JP2577997B2 - Cosmetics - Google Patents

Description

The present invention relates to a novel cosmetic, and more particularly, it contains a long-chain alkyltrimethylol and has good spreadability when applied.
The present invention relates to a cosmetic that gives a refreshing feeling without stickiness, has excellent moisture retention, and has good emulsion stability.

[Conventional technology and its problems]

Conventionally, various humectants have been used in cosmetics. However, when they are used in a small amount, the effect is weak, and when used in a large amount, there are problems such as deterioration of feel and impairment of system stability.

Emulsion type cosmetics are widely used because they can provide appropriate oil and moisture to skin and hair because of their composition. By changing the type and amount of the oil component, various emulsions having different physical properties and feeling in use can be obtained.

However, since the emulsion is a thermodynamically unstable system, its stabilization is difficult, and many studies and attempts have been made so far. One of the measures is to add an emulsifying aid. Such emulsifying auxiliaries include cationic auxiliaries, anionic auxiliaries, amphoteric auxiliaries, and nonionic auxiliaries, but nonionic auxiliaries are most preferred in view of the range of oil components that can be incorporated.

As an example of the addition of a nonionic emulsification aid, it is known that, for example, when a higher alcohol such as cetanol or cetostearyl alcohol is added to a cosmetic emulsion, a liquid crystal structure is obtained, thereby improving the stability. As described above, although the method of adding a higher alcohol is effective in preventing crystallization of high melting point fats and oils, if they are added to maintain a stable state, the viscosity becomes extremely high, the spread at the time of application is poor, and the oily feeling Has the disadvantage that it is strong and sticky. In addition, the liquid crystal structure of a higher alcohol has problems such as precipitation of crystals having a pearl-like luster and a decrease in viscosity due to destruction of the liquid crystal structure.

Therefore, a composition in which a nonionic auxiliary agent that forms a lamellar liquid crystal structure is blended in the composition has been developed. For example, Japanese Patent Publication No. 38-5050 discloses the following general formula (I
I) (Where n represents an integer of 1 to 3) discloses a skin and hair care agent containing a triol represented by the following formula: However, this triol has the disadvantage that it becomes reverse middle liquid crystal in an aqueous solution, has a strong oily feeling, and has an insufficient moisturizing effect.

JP-A-63-23737 discloses an aqueous dispersion of niosomes comprising a lipid lamella using polyglycerol ether as a nonionic amphiphilic substance, and an aqueous compartment contained between lipid layers. A water-soluble active substance is encapsulated inside to improve stability. However, when forming niosomes that encapsulate active substances in vesicles, they must be treated at a high temperature of 80 ° C or higher, and it is difficult to apply active substances with poor high-temperature stability. .
Further, JP-B-58-8287, JP-B-61-56016, JP-A-57-77613, and JP-A-57-94326 also disclose an aqueous dispersion of lipid globules using polyglycerol ether. Although it is disclosed, at the time of production, homogenization is required, and the production method is complicated, such as dissolving lipids in an organic solvent such as chloroform-methanol and evaporating the solvent, which is disadvantageous in that it is industrially difficult. was there.

As described above, conventional nonionic auxiliaries have a problem that the liquid crystal formation concentration range is narrow, the liquid crystal formation temperature is high, and industrial liquid crystal formation is difficult.

Usually, in cosmetics, when the active ingredient having a high melting point is separated without being uniformly emulsified and dispersed due to the instability of the emulsion, effects such as moisture retention cannot be sufficiently obtained. Some of the nonionic auxiliaries have a moisturizing action, but the action was not sufficient.

For this reason, there has been a demand for the development of a cosmetic which is uniformly stable without a change in crystal transition and the like over a wide concentration range at a use temperature of the cosmetic, has no oily feeling, and has an excellent moisturizing effect.

[Means for solving the problem]

Under such circumstances, the present inventors have conducted intensive studies to solve the above problems, and as a result, by using long-chain alkyltrimethylol, it is possible to obtain a cosmetic having excellent moisturizing properties. When incorporated into emulsified cosmetics, in addition to good moisture retention, it contributes to the stabilization of emulsions and the like, and it is possible to widen the uniform area of high-melting-point active ingredients. The present inventors have found that an excellent cosmetic which can give a comfortable feeling of use can be obtained, and completed the present invention.

That is, the present invention provides the following general formula (I) (Wherein, R represents a straight-chain or branched-chain saturated or unsaturated alkyl group having 8 to 22 carbon atoms).
It is intended to provide a cosmetic characterized by containing more than one kind.

The long-chain alkyltrimethylol used in the present invention is represented by the general formula (I). Specific examples thereof include trimethylolundecane, trimethyloltridecane, trimethylolpentadecane, trimethylolheptadecane, and trimethylolnona. Decane, trimethylol hen eicosane, and the like. Among them, the following general formula (III) (Wherein m and n each represent an integer of 0 to 19;
And the sum of n is 7 to 19).
Further, those in which the sum of m and n in the general formula (III) is 11 to 15 are preferable, and particularly, the sum of m and n is 13 and trimethylol isoheptadecane are preferable. These branched alkyl-type long-chain alkyltrimethylols are lamellar liquid crystals at room temperature, exhibiting excellent compatibility with most solvents,
In addition, it has such characteristics that it is almost uniformly dispersed when mixed with water.

Long-chain alkyltrimethylols are produced, for example, by reacting the corresponding aldehyde with formaldehyde in a suitable solvent in the presence of a base.

As is known, the first step is a condensation reaction in which 1 mole of aldehyde reacts with 2 moles of formaldehyde, and the second step is the Kanizallo reaction in which 1 mole of formaldehyde and a base further react to form trimethylol. And is represented by the following equation.

(In the formula, R has the same meaning as described above.) The aldehyde (IV) used in the above reaction is obtained by catalytic reduction of the corresponding carboxylic acid chloride using, for example, a palladium carbon catalyst or the like [Synthesis ( Synthesis) 767 (1976)]. Examples of the corresponding carboxylic acid include, for example, an acid mainly containing isostearic acid having about 18 carbon atoms and having a methyl branch, which is obtained as a by-product during the production of oleic acid dimer.

Examples of the organic solvent used in this reaction include lower alcohols such as ethanol and isopropanol, and ethers such as tetrahydrofuran and dioxane, or hydrocarbons, and halogenated hydrocarbons.Preferably, isopropanol, Alternatively, it is preferable to use tetrahydrofuran or dioxane. The amount of the organic solvent used is 20 to 1000% by weight based on the aldehyde.
(Hereinafter, indicated by “%”), preferably within the range of 100 to 300%. Usually, the solvent is charged into the reactor before the start of the reaction, but may be added to the reaction system during the reaction.
In addition, these organic solvents can be partially used by mixing water. In some cases, the reaction can be carried out without using these solvents.

Examples of the base used in this reaction include alkali metal hydroxides and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and sodium carbonate and calcium carbonate. However, preferred are sodium hydroxide and potassium hydroxide. The amount of the base to be used is generally in the range of 1.1 to 3.5 molar equivalents, preferably 1.5 to 2.0 molar equivalents, per 1 mol of the aldehyde. The base is usually preferably used in the form of an aqueous solution having a concentration of 50% or less in terms of operation.

Also, formaldehyde can be used as an aqueous solution,
Paraformaldehyde can also be used. The concentration of formaldehyde in the aqueous formaldehyde solution is not particularly limited, but it is advantageous to use a readily available formaldehyde aqueous solution having a concentration of 5 to 50%. The amount of formaldehyde used is in the range of 4 to 30 moles, preferably 5 to 8 moles, per mole of aldehyde.

In this reaction, the order of addition of the aldehyde, formaldehyde, and base is not particularly limited, but a method in which the aldehyde and the base are respectively simultaneously dropped into the formaldehyde solution gives preferable results. The reaction temperature is usually about 20 to 100
° C, preferably within the range of 30 to 60 ° C.

The long-chain alkyltrimethylol thus obtained can be used alone or in combination of two or more. The amount of the long-chain alkyltrimethylol in the cosmetic of the present invention is not particularly limited, but is usually 0.01 to 80%, particularly 0.1-60% is preferred.

In order to further increase the effects of the present invention, a surfactant can be used in combination. As such a surfactant, any of a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant can be used. Particularly, for a skin cosmetic, the nonionic surfactant is used for the hair. For cosmetics, cationic surfactants are preferred. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, glyceryl ether, and the like. As the cationic surfactant,
A typical example is a quaternary ammonium salt. Any quaternary ammonium salt is preferably used as long as it is generally used for cosmetics.
Preferred are branched quaternary ammonium salts represented by the following general formulas (V) and (VI) described in JP-A-267505.

(Where R ₁ is And (b) an alkyl group selected from the group consisting of linear alkyl groups represented by CH ₃ CH _{2 q} , wherein R ₄ is a methyl or ethyl group, and p and q are total alkyl groups. The number of carbon atoms being 8-16), the branching ratio of the group R ₁ (a)
/ (A) + (b) is 10 to 100% by weight, and R
₂ , R ₃ represents a group selected from a benzyl group and an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and X ⁻ represents a halogen ion or an organic anion. [Wherein R _5, R ₆ are in an alkyl group having 2 to 12 carbon atoms, R ₇
Is the base Or an alkyl group having 1 to 3 carbon _{atoms, R 2, R 3, X} - is definitive as having the same meaning] These surfactants to formula (I) is 0.01 to 30% in the total composition, preferably 0.1 ~ 10% is blended.

Further, the cosmetic of the present invention may contain, if necessary, components usually used for cosmetics, pharmaceuticals, foods, etc., for example, higher alcohols having a linear or branched alkyl or alkenyl group; liquid paraffin, Hydrocarbons such as petrolatum and solid paraffin; lanolin derivatives such as liquid lanolin and lanolin fatty acids; silicon derivatives such as dimethylpolysiloxane, polyether-modified polysiloxane and amino-modified polysiloxane; higher alcohol higher fatty acid esters and higher fatty acids Fats and oils such as long-chain amidoamines having an alkyl or alkenyl group; animal and plant fats and oils such as mink oil and olive oil; pharmacologic agents such as antidandruff agents, bactericides, vitamins; preservatives such as parabens; Thickeners such as polymers; coloring agents such as dyes and pigments, ultraviolet absorbers,
Astringents, humectants such as propylene glycol, glycerin, carbitol, 3-methyl-1,3-butanediol, and saccharides, water, flavors and the like can be blended.

The cosmetic of the present invention can be produced according to a usual method, for example, a basic cosmetic such as an oil-in-water type, a water-in-oil type emulsified cosmetic, an oily cosmetic; a makeup cosmetic such as a lipstick, a foundation; Detergent; can be applied as a hair cosmetic such as a hair rinse, treatment, and hair styling agent.

[Functions and Effects of the Invention] In the cosmetic of the present invention, long-chain alkyltrimethylol is excellent as a moisturizing component, and since it forms lamellar liquid crystals, it has a low oiliness and good spreadability. Since it is incorporated in the system, the stability of the system is improved and the active ingredient works effectively.

Therefore, the cosmetic of the present invention is excellent in moisturizing property, spreads well at the time of application, gives a refreshing feeling without stickiness,
Moreover, the emulsion stability is also good.

〔Example〕

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 A 80% aqueous solution of a humectant sample was prepared, and about 1.5 g of a 30% dia.
The solution was placed in a petri dish of mm, and allowed to stand in a P ₂ O ₅ desiccator, and the change over time in the solution was measured to evaluate the water retention ability.

(Sample) Product of the present invention 1. Trimethylol isoheptadecane Comparative product 1. Propylene glycol 〃 2. Glycerin The results are shown in FIG.

The product of the present invention exhibited excellent water retention ability as compared with a commonly used humectant.

Example 2 A hair rinse composition having the composition shown in Table 1 was prepared, and its rinsing performance was examined. The results are shown in Table 1. The test method used in the examples is as follows.

[Hair treatment]

Bundle 20g (15cm length) of Japanese women's hair that has never been subjected to beauty treatments such as cold perm and bleach.
2 g of the agent was uniformly applied, then rinsed with running water for 30 seconds, towel-dried, and then dried with a dryer.
In addition, a hair cosmetic of a type without soot was air-dried after applying a predetermined amount of agent to the hair bundle. Various evaluations were made on this hair bundle.

[Higher alcohol adsorption amount]

0.5 g of the hair rinsed by the above method was taken, and the higher alcohol was extracted with chloroform. After concentration, it was dissolved in a fixed amount of chloroform containing an internal standard substance, and the higher alcohol adsorption amount was determined from the peak area by gas chromatography.

〔sensory evaluation〕

The treated hair bundle was subjected to a sensory evaluation by a specialized panelist according to the following criteria.

・ Smoothness: particularly excellent ◎, good ○, neither can be said △,
Inferior × ・ Less oily feeling: No oily feeling ◎, almost no oily feeling ○, Oily feeling (sticky) can be felt △, Oily feeling is strong × ・ Humidity: Excellent moisturizing ◎, Moisturizingが あ る: Neither can be said, 感: Moisture cannot be felt × [Dissolved state] The hair rinse composition was observed with a polarizing microscope equipped with a hot stage.

：: A uniform crystal is formed.

X: Uniform liquid crystal is not formed.

Example 3 A hair rinse composition having the composition shown in Table 2 was prepared, and its rinsing performance was examined. The results are shown in Table 2.

(Preparation method) The mixture heated to 70 ° C and the mixture obtained by heating and dissolving at the same temperature were added to the mixture, and the mixture was stirred and emulsified. The mixture was cooled to 45 ° C with stirring, and added. It was further cooled to room temperature to obtain a hair rinse composition.

Each of the obtained hair rinsing agent compositions exhibited good rinsing performance and also had good stability.

 The sensory evaluation was performed in the same manner as in Example 2.

(Storage stability)

The sample was placed in a 100 ml transparent glass container, and after storage, the appearance was visually observed. The evaluation was shown based on the following criteria.

：: The whole is uniform, and no abnormality such as dispersion and aggregation is observed.

×: Non-uniform, separation, aggregation, etc. are recognized.

Example 4 Hair treatment composition: (Product 7 of the present invention) 2-dodecylhexadecyl trimethylammonium chloride 1.5 (%) stearyltrimethylammonium chloride 1.0 dimethylpolysiloxane (500cs) 1.0 cetostearyl alcohol 3.0 trimethylol isoheptadecane 3.0 liquid paraffin 3.0 Polypeptide (collagen hydrolyzate) 5.0 Hydroxyethylcellulose (1% aqueous solution viscosity 8,000cp) 0.5 Polyoxyethylene oleyl ether (EO = 5) 0.5 Methylparaben 0.2 Perfume 0.4 Purified water Balance meter 100.0 Excellent smoothness and flexibility And light with little oiliness,
A hair treatment composition moist and giving a good feel was obtained.

Example 5 Hair cream composition: (Product 8 of the present invention) Di-2-hexyldecyldimethyl ammonium chloride 2.0 (%) Cetyltrimethylammonium chloride 1.0 Modified silicone aqueous emulsion ^{* 2} 2.0 Trimethylol isoheptadecane 1.0 Cetyl alcohol 5.0 Dipropylene glycol 6.0 Glycerin 10.0 Liquid paraffin 3.0 Perfume 0.4 Purified water Balance meter 100.0 * 2: "SM8702C" (manufactured by Toray Silicone Co., Ltd.) Modified silicone polymer Amodimethicone 40% active ingredient Excellent smoothness, flexibility A hair cream composition having no sticky feeling and giving a good feeling was obtained.

Example 6 Styling lotion composition: (Product 9 of the present invention) 2-dodecylhexadecyl trimethylammonium chloride 0.5 (%) trimethylol isoheptadecane 0.2 Modified aqueous silicone emulsion ^{* 2} 1.0 Methacrylate polymer ^{* 3} 1.0 Polyethylene glycol 1.0 Ethanol 20.0 Fragrance 0.3 Purified water Balance meter 100.0 * 2: Same as in Example 4 * 3: Mitsubishi Yuka Co., Ltd., Yuka Former AM-75 Gives excellent hairstyle retention to hair with good feel Thus, a setting agent composition was obtained.

Example 7 Conditioning mousse composition: (Product 10 of the present invention) dialkylbemethylammonium chloride ^{* 1} 0.5 (%) methylphenylpolysiloxane (300cs) 1.0 isotridecyl myristate 1.0 3-methyl-1,3-butanediol 1.0 Glycerin 2.5 Liquid paraffin 2.5 Trimethylol isoheptadecane 0.2 95% ethyl alcohol 5.0 Methyl paraben 0.1 Flavor 0.1 Propellant (LPG) 10.0 Purified water Balance meter 100.0 * 1: Same as in Example 3 Conditioning mousse composition that gives a good feel I got

Example 8 Cream: (Product 11 of the present invention) Oil phase component: Cetanol 2.0 (%) Stearic acid 3.0 Trimethylol isoheptadecane 3.0 Trimethylol tridecane 2.0 Lipid (cholesteryl isostearate) 8.0 Monolauryl glycerin 2.0 Polyoxy Ethylene (20) sorbitan monolaurate 2.0 Aqueous phase component: Dipropylene glycol 10.0 1,3-butylene glycol 5.0 Ethyl paraben 0.1 Methyl paraben 0.2 Perfume 0.1 Purified water Balance meter 100.0 The cream of the present invention has a good feeling of use and is excellent. It showed a moisturizing effect.

Example 9 Emulsion: (Inventive product 12) Oil phase component: Cetanol 0.5 (%) Vaseline 1.0 Trimethylol isoheptadecane 10.0 Polyoxyethylene (10) monooleate 2.0 Stearic acid 2.0 Water phase component: 1,3- Butylene glycol 3.0 Dipropylene glycol 6.0 Triethanolamine 1.0 Ethyl paraben 0.1 Methyl paraben 0.2 Perfume 0.1 Purified water Balance meter 100.0 The emulsion of the present invention exhibited an excellent moisturizing effect.

Example 10 Cosmetic base: (Product 13 of the present invention) Glycerin 15 (%) Polyoxyethylene octyl dodecyl ether (20E.O.) 10 Trimethylol isoheptadecane 10 Squalane 50 Purified water Balance meter 100 Heating all the above components A one-phase cosmetic base was prepared by dissolving, mixing and cooling. By using this base as a base, various oil-soluble substances can be blended.

Example 11 Emulsion type foundation: (Product 14 of the present invention) Oil phase component: Stearic acid 5.0 (%) Cetostearyl alcohol 1.0 Trimethylol tridecane 0.5 Trimethylol isoheptadecane 6.0 Lipid (cholesteryl isostearate) 6.0 Monolauric acid Glycerin ester 2.0 Propylene glycol monolaurate 3.0 Aqueous phase component: Glycerin 10.0 Triethanolamine 1.2 Ethyl paraben 0.1 Methyl paraben 0.1 Perfume 0.1 Purified water Balance Powder component: Titanium oxide 8.0 Talc 4.0 Iron oxide 0.5 Total 100.0 The foundation of the present invention has a feeling of use. Good, showing excellent moisturizing effect.

Example 12 Lipstick: (Product 15 of the present invention) Microcrystalline wax 6.0 (%) Candelilla wax 3.0 Glycerin distearate 5.0 Trimethylol isoheptadecane 10.0 Lipid [cerebroside (manufactured by Sedary Research Laboratory)] 2.0 Jojoba oil 6.0 Olive oil Balance Lanolin 10.0 Pigment 7.0 Fragrance 0.1 Total 100.0 The lipstick of the present invention had a good feeling in use and exhibited an excellent moisturizing effect.

Example 13 Shampoo: (Product 16 of the present invention) Triethanolamine salt of lauryl sulfate 20 (%) Diethanolamide laurate 3 Trimethylol isoheptadecane 2 Fragrance 0.3 Dye Trace amount purified water Balance meter 100.0 The shampoo of the present invention has a good feeling in use. And had a good conditioning effect.

Example 14 Shampoo: (Product 17 of the Invention) N-Lauroyl-N'-carboxymethyl-N '-(2-hydroxyethyl) ethylenediaminetriethanolamine 12 (%) Polyoxyethylene (4) lauryl disodium sulfosuccinate 5 Lauric acid diethanolamide 3 Cationic polymer (Mercoat 100, Merck Co., Ltd.) 0.2 Trimethylol isoheptadecane 0.2 Preservative 0.1 Perfume, dye Suitable amount of purified water Balance meter 100.0 The shampoo of the present invention has extremely weak irritation to the skin and is good. There was a great conditioning effect.

Example 15 Cream for cleansing: (Product 18 of the present invention) Sorbitol 10 (%) Polyoxyethylene octyl dodecyl ether (25E.O.) 15 Trimethylol isoheptadecane 60 Glycerin 5 Dibutylhydroxytoluene 0.1 Methyl paraben 0.1 Perfume 0.1 Purified water Balance Total 100.0 The cleansing cream of the present invention was excellent in stability and also excellent in stain removal ability.

Example 16 Soap: (Invention product 19) Tallow / coconut soap = 8/2 (parts) 97.3 (%) Trimethylol nonane 0.5 Trimethylol isoheptadecane 0.5 Perfume 1.5 Dye 0.2 Total 100.0 The soap of the present invention has a feeling of use. Was good and had the effect of suppressing bulkiness.

Example 17 Facial cleanser in paste form (Product 20 of the present invention) Potassium coconut fatty acid 15.0 (%) Potassium tallow fatty acid 25.0 Glycerin 5.0 Sorbitol 2.0 Trimethylol isoheptadecane 1.0 Polyethylene glycol 6000 10.0 Perfume 0.5 Methyl paraben 0.3 Purified water Balance meter 100.0 Invention The paste-like facial cleanser had a good feeling in use and had an effect of suppressing bulkiness.

Example 18 Body shampoo: (Product 21 of the present invention) Lauryl phosphoric acid 8.0 (%) rallic acid 3.2 Triethanolamine 10.0 Glycerin 3.0 Trimethylol isoheptadecane 2.0 Dibutylhydroxytoluene 0.1 Hydroxyethylcellulose (1% aqueous solution viscosity 8.000 cp) 0.5 Ethanol 3.0 Perfume 0.5 Purified water Balance meter 100.0 The body shampoo of the present invention had a good feeling of use and was effective in reducing bulkiness.

[Brief description of the drawings]

FIG. 1 is a drawing showing the change over time in the water retention ability (change in water content) of a sample in Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location A61K 7/11 A61K 7/11 7/50 7/50

Claims (2)

(57) [Claims] 1. The following general formula (I) (Wherein, R represents a linear or branched, saturated or unsaturated alkyl group having 8 to 22 carbon atoms).
Cosmetics characterized by containing more than one kind. 2. The cosmetic according to claim 1, wherein in formula (I), R is a branched alkyl group having 16 carbon atoms.