JP6932921B2 - A method for producing an oil / fat composition containing fine intermolecular compound crystals, and a method for crystallizing an intermolecular compound. - Google Patents

Description

The present invention relates to fats and oils used in processed foods, cosmetics, pharmaceuticals, etc., and particularly relates to a method for producing a fats and oils composition containing finely divided intermolecular compound crystals of triacylglycerol, and a method for crystallizing intermolecular compounds.

Conventionally, hydrogenated vegetable oil has been frequently used for solid fat foods such as chocolate and margarine because it can obtain good hardness and texture. Trans-acids and saturated fatty acids produced by partial hydrogenation have good solid fat content and ductility and are very excellent in terms of physical properties, but due to concerns that they increase health risks such as arteriosclerosis and heart disease, nutrition In terms of surface, it is desirable to reduce it. On the other hand, unsaturated fatty acids are attracting attention as a health function of fats and oils, and the use of high oleic soybean oil and rapeseed oil, which contain a large amount of oleic acid component, which is less likely to be oxidized than highly unsaturated fatty acids, is increasing in liquid oil applications such as frying oil. There is. However, these fats and oils are not suitable for solid fat foods because they are liquid and difficult to solidify when they contain a large amount of oleic acid components. Therefore, it is desired to develop a solid fat food fat and oil having a good solid fat content and spreadability by blending unsaturated fatty acids in a well-balanced manner while suppressing trans acid and saturated fatty acid to a healthy content.

As an alternative technology to trans acid, palm oil containing a well-balanced long-chain fatty acid and unsaturated fatty acid, or a mixed oil of palm fractionated oil and hardened rapeseed oil is used. However, when palm oil is contained, crystallization is slow and palm is used. There is a problem that the oil component becomes coarse and the melting in the mouth deteriorates, and there are cases where the coarsening is suppressed by adjusting the blending of a specific triglyceride and adding an emulsifier (Patent Documents 1 and 2). In addition, there is also an example in which crystallization is accelerated by enzyme esterification and random esterification fats and oils, making it difficult to form coarse crystals (Patent Document 3). Furthermore, since unstable polymorphic α-type and β'crystals transition to energetically stable β-type crystals and coarsen during long-term storage, a method for directly crystallizing stable β-type polymorphisms is also disclosed. (Patent Document 4). However, since the raw material fats and oils contain trans-acids, the processed fats and oils contain a small amount of trans-acids, or even if they do not contain trans-acids, they have not completely replaced the physical properties and functions of trans-acids, and saturated fatty acids are also sufficient. It has not been reduced. There is also a report that the shape is maintained by the combination of emulsifiers and the malleability and texture of margarine are improved (Patent Document 5). There is also an example in which a network structure is formed by an organogel of wax (Non-Patent Document 1). However, these also do not completely replace the physical characteristics and functions, and are inferior in terms of flavor. Therefore, a technique for forming an "intermolecular compound" and increasing the solid fat content by adding a specific TAG in a high amount is attracting attention (Non-Patent Document 2).

An intermolecular compound is a phenomenon in which a strong intermolecular interaction acts between two types of triacylglycerol (TAG) molecules and behaves as if it were one molecule, and the presence of one specific two types of TAG molecules is 1: 1. Occurs below. It is known that when an intermolecular compound is formed, it has a unique melting point different from that of the original TAG, and the solid fat content is higher than that existing alone (Non-Patent Document 3).

By forming an intermolecular compound of TAG containing an oleic acid component, it is possible to maintain physical characteristics and texture without lowering the solid fat content while reducing saturated fatty acids and at the same time containing a high content of oleic acid. However, when the oleic acid component increases, the crystallization of fats and oils is slow, and there are problems that it is difficult to maintain the structure immediately after crystallization over time, and that coarse crystals are formed and the texture deteriorates. Further improvement in texture is required for oil and fat compositions used in cosmetics, pharmaceuticals and the like.

Japanese Patent Application Laid-Open No. 2001-503624 Japanese Unexamined Patent Publication No. 2008-12538 Japanese Unexamined Patent Publication No. 2001-258474 Japanese Unexamined Patent Publication No. 2005-350660 Japanese Patent Application Laid-Open No. 2008-591601

Current Opinion in Colloid & Interface Science 12 (2007) 221-231 Sibbald et.al. J Am. Oil Chem. Soc. DOI 10.1007 / s11746-015-2718-01 Moran DPJ, J. Appl. Chem. (1963) 13,91-100.

Therefore, it is an object of the present invention to provide a method for uniformly refining an intermolecular compound of triacylglycerol for the purpose of improving the texture of an oil / fat composition and improving the stability over time.
Another object of the present invention is to provide a method for miniaturizing the triacylglycerol while promoting the crystallization of the intermolecular compound.

As a result of diligent studies by the present inventor, it was found that the intermolecular compound can be uniformly refined by mixing the composition containing the intermolecular compound of triacylglycerol with the sucrose fatty acid ester, and the present invention 1 was reached. bottom.
Further, it was found that by mixing a composition containing an intermolecular compound of triacylglycerol with a sucrose fatty acid ester and a monoglycerin fatty acid ester, the intermolecular compound can be made finer while promoting crystallization. Reached 2.

That is, the gist of the present invention 1 is as follows.

[1] An oil / fat composition containing an intermolecular compound formed from triacylglycerol represented by St-U-St and triacylglycerol represented by U-St-U or St-St-U. , A method for producing an oil / fat composition containing fine intermolecular compound crystals, which comprises mixing with sucrose fatty acid ester to produce a finely divided crystal of the intermolecular compound.
(However, St represents a saturated fatty acid having 8 to 22 carbon atoms, and U represents an unsaturated fatty acid having 8 to 22 carbon atoms.)

[2] The fineness according to [1], wherein 10% by weight or more of the triacylglycerol contained in the oil / fat composition containing the finely divided crystals of the intermolecular compound forms the intermolecular compound. A method for producing an oil / fat composition containing intermolecular compound crystals.

[3] The fine molecule according to [1] or [2], wherein the content of the intermolecular compound is 10% by weight or more based on 100% by weight of the oil / fat composition containing the finely divided crystals of the intermolecular compound. A method for producing an oil / fat composition containing inter-compound crystals.

[4] The method for producing an oil / fat composition containing micromolecular compound crystals according to any one of [1] to [3], wherein the oil / fat composition mixed with the sucrose fatty acid ester is heated and then cooled.

[5] A method for producing an oil-and-fat-containing food, which comprises using an oil-and-fat composition containing micromolecular compound crystals produced by the production method according to any one of [1] to [4].

[6] An oil / fat composition containing an intermolecular compound formed from triacylglycerol represented by St-U-St and triacylglycerol represented by U-St-U or St-St-U. , A method for crystallization of an intermolecular compound, which comprises mixing with a sucrose fatty acid ester to finely crystallize the intermolecular compound.
(However, St represents a saturated fatty acid having 8 to 22 carbon atoms, and U represents an unsaturated fatty acid having 8 to 22 carbon atoms.)

[7] An oil / fat composition containing crystals containing triacylglycerol as a main component, the crystal having a particle size of 80 μm or less, and triacylglycerol, U-St- represented by St-U-St. An oil / fat composition containing triacylglycerol represented by U or St-St-U, and a sucrose fatty acid ester.
(However, St represents a saturated fatty acid having 8 to 22 carbon atoms, and U represents an unsaturated fatty acid having 8 to 22 carbon atoms.)

[8] The triacylglycerol represented by St-U-St and the triacylglycerol represented by U-St-U or St-St-U have a molar ratio of 1: 0.3 to 3. The oil and fat composition according to [7], which is contained in a proportion.

[9] A method for producing an oil / fat composition containing crystals containing triacylglycerol as a main component, wherein the crystal has a particle size of 80 μm or less, and triacylglycerol represented by St-U-St. A fat and oil composition containing triacylglycerol represented by U-St-U or St-St-U in a molar ratio of 1: 3.0 to 0.3, and a sucrose fatty acid ester are mixed. A method for producing an oil / fat composition, which comprises a step of:
(However, St represents a saturated fatty acid having 8 to 22 carbon atoms, and U represents an unsaturated fatty acid having 8 to 22 carbon atoms.)

The gist of the present invention 2 is as follows.

[10] An oil / fat composition containing an intermolecular compound formed from triacylglycerol represented by St-U-St and triacylglycerol represented by U-St-U or St-St-U. , Sucrose fatty acid ester and monoglycerin fatty acid ester to produce a fat and oil composition containing finely divided crystals of the intermolecular compound. Manufacturing method.
(However, St represents a saturated fatty acid having 8 to 22 carbon atoms, and U represents an unsaturated fatty acid having 8 to 22 carbon atoms.)

[11] A method for producing an oil-and-fat-containing food, which comprises using an oil-and-fat composition containing micromolecular compound crystals produced by the production method according to [10].

[12] An oil / fat composition containing an intermolecular compound formed from triacylglycerol represented by St-U-St and triacylglycerol represented by U-St-U or St-St-U. , A method for crystallization of an intermolecular compound, which comprises mixing a sucrose fatty acid ester and a monoglycerin fatty acid ester to finely crystallize the intermolecular compound.
(However, St represents a saturated fatty acid having 8 to 22 carbon atoms, and U represents an unsaturated fatty acid having 8 to 22 carbon atoms.)

[13] An oil / fat composition containing crystals containing triacylglycerol as a main component, the crystal having a particle size of 80 μm or less, and triacylglycerol represented by St-U-St, U-St-. An oil / fat composition containing triacylglycerol represented by U or St-St-U, a sucrose fatty acid ester, and a monoglycerin fatty acid ester.

[14] A method for producing an oil / fat composition containing crystals containing triacylglycerol as a main component, wherein the crystal has a particle size of 80 μm or less, and triacylglycerol represented by St-U-St. An oil / fat composition containing triacylglycerol represented by U-St-U or St-St-U in a molar ratio of 1: 3.0 to 0.3, and sucrose fatty acid ester and monoglycerin. A method for producing an oil / fat composition, which comprises a step of mixing with a fatty acid ester.
(However, St represents a saturated fatty acid having 8 to 22 carbon atoms, and U represents an unsaturated fatty acid having 8 to 22 carbon atoms.)

According to the present invention 1, the intermolecular compound of triacylglycerol can be uniformly refined, and a good texture is obtained when an oil / fat composition containing the finely divided crystals of the intermolecular compound is mixed with food. Can be obtained.
Further, according to the second invention, the triacylglycerol can be miniaturized while promoting the crystallization of the intermolecular compound.
The micromolecular compound crystal produced by the present invention has a high solid fat content and can impart a good texture, and is blended in processed foods, cosmetics, pharmaceuticals, etc., especially solid fat foods such as chocolate, margarine, and spreads. It can be suitably used as the fat and oil to be produced.

6 is a polarizing microscope image of the P-170-added POP / OPO intermolecular compound crystal (cooling rate 0.5 ° C./min) of Example 1. 6 is a polarizing microscope image of the POS-135-added POP / OPO intermolecular compound crystal (cooling rate 0.5 ° C./min) of Example 2. 9 is a polarizing microscope image of P-170 and MP-added POP / OPO intermolecular compound crystals (cooling rate 2 ° C./min) of Example 3. It is a polarizing microscope image of the emulsifier-free POP / OPO intermolecular compound crystal (cooling rate 0.5 ° C./min) of Comparative Example 1. It is a polarizing microscope image of the MP-added POP / OPO intermolecular compound crystal (cooling rate 0.5 ° C./min) of Comparative Example 2.

The present invention will be described in detail below.
The description of the constituent elements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not specified in these contents.

[Method for producing oil and fat composition containing fine intermolecular compound crystals, method for crystallization of intermolecular compound, method for producing oil and fat composition]
The method for producing an oil / fat composition containing micromolecular compound crystals of the present invention 1 is triacylglycerol represented by St-U-St and triacyl represented by U-St-U or St-St-U. A fat and oil composition containing an intermolecular compound formed from glycerol and a sucrose fatty acid ester are mixed to produce a fat and oil composition containing finely divided crystals of the intermolecular compound. ..
The method for crystallization of the intermolecular compound of the present invention 1 was formed from triacylglycerol represented by St-U-St and triacylglycerol represented by U-St-U or St-St-U. It is characterized in that an oil / fat composition containing an intermolecular compound and a sucrose fatty acid ester are mixed to finely crystallize the intermolecular compound.
The oil / fat composition of the present invention 1 is an oil / fat composition containing triacylglycerol as a main component and having a particle size of 80 μm or less, and is represented by St—U-St. It is characterized by containing triacylglycerol represented by U or St-St-U, and a sucrose fatty acid ester.
The method for producing an oil / fat composition according to the present invention 1 is a method for producing an oil / fat composition containing crystals containing triacylglycerol as a main component and having a particle size of 80 μm or less, and is represented by St-U-St. An oil / fat composition containing glycerol and triacylglycerol represented by U-St-U or St-St-U in a molar ratio of 1: 3.0 to 0.3, and a sucrose fatty acid ester. It is characterized by including a step of mixing and.

The method for producing an oil / fat composition containing micromolecular compound crystals of the present invention 2 is triacylglycerol represented by St-U-St and triacyl represented by U-St-U or St-St-U. An oil / fat composition containing an intermolecular compound formed from glycerol is mixed with a sucrose fatty acid ester and a monoglycerin fatty acid ester to produce an oil / fat composition containing finely divided crystals of the intermolecular compound. It is characterized by that.
The method for crystallizing an intermolecular compound of the present invention 2 was formed from triacylglycerol represented by St-U-St and triacylglycerol represented by U-St-U or St-St-U. It is characterized in that an oil / fat composition containing an intermolecular compound is mixed with a sucrose fatty acid ester and a monoglycerin fatty acid ester to finely crystallize the intermolecular compound.
The oil / fat composition of the present invention 2 is an oil / fat composition containing triacylglycerol as a main component and having a particle size of 80 μm or less, and is represented by St—U-St. It is characterized by containing a triacylglycerol represented by U or St-St-U, a sucrose fatty acid ester, and a monoglycerin fatty acid ester.
The method for producing an oil / fat composition of the present invention 2 is a method for producing an oil / fat composition containing crystals containing triacylglycerol as a main component and having a particle size of 80 μm or less, and is represented by St-U-St. An oil / fat composition containing glycerol and triacylglycerol represented by U-St-U or St-St-U in a molar ratio of 1: 3.0 to 0.3, and a sucrose fatty acid ester. And a step of mixing with a monoglycerin fatty acid ester.

However, in the present invention, St represents a saturated fatty acid having 8 to 22 carbon atoms, and U represents an unsaturated fatty acid having 8 to 22 carbon atoms.

<Triacylglycerol>
Triacylglycerol (TAG) is generally a major constituent of fats and oils, but its structure is glycerin bound to three fatty acids. For example, St-U-St in the present invention has two molecules of St and one molecule of U as fatty acids, and binds to glycerin in the order of St → U → St at the binding positions sn-1, 2, and 3. It shows that it is.
The saturated fatty acid having 8 to 22 carbon atoms represented by St, which constitutes triacylglycerol forming an intermolecular compound in the present invention, preferably has 12 or more carbon atoms, more preferably 16 or more carbon atoms, and preferably has 16 or more carbon atoms. Examples thereof include saturated fatty acids having 20 or less, more preferably 18 or less carbon atoms, and specific examples thereof include lauric acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. Of these, palmitic acid is particularly preferable. In the triacylglycerol represented by St-U-St or St-St-U, the two Sts may be the same or different, but the two Sts are the same. Is preferable.

On the other hand, the unsaturated fatty acid having 8 to 22 carbon atoms represented by U constituting the triacylglycerol is preferably a monounsaturated fatty acid having 16 or more carbon atoms, preferably 20 or less carbon atoms, and is an olein having 18 carbon atoms. Acids are most preferred. In the triacylglycerol represented by U-St-U, the two Us may be the same or different, but it is preferable that the two Us are the same.

The intermolecular compound in the present invention is formed from triacylglycerol represented by St-U-St and triacylglycerol represented by U-St-U or St-St-U. More specifically, a combination of 1,3-St-2-U-glycerol and 1,3-U-2-St-glycerol, or 1,3-St-2-U-glycerol and 1,2- It is formed by mixing equal amounts of each triacylglycerol in combination with St-3-U-glycerol. Here, the equivalent amount means that the molar ratio is 1: 1. However, in the actual production of the intermolecular compound, some errors are allowed, and usually the molar ratio is 1: 3 to 0.3, preferably the molar ratio is 1: 2 to 0.5, and more preferably the molar ratio is 1: 1. The mixture may be mixed in the range of 5 to 0.7, more preferably the molar ratio of 1: 1.1 to 0.9.

The oil / fat composition containing the intermolecular compound according to the present invention is formed from triacylglycerol represented by St-U-St and triacylglycerol represented by U-St-U or St-St-U. It may contain the above-mentioned intermolecular compound, or may consist only of the intermolecular compound, and is represented by the intermolecular compound and St-U-St which does not form the intermolecular compound. It may contain triacylglycerol, triacylglycerol represented by U-St-U or St-St-U, and other glycerides that do not affect the formation of intermolecular compounds.
In addition, it may contain triacylglycerol represented by St-U-St, or other components mixed in the process of producing triacylglycerol represented by U-St-U or St-St-U. ..
For example, when palm olein obtained by separating palm oil is used, it may contain components remaining in the process of separation and purification. Further, another component may be added, and in the present invention, another component may be added after mixing (adding) the sucrose fatty acid ester.

It should be noted that what is usually called fat and oil itself is a composition made of various materials, that is, the fat and oil composition of the present invention may be what is usually called fat and oil itself.
When the fat and oil composition contains an intermolecular compound, for example, an intermolecular compound separated from the fat and oil may be used, and a fat and oil containing a large amount of triacylglycerol represented by St-U-St and U- An intermolecular compound may be obtained by mixing fats and oils containing a large amount of triacylglycerol represented by St-U or St-St-U.
The oil / fat composition containing the intermolecular compound according to the present invention also includes those forming an intermolecular compound, and usually contains triacylglycerol in an amount of 80% by weight or more, preferably 85% by weight or more, and more preferably 90% by weight or more. It includes.

However, if the content of the intermolecular compound in the oil / fat composition is too small, the crystals of the intermolecular compound may be difficult to precipitate, or the purity of the obtained intermolecular compound crystal may decrease. The content of the intermolecular compound in the glycerol (that is, the amount of the triacylglycerol contained in the oil / fat composition forming the intermolecular compound) is 10% by weight or more, particularly 30% by weight or more, particularly 50% by weight. % Or more is preferable.

In the present invention, any embodiment may be taken as long as the oil / fat composition containing the intermolecular compound and the sucrose fatty acid ester are mixed, but as a preferred embodiment, the oil / fat composition containing the above-mentioned intermolecular compound. Is crystallized by mixing (adding) a sucrose fatty acid ester as a crystal micronizing agent.
Further, as another embodiment, for example, a method of adding another fat or oil to a fat or oil composition containing a sucrose fatty acid ester and crystallizing it can be mentioned.
Hereinafter, a method for crystallization by mixing (adding) a sucrose fatty acid ester as a crystal micronizing agent with an oil / fat composition containing the above-mentioned intermolecular compound, which is a preferred embodiment of the present invention, will be described.

The sucrose fatty acid ester used in the present invention is lipophilic and has an HLB value of preferably 0 or more, more preferably 1 or more, preferably 5 or less, more preferably 3 or less, and has a monoester content of usually 30 or more. % Or less, preferably 20% or less, particularly preferably 10% or less. The melting point is usually 30 ° C. or higher, preferably 40 ° C. or higher, usually 80 ° C. or lower, preferably 70 ° C. or lower. The constituent fatty acids usually have 12 or more carbon atoms, preferably 16 or more, usually 22 or less, preferably 18 or less, such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid. One or more saturated or unsaturated fatty acids having 12 to 22 carbon atoms can be mentioned. Among these, saturated fatty acids having 16 to 18 carbon atoms are preferable. One of these sucrose fatty acid esters may be used alone, or two or more thereof may be used in combination.

The details of the mechanism of action of the sucrose fatty acid ester functioning as a crystal micronizing agent for intermolecular compounds are not clear, but it is considered to be due to the following mechanisms of action (1) and (2).
(1) When the intermolecular compounds of triacylglycerol crystallization, they gather together to form a cluster, and the sucrose fatty acid ester intervenes between the intermolecular compounds to disturb the cluster and inhibit the formation of the cluster. ..
(2) The crystal grows like a stack of stacks, and the surface of the crystal has a surface called a flat terrace, a step as a boundary between terraces of different heights, and a kink in which the steps bend to form corners. However, the sucrose fatty acid ester adsorbs and blocks the kink of the already precipitated crystal, thereby inhibiting the adsorption of further intermolecular compounds and suppressing the growth of the crystal.

According to the present invention, due to the crystal refinement effect of the sucrose fatty acid ester as described above, crystals of a uniform and fine intermolecular compound can be precipitated, and a good texture can be obtained when added to foods. become able to.

If the amount of the sucrose fatty acid ester mixed (added) to the fat / oil composition containing the intermolecular compound is too small, the crystal finer effect due to the mixing (addition) of the sucrose fatty acid ester cannot be sufficiently obtained. , The larger the amount of sucrose fatty acid ester mixed (added), the greater the crystal finer effect tends to be. However, even if the amount is excessive, the crystal finer effect peaks and the purity of the intermolecular compound crystal is increased. Is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, usually 5% by weight or less, preferably 1% by weight, based on the intermolecular compound in the fat or oil composition. It is preferable to mix (add) so as to be less than%. The content of the sucrose fatty acid ester in the oil / fat composition is preferably 0.02% by weight or more, more preferably 0.1% by weight or more, particularly preferably 0.5% by weight or more, and usually 10% by weight or less. It is preferably 5% by weight or less, and particularly preferably 2% by weight or less.

After mixing (adding) a predetermined amount of sucrose fatty acid ester to the oil / fat composition containing the intermolecular compound, the temperature is sufficiently higher than the melting point of the intermolecular compound and sucrose fatty acid ester, for example, 50 ° C. or higher, preferably 60. Heat and mix at ° C. or higher, usually 100 ° C. or lower. The mixing time may be such that the intermolecular compound in the fat and oil composition and the sucrose fatty acid ester are sufficiently and uniformly mixed, and is usually about 5 to 30 minutes.

A sucrose fatty acid ester is mixed (added) with an oil / fat composition containing an intermolecular compound, heated, and then cooled to precipitate crystals of the intermolecular compound. The cooling rate at this time is not particularly limited, and the crystals tend to be finer under the quenching condition, but the crystals can be sufficiently fined even under the slow cooling condition of about 0.1 to 2 ° C./min. It is possible.

The sucrose fatty acid ester may be mixed (added) with the oil / fat composition containing the intermolecular compound, heated and mixed, and then diluted with a solvent prior to cooling.

In the present invention, an oil / fat composition containing crystals of a finely divided intermolecular compound (triacylglycerol represented by St-U-St and triacyl represented by U-St-U or St-St-U). The content of the intermolecular compound with respect to 100% by weight of the fat and oil composition obtained by mixing the fat and oil composition containing the intermolecular compound formed from glycerol and the sucrose fatty acid ester is usually 10% by weight or more. It is preferably 30% by weight or more, more preferably 50% by weight or more. The upper limit of the content of the intermolecular compound with respect to 100% by weight of the oil / fat composition is not particularly limited, and the oil / fat composition may be composed of the intermolecular compound and the sucrose fatty acid ester.

The particle size of the crystal containing triacylglycerol as a main component contained in the oil / fat composition produced by the present invention is usually 80 μm or less, preferably 60 μm or less, and more preferably 50 μm or less. When the particle size is not more than the above upper limit, a good texture can be obtained when added to food. The smaller the particle size of the finely divided crystals, the more preferable, and the lower limit thereof is not particularly limited, but is usually 0.01 μm or more, preferably 0.1 μm or more.
The method for measuring the particle size in the present invention is the diameter of each crystal confirmed from a polarizing microscope image having a measurement magnification of 200 times and a measurement range of 420 μm × 560 μm (for each crystal, within the line segment passing through the center of gravity of the crystal). It is calculated from the largest one).
The number of crystals having the above particle size may be usually 50% or more, preferably 70% or more, more preferably 90% or more, and the upper limit is 100% or less in a polarizing microscope image having a measurement range of 420 μm × 560 μm. ..

The average particle size of the crystals containing triacylglycerol as a main component contained in the fat and oil composition produced according to the present invention is usually 80 μm or less, preferably 60 μm or less, and more preferably 50 μm or less. When the average particle size is not more than the above upper limit, a good texture can be obtained when added to food. The smaller the average particle size of the finely divided crystals, the more preferable, and the lower limit thereof is not particularly limited, but is usually 0.01 μm or more, preferably 0.1 μm or more.
In the method for measuring the average particle size in the present invention, 5 to 20 crystals are arbitrarily selected from the crystals confirmed from the polarizing microscope images having a measurement magnification of 200 times and a measurement range of 420 μm × 560 μm, and the diameter of each crystal. It is calculated from the averaged value (the largest of the line segments passing through the center of gravity of each crystal).

Further, in the present invention, from the viewpoint of promoting the crystallization of the intermolecular compound, a monoglycerin fatty acid ester may be further mixed (added) in addition to the sucrose fatty acid ester. The monoglycerin fatty acid ester used is not particularly limited, but preferably has an HLB of 2 or more, more preferably 3 or more, preferably 5 or less, more preferably 4 or less, and has a monoester content of usually 50% by weight. % Or more, preferably 90% by weight or more. The melting point is usually 30 ° C. or higher, preferably 60 ° C. or higher, usually 80 ° C. or lower, preferably 70 ° C. or lower. For example, distilled glycerin fatty acid ester, undistilled glycerin fatty acid ester and the like can be mentioned.
The type of fatty acid is not particularly limited, but usually has 12 or more carbon atoms, preferably 16 or more, usually 22 or less, preferably 18 or less, and generally, lauric acid, myristic acid, palmitic acid, stearic acid, and the like. Oleic acid, behenic acid, erucic acid, and their mixed fatty acids can be used. Among these, palmitic acid and stearic acid are preferable. One of these monoglycerin fatty acid esters may be used alone, or two or more thereof may be used in combination.

The details of the mechanism of action of the monoglycerin fatty acid ester functioning as a crystallization accelerator for the intermolecular compound are not clear, but it is considered to be due to the following mechanisms of action (3) and (4).
(3) The lipophilic and high melting point monoglycerin fatty acid ester preferentially crystallizes, and the crystallization of intermolecular compounds is promoted by the formation of heterogeneous nuclei from the surface thereof.
(4) The crystal grows like a stack of stacks, and the surface of the crystal has a surface called a flat terrace, a step as a boundary between terraces of different heights, and a kink in which the steps bend to form corners. However, the monoglycerin fatty acid ester increases the growth point of the crystal and promotes the growth of the crystal by adsorbing it on the surface of the terrace of the crystal already precipitated and supplying a new step.

Due to the crystallization promoting effect of the monoglycerin fatty acid ester as described above, crystals of the intermolecular compound are precipitated at a higher temperature, and the time required for crystallization of the intermolecular compound can be shortened.

If the amount of the monoglycerin fatty acid ester mixed (added) to the fat / oil composition containing the intermolecular compound is too small, the crystallization promoting effect due to the mixing (addition) of the monoglycerin fatty acid ester cannot be sufficiently obtained. , The larger the amount of monoglycerin fatty acid ester added, the greater the crystallization promoting effect tends to be. However, even if the amount is excessively large, the crystallization promoting effect reaches a plateau and the purity of the intermolecular compound crystal decreases. From the results, it is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, preferably 5% by weight or less, and more preferably 1% by weight, based on the intermolecular compound in the fat or oil composition. It is preferable to mix (add) as follows. The content of the monoglycerin fatty acid ester in the oil / fat composition is preferably 0.02% by weight or more, more preferably 0.1% by weight or more, particularly preferably 0.5% by weight or more, and usually 10% by weight or less. It is preferably 5% by weight or less, and particularly preferably 2% by weight or less.

The ratio of the mixed (added) amount or content of the monoglycerin fatty acid ester to the mixed (added) amount or content of the sucrose fatty acid ester is usually 10% by weight or more, preferably 20% by weight or more, more preferably 40. By weight% or more, usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less.

The total amount of the sucrose fatty acid ester and the monoglycerin fatty acid ester mixed (added) to the fat / oil composition containing the intermolecular compound is preferably 0.01% by weight with respect to the intermolecular compound in the fat / oil composition. The total content of the sucrose fatty acid ester and the monoglycerin fatty acid ester in the fat and oil composition is more preferably 0.05% by weight or more, preferably 5% by weight or less, and more preferably 1% by weight or less. It is preferably 0.02% by weight or more, more preferably 0.05% by weight or more, particularly preferably 0.1% by weight or more, usually 10% by weight or less, preferably 5% by weight or less, and particularly preferably 2% by weight or less. be.
Within this range, it is possible to raise the crystallization temperature of a good intermolecular compound and to refine the crystal.

The timing of mixing (adding) the monoglycerin fatty acid ester is preferably the same as the timing of mixing (adding) the sucrose fatty acid ester described above.

[Manufacturing method of oil-containing foods]
The method for producing an oil-and-fat-containing food of the present invention is to produce an oil-and-fat-containing food using an oil-and-fat composition containing micromolecular compound crystals produced as described above as an oil-and-fat component, and has a high solid-fat content. By using fine intermolecular compound crystals of triacylglycerol, it is possible to produce a food having a high effect of blending fat and oil components.

The food produced by using the oil / fat composition containing the fine intermolecular compound crystals according to the present invention is not particularly limited, and can be widely applied to various foods and drinks using the oil / fat. For example, oil-in-water processed foods such as drinks, desserts, ice cream, dressings, toppings, mayonnaise, and roasted meat sauce; water-in-oil processed foods such as margarine and spreads; peanut butter, flying shortening, baking shortening, etc. Processed fats and oils foods; processed foods such as potato chips, snacks, cakes, cookies, pies, breads, chocolates; bakery mixes; processed meat products; frozen entre; frozen foods and the like. In particular, the fat and oil composition containing micromolecular compound crystals according to the present invention is suitably used for solid fat foods such as chocolate and margarine.

The present invention will be described in more detail by way of examples, but the present invention is not limited to the description of the following examples as long as the gist of the present invention is not exceeded.

[Example 1]
1,3-Dipalmitoyl-2-oleoyl-sn-glycerol (POP, manufactured by Tsukishima Food Industry Co., Ltd.) and 1,3-diore oil-2-palmitoyl-sn-glycerol (OPO, manufactured by Tsukishima Food Industry Co., Ltd.) 1: The mixture was mixed at 1 in equal weight (molar ratio 1: 0.97) and held at 80 ° C. for 10 minutes. Saturated fatty acid type sucrose fatty acid ester (trade name: P-170, manufactured by Mitsubishi Chemical Foods Co., Ltd., bound fatty acid = palmitic acid, HLB = about 1, hereinafter abbreviated as P-170) is added to this so as to be 1% by weight. , N-dodecane (manufactured by Nacalai Tesque) was added to the mixture while stirring and mixing with vortex while heating at 80 ° C. for 10 minutes, diluted to 50% by weight (2-fold dilution), and heated at 60 ° C. for 5 minutes. While stirring and mixing. This solution was cooled at a cooling rate of 0.5 ° C./min or 2 ° C./min to obtain an oil / fat composition containing P-170-added POP / OPO intermolecular compound crystals.
The content of the intermolecular compound with respect to 100% by weight of the oil / fat composition containing the P-170-added POP / OPO intermolecular compound crystals is 49% by weight.

[Example 2]
Mixed acid sucrose fatty acid ester (trade name: POS-135, manufactured by Mitsubishi Chemical Foods Co., Ltd., bound fatty acid = oleic acid, palmitic acid, stearic acid, HLB = about 1, hereafter POS-135) in an equal amount mixture of POP and OPO. (Omitted) was added so as to be 1% by weight, and the mixture was stirred and mixed by vortex while heating at 80 ° C. for 10 minutes. To this, n-dodecane was added to dilute it to 50% by weight (2-fold dilution), and the mixture was stirred and mixed while heating at 60 ° C. for 5 minutes. This solution was cooled at a cooling rate of 0.5 ° C./min or 2 ° C./min to obtain an oil / fat composition containing POS-135-added POP / OPO intermolecular compound crystals.
The content of the intermolecular compound with respect to 100% by weight of the oil / fat composition containing the POS-135-added POP / OPO intermolecular compound crystals is 49% by weight.

[Example 3]
0.5% by weight of P-170 and 0.5% by weight of glycerin monopalmitic acid ester (trade name: monopalmitin, manufactured by Sigma-Aldrich Japan, hereinafter abbreviated as MP) in an equal amount mixture of POP and OPO. The mixture was added so as to be vortexed while heating at 80 ° C. for 10 minutes. To this, n-dodecane was added to dilute it to 50% by weight (2-fold dilution), and the mixture was stirred and mixed while heating at 60 ° C. for 5 minutes. This solution was cooled at a cooling rate of 0.5 ° C./min to obtain an oil / fat composition containing P-170 and MP-added POP / OPO intermolecular compound crystals.
The content of the intermolecular compound with respect to 100% by weight of the oil / fat composition containing P-170 and MP-added POP / OPO intermolecular compound crystals is 49% by weight.

[Comparative Example 1]
An oil / fat composition containing POP / OPO intermolecular compound crystals without an emulsifier added was obtained in the same manner as in Example 1 except that P-170 was not added.

[Comparative Example 2]
MP was added to an equal amount mixture of POP and OPO so as to be 1% by weight, and the mixture was stirred and mixed by vortex while heating at 80 ° C. for 10 minutes. To this, n-dodecane was added to dilute it to 50% by weight (2-fold dilution), and the mixture was stirred and mixed while heating at 60 ° C. for 5 minutes. This solution was cooled at a cooling rate of 0.5 or 2 ° C./min to obtain an oil / fat composition containing MP-added POP / OPO intermolecular compound crystals.

[Example 4]
P-170 was added to an equal amount mixture of POP and OPO so as to be 1% by weight, and the mixture was stirred and mixed by vortex while heating at 80 ° C. for 10 minutes. This mixed solution was cooled at a cooling rate of 0.5 ° C./min to obtain an oil / fat composition containing P-170-added POP / OPO intermolecular compound crystals.
The content of the intermolecular compound with respect to 100% by weight of the oil / fat composition containing the P-170-added POP / OPO intermolecular compound crystals is 99% by weight.

[Example 5]
POS-135 was added to an equal amount mixture of POP and OPO so as to be 1% by weight, and the mixture was stirred and mixed by vortex while heating at 80 ° C. for 10 minutes. This mixed solution was cooled at a cooling rate of 0.5 ° C./min to obtain an oil / fat composition containing POS-135-added POP / OPO intermolecular compound crystals.
The content of the intermolecular compound with respect to 100% by weight of the oil / fat composition containing the POS-135-added POP / OPO intermolecular compound crystals is 99% by weight.

[Comparative Example 3]
An oil / fat composition containing POP / OPO intermolecular compound crystals without an emulsifier added was obtained in the same manner as in Example 3 except that P-170 was not added.

[Comparative Example 4]
MP was added to an equal amount mixture of POP and OPO so as to be 1% by weight, and the mixture was stirred and mixed by vortex while heating at 80 ° C. for 10 minutes. This mixed solution was cooled at a cooling rate of 0.5 ° C./min to obtain an oil / fat composition containing MP-added POP / OPO intermolecular compound crystals.

[Observation of crystals]
The appearance and morphology of the intermolecular compound crystals in the oil and fat compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were observed with a polarizing microscope, and the particle size of the crystals was measured. The observation conditions are as follows.
Polarizing microscope: Nikon OPTIPHOT2-POL
Temperature control device: Japan Hi-Tech Co., Ltd. Cooling and heating stage for microscopes LINKAM10002L
Temperature Program: In Examples 1, 2 and 3 and Comparative Examples 1 and 2, the obtained oil and fat composition was held at 60 ° C. for 5 minutes at an isothermal temperature, and then cooled to −10 ° C. at a cooling rate of 0.5 ° C./min or 2 ° C./min. After cooling in minutes, the morphology and particle size at −10 ° C. were observed. The results of Examples 1, 2 and 3 and Comparative Examples 1 and 2 are shown in Table 1. In Examples 4 and 5 and Comparative Examples 3 and 4, the obtained oil and fat composition was held at an isothermal temperature of 80 ° C. for 5 minutes, cooled to 0 ° C. at a cooling rate of 0.5 ° C./min, and formed at 0 ° C. The particle size was observed. The results of Examples 4 and 5 and Comparative Examples 3 and 4 are shown in Table 2.
The polarizing microscope image of the P-170-added POP / OPO intermolecular compound crystal (cooling rate 0.5 ° C./min) of Example 1 at the time of this polarizing microscope observation is shown in FIG. 1, and the POS-135-added POP / of Example 2 A polarizing microscope image of the OPO intermolecular compound crystal (cooling rate 0.5 ° C./min) is shown in FIG. 2, showing the P-170 of Example 3 and the MP-added POP / OPO intermolecular compound crystal (cooling rate 2 ° C./min). A polarizing microscope image is shown in FIG. 3, and a polarizing microscope image of the emulsifier-free POP / OPO intermolecular compound crystal (cooling rate 0.5 ° C./min) of Comparative Example 1 is shown in FIG. Petrographic microscope images of intermolecular compound crystals (cooling rate 0.5 ° C./min) are shown in FIG. 5, respectively.

In Example 1 (addition of P-170), fine crystals of 10 μm or less (FIG. 1) were formed by cooling at 0.5 ° C./min, and fine spherulites having a particle size of about 10-40 μm were formed by cooling at 2 ° C./min. confirmed. In Example 2 (added with POS-135), fine crystals of 10 μm or less (FIG. 2) were confirmed when cooled at 0.5 ° C./min, and fine crystals having a particle size of about 10-40 μm were confirmed when cooled at 2 ° C./min. rice field.
In Example 3 (P-170 and MP added), an aggregate of fine acicular crystals of 30 to 100 μm when cooled at 0.5 ° C./min is fine with a particle size of about 20 μm or less when cooled at 2 ° C./min. Crystals were confirmed (Fig. 3).
In Comparative Example 1 (without additives), spherulites having a particle size of about 110 to 230 μm (FIG. 4) were formed by cooling at 0.5 ° C./min, and spherulites having a particle size of about 30 to 100 μm were obtained by cooling at 2 ° C./min. confirmed.
In Comparative Example 2 (MP addition), an aggregate of acicular crystals having a particle size of about 130 to 220 μm (FIG. 5) was cooled at 0.5 ° C./min and had a particle size of about 40 to 160 μm when cooled at 2 ° C./min. An aggregate of acicular crystals was confirmed.

In Example 4 (addition of P-170), fine spherulites and fine crystals having a particle size of 30 to 50 μm were confirmed by cooling at 0.5 ° C./min.
In Example 5 (added with POS-135), fine crystals having a particle size of 10 μm or less were confirmed by cooling at 0.5 ° C./min.
In Comparative Example 3 (without additives), spherulites having a particle size of about 30 to 200 μm were confirmed by cooling at 0.5 ° C./min.
In Comparative Example 4 (MP addition), aggregates of fine crystals having a particle size of 10 μm or less were confirmed by cooling at 0.5 ° C./min, but they were unevenly dispersed to form aggregates.

From the above, it was found that the intermolecular compound crystals can be uniformly refined by adding the sucrose fatty acid ester.

[Measurement of crystallization temperature]
The temperature at which the intermolecular compound crystals obtained in Examples 1, 2 and 3 and Comparative Examples 1 and 2 crystallize was measured by differential scanning calorimetry (DSC). The measurement conditions are as follows.
Measuring device: SII Nanotechnology Inc. DSC6100
Reference: α-alumina Temperature program: After maintaining isothermal at 60 ° C. for 10 minutes in a vortex, the mixture was cooled to −20 ° C. at a cooling rate of 0.5 ° C./min or 2 ° C./min.

The intersection of the tangent line and the baseline drawn at the maximum inclination point of the rising portion of the obtained exothermic peak was defined as the crystallization temperature. Table 3 shows the crystallization temperature.

From Tables 1 and 3, it was found that in Example 3 in which the sucrose fatty acid ester and the monoglycerin fatty acid ester were added in combination, the crystallization temperature was raised, the crystallization promoting effect was observed, and the crystals could be made finer.

[Identification of crystalline polymorphism]
The crystal polymorphs of the intermolecular compounds obtained in Examples 1, 2, 4, 5 and Comparative Examples 1 to 4 were confirmed by X-ray diffraction measurement. The measurement conditions are as follows.
Measuring device: Rigaku's sample horizontal strong X-ray diffractometer RINT-TTR
X-ray: Cu-Kα ray, 30V / 250mA, λi = 0.154nm
Measurement range: 2θ = 1.2 ° to 27 °

In each crystal, the diffraction peak of 1.4 nm corresponding to the (003) plane with a long surface spacing of 4.2 nm on the small angle side, and 0.46 nm and 0.39 nm corresponding to the sublattice β type on the wide angle side. Alternatively, diffraction peaks of 0.46 nm and 0.38 nm were confirmed. It was found that the addition of an emulsifier had no effect on polymorphism, and stable 2-chain long β-type crystals could be obtained.

Claims (3)

Triacylglycerol represented by St-U-St and
An oil / fat composition containing an intermolecular compound formed from triacylglycerol represented by U-St-U or St-St-U.
A sucrose fatty acid ester containing a saturated fatty acid having 16 to 18 carbon atoms as a constituent fatty acid is mixed with the sucrose fatty acid ester.
The oil / fat composition mixed with the sucrose fatty acid ester is heated and then cooled under a slow cooling condition of 0.1 to 2 ° C./min .
A method for producing an oil / fat composition containing β-type crystals of the intermolecular compound refined to an average particle size of 0.01 μm or more and 80 μm or less.
Of the triacylglycerol contained in the fat and oil composition containing β-type crystals of the intermolecular compound refined to an average particle size of 0.01 μm or more and 80 μm or less , 30% by weight or more of the triacylglycerol forms the intermolecular compound. A method for producing an oil / fat composition containing micromolecular compound crystals.
(However, St represents a saturated fatty acid having 16 or more and 18 or less carbon atoms, and U represents oleic acid.) The oil / fat composition containing the fine intermolecular compound crystals according to claim 1, wherein the content of the intermolecular compound is 10% by weight or more based on 100% by weight of the oil / fat composition containing the finely divided crystals of the intermolecular compound. How to make things. A method for producing an oil-and-fat-containing food, which comprises using an oil-and-fat composition containing micromolecular compound crystals produced by the production method according to claim 1 or 2.

Images