MXPA00010876A - Phytosterol compositions - Google Patents

Abstract

This invention relates to phytosterols and phytostanols, in particular to fatty acid esters of phytosterols and phytostanols with a specified fatty acid composition. The invention further relates to methods for preparation of the phytosterol and phytostanol esters and their uses.

Description

COMPOSITIONS OF PHYTOSTEROL This invention relates to phytosterols and phytostanols, in particular fatty acid esters of phytosterols and / or phytostanols with a specified fatty acid composition. The invention also relates to methods for the preparation of phytostanol and / or phytosterol esters and their uses. Since 1 950, numerous animal and human studies have been reported, in which plant sterols (phytosterols) have caused significant reductions in serum cholesterol levels. Plant sterols reduce the levels of serocholesterol by reducing the absorption of cholesterol from the digestive tract. The mechanism or mechanisms, by which this reduction in cholesterol absorption takes place, are not completely known. Phytosterols are a group of compounds structurally very similar to cholesterol. The phytosterols that occur more frequently in nature are sitosterol, campesterol and stigmasterol. In all phytosterol preparations, sitosterol is the main component. Most clinical and non-clinical studies have been conducted with the so-called resin oil sterols, which contain high amounts of sitosterol and some sitostanol. In the scientific literature such mixtures of sterol are often referred to as sitosterol. Vegetable fats and oils are the main source of vegetable sterols in our diet. In vegetable oils, a major part of the sterols exists as fatty acid esters. In more recent study plant sterols have been used in crystalline form, sparingly soluble with high daily intakes (up to 20-30 g / day). However, even when administered in relatively small doses (a few grams per day) and under optimal conditions, plant sterols reduce the levels of LDL-cholesterol and total serum. In recent years, the treatment of the plant sterol of hypercholesterolemia has been refined by the use of the fully saturated form of sitosterol, sitostanol. Saturated phytosterols such as sitostanol and campestanol are present in our diet in small amounts. The daily intake of total tin cans in the Finnish diet has been estimated at 30-80 mg / day. However, resin oil sterols (pine tree sterols) contain 1-20% vegetable tin (sitostanol + campestanol). Phytostanols can also be produced by hydrogenation to remove the double bond in corresponding plant sterols. Sitostanol is not virtually absorbed and the cholesterol content of mixed micelles decreases more efficiently than sitosterol, thus showing an improved serocholesterol-lowering effect. Sugano et al (Sugano M., Morioka H and Ikeda I. (1977) J. Nutr. 1 07.201 1 -019) showed that sitostanol had a higher hypocholesterolemic activity than sitosterol in rats. Similar results were obtained with rabbits (Ikeda I., Kawasaki A., Samazima K, and Sugano M. (1981), J. Nutr Sci. Vitaminol 27, 243-251). In addition, sitostanol reduces the formation of aortic atheroma because cholesterol feeds more than sitosterol. Becker e to al. (Becker M., Staab D. and von Bergmann K. (1993) Journal of Pediatrics, 122, 292-296 showed, that sitostanol was significantly more effective than sitosterol in reducing high levels of LDL cholesterol in children with severe familial hypercholesterolemia. The solubility of free sterol and especially of free stanol in edible fats and oils is very low, for example, less than 2% of free sterols dissolve in fats and oils if water is present This problem can be overcome by esterifying the sterols free with fatty acid esters The esters of vegetable sterols have been shown to be the same as the corresponding free sterols in reducing the absorption of cholesterol in rat (Mattson FH, Volpenheim R. H. and Erickson B.A. (1977) J. Nutr. 107, 1 1 39-46), while Mattson went to. (Mattson F.H., Grundy S.M. and Crouse J. R. (1982), Am. J. Clin. Nutr. 35.697-700) found that free sterols were more effective in reducing cholesterol absorption in man. During the digestion of fats, dietary fat, sterol ester and / or stanol together with dietary cholesterol and their esters reach the intestinal oil phase (in intestinal emulsion), from which free sterols and stanols are released through of lipolysis by enzymes such as cholesterol esterase. The free sterols and / or stanols released compete with both bile and dietary cholesterol for micellar solubility and decrease the cholesterol micellar phase concentration when it occurs in lipid core fat material of the micelles mixed in sufficiently high concentrations. Plant stanols such as sitostanol are more effective in decreasing the micellar phase cholesterol than the corresponding sitosterol. The Patent of E. U. 3 751 569 (Erickson B.A.) describes salad oils and pure cooking that have hypocholesterolemic properties. In the liquid glyceride base oil 0.5-1.0% by weight (as free sterol equivalent) of a fatty acid ester of sterol is mixed. Salad or cooking oil was prepared by dissolving liquid glyceride base oil and acid monocarboxylic plant sterols in a mutual solvent and evaporate the solvent (diethyl ether or hexane). The fatty acid moiety was defined as a C 1 -C 2 saturated monocarboxylic acid or an unsaturated fatty acid with up to 24 carbon atoms. The sterol ester is added in a sufficiently small amount to prevent precipitation at refrigerant temperatures. The solubility of different fatty acid esters of phytosterol in triolein is also presented, showing very low solubility for phytosterol esters of C14 and C6 fatty acids. This patent describes the use of certain individual fatty acid esters of phytosterols added to the oil of salad or cooking in relatively small amounts.

H? lB? [i _ »? l_? l ???: ill_? lÉl Saturated plant sterols have been shown to be more effective in reducing the absorption of cholesterol from the digestive tract and thus causing improved reduction of LDL and total serum cholesterol levels. Saturation of vegetable sterols to vegetable steels also reduces their solubility in fats and oils. U.S. Patent 5 502 045 (Miettinen et al) describes a method for producing fatty acid esters of sitostanol and the use of the substance to lower high cholesterol levels. Upon esterification of the sitostanol mixture with fatty acids from a vegetable oil such as rapeseed oil (LEAR) a liposoluble stanol ester was obtained. Examples are given by showing that up to 20% of the fat mixture normally used can be exchanged with this mixture of fatty acid ester of sitostanol based on fatty acid esters of low erucic acid chopper oil. The incorporation of such a liposoluble stanol ester into food products such as margarines and spreads provides a way to introduce the appropriate daily amount of stanol for the optimal reduction of cholesterol absorption. In several clinical studies, these liposoluble stanol esters have been proven to be very effective in reducing the absorption of cholesterol from the digestive tract. The North Karelia stanol study was conducted to verify these findings in a 12-month large-scale randomized double-blind study (Miettinen TA, Puska P., Gylling H., Vanhanen H., and Vartiainen F. (1995) N. Engl. J. Med. 333, 1 308-1 31 2). The results of this study show that a daily intake of 1.8-2.6 g of a liposoluble sitostanol ester (calculated as free stanol) administered in a margarine reduced the total cholesterol with 10% and the LDL-cholesterol with 14 % compared to the reference group that has a margarine without added liposoluble stanol ester. The stanol fatty acid esters with fatty acids based on commercially available PUFA vegetable oils such as sunflower oil, corn oil, or soybean oil, safflower oil, cottonseed oil or mixtures thereof will exhibit texturing properties too high in vegetable oils or their mixtures for the purpose of incorporating into foods such as salad oils, cooking oils, easily emptied dressings, sauces and mayonnaises in sufficiently high quantities for an adequate daily intake of tin and sterols in order to obtain an effect of optional cholesterol decrease. This problem will be solved by the present invention. Another problem in the prior art is the production of food products with very high contents of phytosterols in a form that could be added to a variety of food products in concentration high enough to supply a normal food intake with the appropriate amount of sterols and / or stanols for optimal effect on blood cholesterol levels. This was partially solved in the prior art by producing the fatty acid esters of the phytosterols and phytostanols. Nevertheless, by using the sterol and / or stanol fatty acid esters according to the present invention, even higher amounts of phytosterols and phytostanols may be used in certain food products based on vegetable oil such as salad oils, cooking oils, dressings Easily emptied, sauces and mayonnaises. In addition, the sterol and / or stanol esters according to the present invention can be successfully used in the greased type of products such as margarines, low-fat spreads, cheeses, butter, etc. , whenever there is a desire to use the conventional triglyceride refill and not to use the obtainable texturing properties of sterol esters and / or stanol esters in the manufacture of such products. One reason for such a desire may be that the use of sterol and / or stanol esters according to the present invention is technically not so demanding, making it easier and feasible to produce such products with conventional production technology. Capsules with stanols and free sterols suspended in sunflower oil or mono-olein have been used as a means to lower high cholesterol levels. For example, Denke (Denke (1995) Am. J. Clin. Nutr. 61, 392-396) provided 4 capsules / free stanol meal suspended in sunflower oil to man with moderate hypercholesterolemia as part of a diet that decreases the cholesterol. The total daily intake of sitostanol was 3000 mg provided in 1 2 capsules. The sitostanol capsule regimen did not significantly reduce LDL cholesterol levels ^^ i-¡_- ^ ¿- ^^^ compared to diet alone. Due to the low solubility of free sitostanol in vegetable oils, the use of capsules containing free sitostanol suspended in sunflower oil does not ensure that sitostanol is distributed efficiently in the fat phase of food digestion. This problem can be overcome by using capsules based on esters of sterol and / or stanol according to the present invention, since these esters are liquid at body temperature and will easily dissolve in the fat phase of digestion of foods. In addition, it does not need triglyceride or mono-olein fat as a dispersing agent, making it possible to reduce the size or quantity of the capsules needed to supply the optimum daily amount of sterols and / or tinols. The present invention is based on the discovery of that the sterol and / or stanol fatty acid ester compositions, in which more than 50% of the fatty acid residues comprise polyunsaturated fatty acids (PUFA), preferentially more than 60% and more preferably more than 65%, and less than 7% comprises saturated fatty acids (SAFA), preferentially less of 5%, show basically no texturing property and can thus be used in food products where such a texturing effect is due to the quality of the product or the reason of undesirable production technology or is desired only to a very limited extent. The invention is also based on the fact that the £ ^^^^ g «jk _ * _ statin fatty acid esters based on rapeseed oil with a low content of saturated fatty acids and a high content of unsaturated fatty acids (mainly monosaturated) gives a melting curve DSC (Figure 1), wherein all the stanol fatty acid esters have co-crystallized. In this way, this mixture of fusions of stanol fatty acid esters at a different maximum melting value measured with differential scanning calorimetry (DSC) after a directed crystallization process. The DSC melting curve is obtained after fusing the sample (approximately 8 mg) at 75 ° C for 10 minutes, after which the sample is crystallized on cooling at 10 ° C / minute at -50 ° C, where it is kept for five minutes. The melting curve is obtained by heating at 1 0 ° C / minute at 70 ° C. Surprisingly, it was found that the stanol fatty acid esters in high vegetable PUFA oils show a very different DSC melting curve (Figure 2, stanol esters based on soybean fatty acids), where the stanol esters of acids Polyunsaturated fatty acids seem to merge (melting range from about -5 ° C to about 25 ° C) in a different temperature range, different from monosaturated and saturated stanol fatty acid esters Based on the behavior of the ester mixture of stanol fatty acid based on low erucic rapeseed oil, which shows only a maximum uniform melting value as measured by DSC, a behavior of melting and directed crystallization of stanol ester PUFA similar could be obtained, if the fatty acid composition of The stanol fatty acid esters are changed to significantly lower content of saturated fatty acids and to somehow increase the content of polyunsaturated fatty acids compared to natural elevated PUFA liquid vegetable oils. The high sterol and / or stanol PUFA esters can be produced, for example, by the method described in US Pat. No. 5,502,045 (Miettinen et al.) By direct esterification of esters of fatty acid alcohol obtained from elevated PUFA vegetable oils or their mixtures. Alternative methods of preferably catalytic, direct esterification or enzymatic esterification methods such as those summarized in EP-1 95 31 1 (Myojo et al.) Can be used alternatively. Sterol and / or stanol ester mixtures according to this invention can also be obtained by the method described in the EU Patent 5, 502.045 by direct esterification of a fatty acid alcohol ester having an appropriate fatty acid composition. In addition, in fact, the PUFA fraction of stanol esters in stanol ester mixtures based on vegetable oil PUFA raised in a different temperature range indicates that stanol esters based on high PUFA vegetable oils can be subjected to fractionation with object to obtain esters from stanol with reduced contents of saturated fatty acids and UTIÉÉiUHIUÉÉil increased contents of polyunsaturated fatty acids in the fatty acid part. It is obvious to persons skilled in the art that all fractionation processes of the prior art including 5 solvent, detergent, wet and dry fractionation processes or combinations thereof can be used to obtain the desired compositions. Due to the high viscosity of stanol esters, dry fractionation is not an optimal approach to achieve the desired results. For example, stanol fatty acid esters based on low erucic rapeseed oil show the following viscosity values at specific temperatures: 728 cP at 48 ° C, 80 cP at 100 ° C. The corresponding values for low erucic acid rape are 48.3 cP at 49.3 ° C and 8.4 cP at 100 ° C. The problem with the high viscosity can, however, be overcome by carrying out the fractionation step in a mixture of sterol ester and / or stanol ester and a vegetable oil or a mixture of vegetable oils. Preferably, the mixture of vegetable oil or vegetable oil used is that desired in the final food product. The vegetable oil remarkably reduces the viscosity of the sterol ester and / or stanol ester vegetable oil mixture, making fractionation feasible with any commercially available dry fractionation process of the prior art. Another possibility is to use the excess of high alcohol PUFA esters present in the oily phase obtained after ,, »,« _4jft? »,» R fr.Mtnrt '. - Y.? .. ..,. . .,. ».-. ^.-...,. . and ...... ^ ... ._. , -from the esterification of ester of sterol and / or stanol PUFA according to the method described in the patent of EU 5 502 045 (Miettinen et al.) This mixture of ester of sterol and / or stanol of alcohol ester High PUFA can as such be subjected to a fractionation step to remove higher sterol and / or stanol fusion esters. Saturation of a mixture of plant sterol to the corresponding plant stanol mixture causes marked differences in the melting properties of the corresponding sterol / stanol esters with the same fatty acid composition. For example, the sterol ester based on vegetable oil with low erucic rapeseed oil fatty acids and the corresponding stanol fatty acid ester showed the following amounts of solid fat contents (percent of total fat) at different temperatures as measured by the NMR technique: 1 0 ° C 20 ° C 30 ° C 35 ° C 40 ° C sterol 40.5 1 1, 6 3.5 1, 7 1, 1 stanol 82.3 70.2 34.9 9.4 5.2 Based on these data, it is obvious to persons skilled in the art that any mixture of fatty acid esters of sterol and / or stanol will show values of solid fat content in the intermediate range of the esters of sterol and stanol fatty acid with corresponding fatty acid compositions. The present invention also makes it possible to incorporate increased amounts of plant sterols, vegetable stems or their mixtures in specific foods, such as cooking oil and salad oil, easily emptied dressings, sauces and mayonnaises, wherein the sterol ester content and / or stanol based on high PUFA fatty acid compositions, ordinary would have to be reduced in order not to change the sensory and physical properties of the final product. It is evident from the data presented, that the present invention makes it easier to provide a suitable daily amount for the optimum efficacy of lowering the cholesterol of such specific products, without having to compromise the quality of the product. 10 Another area of potential use of sterol esters, stanol esters or their mixtures with a low fatty acid composition or high PUFA are capsules with esters of tin and / or sterol totally liquid at body temperature, which dissolve rapidly in the fat phase of the digestion of foods in the stomach. The use of sterol and / or stanol esters according to the present invention will overcome the above problems with capsules based on tin steels and / or free sterols suspended in vegetable oils or mono-olein. It is believed that the effect that decreases optimal cholesterol is achieved, if the sterols, stanols or their mixtures are efficiently dissolved in the fat phase of food digestion. It is assumed that sterols and steels need to dissolve in the fat phase of food digestion in order to have an efficient reductive effect on the absorption of cholesterol. In addition, cholesterol dietary responds for only about 1/3 of the amount The total cholesterol of total cholesterol entering the digestive tract daily. Bile cholesterol is the main source of intestinal cholesterol. In order to have an optimal cholesterol-lowering effect from the use of tin cans and plant sterols, they must be presented in the digestive tract each time the food intake causes the gallbladder to contract. Therefore, the use of stanol esters and fat-soluble sterol incorporated in regular food products seems to be an optimal choice for supplying sterols and / or steels. However, there are many occasions, where food products enriched with stanol and / or plant sterol are not available. Therefore, the use of capsules, for example, gelatin capsules or tablets would be another possible approach to supply the optimum daily dose in meals, making available at all times to the sterol / stanol regimen. A stanol or sterol fatty acid ester capsule with a fatty acid composition according to the present invention would be fully fused at body temperature and would dissolve rapidly in the fat phase of food digestion. The efficient dissolution of sterol and / or stanol esters according to the present invention will be ensured without the use of additional dissolution lipid materials, since the sterol and / or stanol esters according to the present invention will be liquid at body temperatures. In addition, no triglyceride or mono-olein fat is needed as a dispersing agent, making it possible to reduce the size or quantity of tiímimj ^^ m ^ t ^ m the capsules needed to supply the optimal amount needed daily of sterols and / or tin. Pure salad and cooking oils with much higher plant sterol contents (sterol equivalent) than those described in the prior art may preferably be produced by using sterol esters according to the present invention. The pure salad and cooking oils described in the prior art are based on the use of phytosterol esters based on individual saturated fatty acid residues with less than 1 2 carbon atoms or individual unsaturated fatty acids with up to 24 carbon atoms. The limited amount of saturated fatty acids contained in the sterol and / or stanol esters according to the present invention is mainly based on the saturated fatty acids naturally contained in the oil mixture. vegetable and vegetable oil PUFA high of origin, mainly saturated fatty acids with more than 14 carbon atoms. The sterol and / or stanol fatty acid esters according to the present invention can be used in low-fat products and in products for consumers who wish to eat only small amounts of foods that contain fat. The stanol esters according to the invention can also be used in an amount in some way increased compared to the prior art. Therefore, by using the fatty acid esters of sterol and / or stanol according to the present invention the daily dose necessary for effective decrease of cholesterol level can •? Ji¡¡j ^ ^ and ^ easily achieved. The compositions according to the invention also have the obvious positive effect from a nutritional point of view since the fatty acid composition in the food product is changed to a lower content of saturated fatty acids and a higher content of unsaturated fatty acids. . Based on the fact that the sterol and / or stanol part is not absorbed, also the amount of absorbable fat is reduced in the food product, since the sterol and / or stanol esters replace approximately an equal amount of normal triglyceride fat. . The use of stanol fatty acid esters defined as in claim 1 or 2, is the preferred way of practicing the present invention. The most commonly used tin solders include sitostanol and optionally campestanol. The term "PUFA vegetable oils high" in this specification is understood to be vegetable oils or mixtures of vegetable oils containing more than 50% of polyunsaturated fatty acids and at least 7% of saturated fatty acids of the fatty acid composition. Typically the elevated PUFA oils include sunflower oil, corn oil, soybean oil, safflower oil, cottonseed oil and mixtures thereof. The amount of saturated fatty acids in the fatty acid composition is about 7.5-49%, more typically 8-25% and more typically about 10-20%. Phytosterol in this specification is understood to mean 4-sterols of desmethyl, 4-sterols of monomethyl and 4,4-sterol of dimethyl (alcohols of triterpene) or their mixtures. The term "phytostanol" in this specification means 4-stanols of desmethyl, 4-stanols of monomethyl and 4,4-stanols of dimethyl preferably obtained by hydrogenation of the corresponding phytosterol. Typical desmethyl 4-sterols are sitosterol, campesterol, stigmasterol, brasicasterol, 22-dehydrobrasicasterol,? 5-avenasterol. The typical dimethyl 4-sterols are cycloartenol, 24-methylenecycloartanol and cyclobranol. Typical phytostanols are sitostanol, campestanol and its 24-epimers, cycloartanol and saturated forms obtained by the saturation of triterpene alcohols (cycloartenol, 24-methylenecycloartanol and cyclobranol). The terms phytosterols and phytostanols in this specification also means all the possible natural mixtures of desmethyl 4-sterol and stanols, 4-stanols and monomethyl stearols and mixtures of natural mixtures. By the terms phytosterol and phytostanol in this specification is further meant any individual 4-sterol of desmethyl, 4-sterol of monomethyl or 4,4-sterol of dimethyl or their corresponding saturated forms. The terms plant stanol and plant sterol are used in this specification as synonyms for phytosterol respectively phytostanol. Sterol and stanol should also mean phytosterol respectively phytostanol. The polyunsaturated fatty acids are defined herein as fatty acids containing 2 or more double bonds.

Preferably, the double bonds should have cis configuration, but one or more double bonds could be in trans configuration. It is known that many vegetable oils commercially available due to thermal isomerization in the deodorization process contain% levels of polyunsaturated fatty acids containing one or more double bonds with trans configuration. In addition, double bonds can be so-called either interrupted or conjugated methylene. Typical polyunsaturated fatty acids derived from vegetable oil are linoleic,? -leoleic and linoleic acid, but also polyunsaturated fatty acids from fish oils such as docosahexaenoic acid and eicosapentaenoic acid can be used. By the term "saturated fatty acids" is meant fatty acids with 4-24 carbon atoms that have no double bond, thus including both branched and straight chain fatty acids. By the term high sterol and / or stanol PUFA esters are understood esters of sterol and / or stanol produced preferentially with fatty acids of vegetable oils PUFA, but also polyunsaturated fatty acids derived from fish oil or mixtures of polyunsaturated fatty acids derived from fish or vegetable oil can be used. Sterol esters, stanol esters or their mixtures may preferably be produced by the method outlined in the U.S. Patent. 5 502 045 (Miettinen et al.) Which uses an ester of fatty acid alcohol with a specified fatty acid composition according to the present invention. Fatty acid alcohol esters can be produced by any process known in the art, such as fractionation of detergent or solvent of fatty acid esters of alcohol obtained from a high PUFA liquid vegetable oil or mixtures of elevated PUFA oils. The corresponding mixtures of fatty acid alcohol esters can also be obtained by distillation processes under reduced pressure. Such distillation processes can preferably be used to remove saturated fatty acids with 1 6 or fewer carbon atoms. Fatty acid alcohol esters with defined fatty acid compositions can also be obtained by alcoholysis of vegetable oils or oil blends with reduced contents of saturated fatty acids, obtained for example according to US Pat. U. 5 670 348 (William et al.). The sterol and / or stanol esters can also be produced by preferably catalytic, direct esterification methods between free fatty acids or fatty acid mixtures of said composition and the sterol and / or stanol. In addition, sterol and / or stanol esters can also be produced by enzymatic esterification, for example, as summarized in EP-1 95 31 1. In addition, mixtures of polyunsaturated fatty acids can be used to obtain sterol and / or stanol esters with the compositions defined.

• JA Stanol esters and / or sterol esters with defined fatty acid compositions can be further obtained by commercially available fractionation processes, such as wet, detergent and dry fractionation of stanol and / or sterol fatty acid esters obtained by esterification of high PUFA fatty acids derived from, for example, vegetable oil or oil mixtures by methods based on, for example, the transesterification process outlined in EU Patent 5 502 045, any preferably catalytic esterification process, direct or through the use of an enzymatic esterification process, for example, as summarized in EP 1 95 31 1. Especially, the solvent fraction can be used to prepare the desired ester and / or stanol ester compositions. When the esterification processes such as those summarized in EP 1 95 31 1 are used, the fractionation can be carried out directly in the reaction solvent used in the esterification process after removing the enzyme and possible water phase. In a preferred embodiment, vegetable oils containing desired sterol and / or stanol fatty acid esters can be obtained by dissolving 1-550% by weight (preferably 1-5%) of sterol fatty acid esters and / or stanol obtained by an esterification process such as that described in US Patent 5 502 045, by using a high PUFA vegetable oil or a mixture of elevated PUFA vegetable oils as a source for the fatty acids. The thus obtained mixture of vegetable oil of sterol esters and / or stanol is heated and mixed to completely dissolve the esters of sterol t / O stanol, after which the extraction of the stearin from the vegetable oil or any process is carried out. of fractionation of the prior art. For example, a dry fractionation process by loading / extraction of the stearin from the vegetable oil can be carried out at 5-20 ° C depending on the type of sterol ester and / or stanol ester. The solid part of the sterol or stanol ester is then removed, for example, by vacuum filtration and the liquid part containing sterol ester, stanol ester or mixtures thereof with the desired fatty acid composition according to the invention is subjected to to normal deodorization before being used in the manufacture of the final product or bottled for use as salad oil or cooking. It is obvious to those skilled in the art that any type of fractionation process in addition to the dry fractionation processes by loading or extracting the stearin from the vegetable oil can be used to crystallize or remove the sterol fatty acid esters and / or stanol with higher melting points, that is, the fatty acid esters of sterol and / or stanol based on mainly saturated fatty acids. In another preferred embodiment the stanol esters and / or the sterol esters with the desired fatty acid compositions can be further obtained by using the excess of methyl ester of fatty acid from the mixture of sterol ester and / or stanol high PUFA obtained after direct esterification described in U.S. Patent 5 502 045 (Miettinen et al.). After the drying step, the mixture of ester of fatty acid ester of sterol ester and / or stanol is cooled to 10-25 ° C, depending on the composition of the ester of stanol and / or sterol produced, and the Higher melting components are allowed to crystallize for 4-6 hours. Optionally, the additional fatty acid alcohol ester is added to facilitate the fractionation process. Any ester of fatty acid alcohol can be used, but the use of high PUFA alcohol ester is preferred. After filtration the pure oily phase is preferably deodorized to remove the excess alcohol fatty acid esters and to obtain an unflavored sterol and / or stanol ester. The sterol and / or stanol esters obtained as such can be preferably mixed in oil mixtures before the final deodorization step of the fat mixture to be used in the production of the final food product. Alternatively, the sterol ester and / or stanol can be deodorized as such and used as such, for example, in the production of capsules. In addition, the deodorized sterol and / or stanol esters according to the present invention can be dissolved in the vegetable oil or vegetable oil mixture to be used as such as, for example, cooking oil and salad or to be used in the production of specific foods , especially low-fat food products, dressings, mayonnaises, sauces or any food product containing fat, where a sterol ester and / or stanol is desirable -jtíi ^ É? áU? with or without texturing properties limited for reasons of production technology or product quality. In another embodiment, the oil may be added to the mixture ready before the fraction to facilitate the procedure. The vegetable oils containing desired sterol esters, stanol esters or mixtures thereof, can be further produced by carrying out the esterification in the oil mixture in a similar manner as described in GB 1 405 346 (Baltes et al. .). The fully interesirified oil obtained is subjected to a subsequent fractionation step such as stearin extraction step of the vegetable oil containing desired quantities of sterol esters, stanol esters or their mixtures. Alternatively, a replacement mixture of ester of sterol and / or stanol of esterified vegetable oil with a high content of sterol ester and / or stanol (20-80% by weight of sterol ester and / or stanol) can be produced by the same approach. The mixture of stanol ester and / or triglyceride sterol obtained can then be mixed in proportions necessary to obtain the desired content of sterol esters, stanol esters or mixtures thereof with the unesterified vegetable oil or vegetable oil mixture for use in the final product before the process extraction of the stearin from the vegetable oil or fractionation to remove mainly higher sterol esters and / or stanols from fusion with saturated fatty acids. In addition, the fractionation process can be carried out after the stage of -HlliñltimiirTlft-t & i t .r T. Wl. ? . . . - IM T , " . . -, and, - -. ^ .... y, yy *. -Ja. ' ".- ^ i. ^. Y. . ,,., "». .! «.. . i .. ..... ....... esterification, using excess fatty acid alcohol esters. Optionally, the fatty acid alcohol ester added is added to facilitate the fractionation process. In addition, the sterol ester and / or stanol ester compositions according to the invention can be produced using "fatty acid starting materials" such as fatty acids, alcohol esters of fatty acids or oils obtained by processes including, for example, using microorganisms, enzymes or new reproductions of plants that produce oil. The following Figures illustrate the invention: Figure 1: a DSC melting curve for stanol esters based on rapeseed fatty acids. Figure 2: a DSC melting curve for stanol esters based on soybean fatty acids. Figure 3: DSC fusion curves for stanol esters based on soybean fatty acids; the stanol esters fractionated to a fatty acid composition of 64.8% PUFA and 7.5% SAFA are compared to the DSC curve in Figure 2. Figure 4: DSC melting curves for stanol esters based on soybean fatty acids; the stanol esters fractionated to a fatty acid composition of 69% PUFA and 5.8% SAFA are compared to the DSC curve in Figure 2. The following examples are presented in order to describe the present invention in more detail.

Example 1 Preparation of stanol fatty acid esters based on fatty acids of soybean oil. 5 The stanol fatty acid esters were produced on a pilot scale, 6 kg of plant stanol (composition: 90% sitostanol, 8% campestanol, 1.5% sitosterol + trace amounts of other unsaturated sterols, obtained by hydrogenation of a sterol mixture of commercial resin oil 10 (Kaukaus Oy)) was dried for 6 hours at 60 ° C under vacuum to remove moisture. The dried stanol was mixed with 8.6 kg of methyl ester mixture of soybean oil and dried at 1100-20 ° C. The temperature of the dry mix was reduced to 90-95 ° C and the sodium ethylate catalyst (21 g) was added. The temperature was reduced to 1110 ° C and the reaction was carried out under vacuum (10-20 mmHg). The conversion was monitored by rapid HPLC analysis. Once the conversion is achieved >98%, the temperature was reduced to 100 ° C and 30% by weight of water or acidified water was added to destroy the catalyst. The water phase is removed and the oily phase is rinsed again with water. The oily phase was dried at 1 10 ° C and the dried material was bleached using 1% by weight of bleaching medium (Tonsil Optimum FF, Südchemie, Germany) for 20 minutes at 11 ° C. After the removal of the bleaching medium by filtration, deodorization was carried out at the standard pilot scale (deodorant of load, capacity 9 kg) to remove the excess of soybean oil. üHMiarittMHi- .... ...,. . ^^^. methyl esters and to obtain an unflavored stanol ester product.

EXAMPLE 2 Preparation of sterol fatty acid ester based on resin oil based on soybean fatty acids The fatty acid esters of sterol ester based on fatty acids derived from soybean oil were prepared by the same procedure as summarized in Example 1, except that the stanol was exchanged for an equivalent amount of commercial resin oil sterol mixture (Kaukas Oy).

Example 3 Preparation of sterol fatty acid ester based on vegetable oil with fatty acids derived from sunflower oil A mixture of sterol fatty acid ester with fatty acids derived from sunflower oil was prepared on a laboratory scale, 295 g of sterols based on vegetable oil (ADM: composition: 48.5% of sitosterol, 26.4% of campesterol, 1 5.2% of stigmasterol, 2.4% of brassicasterol, 2.7% of sitostanol, 0.9% of campestanol and 4.1% of others) was dissolved by heating and the use of vacuum in 424 g of methyl esters of sunflower in a 1 1 glass reactor equipped with a mechanical stirrer. The mixture was dried at 1 30 ° C and a vacuum of < 5 mmHg. The temperature of the dry mix was reduced to 97 ° C and 3.6 g of sodium ethylate were added. The reaction was carried out at 1 30 ° C under a final vacuum of < 5mmHg. After 4 hours, the temperature was reduced to 99 ° C and the oily mixture was rinsed twice with 30% by weight of water.The oily phase was stirred and dried at 1 1 2 ° C under vacuum (<5 mmHg) , after which the oily phase was bleached using 2% by weight of bleach medium (Trisyl silica) for 40 minutes at 1110 ° C under vacuum (<5 mmHg).

EXAMPLE 4 Preparation of a stanol fatty acid ester with a reduced content of saturated fatty acids and an increased content of polyunsaturated fatty acids with solvent fractionation 1 0 g of the stanol ester obtained by the procedure summarized in Example 1 were dissolved in 90 ml of n-hexane in a 200 ml centrifuge tube. The mixture was kept at 10 ° C for 1 9 hours, after which the mixture was centrifuged at a programmable centrifugal temperature. The hexane phase was removed and the hexane evaporated. The obtained stanol ester contained 64.8% polyunsaturated fatty acids (as compared to 58.4 in the initial stanol ester mixture) and 7.5% saturated fatty acids (as compared to 16.7 in the lower ester). initial stanol). The DSC melting curves obtained after a directed crystallization are shown in Figure 3. In another experiment the mixture of 10% stanol ester hexane was crystallized at 5 ° C for 19 hours. After evaporation of the hexane, the stanol ester obtained from the hexane phase contained 69% polyunsaturated fatty acids and 5.8% saturated fatty acids. The DSC melting curve obtained after a directed crystallization process is shown in Figure 5 as well as the curve for the initial stanol ester.

EXAMPLE 5 Preparation of soy stanol esters of stanol ester mixtures and vegetable oil (s) 10 Since the viscosity of stanol esters is high and limits the use of direct crystallization processes, a method by which the viscosity could be reduced. This method is based on dissolving the stanol ester in a vegetable oil or vegetable oil mixture before carrying out the step of fractionation. The vegetable oil or vegetable oil mixture is chosen based on the desired oil in the final food product. 25% by weight of stanol fatty acid ester produced according to the procedure summarized in Example 1 was dissolved in 75% by weight of sunflower oil. The mixture heated to about 70 ° C to dissolve the stanol fatty acid esters. The mixture was then cooled and kept at 9 ° C for 5 hours. The obtained solid phase was filtered and a pure sunflower oil with an equivalent stanol content of 1. 2.6% by weight corresponding to approximately 21% by weight of ester of stanol. The mixture of stanol ester of sunflower oil Mmái? É? it remained pure at 6 ° C for 48 hours. The stanol fatty acid ester in the sunflower oil obtained was analyzed for its fatty acid composition and found to contain 67.9% polyunsaturated fatty acids and 3.5% saturated fatty acids. It is obvious that any commercial dry fractionation process can be used to carry out the fractionation to obtain sterol ester and / or stanol ester compositions defined by this invention. Dry fractionation is made much more convenient by reducing the viscosity, by mixing the sterol ester and / or stanol with a vegetable oil or vegetable oil mixture. For different processes and different specific processing conditions of sterol ester and / or stanol can be found in order to obtain the desired sterol and / or stanol compositions.

Example 6 Preparation of stanol fatty acid esters with a reduced content of saturated fatty acids and an increased content of polyunsaturated fatty acids, by carrying out a fractionation process directly after the esterification step, using the alcohol ester excess of high PUFA oil fatty acid. The stanol fatty acid esters based on soybean oil were produced according to Example 1, except that the mixture of fatty acid methylester of soybean esterol ester oil obtained was subjected to a fractionation process directly after of the drying stage. The temperature was reduced to 20 ° C for 5 hours and the hard fraction was filtered by the use of vacuum filtration. The excess methyl esters of soybean fatty acid were removed during the final deodorization process to obtain an unflavored stanol ester.

Example 7 Preparation of stanol fatty acids with vegetable oil as a means of solubilization with a subsequent fractionation process. The stanol fatty acid esters were produced on a pilot scale, 3 kg of plant stanol (composition: 90% sitostanol, 8% campestanol, 1.5% sitosterol obtained by hydrogenation of a sterol mixture of resin oil commercial (Kaukaas Oy)) was dried for 6 hours at 60 ° C under vacuum to remove moisture. The dried stanol was mixed with 3 kg of soybean oil and 4.5 kg of methyl ester mixture of soybean oil and dried at 1100- 20 ° C. The temperature of the dry mixture was reduced to 90-95 ° C and the sodium ethylate catalyst (21 g) was added. The temperature was increased to 1 10 ° C and the reaction was carried out under vacuum. The conversion was monitored by rapid HPLC analysis. Once the conversion was achieved > 98% of stanols free to stanol esters, the temperature was reduced to 100 ° C and 30% by weight of water or acidified water was added to destroy the catalyst. The water phase was removed and the oily phase was rinsed again with water. The oily phase was dried at 10 ° C and the dried material was bleached using 1 wt.% Bleach medium (Tonsil Optimum, FF, Südchemie, Germany) for 20 minutes at 1 ° C. After removal of the bleach medium by filtration, the excess methyl esters of soybean oil fatty acid were removed and the stanol ester mixture of interesterified oil was lightly deodorized in a standard pilot scale deodorization (charge deodorant, capacity 9 kg). 40% by weight of the obtained mixture was then mixed with 60% by weight of sunflower oil and a fractionation step according to Example 4 was carried out. The liquid fraction obtained was deodorized to obtain a mixture of stanol ester. of vegetable oil with a stanol equivalent of 1.2 2% by weight.

Example 8 Direct preparation of stanol fatty acid esters with a Reduced content of saturated fatty acids and an increased content of polyunsaturated fatty acids The fatty acid esters of soybean oil were subjected to fractional distillation at 182 ° C and 10 mmHg to reduce mainly the amount of palmitic acid content. The ester Methyl of obtained fatty acid contained 67.2% polyunsaturated fatty acids and 4.8% saturated fatty acids. The stanol fatty acids were produced on a laboratory scale using 300 g of hydrogenated vegetable oil steels (composition: 67.3% sitostane, 30.3% campestanol (+ 24-cholestanol methyl), 1.5% sitosterol, 0.8% campesterol and 0.4% others), and y¡a ^^^^ m? j ^^^ u ^ ¡? ¿alUb ??? ? ßt¡¡a ^^ 322 g of methyl esters of distilled soybean fatty acid. The reaction was carried out in a 1.5 liter vitreous reactor equipped with a mechanical agitation device. The conditions used were the same as summarized in Example 1. Since no laboratory scale deodorization equipment was available, the obtained stanol esters were not completely purified. However, the fatty acid composition of the stanol ester was equal to the fatty acid composition of the methyl ester of soybean fatty acid in the esterification reaction. It is obvious that persons skilled in the art that the esters of sterol and / or stanol with fatty acid compositions specified in this invention can also be obtained by esterification with fatty alcohol esters with the specified fatty acid composition produced by any method of the prior art. Furthermore, it is obvious that the esters of sterol and / or stanol according to the invention can be obtained through any esterification process, such as preferably catalytic, direct esterification, transesterification or facilitated esterification of enzyme. It is also obvious that any mixture of sterol and stanol can be used in the preparation of sterol and / or stanol fatty acid compositions according to the present invention. Examples 4 to 7 clearly show that the elevated sterol and / or stanol PUFA esters can be processed to remove stanols and higher sterol ester esters to obtain the sterol and / or stanol compositions according to the present invention. The raised sterol and / or stanol PUFA esters can be produced based on fatty acids of any high PUFA vegetable oil such as soybean oil, sunflower oil, corn oil, safflower oil, cottonseed oil or mixtures thereof. It is obvious to persons skilled in the art that oils or fat mixtures with no such high content of polyunsaturated fatty acids (< 50%) can also be used as starting material for the fatty acid part to be contained in the sterol composition and / or stanol according to the invention. It is obvious to persons skilled in the art that any sterol or stanol composition or commercially available sterols mixtures or their corresponding stanols can be used as starting material to obtain sterol ester and / or stanol mixtures according to the present invention. Furthermore, it is obvious to persons skilled in the art that any natural mixture of plant sterols containing 4-sterols of desmethyl, 4-sterols of monomethyl and 4,4-sterols of dimethyl (alcohols of triterpene) or their corresponding saturated sterols (tin steels) ) or mixtures of sterols and tin cans can be used as an initial material for the preparation of sterol and stanol esters according to this invention. Such possible sources of plant sterol and triterpene alcohols are rice bran oil or oryzanol obtained from rice bran oil, sterols obtained from shea butter or flaxseed oil. - "- - ^ - ia ^^ t» ^^.-.-- <. - .. ^^ ... ^. ^. ^ .. ^. ".. ^^, .. ^^ _ ^. ^^. "^ .. J ..,. ....., _ ..... ..:. *, 1 k. ^.

Claims (37)

1. CLAIMS 1. A sterol and / or stanol fatty acid ester composition, characterized in that the fatty acid moiety comprises a mixture of less than 7% saturated fatty acids and more than 5 50% polyunsaturated fatty acids.
2. 2. The sterol and / or stanol fatty acid ester composition according to claim 1, characterized in that less than 5% of the fatty acid residues comprise saturated fatty acids.
3. 3. The sterol and / or stanol fatty acid ester composition according to claim 1 or 2, characterized in that more than 60%, preferably more than 65% of the fatty acid residues comprise polyunsaturated fatty acids.
4. 4. The fatty acid ester composition of sterol 15 and / or stanol according to claim 1, characterized in that the fatty acid part is a mixture of polyunsaturated fatty acids.
5. 5. The sterol and / or stanol fatty acid ester composition according to any of claims 1-4, characterized in that the fatty acid residues comprise acids 20 fatty acids containing 4-24 carbon atoms.
6. 6. The sterol and / or stanol fatty acid ester composition according to any of claims 1-5, characterized in that the stanol part comprises sitostanol and optionally campestanol. 25
7. 7. The composition of sterol fatty acid ester and / or stanol according to any of claims 1-5, characterized in that any mixture of sterol and stanol is used.
8. 8. The use of a sterol and / or stanol fatty acid ester composition, wherein less than 7% of the residues of 5 fatty acid comprises saturated fatty acids and more than 50% comprises polyunsaturated fatty acids, in food products.
9. The use according to claim 8, characterized in that less than 7% of the fatty acid residues comprise saturated fatty acids and more than 50% comprises fatty acids 10 polyunsaturated, in a mixture of fat or edible oil.
10. The use according to claim 8, characterized in that the food product is a low fat product. eleven .
11. The use according to any of claims 8-10, characterized in that the food product is an oil of 15 salad, a cooking oil, an easily emptied dressing, a sauce, mayonnaise, a spreadable food or butter.
12. 12. The use of a sterol and / or stanol fatty acid ester composition, characterized in that less than 7% of the fatty acid residues comprise saturated fatty acids and more 20 of 50% comprises polyunsaturated fatty acids, as an active ingredient in capsules to be used to decrease the absorption of cholesterol from the digestive tract.
13. The use according to any of claims 8-12, characterized in that the composition comprises a composition 25 of stanol fatty acid ester. nüHMiÉÜ ^ Üi
14. 14. The use according to any of claims 8-1 2, characterized in that the composition is defined as in claim 2.
15. The use according to any of claims 8-1 2, characterized in that any mixture of sterol and stanol is used.
16. 16. A mixture of edible fat or oil with high sterol and / or stanol content comprising a sterol and / or stanol fatty acid ester composition, characterized in that less than 7% of the fatty acid residues comprise saturated fatty acids and more than 50% comprises polyunsaturated fatty acids, and a vegetable oil, oil mixture or fat mixture.
17. 17. A method for preparing a sterol and / or stanol fatty acid ester composition, characterized in that less than 7% of the fatty acid residues comprise saturated fatty acids and more than 50% comprises polyunsaturated fatty acids, which comprises esterifying a mixture of fatty acid of said composition with stanol and / or free sterol by direct catalytic direct esterification or enzymatic esterification or esterifying an alcohol ester of fatty acid mixture of said composition with stanol and / or free sterol in the presence of an interesterification catalyst.
18. 18. A method for preparing a sterol and / or stanol fatty acid ester composition, characterized in that less than 7% of the fatty acid residues comprise saturated fatty acids and more than 50% comprises polyunsaturated fatty acids, characterized in that a high sterol and / or stanol PUFA ester is subjected to fractionation processes such as solvent fractionation , dry fractionation, or fractionation of detergent.
19. The method according to claim 1 8, characterized in that the elevated sterol and / or stanol PUFA ester is produced by esterifying a mixture of high polyunsaturated fatty acid with stanol and / or free sterol by direct catalytic direct esterification or enzymatic esterification or esterifying an ester of alcohol from a mixture of high polyunsaturated fatty acid with stanol and / or free sterol in the presence of an interesterification catalyst.
20. The method according to any of claims 1 - 7 - 9, characterized in that the polyunsaturated fatty acids are derived from elevated polyunsaturated vegetable oils or mixtures of elevated polyunsaturated vegetable oil.
21. The method according to any of claims 1 7-19, characterized in that the polyunsaturated fatty acids are derived from fish oil or a mixture of vegetable oil or oils and fish oil.
22. 22. A method for preparing a mixture of edible fat or oil with high sterol and / or stanol content comprising liquid vegetable oil and a sterol and / or stanol fatty acid ester composition, characterized in that less than 7% of the fatty acid residues comprises saturated fatty acids and more than 50% comprises polyunsaturated fatty acids, wherein the esters of sterol and / or stanol are fractionated from a sterol ester and / or stanol elevated PUFA and a mixture of oil or oil plant to remove sterol esters and / or higher fusion stanol.
23. 23. A method for preparing a sterol and / or stanol fatty acid ester composition, characterized in that less than 7% of the fatty acid residues comprise saturated fatty acids and more than 50% comprises polyunsaturated fatty acids, comprising a) esterify a sterol and / or stanol with an excessive amount of high alcohol ester PUFA in the presence of an interesterification catalyst and b) fractionate the fatty acid ester of sterol and / or stanol in the high PUFA alcohol ester to obtain the composition of defined fatty acid ester.
24. The method according to claim 23, characterized in that the fractionation is facilitated by adding fatty acid alcohol ester, preferably the same high PUFA alcohol ester as used in the esterification, after the esterification step.
25. 25. The method according to claim 23 or 24, which includes a further step of rinsing, drying and optionally bleaching the sterol and / or stanol fatty acid ester and elevated PUFA alcohol ester mixture prior to the fractionation process.
26. 26. The method according to any of claims 23-25, which includes a further step of removing the unreacted elevated PUFA alcohol ester from the fractional mixture, preferably by deodorization.
27. 27. A method for preparing a mixture of edible fat or oil with high sterol and / or stanol content, comprising a sterol and / or stanol fatty acid ester composition, characterized in that at least 7% of the acid residues fatty acid comprises saturated fatty acids and more than 50% comprises polyunsaturated fatty acids, comprising a) esterifying a sterol and / or stanol with an excessive amount of elevated PUFA alcohol ester in the presence of an interesterification catalyst and b) fractionating the ester of Sterol and / or stanol fatty acid in the elevated PUFA alcohol ester to obtain the defined fatty acid ester composition. c) mixing the fatty acid ester of sterol and / or stanol with a vegetable oil or fat mixture.
28. 28. The method according to claim 27, characterized in that step c is carried out before step b.
29. 29. The method according to any of claim 27 or 28, which includes a further step of rinsing, drying and optionally bleaching the sterol and / or stanol fatty acid ester and elevated PUFA alcohol ester mixture before the HM UlUflkíat. fractionation procedure.
30. The method according to any of claims 27-29, which includes an additional step of removing the unreacted elevated PUFA alcohol ester from the fractional mixture, 5 preferably by deodorization.
31. 31 The method according to any of claims 27-30, which includes an additional step of deodorizing the mixture before step c.
32. 32. A method for preparing a mixture of fat or edible oil with high sterol and / or stanol content, comprising a sterol and / or stanol fatty acid ester composition, characterized in that at least 7% of the residues of fatty acid comprises saturated fatty acids and more than 50% comprises polyunsaturated fatty acids, comprising 15 a) interesterifying a sterol and / or stanol and an edible oil with an excessive amount of elevated PUFA alcohol ester in the presence of an interesterification catalyst and b) fractionating the fatty acid ester of sterol and / or stanol to obtain the composition.
33. 33. The method according to claim 32, which includes a further step before the fractionation process comprising rinsing, drying and optionally bleaching and / or deodorizing to obtain a refined, bleached and deodorized blend of interesterified oil and fatty acid ester of Sterol and / or stanol.
34. 34. The method according to claim 32 or 33, characterized in that the edible fat or oil is added to the mixture after the step a or after the refining steps.
35. 35. The method according to any of claims 5 32-34, with a final additional step including deodorizing the edible fat or oil mixture.
36. 36. The method according to any of claims 1 7-35, characterized in that the composition defined according to claim 1 or 2 comprises an acid ester composition. 10 fatty of stanol.
37. 37. The method according to any of claims 1 7-35, characterized in that the composition is defined as in claim 2. tffiüiittáiíia É ^ iiÍMÉÉ ^