JP5717356B2 - Oil composition containing vitamin B1 - Google Patents

Description

  The present invention relates to a vitamin B1-containing oil and fat composition.

Oils and fats are important nutrients along with proteins and carbohydrates, and are particularly useful as energy sources. In addition, fats and oils are used as a heat medium for cooking. In addition, it is an important material that imparts a good flavor of the oil itself. Against the background of health orientation in recent years, attempts have been made to enhance the appeal of products by strengthening nutritional components in edible oils, for example, stabilized tocopherol containing α-, β-tocopherol with high physiological activity at a high content An oil-and-fat composition (Patent Document 1) and the like have been reported.
The tocopherol is a kind of vitamin E, which is a fat-soluble vitamin, and is a component originally contained in fats and oils as a natural component. However, many of the nutritional components are insoluble in oil, and many of them cannot add the amount that they originally want to strengthen.

  On the other hand, vitamin B1 is one of the water-soluble vitamins involved in carbohydrate metabolism, normalization of nerve function, etc., and it is important to take an appropriate amount of vitamin B1 for maintaining human health. It tends to be deficient due to the increase in food consumption and dependence on processed foods. When supplementing vitamin B1 with a nutrient-enriched food, it is desirable to be able to take 1/3 or more of the daily requirement based on the “6th revised Japanese nutritional requirement”.

JP-A-8-173035

Since vitamin B1 has low solubility and exhibits a unique bitter taste, the blending amount thereof must be limited, and there is a problem that the flavor of foods and the like is lowered by blending. The present inventor tried to dissolve the vitamin B1 derivative in an edible oil that has been used in the past and contains triacylglycerol as a main component, but it has been found that a sufficient amount cannot be dissolved.
Therefore, the subject of this invention is providing the oil-fat composition which has few bitter tastes and melt | dissolves vitamin B1 with high concentration.

  As a result of intensive studies, the inventor has found that when the hydroxyl value (OHV) of the oil and fat composition is not less than a certain value and the content of the vitamin B1 derivative and the value of the hydroxyl value satisfy a certain relationship, the vitamin It has been found that the B1 derivative can be dissolved at a high concentration, and that the bitterness is reduced despite the high vitamin B1 derivative concentration.

That is, the present invention is an oil and fat composition containing a vitamin B1 derivative or a salt thereof in an amount of 44 to 8,000 ppm in terms of thiamine and having a hydroxyl value of 9 to 100 mg-KOH / g, the vitamin B1 derivative or a salt thereof The oil and fat composition in which the content C (ppm) in terms of thiamine and the hydroxyl value X (mg-KOH / g) satisfy the relationship of the following formula (1) is provided.
(Equation 1)
[Ln (C / 143)] / X ≦ 0.044 (Ln: natural logarithm) (1)

  According to the present invention, it is possible to provide an oil and fat composition that has little bitter taste and contains a high concentration of vitamin B1 dissolved therein.

The oil and fat composition of the present invention has a hydroxyl value (OHV) of 9 to 100 mg-KOH / g, particularly 20 to 100 mg-KOH / g, more preferably 40 to 100 mg-KOH / g. It is preferable from the viewpoint of improving solubility and suppressing bitterness.
Here, the hydroxyl value is a value measured by “hydroxyl number (pyridine-acetic anhydride method 2.3.6.2-1996)” in “Standard Oil Analysis Test Method 2003 Edition” edited by Japan Oil Chemists' Society.
Details of the method for measuring the hydroxyl value are described in Examples.

The oil and fat composition having a hydroxyl value (OHV) of 9 to 100 mg-KOH / g or more according to the present invention can be prepared by combining oils and emulsifiers alone or in an appropriate combination so that the hydroxyl value is in the above range. It is preferable to use one having a high content of glycerol and / or diacylglycerol.
In the present invention, “oil / fat” includes one or more of triacylglycerol, diacylglycerol, and monoacylglycerol.
In the oil and fat composition of the present invention, the content of diacylglycerol is preferably 10% by mass (hereinafter simply referred to as “%”) or more, more preferably 20% or more, particularly 40% or more. It is preferable from the point of improvement and bitterness suppression. The upper limit is not particularly defined, but is preferably 99% or less, more preferably 98% or less, and still more preferably 97% or less.
In addition, the content of monoacylglycerol is preferably 0 to 5%, more preferably 0 to 2%, particularly 0.1 to 2%, in terms of improving the solubility of vitamin B1 and suppressing bitterness, as an edible oil From the viewpoint of flavor and industrial productivity, it is preferable.

  The fats and oils in the fat and oil composition of the present invention may be made from either vegetable oils or animal fats. Specific raw materials include, for example, vegetable oils such as soybean oil, rapeseed oil, safflower oil, rice bran oil, corn oil, palm oil, sunflower oil, cottonseed oil, olive oil, sesame oil, perilla oil, fish oil, lard, Animal fats and oils such as beef tallow and butter fats, or fats and oils such as transesterified oils, hydrogenated oils and fractionated oils can be mentioned, but those that are not hydrogenated constitute edible fats and oils This is preferable from the viewpoint of reducing the content of trans-unsaturated fatty acids in the total fatty acids.

  Fatty acids constituting the fats and oils in the fat and oil composition of the present invention are not particularly limited, and may be either saturated fatty acids or unsaturated fatty acids, but 40 to 100% are preferably unsaturated fatty acids, more It is preferably 80 to 100%, more preferably 90 to 100% from the viewpoint of appearance and industrial productivity of fats and oils. The number of carbon atoms of the unsaturated fatty acid is preferably 14 to 24, and more preferably 16 to 22 from the viewpoint of physiological effects.

  Moreover, it is preferable that content of a saturated fatty acid is less than 60% among the fatty acids which comprise the fats and oils in an oil-fat composition, More preferably, it is 0-20%, Furthermore, it is 0-10%, an external appearance, It is preferable in terms of physiological effects and industrial productivity of fats and oils. The saturated fatty acid is preferably those having 14 to 24 carbon atoms, particularly 16 to 22 carbon atoms.

  Of the fatty acids constituting the fats and oils in the fat and oil composition, the content of trans-unsaturated fatty acids is 0 to 4%, preferably 0.1 to 3.5%, and more preferably 0.2 to 3%. From the viewpoint of physiological effect, appearance, and industrial productivity of fats and oils.

  Examples of the emulsifier to be added to the oil and fat composition of the present invention include monoacylglycerol, diacylglycerol, polyglycerin condensed ricinoleic acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan Examples include polyol fatty acid esters such as fatty acid esters and propylene glycol fatty acid esters.

  The oil and fat composition in the present invention contains 44 to 8,000 ppm of vitamin B1 derivative or a salt thereof in terms of thiamine, and the content thereof is further 44 to 5,000 ppm, particularly 44 to 3,000 ppm, more preferably. Is preferably from 150 to 3,000 ppm from the viewpoint of stability and physiological effects. The content of the vitamin B1 derivative in the oil / fat composition can be measured by the method described in Examples.

Examples of the vitamin B1 derivative or salt thereof in the present invention include bisbenchamine disulfide, benfotiamine, fursultiamine, octothiamine, dibenzoylthiamine, chicotiamine, sulbutiamine, acetylamine, dicetiamine, or salts thereof. The salt may be a pharmaceutically acceptable salt, for example, a mineral salt such as nitrate, hydrochloride, sulfate, etc .; acetate, propionate, tartrate, fumarate, maleate, malic acid Organic salts such as salt, citrate, methanesulfonate, p-toluenesulfonate, trifluoroacetate and the like can be mentioned. These can be used by appropriately selecting one or two or more. Of these, vitamin B1 derivatives, particularly bisbenchamine disulfide, are preferred in terms of solubility and physiological effects.
The vitamin B1 derivative or a salt thereof is a known compound, and as a method for obtaining the vitamin B1 derivative, a commercially available product may be used, or it can be produced based on a known method.

In the oil and fat composition of the present invention, the content C (ppm) of the vitamin B1 derivative or its salt in terms of thiamine and the hydroxyl value X (mg-KOH / g) satisfy the relationship of the following formula (1).
[Ln (C / 143)] / X ≦ 0.044 (Ln: natural logarithm) (1)
Ln: natural logarithm

Furthermore, when the content C (ppm) of the vitamin B1 derivative or its salt in terms of thiamine and the hydroxyl value X (mg-KOH / g) satisfy the following formula (2), the bitterness derived from the vitamin B1 derivative is further suppressed. The inventor has found that this can be done.
[Ln (C / 82)] / X ≦ 0.04 (2)
Ln: Same as above

That is, in the present invention, the amount of the vitamin B1 derivative that is dissolved varies depending on the hydroxyl value of the oil and fat composition. Specifically, when the content C of the vitamin B1 derivative or a salt thereof in terms of thiamine is 44 ppm or more and 8,000 ppm or less, the hydroxyl value of the oil or fat composition is 9 mg-KOH / g or more and 100 mg-KOH / g or less. However, when the content C is 500 ppm or more and 8,000 ppm or less, the hydroxyl value is preferably 30 mg-KOH / g or more and 50 mg-KOH / g from the viewpoint of improving the solubility of vitamin B1 and suppressing the bitterness. More preferably, it is the above.
When the content C is 1,000 ppm or more and 8,000 ppm or less, the hydroxyl value is preferably 50 mg-KOH / g or more, more preferably 66 mg-KOH / g or more from the same point. . When the content C is 1,500 ppm or more and 8,000 ppm or less, the hydroxyl value is preferably 60 mg-KOH / g or more, more preferably 76 mg-KOH / g or more from the same point.

The oil and fat composition of the present invention can further contain vitamin C or a derivative thereof, or nicotinamide, dissolved therein. Examples of vitamin C or derivatives thereof include ascorbic acid, ascorbyl palmitate, ascorbate stearate, and the like. Nicotinamide is a kind of niacin belonging to the vitamin B group.
The content of vitamin C or a derivative thereof in the oil and fat composition is preferably 420 to 8,400 ppm, particularly 2,100 to 8,400 ppm in terms of ascorbic acid. Further, the content of nicotinic acid amide is preferably 1,000 to 20,000 ppm, particularly preferably 1,000 to 6,000 ppm.

  An antioxidant may be added to the oil and fat composition of the present invention from the viewpoint of improving the storage stability and flavor stability, as in the case of general edible oils and fats. Antioxidants include natural antioxidants, tocopherols, BHT, BHA, phospholipids, organic carboxylic acids, polyphenols and the like.

  The water content in the oil and fat composition of the present invention is preferably 15,000 ppm or less, more preferably 10,000 ppm or less, particularly 3,000 ppm or less, in terms of storage stability and usability during cooking. To preferred.

  The oil and fat composition of the present invention can be used in the same manner as general edible oils and fats, and can also be used for various foods and drinks, feeds and pharmaceuticals. Food / beverage products include, for example, drinks, desserts, ice creams, dressings, toppings, mayonnaise, roasted meat and other oil-in-water processed foods; margarine, spreads and other water-in-oil processed oils; peanut butter Processed fats and oils such as baking shortenings; processed foods such as potato chips, snacks, cakes, cookies, pies, breads, chocolates; bakery mixes; processed meat products; frozen entrées;

[Analysis method]
(i) Glyceride composition About 10 mg of an oil and fat sample and 0.5 mL of a trimethylsilylating agent (“silylating agent TH”, manufactured by Kanto Chemical) were added to a glass sample bottle, sealed, and heated at 70 ° C. for 15 minutes. To this, 1.0 mL of water and 1.5 mL of hexane were added and shaken. After standing, the upper layer was analyzed by gas chromatography (GLC).

(ii) Fatty acid composition Fatty acid methyl ester was prepared according to “Fatty acid methyl ester preparation method (2.4.1.-1996)” in “Standard oil analysis test method” edited by Japan Oil Chemists' Society. , American Oil Chemists. It was measured by Society Official Method Ce 1f-96 (GLC method).

(iii) Hydroxyl value In accordance with “Hydroxyl number (pyridine-acetic anhydride method 2.3.6.2-1996)” in “Standard Analysis Method for Fats and Oils” edited by the Japan Oil Chemists' Society, a sample of fats and oils was placed in a round-bottom flask on the neck. 5 g was weighed, 5 ml of acetylating reagent was added, a small funnel was placed on the neck of the flask, and the bottom of the flask was submerged in a heating bath to a depth of about 1 cm and heated to 95-100 ° C. After 1 hour, the flask was taken out of the heating bath, cooled, 1 ml of distilled water was added from the funnel, and again placed in the heating bath and heated for 10 minutes. The solution was cooled again to room temperature, and the liquid condensed on the funnel and the neck of the flask was washed into the flask with 5 ml of neutral ethanol and titrated with a 0.5 mol / L potassium hydroxide-ethanol standard solution using a phenolphthalein indicator. In addition, the blank test was performed in parallel with this test, and the value calculated from the titration result based on the following formula was defined as “hydroxyl value (mg-KOH / g)” (OHV).
Hydroxyl value = (A−B) × 28.05 × F / C + acid number (A: 0.5 mol / L potassium hydroxide-ethanol standard solution used in blank test (ml), B: 0.5 mol of this test) / L potassium hydroxide-ethanol standard solution usage (ml), F: factor of 0.5 mol / L potassium hydroxide-ethanol standard solution, C: sampling amount (g))

(Iv) Quantification of bisbenchamine disulfide 0.3 g of Tween 80, 5 ml of acetic acid buffer solution and 1 ml of 10% thiourea solution were added to 0.5 g of an oil and fat sample to adjust the pH to 4.5.
3 ml of 2.5% -Takadiastase solution was added and left overnight at 40 degrees. 5 ml of 2N hydrochloric acid and 70 ml of ethanol were added and treated at 70 ° C. for 30 minutes with occasional stirring. The extract was adjusted to a volume of 100 ml with distilled water and filtered. 1 ml of 0.7% -cysteine solution was added to 5 ml of the extract, and 1 ml of 4N-sodium hydroxide solution was added and reacted at room temperature for 30 minutes, and then 1 ml of 4N-hydrochloric acid was added and the volume was adjusted to 20 ml with distilled water Was subjected to HPLC.
HPLC conditions:
Column: ODS-3 (4.6 ID × 250 mm), GL Sciences column temperature: 40 ° C.
Mobile phase: (0.01 mol-sodium dihydrogen phosphate + 0.15 mol / L-sodium perchlorate) mixed solution (pH 2.2): methanol = 95: 5
Mobile phase flow rate: 1 ml / min
Injection volume: 20 μl
Detection: Fluorescence detector Ex = 375 nm, Em = 440 nm
Reaction solution: 0.05% potassium ferricyanide + 15% -sodium hydroxide Reaction solution flow rate: 0.4 ml / min

(V) Determination of nicotinic acid amide 2 g of methanol was added to 1 g of an oil and fat sample, and the mixture was well stirred with a vortex mixer. To the residual liquid, 2 ml of methanol was added and extracted in the same manner. The extraction operation was performed three times with methanol, and the methanol phases were combined and dried under a nitrogen stream at room temperature. After dissolving in 1 ml of acetonitrile, it was washed 3 times with 1 ml of hexane. The acetonitrile phase after washing was dried at room temperature under a nitrogen stream, dissolved and fixed in acetonitrile again, and subjected to HPLC.
HPLC conditions:
Column: ODS-3 (4.6 ID × 250 mm), GL Sciences column temperature: 40 ° C.
Mobile phase: 0.05N-mixed solvent gradient of sodium dihydrogen phosphate (A) / methanol (B): A / B = 95/5 (0 min) → A / B = 5/95 (50 min)
Mobile phase flow rate: 0.5 ml / min
Injection volume: 20 μl
Detection: UV detector 260 nm

(Vi) Quantitative determination of ascorbyl palmitate 0.5 g of ascorbic acid and 20 ml of 80% ethanol were added to 5 g of an oil and fat sample, and the mixture was stirred with a vortex mixer. After stationary separation, the ethanol layer was collected, 10 ml of 80% -ethanol was added to the residue, the same operation was performed, and the ethanol layer was collected. Again, 10 ml of 80% ethanol was added to the residue, and the same operation was performed. The obtained ethanol layers were combined, and the volume was adjusted to 50 ml with 0.05 N-acetic acid buffer (pH 4) (buffer A), followed by filtration through a glass filter. 2 ml of the filtrate was loaded onto a solid phase extraction column (Sep-Pak C18) previously treated with 10 ml of methanol and 5 ml of buffer solution (A), and 10 ml of distilled water and 5 ml of a mixed solution of buffer solution A: ethanol = 1: 1. After washing, elution was performed with 4 ml of methanol. 0.2 ml of 1% homocysteine aqueous solution was added to the eluate, treated at 40 ° C. for 15 minutes, and the volume was adjusted to 10 ml with 1% ascorbic acid aqueous solution and subjected to HPLC.
HPLC conditions:
Column: ODS-3 (4.6 ID × 250 mm), GL Sciences column temperature: 40 ° C.
Mobile phase: methanol / 0.05 M acetate buffer (pH 6.5) = 85: 15 mixed solution mobile phase flow rate: 1 ml / min
Injection volume: 20 μl
Detection: UV detector 265nm
(Vii) Measurement of moisture content The moisture content of the oil and fat composition was measured by a Karl Fischer coulometric titration method using Tightland 851 (manufactured by Metrohm Japan).

[Preparation of raw oil and fat (1)]
A mixed fatty acid of soybean oil fatty acid: rapeseed oil fatty acid = 7: 3 (mass ratio) and 15 parts by mass of glycerin were mixed, and an esterification reaction was performed with an enzyme to obtain a diacylglycerol-containing fat. Fatty acid and monoacylglycerol were removed from the resulting esterified product by distillation, acid-treated (2% of 10% aqueous citric acid solution was added), washed with water, and deodorized to obtain oil (1). Table 1 shows the glyceride composition and the fatty acid composition.

  Rapeseed oil (manufactured by Nisshin Oillio Group Co., Ltd.) was used as raw material fat (2), and glycerin fatty acid monoester (O-95R, manufactured by Kao Corporation) was used as raw material fat (3). Table 1 shows the glyceride composition and fatty acid composition of the raw oils and fats (2) and (3).

[Preparation of fats and oils A to G]
The fats and oils A to G were prepared by mixing the raw fats and oils (1) to (3) at a mass ratio shown in Table 2. Table 2 shows the glyceride composition and the hydroxyl value of the fats and oils A to G.

[Solubility test]
The state after leaving the oil / fat composition after heating and stirring at room temperature for 24 hours was observed, and the solubility was evaluated according to the following criteria.
○: Dissolved transparently ×: Turbid and undissolved

〔sensory evaluation〕
The fat and oil compositions 1 to 2 g were eaten with a specialized panel, and the bitterness was evaluated according to the following criteria.
3: Bitter 2: Slightly bitter 1: Not bitter

Example 1
Add bisbenchamine disulfide (manufactured by Mitsubishi Tanabe Seiyaku) to the fats and oils A to G in the mass ratios shown in Tables 3 and 4, and perform heating and stirring for 2 hours in an 80 ° C. hot water bath. Thus, oil and fat compositions 1 to 24 were prepared. Analytical values are shown in Tables 3 and 4.

  Next, the above-described solubility test and bitter sensory evaluation were performed using each oil and fat composition. The results are shown in Tables 3 and 4.

As can be seen from Tables 3 and 4, the oil and fat composition of the present invention was able to contain the vitamin B1 derivative dissolved at a high concentration and had little bitterness. In oil composition 15-24, undissolved vitamin B1 derivative was observed.
Furthermore, the fat and oil compositions 2, 4, 6, 7, 9, 11, 13, and 14 were preferable as edible oils because the bitterness derived from the vitamin B1 derivative was further suppressed.

Example 2
Add bisbenchamine disulfide (manufactured by Mitsubishi Tanabe Pharma Corporation) and L-ascorbyl palmitate (manufactured by DSM Nutrition) or nicotinamide (manufactured by Sigma-Aldrich) at a mass ratio shown in Table 5 to fat C or G. The oil and fat compositions 25-30 were prepared by heating and stirring for 2 hours in a 80 degreeC hot water bath. The analytical values are shown in Table 5.

  Next, using each oil and fat composition, a solubility test and a bitter taste sensory evaluation were performed in the same manner as described above. The results are shown in Table 5.

  As can be seen from Table 5, the oil-and-fat composition of the present invention can contain ascorbyl palmitate or nicotinamide at a high concentration in addition to the vitamin B1 derivative, and has little bitterness.

Claims (5)

Vitamin B1 derivative or a salt thereof contained 44~8,000ppm with thiamine terms, hydroxyl value Ri 9~100mg-KOH / g der, 80 to 100 wt% of the fatty acid constituting the fat or oil is Ru unsaturated fatty der An oil / fat composition, wherein the content C (ppm) of the vitamin B1 derivative or salt thereof in terms of thiamine and the hydroxyl value X (mg-KOH / g) satisfy the relationship of the following formula (1).
(Equation 1)
[Ln (C / 143)] / X ≦ 0.044 (Ln: natural logarithm) (1) The fat and oil composition according to claim 1, wherein the content C (ppm) of the vitamin B1 derivative or a salt thereof in terms of thiamine and the hydroxyl value X (mg-KOH / g) satisfy the relationship of the following formula (2).
(Equation 2)
[Ln (C / 82)] / X ≦ 0.04 (Ln: natural logarithm) (2)   The fat and oil composition according to claim 1 or 2, wherein the vitamin B1 derivative is bisbenchamine disulfide.   Furthermore, the fats and oils composition of any one of Claims 1-3 containing vitamin C or its derivative (s), or nicotinic acid amide.   It is an edible oil, The oil-fat composition of any one of Claims 1-4.