WO2020218315A1

WO2020218315A1 - Crystallization accelerator for oil and fat

Info

Publication number: WO2020218315A1
Application number: PCT/JP2020/017274
Authority: WO
Inventors: 貴雄六本木; 卓也村井
Original assignee: 阪本薬品工業株式会社
Priority date: 2019-04-25
Filing date: 2020-04-22
Publication date: 2020-10-29
Also published as: JP7083070B2; JPWO2020218315A1; SG11202110004UA

Abstract

The purpose of the present invention is to provide a novel crystallization accelerator for oil and fat. This crystallization accelerator for oil and fat is characterized by having an HLB of 5-9 and a melting point of 58-69ºC and containing a polyglycerin fatty acid ester. The crystallization accelerator may have an average degree of polymerization of polyglycerin of 2-10. Moreover, the crystallization accelerator may have an esterification rate of 20-60%. Furthermore, the polyglycerin fatty acid ester may have a freezing point of 53-65ºC.

Description

Fats and oils crystallization accelerator

The present invention relates to an oil / fat crystallization accelerator.

In products containing fats and oils, the crystal behavior and characteristics of fats and oils have an important effect in many situations from the development, manufacture, storage, and distribution of the products. Therefore, the technology for controlling oil and fat crystals is one of the most important issues. In particular, in a composition in which the proportion of fats and oils in the composition is high, the crystal behavior of the fats and oils used has a large effect, and there are various problems.

For example, as a method of suppressing the coarsening of crystals during storage after production, Patent Document 1 discloses an oil / fat crystal modifier containing diglyceride in order to prevent deterioration of physical properties due to the coarsening of oil / fat crystals. There is.

Further, in Patent Document 2, as a method for producing an oil / fat composition in which granular crystals having a diameter of 20 μm or more are not formed even under long-term storage, rapid cooling with a refrigerant of −20 ° C. or less or unstable crystal particles of oil / fat is described. Disclosed is a method for producing an oil or fat or an oil or fat composition which produces unstable crystals by adding the above and does not produce granular crystals.

Furthermore, as a prior art, in addition to a method of suppressing crystal coarsening, the use of a crystallization accelerator has also been proposed. For example, Non-Patent Document 1 describes that an emulsifier that is lipophilic and has a high melting point serves as a template for fat and oil crystals and promotes crystallization. In addition, Non-Patent Document 2 and the like describe Behen of polyglycerin. Acid esters are known to have a high crystallization promoting effect and a crystal refining effect.

Japanese Unexamined Patent Publication No. 2000-345185 Japanese Unexamined Patent Publication No. 2001-7292

However, in the prior art, since the focus is on suppressing the coarsening of crystals during long-term storage, the fundamental problem of sufficiently crystallizing fats and oils during the manufacturing process can be solved. In addition, the crystallization accelerator needs to heat the fat and oil sufficiently in order to dissolve it, and there is a concern that the workability is poor and the fat and oil is likely to deteriorate due to heating. It was not suitable as a solution from the viewpoint of promoting crystallization in a short time. Therefore, there is a fact that further development of technology for promoting crystallization is desired.

Therefore, the main object of the present invention is to provide a novel crystallization accelerator for fats and oils.

That is, the present invention provides an oil / fat crystallization accelerator, which comprises a polyglycerin fatty acid ester having an HLB of 5 to 9 and a melting point of 58 to 69 ° C.
The crystallization accelerator according to the present invention may have an average degree of polymerization of polyglycerin of 2 to 10.
Further, the crystallization accelerator according to the present invention may have an esterification rate of 20 to 60%.

According to the present invention, it is possible to provide a novel crystallization accelerator for fats and oils.
The effects of the present invention are not necessarily limited to the effects described herein, and may be any of the effects described in the present disclosure.

Hereinafter, suitable embodiments for carrying out the present invention will be described.
It should be noted that the embodiments described below show typical embodiments of the present invention, and the scope of the present invention is not narrowly interpreted by these.

The polyglycerin fatty acid ester is obtained by an esterification reaction of polyglycerin and fatty acid obtained by dehydration condensation of glycerin, and the type of polyglycerin (degree of polymerization), type of fatty acid (number of carbon atoms, number of double bonds), ester composition, etc. There are many types. And it is known that each type exhibits different properties.

The fat and oil crystallization accelerator according to the present invention is characterized by containing a polyglycerin fatty acid ester having an HLB of 5 to 9 and a melting point of 58 to 69 ° C.

Generally, when adding a polyglycerin fatty acid ester to an oil, one having a low HLB (preferably 3 or less) that is easily compatible with fats and oils is selected. Further, when the melting point of the polyglycerin fatty acid ester is high, it tends to crystallize before fats and oils and become nuclei, so that it was considered to be suitable as a crystallization accelerator. However, as a result of diligent experimental studies by the inventors of the present application, surprisingly, by setting the HLB range to 5 to 9 and setting the melting point to the range of 58 to 69 ° C., the crystallization speed can be increased. It has been found that it is possible to provide a crystallization accelerator capable of producing fine crystals quickly. Further, the polyglycerin fatty acid ester according to the present invention has a good handling property because the melting point is not too high.

In the crystallization accelerator according to the present invention, the HLB of the polyglycerin fatty acid ester is 5 to 9. Here, HLB is an index showing the degree of hydrophilicity and lipophilicity, and is a value calculated by the Atlas method in the present invention. The HLB by the Atlas method is calculated from the following formula (1).

In the present invention, the melting point and the freezing point can be measured by using a conventionally known method, for example, using a differential scanning calorimeter (DSC).

In the crystallization accelerator according to the present invention, the melting point is 58 to 69 ° C, preferably 58 to 66 ° C.

In the crystallization accelerator according to the present invention, the freezing point is preferably 53 to 65 ° C. As a result, a sufficient crystallization promoting effect can be obtained.

In the present invention, the average degree of polymerization of polyglycerin constituting the polyglycerin fatty acid ester is not limited, but is preferably 2 to 10, and more preferably 4 to 10. Here, the average degree of polymerization is the average degree of polymerization (n) of polyglycerin calculated from the hydroxyl value by the end group analysis method. Specifically, it is calculated from the following formula (2) and the following formula (3).

The hydroxyl value in the above formula (3) is a numerical value that is an index of the number of hydroxyl groups contained in polyglycerin, and acetic acid required for acetylating the free hydroxyl group contained in 1 g of polyglycerin is contained in the medium. The number of milligrams of potassium hydroxide required for summing. The number of milligrams of potassium hydroxide is calculated according to "Established by the Japan Oil Chemists'Association, Standard Oil and Fat Analysis Test Method, 2003 Edition" compiled by the Japan Oil Chemists' Society.

The polyglycerin fatty acid ester can be produced by a conventionally known esterification reaction. For example, it can be produced by subjecting a fatty acid and polyglycerin to an esterification reaction in the presence of an alkaline catalyst such as sodium hydroxide. Esterification is carried out until the esterification rate of the polyglycerin fatty acid ester reaches a desired value.

In the crystallization accelerator according to the present invention, the esterification rate is preferably 20 to 60%, more preferably 30 to 45%. Here, the esterification rate is defined as the average degree of polymerization (n) of polyglycerin calculated from the hydroxyl value, the number of hydroxyl groups of this polyglycerin (n + 2), and the number of moles of fatty acid added to polyglycerin (M). Then, it is a value calculated by the following formula (4). The hydroxyl value is a value calculated by the above formula (3).

The fatty acid constituting the polyglycerin fatty acid ester is not particularly limited, but a saturated or unsaturated fatty acid having 8 to 24 carbon atoms is usually used. The fatty acid may be a mixture, and specific examples of the fatty acid include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, ventadecyl acid, palmitic acid, palmitreic acid, margaric acid, stearic acid, and oleic acid. , Paxenoic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid, erucic acid, behenic acid and the like. Among these, saturated fatty acids having 16 to 18 carbon atoms are particularly preferable in terms of the balance between the meltability and the solid fat content and the handleability of the fat and oil composition.

The use of the crystallization accelerator according to the present invention is not particularly limited, and it can be widely used in the fields of foods and drinks containing fats and oils, cosmetics, non-pharmaceutical products, pharmaceuticals, etc., especially in a short time during the manufacturing process. The effect of the present invention can be exhibited in fat and oil compositions such as whipped cream, coffee whitener, margarine, shortening, chocolate, dairy beverage, and functional fat and oil, which are required to have the effect of promoting crystallization.

The oil and fat contained in the oil and fat composition is also not particularly limited, and for example, rapeseed oil, soybean oil, sunflower seed oil, cottonseed oil, peanut oil, rice bran oil, corn oil, saflower oil, olive oil, capoc oil, sesame oil, and evening primrose. Vegetable fats and oils such as oils, palm oils, shea butter, monkey fats, cacao fats, coconut oils and palm kernel oils; animal fats and oils such as milk fats, beef fats, lards, fish oils and whale oils alone or mixed oils, or cured thereof. , Processed oils and fats that have been separated, ester exchanged, etc. can be mentioned. Among these, the crystallization accelerator according to the present invention is particularly suitable for palm-based fats and oils having a slow crystallization rate, transesterified fats and oils, and the like. As the transesterification oil, a lauric-based transesterification oil or the like is suitable.

The method for using the crystallization accelerator according to the present invention is that the crystallization promoting effect is obtained by melting the fat and oil in a desired fat and oil, and undergoing a crystallization step from the state where the fat and oil and the crystallization accelerator are completely melted. It is demonstrated. At this time, the crystallization promoting agent according to the present invention is preferably added in an amount of 0.02 to 5% by weight based on the fat or oil to obtain a sufficient crystallization promoting effect.

Hereinafter, the present invention will be described based on examples.
It should be noted that the examples described below show an example of a typical example of the present invention, and the scope of the present invention is not narrowly interpreted by this.

The polyglycerin according to the present invention is a polyglycerin having an average degree of polymerization of 2 and "Diglycerin S" manufactured by Sakamoto Pharmaceutical Co., Ltd., and a polyglycerin having an average degree of polymerization of 4 and "Polyglycerin # 310" manufactured by Sakamoto Pharmaceutical Co., Ltd. , "Polyglycerin # 500" manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. was used for polyglycerin having an average degree of polymerization of 6, and "Polyglycerin # 750" manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. was used for polyglycerin having an average degree of polymerization of 10. ..

<Synthesis example 1>
100 g of polyglycerin having an average degree of polymerization of 2 and 239 g of stearic acid were placed in a reaction vessel and reacted at 245 ° C. under alkaline and nitrogen flow with sodium hydroxide to obtain a polyglycerin fatty acid ester having an esterification rate of 35%.

<Synthesis example 2>
100 g of polyglycerin having an average degree of polymerization of 4 and 157 g of stearic acid were placed in a reaction vessel and reacted at 245 ° C. under alkaline and nitrogen flow with sodium hydroxide to obtain a polyglycerin fatty acid ester having an esterification rate of 31%.

<Synthesis example 3>
100 g of polyglycerin having an average degree of polymerization of 4 and 191 g of stearic acid were placed in a reaction vessel and reacted at 245 ° C. under alkaline and nitrogen flow with sodium hydroxide to obtain a polyglycerin fatty acid ester having an esterification rate of 37%.

<Synthesis example 4>
100 g of polyglycerin having an average degree of polymerization of 6 and 123 g of stearic acid were placed in a reaction vessel and reacted at 245 ° C. under alkaline and nitrogen flow with sodium hydroxide to obtain a polyglycerin fatty acid ester having an esterification rate of 30%.

<Synthesis example 5>
100 g of polyglycerin having an average degree of polymerization of 6 and 184 g of stearic acid were placed in a reaction vessel and reacted at 245 ° C. under alkaline and nitrogen flow with sodium hydroxide to obtain a polyglycerin fatty acid ester having an esterification rate of 45%.

<Synthesis example 6>
100 g of polyglycerin having an average degree of polymerization of 6 and 225 g of stearic acid were placed in a reaction vessel and reacted at 245 ° C. under alkaline and nitrogen flow with sodium hydroxide to obtain a polyglycerin fatty acid ester having an esterification rate of 55%.

<Synthesis example 7>
100 g of polyglycerin having an average degree of polymerization of 10 and 153 g of stearic acid were placed in a reaction vessel and reacted at 245 ° C. under alkaline and nitrogen flow with sodium hydroxide to obtain a polyglycerin fatty acid ester having an esterification rate of 38%.

<Synthesis Example 8>
100 g of polyglycerin having an average degree of polymerization of 10 and 184 g of stearic acid were placed in a reaction vessel and reacted at 245 ° C. under alkaline and nitrogen flow with sodium hydroxide to obtain a polyglycerin fatty acid ester having an esterification rate of 45%.

<Synthesis example 9>
100 g of polyglycerin having an average degree of polymerization of 6 and 31 g of palmitic acid and 101 g of stearic acid are placed in a reaction vessel and reacted at 245 ° C. under alkaline and nitrogen flow with sodium hydroxide to produce a polyglycerin fatty acid ester having an esterification rate of 33%. Got

<Comparative example 1>
Polyglycerin behenic acid ester Product name: HB-750 (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)

<Comparative example 2>
Polyglycerin behenic acid ester Product name: DDB-750 (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)

<Comparative example 3>
Polyglycerin stearate product name: MS-3S (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)

<Comparative example 4>
Polyglycerin stearate product name: PS-3S (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)

<Comparative example 5>
Polyglycerin stearic acid ester Product name: TS-5S (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)

<Comparative Example 6>
Polyglycerin stearic acid ester Product name: DAS-7S (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)

<Comparative example 7>
100 g of polyglycerin having an average degree of polymerization of 4 and 157 g of palmitic acid were placed in a reaction vessel and reacted at 245 ° C. under alkaline and nitrogen flow with sodium hydroxide to obtain a polyglycerin fatty acid ester having an esterification rate of 33%.

The following measurements were carried out using the polyglycerin fatty acid esters of Synthesis Examples 1 to 9 and Comparative Examples 1 to 7 produced as described above.

<Measurement of freezing point and melting point>
The freezing point and melting point of each polyglycerin fatty acid ester were measured with a differential scanning calorimeter (model number: DSC8320, manufactured by Rigaku Co., Ltd.). Each sample was weighed 5 mg into an aluminum cell and covered with a sample sealer. As a control, 5 mg of alumina was used. After cooling the cell from 85 ° C to 25 ° C at 5 ° C / min and holding it for 5 minutes, the on-set temperature of the heat generation peak during cooling when heated to 85 ° C at 5 ° C / min is set to the freezing point and the endothermic peak during heating. The off-set temperature of was taken as the melting point.

<Measurement of fixed fat content (SFC) and sample preparation for microscopic observation>
0.5% by weight of each polyglycerin fatty acid ester was added to each of the refined palm oil, the cured palm kernel oil, and the transesterified oil, and then uniformly dissolved at 80 ° C. Specifically, the transesterified oil was a lauric-based transesterified oil, which was a mixed oil of palm kernel oil, coconut oil, and rapeseed extremely hydrogenated oil, and had a melting point of 27.2 ° C.

<Measurement of solid fat content (SFC)>
SFC was measured by desktop NMR (model number: minispec mq20, manufactured by BRUKER) according to AOCS Official Method Cd 16b-93 (1999). In addition, SFC is an abbreviation for Solid Fat Content, and indicates the content (%) of solid fat present in fats and oils at a constant temperature. Therefore, the higher the SFC of the fat and oil after a certain period of time from the start of crystallization, the faster the crystallization of the fat and oil, and the higher the crystallization promoting effect.

The sample was placed in a sample tube for measurement at a height of about 5 cm and heated at 80 ° C. for 10 minutes to melt it. After that, the refined palm oil was transferred to a circulating constant temperature water tank (model number: NCB-1200, manufactured by Tokyo Rika Kikai Co., Ltd.) at 25 ° C, the cured palm kernel oil at 25 ° C, and the ester exchange oil at 20 ° C. The SFC was measured after 10 minutes, for the cured palm kernel oil after 3 minutes, and for the ester exchange oil after 10 minutes. The evaluation was carried out using HB-750 and DDB-750, which are not added (Blank) and are widely used as crystallization accelerators, as indexes.
[Evaluation criteria]
X: Equivalent to or lower than additive-free SFC Δ: Higher than additive-free SFC and lower than HB-750 ○: Equivalent to or higher than HB-750 SFC and lower than DDB-750 SFC ⊚: Equivalent to or higher than the SFC of DDB-750

<Measurement of crystal size>
10 μL of each sample was dropped on a slide glass, covered with a cover glass to prepare a preparation, which was heated to 80 ° C. at 20 ° C./min on a cooling / heating stage (model number: 10030, manufactured by Lincolm), and then 5 ° C. At / min, refined palm oil is cooled to 25 ° C, cured palm kernel oil to 25 ° C, transesterified oil to 20 ° C, refined palm oil after 20 minutes, cured palm kernel oil after 10 minutes, transesterified oil. After 15 minutes, the crystal morphology was observed with a polarizing microscope (model number: BX50, manufactured by Olympus Co., Ltd.) and photographed with the attached digital camera (model number: DP20, manufactured by Olympus Co., Ltd.). The crystal size was measured from the image. The evaluation was carried out using HB-750 and DDB-750, which are not added (Blank) and are widely used as crystallization accelerators, as indexes.
[Evaluation criteria]
X: Equivalent to or larger than the additive-free crystal size Δ: Smaller than the additive-free crystal size and larger than HB-750 ◯: Equivalent to or smaller than the crystal size of HB-750 and larger than DDB-750.
⊚: Equivalent to or smaller than the crystal size of DDB-750

<Measurement result>
The measurement results, HLB, and esterification rate (%) of the polyglycerin fatty acid esters of Synthesis Examples 1 to 9 and Comparative Examples 1 to 7 are shown in Table 1 below.

<Discussion>
The polyglycerin fatty acid esters of Synthesis Examples 1 to 9 are polyglycerin behenic acid esters having a crystallization promoting effect when any of refined palm oil, hardened palm kernel oil, and transesterified oil is used (Comparative Example). It was confirmed that the values were equal to or higher than those of 1 and 2), the SFC value was larger and the crystals were finer than those of the polyglycerin fatty acid esters of Comparative Examples 3 to 7. Therefore, by setting the HLB to 5 to 9 and the melting point to 58 to 69 ° C., it was possible to obtain a polyglycerin fatty acid ester having good handleability and a high effect of promoting crystallization of fats and oils.

According to the present invention, it is possible to provide a novel crystallization accelerator for fats and oils. The crystallization accelerator according to the present invention can be widely used in the fields of foods and drinks containing fats and oils, cosmetics, quasi-drugs, pharmaceuticals, etc., based on its excellent crystallization promoting effect.

Claims

The fat and oil crystallization accelerator contains at least a polyglycerin fatty acid ester and contains.
The polyglycerin fatty acid ester is characterized by having an HLB of 5 to 9 and a melting point of 58 to 69 ° C.
In the crystallization accelerator according to claim 1,
The average degree of polymerization of polyglycerin constituting the polyglycerin fatty acid ester is 2 to 10.
In the crystallization accelerator according to claim 1 or 2.
The esterification rate of the polyglycerin fatty acid ester is 20 to 60%.
In the crystallization accelerator according to any one of claims 1 to 3.
The polyglycerin fatty acid ester is characterized by having a freezing point of 53 to 65 ° C.
In the crystallization accelerator according to any one of claims 1 to 4.
The HLB is a value calculated by the Atlas method.
In the crystallization accelerator according to any one of claims 1 to 5,
The fatty acid constituting the polyglycerin fatty acid ester is a saturated fatty acid or an unsaturated fatty acid having 8 to 24 carbon atoms.
In the crystallization accelerator according to any one of claims 2 to 6.
The average degree of polymerization of polyglycerin constituting the polyglycerin fatty acid ester is 4 to 10.