JP2516779B2 - Hard butter-like substance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a hard butter-like substance. Specifically, it relates to a hard butter-like substance composed of sucrose fatty acid ester.

(Prior art and problems) Hard butter is known as an oil and fat that has an appropriate hardness at room temperature, melts rapidly at temperatures near body temperature, and has an extremely narrow plasticity range, and is also called cocoa butter substitute. For example, as a fat component of chocolate confectionery raw material, or used for coating bakery products,
It is also used as a suppository base.

As the conventional hard butter, for example, (a) a material obtained by collecting 1,3-disaturated fatty acid-2-unsaturated fatty acid triglyceride, which is a characteristic component of cocoa butter, from a natural or synthetic fat or oil raw material, (B) Triglyceride (high trans acid type hard butter) containing trans isomer of unsaturated fatty acid, which is obtained by hydrogenating an oil / fat raw material containing unsaturated fatty acid as a fatty acid component under adjusted conditions, It is known that fatty acids such as coconut oil and palm kernel oil which are mainly composed of lauric acid are used as they are or hydrogenated (lauric acid type hard butter).

These hard butters are all triglycerides in the chemical structure, that is, fatty acid triesters of glycerin, and since they are obtained by controlling these structures as appropriate, when ingested into the body, lipid It may be decomposed by a degrading enzyme and metabolized to serve as a nutritional source, leading to undesirable health management problems such as obesity.

In addition to the above triglycerides, sorbitan esters of palmitic acid or acetic acid are also known to be used as substitutes for cocoa butter, but lack flavor and have a problem with stability, resulting in poor practicality.

(Means for Solving Problems) The present inventors aim to obtain a hard butter-like substance that has excellent properties and flavor and is non-caloric and preferable for health management as a substitute for hard butter. During the search, sucrose fatty acid esters having a fatty acid ester bond number (substitution degree) of 4 or more with respect to sucrose are not taken into the lipid metabolism system when ingested into the body and are substantially non-caloric. As a result of investigating the applicability of various sucrose fatty acid esters as hard butter, focusing on the fact that they are known to be volatile substances, it was found that they consist of specific fatty acid components and have a composition with a specific degree of ester substitution. It was confirmed that the sucrose fatty acid ester having ## STR4 ## meets the above-mentioned object, and the present invention was achieved.

That is, the gist of the present invention is a polyester of sucrose fatty acid having a fatty acid derived from lauric oil and fat, lauric acid or myristic acid as a main constituent fatty acid, and having a substitution degree of 1 to 3.
In the hard butter-like substance consisting of sucrose fatty acid polyester having an average ester substitution degree of 5 or more and 6.8 or less.

 Hereinafter, the present invention will be described in detail.

In general, for a certain fat or oil to be useful as hard butter, the change in the content ratio of the solid fat with respect to various temperatures is similar to the change in the content ratio of the solid fat with respect to the temperature of cocoa butter, in other words, In addition, it is necessary that the plasticity range be extremely narrow at room temperature and rapidly melt at a temperature near body temperature, that is, the plasticity range is extremely narrow.

As a method of grasping such properties, it is performed by knowing the change in the content ratio of solid fat at various temperatures.

And the content ratio of solid fat in a certain fat is pulse NM
The R-based method is currently used as a general method because of its rapidity and convenience, and its measured value is
It is called solid fat content (SFC).

Solid fat content (SFC) based on pulsed NMR in the present invention
The measurement method is that the protons oriented in a magnetic field are 90 °
When a pulse signal in the direction is given, the magnetic resonance of protons is weak in solid fat, but strong in liquid oil, so the solid fat signal disappears quickly, and only the liquid oil signal is separated after a certain period of time. Reading the solid fat content (SF
C) shall be instructed and specifically measured as shown in Examples below [Oil Chemistry, Vol. 33,
No. 3, pp. 36-39 (1984)].

The present invention is such that the change in the content ratio of solid fat with respect to various temperatures is adjusted to be similar to that of cocoa butter, it is not incorporated into the lipid metabolism system when ingested in the body, has low caloricity, and It provides a hard butter-like substance that does not impair the flavor.

The hard butter-like substance of the present invention comprises a fatty acid derived from lauric oil and fat, a polyester of sucrose fatty acid having lauric acid or myristic acid as a main constituent fatty acid.

The fatty acid derived from lauric oil and fat is a coconut oil, which indicates a fatty acid obtained from so-called lauric oil and fat such as palm oil or a hydrogenated product thereof, and the total amount of lauric acid and myristic acid is 50% (weight). The above is an indication of a mixture of 80 to 20% lauric acid and 20 to 80% myristic acid in the total amount.

The fatty acid component is not limited to the fatty acids derived from the above-mentioned lauric oil and fat, and may be those having lauric acid or myristic acid, which are separately prepared, as the main constituent components.

The sucrose fatty acid ester according to the present invention has a fatty acid component of the above-mentioned specific one and an ester substitution degree of 1
It is necessary that the ester of ~ 3 is 20% by weight or less, and the average degree of substitution of the remaining ester is 5 or more and 6.8 or less.

There are eight types of sucrose fatty acid esters, from monoesters to octaesters, depending on the degree of substitution of fatty acid for one molecule of sucrose. Of these, eight are incorporated into the lipid metabolism system when ingested into the body. The substance which is substantially non-caloric is a substance having a tetraester or more, that is, a fatty acid having a substitution degree of 4 or more.

Further, in terms of taste, in order to eliminate the concern about the taste of fatty acid, it is essential that the level of the monoester in the sucrose fatty acid ester is substantially absent. The reason for this is that, although the degree varies depending on the type of the fatty acid component, the monoester body has extremely high hydrophilicity and greatly affects the taste. The degree thereof is more remarkable as the number of carbon atoms in the fatty acid component is smaller. For example, in the case of a monoester of fatty acid component having myristic acid (14 carbon atoms) or less, bitterness is felt even if it is present at about 1%.

In addition to the low-calorie properties described above and the fact that the flavor is not impaired, it has a moderate hardness at the above-mentioned normal temperature and has a very narrow plastic range in which it rapidly melts at a temperature near body temperature. In order to have the properties required as butter, the hard butter-like substance of the present invention comprises
As the fatty acid component of the sucrose fatty acid ester, a fatty acid derived from the lauric oil and fat, a fatty acid mainly containing lauric acid or myristic acid is selected, and an ester having an ester substitution degree of 1 to 20% by weight or less, preferably 10 weight%
It is particularly preferable that the content is 5% by weight or less and closer to 0%, and the average degree of substitution of the remaining ester is 5 or more and 6.8 or less.

That is, it does not contain an ester having an ester substitution degree of 1 to 3, or even if it contains it, the total amount of them is required to be 20% by weight or less of the whole. It is not suitable as a hard butter substitute because of its non-caloric nature.

Also, the ester having an ester substitution degree of 1 to 3 is 20% by weight or less, and the average degree of substitution of the remaining ester is 5 or more and 6.8 or less.
Even in the following composition, the fatty acid component is a fatty acid derived from the above-mentioned lauric oil and fat, in the case other than those mainly composed of lauric acid or myristic acid, as shown in Comparative Examples below, as hard butter It is not possible to obtain a material that has a required hardness at room temperature and rapidly melts at a temperature near body temperature, which is required.

In addition, fatty acids derived from lauric oils and fats, fatty acid components other than those mainly composed of lauric acid or myristic acid, such as palmitic acid (16 carbon atoms) and stearic acid (12 carbon atoms).
Sucrose fatty acid esters using higher fatty acids such as 18) and extremely lower fatty acids such as acetic acid (having a carbon number of 6 or less) in an appropriate ratio also produce the hard butter-like substance of the present invention. Similarly, it is possible to have a hardness that is moderate at room temperature and that melts rapidly at temperatures near body temperature, but as mentioned above, it is not suitable as a hard butter substitute in terms of flavor and aroma. Appropriate.

The hard butter-like substance of the present invention can be produced by various known methods for producing sucrose fatty acid ester.

For example, (a) sucrose and the lower alcohol ester of the above fatty acid are heated in a suitable organic solvent under reduced pressure to cause transesterification reaction, and the solvent is changed as the reaction progresses. A method in which the reaction is completed by distilling off and finally leaving no organic solvent remaining, (b)
Sucrose and the lower alcohol ester of the above fatty acid are melt-mixed in the presence of soap with or without a solvent, and heated under reduced pressure using an alkaline catalyst to carry out a transesterification reaction. Methods, or (c) sucrose and chlorides of the above fatty acids, esterification in the presence of an alkaline catalyst, with or without the use of an organic solvent, and the like. It is necessary to select reaction conditions depending on the raw materials. In addition, in some cases, the sucrose fatty acid ester obtained by these methods may be appropriately mixed to prepare.

(Effect of the invention) As is clear from the description (SFC value) of the Examples and Reference Examples described later, the hard butter-like substance of the present invention has a high solid fat content at a temperature of about 25 ° C. or lower, and an appropriate hardness. However, it has the property that the solid fat content rapidly decreases and melts at about 30 to 40 ° C, and it has low calorie properties and does not impair the flavor, and has sufficient suitability as hard butter. It is a thing.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these examples as long as the gist thereof is not exceeded. In addition, "parts" in the examples means "parts by weight".

Example 1 A fully dried reactor was charged with 977 parts of granulated sugar and 4000 parts of dimethyl sulfoxide (solvent, hereinafter referred to as DMSO), and the solvent was refluxed for 20 minutes while boiling under a reduced pressure of 23 Torr, and then DMSO was distilled off. It was taken out and dehydrated. When the amount of distillate reached 1000 parts, distilling was stopped and the water content in the system was measured. As a result, the residual water content was 0.06% by weight.

Next, 43.7 parts of anhydrous potassium carbonate and 3523 parts of methyl laurate (containing 98% purity and 2% capric acid) were charged, the solvent was refluxed while boiling under reduced pressure of 23 Torr, and methanol was distilled off. When the reaction solution became substantially uniform, the solvent was distilled off, and the reaction was performed under reduced pressure of 7 Torr at 110 ° C for 7 hours, and then the product was neutralized and purified. As a result, 3880 parts of sucrose fatty acid ester was obtained.

The sucrose fatty acid ester thus obtained is 98
% Of lauric acid and 2% of capric acid, and had the ester composition shown in Table 1.

The total content of monoester, diester and triester in this sucrose fatty acid ester is 8.2.
(%) And the average degree of substitution of the remaining ester is 5.8.
Met.

The solid fat content (SFC) at each temperature of the sucrose fatty acid ester was measured by pulsed NMR.

(Measurement method) A sample consisting of sucrose fatty acid ester was previously heated to 70 ° C, melted and put into a test tube for measurement, which was allowed to stand at 0 ° C for 30 minutes, then at 26.7 ° C for 30 minutes, and then again. 0 ° C
After the sample was allowed to stand at, the temperature of the sample was sequentially raised and kept at the following temperatures for 30 minutes, and pulsed NMR measurement was performed. SFC at T ℃
Is calculated by the following formula.

The same measurement was performed using olive oil as the standard liquid oil. The results are shown in Table 2.

Example 2 Instead of the methyl laurate used in Example 1, 70% methyl laurate, 10% methyl myristate, 5% methyl palmitate, 3% methyl caprate and 3% methyl caprylate. Fatty acid methyl containing 3500
The same treatment as in Example 1 was performed except that the parts were used.

By the above method, sucrose fatty acid ester having the fatty acid composition shown in Table 3 below and the ester composition shown in Table 4 was produced.

The total content of monoester, diester and triester in this sucrose fatty acid ester was 16.8.
(%) And the average degree of substitution of the remaining ester is 5.4.
Met. The solid fat content (SFC) at each temperature of the above sucrose fatty acid ester was measured according to the measuring method in Example 1, and the results are shown in Table 5.

Example 3 Example 1 except that the amount of methyl laurate used in Example 1 was 4370 parts and the reaction time was 10 hours.
The same process was performed.

By the above method, 98% lauric acid (12 carbon atoms)
And a fatty acid composition consisting of 2% capric acid (10 carbon atoms), and a sucrose fatty acid ester having the ester composition shown in Table 6 was produced.

The total content of monoester, diester and triester in this sucrose fatty acid ester is 2.9.
% (%), The average degree of substitution of the remaining ester is 6.4
Met. The solid fat content (SFC) at each temperature of the above sucrose fatty acid ester was measured according to the measuring method in Example 1, and the results are shown in Table 7.

Example 4 Example 1 except that the amount of methyl laurate used in Example 1 was 5130 parts and the reaction time was 11 hours.
The same process was performed.

By the above method, sucrose fatty acid ester having the same fatty acid composition as in Example 1 and the ester composition shown in Table 8 was produced.

The total content of monoester, diester and triester in this sucrose fatty acid ester is 4.1.
(%) And the average degree of substitution of the remaining ester is 6.8.
Met. The solid fat content (SFC) at each temperature of the above sucrose fatty acid ester was measured according to the measuring method in Example 1, and the results are shown in Table 9.

Example 5 The same treatment as in Example 1 was carried out except that the amount of methyl laurate used in Example 1 was changed to 4500 parts and the reaction time was changed to 10.5 hours.

By the above method, sucrose fatty acid ester having the same fatty acid composition as in Example 1 and the ester composition shown in Table 10 was produced.

The total content of monoester, diester and triester in this sucrose fatty acid ester is 3.5.
(%) And the average degree of substitution of the remaining ester is 6.6.
Met. The solid fat content (SFC) at each temperature of the above sucrose fatty acid ester was measured according to the measuring method in Example 1, and the results are shown in Table 11.

Example 6 Example 1 except that the amount of methyl laurate used in Example 1 was 4000 parts and the reaction time was 9 hours.
The same process was performed.

By the above method, sucrose fatty acid ester having the same fatty acid composition as in Example 1 and the ester composition shown in Table 12 was produced.

The total content of monoester, diester and triester in this sucrose fatty acid ester is 4.6.
% (%), The average degree of substitution of the remaining ester is 6.2
Met. The solid fat content (SFC) at each temperature of the above sucrose fatty acid ester was measured according to the measuring method in Example 1 and the results are shown in Table 13.

Example 7 Instead of the methyl laurate used in Example 1, 3500 parts of fatty acid methyl prepared from laurate-based fats and oils containing 78.7% methyl laurate, 21.2% methyl myristate and 0.1% methyl palmitate. Use
The reaction time was 10 hours, and the same treatment as in Example 1 was carried out.

By the above method, having the fatty acid composition of the following Table 14,
A sucrose fatty acid ester having an ester composition of 15 was produced.

The total content of monoester, diester and triester in this sucrose fatty acid ester is 3.5.
(%) And the average degree of substitution of the remaining ester is 6.3.
Met. The solid fat content (SFC) at each temperature of the above sucrose fatty acid ester was measured according to the measuring method in Example 1 and the results are shown in Table 16.

Example 8 The methyl laurate used in Example 1 was replaced with 3500 parts of fatty acid methyl ester containing 49.7% methyl laurate, 49.9% methyl myristate and 0.4% methyl palmitate, and a reaction time of The treatment was carried out in exactly the same manner as in Example 1 except for 10 hours.

By the above method, having the fatty acid composition of the following Table 17,
A sucrose fatty acid ester having an ester composition of 18 was produced.

The total content of monoester, diester and triester in this sucrose fatty acid ester is 4.4.
(%) And the average degree of substitution of the remaining ester is 6.3.
Met. The solid fat content (SFC) at each temperature of the above sucrose fatty acid ester was measured according to the measuring method in Example 1 and the results are shown in Table 19.

Comparative Example 1 Example 1 except that the amount of methyl laurate used in Example 1 was 3000 parts and the reaction time was 5 hours.
The same process was performed.

By the above method, sucrose fatty acid ester having the same fatty acid composition as in Example 1 and the ester composition shown in Table 20 was produced.

The total content of monoester, diester and triester in this sucrose fatty acid ester was 90.2.
Weight (%), average degree of substitution of residual ester is 4.2
Met. The solid fat content (SFC) at each temperature of the above sucrose fatty acid ester was measured according to the measuring method in Example 1 and the results are shown in Table 21.

Comparative Example 2 Instead of the methyl laurate used in Example 1, 4000 parts of fatty acid methyl ester consisting of 67.6% methyl stearate, 30.5% methyl palmitate and 1.9% methyl myristate was used, and the reaction time was changed. The treatment was carried out in exactly the same manner as in Example 1 except for 10 hours. According to the above method, the fatty acid composition is 67.6% stearic acid (18 carbon atoms), 30.5% palmitic acid (16 carbon atoms) and 1.9% myristic acid (14 carbon atoms), and has the ester composition shown in Table 22. A sucrose fatty acid ester was produced.

The total content of monoester, diester and triester in this sucrose fatty acid ester was 5.2.
Weight (%), the average degree of substitution of the remaining ester is 6.0
Met. With respect to the sucrose fatty acid ester, the solid fat content (SFC) at each temperature was measured according to the measuring method in Example 1, and the results are shown in Table 23.

Comparative Example 3 Instead of the methyl laurate used in Example 1, 80.2% palmitic acid (16 carbon atoms), 18.2% stearic acid (18 carbon atoms), 0.9% myristic acid (1 carbon atom)
4) and fatty acid methyl 40 consisting of 0.7% other fatty acids
The same treatment as in Example 1 was carried out except that 00 parts were used and the reaction time was 10 hours. By the above method, 8
0.2% palmitic acid (16 carbons), 18.2% stearic acid (18 carbons), 0.9% myristic acid (14 carbons)
And a fatty acid composition consisting of 0.7% other fatty acids, Table 2
A sucrose fatty acid ester having an ester composition of 4 was produced.

The total content of monoester, diester and triester in this sucrose fatty acid ester is 10.8.
(%) And the average degree of substitution of the remaining ester is 5.8.
Met. The solid fat content (SFC) at each temperature of the above sucrose fatty acid ester was measured according to the measuring method in Example 1, and the results are shown in Table 25.

Comparative Example 4 With respect to the sucrose fatty acid ester of Comparative Example 1 completely acetylated with acetic acid, the solid fat content (SFC) at each temperature was measured according to the measuring method in Example 1 and the results are shown in Table 26. Met.

Reference Example 1 The results of measuring the solid fat content (SFC) of cocoa butter at each temperature according to the measuring method in Example 1 are shown in Table 27.

Reference Example 2 The solid fat content (SFC) of Parquena H (lauric acid type hard butter manufactured by Fuji Oil Co., Ltd.) at each temperature was measured according to the measuring method in Example 1 and the results are shown in Table 28. .

Reference Example 3 The results of measuring the solid fat content (SFC) of Melano STS (high trans acid type hard butter manufactured by Fuji Oil Co., Ltd.) at each temperature according to the measurement method in Example 1 are shown in Table 29. It was

Claims (1)

(57) [Claims] 1. A polyester of sucrose fatty acid having a fatty acid derived from lauric oil and fat, lauric acid or myristic acid as a main constituent fatty acid, wherein the degree of substitution is 1 to 3
20% by weight or less, the average degree of substitution of the remaining ester is 5
A hard butter-like substance composed of a sucrose fatty acid polyester body having a content of 6.8 or more.