JP3608011B2 - Antioxidant for polyunsaturated fatty acid or oil containing fat containing polyunsaturated fatty acid - Google Patents

Description

。
【００２２】
なお、下記において用いた（実験に供した）精製魚油の脂肪酸組成は以下の通りである。
【００２３】
【表２】

。
【００２４】
実施例１〜６及び比較例１〜４
（液体油に対するショ糖脂肪酸エステルの溶解性）
上記調製例１〜６及び比較調製例１〜４で調製したショ糖脂肪酸エステルを精製魚油に５重量％添加し、一旦７０℃まで加熱溶解した後、２０℃まで冷却し、２４時間静置した。その状態を観察した。結果を下記［表３］に示す。
【００２５】
【表３】

［表３］から明らかなように、調製例１〜６のショ糖脂肪酸エステルは、精製魚油に対する溶解性が良好である。
【００２６】
実施例７〜１４及び比較例５〜８（ショ糖脂肪酸エステルの抗酸化力の評価）
上記調製例１〜６及び比較調製例１〜４で調製したショ糖脂肪酸エステルの抗酸化力の評価を実施した。
【００２７】
評価は上記実施例で用いた精製魚油を対象にしてショ糖脂肪酸エステルを所定量添加し、一旦７０℃まで加熱して溶解させた後、６０℃のオーブンテスト（酸化促進テスト）に供して一定時間経過後、ＰＯＶ（過酸化物価）を測定することで行った。
【００２８】
なお、ＰＯＶは基準油脂分析試験法に従い測定した。結果を下記［表４］に示す。
【００２９】
【表４】

［表４］から明らかなように、調製例１〜６のショ糖脂肪酸エステルを精製魚油に対して添加することにより、精製魚油の酸化が抑制されていることが分かる。特に、前記のショ糖脂肪酸エステルを０．５重量％以上添加することにより、１４日目のＰＯＶを、無添加の場合の１／２以下とすることができ、酸化防止作用が顕著であることが判る。
【００３０】
実施例１５〜２０（油脂の着色に対するショ糖脂肪酸エステルの影響）
上記実施例で用いた精製魚油にショ糖脂肪酸エステルを１重量％加え、６０℃で２週間保存したときの着色の程度をＧ Ｎｏ．（ガードナーナンバー）で評価した。結果を下記［表５］に示す。
【００３１】
【表５】

［表５］から明らかなように、調製例１〜６のショ糖脂肪酸エステルは、油脂を著しく着色させない。
【００３２】
【発明の効果】
本発明の酸化防止剤は、多価不飽和脂肪酸あるいは多価不飽和脂肪酸を含有する油脂に対する抗酸化性に優れ、液体油に対する溶解性にも優れ、かつ、添加しても油脂を着色するおそれがない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antioxidant, and more particularly, to an antioxidant for polyunsaturated fatty acids or polyunsaturated fatty acid-containing oils and fats.
[0002]
[Prior art and problems to be solved by the invention]
Linoleic acid, linolenic acid, and polyunsaturated fatty acids such as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) are important substances as precursors of essential fatty acids or prostaglandins. It is also attracting attention in terms of physiological activities such as thrombotic action and senile dementia prevention. These are used in foods in the form of fatty acids or fats.
[0003]
Currently, oxidation is the biggest obstacle to using these polyunsaturated fatty acids or polyunsaturated fatty acid-containing fats and oils.
[0004]
When there are many unsaturated bonds, oxidation tends to proceed, and harmful peroxides are generated and acid odor is produced. Therefore, when used in foods, it is necessary to take measures to prevent oxidation.
As a method of preventing oxidation,
(1) Addition of antioxidant (2) Coating of fatty acid or oil and fat, powdering, etc. are mentioned, but the effect is not sufficient.
[0005]
For example, although BHT (butylated hydroxytoluene), BHA (t-butylhydroxyanisole), tocopherol, etc. are currently approved as antioxidants in Japan, there are restrictions on the use of BHT and BHA, and safety The use was almost refrained from doubt. Furthermore, there is an optimum amount of tocopherol that gives the strongest antioxidant power, and there is a limit to the antioxidant power that can be expected.
[0006]
In addition, the technology of coating and powdering is effective to some extent, but this technology cannot completely block oil and air, and it is also disadvantageous in terms of the complexity of the process and cost. On the other hand, it was not a satisfactory method considering the restrictions on use resulting from the form.
[0007]
Conventionally, it is known that certain food emulsifiers have an antioxidant effect on fats and oils. For example,
1) Aoyama et al. Examined the antioxidant properties of sucrose fatty acid esters to fats and oils. Although sucrose fatty acid esters do not exhibit an antioxidant effect on palm oil, they are a little antioxidant against lard. It has been reported to show an effect (Aoyama Satoshi, Maruyama Takenori, Kanematsu Hiroshi, Shintani Tsutomu: Yukagaku, 34 , 554 (1985)).
[0008]
However, Aoyama et al. Reported nothing about fats other than lard and palm oil, such as fish oil, but the sucrose fatty acid ester mentioned here is mainly composed of stearic acid and palmitic acid. It is.
[0009]
In addition, sucrose fatty acid esters mainly composed of stearic acid and palmitic acid reported by Aoyama et al. Have poor solubility in fats and oils, so when added to liquid oil such as fish oil, it becomes cloudy and precipitates may be formed depending on the storage temperature. When used in the food industry, it points out inconveniences such as clogging with a strainer and poor appearance.
[0010]
2) Hara et al. Have reported on the antioxidant behavior of phospholipids (lecithin) against highly unsaturated fatty acids in fish oil (Setuko Hara, Norio Okada, Hidehiko Hibino, Yoichiro Totani: Yukagaku, 41 , 130 (1992)). .
[0011]
According to the above report, although lecithin has an antioxidant power against fish oil, it needs to be added in an amount of 5-8% or more with respect to fish oil.
[0012]
The present invention has been made paying attention to such conventional problems, and its purpose is excellent in antioxidation to polyunsaturated fatty acids or fats and oils containing polyunsaturated fatty acids, and to liquid oils. An object of the present invention is to provide an antioxidant which is excellent in solubility and which does not have a risk of coloring fats and oils even when an effective amount is added.
[0013]
[Means for Solving the Problems]
The antioxidant for polyunsaturated fatty acids or polyunsaturated fatty acid-containing oils and fats according to claim 1 comprises a sucrose fatty acid ester, and the content of saturated fatty acids having 8 to 22 carbon atoms in the fatty acids is 20 to 20. It is composed of sucrose fatty acid ester in which the content of unsaturated fatty acid having 80% by weight and 8 to 22 carbon atoms is 80 to 20% by weight and the average substitution degree of the fatty acid with respect to sucrose is 2 to 6 It is.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the saturated fatty acid having 8 to 22 carbon atoms include lauric acid, myristic acid, palmitic acid, and stearic acid. Examples of the unsaturated fatty acid having 8 to 22 carbon atoms include palmitooleic acid, oleic acid, and linoleic acid. And linolenic acid.
[0015]
When the proportion of saturated fatty acids is less than 20% (when the proportion of unsaturated fatty acids exceeds 80%), the antioxidant power becomes weak, and when the proportion of saturated fatty acids exceeds 80% (the proportion of unsaturated fatty acids is less than 20%) In the case of), the solubility in liquid oil deteriorates.
[0016]
Moreover, the average substitution degree of the fatty acid with respect to sucrose is 2-6. When the average degree of substitution is less than 2, the solubility in fats and oils is deteriorated, and when it exceeds 6, the antioxidant power is weakened.
[0017]
The polyunsaturated fatty acid targeted by the antioxidant of the present invention has two or more unsaturated bonds. For example, linoleic acid, α-linolenic acid, γ-linolenic acid, eleostearic acid, EPA, DHA However, it is not particularly limited.
Moreover, the fats and oils which are the objects of the present invention have a polyunsaturated fatty acid content of 30% or more in the constituent fatty acids. This is because a nutritionally desirable fatty acid intake ratio is set to saturated fatty acid: monounsaturated fatty acid: polyunsaturated fatty acid = 1: 1.5: 1. Such fats and oils include cocoon oil, cocoon oil, cocoon oil, marine chlorella oil, menhaden oil, apricot kernel oil, linseed oil, orange seed oil, pumpkin seed oil, sesame oil, evening primrose seed oil, sunflower oil, cottonseed oil, etc. Although not limited to these, even if the content of polyunsaturated fatty acids in the raw material oil is low, the content of unsaturated fatty acids is 30% by a purification technique such as extraction or fractionation. If it becomes the above, it will become the target fats and oils of this invention.
[0018]
The sucrose fatty acid ester of the present invention is added in an amount of 0.5 to 10% by weight based on a polyunsaturated fatty acid or an oil containing the polyunsaturated fatty acid.
[0019]
When it is less than 0.5% by weight, the antioxidant power is weakened, and when it exceeds 10% by weight, the cost is increased, which is economically disadvantageous.
[0020]
【Example】
Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 4 (Preparation of sucrose fatty acid ester)
Sucrose fatty acid esters were prepared by the Snell method. For the prepared sucrose fatty acid ester, the composition of the constituent fatty acid and the degree of substitution of the fatty acid were determined by GLC (gas chromatography), GPC, and OHV (hydroxyl value) measurement. The analysis results are shown in [Table 1] below.
[0021]
[Table 1]

.
[0022]
In addition, the fatty acid composition of the refined fish oil used in the following (for the experiment) is as follows.
[0023]
[Table 2]

.
[0024]
Examples 1-6 and Comparative Examples 1-4
(Solubility of sucrose fatty acid esters in liquid oil)
5% by weight of the sucrose fatty acid ester prepared in the above Preparation Examples 1-6 and Comparative Preparation Examples 1-4 was added to purified fish oil, once heated to 70 ° C and dissolved, then cooled to 20 ° C and allowed to stand for 24 hours. . The state was observed. The results are shown in [Table 3] below.
[0025]
[Table 3]

As is clear from [Table 3], the sucrose fatty acid esters of Preparation Examples 1 to 6 have good solubility in purified fish oil.
[0026]
Examples 7 to 14 and Comparative Examples 5 to 8 (Evaluation of antioxidant power of sucrose fatty acid ester)
The antioxidant power of the sucrose fatty acid esters prepared in Preparation Examples 1-6 and Comparative Preparation Examples 1-4 was evaluated.
[0027]
Evaluation is made by adding a predetermined amount of sucrose fatty acid ester to the refined fish oil used in the above examples, once heated to 70 ° C. and dissolved, and then subjected to an oven test (oxidation promotion test) at 60 ° C. After the passage of time, POV (peroxide value) was measured.
[0028]
The POV was measured according to the standard oil and fat analysis test method. The results are shown in [Table 4] below.
[0029]
[Table 4]

As is apparent from [Table 4], it can be seen that the oxidation of the purified fish oil is suppressed by adding the sucrose fatty acid esters of Preparation Examples 1 to 6 to the purified fish oil. In particular, by adding 0.5% by weight or more of the sucrose fatty acid ester, the POV on the 14th day can be reduced to 1/2 or less of the case of no addition, and the antioxidant action is remarkable. I understand.
[0030]
Examples 15 to 20 (Effect of sucrose fatty acid ester on fat and oil coloring)
When the sucrose fatty acid ester was added at 1% by weight to the refined fish oil used in the above examples and stored at 60 ° C. for 2 weeks, the degree of coloring was determined according to G No. (Gardner number) evaluated. The results are shown in [Table 5] below.
[0031]
[Table 5]

As is apparent from [Table 5], the sucrose fatty acid esters of Preparation Examples 1 to 6 do not significantly color the fats and oils.
[0032]
【The invention's effect】
The antioxidant of the present invention is excellent in antioxidation property to oils and fats containing polyunsaturated fatty acids or polyunsaturated fatty acids, excellent in solubility in liquid oils, and may be colored even if added. There is no.

Claims (1)

An antioxidant comprising sucrose fatty acid ester,
In the fatty acid, the content of the saturated fatty acid having 8 to 22 carbon atoms is 20 to 80% by weight, the content of the unsaturated fatty acid having 8 to 22 carbon atoms is 80 to 20% by weight, and The antioxidant for polyunsaturated fatty acids or polyunsaturated fatty acid containing fats and oils which consists of sucrose fatty acid ester whose average substitution degree of a fatty acid is 2-6.