JPS6351930A - Surfactant composition - Google Patents

Abstract

PURPOSE:To improve acid resistance, salt resistance and penetration force, by preparing a surfactant by setting the compounding wt. ratio of sugar fatty acid ester with HLB of below 10 and lysophosphatide being essential components to 40/60-95/5. CONSTITUTION:Sugar fatty acid ester with HLB of below 10 and lysophosphotide are compounded in a compounding wt. ratio of 40/60-95/5 to prepare a surfactant composition. As a concrete method for preparing the surfactant composition, when lysophosphatide high in saturated fatty acid content is used, sugar fatty acid ester and said phosphatide may be mixed in a powder form and, when lysophosphatide high in unsaturated fatty acid is used, a method for preparing an aqueous solution or paste of the mixture consisting of said phosphatide and sugar fatty acid ester can be employed. As sugar fatty acid ester, a mixture of 12-22C saturated and/or unsaturated fatty acid and mono, di- or polyester of sucrose is pref.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] 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 sucrose fatty acid esters.

[Problems to be solved by the prior art and the invention] Sucrose fatty acid esters can be used as surfactants with a wide range of water injection/lipophilicity balances (HLB) depending on the type and number of fatty acids bonded to sucrose. It is widely used in foods, cosmetics, etc. as a surfactant that exhibits properties such as dispersion, solubilization, penetration, and foaming, and is a surfactant that has good biodegradability and is recognized as safe.

In particular, sucrose fatty acid esters with an HLB of 5 to 10 are suitable for oil-in-water emulsification of edible fats and oils, and those with an HLB of 3 to 5 are suitable for water-in-oil emulsification.

However, although sucrose fatty acid ester is a nonionic surfactant, it cannot be used in acidic (for example, pH 5 to 6) aqueous solutions or inorganic salt water such as common salt. 8 liquid (e.g. salt concentration 1
%), it will solidify easily and the surface active effect will be weakened.

In foods, etc., there are many aqueous solutions of this level, which narrows the range of applications of sucrose fatty acid esters.

In order to improve this point, a method of adding a small amount of sodium lauryl sulfate (Shokuhin Kogyo, late March 1965 issue, p. 95)
has been proposed, but although it is effective for acidic aqueous solutions, it is ineffective for salt water i8J.

[Means for solving problems]

The purpose of the present invention is to improve the above-mentioned drawbacks of sucrose fatty acid esters with a lower HLBIO, and improve acid resistance, salt resistance, and ? ! An object of the present invention is to provide a surfactant composition with improved I penetration power, etc.

The surfactant composition of the present invention contains 1 as an essential component.
(It contains less than LBIO of sucrose fatty acid ester and lysophosphatide, and the weight ratio of the sucrose fatty acid ester and lysophosphatide is 40/60 to 9515, preferably 40/60 to 80/20. It is something to do.

HLBI, which is one of the essential components of the composition of the present invention
The sucrose fatty acid ester having a carbon atom number of less than 12
A mixture of one or more of mono-, di-, and polyesters of ~22 saturated and/or unsaturated fatty acids and sucrose is preferred; in the case of sucrose fatty acid esters of fatty acids with 11 or less carbon atoms, emulsifying power is weak, etc. They are less useful, the effect of the addition of lysophosphatides of the present invention is not very visible, and fatty acids having 23 or more carbon atoms are not very common.

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

Lysophosphatide derived from natural products is known to exist together with diacylphosphatide in living organisms, for example, it is contained in the lipids of grains such as soybeans, rapeseed, and wheat, and the lipids of animal cells. In addition, phospholipase A-2 from pig pancreatic juice or snake venom or phospholipase A-1 from bacteria is allowed to act on diacylphosphatide in animal lipids such as egg yolk and seed lipids such as soybean. It can also be produced by hydrolyzing, removing the generated fatty acids with acetone, etc., and purifying with silica gel chromatography, etc., if necessary.
JP-A No. 46-13263, No. 52-136966, No. 5
8-51853), 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 oxidative stability can be obtained.

Also, Journal of American Oil ') Mistso → Noi 7 Tei 1981 IO issue 886-88
On page 8, it is described that lysophosphatides of various compositions can be obtained by variously changing the conditions under which phospholibase 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 as a raw material. Others, Journal of Biological Chemistry, Vol. 188, 471-47
Method for obtaining phosphatidylcholine from egg yolk as described in page 6 (1951), Japanese Patent Publication No. 60-16, No. 59-4265.
The method of obtaining phosphatidylcholine by the method described in No. 5, No. 57-123496 and No. 56-23997 can also be applied to the present invention. The optical activity of such natural lysophosphatide is levorotatory, and the safety of oral administration to animals has been confirmed (Journal Science of Food and Agriculture, Vol. 32, 451). ~458 pages).

Also, analysis of phosphatides used in the present invention? Examples of the method for removing ζ include the thin layer chromatography method, the TLC-FID method (Iatoscan method), and the 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. , the lysophosphatide (a) may further contain sophosphatidylethanolamine, and a small amount of lysophosphatidyl inositol, lysophosphatidic acid, and lysophosphatidylserine. may contain one or more lysophosphatides.

Furthermore, when producing lysophosphatide (a) from natural products, due to the characteristics of the production method, the above-mentioned lysophosphatide (a) is usually used.
It often contains dianlphosphatide (b) corresponding to a), but when it contains these, the total amount of phosphatide (13i(b)) is compared to lysophosphatide (a).
) is preferably 30% by weight or more because it remains effective even in acidic liquids, and in particular, if it is 40% by weight or more, there is a high level of 'run' property. Even a 1 degree saline solution is effective.

Generally, the larger the amount of lysophosphatide relative to the total amount of phosphatide, the smaller the amount of lysophosphatide used tends to be.

In the composition of the present invention, PtJ! The blending ratio of fatty acid ester and lysophosphatide is 40/60 by weight.
9515, preferably 40/60 to 80/20.

If the content of lysophosphatide is less than 5%, the improvement effect of the present invention will not be obtained, and if the content is in the range of 5 to 10%, low level saline solution,
Although it is possible to emulsify oils and fats in water containing proteins, gums, etc. with an acidic solution that is not relatively low in p)l, it is preferably 109A or higher; on the other hand, lysophosphatide is 60% If the amount is larger, the performance will not particularly deteriorate, but it will become expensive, which is not preferable.

The method for obtaining the composition of the present invention is not particularly limited, but for example, lysophosphatide containing a large amount of saturated fatty acids may be mixed with sucrose fatty acid ester in powder form (or lysophosphatide containing a large amount of unsaturated fatty acids may be mixed with the powder). Then, there are methods such as preparing an aqueous solution or aqueous paste of a mixture with sucrose fatty acid ester, dissolving it in a solvent such as alcohol, or dissolving it and then drying it to use it as a powder.

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, fermentation holes in 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.
Emulsification of oily substances such as vegetable essential oils and paraffin, dispersion of cocoa powder, instant food powder, spices such as mustard powder and wasabi powder, fungicides such as butyl paraoxybenzoate, various pigment powders, etc., or the dispersion of these powders. The composition of the present invention dissolved in water, alcohol, etc. can be coated on a powder or the like by impregnating or spraying to make it easily dispersible in water.

〔Example〕

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

The percentage of lysophosphatide in each test for each aqueous paste (including the composition of the present invention) obtained in each example is calculated in terms of pure content, and is the value based on the total amount of sucrose fatty acid ester and lysophosphatide. . Furthermore, the term "phosphatide" means a composition containing lysophosphatide and diacylphosphatide.

Example 1 A phosphatide 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 silicate alcohol to obtain 95% lysophosphatidylcholine, 2% lysophosphatidylethanolamine, and 97% total sophosphatide content.
of phosphatide was obtained.

This phosphatide and sucrose fatty acid ester of HLB7 (
Ritto Sugar Ester S-7 manufactured by Mitsubishi Kasei Foods ■
70, the main constituent fatty acid being stearin a) was mixed in various weight proportions to obtain a 20% by weight aqueous paste.

+11 Acid resistance and salt resistance test Add water to 2.5 g of each paste to make 100 ml,
To 1 volume part of this aqueous solution, 1 volume part of 0.2 morphthalic acid buffer having a pH of 3 was added (acidic solution) to which 1 volume part of 20% saline was added (salt solution) to which 1 volume part of water was added (control) ), heated to 60°C for 10 minutes, and then allowed to cool indoors.

When only sucrose fatty acid ester was used, acid and salt caused immediate flocculation and precipitation, but when lysophosphatide was 10 to 60%, white turbidity progressed slowly, and when lysophosphatide was 10 to 60%, there was almost no white turbidity. In addition, the light transmittance at 720 nm after 1 day was 42% for the control in the case of sucrose fatty acid ester only, and 0% in the case of acidic solution and salt solution (both acidic and salt solutions generate precipitates, so the precipitates are redispersed and measured). However, 40% of lysophosphatide
96% for the control when lysophosphatide is 60%, 59% for the salt solution, 99% for the control when lysophosphatide is 60%, and 5% for the acidic solution.
1%, and 94% in the base solution.

(2) Emulsification stability test of liquid paraffin and saline solution 2.5g of each paste, 35ml of liquid paraffin 1.5% saline solution 5
5 ml was emulsified using a Nippon Seiki homogenizer AM-8 at 45° C. and 12,000 rpm for 5 minutes. The emulsion was placed in a glass cylinder and stored in an incubator that cycles between 20°C and 35°C every 12 hours, and its condition was observed.

The period until the oil layer of 2% by volume was separated from the entire emulsified system was 1 day in the case of only sucrose fatty acid ester, but
Contains 10% lysophosphatide, 10 days, 2
17th if it contains 0%, 28th if it contains 30%, 50th
%, it was 42 days. In addition, when 0.25 g of lysophosphatide alone is added (same as the amount of lysophosphatide in the composition of the present invention containing 50% lysophosphatide, 7 degrees), it takes 6 days, and sucrose fatty acid ester The effect of combined use was observed.

(3) Emulsification stability test of corn salad oil and soy sauce 2.5 g of each paste, 50 g of corn salad oil, 1 koi (chi soy sauce 56
g at 55°C using a Nippon Seiki homogenizer AM-8.
Emulsify at 13000 rpm for 6 minutes. The emulsion was placed in a glass cylinder and stored in an incubator that cycled at 20°C for 8 hours and 40°C for 16 hours, and its condition was observed.

The period until the 2% oil layer separates is 4 days in the case of only sucrose fatty acid ester, and the emulsified particles in the emulsified creaming layer aggregate and cannot be redispersed even by shaking, and emulsification is completed after 21 days. was destroyed. 14 days if it contains 10% lysophosphatide, 60 days if it contains 20% or more
The redispersibility of the subsequent creaming layer was also good.

(4) Surface activity test Dissolve 5 g of each paste in water to make 200 ml. The surface tension of this aqueous solution at 25°C (according to the Kyowa Kagaku surface tension meter CBVP, A-3) and the penetrating power (according to the wood method campus disk method) ) was measured as the penetration time.

In the case of only sucrose fatty acid ester, the surface tension is 34.8d.
yne/cm, penetration time is more than 30 minutes,
When containing 20% lysophosphatide, the surface tension is 3
The surface tension was 1.5 dyne/am, the penetration time was 6 minutes 48 seconds, and when the content was 40%, the surface tension was 3Q, 9 dyne/am, and the penetration time was 4 minutes 59 seconds.

Example 2 HLB was added to 30 parts by weight of phosphatide used in Example 1.
Corn was prepared in the same manner as in Example 1 using a 20% by weight aqueous paste containing 70 parts by weight of sucrose fatty acid ester of No. 9 (manufactured by Mitsubishi Kasei Foods ■, Ryoto Sugar Ester S-970, the main constituent fatty acid being stearic acid). Emulsion stability tests were conducted on salad oil and soy sauce.

The period until the 2% oil layer separates is 7 days in the case of only sucrose fatty acid ester, and the emulsified particles in the emulsified creaming layer aggregate and cannot be redispersed even by shaking, and emulsification is completed after 21 days. was destroyed. When lysophosphatide was included, there was no oil separation even after 60 days, and the redispersibility of the creaming layer was good.

Further, a similar emulsification test was conducted by replacing the soy sauce with reduced orange juice having a pH of 3.5.

The period until the 2% oil layer separated was 35 days when using only sucrose fatty acid ester, but when lysophosphatide was included, there was no oil separation even after 60 days, and the redispersibility of the creaming layer was also improved. It was good.

Example 3 30 parts by weight of phosphatide used in Example 1 and HLB
In the same manner as in Example 1, using a 20% by weight aqueous paste containing 70 parts by weight of sucrose fatty acid ester of No. 5 (Mitsubishi Kasei Foods type, Ryoto Sugar Ester S-550, main constituent fatty acid is stearic acid). Corn salad oil/
When we conducted an emulsion stability test on soy sauce, we found that when using only sucrose fatty acid ester, 2% oil separated after 4 days and the emulsion was destroyed after 15 days, but when it contained lysophosphatide, it took 60 days. Afterwards, only 1% of the oil layer was separated.

In addition, when a similar emulsification test was conducted by replacing soy sauce with reduced orange juice with a pH of 3.5, 2% of the oil was separated after 8 days in the case of only sucrose fatty acid ester, and the emulsification was destroyed after 21 days. However, if it contains lysophosphatide, it is 60
There was no separation of the oil layer even after several days.

Example 4 Defatted phospholipid was obtained by acetone precipitation from soybean phospholipid,
After treating this with recitase IOL, phosphatide is extracted with a mixed solvent of isopropyl alcohol and hexane, and the mixture is treated with acetone to remove fat. This was extracted with alcohol to obtain phosphatide containing a large amount of lysophosphatide. This phosphatide paste contains 52% zophosphatidylcholine and 11% lysophosphatidylethanolamine.
The total zophosphatide content was 169%.

This phosphatide and HLB5 IF, It! A 20% by weight aqueous paste was obtained by mixing fatty acid ester (manufactured by Mitsubishi Kasei Foods ■, Rirato Sugar Ester S-570, the main constituent fatty acid being stearic acid) in various weight proportions.

Emulsion stability tests for corn salad oil and soy sauce were conducted in the same manner as in Example 1 using each paste.

Those containing 11% by weight of lysophosphatide are 15% by weight.
Although the redispersibility and uniformity of the creaming layer were inferior to those containing lysophosphatide, almost no oil separation was observed even after 60 days, and of course when lysophosphatide was more than 15% by weight, Even after several days, almost no oil separation was observed.

Example 5 The phosphatide used in Example 4 and Yoto Shegar Ester 5-770 were mixed in various weight proportions to obtain a 20% by weight aqueous paste.

60g of each paste, 600g of rapeseed salad oil, and 400g of Koikuchi soy sauce were pre-emulsified by heating and stirring, and the first stage pulp was 300kr/ca using a Manton-Gorlin homogenizer model 15M-8BA! , 2nd stage valve 20kg/-
The mixture was homogenized twice at 40° C. to obtain an emulsion. Each emulsion was left at 40°C for 60 days and the stability of the emulsion was observed.

In the case of only sucrose fatty acid ester, 5% of the oil layer was separated in 2 days, but in the case of containing 11% of lysophosphatide, 60% of the oil layer was separated in 2 days.
Even after several days, only a small amount of oil separated, but in the case of 23% and 41% lysophosphatide, there was no separation of oil, creaming amplitude was slow, and good redispersibility was exhibited.

In addition, 5 g of each paste was dissolved in water to make 200 ml, and the surface tension and penetration power of this aqueous solution at 25°C were determined according to Example 1.
It was measured in the same way.

In the case of only sucrose fatty acid ester, the surface tension is 34.1L.
dyne/cm, penetration time is 30 minutes or more, whereas when 15% lysophosphatide is contained, the surface tension is 31.5 dyne/cm, penetration time is 9 minutes 53 seconds, 31.
When containing 5%, the surface tension is 29.6 dyne/am,
Penetration time 4 minutes 25 seconds, surface tension 2 when containing 51%
9.8 dyne/cm, penetration time is 2 minutes 23
Improvement in surfactant ability was observed.

In addition, each base) Ig was dissolved in water to make 100 ml, and 20 ml of this aqueous solution and titanium white for pigments or ultrafine calcium carbonate Ig were placed in a Nessler tube, shaken vigorously up and down to disperse, and then dissolved in 30% saline. After adding 5 ml and shaking again, leave it in the room for dispersion and sedimentation.
I guessed it.

In the case of only sucrose fatty acid ester, the mixture immediately coagulated and precipitated, but in the case of containing 23% or more of lysophosphatide, it remained stably dispersed even after 3 hours.

Example 6 Lysophosphatidylcholine 45 was prepared in the same manner as in Example 4.
%, lysophosphatidylethanolamine was the main component, and phosphatides with a total zophosphatide content of 56% were obtained.

This phospheptide sheet sugar ester S-
970 in various weight proportions to obtain a 20% by weight aqueous paste.

Using this paste, an emulsion stability test of corn salad oil and soy sauce was conducted in the same manner as in Example 1.

The time it took for the 2% oil layer to separate was 7 days in the case of sucrose fatty acid ester only, and the emulsification was broken after 21 days, but in the case of 12% or more lysophosulfate, the emulsification remained even after 60 days. There was almost no oil separation, and the redispersibility was good when the content was 19% or more. Example 7 Soybean phospholipids defatted with acetone were treated with 10 L of recitase, and fatty acids were removed by acetone treatment again. was dried to obtain phosphatides mainly containing 24% lysophosphatidylcholine and 8% lysophosphatidylethanolamine, with a total zophosphatide content of 37%.

This phosphatide and yoto shegar ester S-
770 in various weight proportions to obtain a 20% aqueous paste.

Dissolve 2.5g of this paste in water to make 100ml,
Using this, an acid resistance test was conducted in the same manner as in Example 1.

In the case of only sucrose fatty acid ester, it immediately coagulated and precipitated, but in the case of 8.5% or more of lysophosphatide, the white turbidity was only slightly increased.

The light transmittance at 720 nm after 1 day is 9% of lysophosphatide.
control 71%, acidic) night 41%, lysophosphatide 14% control 68%, acidic solution 45%, lysophosphatide 20% control 64%, acidic solution 50%, lysophosphatide 27% The control was 62%, the acidic solution was 56%, and the lysophosphatide was 36%, whereas the control was 57% and the acidic solution was 62%.

In addition, as a result of conducting a juice/corn salad oil emulsion stability test in the same manner as in Example 1 using each of the above pastes, it was found that in the case of only sucrose fatty acid ester, there were 2 separated oil layers after 21 days.
%, but when containing 11% lysophosphatide, only slight oil separation was observed even after 60 days, and when containing 20% or more of lysophosphatide, 60%
Even after several days, almost no oil separation was observed, indicating stable emulsification.

〔Effect of the invention〕

The effect of the present invention is to provide a surfactant composition that has improved instability in acidic solutions and salt solutions, which is a drawback of sucrose fatty acid esters.

Another advantage of the present invention is that it provides a surfactant that is inexpensive and has good performance by combining sucrose fatty acid ester and lysophosphatide.

Procedural amendment July 1, 1988 1, Indication of the case Japanese Patent Application No. 141627/1981 2, Name of the invention Surfactant composition 3, ? ! Relationship with the case of a person making a correction Patent applicant (038) Asahi Denka Kogyo Co., Ltd. 4, Representative F Kojin, 6-29 Akasaka 9-chome, Minato-ku, Tokyo Voluntary amendment (amendment within 1 year and 3 months from the patent filing date) )6,?
! Detailed description of the invention in the positive subject specification.

7. Contents of the amendment +11 Page 4, lines 12-13 and Page 8, lines 13-14
Corrected 80/20J to r90/10J respectively.

B 24- January 1988 Commissioner of the Patent Office Kuro 1) Akio Tono 2, Name of the invention Surfactant composition 3, Relationship with the person making the amendment Patent applicant (038) Asahi Denka Kogyo Co., Ltd. Nippon Shoji Co., Ltd. 4, Agent: 6-29 Akasaka 9-chome, Minato-ku, Tokyo, Bashifi, No. 601, Rinogizaka Voluntary amendment (amendment within 1 year and 3 months of filing) 6: Invention of the specification subject to amendment Detailed explanation field.

7. Contents of correction

Claims (4)

[Claims] (1) Contains sucrose fatty acid ester with an HLB of less than 10 and lysophosphatide as essential components, and the weight ratio of the sucrose fatty acid ester and lysophosphatide is 40/6.
A surfactant composition characterized in that the ratio is 0 to 95/5. (2) A patent characterized in that the sucrose fatty acid ester with an HLB of less than 10 is one or a mixture of two or more of mono-, di-, and polyesters of saturated and/or unsaturated fatty acids having 12 to 22 carbon atoms and sucrose. A surfactant composition according to claim (1). (3) Lysophosphatide (a) contains lysophosphatidylcholine as a main component, lysophosphatidylethanolamine, and lysophosphatidylinositol, lysophosphatidic acid, and lysophosphatidylserine. The lysophosphatide (a) further contains a diacylphosphatide (b) corresponding to the lysophosphatide (a). In the case of a surfactant according to claim (1), the amount of lysophosphatide (a) is 30% by weight or more based on the total amount of phosphatide [(a) + (b)]. agent composition. (4) When lysophosphatide (a) is substantially lysophosphatidylcholine (monoacylphosphatidylcholine), and the lysophosphatide (a) further contains diacylphosphatide (b) is the ratio of lysophosphatide (a) to the total amount of phosphatide [(a) + (b)].
) is 30% by weight or more, the surfactant composition according to claim 1.