JP2002121587A - Plastic fat composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic fat composition sharp and excellent in melt characteristic, wide in the range of plasticity, and excellent in low-absorbency feature. SOLUTION: The composition is characterized in that therein a triglyceride containing an unsaturated fatty acid at position 2 and saturated fatty acids having 16 or more carbons at positions 1 and 3 (hereinafter to be referred to as 'symmetric triglyceride') occupies 50 wt.% or more in all the triglycerides and the lower limit X (wt.%) of the rate of the symmetric triglyceride containing polyvalent unsaturated a fatty acid at positions 2 in all the symmetric triglycerides is described by formula (1) which is X=20×N/[N+N']+20. In formula (1), N denotes the weight of bivalent unsaturated fatty acids out of position-2 polyvalent unsaturated fatty acids in the symmetric triglycerides containing a polyvalent unsaturated fatty acid at position 2 and N' denotes the weight of the unsaturated acid higher than trivalent out of position-2 polyvalent unsaturated fatty acids in symmetric triglycerides containing a polyvalent unsaturated fatty acid at position 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a plastic oil / fat composition having low absorbency, high nutritional value and excellent melting properties, which can be suitably used as confectionery or baking fat such as margarine, fat spread and shortening. About.

[0002]

2. Description of the Related Art
Because the melting properties of plastic fats were broad,
It was not always a good one. In order to impart sharp melting properties to plastic fats, that is, good melting properties in the mouth, use a fat-and-oil composition having symmetrical triglycerides as a main component which is excellent in sharp melting properties and used as hard butter in chocolate and the like. However, when such fats and oils are used in plastic fats such as margarine, fat spread, shortening, etc., they are hard at low temperatures, have a narrow plastic range, and have problems such as coarseness due to temporal crystal coarsening under non-tempering conditions. Was impossible.

[0003] On the other hand, symmetric triglycerides having low absorption have been favored as edible oils and fats from recent health consciousness.
From such a viewpoint, a plastic fat using a symmetric triglyceride is desired.

[0004] Accordingly, an object of the present invention is to provide a plastic fat composition having sharp and excellent melting properties, a wide plasticity range, and excellent low absorbency. Another object of the present invention is to provide a good plastic oil / fat composition free from problems such as graininess due to crystal coarsening.

[0005]

Means for Solving the Problems The present inventors have accomplished the present invention as a result of intensive studies in view of the above.

[0006] That is, the present invention relates to the method of
The proportion of triglycerides containing unsaturated fatty acids at positions and saturated fatty acids having 16 or more carbon atoms at positions 1 and 3 (hereinafter, simply referred to as symmetric triglycerides) is 50% by weight or more, and all symmetric The lower limit value X (% by weight) of the proportion of the symmetric triglyceride containing a polyunsaturated fatty acid at the 2 position in the triglyceride is represented by the following formula (1).
It is a plastic fat composition characterized by being represented by these.

Embedded image (Wherein, N is the weight of the diunsaturated fatty acid among the polyunsaturated fatty acids at the 2 position in a symmetric triglyceride containing a polyunsaturated fatty acid at the 2 position, and N ′ is the polyvalent unsaturated fatty acid at the 2 position. In a symmetric triglyceride containing unsaturated fatty acids, it is the weight of tri- or higher-valent unsaturated fatty acids among polyunsaturated fatty acids at two positions.)

[0007] The present invention also relates to the above plastic fat composition, wherein 90% by weight or more of the polyunsaturated fatty acid is linoleic acid and / or linolenic acid, and 70% by weight or more of the saturated fatty acid is carbon. The above-mentioned plastic fat composition which is a saturated fatty acid having 16 to 18 atoms.

Further, the present invention relates to the above plastic fat composition wherein the proportion of the symmetric triglyceride in which the 2-position is a trans fatty acid in the total symmetric triglyceride is 1 to 20% by weight. In the triglyceride, the weight ratio of palmitic acid to stearic acid in the saturated fatty acid constituting the triglyceride (weight of palmitic acid / weight of stearic acid: hereinafter referred to as P / St ratio) is more than 0.5. And the weight ratio of linolenic acid to linoleic acid (weight of linolenic acid / weight of linoleic acid: hereinafter, referred to as Ln / L ratio) in the unsaturated fatty acid constituting the triglyceride is symmetric. It is the above-mentioned plastic fat composition which is 1 or more.

[0009]

Embodiments of the present invention will be described below.

[0010] As described above, among the triglycerides, "a triglyceride containing an unsaturated fatty acid at position 2 and a saturated fatty acid having 16 or more carbon atoms at positions 1 and 3" is simply referred to in this specification. "Symmetric triglycerides"
Called.

In the plastic fat composition of the present invention, the proportion of the symmetric triglyceride in the total triglyceride is 50%.
% By weight, preferably 60% by weight or more.

If the proportion of the symmetric triglyceride is less than the above, the object of the present invention for obtaining low absorption using the symmetric triglyceride cannot be achieved.

The upper limit of the symmetric triglyceride ratio is not particularly limited, and may be 100% by weight.
From the viewpoint of industrial suitability, it can be said that preferably 95% by weight or less, more preferably 90% by weight or less.

The unsaturated fatty acid occupying the two positions of the symmetric triglyceride may be any unsaturated fatty acid known as a constituent fatty acid of edible fats and oils, such as oleic acid, elaidic acid, erucic acid, linoleic acid, linolenic acid, arachidone. Examples thereof include acids, EPA, DHA, and the like, and two or more of these may be mixed.

The saturated fatty acid having 16 or more carbon atoms occupying the 1,3 positions of the symmetric triglyceride may be any saturated fatty acid known as a constituent fatty acid of edible fats and oils, such as palmitic acid, stearic acid, arachiic acid, and the like.
Examples include behenic acid and lignoceric acid, and these may be used in combination of two or more.

As saturated fatty acids having 16 or more carbon atoms occupying the 1,3 positions of the symmetric triglyceride, saturated fatty acids having 16 to 18 carbon atoms are preferable from the viewpoint of industrial applicability. For example, palmitic acid and stearic acid include Often,
These may be mixed.

The plastic fat composition of the present invention contains the lower limit of the proportion of the symmetric triglyceride in such a symmetric triglyceride and containing the polyunsaturated fatty acid at two positions in the total symmetric triglyceride. X (% by weight)
This is represented by the following equation (1).

[0018]

Embedded image (Wherein, N is the weight of the diunsaturated fatty acid among the polyunsaturated fatty acids at the 2 position in a symmetric triglyceride containing a polyunsaturated fatty acid at the 2 position, and N ′ is the polyvalent unsaturated fatty acid at the 2 position. In a symmetric triglyceride containing unsaturated fatty acids, it is the weight of tri- or higher-valent unsaturated fatty acids among polyunsaturated fatty acids at two positions.)

Furthermore, a preferable lower limit value X 'of the proportion of the symmetric triglyceride containing a polyunsaturated fatty acid at the 2-position.
(% By weight) is represented by the following equation (2).

[0020]

Embedded image (Wherein N and N ′ are the same as above)

The upper limit of the proportion of the symmetric triglyceride containing a polyunsaturated fatty acid at the 2-position in the total symmetric triglyceride is not particularly limited, and may be 100% by weight, but is preferably 80% by weight. % By weight or less is good.

If the proportion of the symmetrical triglyceride containing a polyunsaturated fatty acid at the 2 position in the total symmetrical triglyceride is less than the above lower limit, it is hard at low temperatures and becomes unsuitable as a plastic fat. In addition, those exceeding the above preferable upper limit tend to be hardened at low temperatures, and may not always be preferable as plastic fats and oils.

The polyunsaturated fatty acid occupying two positions of the symmetrical triglyceride may be any polyunsaturated fatty acid known as a constituent fatty acid of edible fats and oils, such as linoleic acid, linolenic acid, arachidonic acid, EPA, DHA and the like can be exemplified, and two or more of these may be mixed. As these polyunsaturated fatty acids, linoleic acid and linolenic acid are preferable in terms of stability, and these may be mixed.

The plastic fat composition of the present invention is preferably
The proportion of the symmetric triglyceride in which the trans-fatty acid is located at the 2-position in the total symmetric triglyceride is preferably 1 to 20% by weight, more preferably 5 to 15% by weight. When the proportion of the symmetric triglyceride in which the 2-position is a trans fatty acid is within the above range, the crystal stability of the plastic fat composition of the present invention is improved, and the crystal is not coarsened over time, which is preferable. .

The plastic oil composition of the present invention is preferably a symmetric triglyceride having a P / St ratio of more than 0.5, more preferably not less than 1.0, in a saturated fatty acid constituting the triglyceride. Something is good. When the P / St ratio is as described above, the plasticity at a low temperature is improved, and a good plastic fat composition having a wider plasticity range is obtained.

The plastic fat composition of the present invention preferably has an Ln / L ratio of 0.1 or more, more preferably 0.2 or more, in the unsaturated fatty acid constituting the symmetric triglyceride. Good. When the Ln / L ratio is as described above, the crystal stability of the plastic fat composition of the present invention is improved, and the crystal is not coarsened over time, which is preferable.

The method for producing the above-mentioned plastic oil composition of the present invention is not limited at all, and it is sufficient that the composition finally becomes the above-mentioned composition. For example, fractionated fractions of various oils and fats, or transesterified oils are appropriately mixed, Alternatively, the composition may be prepared so as to have the above composition by further performing a treatment such as fractionation or transesterification. One example considered to be industrially preferable is a symmetric triglyceride containing a polyunsaturated fatty acid at the 2-position. And fat composition mainly containing glycerol and symmetrical triglyceride (triglyceride containing unsaturated fatty acid in 2 position and saturated fatty acid having 16 or more carbon atoms in 1 and 3 position) Can be suitably mixed to obtain a fat or oil composition having the above composition.

In order to obtain a fat / oil composition containing a symmetrical triglyceride as a main component containing a polyunsaturated fatty acid at the above two positions, for example, a polyunsaturated fatty acid containing a large amount of a polyunsaturated fatty acid as a constituent fatty acid It can be produced by transesterifying a fat-containing oil and a saturated fatty acid and / or a saturated fatty acid alcohol ester with a lipase having regiospecificity.

The polyunsaturated fatty acid-containing fats and oils containing a large amount of polyunsaturated fatty acids include, for example, corn oil, soybean oil, rice oil, evening primrose oil, linseed oil, fish oil, safflower oil, sunflower Fats and oils containing a large amount of polyunsaturated fatty acids such as linoleic acid and linolenic acid as constituent fatty acids, and mixtures of these fats and oils and slightly hydrogenated oils.

Examples of the saturated fatty acid include palmitic acid and stearic acid, and examples of the saturated fatty acid alcohol ester include the saturated fatty acid and a C1-6 fatty acid.
Esterified with a linear saturated monohydric alcohol, etc.,
For example, methyl palmitate, ethyl palmitate, methyl stearate, and ethyl stearate can be mentioned.

The lipase having the above-mentioned regioselectivity acts only on the fatty acids at the 1,3-positions of glyceride, and examples thereof include liposomes lipase, Aspergillus lipase, mucor lipase and the like. it can.

The transesterification reaction as described above may be performed by a known method as described in, for example, Japanese Patent Publication No. Sho 62-43678. By removing the carrier support and the like and performing distillation, fractionation, and the like, a fat-and-oil composition rich in symmetric triglycerides having polyunsaturated fatty acids at two positions can be obtained.

As another method for obtaining a fat / oil composition containing a symmetric triglyceride as a main component containing a polyunsaturated fatty acid at the above-mentioned two positions, palm oil, monkey fat, shea fat,
Position-specifically, fats and oils containing symmetric triglyceride as a main component, such as cocom fat, mango fat and fractionated fats thereof, and fats and oils containing polyunsaturated fatty acids containing a large amount of polyunsaturated fatty acids as constituent fatty acids (same as above) It can be produced by transesterification and fractionation using a lipase having the property (similar to the above).

Here, in both of the above two methods, if the distillation and fractionation are performed so that the symmetrical triglyceride having a polyunsaturated fatty acid at two positions is 60% by weight or more, the plastic fat composition of the present invention can be obtained. It is preferable because the above composition can be easily obtained.

Also, by separating oils and fats containing symmetric triglycerides having polyunsaturated fatty acids at two positions, such as high stearic acid soybean, palm oil, and mora butter, polyunsaturated fatty acids are contained at the two positions. An oil / fat composition containing a symmetric triglyceride as a main component can be obtained.

The oil / fat composition containing a symmetrical triglyceride having a polyunsaturated fatty acid at two positions as a main component obtained by the above-mentioned method is used to prepare palm oil, monkey fat, shea butter, cocoum fat, mango fat and / or An oil or fat composition mainly containing a symmetric triglyceride such as these fractionated fats (a triglyceride containing an unsaturated fatty acid at position 2 and a saturated fatty acid having 16 or more carbon atoms at positions 1 and 3) has the above composition The plastic fat composition of the present invention can be obtained by appropriately mixing such that

The composition of the plastic fat composition of the present invention, that is,
The composition of the constituent fatty acids in the triglyceride can be known by a known method, for example, the amount of a symmetric triglyceride can be known by liquid chromatography,
The 2-position fatty acid can be hydrolyzed with a 1,3-position specific lipase and then isolated by gas chromatography after isolating only the 2-position fatty acid.
A symmetric triglyceride having a polyunsaturated fatty acid at a position and a symmetric triglyceride (a triglyceride containing an unsaturated fatty acid at the 2 position and a saturated fatty acid having 16 or more carbon atoms at the 1 and 3 positions) What is necessary is just to adjust suitably the ratio of the fats and oils composition to be performed.

[0038]

Next, examples of the present invention will be described together with comparative examples.

[Examples 1 to 4 and Comparative Examples 1 and 2] 300 g of safflower oil, 300 g of palmitic acid, 500 g of industrial hexane, 0.9 g of Rhizopus dermer (100,000 U /
g) was subjected to a transesterification reaction at 40 ° C. for 24 hours. After completion of the reaction, hexane was distilled and the solvent was fractionated to obtain an oil / fat composition containing 61% by weight of a symmetric triglyceride having a polyunsaturated fatty acid at two positions. The obtained oil / fat composition was blended with palm fractionated fat (IV = 45) at various ratios to obtain various plastic oil / fat compositions. The analytical values are shown in Table 1 below. The solid fat content (SFC) was measured by pulse NMR, and the hardness was measured as stress by a rheometer (5 mm diameter circular adapter). Also,
From the relationship between temperature and SFC, the quality of sharp melting characteristics is good (excellent: the difference between SFC at 20 ° C and SFC at 30 ° C is 55 or more and SFC at 30 ° C is less than 20;
Good: The difference between the SFC at 10 ° C. and the SFC at 30 ° C. was 50 or more and the SFC at 30 ° C. was less than 20, poor: the condition of good was not satisfied. : Less than 15, good: 15 or more and less than 20, poor: 20 or more). The crystal stability was determined by melting the obtained plastic fat composition at 60 ° C., taking 10 mg of the composition on a slide glass, placing a cover glass thereon, and solidifying at 5 ° C. for 30 minutes. After storage at 1 ° C. for one month, the particle size of the crystals observed with a polarizing microscope (excellent: all crystals have a particle size of 1 μm or less, good: do not satisfy the conditions of excellent, but all crystals have a particle size of less than 10 μm,
Poor: Crystals of 10 μm or more were present).

[0040]

[Table 1]

Examples 5 to 9 and Comparative Example 3 Linseed oil 3
00g, 400 g of ethyl palmitate and 0.9 g (100,000 U / g) of Rhizopus delemer were subjected to transesterification at 50 ° C. for 24 hours. After completion of the reaction, the fatty acid ethyl ester was distilled off, and the solvent was fractionated to obtain an oil or fat composition containing 65% by weight of a symmetric triglyceride having a polyunsaturated fatty acid at two positions. The obtained oil / fat composition was blended with palm fractionated fat (IV = 45) at various ratios to obtain various plastic oil / fat compositions. These analytical values are shown in Table 2 below. In addition, solid fat content (SFC), stress as hardness,
Crystal stability was measured as described above.

[0042]

[Table 2]

[Examples 10 to 14] Safflower oil 300
g, stearic acid 300 g, industrial hexane 500 g,
0.9 g of lipase from Rhizopus dermar (100,000 U /
g) was subjected to a transesterification reaction at 40 ° C. for 24 hours. After completion of the reaction, hexane was distilled and the solvent was fractionated to obtain an oil / fat composition containing 61% by weight of a symmetric triglyceride having a polyunsaturated fatty acid at two positions. Next, take 300 g of linseed oil, 400 g of ethyl palmitate, and 0.9 g (100,000 U / g) of lipase derived from Rhizopus delemer,
The transesterification reaction was performed at 50 ° C. for 24 hours. After completion of the reaction, the fatty acid ethyl ester was distilled off, and the solvent was fractionated to obtain an oil or fat composition containing 65% by weight of a symmetric triglyceride having a polyunsaturated fatty acid at two positions. These obtained oil and fat compositions were blended in various ratios with palm fractionated fat (IV = 45) to obtain various plastic oil and fat compositions. The analytical values of these in the same manner as described above are shown in Table 3 below.

[0044]

[Table 3]

[Examples 15 to 20] Cotton seed stearin 1k
2 kg of acetone was added to the resulting mixture, and the mixture was heated to 40 ° C. with stirring to completely dissolve. Next, after cooling to 5 ° C. to precipitate crystals, the mixture was filtered with a filter cloth to obtain a crystal part. The obtained crystal part was desolvated with an evaporator and purified by a conventional method.
A cottonseed stearin fractionated fat containing 68% by weight of a symmetric triglyceride having a polyunsaturated fatty acid at the position was obtained. In addition, linseed oil 300 g, ethyl palmitate 400 g,
0.9 g of lipase derived from Rhizopus delemar (100,000 U /
g) was subjected to a transesterification reaction at 50 ° C. for 24 hours. After completion of the reaction, the fatty acid ethyl ester was distilled off, and the solvent was fractionated to obtain an oil or fat composition containing 65% by weight of a symmetric triglyceride having a polyunsaturated fatty acid at two positions. Also, 0.3 g of a nickel catalyst and 150 ppm of methionine were added to 900 g of palm fractionated fat (IV = 35).
To give hydrogenated isomerized hydrogenated oil to obtain a hydrogenated palm fractionated fat containing 53% by weight of a symmetric triglyceride containing a trans fatty acid at the 2 position. These three types of fats and oils, palm fractionated fat (IV = 45) and rapeseed oil (IV = 117) are blended in various ratios to obtain various types of plastics having symmetric triglyceride contents substantially equal to each other. An oil / fat composition was obtained. The analysis values of these in the same manner as described above are shown in Table 4 below.

[0046]

[Table 4]

[Examples 21 to 23] Safflower oil 300
g, stearic acid 300 g, industrial hexane 500 g,
0.9 g of lipase from Rhizopus dermar (100,000 U /
g) was subjected to a transesterification reaction at 40 ° C. for 24 hours. After completion of the reaction, hexane was distilled and the solvent was fractionated to obtain an oil / fat composition containing 61% by weight of a symmetric triglyceride having a polyunsaturated fatty acid at two positions. Next, take 300 g of linseed oil, 400 g of ethyl palmitate, and 0.9 g (100,000 U / g) of lipase derived from Rhizopus delemer,
The transesterification reaction was performed at 50 ° C. for 24 hours. After completion of the reaction, the fatty acid ethyl ester was distilled off, and the solvent was fractionated to obtain an oil or fat composition containing 65% by weight of a symmetric triglyceride having a polyunsaturated fatty acid at two positions. Also, 0.3 g of nickel catalyst was added to 900 g of palm fractionated fat (IV = 35),
Methionine (150 ppm) was charged, hydrogen was blown at 200 ° C., hydrogenated at 200 ° C., and hydrogenated by isomerization to obtain a hydrogenated palm fractionated fat isomerized oil containing 53% by weight of a symmetric triglyceride containing a trans fatty acid at two positions. The obtained two or three kinds of fats and oils compositions were blended in various ratios to obtain various kinds of plastic fats and oils compositions having almost the same amount of symmetric triglyceride. The analytical values of these in the same manner as described above are shown in Table 5 below.

[0048]

[Table 5]

The plastic fat compositions of the present invention of Examples 1 to 23 had sharp melting properties and good plasticity at low temperatures. In addition, since it is mainly composed of symmetric triglyceride, it has low absorbency and is rich in polyunsaturated fatty acids, so that it is nutritionally excellent. Furthermore,
Many of the examples were preferred because of their excellent crystal stability. In contrast, the plastic fat compositions of Comparative Examples 1 to 3 were inferior in plasticity and crystal stability at low temperatures.

[0050]

The plastic fat composition of the present invention has sharp and excellent melting characteristics, has a wide plasticity range, and is excellent in low absorption. Further, the plastic fat composition of the present invention contains a large amount of polyunsaturated fatty acids, and also has a characteristic of being nutritionally excellent in this respect. Further, among the plastic oil and fat compositions of the present invention, preferred are good plastic oil and fat compositions which are free from problems such as graininess due to crystal coarsening.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C11C 3/08 A23D 7/00 502 3/10 9/00 516 (72) Inventor Satsuki Hashimoto 7-chome Higashiogu, Arakawa-ku, Tokyo No. 2 35 Asahi Denka Kogyo Co., Ltd. (72) Inventor Maruzen Shoji 7-35 Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd. F term (reference) 4B026 DC05 DC06 DG01 DH01 DP03 DX02 4H059 BA26 BA30 BA33 BB02 BB04 BB06 BC06 BC13 BC48 CA35 CA37

Claims (6)

[Claims] 1. The proportion of triglycerides containing unsaturated fatty acids at the 2 position and saturated fatty acids having 16 or more carbon atoms at the 1 and 3 positions (hereinafter simply referred to as symmetrical triglycerides) in all triglycerides is 50% by weight. % Or more,
In addition, the lower limit value X (% by weight) of the proportion of the symmetric triglyceride containing a polyunsaturated fatty acid at the 2 position in the total symmetric triglyceride is represented by the following formula (1). Characteristic plastic fat composition. Embedded image (Wherein, N is the weight of the diunsaturated fatty acid among the polyunsaturated fatty acids at the 2 position in a symmetric triglyceride containing a polyunsaturated fatty acid at the 2 position, and N ′ is the polyvalent unsaturated fatty acid at the 2 position. In a symmetric triglyceride containing unsaturated fatty acids, it is the weight of tri- or higher-valent unsaturated fatty acids among polyunsaturated fatty acids at two positions.) 2. The plastic fat composition according to claim 1, wherein 90% by weight or more of the polyunsaturated fatty acid is linoleic acid and / or linolenic acid. 3. The plastic fat composition according to claim 1, wherein 70% by weight or more of the saturated fatty acid is a saturated fatty acid having 16 to 18 carbon atoms. 4. Occurrence of 2 in all symmetric triglycerides
The plastic fat composition according to any one of claims 1 to 3, wherein the proportion of the symmetric triglyceride in which the position is a trans fatty acid is 1 to 20% by weight. 5. The all-symmetric triglyceride according to claim 1, wherein the weight ratio of palmitic acid to stearic acid (weight of palmitic acid / weight of stearic acid) in the constituent saturated fatty acids is more than 0.5. The plastic fat composition according to any one of the above. 6. The weight ratio of linolenic acid to linoleic acid (weight of linolenic acid / weight of linoleic acid) of the unsaturated fatty acid constituting the symmetric triglyceride is 0.1 or more. The plastic fat composition according to any one of the above.