JPH0367548B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an oil gelling agent comprising a phosphate ester salt.

[Conventional technology and problems]

Oil gels are widely used in cosmetics, cosmetics, viscosity adjustment, shape-retaining binding, etc.

Conventionally, gelling agents for gelling oil include metal salts of fatty acids such as calcium, lithium, and aluminum, fatty acids such as hydrogenated castor oil, D
- 1:2 dehydrated condensates of sorbitol and benzaldehyde, derivatives such as amides, esters, and amine salts of N-amino acids, and hydrogenated lecithins are known. In addition, regarding phosphate ester compounds, aluminum salts and iron salts of mixtures of monoalkyl phosphates and dialkyl phosphates that have linear alkyl groups thicken and gel liquid oils such as hydrocarbons, so they are lubricating. It is known to be effective as an additive ingredient in oils (eg US Pat. No. 3,494,949). However, these are complicated to manufacture because they are synthesized by salt exchange after neutralization with sodium hydroxide, and because excess base interferes with gel formation, carboxylic acid anhydrides are added to improve stability. The disadvantage was that it had to be done.

Furthermore, oils that are gelatinized are generally colorless and transparent; however, because the gelling agent creates a higher-order structure in the oil or causes a certain molecular arrangement, the resulting oil gel may be cloudy. However, there are very few that turn oil into a transparent or translucent gel, and there is a problem in that the oils that can be used are limited.

Therefore, in the field of cosmetics and cosmetics, transparent or translucent gels are desired from the viewpoint of product form and usage, so oils that have excellent stability and transparency and can be gelled are limited. Not done, and moreover,
In some cases, there has been a desire for an oil gelling agent that forms a stable, transparent or translucent gel even when water or a third component such as water and an alcohol or polyol coexists.

[Means for solving problems]

As a result of various studies to overcome the above-mentioned drawbacks, the present inventors found that a monoalkyl phosphate ester salt having a branched chain alkyl group, which can be easily produced, has little skin irritation, and is highly safe, has been found to be suitable for gelling. The present invention has been completed based on the discovery that an oil gel that is transparent or translucent and stable in terms of strength can be produced regardless of the type of oil to be used.

That is, the present invention is based on the following general formula () (In the formula, R represents a branched alkyl or alkenyl group having 8 to 36 carbon atoms, and X represents an alkali metal, alkanolamine, or basic amino acid. However, one of the two Xs is a hydrogen atom. The present invention provides an oil gelling agent comprising a monoalkyl phosphate ester salt represented by:

The branched alkyl group or alkenyl group of the monoalkyl phosphate ester salt of the present invention represented by formula () includes those branched from the α-position and those branched from the β-position of the alkyl group or alkenyl group. , or multi-branched ones,
Those branched from the β position, such as 2-ethylhexyl, 2-ethylhexadecyl, 2-butyltetradecyl, 2-hexyldecyl, 2-butylhexadecyl, 2-octyldodecyl, 2-decyltetradecyl, 2- tetradecyl octadecyl,
2-ethyl octadecyl, 2-dodecylhexadecyl, 2-hexadecyl eicosyl, etc. are preferred, and among these, those having 10 to 28 carbon atoms, such as 2-
Particularly preferred are hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, and the like. Examples of alkali metals include sodium, potassium, lithium, etc. Among them, sodium and potassium are preferred. Examples of alkanolamines include triethanolamine, monoethanolamine, alkanolamines having hydroxylalkyl having 2 to 3 carbon atoms, and examples of basic amino acids include lysine, histidine, arginine, etc. Among them, arginine is particularly preferable. These monoalkyl phosphate ester salts are obtained by converting high-purity monoalkyl phosphate esters obtained by known methods (e.g., JP-A-61-17594) into known methods (e.g., JP-A-58-180496). , an alkali metal hydroxide, an alkanolamine, or a basic amino acid aqueous solution.
It can be easily obtained by neutralizing an equivalent amount and then distilling off the solvent.

Examples of oils that can be gelled using the oil gelling agent of the present invention include lubricating oils such as turbine oil, machine oil, motor oil, and gear oil; hexane;
Hydrocarbons such as heptane; all oils that are liquid at room temperature, such as silicone oil, higher alcohol higher fatty acid esters, higher fatty acids, squalane, animal and vegetable oils such as castor oil, olive oil, and soybean oil. Among them, aliphatic straight chain saturated hydrocarbons or aliphatic branched chain hydrocarbons, such as normal hexane, normal heptane, normal octane,
Normal decane, normal dodecane, normal tetradecane, normal hexadecane, normal octadecane, isooctane, isodecane, isododecane, isotetradecane, isohexadecane,
Mineral oils such as isooctadecane and isoparaffin; isostearyl cholesteryl ester, 2-
Ester oils such as ethylhexanoic acid triglyceride, octadecyl myristate, isopropyl palmitate, isopropyl myristate, decyl oleate, butyl acetate; or squalane,
Animal and vegetable oils such as castor oil, olive oil, soybean oil, cottonseed oil, and camellia oil are preferred, and these may be used alone or in combination of two or more. Furthermore, water or a third component such as water and alcohol or polyol may coexist in the oil gel containing one or more types of oil. Examples of alcohols and polyols include ethanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, hexanediol, butylene glycol, heptanediol, propylene glycol, and sorbitol.

Gelling of oil using the oil gelling agent of the present invention is carried out by the following method. In other words, a monoalkyl phosphate ester salt of formula () is added to a system containing oil.
A transparent or translucent oil gel can be obtained by mixing 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, heating until the monoalkyl phosphate ester salt is dissolved, and leaving it at room temperature. In this case, the above-mentioned aliphatic straight-chain saturated hydrocarbons or aliphatic branched-chain hydrocarbons, such as normal hexane, normal heptane, normal octane, normal decane, normal dodecane, normal tetradecane, normal hexadecane, normal octadecane, isooctane, isodecane, isododecane, Preferably mineral oils such as isotetradecane, isohexadecane, isooctadecane, etc. and isoparaffin are present. The oil-containing system may contain from 0.01 to 20 parts by weight, preferably from 0.01 to 5 parts by weight, of water. Furthermore, when water and a third component such as alcohol or polyol coexist in addition to oil, 0.05 to 5 parts by weight of monoalkyl phosphate salt, preferably 0.5 to 2 parts by weight, and 0.5 to 50 parts by weight of water. Parts by weight, preferably 2 to 30 parts by weight, and 20 to 50 parts by weight, preferably 8 to 40 parts by weight of alcohol or polyol are mixed and stirred at room temperature until homogeneous.
It is preferable to add parts by weight to form a gel.

[Effect]

The mechanism by which phosphate ester salts having branched-chain alkyl or alkenyl groups form transparent or semi-transparent oil gels regardless of the type of oil is not necessarily clear, but branched-chain alkyl or alkenyl groups have special properties in oil. It is thought that a transparent or translucent oil gel is formed to create a higher-order structure. Additionally, phosphate ester salts with branched-chain alkyl and alkenyl groups have lower Kraft points and phase transition temperatures than phosphate ester salts with straight-chain alkyl and alkenyl groups, and form transparent or translucent stable oil gels. It is thought that this contributes to the

[Effects of the Invention] The oil gelling method of the present invention is capable of forming a transparent or translucent stable oil gel regardless of the target oil, and is highly safe with low toxicity and skin irritation. It can be used in a wide range of applications, not only as a base for industrial products such as lubricating oil additives and crude oil spill prevention agents, but also as a base for cosmetics, cosmetics, and gel fragrances.

〔Example〕

The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 0.5 g of mono-2-hexyldecyl phosphate disodium salt obtained by a known method and 9.5 g of isoparaffin
Mix and stir in an oil bath at 120°C. At 100°C, mono-2-hexyldecyl phosphate disodium salt dissolves and becomes transparent. This was left at room temperature to obtain a translucent oil gel.

Example 2 0.5 g of mono-2-hexyldecyl phosphate disodium salt obtained by a known method and normal octane
Mix and stir 9.5g in an oil bath at 120°C. 100
At ℃, mono-2-hexyldecyl phosphate disodium salt dissolves and becomes transparent. This was left at room temperature to obtain a translucent oil gel.

Example 3 1.0 g of mono-2-hexyldecyl phosphate dipotassium salt obtained by a known method and 9.0 g of isoparaffin
Mix and stir in an oil bath at 120℃. At 100°C, mono-2-hexyldecyl phosphate dipotassium salt dissolves and becomes transparent. This was left at room temperature to obtain a translucent oil gel.

Example 4 0.5 g of mono-2-hexyldecyl phosphate mono-L-arginine salt obtained by a known method and 9.5 g of normal octane were mixed and stirred in an oil bath at 120°C. At 80°C, mono-2-hexyldecyl phosphate L-arginine salt dissolves and becomes transparent. This was left at room temperature to obtain a transparent oil gel.

Example 5 0.5 g of mono-2-hexyldecyl phosphate mono-L-arginine salt obtained by a known method and 9.5 g of n-dodecane were mixed and stirred in an oil bath at 120°C. Mono-2-hexyldecyl phosphate mono-L at 80℃
-The arginine salt dissolves and becomes transparent. This was left at room temperature to obtain a transparent oil gel.

Example 6 0.5 g of mono-2-hexyldecyl phosphate mono-L-arginine salt obtained by a known method and 9.5 g of normal hexadecane were mixed and stirred in an oil bath at 120°C. At 80°C, mono-2-hexyldecyl phosphate mono-L-arginine salt dissolves and becomes transparent. This was left at room temperature to obtain a transparent oil gel.

Example 7 0.5 g of mono-2-hexyldecyl phosphate mono-L-arginine salt obtained by a known method and 9.5 g of isoparaffin are mixed and stirred in an oil bath at 120°C.
At 80°C, mono-2-hexyldecyl phosphate mono-L-arginine salt dissolves and becomes transparent. This is left at room temperature to form a transparent oil gel.

Example 8 1.0 g of mono-2-hexyldecyl phosphate mono-L-arginine salt obtained by a known method and 9.0 g of isoparaffin were mixed and stirred in an oil bath at 120°C.
At 80°C, mono-2-hexyldecyl phosphate mono-L-arginine salt dissolves and becomes transparent. This is left at room temperature to form a transparent oil gel.

Example 9 1.0 g of mono-2-octyldodecyl phosphate disodium salt obtained by a known method and isoparaffin
Mix and stir 9.0g in an oil bath at 120°C. 90℃
Disodium mono-2-octyldodecyl phosphate dissolves and becomes transparent. This was left at room temperature to obtain a translucent oil gel.

Example 10 1.0 g of mono-2-decyltetradecyl phosphate disodium salt obtained by a known method and 9.0 g of isoparaffin are mixed and stirred in an oil bath at 120°C. 90
At ℃, mono-2-decyltetradecyl phosphate disodium salt dissolves and becomes transparent. This was left at room temperature to obtain a translucent oil gel.

Example 11 1.0 g of mono-2-hexyldecyl phosphate mono-L-arginine salt obtained by a known method, 9.0 g of isoparaffin, and 0.05 g of water are mixed and stirred in an oil bath at 120°C. At 80°C, mono-2-hexyldecyl phosphate mono-L-arginine salt dissolves and becomes transparent. This is left at room temperature to form a transparent oil gel.

Example 12 1.0 g of mono-2-hexyldecyl phosphate mono-L-arginine salt obtained by a known method, 6.0 g of isoparaffin, and 3.0 g of squalane are mixed and stirred in an oil bath at 120°C. At 80°C, 2-hexyldecyl phosphate mono-L-arginine salt dissolves and becomes transparent.
This was left at room temperature to obtain a transparent oil gel.

Example 13 1.0 g of mono-2-octyldodecyl phosphate disodium salt obtained by a known method and isoparaffin
Mix and stir 6.0g and 3.0g of silicone oil in an oil bath at 120℃. At 90°C, 2-octyldodecyl phosphate disodium salt dissolves and becomes transparent. This was left at room temperature to obtain a translucent oil gel.

Example 14 0.28 g of mono-2-hexyldecyl phosphate mono-L-arginine salt obtained by a known method, 0.82 g of water,
After stirring 4.32 g of glycerin at room temperature to make it homogeneous, add 2-ethylhexanoic acid triglyceride.
A transparent oil gel was obtained by mixing 94.6 g.

Example 15 0.5 g of mono-2-hexyldecyl phosphate mono-L-arginine salt obtained by a known method, 2.5 g of water, and 10.0 g of glycerin were stirred at room temperature to make them homogeneous, and then 87.0 g of liquid paraffin was mixed. A clear oil gel was obtained.

Example 16 0.28 g of mono-2-hexyldecyl phosphate mono-L-arginine salt obtained by a known method, 0.82 g of water,
After stirring 10.0 g of glycerin at room temperature to make it homogeneous, 88.9 g of pentaerythritol 2-ethylhexanoate was mixed to obtain a translucent oil gel.

Example 17 0.5 g of mono-2-octyldodecyl phosphate mono-L-arginine salt obtained by a known method and 2.5 g of water,
Glycerin 8.0g, 1,3-butylene glycol
After stirring 2.0 g at room temperature, 87.0 g of 2-ethylhexanoic acid triglyceride was mixed to obtain a transparent oil gel.

Example 18 In Example 1, mono-2-hexyldecyl phosphate di-triethanolamine salt was used instead of 0.5 g of mono-2-hexyldecyl phosphate disodium salt.
A translucent oil gel was obtained by carrying out the same operation as in Example 1 except that 0.5 g was used.

Example 19 In Example 1, mono-2-hexyldecyl phosphate di-monoethanolamine salt was used instead of 0.5 g of mono-2-hexyldecyl phosphate disodium salt.
A translucent oil gel was obtained by carrying out the same operation as in Example 1 except that 0.5 g was used.

Comparative Example 1 0.5 g of monohexadecyl phosphate mono-L-arginine salt obtained by a known method and 9.5 g of isoparaffin were
Although it was mixed and stirred in an oil bath at 120℃, it did not dissolve.
Completely separates from oil and does not form a gel.

Comparative Example 2 0.5 g of monohexadecyl phosphate disodium salt obtained by a known method and 9.5 g of isoparaffin were heated at 120°C.
Although it was mixed and stirred in an oil bath, it did not dissolve, completely separated from the oil, and did not form a gel.

Comparative Example 3 0.5 g of dipotassium monohexadecyl phosphate obtained by a known method and 9.5 g of isoparaffin were mixed and stirred in an oil bath at 120° C., but the mixture did not dissolve and was completely separated from the oil to form a gel.

Comparative Example 4 0.28 g of monohexadecyl phosphate mono-L-arginine salt obtained by a known method, 0.82 g of water, and 4.32 g of glycerin were stirred at room temperature to make them homogeneous.
When 94.6 g of 2-ethylhexanoic acid triglyceride was mixed, a cloudy white oil gel was obtained.

Comparative Example 5 0.5 g of calcium stearate and 9.5 g of isoparaffin are mixed and stirred in an oil bath at 120°C.
When the calcium stearate salt was dissolved and left at room temperature, an oil gel was formed, but a transparent gel was not obtained, but a cloudy gel was formed.

Test Example 1 A stability test was conducted on the oil gels obtained in Examples 7 and 8 by leaving them in a constant temperature room at 40°C for 20 days. As a result, there was no change in transparency compared to when gelatinized. It was confirmed that it was a stable oil gel with no fluidity and no oil oozing.

Test Example 2 The oil gel obtained in Example 17 was tested at -5, 10, 25,
As a result of leaving it at 40 and 50°C for one month, it was confirmed that it was a stable oil gel without separating at either temperature.

Test Example 3 5 g of polyoxyethylene sorbitan monostearate, 4 g of water, 1.5 g of glycerin, and 6 g of 1,3-butylene glycol were stirred at room temperature to make them homogeneous, and then 83.5 g of 2-ethylhexanoic acid triglyceride was mixed. The stability of the oil gel was examined in the same manner as in Test Example 2. As a result, oil oozed out at 10°C, and water and oil were completely separated at temperatures above 25°C.

Claims (1)

[Claims] First-order general formula () (In the formula, R represents a branched alkyl or alkenyl group having 8 to 36 carbon atoms, and X represents an alkali metal, alkanolamine, or basic amino acid. However, one of the two Xs is a hydrogen atom. An oil gelling agent consisting of a monoalkyl phosphate ester salt represented by