JP6645285B2 - Method for producing intermolecular compound crystal for chocolate and method for promoting crystallization of intermolecular compound for chocolate - Google Patents

Description

  The present invention relates to fats and oils used for processed foods, cosmetics, pharmaceuticals, and the like, and more particularly, to a method for producing intermolecular compound crystals and a method for accelerating crystallization of intermolecular compounds in a fat and oil composition containing an intermolecular compound of triacylglycerol.

  Conventionally, hardened oils obtained by hydrogenating vegetable oils have been frequently used for solid fat foods such as chocolate and margarine, because good hardness and texture can be obtained. Trans-acids and saturated fatty acids produced by partial hydrogenation have good solid fat content and spreadability, and are extremely excellent in physical properties.However, due to concerns about increasing health risks such as arteriosclerosis and heart disease, nutrition In terms of surface, it is desirable to reduce it. Therefore, development of fats and oils for solid fat foods having good solid fats while suppressing trans acids and saturated fatty acids to a healthy content is desired.

  As an alternative to trans-acids, palm oil containing a large amount of long-chain fatty acids, or a mixed oil of palm fractionated oil and hydrogenated rapeseed oil is used. There is a problem in that the mouth is deteriorated, and there are examples in which coarsening is suppressed by adjusting the blending of a specific triglyceride and adding an emulsifier (Patent Documents 1 and 2). There is also an example in which enzymatic esterification and random esterification of fats and oils accelerate crystallization and make it difficult to form large crystals (Patent Document 3). Further disclosed is a method of directly crystallizing a stable β-form polymorph since the unstable polymorph α-form and β′-form crystals are transformed into energetically stable β-form crystals during long-term storage and coarsened. (Patent Document 4). However, the raw oils and fats contain trans acids, so the processed fats and oils do not contain a small amount of trans acids, or even if they do not contain them, they have not completely replaced the properties and functions of trans acids. Not reduced. In addition, there is a report that the formability and texture of margarine are improved by maintaining a shape by a combination of an emulsifier (Patent Document 5). There is also an example in which a network structure is formed with wax organogel (Non-Patent Document 1). However, these do not completely substitute for the physical properties and are inferior in flavor. Therefore, a technique of increasing the content of solid fat by forming a "molecular compound" by blending a specific TAG at a high level is attracting attention (Non-Patent Document 2).

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

  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 more oleic acid components that are less susceptible to oxidation than polyunsaturated fatty acids, is increasing in liquid oil applications such as frying oil. ing. However, these fats and oils are not suitable for solid fat foods because they contain a large amount of oleic acid and are hard to solidify in a liquid state. Therefore, by forming an intermolecular compound of TAG containing an oleic acid component, it is possible to maintain the physical properties and texture without lowering the solid fat content while reducing the saturated fatty acids and at the same time containing high oleic acid. Become. However, when the oleic acid component increases, the crystallization temperature of fats and oils decreases, and the crystallization is slow and progresses gradually.It is difficult to maintain the structure immediately after crystallization over time, and in the conventional manufacturing conditions, There is a problem that crystallization cannot be performed sufficiently.

JP 2001-503624 A JP 2008-12538 A JP 2001-258474 A JP 2005-350660 A JP 2008-519601 A

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, the present invention focuses on the problem of slow crystallization, and aims to provide a method capable of promoting the crystallization of an intermolecular compound of triacylglycerol and producing an intermolecular compound crystal in a short time.

As a result of intensive studies by the present inventors, it has been found that crystallization of an intermolecular compound can be promoted by adding a monoglycerin fatty acid ester to a composition containing a triacylglycerol intermolecular compound, and the present invention has been achieved.
That is, the present invention provides the following.

[1] A fat or oil composition containing an intermolecular compound formed from a triacylglycerol represented by St-U-St and a triacylglycerol represented by U-St-U or St-St-U. And producing a crystallized intermolecular compound by adding a monoglycerin 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.)

[2] The method for producing intermolecular compound crystals according to [1], wherein the fat or oil composition to which the monoglycerin fatty acid ester is added is heated and then cooled.

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

[4] A method for producing an oil-and-fat-containing food, which is produced using the intermolecular compound crystal produced by the production method according to any one of [1] to [3].

[5] A fat or oil composition containing an intermolecular compound formed from a triacylglycerol represented by St-U-St and a triacylglycerol represented by U-St-U or St-St-U. A method for promoting crystallization of an intermolecular compound, characterized by adding a monoglycerin 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.)

ADVANTAGE OF THE INVENTION According to this invention, crystallization of a triacylglycerol intermolecular compound is promoted, and it becomes possible to manufacture an intermolecular compound crystal in a short time.
According to the present invention, crystallization of an intermolecular compound of triacylglycerol containing substantially no trans acid, containing a saturated fatty acid and an oleic acid component having excellent oxidation resistance in a well-balanced manner is promoted, and the production time is shortened. By doing so, productivity can be increased.
Further, according to the present invention, it is possible to sufficiently solidify during the production and form a stable β-form having a two-chain length. Therefore, the structure immediately after crystallization can be maintained over time, and product deterioration during storage can be prevented.
Further, crystallization of the intermolecular compound can be easily promoted without performing complicated processing such as transesterification.
The intermolecular compound crystals produced according to the present invention have a high solid fat content and can be suitably used as fats and oils to be blended into processed foods, cosmetics, pharmaceuticals, and the like, particularly solid fat foods such as chocolate, margarine, and spreads.

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

[Method for producing intermolecular compound crystal / method for promoting crystallization of intermolecular compound]
The method for producing an intermolecular compound crystal of the present invention is directed to a method for producing a molecule formed from a triacylglycerol represented by St-U-St and a triacylglycerol represented by U-St-U or St-St-U. It is characterized in that a monoglycerin fatty acid ester is added to an oil / fat composition containing an intermolecular compound to produce a crystallized intermolecular compound.
The method for promoting crystallization of an intermolecular compound according to the present invention is formed from a triacylglycerol represented by St-U-St and a triacylglycerol represented by U-St-U or St-St-U. It is characterized in that a monoglycerin fatty acid ester is added to a fat or oil composition containing an intermolecular compound.
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 main component of fats and oils, and its structure is such that three fatty acids are bonded to glycerin. For example, St-U-St in the present invention has two molecules of St and one molecule of U as a fatty acid, and binds to glycerin in the order of St → U → St at binding positions sn-1, 2, and 3. It indicates that.
The saturated fatty acid having 8 to 22 carbon atoms represented by St constituting the triacylglycerol forming the intermolecular compound in the present invention is preferably 12 or more carbon atoms, more preferably 16 or more carbon atoms, and preferably carbon number Saturated fatty acids having 20 or less, more preferably 18 or less carbon atoms are exemplified, and specific examples include lauric acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. Of these, palmitic acid is particularly preferred. In the triacylglycerol represented by St-U-St or St-St-U, two Sts may be the same or different, but the two Sts are the same. Is preferred.

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

  The intermolecular compound in the present invention is formed from a triacylglycerol represented by St-U-St and a 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-st It is formed by mixing equal amounts of each triacylglycerol in combination with St-3-U-glycerol. Here, "equivalent" means that the molar ratio is 1: 1. However, in the actual production of the intermolecular compound, a slight error is allowed, and the mixing may be performed in the range of 1: 1.1 to 0.9.

The fat and oil composition containing the intermolecular compound according to the present invention is formed from a triacylglycerol represented by St-U-St and a triacylglycerol represented by U-St-U or St-St-U. What is necessary is just to contain the said intermolecular compound, and may consist only of the said intermolecular compound, and is represented by an intermolecular compound and St-U-St which does not form an 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.
Further, it may contain a triacylglycerol represented by St-U-St, or another component mixed in a process of producing a triacylglycerol represented by U-St-U or St-St-U. .
For example, when using palm olein obtained by separating palm oil, it may contain components remaining in the process of separation and purification.
What is usually called fats and oils is a composition composed of various materials, that is, the fats and oils composition of the present invention may be what is usually called fats and oils itself.
When the oil or fat composition contains an intermolecular compound, for example, an intermolecular compound separated from the oil or fat may be used, or an oil or fat containing a large amount of triacylglycerol represented by St-U-St; An intermolecular compound may be obtained by mixing an oil or fat containing a large amount of triacylglycerol represented by St-U or St-St-U.
Furthermore, the oil or fat composition containing the intermolecular compound according to the present invention is obtained by diluting triacylglycerol with a solvent such as an organic solvent such as alkane (n-dodecane, hexane, etc.), acetone, ethanol, isopropylene alcohol. It may be. The solvent is not particularly limited as long as it can dissolve the intermolecular compound.
The oil / fat composition containing the intermolecular compound according to the present invention 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, more preferably 90% by weight or more. Including.

  However, if the content of the intermolecular compound in the oil / fat composition is too small, crystals of the intermolecular compound may not be easily precipitated, or the purity of the obtained intermolecular compound crystal may be reduced. The content of the intermolecular compound in glycerol (that is, the amount forming the intermolecular compound in the triacylglycerol contained in the fat or oil composition) is 10% by weight or more, particularly 30% by weight or more, especially 50% by weight. % Is preferable.

  In the present invention, a monoglycerin fatty acid ester as a crystallization accelerator is added to the oil / fat composition containing the above intermolecular compound to cause crystallization.

The monoglycerin fatty acid ester used in the present invention 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. It is usually at least 50% by weight, preferably at least 90% by weight. The melting point is usually at least 30 ° C, preferably at least 60 ° C, usually at most 80 ° C, preferably at most 70 ° C. 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, and usually 22 or less, preferably 18 or less. Generally, lauric acid, myristic acid, palmitic acid, stearic acid, Oleic acid, behenic acid, erucic acid, and their mixed fatty acids can be used. Among these, palmitic acid and stearic acid are preferred. 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 are thought to be due to the following mechanisms (1) and (2).
(1) The lipophilic and high-melting monoglycerin fatty acid ester is preferentially crystallized, and the formation of heterogeneous nuclei from the surface promotes crystallization of the intermolecular compound.
(2) The crystal grows like building blocks, and the surface of the crystal has a flat terrace, a step as a boundary between terraces of different heights, and a kink in which the step is bent to form a corner. However, the monoglycerin fatty acid ester adsorbs on the terrace surface of the already precipitated crystal to supply a new step, thereby increasing the crystal growth point and promoting the crystal growth.

  With the crystallization accelerating effect of the monoglycerin fatty acid ester as described above, according to the present invention, in the cooling step after the addition of the monoglycerin fatty acid ester described later, the crystal of the intermolecular compound is precipitated at a higher temperature, The time required for crystallization of the intermolecular compound can be reduced.

  If the amount of the monoglycerin fatty acid ester added to the fat or oil composition containing the intermolecular compound is too small, the crystallization promoting effect due to the addition of the monoglycerin fatty acid ester cannot be sufficiently obtained. As the amount of addition increases, the crystallization accelerating effect tends to increase.However, even if the amount is excessively large, the crystallization accelerating effect reaches a plateau, and the purity of the intermolecular compound crystal is reduced. It is preferably added in an amount of 0.01% by weight or more, more preferably 0.05% by weight or more, preferably 5% by weight or less, more preferably 1% by weight or less, based on the intermolecular compound in the oil / fat composition. Is preferred. The content of the monoglycerin fatty acid ester in the fat or oil 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. , Preferably 5% by weight or less, particularly preferably 2% by weight or less.

  After adding a predetermined amount of the monoglycerin fatty acid ester to the oil and fat composition containing the intermolecular compound, a temperature sufficiently higher than the melting points of the intermolecular compound and the monoglycerin fatty acid ester, for example, 50 ° C. or higher, preferably 60 ° C. or higher, Usually, the mixture is heated and mixed at 100 ° C. or less. The mixing time may be such that the intermolecular compound in the oil or fat composition and the monoglycerin fatty acid ester are sufficiently uniformly mixed, and is usually about 5 to 30 minutes.

  The monoglycerin fatty acid ester is added to the oil / fat composition containing the intermolecular compound, heated, and then cooled to precipitate crystals of the intermolecular compound. The cooling rate at this time is not particularly limited, and is about 0.1 to 10 ° C / minute.

  In addition, after adding the monoglycerin fatty acid ester to the fat or oil composition containing the intermolecular compound and heating and mixing the mixture, the mixture may be diluted with the above-mentioned solvent to about 50 to 80% by weight before cooling. By doing so, a higher purity intermolecular compound crystal can be obtained, and the crystallization time can be shortened.

[Production method of oil-containing food]
The method for producing a fat-containing food of the present invention is to produce a fat-containing food using the intermolecular compound crystal produced as described above as a fat component, and the solid fat content of the triacylglycerol is high. By using the compound crystal, a food having a high effect of blending the fat component can be produced.

  Foods produced using the intermolecular compound crystals according to the present invention are not particularly limited, and can be widely applied to various foods and drinks using oils and fats. For example, oil-in-water type oil-and-fat processed foods such as drinks, desserts, ice creams, dressings, toppings, mayonnaise and grilled meat sauce; water-in-oil-type oil-and-fat processed foods such as margarine and spread; peanut butter, flying shortening, baking shortening, etc. Processed oils and fats foods; Processed foods such as potato chips, snacks, cakes, cookies, pies, breads, chocolates, etc .; Bakery mixes; Processed meat products; Frozen entrées; In particular, the intermolecular compound crystal according to the present invention is suitably used for solid fat foods such as chocolate and margarine.

  The present invention will be described more specifically with reference to examples, but the present invention is not limited to the description of the following examples unless it exceeds the gist.

[Example 1]
1,3-dipalmitoyl-2-oleoyl-sn-glycerol (POP, manufactured by Tsukishima Foods) and 1,3-dioleoyl-2-palmitoyl-sn-glycerol (OPO, manufactured by Tsukishima Foods) are as follows: 1 and mixed at 80 ° C. for 10 minutes. Glycerin monopalmitate (trade name: monopalmitin, manufactured by Sigma-Aldrich Japan Co., Ltd .; hereinafter abbreviated as MP) was added to 1 wt%, and the mixture was further vortex-mixed while heating at 80 ° C. for 10 minutes. The melt obtained by stirring and mixing was cooled at a cooling rate of 0.5 ° C./min or 2 ° C./min to obtain MP-added POP / OPO intermolecular compound crystals.

[Example 2]
In the same manner as in Example 1, POP and OPO were mixed in an equal amount of 1: 1 and stored at 80 ° C. for 10 minutes.
Thereafter, MP was added to a concentration of 0.05% by weight, and n-dodecane (manufactured by Nacalai Tesque) was added to the mixture obtained by stirring and mixing with vortex while heating at 80 ° C. for 10 minutes, and diluted to a concentration of 50% by weight. Then, 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 MP-added POP / OPO intermolecular compound crystals.

[Example 3]
MP-added POP / OPO intermolecular compound crystals were obtained in the same manner as in Example 2 except that the amount of MP added was changed to 1% by weight.

[Example 4]
MP-added POP / OPO intermolecular compound crystals were obtained in the same manner as in Example 2 except that the amount of MP added was 5% by weight.

[Comparative Example 1]
A POP / OPO intermolecular compound crystal without MP was obtained in the same manner as in Example 1 except that MP was not added.

[Comparative Example 2]
A POP / OPO intermolecular compound crystal without MP was obtained in the same manner as in Example 2 except that MP was not added.

[Measurement of crystallization temperature]
The temperature at which the intermolecular compound crystals obtained in Examples 1 to 4 and Comparative Examples 1 and 2 crystallized was measured by differential scanning calorimetry (DSC). The measurement conditions are as follows.
Measurement device: DSC6100, SII Nanotechnology Inc.
Reference: α-alumina Temperature program: After isothermally maintaining at 80 ° C. or 60 ° C. for 10 minutes with a vortex, it was cooled to 0 ° C. or −20 ° C. at a cooling rate of 0.5 ° C./min or 2 ° C./min.

  The intersection of the tangent drawn at the maximum slope point of the rising portion of the obtained exothermic peak and the baseline was defined as the crystallization temperature. Table 1 shows the crystallization temperatures.

Table 1 shows the following.
Comparison between Comparative Example 1 and Example 1 showed that the addition of MP increased the crystallization temperature, and a crystallization promoting effect was observed. Changing the cooling rate also had an accelerating effect. Comparing Comparative Example 2 with Examples 2 to 4, a crystallization accelerating effect due to the addition of MP was similarly observed even when crystallization was performed in a solution, and the accelerating effect was obtained even when the cooling rate was changed. Furthermore, the effect increased in proportion to the MP concentration. From this result, it was found that the crystallization-promoting effect of MP can be obtained not only in the bulk state but also in a dilute solution.

[Identification of polymorphism]
Crystal polymorphs of the intermolecular compounds obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were confirmed by X-ray diffraction measurement. The measurement conditions are as follows.
Measuring device: Rigaku Corporation Sample horizontal type strong X-ray diffractometer RINT-TTR
X-ray: Cu-Kα ray, 30 V / 250 mA, λi = 0.154 nm
Measurement range: 2θ = 1.2 ° to 27 °
In any of the crystals, a diffraction peak of 1.4 nm corresponding to a (003) plane having a long-chain spacing of 4.2 nm and a two-chain length 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 at 0.46 nm and 0.38 nm were confirmed. It was found that the addition of MP had no effect on the polymorph, and that a stable β-form crystal could be obtained.

Claims (4)

And triacylglycerol represented by St-U-St, a fat composition containing a U-St-U or St-St-U intermolecular compound formed from a triacylglycerol represented, the fat After adding the monoglycerin fatty acid ester and heating the oil / fat composition to which the monoglycerin fatty acid ester is added so that the content of the monoglycerin fatty acid ester in the composition is 0.02% by weight or more and 10% by weight or less. Cooling at a cooling rate of 0.1 to 10 ° C./minute to produce a crystallized intermolecular compound, a method for producing an intermolecular compound crystal for chocolate, wherein the fatty acid constituting the monoglycerin fatty acid ester is lauric acid; wherein the myristic acid, palmitic acid, stearic acid, is oleic acid, behenic acid, and one or more erucic acid, Method for producing Yokoreto for intermolecular compound crystals.
(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 method for producing an intermolecular compound crystal for chocolate according to claim 1, wherein 10% by weight or more of the triacylglycerol contained in the oil / fat composition forms the intermolecular compound. Wherein the prepared using claim 1 or chocolate for intermolecular compound produced by the production method described in 2 crystal, manufacturing method of the chocolate. And triacylglycerol represented by St-U-St, a fat composition containing a U-St-U or St-St-U intermolecular compound formed from a triacylglycerol represented, the fat After adding the monoglycerin fatty acid ester and heating the oil / fat composition to which the monoglycerin fatty acid ester is added so that the content of the monoglycerin fatty acid ester in the composition is 0.02% by weight or more and 10% by weight or less. A method for promoting crystallization of an intermolecular compound for chocolate, which is cooled at a cooling rate of 0.1 to 10 ° C./min , wherein the fatty acid constituting the monoglycerin fatty acid ester is lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, and is characterized in that one or two or more of erucic acid, chocolate for intermolecular compound crystals Promoting 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.)