JP3120906B2 - Method for producing triglyceride containing β-palmitic acid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a glyceride at the β-position (2
) Palmitic acid (hereinafter referred to as β-palmitic acid)
And a method for producing an oil or fat in which about 50% is bound . More specifically, the present invention relates to a method for reforming vegetable oils and fats , particularly palm oil, by combining a random transesterification reaction using a catalyst with a transesterification reaction using an enzyme.

[0002]

2. Description of the Related Art Conventionally, there has been known a method of chemically transesterifying fats and oils using sodium methylate or caustic soda as a catalyst. However, according to this method, the acyl group bonded to the triglyceride is changed to the α-position (1,3
Position) and the β position (2 position) tend to be exchanged (random transesterification). In contrast, enzymatic transesterification is also known, but the enzymatic reaction has specificity in the chain length and position of the fatty acids that make up triglyceride, and enzymatic transesterification utilizing this specificity is also actively developed. Have been. For example, the α-position of triglyceride (positions 1 and 3
Of cocoa butter, in which palmitic acid and stearic acid are bonded at the (position) and oleic acid at the β-position (position 2), have been tried (for example, JP-A-52-104506 and JP-A-52-104506). As a representative enzyme used in these reactions, Aspergillus niger , Mucormiehei
And lipases derived from Rhizopus delemar .

On the other hand, studies on the physiological effects of certain fatty acids such as polyunsaturated fatty acids have been progressing, and the effects of fatty acid binding positions in triglycerides are becoming clear. For example, in terms of the relationship between the binding position of behenic acid and the absorption rate, the absorption rate of triglyceride with behenic acid bound at the β-position is lower (Hiroyuki Mori, Food Processing Technology, 11,25-28,199
1) Triglycerides with linoleic acid bound to the β-position lower blood and liver cholesterol levels than those linked to the α-position (Yamamoto, Atherosclero)
sis, 13, 171-184, 1971). In particular, triglycerides with palmitic acid bound to the β-position show much higher absorption than triglycerides with palmitic acid bound to the α-position.
(J. Nutr. 99, 293-
298, (1969) J. Nutr. 95, 583-590, (1968)]. Filer et al. Studied the absorption of fat and fatty acids by feeding 11 infants with artificial formulas supplemented with fats having different β-palmitic acid contents. Fats are 3.63 g / 100 ml and 3.72 g / lard of lard (85% of palmitic acid binds to β-position) or transesterified lard (33.9% of palmitic acid to β-position).
100 ml was added. As a result, the absorptivity of palmitic acid was 94% for lard and 58% for transesterified lard, and the higher the ratio of β-palmitic acid was, the more excellent the absorptivity was.
Furthermore, because β-palmitic acid has a high micelle-forming ability,
The absorption rate of stearic acid was also increased by 88% for lard and 40% for transesterified lard. Tomarelli et al. Also used human milk or a mixture of lard, butter, and coconut oil,
They were added to the diet as 15% fat and administered to rats. As a result of examining the correlation between the rate of absorption of fat and the ratio of fatty acids at the β-position, there was a remarkable correlation with palmitic acid, and a weak correlation with myristic acid and oleic acid. Stearic acid had no correlation. Thus, the β of triglyceride
The presence of palmitic acid at the position shows high absorbency. Furthermore, it is said to be a particularly important fat for infants because of its high content in breast milk.

[0004]

SUMMARY OF THE INVENTION Palmitic acid is abundant in vegetable oils such as palm oil and used as a food material. However, the binding position is often at the α-position (Oil Chemistry Handbook, p.20, 1982 Maruzen). A typical fat and oil highly containing β-palmitic acid is lard which is an animal fat and oil. When lard is used in foods, the “fat odor” of the fat and oil is exhibited. . In addition, even if it is highly deodorized, "return odor" is generated with time, and there has been a problem in its use in the past.

It is an object of the present invention to provide such a "kemono smell".
Another object of the present invention is to produce a triglyceride having a high content of β-palmitic acid, which is free from "return odor". The thus obtained β- palmitic highly containing triglyceride foods and beverages, in particular incorporated into infant milk powder, provides a food or beverage highly absorbent oil is blended.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted various studies on the raw material fats and oils and the synthesis method, and found that the fatty acid triglyceride of the palm oil or the fractionated oil of the raw material was used. after introducing palmitic acid (oil) chemically random transesterification to β-position (2-position), alpha-position (1,3-position) in the optionally-position alpha with lipase specifically acting not The present inventors have found that the introduction of a saturated fatty acid gives a triglyceride highly containing β-palmitic acid, thereby completing the present invention. In addition, in this production method, palmitic acid is highly bound as a raw material fat, but random transesterification between palm oil and its fractionated oil at the β-position with a small amount of the binding results in good yield of human milk. It could also be produced β- palmitic San含 Yes triglycerides comparable to fat.

That is, the present invention relates to palm oil or
The fractional oil ( fatty acid triglyceride ) is chemically and randomly transesterified using a catalyst to increase the palmitic acid content at the β-position of the triglyceride to about 50% ,
Next, this glyceride is converted into β-palmitic acid by introducing an arbitrary unsaturated fatty acid into the α-position by enzymatically transesterifying the unsaturated glyceride with any unsaturated fatty acid using a lipase having a high specificity at the α-position. The present invention relates to a method for producing a highly-containing triglyceride. According to the method of the present invention, the absorption of fats and oils when fatty acid triglycerides are taken can be improved.

[0008] Such a reforming method of the present invention will be described in detail. Fatty acid triglycerides are subject of the process of the present invention (oil) palmitic acid content of 25 wt% or more bound to grayed Riserido, preferably 50 wt% or more vegetable oils and their fractionated oil and fat used. There are palm oil and its fractions oil as such fats and oils. In the present invention, first, chemical random transesterification is performed. In this transesterification, an alkali metal catalyst (such as sodium methylate) is used in an amount of 0.01 to 1 with respect to 100 parts by weight of the oil or fat.
0 parts by weight, preferably 0.1 to 1 part by weight, is added to carry out the transesterification reaction. The temperature in the above reaction is 20 ° C to 9 ° C.
It is preferably performed at a temperature of 0 ° C, more preferably 40 to 8
It is good to carry out at a temperature of 0 ° C. The reaction time is usually
The time may be from 5 minutes to 10 hours, preferably from 15 to 40 minutes. This transesterification runs between triglycerides.
Dam to you transesterification. Thus, the β-palmitic acid content is increased. Thus, β-palmitic acid containing
The amount is about 40-60%, ie about 50%. About this
The reason for 50% was that the transesterification by lipase
Reduce the reaction temperature as much as possible to prevent deterioration of components, and
The resulting glyceride is contained in human milk fats and oils containing β-palmitic acid.
This is to make the amount similar.

Next, the above fats and oils are washed with acid or water,
The transesterification of the fatty acid at the α-position is performed enzymatically using a lipase having high specificity at the α-position. The lipase used in the present invention, Rhizopus (Rhizopus) genus Aspergillus (Aspergillus) genus, can Mucor (Mucor) microorganism of the genus uses lipase production, also, the lipase having a similar and at least these properties If it is, a thing other than the above may be used, and there is no problem. Such a lipase is commercially available, for example, Amano A (Amano Pharmaceutical), lipozyme (NOVO) and the like. The use form of the lipase is not particularly limited, but from the viewpoint of efficiency, it is preferable to use the lipase by immobilizing it on a carrier by a known method, and when using it in an organic solvent, it is preferable to use a chemically modified enzyme or the like. preferable. The amount of the lipase to be used may be appropriately determined depending on the reaction conditions and the properties of the desired reformed oil, and is not particularly limited. For example, 0.01 to 50 g, preferably about 0.1 to 20 g, per 100 g of fat or oil. It is good. The enzymatic transesterification in the present invention may be carried out by melting the fat or oil in the case of a liquid or solid phase. Also, using an organic solvent such as hexane and isooctane, a buffer such as phosphoric acid or Tris is added to adjust the pH to 4.0 to 10.0.
May be adjusted. The reaction is preferably carried out at a temperature of 30 to 60 ° C, more preferably at a temperature of 35 to 45 ° C. The reaction time is usually 1 hour to 3 days,
Preferably, it should be about 4 to 24 hours. In the transesterification, when unsaturated fatty acids such as oleic acid and linoleic acid are used, these unsaturated fatty acids are introduced at the α-position,
Health-friendly triglycerides can be obtained.

The reaction product thus obtained in the present invention is subjected to treatment such as liquid-liquid distribution, extracted from the reaction solution, and if necessary, purified by means such as column chromatography to obtain β-palmitic acid. Used as a rich fatty acid triglyceride. Such a fatty acid triglyceride having a high β-palmitic acid content is blended in foods and drinks, for example, infant milk powder, baby food, tube feeding, pathological food, and the like. The compounding ratio is preferably about 2 to 30 parts by weight with respect to 100 parts by weight of food or drink.

In the present invention, in order to introduce palmitic acid by random transesterification at the β-position (position 2), it is necessary to use an oil or fat having a high palmitic acid content. As a result, the obtained fats and oils have a high melting point of, for example, 45 to 55 ° C.,
In general, it shows unfavorable physical properties for use as an edible oil and fat. Therefore, the α-position of this triglyceride (1st, 3
Oleic acid or linoleic acid is introduced into the glycerol to lower the melting point of triglyceride, making it preferable as an edible oil and fat. In addition, the triglyceride thus obtained is preferably composed of fatty acids for use in infant milk powder and the like.

Next, the present invention will be described with reference to embodiments of the present invention.

Example 1 0.5 g of sodium methylate was added to 100 g of palm oil (palmitic acid content in glyceride: 43.3%, β-palmitic acid content: 18.7%), and subjected to random transesterification at 80 ° C. for 20 minutes. 95 g of the reaction triglyceride (palmitic acid content 43.1%, β-palmitic acid content 43.4%) was extracted by a conventional method. This reaction triglyceride
Using 10 g of oleic acid (purity 95%) as a substrate and immobilized lipase (Mucor mieh
ei origin, using NOVO Co.) 3 g, 5 wt% of buffer to enzyme (pH 8.0) in n- hexane was added, at 40 ° C. 24
The reaction is carried out for a time, and the enzyme reaction triglyceride is
6.3 g were obtained. The triglyceride had a palmitic acid content of 24.2% and a β-palmitic acid content of 43.3%. The resulting triglyceride has no off-flavors such as "kemono odor"
Further, the absorption rate was high.

[0013]

Example 2 Fractionated oil having a high melting point in palm (palmitic acid content in glyceride: 59.3%, β-palmitic acid content: 21.6%) 100
g, add 0.5% of sodium methylate,
After 30 minutes of random transesterification reaction, 95 g of reacted triglyceride (palmitic acid content 59.3%, β-palmitic acid content 58.4%) was extracted by a conventional method. Using 10 g of this reaction triglyceride and 40 g of oleic acid (95% purity) as substrates, immobilized lipase (M
Using 3 g of ucor miehei ( manufactured by NOVO), the reaction was carried out at 40 ° C. for 24 hours in n-hexane to which a 5 wt% buffer solution (pH 8.0) was added to the enzyme, and the enzyme-reacted triglyceride was 6.5 g by a conventional method. I got The triglyceride had a palmitic acid content of 30.2% and a β-palmitic acid content of 58.3%. The obtained triglyceride had no off-flavor such as "kemono odor" and a high absorption rate.

[0014]

Example 3 Fractionated oil with high melting point in palm (palmitic acid content in glyceride: 59.3%, β-palmitic acid content: 24.6%) 100
g, add 0.5% of sodium methylate,
After 30 minutes of random transesterification reaction, 95 g of reacted triglyceride (palmitic acid content 59.3%, β-palmitic acid content 58.4%) was extracted by a conventional method. Using 10 g of this reaction triglyceride and 40 g of linoleic acid (95% purity) as substrates, immobilized lipase (M
Using 3 g of ucor miehei ( manufactured by NOVO), the reaction was carried out at 40 ° C. for 24 hours in n-hexane to which a 5 wt% buffer solution (pH 8.0) was added, and 7.8 g of enzyme-reacted triglyceride was obtained by a conventional method. I got The triglyceride had a palmitic acid content of 40.2% and a β-palmitic acid content of 58.4%. The obtained triglyceride had no off-flavor such as "kemono odor" and a high absorption rate.

[0015]

REFERENCE EXAMPLE 1 α-Oleic acid and β-palmitic acid triglyceride obtained by the method of Example 1 were blended with 80% of the fat during the preparation of the prepared milk powder to obtain a milk powder containing a fat and oil having a high absorption.

[0016]

Reference Example 2 The enzyme-reacted triglyceride obtained by the method of Example 2 was added to the feed of young rats, and the absorbability was examined. Table 1 shows the composition of the experimental feed.

The rats used were SD male rats of 3 weeks old (Charles River Japan Co., Ltd.).
The animals were divided into groups and fed the feeds shown in Table 1 for 2 weeks. During the breeding period, feed intake and body weight gain were measured, and feed efficiency was calculated every week. In addition, 12 ~
On the 14th day, feces were collected for 3 days, and the amount of unabsorbed palmitic acid and oleic acid were determined. Table 2 shows the feed efficiency, and Table 3 shows the apparent digestion and absorption rates of palmitic acid and oleic acid.

As is clear from the results, the rats fed the fats and oils according to the present invention showed that the feed efficiency was comparable to the control fats (raw fats and oils).
And improved growth. In addition, the digestibility of palmitic acid was significantly improved. Therefore, when palmitic acid is used as a triglyceride source, the use of the triglyceride treated according to the present invention can supply a fat and oil having a much higher digestion and absorption rate. This result can be sufficiently applied to humans, has high absorbency, and can be used as a fat and oil for formula powder similar to breast milk.

[0019]

[Table 1] Experimental feed composition ───────────────────────── Control group The present invention group ───────────── ──────────── Casein 20.0 20.0 DL-methionine 0.3 0.3 Untreated fat and oil 10.0 油 Fatty oil of the present invention ── 10.0 Salt mixture ^* 3.5 3.5 Vitamin mixture ^* 1.0 1.0 Choline bitartrate 0.2 0.2 Cellulose 5.0 5.0 Corn starch 15.0 15.0 Sucrose 45.0 45.0 ───────────────────────── ^* AIN-76 composition

[0020]

[Table 2] Feed efficiency (%) ────────────────────────── 1st week 2nd week ─────────対 照 Control group 46.6 ± 3.9 45.3 ± 2.7 Inventive group 50.8 ± 2.2 ^* 47.5 ± 2.7 ^* ────────────── ──────────── ^* Significantly different from control group (p <0.05) Feed efficiency (%) = weight gain (g) ÷ feed intake (g) x 100

[0021]

[Table 3] Apparent digestion and absorption rate of palmitic acid (%) パ ル Palmitic acid ──────────────── ─ Control group 80.0 ± 3.4 Inventive group 87.6 ± 3.8 ^* ───────────────── ^* Significantly different from control fat group (p <0.01) Apparent digestibility (%) = (Fatty acid intake per day−1 fatty acid excretion per day) ÷ fatty acid intake per day × 100

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masatoshi Yahiro 2-8-13 Kumegawa-cho, Higashimurayama-shi, Tokyo (56) References European Patent Application Publication 376628 (EP, A2) European Publication 496456 (EP, A1) Europe Published 209327 (EP, A1)

Claims (1)

(57) [Claims] 1. A method using palm oil or its fractionated oil as a catalyst.
Chemically and randomly transesterify the triglyceride.
The palmitic acid content at the β-position in the metal to about 50%,
This is done by using a lipase that acts specifically at the α-position
Chemically unsaturated esterification with unsaturated fatty acid
Β-palmichi characterized by introducing an acid into the α-position
A method for producing triglycerides having a high acid content.