JP3462332B2 - Oil gelling agent and cosmetic containing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention comprises a metal salt of a dialkyl phosphate which gives a gel which is transparent and has a moderate viscosity.
The present invention relates to an oil gelling agent useful as a cosmetic material, a cosmetic material, and the like, and a cosmetic containing the oil gelling agent, which has a good feeling in use and stability.

[0002]

2. Description of the Related Art Conventionally used oily cosmetics are liquid or solid (wax),
There is a problem in usability, such as the liquid one is dripping and the solid one is difficult to take out from the container. This is
This is due to the fact that no gelling agent capable of imparting an appropriate viscosity to the oily cosmetic has been found yet. Therefore, various attempts have been made so far to use various compounds as oil gelling agents for cosmetics.

As one of such attempts, for example, a method using a metal salt of dialkyl phosphate as an oil gelling agent is known (Japanese Patent Publication No. 41122/1989). This oil gelling agent gives a good gel in a small amount, and when it is mixed with a cosmetic, a cosmetic having an excellent feeling of use without oozing out of the oil, cracking and the like can be obtained. However, in the above publications, all the metal salts of dialkyl phosphate shown in the examples have straight-chain alkyl groups, and all of them formed a solid gel without transparency. Therefore, these oil gelling agents could not be used in applications where transparency is required.

[0004]

Accordingly, the present invention provides an oil gelling agent which forms a transparent and moderately viscous gel, and a cosmetic composition containing the oil gelling agent, which has a good feeling of use and stability. The purpose is to do.

[0005]

Under such circumstances, the inventors of the present invention have conducted extensive studies, and as a result, found that a metal salt of diisostearyl phosphate can be an oil gelling agent satisfying the above-mentioned requirements, and the present invention has been made. completed.

That is, the present invention provides the following general formula (1):

[0007]

[Chemical 2]

[In the formula, R represents an isostearyl group, and M
Indicates aluminum, iron or calcium, and n indicates 3 when M is aluminum or iron, and 2 when M is calcium. ] An oil gelling agent comprising a metal salt of diisostearyl phosphate represented by the following and a cosmetic containing the same.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), R mainly contains a structure represented by the following formula, which is produced by skeletal isomerization of fatty acids derived from beef tallow or tall oil, and has 14 to 24 carbon atoms.
The so-called isostearyl group as a mixture of

[0010]

[Chemical 3]

[Wherein p + q = 14 and p = q = 7
Has a distribution with the vertex at. ]

In the general formula (1), M represents aluminum, iron or calcium, and n represents a number corresponding to the valence of M. Among them, those in which M is calcium are particularly preferable.

The metal salt of diisostearyl phosphate (1) is
It can be produced according to a known method, for example, an aluminum salt, an iron salt or a calcium salt of an organic acid or an inorganic acid, and diisostearyl phosphoric acid or an alkali metal salt thereof,
It can be obtained by heating a tertiary amine salt and a basic amino acid salt in a solvent such as water, ethanol or water-ethanol in the presence of an alkali hydroxide, if necessary. Examples of the metal salt of an organic acid or an inorganic acid used here include acetic acid, hydrogen chloride, sulfuric acid, nitric acid, phosphoric acid, aluminum salts such as carbonic acid, iron salts or calcium salts, and alkali metal diisostearyl phosphate. The salt is sodium salt,
Examples thereof include potassium salts, the tertiary amine salts include triethanolamine salts, and the basic amino acid salts include arginine salts.

When M is aluminum, aluminum alcoholate and diisostearyl phosphate are added,
The aluminum salt of diisostearyl phosphate can also be produced by a method in which a reaction is carried out by heating in a non-aqueous solvent such as benzene and hydrolysis is carried out if necessary. The aluminum alcoholate used here includes aluminum isopropylate, aluminum sec-butyrate, and mono s.
Examples include ec-butoxyaluminum diisopropylate and the like.

The diisosteryl phosphoric acid used in the above reaction is obtained by a known method, for example, by reacting phosphorus oxyhalide such as phosphorus oxychloride with about 2 moles of isostearyl alcohol directly or in the presence of a base. It can be manufactured.

The solvent used in this reaction is not particularly limited as long as it is inert to the reaction and capable of dissolving phosphorus oxyhalide, and is not particularly limited. For example, an ether solvent such as tetrahydrofuran or dioxane, hexane or heptane. And aliphatic hydrocarbons such as octane, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene. These solvents can be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited, but generally an amount such that the concentration of phosphorus oxyhalide is 60% by weight or less, preferably 30% by weight or less is preferable.

The base which can be used in this reaction is
Examples thereof include organic tertiary amines such as triethylamine, tributylamine and pyridine, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. These bases can be used alone or in combination of two or more.

The oil gelling agent comprising the metal salt of diisostearyl phosphate (1) of the present invention can form a transparent gel having an appropriate viscosity when used together with an oil agent for cosmetics. .

The cosmetic oils to be added to the cosmetic of the present invention include non-polar liquid oils such as straight chain or branched chain saturated or unsaturated hydrocarbons and synthetic ester oils of higher alcohols and fatty acids. Can be mentioned. These may be used alone or in combination of two or more. Among these cosmetic oil agents, particularly non-polar liquid oils such as liquid paraffin and squalane are added with the metal salt of diisostearyl phosphate (1) to have high gel strength, oil retention and shape retention. Show.

In the cosmetic of the present invention, in addition to the metal salt of diisostearyl phosphate (1) and the above-mentioned oil for cosmetics, conventionally used oil, purified water, various surfactants, wetting agents, antiseptic agents are used. Ingredients such as agents, antioxidants, fragrances, powders, intercellular lipids (ceramides, etc.), ultraviolet absorbers, medicinal components and the like can be appropriately added. Examples of other oil agents include silicone oils such as dimethylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane, polyether-modified silicones, higher alcohols, higher fatty acids, waxes, etc. Its gel strength, oil retention and shape retention can be adjusted.

As the surfactant, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester,
Polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester and the like; as a wetting agent, sorbitol, glycerin, propylene glycol, 1,
3-butylene glycol, lactic acid, sodium lactate, polyethylene glycol and the like; preservatives include paraoxybenzoic acid alkyl ester, sodium benzoate, potassium sorbate, phenoxyethanol and the like; antioxidants such as tocopherol, sezamol, sezamoline, Lecithin and the like; powders include titanium oxide, zinc oxide, ultramarine blue, chromium oxide, iron oxide, talc, sericite,
Examples thereof include mica, kaolin, titanium mica, iron oxide coated mica, and organic pigments.

The content of the metal salt of diisostearyl phosphate (1) in the cosmetic of the present invention is generally preferably 0.1 to 30% by weight of the cosmetic oil, and if it is more than this amount, the cosmetic oil has good properties. It is not preferable because it deteriorates the properties (spreading, gloss, familiarity, etc.), and if it is less than this, the effect of the metal salt is not exhibited. Further, in order to maximize the preferable feel of the cosmetic oil agent, 0.1 to 10% by weight is particularly preferable.

The cosmetic of the present invention comprises, for example, a metal salt of diisostearyl phosphate (1), an oil agent for cosmetics and other components,
A gel cosmetic having a uniform appearance can be produced by mixing with a homomixer, homodisper, three rolls or the like at room temperature or under heating and stirring. In addition, a stable W / O and O / W emulsified cosmetic composition can be obtained by adding an emulsifier or a component that becomes an aqueous phase to this.
Further, powder is preferably added to this gel or emulsion in an amount of 10 to 4
By adding 0% by weight, more preferably 15 to 30% by weight, an emulsion or creamy cosmetic can be obtained.

Examples of the dosage form of the cosmetics of the present invention include skin cosmetics, makeup cosmetics such as foundations and lipsticks; skin care cosmetics such as creams and oil gel cleansing. Hair cosmetics and shampoos are used as hair cosmetics. , Rinse and the like.

[0025]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of bis (diisostearylphosphoric acid) calcium salt: To 609 g (1 mol) of diisostearylphosphoric acid, 158 g (1 mol) of calcium acetate and 4.5 parts of an ethanol-water mixture (1: 2) were added. Add liter and stir at 65-70 ℃
The mixture was warmed up and reacted for about 2 hours. After completion of the reaction, extraction with hexane, washing with water, drying, and washing with acetone, 625 g of bis (diisostearylphosphoric acid) calcium salt was obtained. Acid value of this product (KOH mg / g)
Was 0.5.

Synthesis Example 2 Synthesis of tris (diisostearylphosphoric acid) iron salt: To 609 g (1 mol) of diisostearylphosphoric acid, 800 g (1 mol) of 5% sodium hydroxide aqueous solution, 15% iron (III) nitrate 9 water 2700 g (1 mol) of an aqueous salt solution and 2.5 liters of an ethanol-water mixed solution (1: 2) were added, and the mixture was heated to 65 to 70 ° C. with stirring and reacted for about 2 hours. After the reaction was completed, the product was collected by filtration, washed with water and dried to obtain 630 g of iron tris (diisostearylphosphate). The acid value (KOH mg / g) of this product was 2.

Synthesis Example 3 Synthesis of tris (diisostearylphosphoric acid) aluminum salt: To 609 g (1 mol) of diisostearylphosphoric acid, 143 g (0.7 mol) of aluminum acetate and 4 parts of an ethanol-water mixture (1: 2) were mixed. Add 5 liters and stir 65-7
It was heated to 0 ° C. and reacted for about 2 hours. After the reaction was completed, the product was collected by filtration, washed with water and dried to obtain 614 g of tris (diisostearylphosphoric acid) aluminum salt. The acid value (KOH mg / g) of this product was 0.5.

Test Example 1 The oil gelling ability of various phosphoric acid diester polyvalent metal salts was evaluated. That is, 1 g of each compound was placed in a sample tube, 19 g of an oil agent was added thereto, and the mixture was mixed with an ultrasonic mixer for about 3 minutes or heated at about 80 ° C. for 10 minutes to be uniformly dispersed or dissolved. This was left to stand for a whole day and night, and then the state was visually observed and evaluated according to the following criteria. The results are shown in Table 1.

[0030] ⊚: Transparent and viscous thixotropic gel ○: Gel that is transparent and slightly spinnable Δ: Hard gel without transparency ×: insoluble

[0031]

[Table 1]

Invention product 1: Bis (diisostearylphosphate) calcium salt (Synthesis example 1) Invention product 2: Tris (diisostearylphosphate) iron salt (Synthesis example 2) Invention product 3: Tris ( Diisostearylphosphoric acid) aluminum salt (Synthesis example 3) Comparative product 1: Tris (discetylphosphoric acid) aluminum salt Comparative product 2: Tris (distearylphosphoric acid) aluminum salt Comparative product 3: Bis (distearylphosphoric acid) aluminum salt Comparative product 4: Mono (distearylphosphoric acid) aluminum salt Comparative product 5: Bis (dicetylphosphoric acid) aluminum salt Comparative product 6: Bis (dicetylphosphoric acid) calcium salt Comparative product 7: Tris (dicetylphosphoric acid) iron salt

Example 1 A sunscreen jelly having the following composition was prepared by the following method. (Composition) (% by weight) (1) Compound of Synthesis Example 1 (2) Squalane balance (3) Methylphenylpolysiloxane 5 (4) Isooctyl p-dimethylaminobenzoate 2 (5) Perfume Suitable amount

(Production method) (1) to (4) are heated and uniformly dissolved with a disper. To this, (5) is uniformly mixed with a disper to obtain a sunburn prevention jelly. This one is
The liquid did not drip from the fingers during use, was not sticky, and had an excellent feeling in use.

Example 2 A sunscreen cream having the following composition was prepared by the following production method. (Composition) (% by weight) (1) Compound of Synthesis Example 2 (2) Isopropyl palmitate balance (3) Dimethylpolysiloxane (6cs) 5 (4) Octyl methoxycinnamate 3 (5) Titanium oxide 5 (6) Fragrance suitable amount

(Production method) (1) to (4) are heated and uniformly dissolved in a disper. (5) and (6) are mixed uniformly with a disper to obtain a sunscreen cream. This product was excellent in pigment dispersion stability and had a good feeling in use.

Example 3 A creamy W / O type foundation having the following composition was prepared by the following method. (Composition) (wt%) (1) Compound of Synthesis Example 3 10 (2) Dimethylpolysiloxane (6cs) 5 (3) Squalane 40 (4) Glycerin 2 (5) Purified water Remaining amount (6) Pigment Sericite 6 Titanium oxide 8 Iron oxide 12 (7) Nylon powder 5 (8) Dimethylpolysiloxane / polyoxyalkylene copolymer 1

(Production method) (1) to (3) and (8) were heated and uniformly dissolved in a disper, and then (6) and (7).
Was further added and dispersed by a disper. To this, (4) and (5) are added with stirring to emulsify to obtain a foundation. This product was excellent in pigment dispersion stability and sensation during use, and did not drip from the finger during use.

[0039]

EFFECT OF THE INVENTION The oil gelling agent of the present invention forms a transparent gel having an appropriate viscosity, and a cosmetic containing the same has a good feeling in use and stability.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junichi Fukasawa, 1334 Kao Co., Ltd., Wakayama City, Wakayama Prefecture (72) Inventor Katsumi Kita 1334, Minato, Wakayama City, Wakayama Prefecture (56) Reference, JP JP-A-9-175935 (JP, A) JP-A-4-221306 (JP, A) JP-A-62-53913 (JP, A) JP-A-1-319410 (JP, A) JP-A-1-193278 (JP , A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K ^7/ 00-7/50

Claims (3)

(57) [Claims] 1. The following general formula (1): [In the formula, R represents an isostearyl group, M represents aluminum, iron or calcium, n represents 3 when M is aluminum or iron, and 2 represents when M is calcium. ]
An oil gelling agent comprising a metal salt of diisostearyl phosphate represented by: 2. An oil gelling agent comprising diisostearyl phosphate calcium salt. 3. A cosmetic containing the oil gelling agent according to claim 1.