JPS6230546A - Polybasic acid type bio-surfactant emulsified composition - Google Patents

Abstract

PURPOSE:To enable the emulsification in an acidic region, by preparing a polybasic acid type bio-surfactant emulsified composition by a method wherein one or more kind of four specific compounds is compounded and the pH value of the obtained compound is adjusted to 7.0 or less. CONSTITUTION:At least one component among four components of 4,5- dicarboxy-4-pentadecanolide (spiculisporic acid) (hereinbelow, referred to as S-acid), 4,5-dicarboxy-4-pentadecanolide salt, 3-hydroxy-1,3,4-tetradecane tricar boxylic acid (hereinbelow, referred to as O-acid) prepared by opening the lactone ring of 4,5-dicarboxy-4-pentadecanolide and a salt thereof is compounded and the pH value of the obtained compound is adjusted to 7.0 or less to prepare a polybasic acid type bio-surfactant emulsified composition. As a method for adjusting the pH value to 7.0 or less, there is a method for preliminarily adjusting the amount of the base used in the saponification or neutralization of S-acid and O-acid.

Description

[Detailed Description of the Invention] [Field of Industrial Application] This invention provides a polybasic acid type biosurfactant emulsion composition that is widely used in various industrial fields such as cosmetics, pharmaceuticals, quasi-drugs, and toiletry products. It is about things.

[Conventional technology]

In recent years, much research has been conducted in relation to emulsification, new emulsifiers and emulsification technology have made remarkable progress, and highly stable emulsions have come to be widely used in various industrial fields. However, most of them use nonionic surfactants, anionic surfactants, cationic surfactants, or amphoteric surfactants as emulsifiers, and general consumers are concerned about their safety. Many people feel anxious. Also,
Higher fatty acid soaps, which are relatively safe and have a good feel when used, have been used as emulsifiers, but due to the inherent nature of soaps, the pH value of emulsifying compositions is weakly alkaline, with a pH value of 7.0 or higher. This causes problems such as skin irritation, and when applied to the skin, the foaming property is large (and the whiteness does not disappear forever, making it undesirable for use).

Furthermore, when emulsification is carried out using only a nonionic surfactant, there are problems in terms of creaming, etc., so it is desirable to use a soap-based emulsifier in combination.

[Problem that the invention seeks to solve]

As described above, conventional emulsifiers have many problems that need to be resolved, including safety, emulsion stability, and various physical properties such as feel when used.

[Means for Solving the Problems J] In order to solve the above problems, the present invention provides a salt of 45-dicarboxy-4-pentadecanolide (spicrisporic acid), 4,5-dicarboxy-4-pentadecanolide. , 4,5-dicarboxy-4-pentadecanolide with the lactone ring opened, 3-hydroxy-1,3,4-tetradecanetricarboxylic acid or a salt thereof. This method adopts a method of producing a polybasic acid type biosurfactant-based emulsified composition in which the The details will be described below.

First, 4,5-dicarboxy-4-pentadecanolide (spicrisporic acid) in this invention is a substance that is mass-produced in high yield as a metabolic product of Penicillium spicrisporum through a microbial industrial process using glucose as a raw material. It is shown by the structural formula. Below, this 4,5-dicarboxy-4-pentadecanolide (spicrisporic acid)
is abbreviated as S acid.

Such S acid has a melting point of 143-146°C and a specific optical rotation (C
=3.28 g/dl, ethanol) [σ].

=-12.6, acid value 338.2, saponification value 508. O
, 3-hydroxy-1,3,4-tetradecanetricarboxylic acid (hereinafter abbreviated as O acid) of the present invention, which has an iodine value of 0.5 or less, is added to the S acid in excess of the calculated amount. It is a substance obtained by adding an aqueous sodium hydroxide solution, heating it, and then neutralizing it with an acid, and the lactone ring of the S acid is opened to form the structural formula % Formula % Each of these salts of the S acid and the 0 acid are formed. Inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, ammonium hydroxide, calcium hydroxide, magnesium hydroxide, lithium ions, sodium ions, potassium ions, ammonium ions, calcium ions, Basic inorganic salts and basic organic salts containing magnesium ions, basic amino acids such as lysine, teruginine, histidine, ornithine, and basic oligopeptides having them as bases,
Basic amines such as monoethanolamine, jetanolamine, triethanolamine, etc. are used, but each salt may be saponified or neutralized with alcohol in advance to form a salt; It may also be a salt generated by reaction during the manufacturing process. Since it is difficult to saponify or neutralize S acid and 0 acid with water alone, alcohol is used in combination. Examples of alcohols used in this case include methanol, ethanol, propatool, butamele, etc. Monohydric alcohol, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol or higher polyalkylene glycol, or glycerin, diglycerin, Examples include triglycerin or higher polyglycerin, and polyhydric alcohols having two or more hydroxyl groups in the molecule such as glucose, maltose, maltitol, sucrose, and sorbitol, and one selected from these groups. Although there is no particular limitation as long as it is a species or a mixture of two or more species, polyhydric alcohols having two or more hydroxyl groups in the molecule are substantially used.

Therefore, an emulsified composition can be prepared by saponifying or neutralizing S acid and O acid with an alkali in a polyhydric alcohol, adding an oil phase component thereto, and further adding an aqueous phase component if necessary. However, such a method is an oil-in-polyhydric alcohol type emulsification method that has recently attracted attention, and is an extremely convenient method for obtaining the polybasic acid type biosurfactant emulsion composition of the present invention. . In addition, from the viewpoint of physiological safety for the skin, the emulsified composition of the present invention is prepared by saponifying or neutralizing the S acid and the O acid and reducing the amount of base used in order to keep the pH value to 7.0 or less. It is necessary to adjust the pH value to the desired value either by pre-adjustment or by neutralizing excess base with acid.

Now, the titration curve when S acid is neutralized with sodium hydroxide is shown in FIGS. 1 and 2, for example. 1st
The figure shows 0.200g of S acid. After partially neutralizing with an aqueous solution of sodium hydroxide IN, this was diluted to 5Qml with distilled water, and 0.5Qml was diluted with distilled water. Figure 2 shows the relationship between the titration amount and pH value when IN was titrated with an aqueous sodium hydroxide solution, and Figure 2 shows the relationship between the titration amount and pH value when IN was titrated with an aqueous sodium hydroxide solution.
．． Dissolve 200 g in ethanol aqueous solution M (4:1), dilute this with distilled water to 50 ml, and dissolve 0. This figure shows the relationship between the titration amount and pH value when IN was titrated with an aqueous sodium hydroxide solution. Furthermore, the concentration (mol/I) of the sodium salts of S and O acids and 30
The relationship with the surface tension (dyn/cm) at °C is shown in Figure 3. In other words, the critical micelle concentration of the monosodium salt of 0 acid (abbreviated as 0-INa) is 3.6.
At a critical micelle concentration of 8 x 10'M and 0.133%, the surface tension 'cm' at the critical micelle concentration is 38 dγn/cm, showing a surface activity equivalent to that of sodium lauryl sulfate at a critical micelle concentration of 8 x 10'M and 0.24%. , the critical micelle concentration of S acid monosodium salt (S-INa) is 3.9
X 10 M, 0.14%, which is slightly higher than the above-mentioned 0-INa, and the surface tension γcmc is 32 dyn/cm. The surface occupied area of the molecule is 96.0λ2 for 0-INa,
S-INa has 98.8A, which is almost the same, but it is much larger than the sodium lauryl sulfate, which has a surface area of 52 Q2 per molecule, indicating that it is bulky. It is therefore clear that the sodium salts of S and O acids are fatty acid soap type emulsifiers with surface activity comparable to sodium lauryl sulfate.

Next, the foaming power of the sodium salt of S acid (foam volume m+
As is clear from Table 1, when comparing the change over time of S acid with that of sodium lauryl sulfate,
Table - Sodium salt (S-INa), same disodium salt (S-INa)
S-2Na) and the same trisodium salt (S-3Na
) are far less foaming than sodium lauryl sulfate, which confirms that the emulsified composition of the present invention does not turn white when applied to the skin. And S-2N
A skin irritation test of aQ, 5% solution was conducted on 20 healthy female adults. When purified water was used as a control sample and evaluated according to Japanese standards, no skin irritation was observed, as was the case with purified water as a control sample. As mentioned above, although S-2Na has a surfactant ability comparable to that of sodium lauryl sulfate, the reason why it is not irritating to the skin is that it is weakly acidic and the carbon content of S-2Na is weakly acidic. This is thought to be due to the fact that the number of carbon atoms is 17, which is greater than the 12 carbon atoms of lauryl sulfate.

Furthermore, the oil phase component used in this invention is a liquid or semi-solid (grease) hydrocarbon such as liquid paraffin, squalane, petrolatum, or octyldodecyl myristate, inpropyl palmitate, cetyl-2
-Ethylhexanoate, glyceryl tri-2-ethylhexanoate, vitamin E acetate, vitamin A
Ester oils such as palmitate, vitamin C stearate, waxes such as solid paraffin, microcrystalline wax, ceresin wax, beeswax, spermaceti, or olive oil, soybean oil, safflower oil, rice bran oil, almond oil, jojoba oil vegetable oils and fats such as mink oil, animal fats and oils such as mink oil, tardle oil, higher alcohols such as cetanol, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, octyldodecanol, behenyl alcohol, lauric acid, myristic acid, palmitic acid, stearin Acids, higher fatty acids such as oleic acid, linoleic acid, lyluic acid, and isostearic acid, and silicone oil rings such as dimethyl silicone, methylphenyl silicone, and cyclic silicone. It is an oil phase component that is commonly used in
More than one species may be selected and used as appropriate.

On the other hand, the aqueous phase component in this invention refers to the above-mentioned polyhydric alcohol (polyhydroxy compound) having two or more hydroxyl groups in the molecule, as well as those commonly used in the fields of cosmetics, pharmaceuticals, quasi-drugs, toiletry products, etc. It is a widely used water-soluble ingredient. Depending on the purpose of use, the emulsion composition of the present invention may include conventionally used nonionic surfactants, anionic surfactants, amphoteric surfactants, cationic surfactants, lecithin, casein, sodium caseinate, etc. Even when combined with synthetic or natural surfactants such as saponin,
Furthermore, various additives that have been widely used in the past, such as medicinal substances, ultraviolet absorbers, preservatives and sterilizers, antioxidants, flavorings, colorants, and thickening stabilizers made of water-soluble polymers, may be added as appropriate. do not have.

Since the emulsified composition of the present invention is a transparent or translucent homogeneous gel or viscous fluid, it can be used as it is for cosmetics such as sun care jelly, beauty serum, medicated gel I7-, pine surge jelly, etc., and quasi-drugs. Not only can it be used in all kinds of fields, but by adding aqueous components, it can be used in all kinds of fields, including cosmetics such as emulsions, creams, and foundations, toiletry products such as shampoos and conditioners, and external medicines such as acne creams. It is possible.

〔Example〕

Example 1: 10 parts of Stuff 2 as an oil phase component (parts by weight, the same applies hereinafter)
, octyldodecyl myristate 15 parts, semenol 2
1 part of potassium salt of spicrysporic acid and 20 parts of glycerin were dissolved at 75°C (referred to as phase B).
A liquid obtained by heating and dissolving 1 and 2 parts at 75℃ (referred to as phase addition)
The mixture was thoroughly mixed with a homomixer, 52 parts of purified water at 75°C (referred to as phase C) was added as an aqueous phase component, and the mixture was stirred and cooled to 40°C to form an emulsified composition. Obtained. Observe the state of the obtained emulsified composition, and
pH value and viscosity (cp), particle size (μm) at °C
The emulsion stability after 7 days at 45°C was determined and summarized in Table 2.

Table 2 Example 2: An emulsion composition was obtained by exactly the same formulation and operation as in Example 1, except that the disodium salt of spicrisporic acid was used instead of the -potassium salt of spicrisporic acid. The properties of this emulsified composition are also listed in Table 2.

Comparative Example 1: An emulsion composition was prepared in exactly the same manner as in Example 1 except that sodium stearate was used instead of the -potassium salt of spicrisporic acid, but the particle size was changed as shown in Table 2. It was large, had poor stability, and caused a separation phenomenon.

Comparative Example 2: An attempt was made to prepare an emulsified composition using the same procedure as in Example 1, except that the -potassium salt of spicrisporic acid was not used and the amount of purified water was 53 parts, but emulsification could not be achieved. Ta.

Example 3: (Phase A) Spicrisporic acid 1.3 parts Glycerin 81. 3-Butylene glycol Potassium dihydroxide (50% aqueous solution) 0.5 (Phase B) Squalane 10 Olive oil 5 Methyl paraoxybenzoate 0.1 Paraoxy Propyl benzoate 0.1 (phase C) Purified water 72.7 Sodium hyaluronate 0.1 Bovine suntan gum o, part i Epsilon aminocaproic acid 0.1 Same operating procedure as Example 1, i.e. the above B dissolved at 75°C phase, 7
Add the above phase A dissolved with stirring at 5°C while stirring,
After homogenizing with a homomixer, 75 was prepared separately.
C. phase C was added, diluted and dispersed, and the mixture was stirred and cooled to 40.degree. C. to obtain an emulsion. This emulsion had a pH value of 4.82, a viscosity (at 25° C.) of 2700 CP, did not turn white when applied to the skin, was stable, and had a good feeling of use.

Example 4: (Phase A) Spicrisporic acid 5 parts Glycerin 15 Potassium hydroxide (50% aqueous solution) 0.7 (Phase B) Squalane 13 Jojoba oil 2 Octyldodecyl myristate 5 White beeswax 2 parts Behenyl alcohol 3 Stearic acid
6 (C phase) Purified water 47.9
Epsilon aminocaproic acid 0.
1 Water-soluble collagen 0
．． 1 Yokuinin extract 0
．． 1 chamomile extract 0.
1 A skin cream was obtained through the same operating procedure as in Example 3. This skin cream had a pH value of 4.61, did not turn white when applied to the skin, was stable, and had an extremely good feel on use.

Example 5 (Phase A) White petrolatum 25 parts Stearyl alcohol 22 Propylene glycol 12 Disodium spicrisporic acid salt 1.5 Ethyl paraoxybenzoate 0.025 Propyl paraoxybenzoate o, ois part (Phase B) Chlorhexidine gluconate (2 <)% solution) 1
Purified water 38.46 According to the method for producing hydrophilic ointment in the Japanese Pharmacopoeia, revised by Deshi, dissolve the human phase by heating to prepare a mixture at 75°C. To this, phase B ingredients heated to the same temperature are added with stirring, A medicated hydrophilic ointment was obtained by cooling. The pH value of this ointment was 5.80, and when compared with sodium lauryl sulfate, which is used as an emulsifier in the Japanese Pharmacopoeia, it did not appear white when applied to the skin.
The usability was also good.

Example 6 (Phase A) Spicrisporic acid dipotassium salt 1.5 parts Glycerin 15 Maltitol (75% aqueous solution) 15 (Phase B) Squalane 50 Jojoba oil 17.5 Natural vitamin E acetate 0.3 parts Vitamin A palmitate 0 ．．
Methyl 2-paraoxybenzoate 0.1
(Phase C) Elastin extract 0.1 Water-soluble Placenku 0.1 Water-soluble collagen 0.1 Scalp extract 0.1 Stir the A phase dissolved in a solution at room temperature, and add the B phase at room temperature to this. Then, phase C was added and stirred, and when the mixture became uniform, the stirring was stopped to obtain a cosmetic jelly. The pH value of this beauty jelly is 5°60 and the viscosity (25°C) is 82.
50 Cp, and was a transparent jelly with a good feeling of use.

〔effect〕

The polybasic acid-type biosurfactant-based emulsifying composition of the present invention described above enables emulsification in an acidic region, which conventional soap emulsifiers cannot achieve, improves skin physiological safety, and alleviates consumer anxiety. It is clear that the emulsion composition is extremely safe and has excellent stability without causing any adverse effects. In addition, although the surface activity of polybasic biosoap is comparable to that of sodium lauryl sulfate, its foaming properties are low and when the emulsified composition is applied to the skin, it does not turn white like conventional soap emulsifiers. The feeling is extremely good. Furthermore, unlike synthetic surfactants, it has good biodegradability, so it can be said that the emulsified composition of the present invention is extremely significant.

[Brief explanation of drawings]

Figures 1 and 2 show the titrator and pH when spicrisporic acid was titrated with a 0°IN sodium hydroxide aqueous solution.
Relationship with values (Figure 1 shows the case where the diluent of spicrisporic acid is only distilled water, and Figure 2 shows the case where the diluent is an ethanol aqueous solution)
FIG. 3 is a diagram showing the relationship between the concentration and surface tension of the sodium salt of spicrisporic acid and the sodium salt of 3-hydroxy-1,3,4-tetradecanetricarboxylic acid. S...spicrisporic acid, O...3-hydroxy-1,3,4-tetradecanetricarboxylic acid, lNa.
...-sodium salt, 2Na... disodium salt, 3
Na...trisodium salt

Claims (1)

[Claims] 4,5-dicarboxy-4-pentadecanolide (spicrisporic acid), salt of 4,5-dicarboxy-4-pentadecanolide, 3-hydroxy-opened lactone ring of 4,5-dicarboxy-4-pentadecanolide 1,3
, 4-tetradecanetricarboxylic acid or its salt, and has a pH value of 7.0.
A polybasic acid type biosurf actant emulsion composition characterized by the following: