JPS60105686A - Method for modifying phospholipid - Google Patents

Abstract

PURPOSE:To obtain a phospholipid without problems of appearance nor odor in hydrogenating a phospholipid in an organic solvent to produce a hydrogenated phsopholipid to be added to cosmetics, medicines, etc., by adding water to the reaction mixture. CONSTITUTION:A phospholipid and a fat or oil containing the phospholipid are dissolved in an organic solvent, e.g. methanol or ethanol, and water is further added thereto. The hydrogenation is carried out in the presence of a catalyst, e.g. Pd, to afford the aimed white phospholipid. The amount of the water to be added is preferably 5-100wt./wt% based on the phospholipid. The amount of the catalyst to be added is 0.1-5wt./wt% based on the phospholipid, and hydrogenation is carried out under >=2kg/cm<2> H2 pressure. The resultant hydrogenated phospholipid may have <=40g/100g iodine value for converting the hydrogenated phospholipid into the white phospholipid having high stability. EFFECT:Water is gathered around the hydrophilic groups, and ionic parts are neutralized. Thus, the progress of coloration is believed to be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION When hydrogenating phospholipids or fats and oils containing phospholipids, the present invention provides hydrogenated products of white, odorless, and high quality hydrogenated phospholipids. Relating to a method of manufacturing.

Phospholipids, commonly known as lecithin, are usually extracted from plant or animal sources, and their components include e.g. phosphatidylcholine, phosphatidylethanolamine,
It consists of a mixture of phospholipids such as phosphatidyl inositol. Representative examples include egg yolk lecithin and soybean lecithin. Due to its structure, lecithin is hydrophilic and
Because it has a lipophilic functional group in the same molecule, it has amphoteric surfactant action and is used in a variety of applications, including food, cosmetics, and pharmaceutical products. For example, as an anti-aging agent in bread, chocolate and margarine, and as a smoothing emollient in cosmetics.

However, when this lecithin is used, the amount added is
The power is about 0.1 to 0.3 inches, and it is rare that more than 1 inch is used.

One of the reasons for this is that applying lecithin gives the product a yellow to brown color, and it also causes a fishy odor.
Or maybe it's because it smells like beans.

On the other hand, even when used at a low concentration that does not cause color or odor, the instability of lecithin causes deterioration and browning, and as the product deteriorates, coloration and amine odor may occur. This is because the product becomes brownish and gives off an unpleasant odor. This adverse effect is more noticeable in cosmetics and pharmaceutical preparations, which are fine chemicals, rather than in foods.

The oxidation of phospholipids is based on the theory that unsaturated sites in fatty acid side chains are autooxidized under the influence of heat, light, metals, pH, etc., generating pov and cov, and furthermore, this carbonyl group becomes amino It is also thought that it causes condensation polymerization with groups, mainly the primary amino groups of phosphatidyl/ethanolamine, and gradually polymerizes and decomposes, causing coloration and odor generation.

Various modifications have been made to prevent this deterioration and browning phenomenon and to make lecithin free of color and odor, but it is believed that the most effective method is to minimize the unsaturated sites that cause this phenomenon. Conceivable.

This is the reduction of unsaturated sites, that is, the hydrogenation reaction. When this reduction reaction is performed, the product is a naturally occurring product, and there is no risk of creating a new synthetic product through modification. Naturally, it can also be expected to remove color and odor. Attempts have already been made to produce hydrogenated lecithin as described above.

One is the reduction of egg yolk lecithin in alcohol. This was hydrogenated to identify egg yolk lecithin, which was done in the early part of this century.

In reality, lecithins 2 to 52, which are reddish-brown and contain only phospholipids and do not contain neutral lipids, are dissolved in ethanol and hydrogenated using palladium as a catalyst.

Next, there is an example of soybean lecithin (containing neutral lipids). This converts lecithin into benzene, hexane, ether,
Alternatively, hydrogenated soybean lecithin is obtained by dissolving it in a mixed solvent of these and alcohol, adding a platinum metal catalyst, and performing hydrogenation at a temperature of 25 to 65C and a hydrogen pressure of 1 to 3. .

However, the conventional methods described above have the following disadvantages.

The reason is that in the above method, due to hydrogenation, the lecithin retains its red or brown color derived from the raw material.

This defect is particularly common in soybean lecithin, and
Even in egg yolk lecithin, as the phospholipid content increases, the color becomes more intensely red.

The reason for this is that in the case of soybean lecithin, the lecithin before hydrogenation has already deteriorated and has a brownish color, and in the case of egg yolk lecithin, the lecithin before hydrogenation has not deteriorated, but , 50~9o during hydrogenation
For the phospholipids of C, there is a possibility that they deteriorate during hydrogenation because the hydrogenation is carried out at harsh temperatures.

These reddish-brown hydrogenated lecithins are commonly added to cosmetics and quasi-drugs such as emulsions and creams.
When ~5w/w% is added and used as a moisturizer or lubricant, the product takes on a reddish tinge, causing many problems with appearance and odor, and is perceived by consumers and sea bream producers as being of low quality.
I don't like it very much.

As a result of intensive research to improve the above-mentioned drawback of hydrogenation resulting in a reddish-brown color, the inventors of the present invention unexpectedly succeeded in creating a white hydrogenated product by using water. The present invention has now been completed.

The present invention will be explained in detail below.

The present invention is a method for producing white hydrogenated phospholipids, in which water is mixed with a solvent or a catalyst that dissolves phospholipids and fats and oils containing phospholipids, and the mixture is hydrogenated.

The raw material phospholipid may be any oil or fat containing phospholipid, such as soybean lecithin, egg yolk lecithin, and corn lecithin. In addition, regarding the content of phospholipids, phospholipids 2 to 1
00 w/w% and neutral lipids in the range of 98 to 0 w/w%, but the effect of water can be clearly demonstrated when phospholipids are in the range of 50 to 100 w/w% and neutral lipids are in the range of 0 to 50 w/w%. w/w
%.

Solvents for dissolving phospholipids include alcohols such as methanol, ethanol, and inpropyl alcohol, or mixed solvents of these with hexane, benzene, etc., which dissolve water and are suitable for phospholipids and neutral lipids. This is possible if the solvent dissolves the The amount of solvent is not affected much, but hydrogenation efficiency is not good whether it is thin or thick, and the preferred concentration is 10 to 60 w/w%.

Further, the addition rate of water may be in the range of 5 to f 00 w/w to the phospholipid to be hydrogenated, but is more effectively 10 to 50 w/w%.

In actual operation, phospholipids or fats and oils containing phospholipids are dissolved at 10 to 60 w/w in a solvent containing water. To this, the catalyst Pd is added to the lipid at 0.1 to 5 w 7
w % and hydrogenated at H1 pressure 2 +7/cI/ or more. After the hydrogenation is completed, the solution is filtered to remove the catalyst, and the solvent is recovered to obtain hydrogenated lecithin.

In order to make the hydrogenated phospholipid obtained in this way a highly stable white hydrogenated phospholipid, the iodine value should be 401/100f or less, but the iodine value does not have much effect on whiteness. The effect of water is great.

Although there has been no theoretical consideration of the effect of water, one reason is that water gathers around the hydrophilic choline group or ethanolamino group, which is the cause of the coloration of phospholipids. It was thought that this would prevent the progress of discoloration.

From the above, it can be seen that the hydrogenated phospholipid obtained is modified to have a white color, as shown in the examples below.

Example 1 Egg yolk lecithin (moisture 0.7%, phospholipids 98.6%,
Iodine value 72f7100f, peroxide value Omeq/9
)2502 with 50f of water added to Improper Tool 9
38- was added, and the mixture was stirred and dissolved at 50C for 20 minutes. To this, 10% Pd-activated carbon 102 was added, and 2 volumes were placed in an autoclave. Hydrogen pressure 30 Yu/C! IG, liquid temperature 70~
Hydrogenation was carried out at 85C for 120 minutes at fc (100
0 rpm, turbine blade type).

After the reaction was completed, residual hydrogen gas was released into the atmosphere, the reaction solution was pressurized to a nitrogen pressure of I J / all G, and the catalyst was removed by pressure filtration. Next, the resulting clear solution was concentrated under reduced pressure to recover the solvent. A certain molten additive was poured into a tray, cooled to room temperature, and solidified. This solidified hydrogenated product was pulverized into a 12-mesh pass product, and the solvent was completely removed by vacuum drying at room temperature to obtain a white hydrogenated lecithin. Yield 2371, moisture 1.1, phospholipid 9
8.5%, iodine value 5f7100? Met.

Example 2 Egg yolk lecithin (moisture 0.5%, phospholipids 98.0%,
Iodine value 75 r/100 t, peroxide value Omeq/
938 ml of Improper Tool to which 75 ml of water had been added was added to 250 t of water, and the mixture was stirred and dissolved at 50 C for 20 minutes.

Then, 7.5 l of 10% Pd-activated carbon was added and placed in a 101 volume autoclave. Hydrogen pressure 7 kg/crl
G.

Hydrogenation was performed at a liquid temperature of 65 to 75C. Stirring was performed using a turbine blade at 70 rpm. After the reaction is complete,
Hydrogenated lecithin 23 was treated in exactly the same manner as in Example 1.
I got 02. The water content was 1.0%, the phospholipid content was 98.2%, and the iodine value was 209''/j00f.

Example 3 Egg yolk lecithin (moisture 0.5 q6, phospholipid 66.8
%, iodine value 759/100f, perc3ide value o me
q/kg) 300f was added with 696 ml of inpropanol to which 150 g of water was added, and the mixture was stirred and dissolved at 50 C for 20 minutes. Then, 7.5f of 10% Pd-activated carbon was added,
10 was placed in the autoclave. Hydrogen pressure 10kg/d
, hydrogenation was carried out at a liquid temperature of 65 to 75C.

Stirring was performed using a turbine blade at 70 rpm.

After the reaction was completed, the same treatment as in Example 1 was carried out to obtain hydrogenated lecithin 2822. Water content: 0.9%.

Example 4 Soybean lecithin (moisture 0.3%, phospholipid 63.5 m,
Iodine value q2t71oay, peroxide value 1.8meq/
9) 150 t of benzene with 30 - of water added,
It was dissolved in 1000 rnl of ethanol (3:1) mixed solvent. Then, 11 g of 10% Pd-activated carbon was added and placed in a 2-volume autoclave. Hydrogen pressure 80kg/d1 Liquid temperature 7
Hydrogenation was performed at 0-85U.

Stirring was performed using a turbine blade at 100 rpm.

After the reaction was completed, the same treatment as in Example 1 was carried out to obtain hydrogenated lecithin 1302. Moisture 2.1%, phospholipid 63
．． 8%, and the iodine value was 3 meq/kg.

Examples 5-9 High purity egg yolk lecithin (moisture 0.5%, iodine value 72y
/ 100 f, Linzuki quality 98.0%) to xoor・
Add Improper Tool 1125- and dissolve. Then,
152 water was mixed with 10% Pd-activated carbon 92 to moisten it, and after mixing with the lecithin solution, the mixture was transferred to a hydrogenation device.
Under the conditions of a hydrogen pressure of 7 kglcrl and a fi temperature of 65'C, hydrogen was absorbed to give an iodine value of 20F/'100r. Similarly, qy, s.

Hydrogenation was also performed on the samples to which water was added at f, 60 S+, and 150 f. After hydrogenation, the catalyst was removed from the solution by filtration, the solvent was recovered by an evaporator, and then the solution was vacuum-dried at room temperature.

The color, absorbance measurement results, and odor measurement results of the obtained hydrogenated product are as shown in Table 1.

Comparative Example 1 Hydrogenation was performed in the same manner as Examples 5 to 9 without adding water. After hydrogenation, the catalyst was removed from the solution by filtration, the solvent was recovered by an evaporator, and then the solution was vacuum-dried at room temperature.

The color, absorbance measurement results, and odor measurement results of the obtained hydrogenated product were as shown in Table 1.

Table 1 Color, absorbance, and odor measurement results for each water addition rate *1
Measurement of 60 mesh bath products using a 5M-3 color computer manufactured by Suga Test Instruments Co., Ltd. *2 Dissolve hydrogenated lecithin 12 in chloroform 2
Measurement of absorbance as 5-Examples 10 to 14 Highly purified egg yolk lecithin (moisture 0.6%, phospholipid 98.6%)
%) and 500 tnt of a mixed solvent of methanol and water to which 501 g of water was added and dissolved. Then 10% P
After mixing the d-activated carbon 52 with the lecithin solution, it was transferred to a hydrogenation device and hydrogenated at a hydrogen pressure of 80kli+/(m) aiming at an iodine value of 5r/100f or less.Also, 1002.1502. Hydrogenation was also performed on the solution to which 2001.300f had been added.The catalyst was removed from the solution after hydrogenation by filtration, and the solvent was recovered using an evaporator.

The color, absorbance measurement results, and odor results of the obtained hydrogenated product are as shown in Table 2.

Comparative Example 2 Hydrogenation was performed in the same manner as Examples 10 to 14 without adding water. After hydrogenation, the catalyst was removed from the solution by filtration, the solvent was recovered by an evaporator, and then the solution was vacuum-dried at room temperature.

The color, absorbance measurement results, and odor measurement results of the obtained hydrogenated product are as shown in Table 2.

Table 2 Color, absorbance and odor measurement results for each water addition rate*1
Measurement of 60 mesh bath products using a 5M-3 color computer manufactured by Suga Test Instruments Co., Ltd. *2 Hydrogenated lecithin 12 was soaked in chloroform 2
When the absorbance was 61 and the addition of constant water was 150% or more, hydrogen absorption up to an iodine value of 5 was not possible.

Claims (1)

[Claims] A method for modifying phospholipids, which comprises hydrogenating fats and oils containing b#'i phospholipids in the presence of water.