JPH0439374B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to the modification of surfactants used in foods and the like, and particularly to methods for improving various surfactant abilities of polyglycerin fatty acid esters.

[Problems to be solved by conventional technology and invention]

Polyglycerin fatty acid ester exhibits a surfactant effect with a wide range of hydrophilic/lipophilic balance (HLB) depending on the degree of polymerization of glycerin and the type and number of fatty acids bonded to it.
It is widely used in foods, cosmetics, etc. as a surfactant that exhibits properties such as emulsification, dispersion, solubilization, penetration, and foaming, and is a surfactant that has good biodegradability and is recognized as safe.

In general, surfactants suitable for emulsifying edible oils and fats, etc.
The HLB is said to be 7 to 9 for oil-in-water emulsification and 3 to 5 for water-in-oil emulsion, but polyglycerin fatty acid esters with HLB less than 9 must be treated with acidic aqueous solutions or inorganic materials such as salt. It does not dissolve in aqueous salt solutions and is unsuitable for emulsifying edible fats and oils as it is.

Further, penetration power and dispersion power are important properties for a surfactant, but the penetration power and dispersion power of polyglycerin fatty acid esters with an HLB of less than 9 are small, and sufficient surfactant action cannot be obtained.

[Means for solving problems]

The purpose of the present invention is to improve the above-mentioned drawbacks of polyglycerol fatty acid esters with HLB of less than 9, and to provide a surfactant composition with improved acid resistance, salt resistance, emulsifying power, dispersing power, and penetrating power. be.

The surfactant composition of the present invention contains a polyglycerol fatty acid ester with an HLB of less than 9 and lysophosphatide as essential components, and the weight ratio of the polyglycerol fatty acid ester and lysophosulfatide is 40/60~95/5,
The ratio is preferably 50/50 to 90/10.

is one of the essential components of the composition of the present invention
Polyglycerin fatty acid esters with HLB less than 9 include polyglycerin with a degree of polymerization of 4 or more and the number of carbon atoms.
Preference is given to mixtures of one or more mono-, di-, and polyesters with 12 to 22 saturated and/or unsaturated fatty acids. In the case of polyglycerol fatty acid esters of fatty acids having 11 carbon atoms or less, the effect of adding lysophosphatide of the present invention on emulsification and dispersion performance is not seen very much, and fatty acids having 23 or more carbon atoms are not very common. .

Lysophosphatide, which is an essential component of the present invention, preferably has 8 or more carbon atoms as a constituent fatty acid, and the acyl group may be in either α or β position. As such lysophosphatide, both the natural L-type and the synthetic racemic one can be used.

Naturally derived lysophosphatide is known to exist together with diacylphosphatide in living organisms, and is found, for example, in the lipids of grains such as soybean, rapeseed, and wheat, and in the lipids of animal cells. In addition, diacylphosphatide in animal lipids such as egg yolks and plant lipids such as soybeans is hydrated by the action of phospholipase A-2 in pig pancreatic juice or snake venom or phospholipase A-1 in bacteria. Disassemble,
The generated fatty acids can be removed with acetone, etc., and if necessary, they can be purified by silica gel chromatography, etc.
58-51853). In this case, by hydrogenating the obtained lysophosphatide in a suitable solvent in the presence of a catalyst such as nickel, a surfactant with better oxidation stability can be obtained.

Also, Journal of American Oil Chemist Society October 1981 issue 886~
On page 888, it is described that lysophosphatides with various compositions can be obtained by variously changing the conditions under which phospholipase A-2 is allowed to act.

Furthermore, lysophosphatide can also be obtained by fractionating diacylphosphatide using a solvent such as ethyl alcohol and using this fraction as a raw material. In addition, the method for obtaining phosphatidylcholine from egg yolk described in Journal of Biological Chemistry, Vol. 188, pp. 471-476 (1951);
-16, 59-42655, 57-123496, 56-23997
The method for obtaining phosphatidylcholine by the method described in 1. can also be applied to the present invention. The optical activity of natural lysophosphatide is levorotatory, and its safety has been confirmed when administered orally to animals (Journal Science of Food and Agriculture, Vol. 32). 451～458
page).

In addition, methods for analyzing phosphatides used in the present invention include thin layer chromatography, TLC-
Examples include FID method (Iyatroskian method) and high performance liquid chromatography method.

The lysophosphatide used in the present invention can be obtained as described above, but in the present invention, it is preferable to use a lysophosphatide (a) consisting essentially of lysophosphatidylcholine. Preferably, lysophosphatide (a) may further contain lysophosphatidylethanolamine, and a small amount of lysophosphatidyl inositol, lysophosphatidic acid, lysophosphatidylserine. It may contain one or more types of lysophosulfatides selected from the group consisting of: Furthermore, when producing lysophosphatide (a) from natural products, due to the characteristics of the production method, it often contains diacylphosphatide (b), which corresponds to the above-mentioned lysophosphatide (a). When these are contained, it is preferable that the amount of lysophosphatide (a) is 30% by weight or more based on the total amount of phosphatide [(a) + (b)] because it is effective even in acidic solutions. % or more is preferable because it is effective even in strongly acidic and highly concentrated salt solutions.

In general, the larger the amount of lysophosphoratide relative to the total amount of phosphatide, the smaller the amount of lysophosphoratide used tends to be.

In the composition of the present invention, the blending ratio of polyglycerin fatty acid ester and lysophosulfatide is from 40/60 to 95/5, preferably from 40/60 to 95/5 by weight.
90/10, particularly preferably 40/60 to 80/20,
If the lysophosulfatide content is less than 5, there will be no improvement effect of the present invention, while if the lysophosulfatide content is more than 60, the performance will not particularly deteriorate, but it will become expensive, which is undesirable.

The method of obtaining the composition of the present invention is not particularly limited, but for example, it may be prepared as an aqueous solution or an aqueous paste of a mixture of polyglycerin fatty acid ester and lysophosphate, or further concentrated under reduced pressure to form a semi-solid or solid. Alternatively, it can be used after being dissolved in a solvent such as alcohol, or it can be dried without excessive heating after being dissolved and used as a fluid or solid.

Other surfactants may be used in combination with the composition of the present invention without departing from the purpose of the present invention.

Furthermore, since the coexistence of soluble proteins, peptides, and polysaccharides improves emulsification, dispersion, and other performance, it is preferable to coexist them in the composition of the present invention.

The surfactant composition of the present invention can be used for various purposes, such as soy sauce, Worcestershire sauce, salted vegetables, pickles such as Fukujinzuke, fruit juice, fermented milk such as yogurt, dressings, mayonnaise, Examples include application to compositions containing inorganic salts, organic acids, etc. such as tsukudani, processed products such as meat and fish meat, and cosmetics, and effects include emulsification of oily substances such as animal and vegetable oils, vegetable essential oils, and paraffin, and cocoa powder. , instant food powders, spices such as mustard powder, wasabi powder, antifungal agents such as butyl paraoxybenzoate, various pigment powders, etc., or the composition of the present invention is added to powders that are dispersed in these powders, etc. It has the effect of easily dispersing it by coating it by impregnating or spraying it with a solution dissolved in alcohol or the like.

〔Example〕

Examples of the present invention are shown below, but the present invention is not limited to the examples.

In addition, the percentage of lysophosulfatide in each test for the aqueous paste obtained in each example (including the composition of the present invention) is calculated in terms of pure content, and is based on the total amount of polyglycerin fatty acid ester and lysophosulfatide. It is a value.

Example 1 Phosphosphatide containing 70% diacylphosphatidylcholine was obtained from commercially available soybean phospholipids by acetone precipitation and aqueous ethanol fractionation, and porcine pancreatic phospholipase A-2 (manufactured by Novo, Lecitase 10L) was added to this. The generated fatty acids were removed with acetone, fractionated with alcohol, and further fractionated with a silicic acid column and alcohol to produce phosphatide containing 95% lysophosphatidylcholine and 2% lysophosphatidylethanolamine. Obtained.

This phosphatide and HLB8 polyglycerin fatty acid ester (manufactured by Sakamoto Pharmaceutical, SY Glister)
MS・310, the main constituent fatty acids are stearic acid,
The degree of polymerization of polyglycerin was 4) and was mixed in various weight ratios to obtain an aqueous paste of 25% by weight (solid content concentration in the aqueous paste).

(1) Acid resistance and salt resistance test Dissolve 4g of each paste in water to make 200ml, and add 1 part of this aqueous solution to water (control), 0.2M phthalic acid buffer (acidic liquid) with a pH of 3, and 20% saline (salt). Solution) Add 1 part of each and heat to 60℃ for 10 minutes,
After cooling, the light transmittance at 720 nm was measured.

The result was 8% in the case of polyglycerin fatty acid ester alone (control), or separation of surfactant was observed (acidic solution, salt solution), but in the case of 30% lysophosphatide, it was 82% in the control, 75% in acidic liquid,
It was 79% in salt solution. Moreover, at 40% or more, there was almost no difference between the control (87%), acidic solution, and salt solution.

(2) Emulsification stability test of corn salad oil and soy sauce 2g of each paste, 50g of corn salad oil, and 56g of Koikuchi soy sauce were mixed using a Nippon Seiki homogenizer AM-8.
Emulsify for 6 minutes at 55°C and 13,000 rpm.
Take the emulsion in a glass cylinder and heat it to 20℃ for 8 hours.
It was stored in an incubator that cycled at 40°C for 16 hours, and its condition was observed.

30 for polyglycerol fatty acid ester only
After 8 days, 8% of the oil layer was separated, but when it contained 10% lysophosphatide, it was 2%, and when it contained 20% or more, there was almost no separation of oil even after 60 days.

(3) Surface activity test Dissolve 4g of each paste in water to make 200ml, and measure the surface tension (by Kyowa Kagaku surface tension meter CBVP, A-3) and penetration power (by Kimura's canvas disc method) at 25°C of this aqueous solution. ) was measured as the penetration time.

In the case of only polyglycerol fatty acid ester, the surface tension is 36.9 dyne/cm and the penetration time is 30 minutes or more, whereas when it contains 20% lysophosphatide, the surface tension is 31.2 dyne/cm and the penetration time is 4 minutes. 32
In the case of 40%, the surface tension was 30.8 dyne/cm and the penetration time was 3 minutes and 3 seconds.

(4) Dispersion power test of inorganic fine powder Dissolve 2 g of each paste in water to make 250 ml, put 20 ml of this aqueous solution and 1 g of titanium white for pigments into a Nessler tube, shake vigorously up and down to disperse, and then place in a room quietly. The state of dispersion and sedimentation was observed. Furthermore, after adding 5 ml of 30% saline and shaking again, the mixture was left indoors and the state of dispersion and sedimentation was observed.

In the case of only polyglycerol fatty acid ester, it flocculated and sedimented after 20 minutes regardless of whether or not saline was added, but the one containing 10% lysophosulfatide showed almost no sedimentation even after 1 hour without the addition of saline. 20%
The above results showed stable dispersion even after 1 hour regardless of whether or not saline was added.

When ultrafine calcium carbonate was tested in the same way, polyglycerol fatty acid ester alone coagulated and precipitated, and especially when saline was added,
When polyglycerin fatty acid ester was added, aggregation and sedimentation were faster than in simple saline, but those containing 20% or more of lysophosphate showed stable dispersion even after 2 hours.

Example 2 Rhizophosphatide used in Example 1 and
HLB7 polyglycerin fatty acid ester (manufactured by Sakamoto Pharmaceutical Co., Ltd., SY Glister, TS-500, main constituent fatty acid is stearic acid, degree of polymerization of polyglycerin 6) was mixed in various weight proportions to obtain a 25% by weight aqueous paste.

(1) Emulsification stability test of cosalada oil and salt water When tested in the same manner as in Example 1, 7% of the oil layer was separated after 3 days when polyglycerin fatty acid ester was used alone, but when lysophosphatide was used, 10% If it contains, it will be 1%, and if it is 20%, it will be 2% after 2 months, and 30%.
%, it was hardly recognized.

Example 3 Polyglycerol fatty acid ester of phosphatide and HLB4 used in Example 1 (manufactured by Sakamoto Pharmaceutical Co., Ltd.)
SY Glister TS-310, the main constituent fatty acid being stearic acid, and the degree of polymerization of glycerin being 4) were mixed in various weight ratios to obtain a 20% by weight aqueous paste.

(1) Emulsification stability test of corn salad oil and soy sauce When testing was carried out in the same manner as in Example 1 using 2.5 g of each paste, the emulsification was completely destroyed in 3 days when only polyglycerin fatty acid ester was used. , after 7 days if it contains 10% lysophosulfatide.
Oil separation of 10% was observed, and at 20% or more, almost no oil separation was observed even after one month.

Example 4 Lecitase 10-L was applied to defatted phospholipids obtained by acetone precipitation from commercially available soybean phospholipids, phosphatide was extracted with a mixture of isopropyl alcohol and hexane, and defatted by acetone treatment. This was extracted with alcohol to produce 52% lysophosphatidylcholine and lysophosphatidylethanolamine.
14% total lysophosulfatide and 69% phosphatide were obtained.

This rhizophosulfatide and SY Glister MS
-310 was mixed in various weight proportions to obtain a 20% by weight aqueous paste.

(1) Acid resistance and salt resistance test Same as Example 1 using 5g of each paste.
The light transmittance at 720 nm was measured.

The results showed that when only polyglycerin fatty acid ester was used, 8% (control) or separation of the surfactant was observed (acidic solution, salt solution), but when lysophosphatide was 32%, the control was 75%, and the acidic 62% in liquid solution, 45% in salt solution, 80% in control when lysophosulfatide is 41%, 74% in acidic solution, 67% in salt solution, 86% in control when lysophosulfatide is 51% , with acidic liquid
82%, and 82% for the salt solution, with no significant difference.

(2) Surface activity test When a test was conducted in the same manner as in Example 1 at the same concentration, the surface tension was 36.9 dyne/cm and the penetration time was over 30 minutes in the case of only polyglycerin fatty acid ester; When containing 15% phosphatide, surface tension is 30.8 dyne/cm, penetration time is 8 minutes 23 seconds, 32
%, the surface tension is 29.4 dyne/cm, penetration time is 3 minutes 48 seconds, and when it is 51%, the surface tension is 29.5 dyne/cm.
cm, and the penetration time was 2 minutes and 36 seconds.

(3) Emulsion stability test for corn salad oil and soy sauce When the same test was conducted at the same concentration as in Example 1, 8% of the oil layer was separated after 30 days in the case of only polyglycerin fatty acid ester, but in the case of lysophosulfatide, 8% of the oil layer was separated after 30 days. of
When the content was 15%, it was 1%, and when it was 23% or more, it was hardly observed.

(4) Dispersion power test of inorganic fine powder When the test was conducted in the same manner as in Example 1 at the same concentration, in the case of titanium white for pigments, in the case of only polyglycerin fatty acid ester, regardless of the addition of saline solution. Although it flocculated and sedimented after 20 minutes, the one containing 15% lysophosphatide had a concentration of 3% when no saline was added.
There was almost no sedimentation even after hours, and stable dispersion was shown even after 1 hour at 23% or more, even when saline was added.

In the case of ultrafine calcium carbonate, in the case of only polyglycerin fatty acid ester, it immediately coagulates and settles,
Particularly in the case of saline addition, when polyglycerol fatty acid ester was added, flocculation and sedimentation were faster than when using simple saline, but when lysophosulfatide was added at 15%
Those containing the above amount showed stable dispersion even after 2 hours when no saline solution was added, and those containing 32% or more showed stable dispersion even after 2 hours even when saline solution was added.

Example 5 Phosphosphatide and SY Glister TS- mainly composed of 45% lysophosphatidylcholine and 9% lysophosphatidylethanolamine obtained in the same manner as in Example 4, with a total lysophosphatide content of 56%.
500 in various weight proportions to form a 20% by weight aqueous paste.

(1) Emulsion stability test of corn salad oil and soy sauce When tested in the same manner as in Example 1 at the same concentration, in the case of only polyglycerol fatty acid ester, 7.
% separation of the oil layer was observed, but in the case containing 12% lysophosphatide, the separation of the oil layer was 1% after one month, and in the case containing 19% or more, almost no separation of the oil layer was observed even after 2 months.

Example 6 Adding lecitase to soybean phospholipids defatted with acetone
After allowing 10L to act, the product was treated with acetone again to remove fatty acids and dried to produce a product containing 24% lysophosphatidylcholine and 8% lysophosphatidylethanolamine, with a total lysophosphatide content.
SY Glister MS−310 with 37% phosphatide
were mixed in various weight proportions to form a 20% by weight aqueous paste.

(1) Acid resistance test The light transmittance at 720 nm was measured in the same manner as in Example 1 at the same concentration.

The results showed that when polyglycerol fatty acid ester alone was used, it was 8% (control), or separation of the surfactant was observed (acidic liquid), but when lysophosulfatide was used, it was 20%.
In the case of 48% in the control and 49% in the acidic solution, there was no difference between the control and the acidic solution when lysophosphatide was 27% or more.

Comparative Example 1 Commercially available soybean lecithin (containing 65% diacylglycerophosphatide and 35% oil) and HLB8 polyglycerol fatty acid ester were suspended in water at polymerization ratios of 30% and 60% as phosphatide content. , an aqueous paste having a concentration of 25% by weight (solid content other than oil in the aqueous paste) was obtained.

(1) Acid resistance/salt resistance test Dissolve or swell 4g of each paste in water.
200 ml, and for 1 part of this aqueous solution, add water (control),
0.2M phthalate buffer (acidic liquid) with PH3, 20%
One part of each saline solution (salt solution) was added, heated to 60°C for 10 minutes, allowed to cool, and the transmittance at 720 nm was measured.

The results showed that in acidic and salt solutions, the surfactant separated and floated regardless of the ratio of soybean lecithin to polyglycerin fatty acid ester. In water (control), polyglycerol fatty acid ester alone is 8
%, 6% for 30% soybean lecithin, and 4% for 60% soybean lecithin.

(2) Emulsification stability test of corn salad oil and soy sauce 2g of each paste, 50g of corn salad oil, and 56g of Koikuchi soy sauce were mixed using a Nippon Seiki homogenizer AM-8.
Emulsify for 6 minutes at 55°C and 13,000 rpm.
Take the emulsion in a glass cylinder and heat it to 20℃ for 8 hours.
It was stored in an incubator that cycled at 40°C for 16 hours, and its condition was observed.

30 for polyglycerol fatty acid ester only
After 8% of the oil layer separated, soybean lecithin 30%
%, the emulsification broke 10 days after emulsification, and in the case of 60% soybean lecithin, the emulsification broke 1 day after emulsification.

(3) Surface activity test Dissolve or swell 4g of each paste in water.
The surface tension of this aqueous solution at 25°C (according to Kyowa Scientific surface tension meter CBVP, A-3) is 200ml.
and penetration power (by Kimura's canvas disc method)
was measured as the penetration time.

Regardless of the ratio of polyglycerol fatty acid ester and soybean lecithin, the surface tension is 36.9 ~
It was 37.1 dyn/cm and the penetration time was 30 minutes or more.

(4) Dispersion power test of inorganic fine powder Dissolve 2 g of each paste in water to make 250 ml, put 20 ml of this aqueous solution and 1 g of titanium white for pigments into a Nessler tube, shake vigorously up and down to disperse, and then place in a room quietly. The state of dispersion and sedimentation was observed. Furthermore, after adding 5 ml of 30% saline and shaking again, the mixture was left indoors and the state of dispersion and sedimentation was observed.

Regardless of the mixing ratio of polyglycerol fatty acid ester and soybean lecithin, and regardless of the presence or absence of the addition of saline, both coagulated and precipitated within 20 minutes.

Comparative Example 2 After mixing phosphatide used in Example 1 and HLB8 polyglycerin fatty acid ester at a ratio of 3:97,
An aqueous paste having a concentration of 25% by weight (solid content in the aqueous paste) was obtained.

(1) Acid resistance/salt resistance test Dissolve 4g of each paste in water to make 200ml, and add 1 part of this aqueous solution to water (control), 0.2M phthalic acid buffer (acidic liquid) with a pH of 3, and 20% saline ( One part of each salt solution was added, heated to 60°C for 10 minutes, allowed to cool, and the transmittance at 720 nm was measured.

The results showed that the surfactant separated and floated at 8% in water (control) and in acidic and salt solutions.

(2) Emulsification stability test of corn salad oil and soy sauce 2g of each paste, 50g of corn salad oil, and 56g of Koikuchi soy sauce were mixed using a Nippon Seiki homogenizer AM-8.
Emulsify for 6 minutes at 55°C and 13,000 rpm.
Take the emulsion in a glass cylinder and heat it to 20℃ for 8 hours.
It was stored in an incubator that cycled at 40°C for 16 hours, and its condition was observed.

The results showed that 7% of the oil layer was separated after 30 days.

(3) Surface activity test 4g of each paste was dissolved in water to make 200ml, and the surface tension of this aqueous solution at 25°C (according to Kyowa Kagaku surface tension meter CBVP, A-3) and penetration power (according to Kimura's canvas disk method) ) was measured as the penetration time.

The results show that the surface tension is 36.9dyn/cm and the penetration time is
It was hot for over 30 minutes.

(4) Dispersion power test of inorganic fine powder Dissolve 2 g of each paste in water to make 250 ml, put 20 ml of this aqueous solution and 1 g of titanium white for pigments into a Nessler tube, shake vigorously up and down to disperse, and then place in a room quietly. The state of dispersion and sedimentation was observed. Furthermore, after adding 5 ml of 30% saline and shaking again, the mixture was left indoors and the state of dispersion and sedimentation was observed.

The results are 20 with and without the addition of saline.
After a few minutes, it flocculated and settled.

〔Effect of the invention〕

The effects of the present invention are that the instability in strong acid solutions and salt solutions such as common salt, which is a disadvantage of polyglycerin fatty acid esters with relatively low hydrophilicity, is improved, and a surfactant composition that can stably emulsify edible oils and fats, etc. It's because we provided it.

Another object of the present invention is to provide a relatively inexpensive surfactant composition that has improved dispersion power and penetration power, which are the weaknesses of polyglycerol fatty acid esters with an HLB of less than 9.

Claims (1)

[Scope of Claims] 1 Contains a polyglycerin fatty acid ester with an HLB of less than 9 and lysophosulfatide as essential constituents, and the weight ratio of the polyglycerin fatty acid ester and lysophosulfatide is 40/60 to 95/5.
A surfactant composition characterized in that: 2 A polyglycerin fatty acid ester with an HLB of less than 9 and a polyglycerin with a degree of polymerization of 4 or more and the number of carbon atoms
Claim 1 characterized in that it is one or a mixture of two or more of mono-, di-, and polyesters with 12 to 22 saturated and/or unsaturated fatty acids.
The surfactant composition described in . 3. Lysophosphatide (a) contains lysophosphatidylcholine as a main component, lysophosphatidylethanolamine, lysophosphatidyl inositol, lysophosphatidic acid,
It contains one or more lysophosphatides selected from the group consisting of lysophosphatidylserine, and these lysophosphatides (a) are diacylphosphatides corresponding to the lysophosphatides (a). If it further contains (b), the total amount of phosphatide [(a)
2. The surfactant composition according to claim 1, wherein the amount of lysophosphatide (a) is 30% by weight or more based on the amount of lysophosphatide (a). 4 When lysophosphatide (a) is substantially lysophosphatidylcholine (monoacylphosphatidylcholine), and the lysophosphatide (a) further contains diacylphosphatide (b) The surfactant composition according to claim 1, characterized in that the amount of lysophosphatide (a) is 30% by weight or more based on the total amount of phosphatide [(a) + (b)]. thing.