JPH02269199A - Fat and oil - Google Patents

Abstract

PURPOSE:To obtain fats and oils useful for fat and oil raw material for processing hard butter, margarine, shortening, etc., causing neither peculiar smell nor soapy smell, having properly melting properties in the mouth and proper hardness, comprising a specific triglyceride as a substantial component. CONSTITUTION:The aimed fats and oils comprising a triglyceride (GGG/GGU/ UGU) to which fatty acid residue (G) having >=40 deg.C melting point as liberated fatty acid is bonded at the beta-position and to which G or fatty acid residue (U) having <=20 deg.C melting point as liberated fatty acid is bonded at the beta-position, as a substantial component and having 30-50% GGU component in the triglyceride. Fats and oils hardly containing trans-9-octadecenoic acid and dedecanoic acid can be prepared as G.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] This invention relates to fats and oils, particularly to fats and oils useful as raw materials for processed fats and oils such as hard butter, margarine, and shortening.

[Conventional technology]

Cocoa butter, hard butter, and fats and oils for margarine or shortening exhibit solidity or plasticity near room temperature, and have the property of melting near body temperature. Crystal growth and polymorphism of such solid fats are often a problem. For example, prevention of blooming is a problem with cacao butter and hard butter, and prevention of graining is a problem with fats and oils for margarine, and the necessity of tempering and the ease with which graining occurs are discussed.

In the case of hard butter, there are two types depending on whether or not tempering is necessary when manufacturing chocolate and the like.

In other words, for hard butter that does not require tempering,
There are trans-isomerized hydrogenated oils and lauric oils, but the former has the disadvantage that the characteristic odor caused by isomerization tends to impair the flavor of chocolate, while the latter, depending on how it is handled during storage, can give off a so-called so-called saucy odor. There is a problem with this occurring. On the other hand, the type of hard butter that requires tempering is characterized by a high content of 1,3-saturated-2-unsaturated triglyceride, which is an isomer of 1,2-saturated-3 triglyceride. - It is said that it is preferable not to include unsaturated triglycerides, but it is difficult to separate these isomers.

In the case of fats and oils for margarine, lard is said to be a fat that tends to cause graining. Originally, 1°2 ~ saturated -3
-There are almost no natural fats and oils that contain large amounts of unsaturated triglycerides, except for pork fat, but one of the ingredients in natural lard, 2-palmito-oleo-stearin, easily forms large, rough crystals. Random transesterification is carried out to convert into isomers, and 1,
Active use of 2-saturated and 3-unsaturated triglycerides has hardly been made.

[Problem that the invention seeks to solve]

While carrying out various investigations aimed at producing edible processed oils and fats that are easy to handle and have fewer problems caused by crystal growth or polymorphism, the present inventor discovered that a fatty acid with a melting point of 40°C or higher as a free fatty acid was added to the β-position. A triglyceride ((
:, GC, /GGU/UGU) and has a high GGU component in the triglyceride, the solidified surface state is extremely smooth whether it is slowly or rapidly cooled from the molten state. It has been found that there are no problems with crystal growth or polymorphism, such as no change in appearance such as no cracking or roughness even after long-term storage. This is a symmetrical glyceride (G
When UG) solidifies, it shrinks, causing the surface to appear raised or depressed, or cracks occur during long-term storage, or large, rough crystals tend to appear. It is.

While obtaining the above knowledge, the present inventor efficiently
Various studies were conducted with the aim of obtaining an oil or fat containing G/G GU/U GU as a substantial component and having a high GGU component in the triglyceride.

[Means for solving problems]

This invention is an oil and fat that has G G G / G G U / U G U as a substantial component, and the GGU component in the triglyceride is 30 to 50%, and the oil and fat is used in hard butter, margarine, shortening. It is a useful oil and fat as a raw material for processed oils and fats such as.

The above "substantially" means G G G/G that accounts for all triglycerides, including triglycerides in which residues of fatty acids with a melting point of less than 40°C as free fatty acids are bound at the β position.
The ratio of G U/U CU is 70% or more, preferably 8
It is better to account for 0% or more.

The fatty acid of G or U may be a saturated acid, a monoenoic acid, a polyenoic acid, etc., and it is not necessary that each of G or U be a single type of fatty acid. For example, although straight chain fatty acids such as octadecanoic acid and hexadecanoic acid are typical examples of G,
Hexanoic acid can be mentioned as an example of U. Also, cis-9-octadecenoic acid, cis-9, cis-12-octadecadienoic acid, cis-9, cis-12, cis-15-
Although octadecatrienoic acid is a typical example of U, trans-9-octadenoic acid can be mentioned as an example of G.

G G G/G CU/UG In an example of producing fats and oils in which GGU is a substantial component and the GGU component is 30 to 50% in the triglyceride, the β position is selective to the α position of G-rich glycerides. This is a method of introducing U into. That is, specifically, triglycerides consisting essentially of GGG (oils and fats whose IV has been lowered as much as possible by hydrogenation of oils and fats, or high melting point parts obtained by fractionating oils and fats, both of which have a preferable IV, are usually 1.
Less than or equal to 0. Other examples include the method taught in US Pat. No. 3,856,831. ) is used as a glyceride raw material, and a method of selectively introducing U into the α-position of glyceride, which is known per se (for example, JP-A-52-104506, JP-A-55-717)
No. 97, JP-A-55-84397, JP-A-56-12
No. 7094, JP-A-56-163196, JP-A-57
-78496, Japanese Patent Publication No. 58-500638, Japanese Patent Publication No. 59-500649, and Japanese Patent Application Laid-open No. 1984-19495) (more specifically, selectively at the α-position). using a lipolytic enzyme that acts on fatty acid U or a lower alcohol ester of fatty acid U as a fatty acid introduction source,
) and the source fatty acid (U in the case of the present invention) are preferably rearranged randomly. In some cases, the α-position of glyceride to which G is bonded to the β-position is selectively hydrolyzed, and then,
It may be a two-step process in which a desired fatty acid is introduced into the α-position and esterified.

In addition, fats and oils that contain GGG/C, GU/UGU as a substantial component and in which the GGU component accounts for 30 to 50% of the triglyceride are useful as raw materials for processed fats and oils such as hard butter, margarine, and shortening, and can be used as they are. Alternatively, by removing the high melting point portion or the high melting point portion and the low melting point portion from the oil or fat, the GGU component can be used with a higher content.

As the method for removing the high melting point portion or the low melting point portion, a known technique in hard butter production can be adopted. That is, a method using an organic solvent such as hexane or acetone, a method using an aqueous detergent solution, or
Examples include dry fractionation. By this fractionation, it is possible to obtain fats and oils containing 6% or less, preferably 3% or less of GGG in triglycerides. When the target product is hard butter, it is particularly preferable that GGU be 60% or more, preferably 70% or more, and UGU be 40% or less, preferably 30% or less. Among glycerides, the influence of partial glycerides is less than that contained in tempered pufferfish type hard butter, and it is generally acceptable even if the content is around 10%, but if desired, it can be separated by acetone or by using an adsorbent such as silica gel or alumina. It may be removed by

[Effect] If the ratio of GGG/GGU/UGU in triglyceride is low, a large amount of GUG components that are difficult to separate from GGU will be contained, resulting in processed oils and fats that can solve problems such as polymorphism and crystal growth such as pluming and graining. difficult to obtain.

In addition, since the melting points of G and U as free fatty acids are 40°C or higher and 20°C or lower, different fatty acids are introduced into the glyceride, making it difficult to form a β-type crystal form with a "triple chain length" structure, and the above-mentioned Due to the high ratio of GGG/GGtJ/UCU, a stable crystalline form can be quickly obtained.

GGG/GGU/UGU l-liglyceride, GGU
Since the component of is 30 to 50%, the yield is < C
A CU-rich partition can be obtained. Below 30%, the yield is poor (50% is the technical upper limit for fatty acid rearrangement.

Removal of the high melting point segment when using the fats and oils of the present invention is carried out by GG
Lowering the G content improves melting in the mouth, and removing low melting point parts
Reduces GU content and increases hardness at room temperature. Therefore,
Removal of the high melting point section and the low melting point section results in excellent melting properties (
It is possible to obtain hard butter (which is hard in the temperature range around room temperature and suddenly melts in the temperature range around body temperature). This hard butter can be used as an oil that does not require tempering, and as G, it is possible to prepare an oil that contains almost no trans-9-octadecenoic acid or dodecanoic acid, so there is no need for tempering, which does not have or generate a peculiar odor or soy odor. It is also extremely useful as an oil or fat.

If the purpose is to use fats and oils for margarine, it is not necessary to remove the low melting point portion.

[Example/Reference example]

This invention will be explained below with reference to Examples and Reference Examples.

Example 1 Compositions shown in the table below (unless otherwise specified, weight ratios are shown)
The same applies below) (for example, Cl8F1 in the table indicates a fatty acid residue with 18 carbon atoms and 1 unsaturated bond) and hydrogenated rapeseed oil (IV O, 48) and ethyl ester of fatty acid. , mixed at a weight ratio of 4:6, using hexane as a solvent, using immobilized lipase of Rhizopus delemer, with a water content of 200 to 300 ppm in the system, and a temperature of 43°C.
Then, rearrangement was performed to randomize the α-position of glyceride and the fatty acid of ethyl ester (reaction rate 93.1%).

Reactive fats and oils are recovered by removing solvent and removing ethyl ester by distillation, and the high melting point portion (yield 1) is recovered using hexane.
7.7%) and the low melting point portion (yield 43.3%) were removed to obtain a medium melting point portion (yield 38.9%).

The compositions of the above reaction oil and the medium melting point fraction obtained therefrom were as shown in the following table.

S3 in the table. Symbols such as S2U and SO2 and their analysis methods were in accordance with "Oil Chemistry J 34 (1) 36-41 (1-985).The ratio of SO5 and SSO in S2O was separated by silver nitrate treated TLC and densitated. Analysis using a meter showed that the former was less than 5% and the latter was more than 95%.

In addition, in HPLC analysis (high performance liquid chromatography), 550 category 63.7%, PSO, SLS, 500 category 22.
8%, SSS, ASO classification 4.0%, ppo,
POO category: 3.1%, pps category: 2.3% (However, S, O, P, L, and A each represent stearic acid, oleic acid, valmitic acid, linoleic acid, and alaxic acid residues) , GGU component accounts for 75% of all triglycerides.
It was over.

Note that S3. is obtained by removing the high melting point portion from the reaction oil. S20
．． The proportion of unsaturation of 502 or higher is 0.73% and 4, respectively.
2.4% and 56.9%, and could be used as a raw material for margarine. In addition, 5FI (solid fat index) of the medium melting point fraction purified by passing it through a silica gel column
The curve was a desirable melting property for hard butter.

Example 2 High melting point fraction (IVO, 1
3) (composition is in the table below) and the same ethyl ester as in Example 1 were mixed at a weight ratio of 4:6, the fatty acids were rearranged in the same manner as in Example 1 (reaction rate: 92%), and the reacted fats and oils were collected, High melting point part and low melting point part are removed, middle melting point part (composition is in the table below)
I got it.

TLC-FID analysis of the medium melting point fraction revealed that in the triglyceride, S2U component was 81.7%, S3 component was 2.0%,
18% of unsaturated components of 502 or higher, according to HPLC analysis,
550 category 0.2%, PSO, SSL, 500 category 9.
8%, ppo, po.

It was 74.7% in the category and 0.7% in the pps category, and the GGU component exceeded 75% of the total triglyceride. Both of these components showed good melting properties as hard butter.

Example 3 The same highly hydrogenated rapeseed oil as in Example 1 and C6 of 99.
Methyl esters of fatty acids accounting for 8% were mixed at a weight ratio of 4:6, selective transesterification was performed in the same manner as in Example 1 (reaction rate 92%), and the reacted fats and oils were collected. The melting point was obtained.

The triglyceride composition of the above reaction oil and the medium melting point fraction obtained therefrom was as shown in the table below.

Example 4 A medium melting point fraction was obtained in the same manner as in Example 1, except that hydrogenated rapeseed oil and ethyl linoleate were blended in a ratio of 4=6.

The fatty acid composition of both parts is Cl862.1%,
Cl8F234.1%, Cl8F11.3%, C161
, 3%, C200, 9%, and TLC-FID analysis values show that SO2 component in triglyceride is 81.6%, 502
Above unsaturated components 15.9%, S3 components 2.5%, HP
For LC analysis, SSL, PSO.

SOO category 7162%, LPO, LSL category 11.5%
: SSO category 8.1%, LSO, PSL category 4.9%
: The SSS and ASU categories were 0.9%, and the GGU component exceeded 75% of the total triglycerides.

Example 5 Palm oil was separated by solvent, and the high melting point part was removed in the first stage,
The oil and fat from which the liquid side was removed in the second stage was subjected to extreme hardening by hydrogenation (IVO, 12). A medium melting point fraction was obtained in the same manner as in Example 1, except that this hardened oil was used. The analytical values for both parts were as follows.

Reference Example 1 The medium melting point fraction of Example 1 was mixed with cacao butter in various proportions, and for a total of 4 parts, 116 parts of powder and a small amount of pigment were blended, and a bloom test was conducted using this. Ta. That is, after melting at 60°C, cast the mold without tempering, leave it at 5°C for 30 minutes, remove the mold, and store at 20°C, or
Storage was performed alternately at 18°C and 30°C (4 cycles per day).

A reaction oil was obtained in the same manner as in Example 1, except that safflower oil (high oleic) and methyl stearate were used in 4-6, and the medium melting point portion thereof was fractionated to obtain a fat enriched in GUG.

The medium melting point fraction obtained in Example 1 (hereinafter referred to as SSO fat) and the medium melting point fraction obtained in this reference example (hereinafter referred to as SO3 fat) were
Oils and fats mixed in various proportions were prepared, melted at -60"C, then aged at 20"C for 4 hours.
When we calculated the ratio of the transition to the peak at 41°C, we found that SS
It was clearly observed that the transition rate of O is extremely fast and that the transition rate slows down as the SO5 content increases.

In addition, when observing the state in which each of the oils and fats Nos. 1 to 5 were placed in a 100 ml beaker and melted at 60°C and then held at 30°C for 24 hours, the surfaces of Nos. 1 and 2 were smooth and transparent. , and were flat, whereas in Nα3, coarse powdery crystals were observed and the surface was curved in a U-shape, and in Nα4 and Nα5, the surfaces were uneven. Furthermore, when we observed the state of melting at <60°C and holding it at 25°C for 24 hours, we found that Nos. 1 to 4 had smooth surfaces, which became whitish as the SO3 content increased, but No. 5 had smooth surfaces. Instead, a two-tier cave-in was observed near the center.

Reference example 3

Claims (1)

[Claims] (1) A residue of a fatty acid with a melting point of 40°C or higher as a free fatty acid (hereinafter abbreviated as G) is bonded to the β position, and a residue of G or a fatty acid with a melting point of 20°C or lower as a free fatty acid is bound to the α position. Triglyceride (GGG/
GGU/UGU) as a substantial component, and the GGU component in the triglyceride is 30 to 50%.