JPH03206855A - Emulsifier for food - Google Patents

Abstract

PURPOSE:To obtain a food emulsifier composed mainly of lysophosphatidic acid, having excellent emulsifiability, frothability, etc., and giving high-quality bread, etc., by treating a phospholipid mixture with phospholipase D and phospholipase A. CONSTITUTION:A phospholipid mixture (e.g. soybean lecithin) is dispersed in water using a homogenizer, etc., and phospholipase D (e.g. cabbage juice) is added and reacted to the dispersion to form phosphatidic acid. The reaction liquid is reacted with phospholipase A to obtain lysophosphatidic acid. After inactivating the enzyme by heat-treatment, the reaction product is used as a food emulsifier as it is or in the form of concentrated paste or spray-dried powder. bread having high bulkiness and excellent palatability, taste and flavor can be prepared by adding the emulsifier e.g. in the baking of bread.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a food emulsifier. More specifically, the present invention provides a method for converting the phospholipid mixture into phospholipase D (PL-
D) and phospholipase A (PL-8).

Emulsifiers are widely used in the food processing field to promote and stabilize emulsification, foaming, wetting, etc.

Particularly in bread manufacturing, various emulsifiers are used to improve product quality by suppressing the effects of fluctuations in the quality of wheat flour, the main raw material, and stabilizing the manufacturing process.

Soybean lecithin is known as a food emulsifier containing a bread improving agent. Soybean reticin is a phospholipid mixture consisting of 7-osphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, 7-osphatidic acid, and the like.

[For example, Feette, 5eifen, ^nstr
chmittelk 4.168 (1979), especially 1
Section 72 Table 2] o Treating soybean lecithin with 7-ospholipase A (PL-A) to hydrolyze fatty acids at the β-position of lecithin, and the hydrolyzate (which is a mixture of lysophospholipids) It is known that lecithin is more hydrophilic and has a stronger O/W emulsifying effect and is used, for example, as a milk replacer [J, 8m.

0il(:hemists Soc,, 53. 425
-427 (1976), J, Sci, Food^
gnic, 32.451-458 (1981)].

In addition, soybean lecithin contains 7 male 7-olipase D (PL-D).
) is known to produce phosphatidic acid. Furthermore, it is known that the physical properties of the dough and the quality of the product are improved when 7Osfultidic acid is used in the bread making process.
(1979>).

Furthermore, PL-D is contained in carrot juice, cabbage juice, etc., and it is also known that the physical properties of dough and the quality of the product can be improved by using carrot juice in the bread making process.

As a result of various studies aimed at developing a food emulsifier with better properties, the present inventors found that lysophosphatidic acid (LPA) was found to be useful as a food emulsifier (having excellent properties and +-P The present invention was completed by discovering a method for industrially producing a phospholipid mixture containing A at a high concentration.

Next, the present invention will be explained in more detail.

First, the usefulness of LPA, which is the main component in the phospholipid mixture obtained by the method of the present invention, as a food emulsifier will be explained.

This substance promotes emulsification of oil and water, resulting in the formation of a stable emulsion. It also promotes foaming of various foods and forms stable foam. When the substance is added to flour to prepare dough during bread production, the dough is very mechanically resistant and easy to handle, and the baked product has excellent texture and texture. Also, improved bread quality is achieved from low quality flour or flour mixed with grain flours other than wheat flour.

As a specific example of the results, Table 1 shows the results of evaluating the effect of LPA on improving the physical properties of bread dough using commonly used resistography. For LPA, the soot-IJum salt prepared in Example 3 was used, and the additive amount is not shown in weight % based on the wheat flour. Due to the addition of LPA, the time until the dough begins to break down (BP) and the difference between the dough and 1. It is clear that the stability time (ST) of the fabric is significantly extended, indicating that the addition of LPA results in a fabric with high mechanical resistance.

Table 1 Test group for improving fabric properties on LP BP (minutes) ST (minutes) No additives? , 5 5.4 LPA0.15% (W/W) 9.0
9.00.30% 10.5 1
1.00.50% 12.5 13
．． 0LPΔ or phospholipid mixtures with high LPA content are more effective as food emulsifiers than other phospholipids, but this is because LPA is an anionic and highly hydrophilic phospholipid. This is thought to be due to the following. According to the invention, the phospholipid mixture is prepared by converting the phospholipid mixture into phospholipidase D (
This useful LPA-rich phospholipid mixture can be produced by treatment with PL-D) and 7-mole7-olipase A (PL-A). On the contrary,
When treated with PL-D alone, lysophospholipids are not produced, and when treated with PI and A alone, phospholipids mainly composed of neutral lysophospholipids such as lysophosphatidylcholine and lysophosphatidylethanolamine are produced. A mixture forms. a phospholipid mixture according to the invention and PL-D; or
The difference in composition of the phospholipid mixture obtained by treating PL-A alone and the difference in usefulness in actual bread production will be introduced later.

A typical phospholipid mixture is soybean lecithin,
It is used in large quantities in food processing. The composition of commercial soybean lecithin is shown in Table 2.

Table 2 Composition of commercially available soybean lecithin PE PI PS 4 19 029 9 24 19 11 25 9 41 2 21 PA Lysophospholipid 12 15 4 9 4 According to Table 2, 7-osphatidylcholine (PC), phosphatidylcholine (PC), The main components are diethanolamine (PE) and phosphatidylinositol (PI), and the content of lysophospholipids is low. Some products contain large amounts of phosphatidylserine (PS). Soybean lecithin ingredient P
The component that is converted to LPA by L-A is phosphatidylic acid (PA), but the content of PA is generally around 10 mol%, and therefore the LP in the phospholipid mixture obtained by the P>A treatment alone is The total content is around 10 mol%. Even if soybean lecithin, which has the highest PA content, is used and converted to +00% LPA, the LP content is less than 130 mol%. However, according to the present invention, first PL-D
If the PL-A treatment is performed after increasing the PA content by treatment, a phospholipid mixture containing 30% or more of LPA and 9%-F can be prepared. Ua can be done. This process is shown by the following formula.

CH phosphatidic acid R-[:0-0-[:H2 +10-[:II O ↑ CH, -0-P-OH 0]1 residue, or hydrogen) For lecithin mixtures with high PA content, Even if the PL-D treatment and the PL-A treatment are performed simultaneously, a phospholipid mixture with a high LPAP content can be obtained.

However, since the PA content in the phospholipid mixture is generally low, it is desirable to first treat with PL-D and then with PL-A.

Next, a method for producing a phospholipid mixture containing LPA as a main component according to the present invention will be described in detail.

(1) Raw materials Phospholipids are widely distributed in animals and plants, and are particularly abundant in soybeans and eggs, and a mixture of various phospholipids obtained from these is the raw material of the present invention. Soybean lecithin, which is currently widely used in food processing, is the cheapest phospholipid mixture that can be produced in large quantities, and is the most suitable raw material for the present invention. The composition of typical soybean lecithin is already shown in Table 2.

PL-D is widely distributed in plants, and carrots and cabbage have particularly high activity of this enzyme, and extracts from these can be used. The reaction of this enzyme requires Ca ions, and soluble Ca salts such as calcium chloride and calcium lactate are used.

Since PL-A is distributed in animals, and is particularly present in high concentrations in pancreatic juice, which is a digestive fluid of mammals, porcine or bovine pancreatin, which is an enzyme-containing preparation of pancreatic juice, can be used. however,
Due to the manufacturing method of vancreatin, the lysophospholipase present in the lysophospholipid decomposes the target lysophospholipid, so pretreatment as shown in the examples is necessary.

To promote the dispersion of lecithin and to powder it after the reaction,
Skim milk powder, wheat flour, etc. may be present in the reaction solution.

(2) P L -D reaction The phospholipid mixture is dispersed in water and used for the reaction. Some purified phospholipid mixtures are easily dispersed in water, but many require mechanical dispersion;
This is accomplished by the use of a high-speed rotating homogenizer or by ultrasonication.

The concentration of the phospholipid mixture in the reaction solution is sufficient as long as the reaction progresses sufficiently and is easy to handle; in practice, it is 5 to 15%.
(W/11) is desirable. Furthermore, skim milk powder, wheat flour, etc. may be used to promote the dispersion of phospholipids; the presence of such dispersion aids suppresses the separation of phospholipids during the reaction and prevents the formation of dry powder after the reaction. It becomes easier.

The amount of PL-D added must be at a concentration that allows the reaction to proceed sufficiently. Since there is currently no industrially available PL-D preparation, vegetable juices with high PL-D activity may be used. For example, in the case of carrots or cabbage, a phospholipid mixture [00 parts to 10 to 3 parts of carrot or cabbage]
It is sufficient to use juice obtained from 00 parts (for example, crushed compressed juice).

Regarding the Ca ion concentration, the reaction proceeds over a fairly wide concentration range, but for practical purposes, a range of 20 to 200 nM is sufficient.

Regarding the reaction concentration, as long as the temperature does not inactivate the enzyme,
The higher the temperature, the more the reaction progresses. P for carrots and cabbage
When using LD, the temperature is preferably 30 to 40°C.

The reaction proceeds over a fairly wide range of pH.

When using carrot or cabbage PL-D, the pH
S~8 is fine. The reaction time varies depending on the phospholipid concentration, its dispersion state, the amount of enzyme used, pH, etc., but the reaction time is 2 to 20 minutes.
It is desirable to move on to the next PLΔ reaction in time.

(3) PLA reaction The second reforming reaction is started by adding PL-A to the reaction solution after the PL-D reaction.

The amount of PL-A added is the amount of PA produced by the PL-D reaction.
The amount is sufficient to convert a phospholipid mixture containing 7'PA as a main component into a mixture containing 7'PA as a main component. When using a powder preparation of pork pancreatin, it may be added in an amount of 0.5 to 5% (W/W) to the phospholipid mixture.

The reaction pH may be within the same range as in the case of the PL-D reaction, and the reaction time may also be in the same range as in the case of the PL-D reaction.

Since PL-A generally has high thermal stability, the reaction temperature is
The temperature may be higher than in the case of the LD reaction (for example, 50°C), but it may be the same as the PL-D reaction.

After the reaction, it can be used as it is or as a concentrated paste after heat treatment, but if you add powdering aids such as skim milk powder, wheat flour, or sugars and dry it, the storage stability will be improved and it will be easier to handle. It becomes easier. As the drying method, spray drying, drum drying, freeze drying, etc. may be employed.

After the reaction, a phospholipid mixture with high LP content and LP
A can be manufactured. This production is achieved by solvent extraction of the dehydrated concentrate or dried powder of the reaction solution, and the separated purified phospholipid mixture and LPA are used as they are or mixed with other food raw materials such as fats and oils and other emulsifiers. It can be used as The mixing ratio with other food raw materials can vary over a wide range depending on the purpose, and can usually have a value of 1% (w/w) or more as a phospholipid mixture.

In the above description, the most common case was described in which the PL-D reaction is first performed and then the PL,-A reaction is performed. For phospholipid mixtures with high PA content, 2
Even if various enzymatic reactions are performed simultaneously, the LPA content is high.
A phospholipid mixture is obtained, the preparation of which can be carried out according to the above description. The improvement effect of LPA or a phospholipid mixture with a high PA content on bread %a and the method of use will be described below.

The characteristics of the bread-making improving effect of the emulsifier of the present invention are as follows.

(1) Improvement of physical properties of bread dough Dough to which LPA or a phospholipid mixture with high LPA content is added has improved mechanical resistance and workability. That is, the bread dough has appropriate elasticity and extensibility, and stickiness (stickiness) is also suppressed. The effect of LPA on improving the physical properties of fabrics is already shown in Table 1.

(2) Improved product quality Bread produced by adding LPA or a phospholipid mixture with a high LPA content has an increased volume, a glossy internal phase,
Shows well-developed sudachi. Furthermore, the soft feeling is improved,
Aging is also suppressed.

LPA or a phospholipid mixture with a high LPA content may be added to the middle dough, or may be added during the main kneading. Addition amount: Well, 0.2 to 0.5 to wheat flour as a phospholipid mixture
% (W/W), but depending on the type of bread, raw material composition, manufacturing method, etc., and the strength of the desired improvement effect.
．． It may be added in an amount of about 0.05 to 5.0% (W/W). In the case of purified LPA, lower levels may be required, 0. O
It is sufficient to add about I to 2.0% (W/W). LPA can be used as a free acid or as a salt, but as a food emulsifier, a sodium salt or a carunium salt is preferable.

The present invention will be specifically explained below using examples.

Example 1 Soybean lentin paste (manufactured by Hounen Oil Co., Ltd.) was used as the original ItIJ lipid mixture. 900g of this paste and 3 liters of water
600g was dispersed using a high-speed rotation homogenizer, 450g of skim milk powder was added as a dispersion accelerator, and crushed carrot juice 9 was added as a PL-D enzyme source.
Add 00g and 300g of 2M calcium chloride solution, adjust the pH
The reaction was carried out at 6, 5 and 30°C for 4 hours.

Next, PL-A treatment was performed using pancreatin (manufactured by Miles) as an enzyme source for PL-.

180g of 5% (W/W) pancreatin aqueous solution at pH 4
, 0, heated at 90°C for 30 minutes, cooled, added to the PL-D treatment reaction solution, and reacted at 50°C for 16 hours. After the reaction, the reaction solution was heat sterilized at 90°C for 30 minutes, 450 g of skim milk powder was dispersed as a powdering aid, and then a phospholipid mixture containing LPA as the main component was added to the active ingredient [raw material phospholipid] by spray drying. Approximately 1.8 kg of food grade emulsified powder containing 43% (W/W) was obtained.

Phospholipids were extracted from this powder according to a conventional method, and the phospholipid components were separated and quantified by two-dimensional thin layer chromatography. The results are shown in Table 3. L compared to raw lecithin
The content of PA shows a very high value.

Table 3 Composition of lecithin whose main component is LPA Table 4
Reaction composition for phospholipid treatment pc 31 PE 27 PI 25 PA 6 LPA 0 Example 2 (1) Preparation of modified phospholipid mixture Soybean lecithin powder (manufactured by True Lecithin Industries) was used as the phospholipid mixture, By composition, control sample I
(untreated phospholipid mixture), II (PL-D modified phospholipid mixture), III (PLA modified phospholipid mixture) and the modified products of the present invention were prepared.

Sample I Control sample port 00 400 0 00 Control sample ■ 100 1600 80 0
2 modified product 100 1400 80 200
2(1) Calcium chloride solution is 1M aqueous solution.
′乍.

(2) Carrot extract is made by making carrot juice with an equal amount of water and straining it through gauze.

(3) Pancreatin was used after making a 5% (wha) aqueous solution of pork pancreatin (manufactured by Tokyo Kasei Co., Ltd.) at pH 4.0, followed by heat treatment at 85° C. for 30 minutes.

For control sample I, lecithin was dispersed in water, then further dispersed with a high-speed rotation homogenizer, a calcium chloride solution was added, a reaction solution was prepared, and the mixture was heated at a temperature of 90°C or higher for 20 minutes. 100 g of cutose was added and freeze-dried to obtain a powder.

Control sample ■ is a reaction solution prepared in the same manner as control sample I.
Carrot extract was added and a PL-D reaction was carried out at pH 6.5 at 37° C. for 6 hours, followed by treatment in the same manner as Control Sample I.

Control sample ■ is a reaction solution prepared in the same manner as control sample I.
Add the heat-treated pancreatin dispersion and adjust the pH to 6.
After carrying out the PL-A reaction at 5.37° C. for 6 hours, the sample was treated in the same manner as Control Sample I.

The modified product was subjected to the PL-D reaction in the same manner as the control sample (■), and then to the PL- in the same manner as the control sample (■).
It was obtained by the same treatment. These powders have a raw material equivalent of 50
% of phospholipids.

The differences in chemical composition of these control samples and the modified products of the present invention are clearly demonstrated by thin layer chromatography.

The figure is the chromatogram.

The chromatography conditions are as follows.

Test solution: To 1 g of the powder sample, 10-10% of a chloroform-methanol mixture (2:1) and 0.2% of phosphoric acid were added, shaken for 30 minutes, and filtered to make 44 spots of the obtained extract.

Plate: Silica gel 6ONα5721 (Merck & Co., Ltd. product) Developing solvent 1: Chloroform-methanol-28% ammonia-water (65: 30: 5: 2.5) Developing solvent ■: Chloroform-methanol (65: 25:
3) Color development A molybdenum blue reagent (Sinsage reagent) commonly used for detecting phospholipids was sprayed to cause only the phospholipids to develop a blue color.

The control sample ①, which uses raw materials as is, contains a large amount of PE and PClPI. In the control sample ■, PA is the main component, and in the control sample ■, there are many lysophospholipids derived from the phospholipids present in the raw materials. In contrast, the modified product of the present invention is a phospholipid mixture containing LPA as a main component (approximately 50 mol% of the total phospholipids).

(2) Bread making test A bread making test was carried out by adding the various phospholipid mixtures prepared in (1) and using the non-additive group as a control group.

The test plots are shown in Table 5.

Table 5 Bread making test area test Area 11 @ Addition n Control sample ■ ■ Control sample ■ ■ Control sample ■ ■ From 350 g of modified wheat flour, Baker's yeast Log, 0.5 g of yeast food (containing ascorbic acid), and 200 g of water. Make a medium-fermented dough, and add 150g of flour to this when kneading the dough.
, 25g sugar 10g salt.

25 g of shortening and 140 g of water were added, and a sample of bread was made according to a conventional method. The test sample powder was added in an amount of 0.4% (W/W) based on the whole wheat flour at the time of making the dough.

Table 6 shows the physical properties of the dough during production and the evaluation of the finished bread after 2 days.

Table 6 Evaluation Results Test Ward nmrv ■ Soft feel xx ○ ◎ ◎ Inferior
X PLD or PL compared to untreated phospholipid mixture
The phospholipid mixture modified with -A showed good bread-making improving effects. However, the phospholipid modified product according to the present invention shows a good bread-making improving effect.

Example 3 320 g of the powder containing the phospholipid mixture containing LPA as the main component prepared in Example 1 as an active ingredient was extracted three times with 640 m2 each of chloroform/methanol solution A (2:1). The residue was extracted twice using 640 mfj of a mixture of chloroform, methanol, and phosphoric acid (2:1:0.15) to obtain an extract containing LPA. IO this
After neutralization with N caustic soda, the generated sodium phosphate is separated into P,
After dehydrating with anhydrous sodium sulfate, it was concentrated to about 100 ml, and 500 ml of acetone was added thereto to precipitate the sodium salt of LPA. After separating the precipitate, it was washed with acetone, vacuum-dried and smoked, and 20 g of LPA sodium salt was obtained. I got it.

Using this LPA, a resist graph was obtained according to a conventional method. The results are already shown in Table 1, and it was revealed that excellent mechanical resistance was imparted to the fabric.

In addition, this LPA was added at 0.2% (W/W) to wheat flour.
) was added and a bread making test was conducted in the same manner as in Example 2. Compared to the case without the additive, the dough had a good balance of elasticity and extensibility, and was very easy to handle.
Furthermore, the finished bread had a large volume, the internal phase showed good film elongation and uniformity, and the texture was soft, making it an extremely excellent product overall.

[Brief explanation of drawings]

FIG. 1 is a thin layer chromatogram showing the chemical changes associated with enzymatic modification of a phospholipid mixture according to the present invention.

Claims (1)

[Claims] 1. A food emulsifier obtained by treating a phospholipid mixture with phospholipase D and phospholipase A. 2. The food emulsifier according to claim 1, wherein the food emulsifier is for bread.