JPH0475593A - Triglyceride, hard butter containing the same and chocolates using the same - Google Patents

Abstract

PURPOSE:To enable obtaining of hard butter and chocolate having improving effects on fat bloom resistance by using a triglyceride (SXS) in which a specific saturated fatty acid is bound to specific positions. CONSTITUTION:A fatty acid such as palmitic acid is added to coconut oil, etc., rich in relatively short-chain fatty acids and ester interchange reaction thereof is carried out with a lipase having 1,3-regiospecificity. Purification is then performed to produce a 1,3-diS-2-monoX triglyceride (SXS) in which a <=12C saturated fatty acid (X) is bound to the 2-position and a >=16C saturated fatty acid (S) is bound to the 1,3-positions. The resultant SXS in an amount of >=3.2wt.% as a fat bloom resistance improver may be contained in hard butter for use or the SXS or the aforementioned hard butter is added so as to contain >=2.0wt.% SXS in a raw material component of chocolate for use. Thereby, the SXS and the hard butter containing the SXS blended therein have preventive effects on fat bloom without impairing mouth meltability and operating efficiency and are useful for producing chocolates.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel triglyceride, and more specifically, F7) a triglyceride that can be used as a bloom resistance improver, and vert butter containing the same;
The present invention also relates to chocolates produced using the same.

[Conventional technology]

Today, most consumer complaints about chocolate products are related to so-called fan blooms.
To solve this problem, numerous studies have been conducted to prevent or delay the occurrence of fat bloom.

In the past, fat bloom prevention was targeted at oils themselves such as milk fat, hydrogenated peanut oil, and tempered hard butter, but recently, in addition to emulsifying products such as decoction sugar esters, polyglycerin, and sorbitan esters, cacao Products are being produced using specific triglyceride compositions different from fats, and by emulsifying chocolate.

Specifically, examples include: ■ Utilization of mid-melting point fractions of shea oil, monkey oil, and balm oil (Japanese Patent Application Laid-Open No. 1-157341), ■ Method of utilizing specific asymmetric triglycerides (Japanese Patent Laid-Open No.
-138937), ■method using triglyceride containing hehenic acid (JP-A-63-56250, JP-A-63-56250;
-240745, JP-A No. 1-60330), ■ Method using polyglycerin fatty acid ester (JP-A No. 60, No.
-130341, 61-181339, 62-
No. 104547), ■ A method using a combination of a hehenic acid-containing triglyceride and an emulsifier (Japanese Patent Application Laid-Open No. 118-1988)
848), and (2) a method of combining a triglyceride containing erucic acid or a trans fatty acid with an emulsifier (JP-A-1-157342, JP-A-1-285153).

[Problem to be solved by the invention]

However, the various inhibitors listed above often impair other properties even if they exhibit the effect of preventing fat bloom. for example,
With the method (2) of improving heat-resistant shape retention and the method (2) of using an asymmetric triglyceride, there is a problem that the texture inevitably deteriorates, or the viscosity of the dough in tempered pufferfish increases, reducing workability. If this problem is to be avoided, the phant bloom prevention effect must be kept within an insufficient range, and therefore, it is difficult to maintain a significant fat bloom prevention effect. In addition, in the method (2) using a symmetrical triglyceride containing hehenic acid, in order to obtain a sufficient phant bloom prevention effect, it is necessary to use a fine powder of stable crystals, and it is necessary to control the crystal type, crushing technology, etc. Requires.

Furthermore, methods of adding emulsifiers or combining them with hydrogenated oil, as shown in ■ to ■, are limited to non-tempering chocolates, and in the case of tempering chocolates, their effectiveness is limited to the fat bloom generation test temperature of 30°C.
The actual situation is that the temperature is not necessarily sufficient, and it is difficult to say that it is a satisfactory state.

[Means for Solving the Problems] In view of the above circumstances, the present inventors conducted intensive research to solve the above problems, and found that a specific composition has a remarkable effect of improving fat bloom resistance. Completed the invention.

That is, the first aspect of the present invention is 1,3-diS, in which a saturated fatty acid
The second aspect of the present invention is to produce -2,000-X triglyceride (SXS), and the third aspect of the present invention is to produce the triglyceride (SXS) by ethyl exchange using a lipase specific for the 1.3-position. Further, the fourth aspect of the present invention is a hard butter characterized by containing 3.2% by weight or more of the above-mentioned (SXS). (SXS>
Chocolates containing 2.0% by weight or more of:

When the triglyceride (SXS) of the present invention is used as a fat bloom resistance improver, X is C12
The following saturated fatty acids are required, preferably C4 or higher saturated fatty acids. In this case, if X has a longer chain than C14, it is not preferable because it causes an increase in viscosity during the tempering step, which is often a problem during chocolate production, and causes deterioration of depositability. next,
S is not particularly limited as long as it is a saturated fatty acid of C16 or higher, but preferably C76 or CIl+.

When the above-mentioned tric-1-noceride (SXS) is added to chocolate as a composition and used, the SXS in this composition is
The S content is adjusted to be 20% by weight or more, preferably 40% by weight or more. If this content is low, the SXS content in chocolate cannot be efficiently increased, and the quality of chocolate a may be impaired depending on components other than SXS.

In other words, the solvent separates trisaturated triglyceride, which causes a viscosity increase during the tempering process, which is often a problem during chocolate production, and deteriorates depositability, and low-melting components, which cause a deterioration in the snappability of chocolate products. It is preferable to remove it by etc. Specifically, the amount of trisaturated triglycerides other than SXS in the composition is 20% by weight or less, preferably 10% by weight or less, and the total amount of triglycerides in which two or more unsaturated or C12 or less short chain fatty acids are bonded in the molecule. is 50% by weight or less,
The content is desirably 30% by weight or less.

Since the triglyceride of the present invention requires positional specificity at the 1,3-position and the 2-position, it is preferable to use a transesterification method using a lipase having specificity at the 1,3-position. That is, for example, for 1 mole of triglyceride consisting only of short-chain fatty acids such as synthesized medium-chain fatty acid triglyceride, or coconut oil, palm kernel oil, etc. that are relatively rich in short-chain fatty acids, fatty acids such as valmitic acid, stearic acid, or Add 2 to 3 moles of fatty acid ester or add about the same mole of triglyceride, perform transesterification with lipase having β3-position specificity, and if necessary, fractionate components other than SXS from the reaction product, use molecular distillation, etc. It can be manufactured by removing it with .

The transesterification reaction may be carried out by a method using a lipase or a lipase preparation that selectively acts on the 1.3-position, or by a method using dried bacterial cells containing lipase (Japanese Patent Laid-Open No. 6
0 to 34189). In addition, components other than SXS can be separated by a method using an organic solvent such as hexane or acetone, or by a dry fractionation method, and when there is a considerable difference in triglyceride molecular weight, a method such as molecular distillation is preferable. Can be used for Note that the triglyceride of the present invention can also be obtained by a synthetic method.

When such a triglyceride is used as a phantom bloom resistance improver for chocolates, it may be contained directly in the chocolate composition, or it may be contained in hard butter.

When directly incorporated into the chocolate raw material composition, the fat bloom resistance improver is used so that SXS contains 2.0% by weight or more of -F based on the total fats and oils in the chocolate. If the content is less than 2.0% by weight, the effect of preventing fat bloom will be obtained, but the effect will be small.Also, the higher the content, the greater the effect of preventing fat bloom, but if it is too high, it will be difficult to produce tempering type chocolate. In this case, the work becomes difficult.

The reason why the anti-phanotoflume effect is improved by including SXS is that 1 and 3, which are the main components of cacao butter,
-Saturated-2-oleic triglyceride (SO5)
It is presumed that this is due to the special molecular structure of SXS in which oleic acid residue 0 is replaced with short chain saturated fatty acid residue X. That is, between the molecules of SOS triglyceride, which exhibits a complex crystal polymorphism, SXS, which is the same symmetric triglyceride,
It is presumed that this effectively penetrates and significantly delays the crystal transition speed after the formation of β2 type (■ type) crystals, which prevents the fat and oil crystals from becoming coarser and helps prevent fat bloom.

According to experiments conducted by the present inventors, cocoa butter (a)
Or by adding the triglyceride of the present invention to this (SX
Regarding fat (b) containing 5.0% S), it was melted → sampled → rapidly cooled to 0°C → stored at 20°C for 24 hours to generate β crystals of the fat.
C, 3,5 hours and 32°C, 3,5 hours (3,5 hours each for increasing and decreasing temperature)
X
We investigated how the intensity ratio of the β1-type (■-type crystal) peak (3,65 people) to the β2-type (V-type crystal) peak (4,00 people) that appears in line diffraction changes, and how the relative ratio changes. As a result, we obtained the results shown in Table 1.

Note) Numbers in [ ] represent relative ratios.

In addition to the oil specified above, the chocolate i targeted by the present invention includes cacao mass, sugars, dairy products, emulsifiers, flavorings, etc., which are the materials that normally constitute chocolate. Further, the hard butter may be a so-called tempering type or a non-tempering type, for example, a high elaidine type.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited in any way by these Examples.

Fruit 11 Crude 1 PC, P (13-dipalmitoyl-2-butyrate)
Synthesis (1) Synthesis of I3-shibalmitin L3-dihydroxyacetone (50 mmol), valmitic acid (105 mmol) and 4-dimethylaminopyridine (DMAP, 100 mmol) were combined with carbon tetrachloride (
dicyclohexylcarbodiimide (DCC, 105 mmol) was dissolved in CCI4,1000 m
1) was added and stirred at room temperature for 2 hours.

The precipitated dicyclohexylurea (DCUrea) was filtered off, and the filtrate was concentrated under reduced pressure, then methanol was added and the mixture was left to cool.

The precipitated crystals were collected by filtration, and tetrahydrofuran (T
HF, 1000100O, water (10ml) and Na
BF! (1.5 g) was added and left at room temperature for 30 minutes. After terminating the reaction by adding acetic acid (10 ml), chloroform (C) IC13, 500 mI2) was added, and the mixture was washed successively with a 5% aqueous sodium hydrogen carbonate solution, a 10% aqueous citric acid solution, and water, and the organic layer was anhydrous. Dry with sodium sulfate. After filtration, the solvent was distilled off under slight pressure to obtain the desired product. The yield and purity (measured by capillary gas chromatography in a conventional manner) are shown below.

Yield 80.3% (40.2mmo+) Purity 98
．． 7% (monobalmitin 1.3%) (2) PC, P synthesis n-butyric acid (22 mmol), DMAP (20 mmol
), DCC (22mm.

l) and 1,3-shibalmitin obtained in (1) above (
20 mmol) was dissolved in CCC14 (500 I2) and stirred at room temperature for 2 hours. After filtering off the poorly soluble DCIIrea, methanol was added and the mixture was left to cool, and the precipitated crystals were collected by filtration and dried to obtain the desired product.

Yield 95.1% (19.0 mmol) Purity 98.9% (PC4C40.8%, Sibalmitin 0
．． Synthesis of Example 1 (1) of 1,3-dipalmitoyl-2-cabrilate (1,3-cibalmitin (2))
Qmmo1), capric acid (2211111101),
DMAP- (20 mmol), and DCC (22 mmol)
Using 1), the same operation as in Example 1 (2) was performed to obtain the desired product.

Yield 97.2% (19.4 mmol) Purity 98.7% (PCeCs 1.1%, Sibalmitin 0.2%) Triglyceride obtained in Example 1 against cocoa butter (control) (c) 2.5%, 5.0% 10.0
% containing oils and fats (c-1, c-2, c-3), and oils and fats (d-1, d-2, d- Regarding 3), X-ray diffraction measurements were performed.

For measurement, the sample sampled on the glass cell for X-ray diffraction measurements was rapidly cooled at O''C for 30 minutes, stored at 20°C for 24 hours, and then stored at 20°C for 3.5 hours and at 32°C for 3.5 hours. The experiment was carried out while the temperature was maintained at 20°C using an air path that can automatically control periodic temperature changes, with one cycle consisting of alternating cycles of temperature rise and fall (30 minutes each). β1 type appearing in X-ray diffraction (■ type crystal) peak (3,65 people) and β
From the type 2 (type V crystal) peak (4,00 Å), the degree of crystal transition (intensity of 3.65 people/intensity of 4.00 people) and its relative ratio were determined. The results are shown in Table 2.

Table 2: Degree of crystal transition Note) Values in [] represent relative ratios.

As is clear from the results in Table 2, the triglyceride obtained in Example 1.2 has an effect of suppressing metastasis on cocoa butter.

Fuse Charcoal ↓ Tricaprylin (1 mol) and palmitic acid (6 mol)
) with a lipase having 1.3-position specificity,
A transesterified oil was obtained and fractionated using hexane to obtain a medium melting point fraction. The triglyceride composition of both parts is PXX
(P is a palmitic acid residue, × is a capric acid residue) 8.6%, PXP 86.2%, XXX 5.2%
Met.

The method for analyzing triglyceride composition is as follows.

Triglyceride group analysis (gas chromatography) manufactured by Heuret Paracard 11P58905ERI
ES II <Capillary column>J&W Inc, 25 um DB-1 <Analysis conditions> In1tial Temp, 100 C1Rate 10 BiC
/min] Final Temp, 300 [
'CIInjection Temp, 320 [
'C] Director Temp, 320 [”
CICarrier gas (Nz) 25 [KP
a] H2gas 30 [mf/min] to 8ir 400 (m 1
/min] Sample> Concentration 2.5 Img/m 1 ] Injection amount
1.0[μnl Fruit 11 vomiting Except for changing the substrate from tricaprylin to trilaurin,
Transesterification was carried out in the same manner as in Example 4 to obtain a medium melting point fraction. The composition of this fraction is PXX (where X is a lauric acid residue) 9.6%, PXP 83.4%, XXX 7
．． It was 0%.

Transesterification was carried out in the same manner as in Example 4 except that the fatty acid was changed from valmitic acid to stearic acid to obtain a medium melting point fraction. The composition of this fraction is StXχ (St is a stearic acid residue, X is a capric acid residue) 8°7%, 5tXSt
87.0%, XXX 4.3%.

Implementation ■1 Example 4 except that 1 part of coconut oil and 8 parts of stearic acid were used.
Transesterification was carried out in the same manner as above to obtain a medium melting point fraction. The 2-position fatty acid composition and triglyceride composition of this fraction were as shown in Table 3. The 2-fatty acid composition was determined by treating the reaction product with a lipase having specificity at the 1,3-position, and then fractionating 2-monoglyceride from the reaction product using high performance liquid chromatography, and analyzing it using cupillary gas chromatography.

Table 3 Lauric acid (2 mol) was used as the fatty acid and transesterified with lipase which was selectively introduced into the 1,3-position of tripalmitin (1 mol) to obtain a medium melting point fraction. The composition of this fraction is: XPX (where X is a lauric acid residue) 10.1%, PPX 81.2%, PPP
It was 9.7%.

Comparison Section I Transesterification was carried out in the same manner as in Example 4, except that the substrate was changed from tricabrilin to trimyristin, and a medium melting point fraction was obtained. The composition of both parts is PXX (where X is myristic acid residue) 11.2%, PXP 78.4%, XXX
It was 10.4%.

Implementation (1) Using the fat bloom resistance-improved side obtained in Examples 4 to 7, chocolate compositions were obtained according to the chocolate formulations and addition amounts shown in Table 4, and their performance was tested. At the same time, chocolate compositions were obtained in the same manner as above in the case where no improver was added (paired) and in the case where Comparative Examples 1 and 2 were used, and the same performance tests were conducted.

The chocolate is made using the usual manufacturing method, which involves mixing, rolling, conching, and tempering molded chocolate.
After aging for 0 days, a fat bloom generation test was conducted.

Regarding the working conditions, chocolate dough was kettle tempered, and the viscosity for depositing and the mold release property during cooling at 10"C for 130 minutes were observed.

The fat bloom generation test was carried out on aged molded chocolate samples at 20'C3.5 hours and at 32°C.
C 3.5 hours (30 minutes each at rising temperature) alternately repeated once
The occurrence of F.7 blooms was observed when the sample was maintained at 20°C under cycling conditions. The results are shown in Table 5.

[Below, remainder white]

Table 4 Blends of the composition (% by weight) Table 5 Chocolate performance test results As is clear from the results in Table 5, the higher the SXS content in the chocolate oil, the greater the fat bloom. No. and (3), which had a high resistance improvement effect and a low SXS content, had insufficient effects. In addition, in comparing Example 2 (No, ■~■) and Comparative Example 1 (No, @~■), although the fatty acid compositions are almost the same, Comparative Example 1, which is an asymmetric triglyceride, The resistance improvement effect is low, and No.
In case (2), the viscosity increased during tempering. On the other hand, in Example 2 (NO9■), such work problems were completely solved (
There wasn't. Furthermore, Comparative Example 2 (No.

[Co., Ltd.~@) had no effect on improving resistance, had a large increase in viscosity during tempering, and had poor workability.

Implementation Basis: Instead of the cocoa butter in the chocolate mixture (control) shown in Table 4, the fat bloom resistance improver of Example 6 was added to a commercially available tempered hard putter (Helf #20J manufactured by Kanebuchi Chemical Co., Ltd.). A chocolate composition was obtained in the same manner as in Example 8 using hard butter containing 8% by weight of .The phantom bloom resistance of this composition was excellent at 51 cycles under the above conditions.

Jitsuen Cocoa Mass (18 parts), powdered sugar (45 parts), whole milk powder (1
5 parts), and hard butter (22 parts) containing 8% by weight of the fat bloom resistance improver of Example 6 to a commercially available non-temper hard butter (manufactured by Kanebuchi Chemical Co., Ltd. rKcF 500MJ) to make chocolate. A composition was obtained. Chocolate was manufactured by mixing, rolling, conching, molding, and then aging at 20°C for 10 days.

This product had excellent fat bloom resistance.

〔Effect of the invention〕

As described above, the triglyceride of the present invention and the hard butter made by blending it have a remarkable preventive effect against fat bloom without impairing texture or workability, and are effective in preventing chocolates. Extremely useful in manufacturing.

Claims (1)

[Claims] 1) 1,3-di(S)-, in which a saturated fatty acid (X) of C_1_2 or less is bound to the 2-position, and a saturated fatty acid (S) of C_1_6 or more is bound to the 1,3-position. 2-mono(X) triglyceride (SXS). 2) The triglyceride according to claim 1, which is produced by transesterification using a 1,3-position specific lipase. 3) Hard butter containing 3.2% by weight or more of the triglyceride according to claim 1. 4) Chocolates containing 2.0% by weight or more of (SXS) in the raw oil content of the chocolate by adding the triglyceride according to claim 1 or the hard butter according to claim 3.