JPH06247829A - Makeup cosmetic - Google Patents

Abstract

PURPOSE:To obtain a makeup cosmetic, capable of imparting smoothness; to a coated film and good in makeup durability in washing or rubbing by blending a specific sulfonic acid-modified silicone therein. CONSTITUTION:This makeup cosmetic comprises a sulfonic acid-modified silicone expressed by formula I [R1 is alkyl or (substituted)phenyl; R1 is bi-to undecavalent hydrocarbon residue; A is residue produced by reacting isocyanate group with a functional group having active hydrogen; R3 is arylene, alkylene, alkarylene or aralkylene; X is monovalent metal, H, or H.X1 (X1 is ammonia or amine); (m) is 50-200; (p) is 1--10]. For example, a compound expressed by formula II [(m) is 130; (p) is 1] is cited as the compound expressed by formula I. The compound expressed by formula I is obtained by reacting a silicone having the isocyanate group with a compound having a group SO3X and active hydrogen. This cosmetic has high adsorptivity for the skin and is hardly removed by washing or rubbing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a makeup cosmetic, and more particularly to a makeup cosmetic containing a sulfonic acid-modified silicone.

[0002]

2. Description of the Related Art Various silicone derivatives have been used in order to impart smoothness, water repellency, and oil repellency (sweat resistance and sebum resistance) to a coating film for makeup cosmetics and make them last longer. These silicone derivatives have the advantage that they are less sticky than hydrocarbons and ester oils, and are therefore widely used in makeup cosmetics.

However, silicone derivatives generally have a low adsorptivity to keratin keratin, are easily removed from the skin by washing or rubbing, and have a problem of poor makeup retention against washing or rubbing.

Therefore, in order to improve perspiration resistance, sebum resistance, etc., and to improve makeup retention, a high molecular silicone (Japanese Patent Laid-Open No. SHO 6-96) is used.
3-183516), fluorine-modified silicone (JP-A-2-295913, JP-A-2-298338), polyether-modified silicone (JP-A-3-204).
Makeup cosmetics using No. 806) have been developed. Although these techniques have succeeded in improving makeup retention, makeup cosmetics excellent in washing resistance and abrasion resistance are desired in order to further improve makeup retention.

On the other hand, among the silicone derivatives, amino-modified silicone is said to have a relatively high adsorptivity to keratin keratin, and is excellent in makeup retention, but general silicone has smoothness on the skin. However, the effect of imparting a moist feeling was insufficient.

[0006]

SUMMARY OF THE INVENTION The present invention has been made from the above point of view, and provides a makeup cosmetic which imparts smoothness to the coating film of the makeup cosmetic and has a long-lasting makeup durability against washing and rubbing. The challenge is to provide.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventor has found that when a sulfonic acid-modified silicone represented by the following chemical formula 2 is added to a makeup cosmetic composition, a coating film is formed. The present inventors have found that it is possible to impart smoothness and improve the durability of makeup against washing and rubbing, and have reached the present invention.

That is, the present invention is a makeup cosmetic containing a sulfonic acid-modified silicone represented by the following chemical formula 2. Hereinafter, the present invention will be described in detail.

<1> Sulfonic Acid-Modified Silicone Used in the Present Invention The sulfonic acid-modified silicone used in the present invention is represented by the general formula (2).

[0010]

[Chemical 2]

However, each R ₁ independently represents a lower alkyl group or an unsubstituted or substituted phenyl group, and R ₂ is 2 to 1
Indicates a monovalent hydrocarbon residue, the carbon-carbon single bond of which may be interrupted by a residue formed by the reaction of a functional group, and A is formed by the reaction of an isocyanate group with a functional group having an active hydrogen. Is a residue, R ₃ represents an arylene group, a linear or branched alkylene group, an alkali-ylene group or an aralkylene group, and X is a monovalent metal, a hydrogen atom or —H.
X ₁ (where X ₁ represents ammonia or amine), m represents an integer of 50 to 200, and p represents 1 to
Indicates an integer of 10.

The lower alkyl group is preferably a methyl group, an ethyl group or a propyl group. R ₂ is 2 to 1
Indicates a monovalent hydrocarbon residue, preferably having 2 to 25 carbon atoms
Aliphatic residue, aromatic residue, aliphatic aliphatic residue having 1 to 5 carbon atoms or a residue having a repeating unit thereof, or aliphatic aromatic residue having 1 to 5 carbon atoms Alternatively, it represents a residue having the repeating unit. Further, the residue resulting from the reaction of these aliphatic carbon-carbon single bond interrupting functional group, for example, an ether bond generated by the reaction of alcohol and / or epoxide, a functional group having an isocyanate and active hydrogen, such as an amino group, Residue produced by reaction with hydroxyl group, mercapto group, or carboxyl group, for example,

[0013]

[Chemical 3]

And the like. The residue produced by the reaction between the isocyanate group represented by A and the functional group having active hydrogen is the same as above. R ₃ is preferably a phenylene group, a phenylene group substituted with a lower alkyl group having 1 to 4 carbon atoms, an alkylene group having 1 to 5 carbon atoms, and

[0015]

[Chemical 4]

[0016] The monovalent metal represented by X is preferably Li, Na or K. Furthermore, when X ₁ in formula -H · X ₁ is an amine, which is
It is represented by the general formula N (R ₃ ) ₃ , wherein each R ₃ independently represents a hydrogen atom, preferably a linear or branched alkyl group having 1 to 5 carbon atoms, or preferably Represents a straight-chain or branched hydroxyalkyl group having 1 to 5 carbon atoms, preferably having 3 or less hydroxyl groups.

Examples of the amine include triethanolamine, 2-amino-2-methyl-1-propanol,
2-amino-2-methyl-1,3-propanediol,
Examples include monoethanolamine and the like. The value of m is 50
~ 200. The value of p is 1 to 10, preferably 1 to 5. The number average molecular weight (Mn) of the sulfonic acid-modified silicone is 5000 to 15000.

The sulfonic acid-modified silicone used in the present invention can be produced by synthesizing a silicone having an isocyanate group and then reacting the silicone with a compound having a —SO ₃ X group and active hydrogen.

Here, the silicone having an isocyanate group is represented by Chemical Formula 5.

[0020]

[Chemical 5]

Here, R ₁ , R ₂ , m and p are the same as above. The silicone having an isocyanate group can be produced by various methods, for example, by reacting a polyisocyanate containing at least two isocyanate groups having a functional group having active hydrogen.

The silicone having a functional group having active hydrogen is, for example,

[0023]

[Chemical 6]

(Here, m is an integer of 50 to 200) and the like. On the other hand, the polyisocyanate containing at least two isocyanate groups means, for example, hexane methylene diisocyanate (HDI), methylene diphenyl isocyanate (MDI), tolylene diisocyanate (TDI) and

[0025]

[Chemical 7]

(Here, n is preferably 1 to 9) and the like. The amount of the polyisocyanate containing at least two isocyanate groups used is preferably 1.0 to 1.2 in terms of an equivalent ratio to active hydrogen in the silicone having a functional group having active hydrogen.

The reaction conditions are preferably an inert gas atmosphere of nitrogen or the like, a reaction temperature of 0 to 150 ° C., particularly preferably 50 to 100 ° C., a reaction time of 2 hours to 20 hours, and particularly preferably 5 ~ 10 hours are used.

Next, a sulfonic acid-modified silicone is produced by reacting the above-mentioned silicone having an isocyanate group with a compound having a —SO ₃ X group and active hydrogen. Examples of the compound having a —SO ₃ X group and active hydrogen used here include sodium isethionate and sodium sulfanilate. The amount of the compound used is preferably 1.0 to 1.5 in an equivalent ratio to the isocyanate group in silicone.

In the reaction, a solvent such as 1,
4-dioxane, dimethoxyethane, diethyl ether, tetrahydrofuran, a hydrocarbon solvent having 5 to 8 carbon atoms (such as hexane), or the like, or a mixture of two or more thereof may be used. As an example of preferable reaction conditions, the reaction system is placed in an atmosphere of an inert gas such as nitrogen and the reaction temperature is 0 to 200 ° C., more preferably 50 to 150 ° C.
And the reaction time is about 5 to 50 hours, more preferably about 10 to 30 hours.

A method for converting a sulfonic acid group into an ammonium salt or an amine salt is known. For example, a sulfonic acid-modified silicone in which X in the formula 2 is a monovalent metal prepared as described above is dissolved in hexane or heptane, and an aqueous solution of hydrochloric acid or sulfuric acid is added thereto, preferably at a reaction temperature of 0 to
After acidic hydrolysis at 50 ° C., preferably for a reaction time of 5 minutes to 1 hour, the silicone phase is removed and the amine is added to it to give a sulfonic acid-modified silicone in the form of an amine salt.

<2> Makeup Cosmetic of the Present Invention The makeup cosmetic of the present invention contains the sulfonic acid-modified silicone, and is used as a mixture of two or more of the sulfonic acid-modified silicone. May be.

The content of the sulfonic acid-modified silicone is preferably 0.1-40%, more preferably 0.5-3.
It is 0%. If the blending amount is less than 0.1%, the effect of imparting smoothness, cleaning resistance and abrasion resistance to the cosmetic film is poor. Further, when it exceeds 40%, it is difficult to stably mix in a dosage form such as easy separation, and the viscosity of the produced cosmetic is
It may be difficult to obtain the desired physical properties in terms of hardness.

The make-up cosmetics used in the present invention include foundations, lipsticks, eye shadows, mascaras, eyeliners, under-makeups, nail enamel, blushers, eyebrow inks and the like. The dosage form is not particularly limited.

In addition to the above-mentioned sulfonic acid-modified silicone, the makeup cosmetics of the present invention include oils, surfactants, alcohols, etc., which are usually added to makeup cosmetics.
Polymer compounds, powders, water, other ingredients, applications, dosage forms,
It may be appropriately blended depending on the purpose and the like.

The above oils include liquid paraffin,
Liquid oils such as squalane, cetyl 2-ethylhexanoate, isopropyl myristate, olive oil, castor oil; semi-solid to solid fats such as petrolatum, solid para, beef tallow, lanolin, beeswax, whale wax, cholesterol; cetanol, behenyl alcohol, etc. And higher fatty acids such as palmitic acid and stearic acid; fluorine-based oil agents such as perfluoropolyether; and silicone derivatives other than the sulfonic acid-modified silicone used in the present invention.

As the above-mentioned surfactant, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene (hereinafter abbreviated as "POE") sorbitan fatty acid ester, POE glycerin fatty acid ester, POE alkyl ether, POE polyoxypropylene alkyl ether, POE
Nonionic surfactants such as polyoxypropylene copolymer, POE alkyl phenyl ether, POE hydrogenated castor oil, polyethylene glycol fatty acid ester, decaglycerin fatty acid ester, alkyldiethanolamide;
Alkyl sulfate, POE alkyl ether sulfate, POE alkyl ether acetate, alkyl phosphate, POE alkyl ether phosphate, higher fatty acid salt, higher fatty acid hydrolyzed collagen salt, amino acid-based anionic surfactant; sulfosuccinic acid-based Surfactants, anionic surfactants such as olefin sulfonates; amphoteric surfactants such as lecithin, betaine acetate, imidazolinium betaine, etc .; alkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride And the like.

Alcohols include monohydric alcohols such as ethanol, propanol and benzyl alcohol;
Examples include polyhydric alcohols such as 1,3-butylene glycol, propylene glycol, dipropylene glycol, glycerin, polyethylene glycol and sorbitol.

As the polymer compound, polyvinylpyrrolidone, polyvinyl alcohol, vinylpyrrolidone-vinyl acetate copolymer, acrylic resin alkanolamine, N-
Methacryloylethyl N, N-dimethylammonium α-N-
Methyl carboxy betaine / methacrylic acid alkyl ester copolymer, polyvinyl acetate, hydroxyethyl cellulose dimethyl diallyl ammonium chloride, hydroxyethyl cellulose hydroxypropyl trimethyl ammonium chloride ether, carboxy vinyl polymer, carboxymethyl cellulose salt, xanthan gum,
Examples thereof include hydroxyethyl cellulose and the like.

As the powder, metal powder pigments such as talc, mica, titanium dioxide, sericite, carion, pearl pigment, aluminum powder and copper powder,
Iron oxide (red iron oxide), yellow iron oxide, black iron oxide, carbon black, mango violet, cobalt violet,
Chromium oxide, chromium hydroxide, ultramarine, zinc white, bentonite, aluminum silicate, calcium silicate, calcium carbonate, silica, nylon powder, polyester powder, polyethylene powder, polystyrene powder,
Cellulose powder, Red 201, Red 202, Red 205, Red 220, Red 226, Red 405
No. 203, Orange No. 203, Yellow No. 205, Yellow No. 401, Blue No. 404, and other organic pigments, Red No. 3, Red No. 104, Red No. 227, Red No. 401, Red No. 505, Orange No. 205
No. 4, Yellow No. 4, Yellow No. 202, Yellow No. 203, Green No. 3, and Blue No. 1 such as organic pigments such as zirconium, barium, or aluminum lake.

Further, the above-mentioned other components include humectants such as amino acids and hyaluronic acid; ultraviolet absorbers such as oxybenzone and para-aminobenzoic acid ester; antioxidants such as tocopherol and dibutylhydroxytoluene; paraben, phenoxyethanol and the like. Antiseptic; bactericides such as isopropylmethylphenol and trichlorocarban; hydrolysates of proteins such as collagen, keratin, silk (eg hydrolyzed collagen: Promois W42R manufactured by Seiwa Kasei Co., Ltd.); citric acid, citric acid PH adjusting agents such as sodium, plant extracts, anti-inflammatory agents such as dipotassium glycyrrhizinate; propellants such as dimethyl ether and LPG; Na
Examples include inorganic salts such as Cl; astringents such as hamamelis water; chelating agents, various vitamins, and fragrances.

[0041]

The makeup cosmetic of the present invention, when applied to the skin, forms a cosmetic film having a smooth feel. Further, the cosmetic film is adsorbed by keratin keratin of sulfonic acid-modified silicone, so that it can be washed or rubbed. It is hard to remove and has long-lasting makeup.

[0042]

EXAMPLES Hereinafter, production examples of sulfonic acid-modified silicone used in the present invention, examples of the present invention will be given together with comparative examples,
The effects of the present invention will be described in more detail, but the present invention is not limited to these sulfonic acid-modified silicones and examples.

[0043]

[Production Example] A production example of the sulfonic acid-modified silicone used in the present invention will be described.

[0044]

[Production Example 1] 500 ml round bottom flask 6
150 parts by weight and 2.7 parts by weight of silicone having a structure shown in the formula (4) and having a hydroxyl group at one end having an average molecular weight of 10,000 (Cilaplane FM0425 manufactured by Chisso Corporation) and HDI, respectively. (Isocyanate has an equivalent ratio of 1.07 to active hydrogen in the silicone), 1
The reaction was carried out at 00 ° C with stirring. The reaction was followed by IR spectrum, and the reaction was continued until the absorption intensity attributed to the isocyanate of 2200 to 2300 cm ^-1 became half of that at the start of the reaction to produce a silicone having an isocyanate group at the terminal.

Next, 2.3 parts by weight of sodium isethionate (the active hydrogen in the compound has an equivalent ratio of 1.03 to the isocyanate group in the silicone) and 50 parts by weight of 1,4-dioxane are added. The reaction was continued until the absorption of isocyanate disappeared. After the reaction is completed, the product is filtered, and then the low-boiling substance is removed by distillation to obtain a colorless transparent oil 120.
Got gram. This oil has an IR spectrum
It was confirmed to be a sulfonic acid-modified silicone represented by Chemical formula 8.

[0046]

[Chemical 8]

However, m is 130 and p is 1.

[0048]

[Production Example 2] In a 500 ml round bottom flask, a silicone 15 having a hydroxyl group at one end as in Production Example 1 was used.
Contains 0 part by weight and 3.95 parts by weight of MDI (isocyanate has an equivalent ratio of 1. to active hydrogen in the silicone).
The reaction was carried out at 80 ° C. with stirring. The reaction was followed by IR spectrum in the same manner as in Production Example 1 to produce a silicone having an isocyanate group at the terminal, and then 2.34 parts by weight of sodium isethionate (active hydrogen in the compound was based on the isocyanate group in the silicone). The equivalent ratio is 1.05), and 100 parts by weight of 1,4-dioxane are added and reacted until the absorption of isocyanate disappears.

After completion of the reaction, filtration was carried out, and then low-boiling substances were removed by distillation to obtain 100 g of a pale yellow oil. It was confirmed by IR spectrum that this oil was a sulfonic acid-modified silicone represented by Chemical formula 9.

[0050]

[Chemical 9]

However, m is 130 and p is 1.

[0052]

Production Example 3 In a 500 ml round bottom flask, a silicone having a structure represented by the chemical formula (4) in chemical formula 6 and having a hydroxyl group at one end and an average molecular weight of 5,000 (X-22 manufactured by Shin-Etsu Chemical Co., Ltd.) -170D) 100 parts by weight and MDI 5.3
6 parts by weight (isocyanate has an equivalent ratio of 1.07 to active hydrogen in the silicone) were reacted at 80 ° C. with stirring.

The reaction was followed by IR spectrum in the same manner as in Production Example 1 to produce a silicone having an isocyanate group at the terminal, and then 4.95 parts by weight of sodium sulfaniate (active hydrogen in the compound was the isocyanate in the silicone). 100 parts by weight of 1,4-dioxane were added and reacted until the absorption of isocyanate disappeared. After the reaction was completed, the reaction mixture was filtered, and low-boiling substances were subsequently removed by distillation to obtain a light yellow oil 100.
Got gram.

The IR spectrum of this oil is
It was confirmed to be a sulfonic acid-modified silicone represented by 0.

[0055]

[Chemical 10]

However, m is 60 and p is 1.

[0057]

[Production Example 4] Silicone 100 having a hydroxyl group at one end as in Production Example 1 was placed in a 500 ml round bottom flask.
Part by weight and 7.5 parts by weight of PMDI (a mixture of n = 1 to 5) are contained (isocyanate has an equivalent ratio of 1.0 to active hydrogen in the silicone), and reacted at 70 ° C. with stirring. It was

The reaction was followed by IR spectroscopy, 220
After the intensity of the absorption attributed to the isocyanate 0~2300cm ^{over 1} ends the reaction continued until no change has preparing isocyanates of silicone, 6.5 part by weight of sodium isethionate (active hydrogen in the compound Equivalent ratio to isocyanate group in silicone is 1.05
30 parts by weight of 1,4-dioxane and reacted until the absorption of isocyanate disappeared.

After the reaction was completed, the reaction mixture was filtered, and then low-boiling substances were removed by distillation to obtain 90 g of a pale yellow viscous oil. It was confirmed by IR spectrum that this oil was a sulfonic acid-modified silicone represented by Chemical formula 11.

[0060]

[Chemical 11]

However, m is 130 and p is 2 or more and 10 or less.

[0062]

Production Example 5 50 g of the sulfonic acid-modified silicone produced in Production Example 1 was dissolved in 50 ml of hexane, and 1N HCl was added.
The mixture was reacted with 50 ml of an aqueous solution at room temperature for 20 minutes while stirring. After the reaction, the silicone phase was taken out, 1 g of triethanolamine was added, and the mixture was reacted for 30 minutes while stirring,
The unreacted portion was distilled off to obtain 47 g of a milky white oil.

This oil was a triethanolamine salt of a sulfonic acid-modified silicone represented by Chemical formula 12.

[0064]

[Chemical 12]

Hereinafter, the sulfonic acid-modified silicones obtained in the above-mentioned production examples were respectively converted into sulfonic acid-modified silicones 1 to 1.
5 Next, examples using these will be described.

[0066]

Examples 1-4 Pressed powder <Production method> Each silicone compound shown in Table 1 was used, and Table 2 was used.
A pressed powder having the following formulation was produced. Phase A, which has been uniformly mixed and dissolved, is added to phase B, which has been uniformly stirred and mixed, and after mixing and crushing, a die is punched.

[0067]

[Table 1]

[0068]

[Table 2]

<Evaluation> A certain amount of the pressed powder of each of the above Examples and Comparative Examples was applied to the upper arm portion by puffing, and the smoothness of the applied portion, and the goodness of makeup retention against abrasion were evaluated.

(1) Smoothness of coated part The pressed powder of each of the above Examples and Comparative Examples was applied to the upper arm with a fixed amount of puff, and the degree of smoothness of the coated part was sensory-evaluated by a skilled evaluator into four levels. .

⊚: Smooth ○: Slightly smooth Δ: Not smooth ×: Not smooth

(2) Goodness of makeup retention against washing and rubbing After evaluating the smoothness of the coated part in (1), the coated part was coated with 15% sodium polyoxyethylene lauryl ether sulfate (L).
ES) Use an aqueous solution to clean and rinse while rubbing by hand 3
Repeat times. After drying, the level of makeup retention was sensory-evaluated by the remaining color tone. The evaluation was performed by a skilled evaluator in four levels.

⊚: Good ∘: Slightly good Δ: Slightly bad ×: Poor Table 3 shows the results of the above evaluations.

[0074]

[Table 3]

[0075]

Examples 5 to 7 Liquid Foundation Using each of the silicone compounds shown in Table 4, a liquid foundation having the formulation shown in Table 5 was produced. Phase B, which has been uniformly mixed, is added to phase A, which is heated and dissolved at 80 ° C., and uniformly dispersed.
To this, phase C heated and dissolved at 80 ° C. was added with stirring,
Further, phase D heated and dissolved at 80 ° C. is added. Then, it is cooled to room temperature with stirring.

0.3 g of the liquid foundation of each of the above Examples and Comparative Examples was applied to the upper arm in an area of 3 cm × 3 cm, and after drying, the smoothness of the applied part was sensory evaluated. Then, using a 15% LES aqueous solution, washing and rinsing were repeated 3 times while rubbing the coated part by hand, and after drying, the makeup retention was sensory-evaluated by the remaining color tone. The results are shown in Table 4.

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

Examples 8 to 10 Lipsticks Using the silicone compounds shown in Table 6, lipsticks having the formulations shown in Table 7 were produced. Heated and melted at 80 ° C, mixed and homogenized A
Phase B is added to the phase, kneaded with a roll mill, uniformly dispersed, then remelted, phase C is added, poured into a mold, and rapidly cooled to solidify.

The lipstick was applied to the upper arm three times, and the smoothness of the applied part was sensory evaluated. Then, using a 15% LES aqueous solution, washing and rinsing were repeated three times while rubbing the coated part by hand, and after drying, sensory evaluation was performed. The results are shown in Table 6.

[0081]

[Table 6]

[0082]

[Table 7]

From the evaluation results of each of the above-mentioned execution columns, the makeup cosmetics of the present invention are far superior to the makeup cosmetics of the comparative example in smoothness of the application part, durability of the makeup and cleaning. It is clear that In particular, it is not lost from the skin after multiple washes with detergent.

[0084]

EFFECTS OF THE INVENTION The makeup cosmetic of the present invention has an excellent effect of imparting a smooth feel to the applied portion, has high adsorptivity to the skin, and is hard to be removed by washing or rubbing.

Claims (1)

[Claims] 1. A makeup cosmetic containing the sulfonic acid-modified silicone represented by Chemical formula 1. [Chemical 1] However, each R ₁ independently represents a lower alkyl group or an unsubstituted or substituted phenyl group, R ₂ represents a hydrocarbon residue having a valence of ₂ to 11, and its carbon-carbon single bond is a residue generated by reaction of a functional group. May be interrupted by a group, A is a residue formed by the reaction of an isocyanate group and a functional group having active hydrogen, R ₃ is an arylene group, a linear or branched alkylene group, an alkali-alkylene group or an aralkylene group. Group, X represents a monovalent metal, a hydrogen atom or —H · X ₁ (where X ₁ represents ammonia or an amine), m represents an integer of 50 to 200, and p represents 1 Indicates an integer of -10.