JPH0458941B2 - - Google Patents

Description

[Detailed description of the invention]

[Definition] The term "chiyokolate" as used in the present invention is defined in the Code ("Fair Competition Code Regarding the Display of Chiyokolates").
The term is not limited by legal provisions, and is used as a concept that includes all thiocholates and fat-reduced foods that use so-called cocoa fat substitutes. [Industrial Field of Application] The present invention is directed to a thiocolate additive, particularly a heat-resistant thiokolate that suppresses the occurrence of fat bloom even after being placed at temperatures around body temperature for a certain period of time, where it loses its shape retention. The present invention relates to a thiokolate additive that is not only suitable for production but also useful for omitting or simplifying the tempering operation of thiokolate dough. [Conventional technology] Chiyocolate is generally made from cacao mass, cocoa,
It is produced by appropriately mixing cocoa butter, cacao substitute fat, sweetener, milk powder, etc., rolling, conching and tempering, but there is a problem in that it often blooms during storage, impairing its commercial value. This bloom includes fat bloom, which is based on unstable crystals of fats and oils, and sugar bloom, which is based on recrystallization of sugar, and the former fat bloom is particularly common. Therefore, in the production of general thiyocholate products, tempering treatment is performed to transform the thiyocholate fat into a stable crystalline form that is less likely to cause fat bloom.If the treatment is insufficient, bloom may occur extensively. This occurs under certain conditions, and even makes it difficult to separate from the mold. Therefore, tempering treatment is an important process in the production of thiokolate, but if the product thiokolate is exposed to high temperatures near its melting temperature for a certain period of time to the point where it loses its hardness (for example, in summer, when the product is exposed to sunlight) No matter how careful tempering treatment is performed during the manufacturing process, it has been impossible to suppress blooming in such cases. Further, since appropriate tempering conditions vary depending on the composition of the thiocholate oil and fat, the cooling rate, etc., it is not necessarily easy to find the optimal style for each of the various thiokolate products. In particular, most chillers used for tempering are made to achieve a specific cooling rate, so it is necessary to adjust the degree of tempering of the thiokolate according to the characteristics of the chiller used. There is the hassle of having to preliminarily find a unique tempering style depending on the machine (M...G.
Reade, The Manufacture Confectioner,
January 1985). Furthermore, tempering methods used for industrial production usually include at least one process of forcibly cooling a molten oil-based composition and one process of reheating (for example, "Confectionery Dictionary"). (Page 459, Asakura Shoten, October 1981), and the device needs to be equipped with two types of means: cooling and heating (Japanese Patent Application Laid-Open No. 61-40750). However, such repetition of cooling and heating naturally results in energy loss. Therefore, there has been a desire within the industry to omit the troublesome tempering process as much as possible, and in line with this intention, we have produced hard butter with a high elaidin content, lauric hard butter, and random fatty acid sequences through transesterification. Techniques using hard butter that has been converted to hard butter are being implemented. However, since a large amount of cacao butter cannot be blended into such foreign (non-temperable) hard butter, the resulting product has a limit in terms of flavor. [Problems to be Solved by the Invention] Therefore, the problem to be solved by the present invention is to create a high-temperature resistant thiocholate, which was previously unachievable even with proper tempering treatment by adding it to thiokolate. The purpose of the present invention is to develop a thiocolate additive that can suppress the occurrence of bloom even after being exposed to heat for a certain period of time, or in other words, provides a thiokolate that has the property of self-reverting to its original glossy thiokolate even after being exposed to high temperatures. . Another object of the present invention is to provide a thiocholate additive that makes it possible to produce products that take advantage of the flavor of cocoa butter even by omitting or simplifying the tempering method. [Structure of the Invention] As a result of intensive research to solve the above-mentioned problems, the present inventors have stabilized and pulverized oils and fats with a specific glyceride composition, and added and mixed them into a thiocholate compound without melting them. As a result, the drawbacks in heat resistance of conventional thiocolate can be improved and a self-resetting type of thiocolate can be obtained, and at the same time, we have obtained the knowledge that the crushed oil powder is useful for omitting or simplifying tempering, and the present invention reached. That is, the present invention provides a stable crystalline pulverized 2-unsaturated-1,3-disaturated glyceride consisting of an unsaturated fatty acid having 18 or more carbon atoms and a saturated fatty acid having 20 to 24 carbon atoms. The subject matter is a thiocholate additive containing particles. Here, compositions (oils and fats) containing 2-unsaturated-1,3-disaturated glyceride as a main component are described, for example, in JP-A-Sho.
No. 55-71797, No. 56-127094, No. 52-104506,
It can be produced by applying the selective transesterification method using enzyme activity disclosed in specifications such as No. 55-84397 and No. 60-251891. That is, fatty acids mainly containing saturated fatty acids having 20 to 24 carbon atoms (such as arachidic acid, behenic acid, or lignoceric acid) can be used to harden, decompose, and rectify, for example, rapeseed oil, radish oil, lunaria oil, fish oil, or whale oil. The fatty acid or its esters are added to the 2-position of the glyceride by adding an unsaturated fatty acid having 18 or more carbon atoms (mainly oleic acid, but some linoleic acid, arachidonic acid, or erucic acid, etc.). It can be obtained by transesterifying the saturated fatty acid with an oil or fat having a group (optional) and selectively forming an ester bond at the 1,3-position of the saturated fatty acid. In addition, the above-mentioned "main component" refers to the "pulverized particles" of the above-mentioned specific composition, and does not necessarily refer to the ratio to the entire "thiyocolate additive" including the "dispersion medium" described later. is approximately 50% or more, preferably 70%
It is better to include at least %. If the carbon atom chain of the saturated fatty acid of the 2-unsaturated-1,3-disaturated glyceride is shorter than 20, or if the specified glyceride is not the main component in the pulverized particles, the particles will reach a high temperature near body temperature. The particles cannot maintain a crystalline state with a high melting point in the tyyocolate product or thiyocolate dough, and the desired effect of the present invention is not achieved. In addition, even if the glyceride is not a saturated triglyceride at the 1,3-position and an unsaturated triglyceride at the 2-position, but a trisaturated triglyceride which is easily obtained from extremely hard oil and is also saturated at the 2-position, good crystal growth can be achieved. For example, the oil-based composition subjected to tempering does not easily release from the mold after cooling, and even if it somehow does release from the mold, the gloss is poor. Furthermore, the 1, 2-position or 2-, 3-position are saturated fatty acids, 3-
In the case of an isomeric triglyceride in which the position or 1-position is an unsaturated fatty acid, good crystal growth cannot be similarly promoted. And the ground particles should be stable crystals. Here, the stable crystal type can be identified by the peak of the short side spacing (side spacing) obtained in the X-ray diffraction spectrum of the above-mentioned pulverized particles, and RLWille and
How ESLutton names the crystalline forms of cocoa butter [JAOCS, 43 , pp.491-496 (1966)
A crystalline type that is more stable than the type described above is preferable, but the stable crystalline type of the present invention includes a case in which these and other types of crystalline types are mixed. Generally, stable crystals of triglyceride can be obtained by ripening for a certain period of time at a temperature lower than the melting point of the triglyceride (particularly at a temperature below the melting point of the stable crystal type). However, the number of carbon atoms is 18
2-unsaturated-1,3-disaturated glycerides, which are composed of 1 or more unsaturated fatty acids and saturated fatty acids with 20 to 24 carbon atoms, take a longer time to transition to a stable form than other thiocholate fats. Therefore, the required ripening time can be artificially reduced by dividing the fat into small pieces, for example by pulverizing the fat, or by spraying melted fat at a predetermined temperature to make coarse particles. Can be shortened. Furthermore, triglycerides are mixed with a solvent (for example, an organic solvent such as hexane or acetone, or a supercritical gas) to form crystals, and the crystals precipitated from the mixture are generally stable even without further ripening. When removing the solvent, care should be taken not to melt the stable crystals that have taken the trouble to precipitate. If the pulverized particles are not stable crystals, they will not have a good tempering promoting effect and will melt easily, so if the produced thiokolate product is exposed to temperatures near body temperature where it does not have shape retention, the temperature will increase after that. Even if it deteriorates, it can no longer return to its original glossy state. The pulverization can be carried out using a known pulverizing means such as a homomixer or ultrasonic waves, using solidified fats and oils in the form of lumps or coarse particles as is or with a suitable dispersion medium.
Grinding when the solidified fat is already in a stable crystalline form is
It is best to perform this in a low temperature atmosphere where the crystals do not melt.
For example, some cocoa butter is taken into a homomixer,
Preferably, the temperature is adjusted to 30° C. or lower, and small lumps of the solid fat are added thereto and then crushed, or crushed while cooling with dry ice, or so-called freeze-pulverized. The particle size is usually less than 500μm, preferably
The diameter should be 100 μm or less, most preferably 25 μm or less.
If the particle size is too large, the number of nuclei decreases, resulting in poor efficiency in promoting crystallization or poor dispersibility in the tyokolate dough, as well as a somewhat poor texture, which impairs the texture of the product. On the other hand, if the particle size is small, the amount used can be reduced, but care should be taken to prevent the particles from melting by paying attention to the upper limit of the temperature at the time of addition, which will be described later. The thiocholate additive of the present invention can contain an appropriate dispersion medium, which improves the dispersibility and at the same time increases the effect of adding the agent. In addition, the non-oil dispersion medium (for example, saccharide) also has the effect of preventing the pulverized particles of the specific triglyceride from agglomerating into agglomerates during storage of the present thiocholate additive. The above dispersion medium is preferably a thiokolate dough component,
For example, it can be selected from saccharides, milk powder, cocoa mass, cocoa powder, cocoa butter, hard butter, emulsifiers, and the like. However, since these dispersion media do not go through the usual refining process after the addition of this additive, it is desirable to keep the particle size to 50 μm or less so as not to impair the texture of the product. In addition, when the dough component selected as the dispersion medium is an oil-containing substance used in a large amount and the tempering treatment is omitted or simplified, it is preferable that the oil crystals are also stable. The thiocholate additive of the present invention is used in a state containing the above particles. If it is used in the form of a molten liquid containing no particles, even if it crystallizes in the cooling step of producing thiokolate, stabilized crystals of the specific glyceride will no longer be produced. As for the obtained dough, unless it is tempered in the same manner as in the past, the peak temperature of the tyokolate oil itself remains low, as seen in the DSC (differential scanning calorimetry) chart (see Figure 4), making it suitable for use. In other words, it is difficult to form a stable crystal.
Therefore, it is impossible to release the molded Chiyocollate dough from the mold, and even when used in an enrobing manner, fat bloom immediately occurs. In other words, if the additive is not in the form of particles but in a molten liquid state, there is no effect of omitting tempering (the peak temperature of the thiokolate oil and fat increases only when tempering is performed, and the temperature is properly stabilized (second stage). (See Figure 1), because the additive contains particles, the peak temperature of the thiocholate oil and fat increases and stabilizes without the need for conventional tempering (see Figure 1). Regarding the usage of the present invention agent, if the thiocholate compound to be added is a compound before conching treatment, the crushed particles will melt due to the temperature during conching. This is done in the process of cooling and solidifying the melted thiyocolate formulation, therefore preferably below the dough temperature at which the thiyocolate dough is completely melted.
It is best to do this at temperatures below ℃. In this way, the reheating step that is almost always performed in the normal tempering process becomes unnecessary, and not only can labor and equipment be omitted, but also mold casting or enrobing can be performed immediately after dispersing the crushed particles into the dough. Therefore, the higher the dough temperature at the time of addition, the simpler the tempering process becomes, and virtually no tempering step is required. However, even if a conventional tempering process is performed using the agent of the present invention, it is possible to automatically restore the glossy thiyocolate after exposing it to high temperatures near body temperature for a certain period of time, and the oil-based composition It can be added as long as the temperature of the product (dough) is not so low that it no longer has fluidity. The amount of the above-mentioned thiokolate additive added is usually determined within the range of 0.1 to 10% in terms of the amount (weight ratio) of pulverized particles of the specific triglyceride to the thiyocolate dough, and if the dispersion is good, it is usually 2%.
It is sufficiently effective at only % by weight, and the effect does not increase significantly even if more is added. On the other hand, if the amount added is too small, it will not be effective, and if it is too large, it will not melt in the mouth. The thiocholate to be added to the present agent is mainly shea butter rich in SUS (2-unsaturated-1,3-disaturated glyceride) components including cacao butter, palm oil, monkey fat, mango kernel oil, Kokum fat,
This is a thiyocolate using a so-called tempering type oil such as Iritzpe butter or its fractionated oil. The composition after adding and dispersing the above-mentioned thiokolate additive is enrobed onto the deposit/mold or the surface of the confectionery using a conventional method, but temperature control of the hopper, piston, and cylinder of the depositor as well as the tempering mold is conventionally required. It does not have to be as strict as the following aging process (1 to 1).
5 weeks) may also be unnecessary or shortened. Verification that this product is a thiokolate product obtained as described above is confirmed by the fact that this product does not bloom even after repeating the cycle test at 18°C and 37°C several times as described in the Examples below. However, it can also be confirmed by DSC analysis. For example, depending on the particle size of 2-unsaturated-1,3-disaturated glyceride consisting of an unsaturated fatty acid with 18 or more carbon atoms and a saturated fatty acid with 20 to 24 carbon atoms, A peak near 50°C can be observed by DSC analysis. The DSC chart in the attached drawing shows that 30 to 40 mg of sample tyokolate was collected in an aluminum sample pan, set in the DSC sample chamber together with an empty control pan, and then quickly frozen to -40℃ with dry ice.
It was obtained by electrically measuring the amount of heat absorbed under conditions of increasing the temperature at a rate of °C/min. Alternatively, the following method is exemplified as another DSC analysis method that is useful for explaining the action of the present invention and is more accurate. That is, about 2 mg
Collect a sample of about 100% of the sample into a sample pan, set it in the DSC sample chamber together with an empty control pan, and heat it from a low temperature, e.g. -20°C, to around body temperature, e.g. 37°C, for 3 days.
The temperature was raised for the first time at a rate of approximately ℃/min, and after being held at the same temperature for 15 minutes, the temperature was increased from 0℃ to -5℃ for 3
After cooling at a rate of approximately ℃/min and holding at the same temperature for 15 minutes, the temperature was raised a second time at a rate of approximately 3℃/min. It can be confirmed whether there is a substantial difference (difference of about 5°C or more) between the two by comparing the main peak temperature of the absorption heat (the temperature at which the crystals of the main thiocholate fat melt). . In other words, the difference between whether the main peak of the absorbed heat during the second temperature increase can show approximately the same temperature as the peak during the first temperature increase, or whether the temperature will be substantially lower is 2. The difference is whether or not the thiocolate fat that melts during the first temperature rise is a proper, stable crystal. This serves as a criterion for determining whether particles in the additive of the present invention that have the effect of promoting the formation of stable crystals are still present. [Examples] Specific examples and effects of the present invention are described below using Examples, Reference Examples, and Comparative Examples, but these are merely illustrative and do not limit the spirit of the present invention. In each example, "part" and "%" mean weight basis unless otherwise specified. Example 1 A highly hydrogenated high erucine rapeseed oil containing 45% of unsaturated fatty acids having 22 carbon atoms was hydrolyzed and esterified to obtain fatty acid ethyl ester. This fatty acid ester was distilled to obtain a fraction containing 97.9% of saturated fatty acid esters having 20 to 24 carbon atoms, and 70 parts of this fatty acid ester was mixed with 30 parts of high oleic acid sunflower oil. By transesterifying using an enzyme agent that selectively acts on the iodine value 45
A reaction oil was obtained, which was further fractionated with a solvent to obtain a high melting point fraction with a yield of 57.6%. The composition of the bound fatty acids in this fraction is as follows: iodine number 31.6, amount of 2-unsaturated-1,3-disaturated glyceride 76%, unsaturated fatty acids with 18 or more carbon atoms and carbon atoms 20〜
2-unsaturated-1,3- consisting of 24 saturated fatty acids
The disaturated glyceride content was 71.2%. Fatty acid composition (top chain length: number of double bonds, bottom %) 16:0 18:0 18:1 18:2 20:0
22:0 24:0 0.7 1.7 31.6 2.5 4.8 56.7 2.0 This oil was stabilized by temperature control treatment at 25℃ for 2 days and 48℃ for 23 days [X-ray diffraction (Cu-Kα, λ=
1.542), it was found that it corresponds to the type mentioned in the nomenclature of RLWille and ESLutton mentioned above.
Put 1.5 parts and 6 parts of cacao butter into a homomixer,
The mixture was stirred and pulverized at 29 to 29.5°C for 5 minutes. Meanwhile, 20 parts cacao mass, 45 parts sugar, 20 parts whole milk powder
After rolling, conching and tempering a mixture of 7 parts of cacao butter and 0.5 parts of lecithin in the usual manner, the previously prepared pulverized mixture of cacao butter and solid oil was added and mixed, then molded and cooled. After release from the mold, it was aged at 20°C for 7 days. Thiyocolate thus produced was placed at 180° C. for 12 hours and then at 35° C. for 12 hours, and this cycle test was repeated more than 10 times, but no bloom was observed. Similarly, cycle tests at 18°C and 37°C were repeated six times or more, but no bloom was observed. On the other hand, for comparison, thiokolate was produced by melting and adding the pulverized mixture of cacao butter and solid fat, and otherwise performing the same procedure at 18°C.
This is the fourth cycle test at 35℃, and
In the cycle test at 18°C and 37°C, blooming was observed in the first cycle (Control Example 1). In addition,
In the test results of thiokolate produced in the same manner using only cacao butter, significant blooming was observed at the first test (Control Example 2). Reference Example 1 A mixture of 44 parts of sugar, 29.3 parts of whole milk powder, 26 parts of cacao butter, and 0.5 parts of lecithin was rolled, conched and tempered in a conventional manner, and then the solid fat used in Example 1 was placed in dry ice. 1.2 parts of powdered particles were added and mixed, and white thiokolate was produced in the same manner. As a result of cycle testing this Chiyokolate in the same way as the previous example,
No bloom was observed at all. On the other hand, for comparison, when no pulverized solid fat was added, significant blooming was observed in the first test (Comparative Example 3). Example 2 Ethyl ester of behenic acid and high-oleic sunflower oil were converted into glycerides using lipase.
After selectively transesterifying the - and 3-positions, fractionating and concentrating this with a solvent, it is recrystallized with hexane, the solvent is distilled off using a vacuum pump without melting, and then reused while cooling with dry ice. After pulverizing in a mixer, it was sieved and the 42 to 60 mesh (350 to 250 μm) pass segment was used as the additive in this example. This additive. It corresponded to the crystal type mentioned above. According to HPLC analysis, AOS0.2%, BOS2.8
%, BLB2.5%, BOA14.00%%, BOB75.9%,
BOLi (2-oleylheniclignoserin) 4.3
%, and other glycerides 0.4%. Example 3 The oil and fat of Example 2 after vacuum distillation of the solvent was further freeze-pulverized in liquid nitrogen to obtain an average particle size of 15.6 μm.
of thiocholate additive was obtained. Example 4 The additive of Example 2 was mixed with powdered sugar at a weight ratio of 1:1, and the mixture was freeze-pulverized in liquid nitrogen to give an average particle size of approximately
It was ground to 20μm or less and used as a new thiokolate additive. Reference Examples 2 and 3 Yield using Allanbratschia extract oil as raw material
A high melting point part was obtained at 59.1%, which was then aged for a long period of time, and then freeze-pulverized in liquid nitrogen to produce a stable (corresponding to the type mentioned in the nomenclature) crystalline powder (average particle size 11.4 μm). was obtained (Reference Example 2). In addition, highly hydrogenated high-erucinated rapeseed oil containing 45% unsaturated fatty acids with 22 carbon atoms was also pulverized to make the additive of Reference Example 3 (a mixed type according to the nomenclature mentioned above). Constants, fatty acid compositions, and melting points of each oil and fat in Examples 2 to 4 and Reference Examples 2 and 3 (inner diameter of approximately 1
A pulverized sample with a length of approximately 5 mm was placed in a 5 mm capillary glass tube, and the sealed portion was placed in contact with the bulb of the thermometer, and measurements were taken while raising the temperature in a water bath) as shown in Table 1 below. Shown all at once.

【table】

[Table] Reference Examples 4 and 5 Tiyocolate was produced using the additive (pulverized particles) of Example 2 or 3. That is, a molten dough was prepared by mixing, rolling, and conching the oil-based composition of the following formulation according to the conventional method for producing thiokolate, and while stirring the dough while cooling it to 30°C, the previously pulverized particles were mixed. 5 for dough oil
% (1.67% based on the Chiyokolate dough), and then poured into a template without reheating and held at 15°C for 30 minutes to solidify. [Contains Chiyokolate]

[Table] These exhibited good release from the mold and were immediately cycled at 18°C and 37°C over 5 times without aging. Regardless, good luster was restored at 18°C. However, due to the particle size, the thiokolate product of Reference Example 4 had a slightly unpleasant texture, but the product of Reference Example 5 had a good texture. Those using the crushed oils and fats of Reference Examples 2 and 3 as additives (Control Examples 4 and 5), and those with no additives added.
The mold was molded as it was at 30℃ (Comparative Example 6), and the additive from Example 3 was used, but the dough was rolled and conched together with other raw materials to form a molten dough. For comparison, a mold casting was performed as it was at ℃ (additives were melted: Control Example 7). The degree of mold release and gloss condition for each additive are shown in Table 2 below.

[Table] The DSC charts of Chiyocolate of Reference Example 4, Control Example 1, Control Example 6, and Control Example 7 are shown in the attached drawing.
In Control Example 7, although the composition was the same as Reference Example 4, the latent heat peaked around 50°C, that is,
Unsaturated fatty acids with 18 or more carbon atoms and number of carbon atoms
2-unsaturated-1, consisting of 20 to 24 saturated fatty acids;
No peak of crystal particles of 3-disaturated glyceride was observed. Reference Example 6 Using each additive of Example 3 or Reference Example 2, thiokolate was produced in the same manner as in Reference Example 4, except that the dough temperature at the time of addition of the additive was set to 36°C. The results were as shown in Table 3 below.

[Table] In other words, the additive of Example 3 exhibited the effect of omitting the tempering treatment even at a product temperature of 36°C, but the additive of Reference Example 2 exhibited the same effect at a temperature of 30°C (Control Example 4).
It was nothing more than Reference Example 7 Thyokolate was produced in the same manner as in Reference Example 4, except that the agent of Example 4 was used as the thiyocolate additive. In all cases, products with good mold release and gloss were obtained. Reference Example 8 When the thiokolate additive of Example 3 was used, it was dispersed in the following formulation of thiokolate dough in the same manner as in Reference Example 4, and then enrobed onto a cake and cooled. It dried quickly and had a good gloss. A product was obtained, and the tempering promoting effect was observed.

〔Effect of the invention〕

As explained above, by adding and mixing the thiyocholate additive of the present invention into a thiyocholate formulation without melting, the occurrence of bloom can be significantly suppressed even when stored at temperatures near body temperature where thiyocholate itself melts. This provides a valuable tool for retailers of fabrics, especially in the summer or in the tropics. In addition, the above-mentioned thiokolate additive can omit reheating in the tempering operation and special cooling after dispersing the additive, and even if these operations are omitted or simplified, the product can be easily released from the mold or dried quickly. It is possible to easily obtain a product that can be enrobed early and retains properties such as good gloss, luster, or texture, and this allows the production of cocoa butter with the same number of steps as when using non-tempered hard butter. Products with good flavor can be easily obtained. In addition, since the tempering method is more standardized than in the past, the range of preliminary examination of the tempering style is reduced, resulting in great convenience in the production of thiokolate.

[Brief explanation of the drawing]

1 to 4 are DSC charts of thiokolate of Reference Example 4, Control Example 1, Control Example 6, and Control Example 7, respectively.

Claims (1)

[Scope of Claims] 1. 2-Unsaturated- consisting of an unsaturated fatty acid having 18 or more carbon atoms and a saturated fatty acid having 20 to 24 carbon atoms.
Thiocholate additive containing crushed stable crystalline particles having 1,3-disaturated glyceride as a main component. 2. The additive according to claim 1, wherein the additive comprises a dispersion medium.