Nutritive compositions containing fats, and process for their preparation.

0001The present invention relates to nutritional compositions containing fatty substances and to a process for their preparation from fruits of the genus Ribes.

0002Most vegetable oils contain the polyunsaturated fatty acids linoleic (6,9-octadecadienic) and alpha-linolenic (9,12,15-octadecatrienic). Only the oils from the seeds of hops (Humulus), hemp (Cannabis), borage (Borage) and evening primrose (Oenothera) are known to contain gamma-linolenic acid (6,9,12-octadecatrienic), l evening primrose by being the only source available elsewhere at a high price.

0003Gamma-linolenic acid is an essential fatty acid which is metabolized by the body into prostaglandins via dihomo-gamma-linolenic acid and arachidonic acid (5,8,11,14-eicosatetraene), which is even a constituent of cell membranes while alpha-linolenic acid does not contribute in the same way to this metabolic process. The conversion of linoleic acid ÷ gamma-linolenic acid in the tissues is incomplete (4-20% compared to 90-98% for the transformation gamma-linolenic acid → arachidonic acid) and may even be non-existent (eg for cats) in the absence or inactivation of the Δ-6-desaturase enzyme.

0004A lack of essential fatty acids leads in fact to a nutritional deficiency affecting all the metabolic processes mentioned above and which can lead to biochemical disorders or to organic lesions (e.g. coagulation disorders, dermatological lesions, endocrine disorders, myocardial damage, liver, joint, neurological and mental disorders). We can therefore see the benefit of a gamma-linolenic acid intake - for the prevention or treatment of these anomalies.

0005Mention has been made of the possibility of using gamma-linolenic and arachidonic acids as therapeutic and nutritional agents p. ex. in French patents Nos. 2,197,605 and 1,603,383, gamma-linolenic acid being of synthetic origin or extracted from the seed oil of evening primrose (Oenothera) or of borage officinalis (Borage officinalis).

0006In addition, French patent No. 2,255,055 relates to cosmetic or pharmaceutical compositions based on raspberry seed oil, the anti-inflammatory activity of which is mentioned without indicating its composition. The oil being preferably extracted with chloroform (polar solvent), the anti-inflammatory activity is probably due to the presence of minor components. An analysis of this oil also showed that it contained approximately 54% by weight of linoleic acid and 30% of alpha-linolenic acid but did not contain gamma-linolenic acid.

0007Finally, Hungarian patent No. T 13226 mentions that the addition of a ground product or crude oil extracted from paprika seeds, tomatoes or currants to cosmetic products or table oils would inhibit their oxidation. The extraction as provided does not allow the undesirable dyes and waxes to be separated in the products envisaged and the composition of the extract is not mentioned.

0008It has been found quite surprisingly that fruit seed oils of the genus Ribes contain an appreciable percentage, at least 4% by weight of gamma-linolenic acid. In addition, these seeds are available in large quantities in oil cakes from the pressing of fruit juices, the production of jams and jellies or fermentation musts from the production of spirits, liqueurs and schnapps, by-products. which were hitherto used as fuel or as fodder.

0009The invention relates to nutritive compositions containing from 1 to 80% by weight of a fatty substance extracted from fruit seeds of the genus Ribes containing at least 4% by weight of gamma-linolenic acid practically devoid of odorous compounds, free fatty acids, dyes and waxes from these fruits.

0010According to the invention, the term “nutritive composition” designates cosmetic, dermatological (corrective cosmetic) or topical (eg: ophthalmic) compositions. as well as dietetic food or supplementation or pharmaceutical compositions for oral, enteral or parenteral nutrition.

0011According to the invention, the fatty substances entering into the nutritive composition come in practice from blackcurrant (Ribes nigrum), currants (Ribes rubrum), gooseberries (Ribes ova-crispa or grossularia) or from hybrid fruits of these cash. One can of course use a mixture of these fruits.

0012The lipid content of the above-mentioned by-products is 12 to 30% by weight depending on the raw material. The lipid phase in turn contains 4 to 19% by weight of gamma-linolenic acid.

0013As an indication, the seed oil of these fruits consists of triglycerides of the following fatty acids, by weight:<tables id="tabl0001" num="0001"><img file="EP0092085A2_D0001.tif" /></tables>

0014Blackcurrant oil, which is preferred because of its high gamma-linolenic acid content, also contains 1 to 2% by weight of unsaponifiable bodies, such as aliphatic alcohols, hydrocarbons, tocopherols, squalene, β-sitosterol, campesterol. and Δ-7 stigmasterol. Its density is 0.9215 g / cm³ (at 20 ° C) and its viscosity 28.3 centipoise (at 20 ° C).

0015A cosmetic or dermatological composition may be in the form of a fluid water in oil or oil in water emulsion (milk, lotion, shampoo, shaving foam, etc.) or a more consistent emulsion (cream, mask) and generally containing from 1 to 20% by weight of the above fatty substance. It can essentially consist of an oily phase (balm, bath oil, etc.), containing up to 80% of the above fatty substance, or even have a predominant aqueous phase (hair rinsing product, etc. ...). Finally, it can be essentially solid (make-up products, eyeshadow, foundation, lipstick, etc.) and contain from 1 to 30% of the above fatty substance.

0016Its fatty phase may contain, in addition to the above fatty substance, vegetable, animal, mineral or synthetic oils, waxes, long-chain alcohols and polymers of common use in cosmetics.

0017When it comes to emulsions, the compositions contain 1 to 20% by weight of emulsifying agents.

0018The compositions may further contain coloring agents, perfumes, preservatives, pigments, pearlescent agents, antioxidants and fillers.

0019Among the dietetic or supplementation foods envisaged, there may be mentioned infant milks and more particularly infant formulas, sauces, mayonnaises and salad oils. In these products, the fatty substances are dosed so that they provide the equivalent of 0.35 to 2.5% by weight of gamma-linolenic acid and represent 2 to 15% by weight. The fatty substances will advantageously be protected from oxidation by addition of the esters of ascorbic acid with fatty acids p. ex. ascorbyle palmitate.

0020One can also consider using the above fatty substances in animal supplementation, in particular in food p. ex. meat compositions for cats.

0021Finally, the above fatty substances can enter into the composition of medicaments of formulation adapted to the mode of administration and administered p. ex. in the form of syrup or isotonic ocular capsules or emulsions or else be constituents of the fatty phase of emulsions intended for parenteral nutrition and represent 5 to 80% by weight of the composition.

0022The pharmaceutical compositions according to the invention are physically and chemically stabilized (in particular against oxidation) and preferably presented in sterile form. When intended for parenteral nutrition, they are nonpyrogenic and sterile.

0023The invention also relates to a process for preparing fatty substances from fruit seeds of the genus Ribes, characterized in that a vegetable material containing these seeds is ground and that it is extracted by solvents so as to obtain a fatty substance containing at least 4% by weight of gamma-linolenic acid practically devoid of the coloring compounds, free fatty acids, colorings and waxes of these fruits.

0024According to the invention, the term plant material used means the by-products mentioned above. The raw material is generally in the form of highly colored oil cakes and containing the waxes associated with the seeds, waxes and dyes representing from 5 to 7% by weight of the crude oil that would be extracted therefrom, for example. ex. with hexane. Waxes are saturated and monounsaturated esters of fatty alcohols and long chain fatty acids that are solid at room temperature. The waxes and dyes in question are not desired in an oil constituting the nutritive compositions.

0025A raw material of choice is the cake for pressing fruit juices, in particular blackcurrants. We dry it first p. ex. in air for about 1 hour at around 60 ° C. It is coarsely ground and sieved, so as to obtain particles of 1 to 1.5 mm, the sieving yield being 60 to 80% of the weight of the cake. It is advantageous to separate the seeds from the straws by gravity in a stream of air or "elutriation" with a yield by weight of 80 to 90%.

0026According to a preferred embodiment of the process, the seeds are washed with a polar solvent in common use so as to rid them of waxes, dyes and free fatty acids. For cosmetic applications, p. ex. methanol, isopropanol, acetone, ethanol or a mixture of these solvents or else a supercritical fluid, eg carbon dioxide under conditions which give it a polar character. For food and pharmaceutical applications, an authorized solvent p. ex. ethanol or supercritical carbon dioxide.

0027By way of example, washing takes place by extraction of the seeds with ethanol at reflux or by loads, p. ex. a first time for about 2 hours and a second time for about 30-60 minutes, or continuously for about 2 hours and then the residue is wrung.

0028Alternatively, the seeds can be extracted using p. ex. carbon dioxide at 250-350 bar and 60-80 ° C in continuous cycle, the solvent being recovered in gaseous form by reduction of the pressure, recompressed and recycled. It has been found that the extraction makes it possible to remove most of the coloring matters and waxes present in the films and around the seeds indeed, the waxes are deposited by cooling starting from the alcoholic extract while this one is very strongly colored.

0029The drained residue is ground (particles 100 to 300 μ), about 10-15% of water is added thereto and then it is put into the form of pellets or granules by extruding the dough and cutting the sausage. Alternatively, the seeds can be flaked on a flattening cylinder from the dewatered residue which is not ground. These shapings prevent clogging and facilitate the subsequent extraction of the oil by giving the product the porosity allowing good penetration of the solvent, and the flakes in particular resist crushing.

0030The next step is to extract the oil with a non-polar solvent, e.g. ex. hexane in an amount of about 250% by weight of hexane relative to the residue. Alternatively, liquid or preferably supercritical carbon dioxide can also be used in this step, under conditions where it is weakly polar, e.g. ex. at 200-300 bar and 40-60 ° C. One can of course use p. ex. supercritical carbon dioxide in the washing step and in the subsequent extraction step or in only one of these steps, the other being carried out with p. ex. ethanol, respectively hexane.

0031After extraction, it is possible, although these measures are only preferred options, to neutralize the solution in order to remove the residual free fatty acids, after having partially evaporated the solvent, e.g. ex. in the case of hexane so that it contains approximately 10% by weight of oil, by concentrated sodium or potassium hydroxide (2N), cool it to approximately 0-4 ° C for approximately 24 hours and filter it at this temperature so as to completely eliminate the residual waxes. Similarly, the following discoloration and deodorization are preferred options: the solution is discolored with 2-8% by weight of activated carbon relative to the oil used at 20 ° C-60 ° C and then the product is evaporated. hexane. The oil is then deodorized by steam entrainment at 140-220 ° C and preferably at about 180 ° C under a vacuum equal to or less than 1 torr.

0032According to a variant of preparation of the oil, the ground seeds are not washed beforehand but are extracted directly with a solvent. In this case, neutralization, elimination of waxes by decantation, discoloration and deodorization as indicated above are essential for obtaining a pale yellow refined oil.

0033In some cases, it is desired to enrich the fatty substance with gamma-linolenic acid. To do this, the oil freed from waxes and free fatty acids is saponified with an alkaline hydroxide, for example potassium hydroxide in methanol / water at the concentration of approximately 11%, the salts obtained are acidified with a mineral acid, e.g. ex. 2N sulfuric acid, the fatty acids liberated by hexane are extracted, the organic phase is separated and dried p. ex. by addition of sodium sulfate. As a variant, it is possible to directly treat the ground meal with an alkaline hydroxide, to acidify it with a mineral acid, to extract the fatty acids released with hexane and to dry the organic phase as above. The organic phase is fractionated by high pressure liquid chromatography, by passage over columns of silica gel loaded with silver nitrate and elution preferably with a mixture of dichloromethane, toluene and diethyl ether 70/25 / 5-65 / 30/5 in isocratic mode, that is to say with recycling of the solvent mixture of fixed composition and a fraction containing approximately 60% by weight of gamma-linolenic acid and approximately 40% of alpha-linolenic acid is thus obtained. .

0034Almost pure gamma-linolenic acid can be isolated by performing high-pressure liquid phase chromatography with support rated as Ce or C₁₈ in reverse phase with gradient of solvent mixture acetonitrile / water, methanol / water or isopropanol / water.

0035The following examples illustrate the invention. In these examples, the parts and percentages are expressed in weight value.

Example 1

0036100 kg of residue obtained are treated by extracting the blackcurrant juice and drying a first time for 2 hours at reflux with 250 kg of ethanol and a second time for 1 hour at reflux with 250 kg of ethanol. The extract is drained and dried at 80 ° C. for 2 times 30 minutes in an air dryer and it is finely ground in a hammer mill.

0037After humidification with 10-15% water and extrusion of the dough in the form of pellets, the 89 kg of product obtained are extracted with 2 times 205 kg of hexane at reflux for 3 hours then cooled and filtered. The hexane is then evaporated and 14.3 kg of a light yellow oil are obtained, the weight content of free fatty acids of which is 0.16%.

Example 2

0038100 kg of dried residue from the extraction of blackcurrant juice are ground in a hammer mill and the powder is sieved so as to obtain particles of 1 to 1.5 mm with a sieving yield of 60-80%. The product is humidified and pelleted and extracted with hexane as in Example 1. A part of the hexane is evaporated, the free fatty acids are neutralized with a 2N sodium hydroxide solution, the organic phase is separated, it is left to stand at 4 ° C. for 24 hours and it is separated from the hard waxes which settled by filtration. It is treated with 2 to 8% of activated carbon based on the amount of oil in solution, then the solvent is evaporated and the oil is deodorized by steam stripping at 180 ° C. under a vacuum of 0.1 torr. 13 to 16 kg of refined oil are thus obtained.

Example 3

0039100 kg of dried blackcurrant pulp from the pressing of the juices are ground in a disc mill and the ground product is sieved so as to obtain 60.5 kg of particles of between 1 and 1.5 mm. It is sent to an elutriator and 49.5 kg of a heavy fraction consisting essentially of seeds is collected. Wash twice with each time 120 kg of ethanol at reflux. The procedure is as in the example, 1 except that 2 times 120 kg of ethanol are used for washing, that the dried extract is put in the form of flakes using a roller mill flattener instead extrude it and extract the flakes with 2 times 102.5 kg of hexane. 11.1 kg of a light yellow oil are obtained.

Examples of cosmetic compositions 4 to 14

0040<tables id="tabl0002" num="0002"><img file="EP0092085A2_D0002.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0092085A2_D0003.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0092085A2_D0004.tif" /></tables><tables id="tabl0005" num="0005"><img file="EP0092085A2_D0005.tif" /></tables><tables id="tabl0006" num="0006"><img file="EP0092085A2_D0006.tif" /></tables><tables id="tabl0007" num="0007"><img file="EP0092085A2_D0007.tif" /></tables>

0041Plant extracts or biological extracts can be added as desired.<tables id="tabl0008" num="0008"><img file="EP0092085A2_D0008.tif" /></tables><tables id="tabl0009" num="0009"><img file="EP0092085A2_D0009.tif" /></tables><tables id="tabl0010" num="0010"><img file="EP0092085A2_D0010.tif" /></tables><tables id="tabl0011" num="0011"><img file="EP0092085A2_D0011.tif" /></tables><tables id="tabl0012" num="0012"><img file="EP0092085A2_D0012.tif" /></tables>to which 5.4 parts by weight of the following pigments are added per 100 parts by weight of white body:<tables id="tabl0013" num="0013"><img file="EP0092085A2_D0013.tif" /></tables><tables id="tabl0014" num="0014"><img file="EP0092085A2_D0014.tif" /></tables><tables id="tabl0015" num="0015"><img file="EP0092085A2_D0015.tif" /></tables>

0042<tables id="tabl0016" num="0016"><img file="EP0092085A2_D0016.tif" /></tables><tables id="tabl0017" num="0017"><img file="EP0092085A2_D0017.tif" /></tables>

Examples of dietetic foods 15 to 17

0043<tables id="tabl0018" num="0018"><img file="EP0092085A2_D0018.tif" /></tables><tables id="tabl0019" num="0019"><img file="EP0092085A2_D0019.tif" /></tables><tables id="tabl0020" num="0020"><img file="EP0092085A2_D0020.tif" /></tables><tables id="tabl0021" num="0021"><img file="EP0092085A2_D0021.tif" /></tables>as well as the minimum quantities of the following vitamins and trace elements:<tables id="tabl0022" num="0022"><img file="EP0092085A2_D0022.tif" /></tables><tables id="tabl0023" num="0023"><img file="EP0092085A2_D0023.tif" /></tables>

0044Such a powder is prepared p. ex. as described in French Patent No. 2,388,503.

Examples of pharmaceutical compositions 18 to 19

18 - Capsules for oral administration

0045Gelatin capsules are prepared containing 500 mg of blackcurrant oil corresponding to 80 mg of gamma-linolenic acid per capsule.<tables id="tabl0024" num="0024"><img file="EP0092085A2_D0024.tif" /></tables>