JPH0975000A - Food or drink containing oil and fat for nourishing mother and child - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a food or drink containing oil and fat, useful for nourishing mother and child and effective for easily accumulating docosahexaenoic acid in the body by taking a small amount of the food or drink compared with a food, etc., compounded with the same amount of a conventional docosahexaenoic acid source. SOLUTION: The mixed triglyceride to be used as an active component of the objective food or drink for pregnant or nursing woman, dairy product for baby and infant such as a prepared milk powder for baby and a follow-up milk, a weaning food, a food or drink for infant, etc., contains a docosahexaenoic acid residue bonded to the 2-site of a triglyceride in an amount of <40mol% based on the total amount of docosahexaenoic acid residue present in the triglyceride and further contains 1-site and 3-site fatty acid residues distributing regularly or randomly between these sites.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to foods and drinks containing fats and oils for nutrition of mothers and children in which docosahexaenoic acid has high organ accumulation.

[0002]

2. Description of the Related Art Nutritional supplementation or fortification (hereinafter simply referred to as "mother and child nutrition") for mothers and infants is to provide breast milk or infant formula to the infants during pregnancy and after birth, which supplies necessary nutritional components from the mother to the fetus. It is intended for feeding during the lactation period in which necessary nutritional components are supplied via feeding, and for nutritional supplementation from the weaning period to the infant period.

Pregnant and lactating mothers need to take more nutrients than usual. In addition, the composition of breast milk, which is a nutritional source for infants, changes depending on the dietary content of the mother, and it is said that fatty acids and vitamins are particularly susceptible (Ayoku Yonekubo, “Science of Food”, Volume 201, 49th
P., 1994). Therefore, as special-purpose foods, powdered milk for pregnant women and nursing women to which vitamins, lipids, etc. have been added is commercially available.

The only food product that can be substituted if there is a shortage of milk or if breast milk cannot be given for some reason is infant formula (classified as infant formula among special nutrition foods). Various researches and developments have been carried out and various products have been put on the market in order to bring the degree of growth and development of infants fed with this formula to the level of breastfeeding as much as possible. In addition, lactose-free and hypoallergenic milk powder for special treatment are commercially available for infants who do not receive normal infant formula.

If an infant continues to ingest only breast milk or artificial milk for a long period of time, anemia will occur, skin tension will decrease, and resistance to illness will also decrease. Therefore, at the age of a certain month, weaning will occur. In the case of humans, the start of weaning is about 5 months, and foods that are easily cooked according to the progress of weaning are used. Commercially available baby foods are called "baby foods" and include dry types such as powder, granules and flakes, and wet types such as bottled, retort foods and concentrated fruit juices. Follow-up milk is a dairy product prepared for the purpose of nutritional support from weaning to early childhood.

[0006] Studies have also been conducted on the intake of lipids in mother-infant nutrition, particularly the intake of docosahexaenoic acid and its action. It is possible to take an appropriate amount of docosahexaenoic acid for the proper development of the fetus and the infant during pregnancy and lactation. It is considered desirable (supervised by the Health Promotion and Nutrition Division, Health and Medical Bureau, Ministry of Health and Welfare, "Fifth revised Japanese nutritional requirements", 1994.
Year).

Generally, among fatty acids accumulated in the body, n-3 long-chain polyunsaturated fatty acids are used in nerve-related tissues such as cerebral cortex synaptic membrane of animal brain and photoreceptor membrane of retina.
It is widely distributed in the form of phospholipids. Most of these n-3 long-chain polyunsaturated fatty acids are docosahexaenoic acid (total cis-4, 7, 10, 13, 16, 19-do).
cosahexaenoic acid, C _{22: 6} , where the number after C indicates the total number of carbons: the number of double bonds and the same shall apply hereinafter. ), And
Since the content of docosahexaenoic acid in various cerebral brains and retinas of mammals is almost constant irrespective of diet, it is presumed that there is a relationship with the brain and nervous system.

[0008] In an experiment using rats, docosahexaenoic acid was supplied from the mother rat via the placenta during the fetal period when biosynthesis is low and from milk after birth, and docosahexaenoic acid production capacity in vivo is sufficient. It has been suggested that it becomes supplied from the liver at about 7 weeks of age.
Among them, it has been recognized that a group that continuously ingests docosahexaenoic acid through the placenta during the fetal period, after birth, and from the diet after weaning has significantly superior learning ability. (Akito Yonekubo, “Fisheries lipids-its properties and physiological activity”, Seiseisha Koseikaku, page 123, 1993.
Year).

The content of docosahexaenoic acid in Japanese breast milk is about 0.63 to about 1.0% by weight.
~ 3 times higher value. Jensen et al. Changed the fatty acid composition of North American breast milk depending on the type and amount of fat in the diet. For example, when 6 mg of fish oil a day was consumed for 21 days, the content of docosahexaenoic acid in breast milk was 0.37% by weight. It has been reported to increase to 0.70% by weight (RGJe
nsen et al., J. Pediatr., 120, S87, 19
1992).

Lucas et al. Also reported that 7 of 300 premature babies
As a result of examining the intelligence index at the age of 8 years, it was reported that the group fed with breast milk (containing docosahexaenoic acid) had an intelligence index approximately 10 higher than that of the group fed with artificial milk containing no docosahexaenoic acid. (A. Lucas et al., Proc. Nat
l. Acad. Sci. USA, 89, 7840, 199.
2 years).

From these studies, it is considered that docosahexaenoic acid is effective for learning ability and memory retention. Further, it is considered to be an essential component during human growth and growth, and recently, a product for mother-infant nutrition, such as infant formula, which is fortified with docosahexaenoic acid has been developed. However, the docosahexaenoic acid blended in these products is made of fish oil or fish oil concentrate containing a large amount of this, and in order to obtain the above-mentioned desired effect, ingest or administer them in a large amount over a long period of time. Was necessary.

As a material containing docosahexaenoic acid,
Fish oil is often used. Sardine oil, cod liver oil, herring oil, squid oil, and tuna orbital oil are mainly used as fish oils. When the chemical structures of these oils and fats are examined, all of them have a docosahexaenoic acid residue that forms an ester bond at the 2-position of triglyceride. However, 50 mol% or more of the total amount of docosahexaenoic acid residues present in the triglyceride has a triglyceride structure in which there are more docosahexaenoic acid residues bonded at the 2-position than at the 1- and 3-positions.

On the other hand, polyunsaturated fatty acids such as docosahexaenoic acid, on the other hand, are more likely to be oxidized because they have a larger number of double bonds in the molecule than ordinary constituent fatty acids of edible vegetable oils and fats. It is also known to cause harmful effects. When lipid peroxidation proceeds in vivo, it causes damage to biological membranes, ischemic diseases, arteriosclerosis,
It is presumed to cause lesions such as cataract, cancer, Alzheimer's disease, collagen disease, and amyloidosis.

[0014]

DISCLOSURE OF THE INVENTION The present invention has been made in view of such a situation as described above, and it has no side effects on humans and animals, and can be ingested in a smaller amount than the conventional docosahexaenoic acid source. It is an object of the present invention to provide a food and drink containing fats and oils for nutrition of mothers and children in which docosahexaenoic acid is easily accumulated in the organs.

[0015]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and found that fats and oils having a large amount of docosahexaenoic acid at the 1- and 3-positions of a triglyceride structure were used as a source of docosahexaenoic acid. It was found that docosahexaenoic acid has a higher organ-accumulating effect than the commonly used fish oil having a large amount of docosahexaenoic acid at the 2-position, and the above-mentioned object is achieved. The present invention has been completed based on such findings.

In the present invention, 2 having a triglyceride structure is used.
A structure in which the docosahexaenoic acid residues bound to the position are less than 40 mol% of the total amount of the docosahexaenoic acid residues present in the triglyceride, and the fatty acid residues at the 1st and 3rd positions are regularly or randomly distributed between the positions. Oils and fats containing mixed triglycerides with
In addition to the naturally occurring oils and fats such as milk and fats, microbial oils and fats and microalgae oils and fats, oils and fats produced by transesterification using 1,3-position specific lipase are included.

The mixed triglyceride characteristic of the present invention is a triglyceride consisting of a fatty acid containing docosahexaenoic acid and glycerin. When the total amount of docosahexaenoic acid is 100 mol%, the mixed triglyceride is less than 40 mol% and any fatty acid other than docosahexaenoic acid. Is located at the 2-position of the triglyceride, and 60 mol% or more of docosahexaenoic acid and any fatty acid other than docosahexaenoic acid are randomly or non-randomly distributed at the 1- and 3-positions of the triglyceride.

The fatty acids constituting the mixed triglyceride according to the present invention are docosahexaenoic acid and other fatty acids. As the latter fatty acid, any of short-chain, medium-chain and long-chain fatty acids, and saturated and unsaturated fatty acids can be used. Among them, straight-chain, medium-chain having 6 or more carbon atoms Those having a long-chain, saturated or unsaturated fatty acid are preferable. Such fatty acids include caproic acid (C _{6: 0} ), caprylic acid (C _{8: 0} ), capric acid (C _{10: 0} ), lauric acid (C _{12: 0} ), myristic acid (C
_{14: 0} ), palmitic acid (C _{16: 0} ), palmitooleic acid (C _{16: 1} ), stearic acid (C _{18: 0} ), oleic acid (C
_{18: 1} ), elaidic acid (C _{18: 1} ), linoleic acid (C _{18: 2} ), α-linolenic acid (C _{18: 3} , 9, 12, 15)
-Octadecatrienoic acid), α'-linolenic acid (C _{18: 3} , 5,8,11-octadecatrienoic acid), γ
-Linolenic acid ( _C18: 3,6,9,12-octadecatrienoic acid), Eleostearic acid ( _C18: 3,9,11,1)
3-octadecatrienoic acid), octadecatetraenoic acid ( _C18: 4,6,9,12,15-octadecatetraenoic acid), arachidic acid (C20 _{: 0} ), arachidonic acid (C20 _{: 4).} ), Gadoleic acid (C _{20: 1} ), eicosapentaenoic acid (C _{20: 5} , 5,8,11,14,17-eicosapentaenoic acid), behenic acid (C _{22: 0} ), erucic acid (C
_{22: 1} ), brassic acid (C _{22: 1} ), docosapentaenoic acid (C _{22: 5} , 7, 10, 13, 16, 19-docosapentaenoic acid) and the like. These fatty acids may be used alone or may be used as a mixed fatty acid in any proportion. Among these, myristic acid, palmitic acid, stearic acid, oleic acid,
Linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid and docosapentaenoic acid are preferred.

In order to produce the mixed triglyceride according to the present invention composed of docosahexaenoic acid and other fatty acids, a technique such as a chemical synthesis method, a transesterification method, or an oil and fat extraction method from the natural product can be used. Good. Examples of the chemical synthesis method include a desired amount and composition of fatty acid,
Fatty acid anhydrides or fatty acid halides (fatty acid chlorides) and glycerin, acidic substances (hydrochloric acid, sulfuric acid, paratoluene sulfonic acid, etc.), alkaline substances (sodium hydroxide, potassium hydroxide, etc.), metals (zinc, tin, titanium) , Nickel, etc.), metal oxides (zinc oxide, alumina, ferrous oxide, etc.), metal halides (aluminum chloride, tin chloride, etc.) in the presence or absence of esterification catalysts, etc. in a nitrogen gas stream. At 100 to 250 ° C., the esterification reaction may be carried out for 1 to 25 hours while removing the produced water.

The esterification product may be subjected to alkali deoxidation treatment, adsorption / fractionation treatment using activated carbon, activated clay, alumina, silica gel, ion exchange resin or the like, hydrophilic organic solvent such as methanol or ethanol and / Or n
-Solvent fractionation treatment using a lipophilic organic solvent such as hexane or xylene to remove impurities such as free fatty acids, monoglycerides, diglycerides, coloring substances, and odorous components. Fractionation or concentration of the triglyceride component such that the content of the docosahexaenoic acid residue bonded to the position is less than 40 mol% of the total content of the docosahexaenoic acid residue bonded to the 1st, 2nd and 3rd positions of the triglyceride. You may. The mixed triglyceride according to the present invention is preferably deodorized by blowing steam under heating and under reduced pressure.

In order to obtain the mixed triglyceride according to the present invention by using the transesterification method, for example, the fatty acid triglyceride (component a-1) containing a large amount of docosahexaenoic acid as a raw material and docosahexaenoic acid are not substantially contained. A small amount of a fatty acid (component a-2), a lower alcohol ester of component a-2 (methyl ester, ethyl ester, etc.) or a triglyceride of component a-2 is mixed in a desired ratio, or docosahexaenoic acid is added. A catalyst is prepared by mixing a required amount of a triglyceride of a fatty acid (component b-1) which is substantially free or contained in a small amount and a fatty acid (component b-2) containing a large amount of docosahexaenoic acid or a lower alcohol ester of a component b-2. As an alkaline substance such as sodium hydroxide and potassium hydroxide, sodium methylate, and nato Umuechirato, metal alcoholates (metal alkoxides) such as lithium butyrate, basic anion exchange resins, ion exchange resins such as acid cation exchange resins, or that causes an ester exchange reaction using a lipase is simple. When transesterification is carried out using a specific lipase as a catalyst, a new fatty acid group can be selectively introduced at the 1-position and 3-position of the triglyceride, as will be described later, and the method for producing the mixed triglyceride according to the present invention. As desirable.

The raw material for the transesterification is, as the component a-1, a fish oil such as sardine oil, cod liver oil, herring oil, squid oil and orbital orbital oil, and a compressed material obtained from a marine mammal such as whale, seal and fur seal. Alternatively, extracted oil, milk fat of the animal, chlorella, spirulina, donariella, etc., and also genus Nannochloropsis (eg Nannochloropsis ocul
ata), Trust chytrium (eg Thraustochytri
um aureum), Crypthecodinium (eg Crypth
ecodinium cohnii), isochrysis (eg Isochrys
fats and oils extracted from microalgae belonging to
Fats and oils derived from microorganisms such as the genus Mortierella, and triglyceride of mixed fatty acid with docosahexaenoic acid or the above-mentioned various fatty acids (see paragraph 0018) containing the docosahexaenoic acid at an arbitrary ratio can be used. Component a-
Various fatty acids (see paragraph 0018) or their derivatives can be used as 2.

As the component b-1, there are triglycerides obtained from plants, animals, microorganisms, microalgae, etc., soybean oil,
Rapeseed oil, cottonseed oil, corn oil, palm oil, palm oil, safflower oil, high oleic safflower oil, sunflower oil, high oleic sunflower oil, olive oil, peanut oil, cacao butter, chinese tallow, sal butter, shea butter, Beef tallow, lard, hydrogenated oils and fats thereof, fractionated oils and fats, and the component a
Examples of the triglyceride of No. 2, medium-chain fatty acid triglyceride and the like can be exemplified, and as the component b-2, there is a fatty acid obtained by the hydrolysis treatment of the component a-1.

In the transesterification reaction, for example, the raw materials are mixed in a molar ratio of component a-1: component a-2 = 1: 0.1.
5, component b-1: component b-2 = 1: 2 to 10 are mixed, and when an alkali or a metal alcoholate is used as a catalyst, it is in an anhydrous state and is 0.5 to 0.5 at 80 to 120 ° C. Allow transesterification for 3 hours. Similarly, when an ion exchange resin is used, it is also in an anhydrous state, but it is preferable to circulate and contact the raw materials in a column system at room temperature to 40 ° C. When using lipase as a catalyst, the water content in the raw material is set to 1% by weight or less, and commercially available lipase powder or a known carrier such as celite, diatomaceous earth, activated carbon, porous glass, ion exchange resin, chitosan, high Immobilized lipase immobilized on molecular gel, cellulose powder or the like is added, and transesterification reaction is performed at 20 to 80 ° C. for 0.5 to 20 hours.

As the lipase, those originating from the microorganisms described below or those originating from animal organs can be used. Ie Aspergillus niger,
Genus Mucor (eg Mucor miehei), genus Candida (eg Candida cyrindracea), genus Pseudomonas (eg Pseudomonas fragi), genus Alcaligenes (eg Alcaligene described in Japanese Patent Publication No. 58-36953).
s sp.), genus Rhizopus (eg Rhizopus delemar), genus Geotrichum (eg Geotrichum candidum) and the like, and lipases of porcine pancreatic lipase of microbial origin. Of these, lipases originating from microorganisms of the genus Aspergillus, genus Mucor, genus Alcaligenes and genus Rhizopus, and porcine pancreatic lipase specifically act on the 1- and 3-positions of glycerides, and therefore, when producing the triglyceride according to the present invention, It is suitable.

The transesterification reaction products obtained by the above-mentioned various transesterification processes can be the mixed triglycerides according to the present invention, depending on the kind of the raw materials selected, but the transesterification products can be obtained by the chemical synthesis method. As in the case of the esterification products obtained, if necessary, alkali deoxidation treatment, adsorption / fractionation treatment, solvent fractionation treatment or solventless fractionation (wintering) treatment, etc. are performed in an appropriate combination to remove impurities. The mixed triglyceride according to the present invention can be obtained by fractionating or concentrating the glyceride component. The triglyceride is preferably deodorized.

The mixed triglyceride according to the present invention can also be obtained by a method for extracting fats and oils from natural products. That is, among those described as the raw materials for transesterification (component a-1), whales and seals (harbor)
seal, harp seal, etc.), body tissues of marine mammals such as fur seals, milk secreted from the animals, cells of microalgae such as chlorella, spirulina, and Donaliella, or cultured cells thereof, Nannochloropsis genus,
Microalgae belonging to the genus Thraustochytrium, genus Crypthecodinium, genus Isochrysis, etc., for example Nannochloropsis oculata
), Trustchytrium aureum (Thraustochytr
ium aureum), Cryptecodynium cornie (Cry
pthecodinium cohnii), Isocrisis galvana (Iso
chrysis galbana) etc. or these cultured cells are used as raw materials. In addition, when it originates from a microorganism, it does not matter if the triglyceride obtained therefrom satisfies the glyceride structure according to the present invention.

These are pressed or n-hexane,
Chloroform, benzene, methanol, extraction or fractionation using an organic solvent such as diethyl ether to obtain an oil content, which is subjected to degumming, alkaline deoxidation, decolorization, deodorization, etc. to give free fatty acids, phospholipids, The glyceride fraction can be obtained by removing impurities such as glycolipids, unsaponifiable substances, coloring substances and odorous components. This glyceride fraction can be used as the mixed triglyceride according to the present invention. The glyceride fraction is further fractionated by solvent-free low temperature fractionation, solvent fractionation or a silica gel column to give a docosahexaenoic acid residue bonded to the 2-position of triglyceride. It is also possible to produce triglycerides with even fewer groups.

The mixed triglyceride according to the present invention produced by the above-mentioned chemical synthesis method, transesterification method, extraction method from natural products, etc. is less than 40 mol% of the total amount of docosahexaenoic acid as its constituent fatty acid. Is an ester bond at the 2-position of the triglyceride, but it is more preferably less than 20 mol%. 40 mol%
In the above case, the desired effect of the present invention becomes small. Further, it has a structure in which 60 mol% or more of the total amount of docosahexaenoic acid and fatty acids other than docosahexaenoic acid are randomly or non-randomly distributed at the 1- and 3-positions of triglyceride to form an ester bond. The mixed triglyceride according to the present invention can be used as an oil or fat as it is, or can be used as an oil or fat by mixing it with an ordinary edible oil or fat as an active ingredient, for example, an animal or vegetable oil or fat as described as the component b-1. At this time, the content of the mixed triglyceride according to the present invention is preferably 5 to 100% by weight, more preferably 10 to 100% by weight, based on the total fat and oil.
Most preferably, it is 20 to 100% by weight. If it is less than 5% by weight, the desired effect of the present invention is small.

In the present invention, the oil and fat prepared by the above-mentioned method, that is, the triglyceride composed of the fatty acid containing docosahexaenoic acid and glycerin,
Less than 40 mol% of the total amount of docosahexaenoic acid and fatty acids other than docosahexaenoic acid are distributed in the second position of the triglyceride, and 60 mol% or more of the total amount of docosahexaenoic acid and any fatty acid other than docosahexaenoic acid are 1% of triglyceride. An oil or fat consisting of mixed triglycerides which are randomly or non-randomly distributed at the 3rd and 3rd positions and ester-bonded to each other, or the mixed triglyceride and any of the edible animal and vegetable oils and fats, wherein the mixed triglyceride content is 5% by weight or more. Provided are foods and drinks for nutrition of mothers and children in which fats and oils blended as described above are blended as an essential component.

Since the fats and oils according to the present invention contain polyunsaturated fatty acids, they can be handled in the same manner as ordinary edible fats and oils, except for applications such as frying oil which is heat-treated for a long time. Can be processed with raw materials. To avoid quality deterioration, tocopherol, ascorbic acid ester (palmitate, stearate, etc.), β-carotene,
It does not matter if other antioxidants are blended in appropriate amounts, or oil-soluble dyes and fragrances are added.

The fat-and-oil-containing food and drink for mother-child nutrition referred to in the present invention includes milk and powdered milk for pregnant women and lactating women, special-purpose food and oil containing fat and oil for mothers during pregnancy and lactation, such as food and drink, and infant formula. Baby products such as follow-up milk,
The target range is baby foods and foods for infants containing fats and oils.

Various types of foods and drinks containing fats and oils for mother and child nutrition of the present invention can be prepared using known raw materials for foods and fats and oils according to the present invention. For example, in the case of maternal, lactating milk powder or milk, infant formula, or follow-up milk, dairy products and those in which the components of the dairy product are replaced or added, and the oil and fat according to the present invention are mixed with a surfactant. It can be prepared by dispersing, emulsifying or solubilizing it, and the oil or fat according to the present invention can be used after being powdered.

As the surfactant, those which are usually used in food production can be used, and examples thereof include glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester and propylene glycol fatty acid ester. Also, soybean, egg yolk, and other sources of lecithin, lysolecithin, fractions thereof (phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol and their lyso forms), and derivatives of lecithin in which the base moiety is exchanged with an alcohol group (phosphatidylethanol, phosphatidylglycerol, etc.). ), An emulsifier such as soybean protein and its hydrolyzate can also be used without particular limitation. Further, the pulverization treatment is a method of adsorbing the fat or oil according to the present invention to dextran, cyclodextrin, starch, a hydrolyzate thereof, an enzyme or a chemically treated product thereof, or a fat or oil according to the present invention using gum arabic or gelatin. The method of encapsulating can be used.

At this time, the mixed triglyceride according to the present invention with respect to the whole food and drink when drinking the dairy product has a docosahexaenoic acid content of 0.001% by weight or more, preferably 0.005 to 20% by weight, and more preferably 0. 01
10 to 10% by weight. If it is less than 0.001% by weight, the desired effect of the present invention cannot be expected. Although it may be added at a content of more than 20% by weight, such a large amount causes docosahexaenoic acid to be accumulated in the organ even if it is not the fat according to the present invention.

In addition, in foods and drinks containing fats and oils for mothers during pregnancy and lactation (other than the above-mentioned dairy products) and baby foods and foods for infants containing fats and oils, known fats and oils according to the present invention are used as raw materials. Or by replacing all or part of the oil / fat component of the food raw material with the oil / fat according to the present invention. The content of the mixed triglyceride according to the present invention with respect to the whole food and drink is 0.001% by weight or more, preferably 0.005 to 80% by weight, more preferably 0.01 to 80% by weight, as the content of docosahexaenoic acid. It should be so. If it is less than 0.001% by weight, the desired effect of the present invention cannot be expected. The upper limit value can be appropriately set within a known range according to the type of the food or drink.

By ingesting the oil and fat-containing food and drink for mother and child nutrition of the present invention, docosahexaenoic acid can be efficiently accumulated in the organ. Moreover, this effect is remarkably greater than that of the food and drink containing the conventional docosahexaenoic acid source such as fish oil.
Furthermore, the food and drink of the present invention can be used for the purpose of maintaining or improving brain and nerve functions based on the above effects.

[0038]

【Example】

Reference Example 1 1 kg of triolein and fish oil (manufactured by Tama Biochemical Co., Ltd., trade name: EPA-18) were hydrolyzed mixed fatty acids at low temperature fractionated fish oil hydrolyzed fatty acid concentrate (C _{20: 5} : 3 in total fatty acids).
7.4 mol%, C22 _{: 5} : 5.4 mol%, C22 _{: 6} : 25.
2 mol%. BHT added 0.01% by weight) and 1: 5
(Molar ratio), and after adjusting the water content to 0.2% by weight, a glass column (10 cmφ) filled with Lipozyme IM20 (trade name; lipase derived from Mucor miehei, manufactured by Novo Nordisk Co., Ltd.) X 60 cm)
Then, a selective transesterification reaction was carried out at 40 ° C.

After removing free fatty acids from the transesterification reaction product by steam distillation and washing with water, stainless steel filled with silica gel (Wako Pure Chemical Industries, Ltd., trade name: Wakogel C100) impregnated with n-hexane. The mixture was applied to a column and eluted with n-hexane to remove diglyceride to obtain 720 g of mixed triglyceride according to the present invention. The total fatty acid composition constituting the present triglyceride and the fatty acid compositions at the 1st, 3rd and 2nd positions of the glyceride were determined by GLC analysis. Table 1 shows the results. Of the fatty acids constituting this triglyceride, 4 mol% of the total amount of C _{22: 6} (docosahexaenoic acid) was distributed at the 2-position of the triglyceride. This triglyceride was used as a test oil for the following animal experiments.

Sodium methoxide (0.1% by weight) was added to a part of the present triglyceride, and a random transesterification reaction was carried out at 100 ° C. under reduced pressure, followed by filtration through Celite to give a random transesterification reaction of the present triglyceride. I got a thing. The total fatty acid composition, the respective fatty acid compositions at the 1st, 3rd and 2nd positions were determined in the same manner as described above (see Table 1). At the 2-position of this triglyceride, the total amount of docosahexaenoic acid is 45
The mol% was distributed. This random transesterification product was used as a control oil for animal experiments.

[0041]

[Table 1] * Total carbon number: Displayed as the number of double bonds

Seven 4-week-old male SD rats were used as one test group, and 5% by weight of either test oil or control oil was mixed in the feed (see Table 2; 85 as docosahexaenoic acid).
Contains 00 ppm. ) Was used for breeding experiments. During this time,
The feed was prepared and fed daily to prevent oxidative degradation of the prepared feed. After free feeding of water and each of the above feeds for 3 weeks, the docosahexaenoic acid content in phospholipids (phosphatidylcholine, phosphatidylethanolamine, etc.) in the organs and blood of each test group rat Docosahexaenoic acid content in fatty acids.
The same shall apply hereinafter). Table 3 shows the results. No significant difference was observed in feed intake, body weight gain and liver weight in each test plot. The test for significant difference was based on the T test method (the same applies hereinafter).

From the results of this experiment, the mixed triglyceride according to the present invention (test oil) had no adverse effect on rats, and in the group to which the test oil was added, phosphatidylethanolamine in the brain and phosphatidylcholine in blood were converted to docosahexaenoic acid. It was revealed that a large amount of docosahexaenoic acid was present and that docosahexaenoic acid had a high potential for organ accumulation.

[0044]

[Table 2] * 1 Nippon Claire Co., Ltd., AIN-93G-MX * 2 Nippon Claire Co., Ltd., AIN-93-VX * 3 t-Butylhydroquinone

[0045]

[Table 3] 1): Phosphatidylcholine, 2): Phosphatidylethanolamine Note) * indicates that there is a statistically significant difference at the risk rate of 5% or less compared to the control oil added group (the same applies below).

Reference Example 2 A test fat and oil (fat and fat containing the mixed triglyceride of the present invention) and a control fat and oil were prepared as follows. The test fat and oil was harp seal fat and oil with dry ice / acetone refrigerant.
It was cooled at 80 ° C. for 1 hour, and the precipitated crystal part was filtered off with filter paper to prepare. The control fats and oils were two types of fish oils with different fatty acid composition (mixed oil of cod liver oil and miscellaneous fish oil, tuna orbital oil), cooled with dry ice / acetone refrigerant in the same manner, and separated and blended to obtain a test fat and total fatty acid. The compositions were matched. Table 4 shows these fatty acid compositions.

[0047]

[Table 4] *: Same as the notes in Table 1.

Seven 4-week-old SD male rats were used as one test group, and the fats and oils containing 20% by weight of each of the above-mentioned test fats and control fats and oils (20 or more parts by weight of test or control fats, 50 parts by weight of palm oil, A mixed fat containing 5 parts by weight of oleic safflower oil and 25 parts by weight of high linoleum safflower oil (see Table 5 for the composition of fatty acids), each containing 10% by weight (the composition of the feed is 10% by weight of 5% by weight of fat). And the same as in Reference Example 1 except that 41.7% by weight of corn starch was changed to 36.7% by weight, and 3 parts of docosahexaenoic acid was used, respectively.
Contains 600ppm. ), A breeding experiment was conducted. During this period, the feed was prepared and fed daily in order to prevent oxidative deterioration of the prepared feed. After free feeding of water and each of the above-mentioned feeds and feeding for 3 weeks, the content of docosahexaenoic acid in the phospholipids in the organs and blood of each test group rat was measured. The results are shown in Table 6. No significant difference was observed in feed intake, body weight gain and liver weight in each test plot.

From the results of this experiment, it is clear that the fats and oils according to the present invention have no adverse effects on rats and that docosahexaenoic acid is present in large amounts in phosphatidylethanolamine in brain and phosphatidylcholine in blood. It was recognized that the organs of the plant had high accumulation potential.

[0050]

[Table 5] *: Same as the notes in Table 1. * *: Ratio of each fatty acid among saturated fatty acids, monounsaturated fatty acids, n-6 fatty acids (denoted by n-6 in the table) and n-3 fatty acids (denoted by n-3 in the table).

[0051]

[Table 6] 1), 2) and *: Same as the notes in Table 3.

Reference Example 3 Eight 9-week-old female SD rats were used as one test group, and Reference Example 2 was used.
Each feed used in (36 docosahexaenoic acid each
(Containing 00 ppm) for 3 weeks, and then mated with male rats for pregnancy. The same diet was given during pregnancy and after delivery. The content of docosahexaenoic acid in milk fat of the milk of mother rats and the content of docosahexaenoic acid of brain phospholipids (phosphatidylethanolamine) in the rat 2 weeks after birth were measured. The results are shown in Tables 7 and 8. Breeding with the feed containing the oil / fat according to the present invention increased the content of docosahexaenoic acid in the milk of mother rats and also the content of docosahexaenoic acid in the phosphatidylethanolamine of rat rat brain. From these results, it was confirmed that the fats and oils according to the present invention have high organ accumulation of docosahexaenoic acid.

[0053]

[Table 7] *: Same as the notes in Table 3.

[0054]

[Table 8] *: Same as the notes in Table 3.

Reference Example 4 A rat breeding experiment was carried out in the same manner as in Reference Example 2 by adding fats and oils containing the test fats and control fats used in Reference Example 2 in different mixing ratios to the feed. That is, 7 4-week-old male SD rats were used as one test group, and the fat or oil containing 10 wt% of the test fat or control fat or oil described in Reference Example 2 (10 wt parts of the test fat or control fat or oil, 50 parts by weight of palm oil) was added. , A mixed fat of 10 parts by weight of high oleic safflower oil and 30 parts by weight of high linoleum safflower oil. Refer to Table 9 for the fatty acid composition. Same as the above, each containing 1700 pp of docosahexaenoic acid). During this time, the feed was prepared daily to prevent oxidative deterioration of the prepared feed.
After free feeding of water and each of the above-mentioned feeds and feeding for 3 weeks, the content of docosahexaenoic acid in the phospholipids in the organs and blood of each test group rat was measured. Table 1 shows the results.
0 is shown. No significant difference was observed in feed intake, body weight gain and liver weight in each test plot.

From the results of this experiment and the results of Reference Example 2,
The oil and fat according to the present invention has no side effect on rats,
Included a large amount of docosahexaenoic acid in phosphatidylethanolamine in the brain and phosphatidylcholine in blood, including the case of fats and oils mixed with a small amount of test fat compared to the control fat, and it was confirmed that docosahexaenoic acid had a high potential for organ accumulation. Was given.

[0057]

[Table 9] * And **: Same as the notes in Table 5.

[0058]

[Table 10] 1), 2) and *: Same as the notes in Table 3.

Reference Example 5 Microalga Crypthecodium
inium cohnii, ATCC 30336) was planted in 30 liters of the medium shown in Table 11, aerobically cultured at 30 ° C. for 100 hours in a jar fermenter, and cultured alga cells were collected by centrifugation and collected. Lyophilized (yield 625 g). The dried algal cells were crushed and extracted in a mixed solvent of chloroform: methanol = 1: 1 (weight ratio) with a hiscotron (trade name; manufactured by Nichine Medical Science Co., Ltd.) to obtain 520 g of an oil component. The oil was supplied to a stainless steel column filled with silica gel (Wako Pure Chemical Industries, Ltd., trade name: Wakogel C100) dispersed in n-hexane, and diethyl ether: n-hexane = 10: 9.
Elution was performed at 0 (volume ratio) to obtain 250 g of the triglyceride according to the present invention. The fatty acid composition of the present triglyceride (this was used as a test fat) was determined in the same manner as in Reference Example 1 (see Table 12).

[0060]

[Table 11] (PH: 6.8)

* 1: Vitamin mix aqueous solution (weight per 1 liter of the aqueous solution) Biotin: 0.003 g Thiamine: 1.000 g * 2: Metal mix aqueous solution (weight per 1 liter of the aqueous solution) Na ₂ EDTA: 1.00 _{g FeCl 3 · 6H 2 O:} 0.05 g H 3 BO 3: 1.00 g MnCl 2 · 4H 2 O: 0.15 g ZnCl 2: 0.01 g CoCl 2 · 6H 2 O: 0.005g

[0062]

[Table 12] *: Same as the notes in Table 1.

The thus-obtained triglyceride derived from microalgae (test fat and oil) and the control fat and oil described in Reference Example 2 in an amount of 10% by weight (10 parts by weight of the test fat or oil, 50 parts by weight of palm oil, Hiole) 10 parts by weight of Ick safflower oil and 3 of high linoleum safflower oil
0 parts by weight of mixed fats and oils. See Table 13 for fatty acid composition. 10% by weight of each feed (the feed composition is the same as in Reference Example 2 except for the fat content. 3600 pp of docosahexaenoic acid, respectively)
Contains m. ) Was prepared and the same breeding test as in Reference Example 4 was performed. The content of docosahexaenoic acid in phospholipids in the organs and blood of rats in each test group was measured. Table 1 shows the results.
4 shows. No significant difference was observed in feed intake, body weight gain and liver weight in each test plot.

From the results of this experiment and the results of Reference Example 2,
The oil and fat according to the present invention has no side effect on rats,
Included a large amount of docosahexaenoic acid in phosphatidylethanolamine in the brain and phosphatidylcholine in blood, including the case of fats and oils mixed with a small amount of test fat compared to the control fat, and it was confirmed that docosahexaenoic acid had a high potential for organ accumulation. Was given.

[0065]

[Table 13] * And **: Same as the notes in Table 5.

[0066]

[Table 14] 1), 2) and *: Same as the notes in Table 3.

Example 1 Eight mice immediately after weaning were used as one test group, and one of the test fats and oils described in Reference Examples 4 and 5 was used as one test fat.
A feed containing 0% by weight was administered for 6 weeks. At the 6th week, the learning ability was examined using a T-type water maze (manufactured by Natsume Seisakusho, model: KN-83).

As a result, in the first experiment, the group administered with the feed containing the oil / fat according to the present invention (test oil / fat) was less likely to get lost in the dead end than the control oil / fat administered group, and reached the exit. Approximately 2 minutes 30 in the control fat and oil administration group
Although it was seconds, it was about 1 minute and 30 seconds, which was short. Reference example 4
The test fat and oil of Example 2 and the test fat and oil of Reference Example 5 had almost the same results. In the second experiment, the number of times of hesitation decreased in any of the test groups, but the time to reach the outlet was shorter in the test oil and fat administration group than in the control oil and fat administration group. From the above results, it was confirmed that the oil and fat according to the present invention has a large effect of improving the memory learning ability.

Example 2 10 parts by weight of β-cyclodextrin (manufactured by Kanto Chemical Co., Inc., reagent grade) was added to 100 parts by weight of water, and after sufficiently stirring, according to the present invention prepared in Reference Examples 4 and 5. 10 parts by weight of any one of oils and fats (oils and fats containing 10% by weight of test oils and fats) was added and stirred at room temperature for 2 hours. Then, this was freeze-dried to obtain a powdery fat and oil-containing material (inclusion material).

After mixing 16 parts by weight of skimmed milk powder (trade name: skim milk, manufactured by Snow Brand Milk Products Co., Ltd.) with 0.85 parts by weight of any one of the above-mentioned powdery fat and oil-containing products, 140 ml of warm water at 40 ° C. A liquid dairy product (46 ppm of docosahexaenoic acid) that can be used as maternal, lactating milk, infant formula, or follow-up milk
, 98 ppm) was obtained. With 10 professional panels,
When the flavor and texture of these dairy products were evaluated, they did not feel any discomfort.

Example 3 Eight 9-week-old SD female rats were used as one test group, and Example 2 was used.
A dairy product prepared in the same manner as in Example 2 using the dairy product prepared in Example 1 and the respective control fats and oils used in Reference Examples 4 and 5 (the docosahexaenoic acid content in the dairy product is
Prepared by the method of Example 5 was 46 ppm, and that prepared in Reference Example 5 was 98 ppm), and solid feed (manufactured by CLEA Japan, Inc., trade name: CE-2 together with the solid feed in an amount of 2 to 2.5 times by weight). After feeding for 3 weeks at the same ratio, they were mated with male rats for pregnancy.The same feed was given during pregnancy and after childbirth.There was no significant difference in feed intake and body weight gain in each test group. The docosahexaenoic acid content in milk fat of the milk of the mother rat and the docosahexaenoic acid content of phospholipids in the brain of the rat 2 weeks after birth were measured.

As a result, when the dairy product containing the fat according to the present invention was administered, the content of docosahexaenoic acid in the milk of the mother rat was increased and the brain of the rat rat was increased, as compared with the case of the dairy product containing the control fat. The content of docosahexaenoic acid in phosphatidylethanolamine in the solution also increased. From the above results, it was confirmed that docosahexaenoic acid was much accumulated in the organs by ingesting the food or drink containing the oil or fat according to the present invention.

Example 4 3 parts by weight of gelatin and 30 parts by weight of water were mixed with heating to prepare an aqueous gelatin solution, which was then mixed with stirring 4
Cooled to 0 ° C. To this, 6 parts by weight of the oil / fat according to the present invention (oil / fat containing 10% by weight of any one of the test oils / fats) prepared in Reference Examples 4 and 5 was added, followed by emulsification into an oil-in-water type using a homogenizer, and then 10 parts by weight. % Arabic gum aqueous solution (30 parts by weight) was added and mixed. While maintaining the temperature at 40 ° C. and continuing stirring, 140 parts by weight of water having the same temperature and 5 parts by weight of 10% by weight acetic acid were added, and the mixture was cooled to 5 ° C. and pH was adjusted to 4.0.
To 30% by weight aqueous ethanol solution 100
0 parts by weight were mixed with stirring. The slurry is washed with ethanol, dried at 30 ° C. under reduced pressure, and particle size: 10-5
A 0 μm microcapsule oil-and-fat-containing material was obtained.

After mixing 16 parts by weight of skimmed milk powder (the same as that used in Example 2) with 0.3 to 2.0 parts by weight of the above-mentioned oil-and-fat composition containing microcapsules, 40 ° C.
Dissolve it in 140 ml of warm water and milk for pregnant and lactating women,
Liquid dairy products that can be used as infant formula or follow-up milk (16 docosahexaenoic acids each)
ppm, including 228 ppm) was obtained. When the flavor and texture of this dairy product were evaluated by 10 expert panels, it was found that there was no discomfort.

Example 5 8 parts by weight of the oil / fat according to the present invention prepared in Reference Examples 4 and 5 (oil / fat containing 10% by weight of any one of the test oils / fat), 83 parts by weight of corn starch and 3 parts by weight of salt were added with lukewarm water. It was cooked while melting, and when the precipitate was gone and it was gelatinized white, the heat was turned off. In addition to this
A mixture of 30 parts by weight, sugar 35 parts by weight and cut vegetables 10 parts by weight, and 22 parts by weight of beef liver and 44 parts by weight of grated horse mackerel, each boiled in soy sauce and chopped, Stir well and boil.
This was cooled to about human skin, 90 parts by weight of yogurt and 100 parts by weight of egg were added and stirred well to obtain a special-purpose food for pregnant women and nursing women or a food used for baby food. This one has energy of 1228kcal, protein of 58.1g,
It contained 25.1 g of lipids and 187.4 g of sugars, contained 43 to 90 ppm of docosahexaenoic acid, and had no problem in flavor and appearance.

[0076]

EFFECTS OF THE INVENTION The food and drink containing fat and oil for mother-infant nutrition of the present invention is
It has no side effects on animals including humans, and docosahexaenoic acid in the living body has phosphatidylcholine compartment in plasma, phosphatidylcholine compartment in brain and phosphatidylethanolamine as compared with similar foods and drinks containing the conventional docosahexaenoic acid source. Accumulate a large amount as each constituent fatty acid of the category. Therefore, the food and drink containing fats and oils for maternal and child nutrition of the present invention exhibits a high effect of accumulating docosahexaenoic acid on organs by ingesting a smaller amount than the food and drink for maternal and child nutrition containing a conventional source of docosahexaenoic acid such as fish oil. In addition, the food and drink for mother-infant nutrition of the present invention can be used for the purpose of maintaining and improving brain and nerve functions and sufficiently exerting physiological and pharmacological actions of docosahexaenoic acid.

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[Procedure amendment]

[Submission date] August 12, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

[0008] In an experiment using rats, docosahexaenoic acid was supplied from the mother rat via the placenta during the fetal period when biosynthesis is low and from milk after birth, and docosahexaenoic acid production capacity in vivo is sufficient. It has been suggested that it becomes supplied from the liver at about 7 weeks of age.
Among them, it has been recognized that a group that continuously ingests docosahexaenoic acid through the placenta during the fetal period, after birth, and from the diet after weaning has significantly superior learning ability. ( Fujimoto Kenshiro eds. , "Fisheries lipids-its characteristics and physiological activity", Seiseisha Koseikaku, page 123, 1993.
Year).

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

Lucas et al. Also reported that 7 of 300 premature babies
As a result of examining the intelligence index at the age of 8 years, it was reported that the group fed with breast milk (containing docosahexaenoic acid) had an intelligence index approximately 10 higher than that of the group fed with artificial milk containing no docosahexaenoic acid. Hiritsu Suzuki, “Food and Kai
Departing ", Vol. 27, No. 8, pp. 6-9, 1992,
Health Industry Newspaper, Inc.) .

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

The raw material for the transesterification is, as the component a-1, a fish oil such as sardine oil, cod liver oil, herring oil, squid oil and orbital orbital oil, and a compressed material obtained from a marine mammal such as whale, seal and fur seal. Alternatively, extracted oil, milk fat of the animal, chlorella, spirulina, donariella, etc., and also genus Nannochloropsis (eg Nannochloropsis ocul
ata , UTEX LB 2164, etc. ), Trust chytrium (eg Thraustochytrium aureum , ATCC 28211, 34304)
Etc. ), Crypthecodiniu (eg Crypthecodiniu
m cohnii , ATCC 30021, 30334, 30336, 50052
Etc. ), isochrysis (eg Isochrysis galbana , CC
AP 927/1, UTEX LB 987, etc. ), oils and fats extracted from microalgae belonging to, etc., microorganisms such as Mortierella (Mortierella) genus (M. isabellina, IFO 6336, 6739, 7873, 78)
84, ATCC 44853, etc.) , or triglyceride of mixed fatty acid with docosahexaenoic acid or the above-mentioned various fatty acids containing the docosahexaenoic acid in any proportion (see paragraph 0018). ATCC: American Type Cul
ture Collection (USA), CCAP: Culture Collectiono
f Alage and Protozoa (UK), UTEX: Culture Collec
tion of Alage at the University of Texas (USA),
IFO: An abbreviation for Osaka Fermentation Research Institute. As the component a-2, the above various fatty acids (see paragraph 0018) or derivatives thereof can be used.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction contents]

Seven 4-week-old SD male rats were used as one test group, and the above-mentioned test fats and control fats and oils containing 20% by weight each (20 parts by weight of test fats or control fats and 50 parts by weight of palm oil) were used. , A mixed oil of 5 parts by weight of high oleic safflower oil and 25 parts by weight of high linoleum safflower oil. See Table 5 for the fatty acid composition. Wt% and cornstarch 41.7 wt% 36.7 wt% except that it was the same as Reference Example 1. Docosahexaenoic acid contained 3600 ppm). During this period, the feed was prepared and fed daily in order to prevent oxidative deterioration of the prepared feed. After free feeding of water and each of the above-mentioned feeds and feeding for 3 weeks, the content of docosahexaenoic acid in the phospholipids in the organs and blood of each test group rat was measured. The results are shown in Table 6. No significant difference was observed in feed intake, body weight gain and liver weight in each test plot.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction contents]

The triglyceride derived from microalgae (test fat and oil) thus obtained and the control fat and oil described in Reference Example 2 were used.
Used, the mixed oil and fat. The fatty acid composition of each 10 wt% including fat (test oils or control oil 10 parts by weight, palm oil 50 parts by weight, high-oleic safflower oil 10 parts by weight of high-linoleic safflower oil 30 parts by weight Table 13) was mixed with each other in the amount of 10% by weight (the composition of the feed was the same as in Reference Example 2 except for the fat content. Each contained 3600 ppm of docosahexaenoic acid), and the same breeding test as in Reference Example 4 was performed. The content of docosahexaenoic acid in phospholipids in the organs and blood of rats in each test group was measured. The results are shown in Table 14. No significant difference was observed in feed intake, body weight gain and liver weight in each test plot.

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Claims (5)

[Claims] 1. The docosahexaenoic acid residue bonded to the 2-position of the glyceride is less than 40 mol% of the total amount of the docosahexaenoic acid residue present in the triglyceride, and the 1-position and the 3-position.
Foods and drinks containing fats and oils for maternal and child nutrition with a high organ accumulating property of docosahexaenoic acid containing, as an active ingredient, a mixed triglyceride having a structure in which fatty acid residues at positions are distributed regularly or randomly among those positions. 2. The mixed triglyceride comprises an active ingredient composed of naturally occurring fats and oils containing marine mammal fats and oils, milk fats, and microalgae fats and oils, or concentrated and transesterified products thereof. The oil-and-fat-containing food and drink for mother-child nutrition according to 1. 3. The food and drink containing fat and oil for maternal and child nutrition according to claim 2, wherein the marine mammal is a whale or a seal. 4. The oil and fat-containing food and drink for nutrition for mothers and children according to claim 2, wherein the microalga belongs to the genus Nannochloropsis, the genus Trustchitrium, the genus Isochrysis, or the genus Crypthecodinium. 5. The food and drink containing fat and oil for mother-infant nutrition according to claim 1 or 2, wherein the mixed triglyceride comprises an active ingredient composed of triglyceride produced by transesterification using a 1,3-position specific lipase. Stuff.