are introduced into the mixer.

The temperature of the product is raised from 49.5 ° C to 52 ° C to + 0.2 ° C / min and is then maintained at 52 ° C for 30 minutes. The heating of the coolant is then stopped and, by natural cooling, the temperature of the product is reduced to 30 ° C. The stirring and the circulation of nitrogen are stopped. The mixer is drained.

The product is sieved at 800 μιτι; the passer is 56% by weight of the total mass. The refusal at 800 μιτι is milled using a grinder Quadro Comill equipped with a grid of 800 μιτι. The 2 fractions are then combined and the mixture is homogenized to give the final product.

The melting point of the granules is determined by differential scanning calorimetry as previously described. The thermogram obtained has a main peak which corresponds to the new vanillin / ethyl vanillin compound. The melting temperature (Tonset) corresponding to the maximum slope of the peak is 59.5 ° C.

The X-ray diffraction spectrum of the granules shows the characteristic lines at the angles 2Θ = 20.7 - 25.6 - 27.5 - 28.0 as illustrated in Figure 1 and which differentiate it from the spectra of vanillin and vanillin. 'ethyl vanillin. The flowability index and the caking index, measured as previously described with the aid of an annular cell, are 5.70 and 0.09, respectively. Example 2

The procedure of Example 1 is repeated with only modifications:

a stirring speed of 40 rpm,

a rise ramp under wet nitrogen of + 0.5 ° C / min,

a final temperature under dry nitrogen of 55 ° C,

- no isothermal bearing before cooling.

The increase in the final co-granulation temperature makes it possible to eliminate the isothermal stage guaranteeing the complete transformation of the vanillin-ethyl vanillin mixture in the new compound. On the other hand, the growth of the granules is more important since, at the mixer outlet, the passing at 800 μιτι represents only 27% of the total mass, which forces to grind 73% of the product.

After milling the refusal at 800 μιτι and mixing the two fractions, the product obtained has a flowability index of 6.30 and a caking index of 0.10.

Example 3

The procedure of Example 1 is repeated with the only difference that the 15 g of Tixosil 365 silica are replaced by 150 g of Roquette IT12 maltodextrin.

At the output of the mixer, the passing at 800 μιτι represents 55% of the total mass.

After milling the refusal at 800 μιτι and mixing the two fractions, the product obtained has a flowability index of 5.90 and a caking index of 0.12.

Example 4

In this example, a composition is prepared in the form of granules comprising 50% by weight of the granules prepared according to Example 1 and 50% by weight of Roquette IT6 maltodextrin. The mixing operation of about 5 minutes is carried out at room temperature under ambient air in the plow mixer with a rotation speed of 60 rpm.

The mixture thus obtained has a flowability index of 8.80 and a caking index of 0.62.

Its aromatic power is equivalent to that of pure vanillin.

Claims

1 - Process for the preparation of a composition essentially comprising a compound based on vanillin and ethyl vanillin in a vanillin / ethyl vanillin molar ratio of 2, characterized in that it comprises a co-granulation operation of vanillin and ethyl vanillin implemented in powder form and in such quantities that the vanillin / ethyl vanillin molar ratio is at least 2, conducted at a temperature of between 50 ° C. and 57 ° C., followed by an operation making it possible to reduce the temperature of the composition obtained at room temperature.

2 - Process according to claim 1 characterized in that vanillin and ethyl vanillin are used in the following proportions:

from 65 to 72%, by weight of vanillin,

from 28 to 35% by weight of ethyl vanillin.

3 - Process according to one of claims 1 and 2 characterized in that the vanillin and ethyl vanillin are used in the following proportions:

from 67 to 70% by weight of vanillin,

30 to 33% by weight of ethyl vanillin.

4 - Process according to one of claims 1 to 3 characterized in that it carries out with stirring, the mixture of vanillin powders and ethylvanillin and is brought from room temperature to the temperature of co- granulation.

5 - Process according to claim 4 characterized in that the co-granulation temperature is chosen between 50 and 57 ° C, preferably between 50 and 55 ° C.

6 - Process according to one of claims 4 and 5 characterized in that one carries out the rise in temperature, gradually. 7 - Process according to one of claims 4 to 6 characterized in that one maintains once the co-granulation temperature reached, stirring mixture at this temperature for a period of time sufficient to obtain the transformation of reagents in new expected compound. 8 - Process according to one of claims 1 to 7 characterized in that the various operations described above are conducted under an inert gas atmosphere, preferably nitrogen.

9 - Process according to one of claims 1 to 7 characterized in that one begins the mixing of the powders under wet nitrogen, then the temperature is gradually increased and when the latter is greater than or equal to 44 ° C and below 49 ° C, dry nitrogen is introduced.

1 1 - Process according to claim 9 characterized in that the nitrogen stream contains 1 to 5% by weight of water, preferably 2 to 3% of the weight of water. 12 - Process according to claim 1 characterized in that one carries out the cooling of the composition obtained with stirring and under an inert atmosphere to a temperature below 40 ° C, preferably to a temperature below 35 ° vs. 13 - Method according to one of claims 1 to 12 characterized in that the composition obtained is shaped according to a grinding technique.

14 - Method according to one of claims 1 to 13 characterized in that one or more excipients in the composition.

15 - Process according to claim 14 characterized in that the excipient or excipients are added all or part by dry mixing with the previously obtained composition or during the manufacture of said composition, preferably during the step of co -granulation of the vanillin and ethyl vanillin mixture.

16 - Composition obtained according to the process described in one of Claims 1 to 15, comprising:

from 80 to 99%, preferably from 80 to 94% by weight, of a mixture of the new vanillin / ethyl vanillin and vanillin compound,

from 1 to 20%, preferably from 1 to 10% by weight, of other crystalline phases. 17 - Composition according to claim 16, characterized in that the mixture obtained comprises:

from 80 to 94%, preferably from 86 to 94% by weight of the new vanillin / ethyl vanillin compound,

from 6 to 20%, preferably from 6 to 14% by weight of vanillin.

18 - Composition comprising at least one composition described in one of claims 16 and 17 and at least one excipient selected from fatty substances; fatty alcohols; sugars; polysaccharides; silica; vanillin and ethyl vanillin.

19 - Composition according to claim 18, characterized in that the excipient is chosen from:

sugars, preferably glucose, sucrose, fructose, galactose, ribose, maltose, sorbitol, mannitol, xylitol, lactitol, maltitol; inverted sugars: glucose syrups and sucroglycerides derived from fatty oils, preferably coconut oil palm oil, hydrogenated palm oil and hydrogenated soybean oil; sucrose esters of fatty acids, preferably sucrose monopalmitate, sucrose monodistearate and sucrose distearate,

starch hydrolysates,

dextrins and maltodextrins resulting from the hydrolysis of a starch (wheat, maize) or of a starch (potato) as well as β-cyclodextrins, preferably maltodextrins having a DE of less than 20, preferably included between 5 and 19 and more preferably between 6 and 15,

cellulose, its ethers, especially methylcellulose, ethylcellulose, methylethylcellulose, hydroxypropylcellulose; or its esters, in particular carboxymethylcellulose or carboxyethylcellulose optionally in soded form, gums such as carrageenan gum, Kappa or Iota carrageenan, pectin, guar gum, locust bean gum, and xanthan gum, alginates, gum arabic, acacia gum, agar -agar,

flour, preferably wheat flour (native or pregel); starches, preferably potato starch,

- gelatin,

- silica,

an antioxidant agent, preferably vitamin E,

an emulsifying agent, preferably lecithin,

vanillin or ethyl vanillin.

20 - Composition according to one of claims 18 and 19 characterized in that it comprises from 0.1 to 90% by weight of excipient (s), preferably from 20 to 70% by weight of excipient (s) ).

21 - Application of the composition described in one of claims 16 to 20 as a flavor in the field of food and feed, pharmacy, and as perfume, in the cosmetics industry, perfumery and detergency .

22 - Application according to claim 21, characterized in that the composition of the invention is used during the manufacture of a paste, preferably in a fatty substance, in the field of dry biscuits and industrial pastry; in the field of chocolate, especially for the preparation of chocolate plates, cover chocolates or chocolate filling; during the manufacture of sweets of all kinds: sugared almonds, caramels, nougats, boiled sweets, melting sweets and others; in the dairy industry, and more particularly in flavored and gelled milks, desserts, yogurt, ice cream and ice cream; in the preparation of vanilla sugar, by impregnation of the sugar with it; in the preparation of different drinks, preferably grenadine and chocolate drinks; in instant drink preparations such as powdered flavored beverages, powdered chocolate or in instant preparations in the form of a powder for the preparation of desserts of all kinds; for the denaturation of butter. 23 - Application according to claim 21 characterized in that it implements the composition of the invention in the animal feed, particularly for the preparation of flours. 24 - Application according to claim 21 characterized in that it implements the composition of the invention as odor masking agent, especially in the pharmaceutical industry; in the field of cosmetics for the preparation of creams, milks and blushes and other products, as a perfume base in perfumery and in the field of detergency, especially in the soap industry.