JPH0357758B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a method for modifying fats and oils rich in 2-oleodipalmitin. Oils and fats, which are natural products, are generally mixed triglycerides, and have a variety of compositions and uses. There is a group of oils and fats, so-called vegetable butters, which are particularly rich in glycerides with oleic acid in the 2nd position and stearic acid or palmitic acid in the 1st and 3rd positions (hereinafter referred to as "S ₂ U"). Cocoa butter is the most typical fat and oil belonging to this group, with S ₂ U accounting for more than 3/4 of triglycerides, containing POSt, StOSt, and POP in order, and has unique physical properties (P, O , St indicate a palmitic acid residue, an oleic acid residue, and a stearic acid residue, respectively, which bind to triglyceride; for example, POSt indicates 2-oleo-1,3-palmitostearin). Cocoa butter is also representative of the most expensive fats and oils, and is said to be the most luxurious of so-called vegetable butters. For this reason, great efforts have been made to produce oils and fats that have physical properties similar to cocoa butter. One such effort has been directed toward the use of fractionation methods, such as trisaturated triglycerides (hereinafter referred to as " _S3 "), from less expensive fats and oils than cocoa butter, often cheaper vegetable butters. `` <sub>S 2 U</sub> It has become common practice to obtain a fraction rich in `` and utilize it. As this technology becomes more sophisticated, the "StOSt"-rich fraction and the "POP"-rich fraction obtained by such fractionation methods are mixed, or the fatty acids bound at positions 1 and 3 of the mixed oil are further randomized. This led to the addition of a means to do so.
However, this technique has little cost advantage or requires further processing, as it is more expensive to extract oil from the StOSt-rich fraction than from the POP-rich fraction. There are drawbacks that bring little benefit. this is,
Most of the plants that can be relied upon as a source of "StOSt" are wild species, and are not grown under the protection of humans on farms, so they are rare and valuable, and the production amount fluctuates greatly depending on weather etc. It is. The present invention does not rely on such an expensive StOSt source, but rather uses _S3 and
The _SU2 -rich fraction is used as a modifier to produce an inexpensive
It relies on POP sources and attempts to modify them to a quality comparable to high-grade vegetable butters such as cocoa butter. In other words, this invention converts oils and fats rich in POP into S ₃
Alternatively, together with fats and oils that are rich in SU ₂ and the main component of the bound saturated fatty acids is stearic acid, the bound fatty acids at the 1 and 3 positions are selectively randomized by the action of a lipase that is specific for the 1 and 3 positions, and then S ₂ U
This is a method for modifying fats and oils that consists of separating the fraction that is rich in oils and fats. This invention will be explained in more detail below. In this invention, the object of modification is a fat rich in POP, and the modifier is a fat rich in S ₃ or SU ₂ and the main component of the bound saturated fatty acid is stearic acid. All of these fats and oils can be obtained at low cost by fractionating or curing natural fats and oils, regardless of whether they are synthetic products, natural products, fractionated or cured products, etc. POP-rich oils and fats include palm oil, preferably POP
Palm oil medium melting point fraction containing 50% by weight or more can be used. However, palm oil contains a small amount of POP isomers, such as PPO, and if such isomers remain in the product, it may impair the crystallinity of the oil and may impair the heat resistance when used in thiokolate. However, even if these substances are contained, there is almost no problem as long as POPs contain 60% by weight or more in the middle melting point fraction of palm oil. It has been found that it can be removed from the side without causing any adverse effects. For oils and fats rich in _S3 , the parts removed by conventional two-stage separation of oils and fats, wintering sediments, hardened oils (hydrogenated oils), etc. can be used, and the origin is _C16 or less. Most oils can be selected as long as they do not contain large amounts, such as soybean oil, rapeseed oil with low erucin content, pork fat,
A wide variety of fats and oils are used, including safflower. The S ₃ -rich fat or oil is used in an amount usually 0.1 times or more by weight, optimally 0.2 to 3 times the weight of the 2-oleodipalmitin-rich fat or oil. If the amount is less than 0.1 times by weight, the reforming effect will be poor, and if it is too much, the fractionation efficiency will be poor and the yield of S ₂ U will be low. Oils and fats rich in S ₃ are similar to fats and oils rich in POP _.
The higher the purity, the more preferable it is, but preparing it by extreme curing has the effect of making it extremely easy to achieve high purity. The degree of curing is preferably at least an IV of 10 or less, preferably an IV of 5 or less. Curing (hydrogenation) has traditionally been a method often used to produce hard butter, but there is no precedent for producing good hard butter using extreme hardening, and even in the case of non-extreme hardening, which is often used However, the present invention does not have these drawbacks at all, although it is difficult to suppress the production of trans isomers, making it difficult to use in combination with cocoa butter and make tempering operations difficult. When oils and fats rich in _S3 are used as a modifier, due to their high melting point, it is usually necessary to use a solvent during the randomization process described below, but free fatty acids, monoacyl radicals, etc. This method has the advantage that it does not require solvent removal treatment before fractionation, as is the case when using . Oils and fats rich in _SU2 whose main component of bound saturated fatty acids is stearic acid have 1 stearic acid residue.
Or, it is at the 3rd position, and an unsaturated fatty acid is usually bonded to the 2nd position. If the bound unsaturated fatty acids are rich in oleic acid, it can contribute to improving the yield of the product. Specifically preferred fats and oils include shea butter, monkey fat, mango butter, cocum butter, etc.
An example is a low melting point fraction removed by so-called two-stage fractionation. When SU ₂ is used as a modifier, the ratio to POP-rich fats and oils is usually 0.2 times or more by weight,
Optimally, a range of 0.6 to 9 times by weight is selected.
If it is less than 0.2 times the weight, the modification effect will be poor;
The best modification effect is obtained in the range of 9 to 9 times the weight. It is necessary for modification that the main component of the bound saturated fatty acids of these _S3 -rich fats and _SU2 -rich fats and oils is stearic acid, but stearic acid is required as a minor component.
This does not preclude the inclusion of the above fatty acids, such as arachidic acid. In this invention, when using S ₃ type or SU ₂ type glyceride as a modifier, there are several advantages over when using free fatty acids, monoacyl derivatives, etc. First, when using free fatty acids, etc., the amount ultimately removed is limited to the level of deodorization (distillation) normally equipped in the oil and fat industry.
Since the throughput exceeds the capacity of the equipment, separate equipment or modified equipment is required, but according to the present invention, it can be processed with a conventional sorting equipment. Second, if free fatty acids are included in the subsequent fractionation process, they have the disadvantage of reducing the removal accuracy of the _S3 component, so it is necessary to remove them in advance before the subsequent fractionation process. For this reason, the solvent must also be removed in advance, which requires a double operation to remove the solvent after the subsequent fractionation step, but according to the method of this invention, this is not necessary after the random treatment. This problem does not arise because the remaining portion of the modifier is removed by the fractionation process itself. The above-mentioned POP-rich fats and oils, together with modifiers, selectively randomize the bound fatty acids at the 1st and 3rd positions. This randomization treatment can be carried out by using a lipase having specificity for the 1 and 3 positions, but in the present invention, it is preferable to carry out this in a non-hydrostatic system. If water is added to the system undergoing randomization, and as a result, the oil contains more than 0.2% of water, hydrolysis will occur during the randomization process, resulting in the production of diglycerides that are difficult to remove industrially. However, even after the subsequent fractionation step, the properties measured by the cooling curve are not good. Therefore, it is difficult to fully achieve the purpose of modification. Although there are some differences in the specificity (selectivity for positions 1 and 3) of lipases with specificity for positions 1 and 3,
In addition to those originating from microorganisms such as Rhizopus genus (Rhizopus niveus, Rhizopus jabonicus), Mucor genus (Mucor, Zibanicus, Mucor deremer), and Aspergillus genus (Aspergillus niger), there are pancreatic lipases, rice sugar lipases, etc. Among these, those with higher selectivity for the 1 and 3 positions are preferred. The temperature for the randomization treatment may be in any range as long as the lipase exhibits activity, and a temperature range of about 20 to 75°C is usually adopted. If fats and oils that do not melt at the treatment temperature remain, use a solvent that is inert to the enzyme, preferably a solvent that can also be used in the subsequent fractionation process, to keep the fats and oils in a liquid state. Make it. Such treatment time is usually 1 to 72 hours. After the randomization process, remove lipase,
The S ₂ U-rich fraction is separated to produce a product. Such fractionation means are well known to those skilled in the art, and means such as wintering, solvent fractionation, drug fractionation, etc. can be employed. The fraction to be removed here is
When using fats and oils rich in S ₃ as a modifier, it is the high melting point part after randomization, and when using fats and oils rich in SU ₂ , it is the low melting point part after randomization, but if necessary, two-stage fractionation is performed. Both the high melting point portion and the low melting point portion may be removed. The modified product obtained by this invention was originally POP
The disadvantages of fats and oils rich in oils, such as the disadvantages of heat resistance and tempering properties when used in large quantities as hard butter, have been improved, and in some cases it can be used alone or as a POP such as cocoa butter. When used in combination with rich fats and oils themselves, the quality is such that good thiocholate can be produced. This invention will be explained below with reference to Examples. Example 1 60 parts of palm oil medium melting point fraction (IV33, POP content in triglycerides 66%) was added to extra hard soybean oil (IV0.9)
40 parts and 400 parts of hexane, and 5 parts of an enzyme agent showing selectivity for the 1st and 3rd positions was added to this, and 45 parts of
After randomization by stirring at ℃ for 3 days, the enzyme agent was separated. The enzyme preparation was prepared by dissolving 20 parts of commercially available lipase (originated from Rhizopus niveus; 3000 international units) in 80 parts of cold water, thoroughly mixing with 75 parts of Celite, and then drying at 20°C for 4 days. After the randomization treatment, hexane was subjected to solvent fractionation by a conventional method without being separated. i.e. 10
The high melting point fraction was cut off at -15°C, and the low melting point fraction was cut off at -15°C, and the yield of the intermediate melting point fraction was 40 parts after hexane removal. This fat has a melting point (softening point) of 33.3℃ and a
S ₂ U was 88.2%, and the fatty acid composition and solid fat content at 25°C and 30°C were as shown in the table below. Also,
Thyokolate was produced using this fat and oil, and the tempering properties and heat resistance were good, and the raw material oil was clearly modified.

[Table] Example 2 45 parts of palm oil medium melting point fraction (IV30, POP content in triglycerides 75%) was added to extra hard soybean oil (IV0.5)
It was dissolved in 400 parts of hexane together with 55 parts, and randomized in the same manner as in Example 1. Regarding solvent fractionation, cut the high melting point fraction at 10℃ 1
The yield of oil and fat obtained by stage fractionation was 40 parts after hexane was removed. This oil has a melting point (softening point) of 32.9℃ and a _S2U content.
The solid fat content is 84.1% at 25℃.
The physical properties were 73.6 and 58.3 at 30°C, very close to those of cocoa butter, and the fatty acid composition was as shown in the table below.

[Table] Example 3 Palm oil medium melting point fraction (IV34, POP content in triglycerides 64%) 77 parts and shea butter low melting point fraction (IV75, SU ₂ content 52%, stearic acid content in bound saturated fatty acids 84 parts) %, oleic acid content in bound unsaturated fatty acids: 87%), 10 parts of an enzyme agent (originally Rhizopus japonicus) was added, and the mixture was stirred at 40°C for 7 days to carry out randomization. Add 500 parts of hexane to the oil and fat after separating the enzyme agent,
A two-stage fractionation process was carried out using a conventional method to obtain 22 parts of a medium melting point fraction. This oil had a SU ₂ content of 76.2 and a fatty acid composition as shown in the table below.

【table】

Claims (1)

[Scope of Claims] 1. Fats and oils rich in 2-oleodipalmitin are combined with fats and oils rich in trisaturated or monosaturated diunsaturated glycerides, and the main component of the saturated fatty acid is stearic acid, and the bonds at the 1 and 3 positions. 1. A method for modifying fats and oils, which comprises selectively randomizing fatty acids by applying a lipase specific for the 1 and 3 positions, and then separating a fraction rich in disaturated monounsaturated glycerides. 2 The weight ratio of fats and oils rich in trisaturated glycerides to fats and oils rich in 2-oleodipalmitin is 0.1.
The modification method according to claim 1, which is the above. 3. The modification method according to claim 2, which obtains fats and oils rich in trisaturated glycerides with extreme effect. 4. The modification method according to claim 2, wherein the randomization treatment is performed in the presence of a solvent and the fractionation treatment is performed without removing the solvent. 5. The modification method according to claim 1, wherein the main component of the bound unsaturated fatty acid of the fat and oil rich in monosaturated diunsaturated glycerides is oleic acid. 6. The modification method according to claim 5, wherein the weight ratio of the fat and oil rich in monosaturated diunsaturated glycerides to the fat and oil rich in 2-oleodipalmitin is 0.2 or more. 7. The modification method according to claim 1, wherein the randomization treatment is performed in a non-hydrostatic system.