JP4045235B2 - Transparent cosmetics - Google Patents

Description

  The present invention relates to a transparent cosmetic that has good spreading and skin familiarity when applied, and has a high permeation to the skin.

  Transparent cosmetics contain a large amount of water and water-soluble ingredients, so they have a refreshing feeling of use, but are repelled by sebum, and can be applied to the skin, and the cosmetics are familiar and penetrated. There were problems such as poor nature. For this reason, attempts have been made to improve the applicability to the skin by using a water-soluble polymer or a cationic cross-linkable copolymer as a thickener to increase the viscosity of the cosmetic. For example, Patent Document 1 describes a copolymer having a cationic group and a crosslinked structure in a molecule and exhibiting a specific viscosity behavior. However, when such a thickener is blended, the applicability to the skin is improved, but the familiarity and penetration feeling of the cosmetic itself is not sufficient.

On the other hand, in order to increase the familiarity of cosmetics to the skin, it is common to use a surfactant. However, the surfactants have the disadvantages that the skin after use remains sticky and sticky, and bubbles tend to form during use and are difficult to disappear.
JP 2000-143461 A

  An object of the present invention is to provide a transparent cosmetic that has good spreadability at the time of application, has good familiarity with the skin, and has a high permeation into the skin.

  The inventor of the present invention can obtain a transparent cosmetic that has good spreading and skin penetration and high skin penetration feeling by combining a specific cationic crosslinked copolymer and a polyether-modified silicone. I found out.

That is, the present invention includes the following components (A), (B) and (C):
(A) at least one cationic group-containing vinyl monomer, at least one amide group-containing vinyl monomer, and at least one cross-linkable vinyl monomer having two or more vinyl groups in the molecule. A cationic cross-linked copolymer obtained by radical polymerization of the seed,
(B) 0.04 to 0.4% by mass of a terminal-modified or side-chain-modified polyether-modified silicone,
(C) To provide a transparent lotion or cosmetic liquid containing 70% by mass or more of water.

  The transparent cosmetic composition of the present invention has good spread and familiarity with the skin at the time of application, and has a high penetration feeling into the skin.

The cationic crosslinked copolymer of component (A) used in the present invention comprises at least one cationic group-containing vinyl monomer (hereinafter referred to as monomer (a ₁ )) and an amide group-containing vinyl monomer ( Hereinafter, at least one monomer (a ₂ )) and at least one cross-linkable vinyl monomer (hereinafter referred to as monomer (a ₃ )) having two or more vinyl groups in the molecule. The essential constituent monomer is obtained by radical polymerization.

As the monomer (a ₁ ), (meth) acrylic acid ester or (meth) acrylamides having a dialkylamino group, styrenes having a dialkylamino group, vinylpyridines, N-vinyl heterocyclic compounds, amino groups And a monomeric acid neutralized product or a quaternary ammonium salt, a diallyl-type quaternary ammonium salt, and the like.
Among these, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, quaternary ammonium salt quaternized with quaternizing agent of diethylaminopropyl (meth) acrylamide, or dimethyl Diallylammonium chloride and the like are preferable.

  Examples of the acid for obtaining the acid neutralized product include hydrochloric acid, sulfuric acid, acetic acid, citric acid, succinic acid, adipic acid, sulfamic acid, and the like. Preferred quaternizing agents for obtaining a quaternary ammonium salt Examples thereof include alkyl halides such as methyl chloride and methyl iodide, diethyl sulfate, and di-n-propyl sulfate.

As the monomer (a ₂ ), the general formula (1) or (2)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, R ² and R ³ together represent — (CH ₂ ) _n — (n is an integer of 3 to 6) or — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, and the adjacent nitrogen atom is Forming a ring containing)

(In the formula, R ¹ represents the same meaning as described above, and A ¹ represents — (CH ₂ ) _m — (m represents an integer of 2 to 5)).
The monomer represented by these is mentioned.

  Specifically, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, Nt-butylacrylamide, N- (meth) acryloylmorpholine, N-vinyl piperidone, N-vinyl pyrrolidone and the like can be mentioned. Among these, a feeling of use is preferable when N, N-disubstituted acrylamide is used, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like are more preferable.

Examples of the monomer (a ₃ ) include polyhydric alcohols or (meth) acrylic acid esters of unsaturated alcohols, acrylamides, divinyl compounds, polyallyl compounds, and the like. Of these, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, allyl etherified pentaerythritol, vinyl (meth) acrylate, allyl (meth) acrylate, and the like are preferable. .

A preferable blending ratio of the monomer (a ₁ ) and the monomer (a ₂ ) is 2/98 to 98/2 in terms of a molar ratio of (a ₁ ) / (a ₂ ), more preferably 3 / 97 to 60/40. It is preferable for the molar ratio to be within this range, since both the properties of thixotropy and the retention of viscosity at a low share rate are adequately exhibited. When the mixing ratio of the monomer (a ₁ ) exceeds the range shown here, the thixotropy tends to be lacking. Further, when the blending ratio of the monomer (a ₂ ) is excessive from the range shown here, the viscosity at the low shear rate tends to be lowered.

The ratio of the monomer (a ₃ ) is preferably 0.0002 to 2 in terms of molar ratio with respect to the total amount of monomers, particularly preferably 0.0002 to 1%, and more preferably 0.0002 to 0.4. When the proportion of the monomer (a ₃ ) is in the above range, the hydrogel formed from the resulting copolymer has a sufficient viscosity, and the hydrogel feels soft and slippery.

  The cationic cross-linked copolymer of component (A) constitutes other vinyl monomers copolymerizable therewith in addition to one or more of the above-mentioned three types of vinyl monomers as essential constituent units. Can be an ingredient. Examples of other vinyl monomers include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate and ethyl (meth) acrylate; anionic group-containing monomers such as acrylic acid and methacrylic acid; N- ( And betaines such as 3-sulfopropyl) -N-acryloyloxyethyl-N, N-dimethylammonium betaine and N-carboxymethyl-N-methacryloyloxyethyl-N, N-dimethylammonium betaine.

  The cationic cross-linked copolymer is obtained by radical polymerization of the monomer by a conventional method, and can be produced using an aqueous solution polymerization method, a reverse phase suspension polymerization method, a precipitation polymerization method, or the like. Among these, water or a hydrophilic organic solvent that can be uniformly mixed with water, or a mixture of these, the monomer component is uniformly dissolved and vacuum degassed or replaced with an inert gas such as nitrogen or carbon dioxide. It is preferable to carry out the reaction at an initiation temperature of 20 to 90 ° C. and a reaction time of about 1 to 10 hours using an aqueous solution polymerization method in which the dissolved oxygen in the system is removed by, for example, and then reacted by adding a polymerization initiator.

As the polymerization initiator, it is possible to use a peroxide that dissolves uniformly in a solvent, an organic inorganic peracid or a salt thereof, a diazeneyl di-type compound alone, or a redox type that is combined with a reducing agent.
Typical examples are t-butyl peroxide, t-amyl peroxide, cumyl peroxide, acetyl peroxide, propionyl peroxide, benzoyl peroxide, benzoylisobutyryl peroxide, lauroyl peroxide, t-butyl hydroperoxide. Oxide, cyclohexyl hydroperoxide, tetralin hydroperoxide, t-butyl peracetate, t-butyl perbenzoate, bis (2-ethylhexyl peroxydicarbonate), 2,2′-azobis i-butyronitrile, phenylazotriphenylmethane 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2-azobi [2- (2-imidazolin-2-yl) propane] dihydrochloride, sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, persulfate and triethylamine, triethanolamine, dimethylaniline, etc. A combination with a secondary amine is exemplified.

  One or more cationic cross-linked copolymers can be used, and it is preferable to contain 0.01 to 5% by mass, particularly 0.1 to 2% by mass in the total composition, from the viewpoint of usability.

The polyether-modified silicone of component (B) used in the present invention is a terminal-modified or side-chain-modified one, and includes a pendant type (comb type), a both-end modified type, a one-end modified type, and the like.
Examples of such modified silicones include dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane / methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane / methyl (polyoxyethylene / polyoxypropylene) siloxane. A copolymer etc. are mentioned.
More specifically, the following general formulas (3), (4), (5)

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkylene group having 0 to 5 carbon atoms, j is an integer of 1 to 100, k is an integer of 1 to 20, p is an integer of 1-50, q is an integer of 0-50)
The thing represented by is mentioned.

  Moreover, as a commercial item, as a pendant type (comb type), FZ-2404, FZ-2405, FZ-2408, FZ-2411, FZ-2412, SS-2801, SS-2802, SS-2804, FZ-2184 , FZ-2161, FZ-2162, FZ-2104, L-7604, FZ-2188, FZ-2163, FZ-2118, FZ-2170, FZ-2105, L-77 (Nippon Unicar), KF- 6011, KF-6013, KF-6018 (the above, Shin-Etsu Chemical Co., Ltd.), SH3771M (the above, Toray Dow Corning Silicone), TSF4440, TSF4441, TSF4452 (the above, GE Toshiba Silicone), etc. can be used. .

  Moreover, as a polyether modified silicone of a component (B), the thing of HLB10 or more, especially HLB10-18 is preferable from a compatible point with water. Here, HLB is based on a value obtained from the cloud number (cloud number: an index correlated with HLB and applied to ether type nonionic surfactants).

One or more kinds of polyether-modified silicones can be used, and 0.01 to 1% by mass, particularly 0.04 to 0.4% by mass in the total composition reduces the surface tension of the entire cosmetic. And preferable from the viewpoint of usability.
As a ratio of a component (A) / (B), 0.01-500, Preferably the range of 0.1-100 is good from the point of a usability | use_condition.

  The component (C) water is contained in an amount of 70% by mass or more, preferably 70 to 99.98% by mass in the entire composition.

  In addition to the above components, the cosmetic of the present invention includes components used in normal cosmetics such as salts, pH adjusters, pigments, preservatives, antioxidants, ultraviolet absorbers, plant extracts, fragrances, chelates. Medicinal components such as an agent, an astringent, a bactericidal agent, and an activator can be contained.

The cosmetic of the present invention can be produced by a usual method, for example, by adding the above components to water, stirring, and performing filtration or the like as necessary.
The cosmetic of the present invention preferably has a viscosity at 25 ° C. of 0.1 to 100 mPa · s, particularly 0.1 to 50 mPa · s (using a B8L viscometer, Tokimec), lotion, cosmetic liquid, etc. It can be applied as a skin cosmetic.

  The cosmetic of the present invention is transparent. In the present invention, the term “transparent” means that the transmittance is measured using a spectrophotometer (Shimadzu UV-visible spectrophotometer UV-160, Shimadzu Corporation; optical path length: 10 mm), and the transmittance of purified water is 100 as a control. The thing in the area | region of 80-100. When the transmittance is less than 80, the cosmetic is translucent to cloudy.

  In addition, the cosmetic of the present invention preferably has a surface tension at 25 ° C. of 35 mN / m or less, particularly 30 to 10 mN / m from the viewpoint of usability. In the present invention, the surface tension is measured by the Wilhelmy method. Specifically, the surface tension is drawn by hanging a suspension plate (made of platinum) on the liquid surface. Is a method of directly measuring with a balance.

Production Example 1 (Production of Cationic Crosslinked Copolymer)
In a reaction vessel, N, N-dimethylaminoethyl diethyl methacrylate sulfate (MOEDES: Nitto Chemical Industries, Ltd.) 23.85 g, N, N-dimethylacrylamide (DMAAm) 71.37 g, polyethylene glycol (9EO) dimethacrylate ( NK-9G: Shin-Nakamura Chemical Co., Ltd.) Pre-nitrogen-substituted monomer aqueous solution consisting of 0.0429 g and ion-exchanged water 350 g was added, nitrogen was further blown for 20 minutes, and the temperature of the reaction system was raised to 55 ° C. while substituting nitrogen. did. Next, 0.22 g of a polymerization initiator (2,2′-azobis (2-amidinopropane) dihydrochloride) was added. Polymerization started after 30 minutes to 1 hour, and the whole became a soft gel. Stirring was continued as it was, and the polymerization was stopped 4 hours after the addition of the polymerization initiator. The bowl-shaped contents were taken out, washed with stirring in 5 L of ethanol for 10 minutes, and dried. Thereafter, the mixture was pulverized with a coffee mill and a jet mill, and the pulverized particles were classified with a high volta to obtain a cationic cross-linked copolymer (1).

Production Example 2
Cationic crosslinked copolymers (2) to (8) were produced in the same manner as in Production Example 1 using the monomers shown in Table 1.

Examples 1-5, Comparative Examples 1-5
Cosmetics having the compositions shown in Table 2 were produced by a conventional method. About the obtained cosmetics, transparency and surface tension were measured, and the spread at the time of application | coating, the familiarity to skin, and the osmosis | permeation feeling to skin were evaluated. The results are also shown in Table 2.

(Evaluation methods)
(1) Transparency:
Using a spectrophotometer (Shimadzu UV-visible spectrophotometer UV-160, Shimadzu Corporation; optical path length 10 mm), the transmittance when the transmittance of purified water was set to 100 as a control was measured. Those having a transmittance of 80 to 100 are indicated by ◎, and those having a transmittance of less than 80 are indicated by ×.

(2) Surface tension:
The surface tension at 25 ° C. was measured with a surface tension meter PROCESSOR TENSIOMETER K14 (KRUSS, Wilhelmy method).

(3) Spreading at the time of application, familiarity with skin, and penetration into skin:
When 10 female panelists applied 0.05 to 0.1 g of each cosmetic on the forearm flexion side after washing, sensory evaluation was performed for the spread at the time of application, the familiarity with the skin, and the penetration into the skin. Evaluation is 2 points for good, 1 point for good, 0 for normal, -1 for not good, -2 for bad, and determine the average score of the panelers. did.
A: The average score is 1.5 to 2.0.
A: The average score is 0.5 to 1.4.
(Triangle | delta): An average point is -0.5-0.4.
X: Average point is -2.0 to -0.6.

Examples 6-9
Cosmetics having the compositions shown in Table 3 were produced by a conventional method.
Each of the obtained cosmetics is transparent, and has excellent spreadability upon application, familiarity with the skin, and permeation into the skin.

Claims (4)

The following components (A), (B) and (C):
(A) at least one cationic group-containing vinyl monomer, at least one amide group-containing vinyl monomer, and at least one cross-linkable vinyl monomer having two or more vinyl groups in the molecule. 0.01-5% by mass of a cationic cross-linked copolymer obtained by radical polymerization of seeds ,
(B) The following general formula (3)

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, j is an integer of 1 to 100, k is an integer of 1 to 20, p is an integer of 1 to 50, and q is an integer of 0 to 50. Indicates an integer)
0.04 to 0.4% by mass of a side chain-modified polyether-modified silicone represented by
(C) A transparent lotion or cosmetic liquid containing 70% by mass or more of water.   The transparent lotion or cosmetic liquid according to claim 1, wherein the polyether-modified silicone of component (B) is HLB 10 or more. In the component (A), the amide group-containing vinyl monomer is represented by the general formula (1) or (2).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, R ² and R ³ together represent — (CH ₂ ) _n — (n is an integer of 3 to 6) or — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, and the adjacent nitrogen atom is Forming a ring containing)

(In the formula, R ¹ represents the same meaning as described above, and A ¹ represents — (CH ₂ ) _m — (m represents an integer of 2 to 5)).
The transparent lotion or cosmetic liquid according to claim 1 or 2, which is represented by:   The surface lotion in 25 degreeC is 35 mN / m or less, The transparent lotion or cosmetic liquid of any one of Claims 1-3.