JPS63312398A - Production of fat and oil - Google Patents

Abstract

PURPOSE:To obtain a novel stable fat and oil, utilizable in the field of medicines and foods and having excellent digestibility and absorbability, by subjecting a glyceride and fatty acid, etc., to ester interchange reaction and fractionating the resultant reaction product by reversed phase type partition column chromatography. CONSTITUTION:A glyceride and another glyceride or a fatty acid (ester) are subjected to ester interchange reaction in the presence of a catalyst having specificity for the 1,3-positions and, as necessary, the resultant reaction product is treated with a hydrous solvent to remove free fatty acids and/or partial glycerides. The ester interchange reaction product of hydrous treated substance thereof is fractionated by reversed phase partition chromatography to afford the aimed fat and oil having 2-16C fatty acid residue in the 1,3-positions of the glyceride and >=8C fatty acid residue having a larger number of carbon atoms. in the 2-position than that in the 1,3-positions.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of industrial application of Tal The present invention is directed to a novel glyceride in which the chain length of the fatty acid residue at the 2nd position is larger than that of the fatty acid residue at the 1st or 3rd position. Concerning a method for producing special structured fats and oils. The special structure oil and fat obtained by the present invention is used in the pharmaceutical field, food field, etc.

(bl Conventional Technology) Oils and fats used in various industries, including food and medicine, are mainly isolated and purified from the tissues of animals and plants, and the composition of their glycerides consists of various fatty acids. It is a randomly distributed mixture.On the other hand, vegetable oils such as soybean oil, rapeseed oil, and safflower oil contain a lot of linoleic acid, an essential fatty acid, and animal oils such as beef tallow and fish oil contain It has the characteristics of containing short chain and highly unsaturated fatty acids of C16 or higher (EPA: eicosapen citric acid, DHA: nidocosahexaenoic acid, etc.).In particular, linoleic acid has a serum cholesterol lowering effect, and EPA and DHA In recent years, it has been emphasized that the intake of these long-chain polyunsaturated fatty acids is important for maintaining health because they inhibit platelet aggregation, lower serum cholesterol, and prevent cerebral thrombosis. Increasingly, safflower oil and fish oil refined products are used in various foods, but the digestibility of these fatty acid-rich oils and fats is not very good.Especially in cases where the digestive function of the sick and elderly is impaired. Digestive and absorption problems become even more serious for people who have a weakened body.

On the other hand, for such long-chain fatty acids, the number of carbon atoms is 8 to 1.
It is known that fats and oils consisting of relatively short fatty acids of about 2, ie, medium-chain fatty acid glycerides (MCT), are absorbed very quickly and are easily metabolized, and are used as a lipid source for liquid foods.

However, MCT often causes side effects such as gastrointestinal complaints (diarrhea, etc.) due to its rapid absorption and metabolism, and the production of ketone bodies when ingested in large amounts. Because it is difficult to use MCT extensively as an energy source,
It has been proposed to use MCT and LCT (long chain fatty acid triglyceride) together, that is, a mixture of both, or a random transesterification product of both, but these methods are still insufficient in terms of digestibility and absorption. Ta.

In addition, the long-chain highly unsaturated fatty acids mentioned above are easily oxidized, degraded, and modified, and no satisfactory product has been obtained from mere mixtures with other fats and oils or from random ester exchange products.

On the other hand, a method using 1.3-specific lipase is known as a means of transesterification. For example, glyceride and fatty acid are usually mixed in the coexistence of an organic solvent such as hexane, and the enzyme expresses the function. Lipase to which a small amount of water has been added for the purpose of hydration is allowed to coexist, and the lipase is left standing or stirred for several hours to several tens of hours, or the lipase is brought into contact with immobilized lipase adsorbed or bonded to a support carrier.

Through such a reaction, the fatty acid residues of one raw material, glyceride, are substituted with the free fatty acid residues of the other raw material, and a transesterification reaction product is obtained, but the reaction product is actually unreacted products, 1st or 3rd place exchanged products of glycerides, 1st and 2nd place exchanged products, 2nd and 3rd place exchanged products, 1st and 2nd and 3rd place exchanged products in addition to the 1st and 3rd place exchanged products,
Furthermore, it contains diglycerides and monoglycerides that are presumed to be hydrolysates, and since the transesterification reaction is an equilibrium reaction, it has a complex mixture composition in which the free fatty acids of the raw material and the free fatty acids produced by the transesterification coexist. Become a thing. From such a composition, Glylide 1 and 3
Conventionally, methods for isolating only position-exchanged products include removing free fatty acids and partial glycerides using alkali washing, distillation, ion exchange resin treatment, silica gel column chromatography, etc., and then measuring the melting point of the glyceride. The desired glyceride was obtained by solvent or solvent-free fractionation that took advantage of the differences in physical properties.

However, in conventional alkaline cleaning methods, there is a large loss of target components due to emulsification phenomenon during operation, and in steam distillation and molecular distillation, due to the heat history caused by the processing, when using short-chain to medium-chain fatty acids, A major drawback is that thermal transfer of fatty acid groups occurs between glycerides or between glycerides and free fatty acids coexisting with the glycerides, and it is difficult to obtain components that are specific to the position of the glyceride, especially in the case of 1- and 3-position transesterification products. In ion exchange resin treatment, a similar phenomenon occurs due to pH fluctuations during operation, and in column chromatography such as silica gel, large amounts of complex mixed solvents must be used, and large amounts of free fatty acids coexist. In some cases, it has various disadvantages such as a limited amount of processing and an unavoidable increase in cost. In addition, in the fractionation of glyceride composition, methods that use or do not use solvents mainly utilize the difference in melting point of each component, but when two or more components coexist, the melting point decreases between them. In conjunction with the mixing ratio of each component, temperature control for separation requires extremely delicate operation methods, and it is difficult to obtain highly pure target components with a single operation, so the equipment and equipment must be large. When considering industrial use, which is unavoidable, it has an extremely large drawback.

(C1 Problems to be Solved by the Invention The purpose of the present invention is to solve the problem of conventional fats and oils in the production of a novel special structure of fats and oils that can be used in the pharmaceutical and food fields, have good stability, and are extremely digestible and absorbable. The object of the present invention is to provide a new manufacturing method that solves the drawbacks and insufficient effects.

A means for solving the fd1 problem, that is, the present invention, is that the fatty acid residue at the 1.3-position of the glyceride has 2 to 16 carbon atoms, the fatty acid residue at the 2-position has 8 or more carbon atoms, and The number of carbon atoms in the fatty acid residue at position is 1.3
In the production of fats and oils having a carbon number larger than the number of carbon atoms in the fatty acid residue at position 1, it is necessary to: Accordingly, free fatty acids and/or partial glycerides are removed by treating the transesterified product with a water-containing solvent, and ■ the transesterified product or its water-containing solvent-treated product is subjected to reversed-phase distribution column chromatography. The present invention relates to a method for producing the oil and fat, which comprises fractionation.

In the present invention, the fatty acids at the 1st and 3rd positions must have a residue of 2 to 16 carbon atoms, and the fatty acid at the 2nd position must have a residue of 8 or more carbon atoms. The fatty acids may be either saturated or unsaturated, and may include geometric isomers, side chain isomers, and the like. Furthermore, the present invention is not affected by fatty acids having an even or odd number of carbon atoms. Examples of these fatty acids are acetic acid, butyric acid, caproic acid, caprylic acid, 2-nif-)L
iHexanoic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid, α-lylunic acid (18:3. ω)
3. all-cisΔ9+ 12+ I5), γ-lylunic acid (18:3.ω6.all-cisA6-+9+
+2), 7'-lylunic acid (18:3.ω6.al
l-cisΔ5°9+12), behenic acid, erucic acid,
Arachidonic acid, eicosapencitric acid, docosahexaenoic acid, etc. can be used. Various types of these fatty acids can be used individually or in combination as appropriate depending on the properties, physiology, or nutritional effects of the target oil or fat, but 1. ° It is desirable to have a saturated fatty acid in the 3rd position and an unsaturated fatty acid in the 2nd position.

Furthermore, in the glyceride according to the present invention, it is specified that among the fatty acids bonded to each position of the glyceride, the number of carbon atoms in the fatty acid residue at the 2nd position is larger than that at the 1st or 3rd position. This can be produced by the method described below by appropriately selecting the various fatty acids mentioned above. Yellowtail-2-Oreo-3-
Examples include laurin, 1,3-cicapro 2-eicosapene citrate glyceride, and the like.

One of the features of producing such special structured fats and oils is that glyceride and glyceride or fatty acid or fatty acid ester are subjected to a transesterification reaction in the presence of a catalyst having specificity for the 1.3-position.

The glyceride to be used as a raw material may be either a synthetic product or a natural product. For example, monoacid group and/or mixed acid group glycerides of the various fatty acids mentioned above can be used, and soybean oil, rapeseed oil, sesame oil, safflower oil, and sunflower oil can be used. Vegetable fats and oils such as , corn oil and palm oil, and animal fats and oils such as beef tallow, lard and fish oil can be used. Note that these glycerides may contain partial glycerides such as diglyceride.Furthermore, at least 50% or more of the fatty acids at the 2nd position of at least one of the glycerides used as the raw material of the present invention are of the same type. Examples of these include synthetic products such as the aforementioned monoacid group and mixed acid group glycerides, natural products such as oleic safflower oil, oleic sunflower oil, tea oil, etc., and the aforementioned fractionation of animal and vegetable oils and fats. Based on the type of fatty acid to be used as a raw material and the above-mentioned examples, select a fatty acid with a chain length and degree of unsaturation appropriate to the glyceride composition of the target special structured oil and fat. can do.

In addition, the fatty acid ester to be used as a raw material is monovalent and/or divalent lower alcohol ester of any of the above-mentioned fatty acids, that is, each monoalcohol ester of the fatty acid such as methyl, ethyl, propyl, isopropyl, butyl, or ethylene glycol, Propylene glycol, 1.3-
Diol esters such as butanediol can be used. For the interglyceride reaction of such raw materials, glyceride and glyceride or fatty acid or fatty acid ester, and the reaction of glyceride and fatty acid diester, 1 mol: 1 to 5 mol, preferably 1 mol: 2 to 3 mol, glyceride and fatty acid. Alternatively, in the case of reaction with fatty acid monoester, the raw materials are mixed at a ratio of 1 mol:2 to 7 mol, preferably 1 mol:3 to 5 mol. If the mixing ratio of the raw materials is outside this range, the reaction may not proceed sufficiently, or the reaction may proceed too much, resulting in a large amount of 2-position exchanger being produced as a by-product, which is not preferable. After saturating this with water at a predetermined temperature necessary for the transesterification reaction, a catalyst with specificity at the 1.3 position is added,
Stirring or bringing the catalyst into contact with an immobilized catalyst immobilized on a fixed support that does not substantially participate in the transesterification reaction (for example, by continuously passing the raw material through a column packed with the immobilized catalyst) , the ester group reaction is carried out in the presence of a solvent or in the absence of a solvent. Here, LIPOZYME (NOVO
Commercial products such as Talipase (manufactured by Tanabe Seiyaku), Lipase (manufactured by Seikagaku Corporation), Lipase D, Lipase F-AP, Lipase M, Lipase AP, Lipase R, Neurase (manufactured by Amano Pharmaceutical), etc. products can be used.

Another feature of the present invention is a means for efficiently removing free fatty acids and/or partial glycerides from a mixed component, which is a reaction product obtained by such a reaction, by washing the reaction product with a water-containing solvent. It is something to do. That is, a water-containing solvent having a water content of 5 to 95%, preferably 10 to 80%, more preferably 10 to 70% is added 0.5 to 20 times by weight, preferably in an amount of 2 to 5 N, based on the transesterification reaction product. By adding twice as much, stirring, leaving to stand at -10 to 60°C, preferably 0 to 10°C, and separating the layers by decantation,
Free fatty acids and/or partial glycerides can be removed to a remarkable degree, there is little loss of triglycerides, there is no coloration due to heat treatment, no rearrangement of fatty acids in glycerides, especially short-chain to medium-chain fatty acids, as well as long-chain fatty acids. There is a big advantage. The types of solvents that can be used as the water-containing solvent are not particularly limited as long as they can be uniformly mixed and dissolved in water, but linear alcohols with 8 or less carbon atoms, i.e., methanol, ethanol, propatool, butanol, hexanol , octatool, etc. are preferred.

Note that this means can be adopted as necessary.

-13~ Still another feature of the present invention is a means for fractionating the target glyceride from the triglyceride composition purified by the water-containing solvent treatment or the transesterification product itself, and is a reversed-phase type. It is fractionated using partition column chromatography. As the resin to fill the column, silica gel-based adsorbents in which silanol groups (SiOH) are chemically modified with octadecyl or octyl groups can be used. Commercially available products such as ring addition-reacted silica gel (manufactured by Ise Kagaku ■) can be used, but ODS is practically preferred.

As the eluent, various solvents such as acrylonitrile, water, methanol, and ethanol can be used alone or as a mixed solvent of two or more, but ethanol/acetone-971-1'/9 (v/v), preferably ethanol It is economical to use a mixed solvent of /acetone-971 to 6/4 (v/v). The glyceride component fractionated by this column treatment is extremely pale in color and can be increased in purity up to 100%, but the purity can be adjusted as appropriate depending on the intended use.

It was found that the special structured fats and oils obtained by the present invention have extremely superior oxidative stability compared to mixed glycerides having the same proportion of fatty acid groups, random transesterification products, etc. (see Table 1). ).

=15~ The fat and oil of the present invention is particularly suitable as a fat and oil component for fat emulsion infusions and enteral nutrients, and is also useful as a fat and oil component for other bases of suppositories.

Furthermore, since the fats and oils of the present invention are normally liquid at room temperature, they can be used in dressings, mayonnaise, or as fats and oils components in liquid therapeutic foods.

Furthermore, the fats and oils of the present invention can also be used as fats and oils added to feed for fisheries and livestock. That is, mammals and fish generally have weak digestive, absorption, and metabolic abilities during their childhood, and if appropriate fats and oils are not administered, problems such as diarrhea may occur.

Therefore, it is effective to use the glyceride of the present invention in such cases as well.

tel Examples Example 1 Mixed fatty acids obtained by saponification and decomposition of safflower oil were treated with urea and methanol adduct method, and further distilled to obtain high purity linoleic acid (GLC purity: 99.2%) . Mix this with glycerin, esterify, deacidify, and
Linoleic acid triglyceride was obtained by decolorizing and deodorizing the ends.

3 moles of capric acid (manufactured by Henkel; GLC purity 99.5%) are mixed with 1 mole of this linoleic acid triglyceride, saturated with water at 40°C, and 1 Qwt relative to the raw material is mixed.
% of lipase (Talipase, manufactured by Tanabe Seiyaku ■) was added and stirred at 40 to 45°C for 10 hours. After the reaction, enzyme proteins and the like were removed by heating and filtration to obtain a crude transesterification reaction product (acid value = 76).

Next, 4 times the weight of an ethanol solution with a water content of 20% was added to the reaction product, and after stirring, the mixture was allowed to stand at 5°C, and then the oil layer was separated. The acid value of this water-containing ethanol-washed product was 0.5.

Furthermore, the ethanol-washed product was washed with octadecasilane (ODS).
; Yamamura Chemical Research Disruption YMC-ODS.

Ethanol/acetone-9/1 (v/v) as eluent in a column packed with 60A 30/210 μm)
The liquid is passed through the liquid, separated into each fraction, and 1,3-cicabro-2-riruin (
10・shi・10) was obtained. The composition of this oil and fat is shown below.
Shown in 3.

Table-3 Composition of special structure oil (10・L・10) L:
Linoleic acid Example 2 Oleic safflower oil (oleic acid content in total fatty acids: 6.0%, oleic acid content in 2-position fatty acids: 80.5%)
) and 2 moles of medium-chain triglyceride (a random ester of caprylic acid/capric acid - 75/25) were mixed, saturated with water at 60 to 65°C, and used as a raw material for transesterification reaction. On the other hand, inner diameter 5cm and length 50
Immobilized lipase (LIPOZYME manufactured by NOVO) was filled in a stainless steel circular tube of 5 cm in size, and the above raw materials were added to the tube for 5 Q.
The transesterification reaction was carried out by passing the mixture at a flow rate of 127 m.

The reactant has an acid value of 6.5, a hydroxyl value of 9.7, and an ester group exchanged at the 1.3 position in all glycerides, that is, 1,3-cicaprylo-2-olein (8.0.8), ■, 3 - Content of cicapro-2-olein (10.0.10) and 1-caprylo-2-osireo-3-caprin (8.0.10): 38.4%.

Next, 2 times the weight of an isopropanol solution with a water content of 40% was added to the reactant, and after stirring, the mixture was left to stand at 5°C to separate the oil layer. The acid value of the product washed with this water-containing solvent was 0.1.

Further, the washed product was fractionated by ODS column chromatography in the same manner as in Example 1, and the target novel special structure oils and fats were 8.0.8.10.0.1o and 8.0.10.
I got it. The composition of this oil and fat is shown in Table 4.

21 Example 3 Glycolipids (mono- and/or digalactosyl diglycerides) containing a high amount of eicosapencitric acid were obtained from cultured cells of marine chlorella (C, minutissima), and the sugar chains were acid-decomposed using a conventional method. The fatty acid is 12:O(1,
3%), 14:0 (8.5%), 16:0 (1.8%)
, 16:H3,0%) 18:O(1,3%), 18:
Hl, 3%), 18:2 (1,5%).

20:4 (4,1%), 20:5 (77,3
A diglyceride containing eicosapene citric acid as the main component was isolated.

5 moles of caprylic acid (manufactured by Henkel, GLC purity 99.7%) was mixed with 1 mole of this diglyceride, and treated in the same manner as in Example 2 to obtain an ester group exchange reaction product (acid value:
121 hydroxyl value: 13.4. 1.3 of total glycerides
-Cicaprilo 2-eicosapene citrate triglyceride content: 41.3%).

Next, an ethanol solution with a water content of 65% was added to the reaction product in an amount of 5 times its weight, and the same treatment as in Example 2 was performed to separate the oil layer. Acid value of this washed product: 0.2. Hydroxyl value: 3.0
Met.

Further, the washed product was fractionated by ODS Color 2 Norm chromatography in the same manner as in Example 1 to obtain the desired novel special structure fat 8.E.8. The composition of this oil and fat is shown in Table-5.

Example 4 Linoleic acid triglyceride (GLC purity: 99.5%
), acetic acid, and Lipase R (manufactured by Amano Seiyaku ■) to obtain an ester group exchange reaction product in the same manner as in Example 1. After deoxidizing using an ethanol solution with a water content of 70%, the glyceride component was removed by ODS column chromatography. Fractionate and target new special structured fats and oils 1,3-diaceto2-lyluine (2・L・
2) was obtained. The composition of this oil and fat is shown in Table-6.

Table 6 Composition of special structure oil (2・L・2) (f1 Effect of the invention According to the method of the present invention, the fatty acid at the 2-position of glyceride contains almost no component resulting from the transesterification reaction, and almost completely Oils and fats with a special structure with excellent antioxidation properties consisting only of the 1.3-position ester group-exchanged product can be obtained.Also, by simply washing the ester group-exchanged product with a water-containing solvent, coexisting free fatty acids and partial glycerides can be removed. In addition, other glyceride components can be almost completely separated using reversed-phase distribution column chromatography, and the target oil and fat with a special structure can be purified to a high degree of purity.

Patent Applicant Nisshin Oil Co., Ltd. Procedural Amendment Document 1986-7 JB1 Day 1, Indication of the Case 1988 Patent Application No. 149693 2, Name of the Invention Process for Manufacturing Oils and Fats 3, Person Making the Amendment Relationship to the Case Patent Application Address: 23-1 Shinkawa-chome, Chuo-ku, Tokyo For inquiries regarding this matter, please contact the address below.

Postal code 221 Address 6, Kanayou-ku, Yokohama City, Kanagawa Prefecture Name Nisshin Oil Co., Ltd. Research Lightning 2nd Engineer nAFI (A 61)l'l"l!
4. Subject of amendment (1) Detailed explanation of the invention in the specification column 5, Contents of amendment (11. On page 5, line 5 of the specification, "immobilized lipase" is corrected to "immobilized lipase."

(2) On page 5, line 6, "glyceride" is corrected to "glyceride."

(3) On page 11, line 4 from the bottom, ``For reactions'' should be corrected to read ``For one reaction.''

(4) In the sample name column of N004 in Table 1 on page 16, “Medium chain triglyceride (caprylic acid/capric acid-75/2
Random esters of mixed fatty acids of
Random esterified product of mixed fatty acids of 5/25)" is corrected.

Claims (5)

[Claims] (1) The number of carbon atoms in the fatty acid residues at positions 1 and 3 of glyceride is 2.
- 16, the number of carbon atoms in the fatty acid residue at the 2nd position is 8 or more, and the number of carbon atoms in the fatty acid residue at the 2nd position is larger than the number of carbon atoms in the fatty acid residues at the 1st and 3rd positions. [1]
Performing a transesterification reaction between glyceride and glyceride, fatty acid, or fatty acid ester in the presence of a catalyst having 1- and 3-position specificity, [2] Treating the transesterified product with a water-containing solvent as necessary. and [3] fractionating the transesterification reaction product or its water-containing solvent-treated product by reverse-phase distribution column chromatography. (2) The production method according to claim 1, wherein 50% or more of the fatty acids at position 2 of the glyceride are the same fatty acid. (3) The production method according to claim 1, wherein the catalyst having 1- and 3-position specificity is a lipase. (4) The production method according to claim 1, wherein the water-containing solvent is a linear alcohol having 8 or less carbon atoms and a water content of 10 to 80%. (5) The production method according to claim 1, wherein the reversed-phase distribution column chromatography uses octadecylsilylated silica gel.