JPH0510969B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a polybasic acid type biosurfactant emulsion composition that is widely used in various industrial fields such as cosmetics, pharmaceuticals, quasi-drugs, and toiletry products. [Prior art] In recent years, a large number of studies have been conducted related 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 that way. In addition, 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 properties of soaps, the PH value of emulsified compositions is low.
It is weakly alkaline with a value of 7.0 or higher, which causes problems such as skin irritation, and when applied to the skin, it has a large foaming property and the whiteness does not disappear forever, making it undesirable for use. Furthermore, when emulsifying with only a nonionic surfactant, there are problems in terms of creaming, etc., so it is desirable to use a soap-based emulsifier in combination. [Problems to be Solved by the Invention] As described above, conventional emulsifiers have had many problems that need to be solved, including safety, as well as various physical properties such as emulsion stability and usability. [Means for Solving the Problems] In order to solve the above problems, the present invention includes 4,5-dicarboxy-4-pentadecanolide (spicrisporic acid) and 4,5-dicarboxy-4-pentadecanolide as oil phase components. - Adding at least one component of the following four components: a salt of pentadecanolide, 3-hydroxy-1,3,4-tetradecanetricarboxylic acid ring-opened with the lactone ring of 4,5-dicarboxy-4-pentadecanolide, or a salt thereof; This method adopts a method of preparing a polybasic acid type biosurfactant emulsion composition by adjusting the pH value to 7.0 or less. 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 metabolite of Penicillium spicrisporum through a microbial industrial process using glucose as a raw material, and has the constitutive formula: It is indicated by. Below, this 4,5-dicarboxy-4
-S pentadecanolide (spicrisporic acid)
Abbreviated as acid. Such an S acid has a melting point of 143-146°C, a specific optical rotation (c = 3.28 g/dl, ethanol) [α] ²⁶ _D = -12.6,
It has an acid value of 338.2, a saponification value of 508.0, and an iodine value of 0.5 or less. Next, 3-hydroxy-1,3,4 of this invention
-Tetradecanetricarboxylic acid (hereinafter abbreviated as O acid) is a substance obtained by adding an excess of sodium hydroxide aqueous solution than the calculated amount to the S acid, heating it, and neutralizing it with acid, and it is a lactone of S acid. Structural formula with open ring It is indicated by. To form the respective salts of such S and O acids, an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, ammonium hydroxide, calcium hydroxide, magnesium hydroxide; Basic inorganic salts and basic organic salts containing lithium ions, sodium ions, potassium ions, ammonium ions, calcium ions, and magnesium ions, basic amino acids such as lysine, arginine, histidine, ornithine, and basic oligos having these as bases. Peptides, basic amines such as monoethanolamine, diethanolamine, 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 produced by reaction during the manufacturing process. Note that it is difficult to saponify or neutralize S acid and O acid with water alone, so alcohol is used in combination. Examples of alcohols used in this case include methanol,
Monohydric alcohols such as ethanol, propanol, butanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,
4-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol or higher polyalkylene glycols, or glycerin, diglycerin, triglycerin or higher polyglycerols, as well as glucose, maltose, maltitol, sucrose, sorbitol, etc. Polyhydric alcohols having two or more hydroxyl groups in the molecule are not particularly limited as long as they are one or a mixture of two or more selected from these groups. Specifically, polyhydric alcohols having two or more hydroxyl groups in the molecule are used. Therefore, the S acid and the O acid are saponified or neutralized with an alkali in a polyhydric alcohol, and an oil phase component is added thereto, and if necessary, an aqueous phase component is added to prepare an emulsified composition. However, such a method is an oil-in-polyhydric alcohol 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. It is. In addition, the emulsified composition of this invention has a PH of
In order to keep the value below 7.0, the amount of base used to saponify or neutralize the S acid and O acid is adjusted in advance, or the excess base is neutralized with acid to achieve the desired PH value. It is necessary to arrange it. Now, the titration curve when S acid is neutralized with sodium hydroxide is shown in FIGS. 1 and 2, for example. Figure 1 shows the titer when 0.200g of S acid is partially neutralized with 0.1N aqueous sodium hydroxide solution, diluted to 50ml with distilled water, and titrated with 0.1N aqueous sodium hydroxide solution. Figure 2 shows the relationship between PH values and the titration when 0.200 g of S acid is dissolved in an aqueous ethanol solution (4:1), diluted to 50 ml with distilled water, and titrated with a 0.1N aqueous sodium hydroxide solution. The relationship between the amount and the PH value is shown. Furthermore, the concentration (mol/) of sodium salts of S acid and O acid and the surface tension at 30 °C
dyn/cm) is shown in Figure 3. That is, the monosodium salt of O acid (O-1Na
) has a critical micelle concentration of 3.6×10 ^-3 M,
Surface tension _cnc at critical cemil concentration at 0.133%
is 38dyn/cm, and the critical cemil concentration is 8×
10 ^-3 M, 0.24% sodium lauryl sulfate, and has a surface activity similar to that of the monosodium salt of S acid (S-
The critical micelle concentration of 1Na) is 3.9×10 ^-3 M, 0.14%, which is slightly higher than the above O-1Na, and the surface tension _cnc is
It is 32dyn/cm. The surface area occupied by the molecule is O-
96.0 Å ² for 1Na and 98.8 Å ² for S-1Na, which are almost the same, but the surface area of one molecule is much larger than that of sodium lauryl sulfate, which is 52 Å ² , indicating that it is bulky. . Therefore, S
It appears that the sodium salts of acids and O-acids are fatty acid soap-type emulsifiers with surface activities comparable to sodium lauryl sulfate. Next, the foaming power (foam volume
ml over time) with that of sodium lauryl sulfate, it is clear from Table 1 that S acid

〔Example〕

Example 1 A solution of 10 parts of squalane (parts by weight, same hereinafter), 15 parts of octyldodecyl myristate, and 2 parts of cetanol as oil phase components at 75°C (referred to as phase B) was mixed with monopotassium salt of spicrysporic acid. 1 part of glycerin and 20 parts of glycerin were heated and dissolved at 75°C (referred to as phase A) and added with stirring, and this was thoroughly mixed with a homomixer to form 52 parts of purified water at 75°C as an aqueous phase component. (referred to as phase C) was added thereto, and the mixture was stirred and cooled to 40°C to obtain an emulsified composition. Observe the state of the obtained emulsified composition and check the PH value, viscosity (cp), and particle size (μm) at 25°C.
The emulsion stability after 7 days at 45°C was determined and summarized in Table 2.

〔effect〕

The polybasic acid type biosurfactant emulsion composition of the present invention described above is emulsified in an acidic region that cannot be achieved with conventional soap emulsifiers, so it has improved skin physiological safety and is suitable for consumption. It is clear that the emulsion composition is extremely safe and has excellent stability, without causing anxiety among people.
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 feel 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 spicrisporic acid.
The relationship between the titration amount and PH value when titrated with a 0.1N aqueous sodium hydroxide solution (Figure 1 shows the case where the diluent of spicrisporic acid is distilled water only, 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, 1Na...monosodium salt, 2Na...disodium salt, 3Na...trisodium salt.

Claims (1)

[Claims] 1 In the oil phase component, 4,5-dicarboxy-4-pentadecanolide (spicrisporic acid), 4,5
- salt of dicarboxy-4-pentadecanolide,
The lactone ring of 4,5-dicarboxy-4-pentadecanolide was opened to form a 3-hydroxy-1,3,
A polybasic acid type biosurfactant emulsion composition prepared by adding at least one of the four components of 4-tetradecanetricarboxylic acid or a salt thereof and adjusting the pH value to 7.0 or less.