JP6327665B2 - Skin care cosmetics - Google Patents

Description

  The present invention forms a soft and elastic film without stickiness during and after use, and is excellent in sustainability because it is uniformly adsorbed to the skin surface by ionic interaction, and a protective film that does not feel sticky or dry The present invention relates to a skin care cosmetic that gives firmness to the skin.

  Skin care cosmetics that are soft and rich in elasticity and give a youthful impression when there is a feeling of elasticity, but because the feeling of elasticity is lost due to aging or drying of the skin, etc. Various proposals have been made. Among these, there are cosmetics that improve elasticity by applying various cosmetic ingredients such as vitamins, collagen, and hyaluronic acid to the skin and improving the physiological state of the skin, but these lack immediate effects, It takes time to realize a sense of elasticity.

On the other hand, cosmetics that give a firm feeling by forming a film on the skin instead of such medicinal ingredients have also been proposed, for example, water-in-oil emulsification containing glyceryl isostearate and polyvinyl alcohol. Composition (Patent Document 1), composition for external use (Patent Document 2) in which oily particles having a particle diameter of 10 to 2000 μm are dispersed in an aqueous phase containing polyvinyl alcohol, skin cosmetics containing agar and specific silicone oil (Patent Document 3), oil-in-water emulsified cosmetics (Patent Document 4) using stearyl stearate and hydrocarbon wax in combination are disclosed.

JP 2010-229103 A JP 2011-46629 A JP 2010-235473 A JP 2010-235472 A

However, in Patent Documents 1 and 2, a film is formed on the skin to produce a sense of elasticity, and further, an effect of preventing moisture transpiration and a moisturizing effect are imparted. However, polyvinyl alcohol has a high film strength and is stiff. There was a case of feeling sensation or distorting without fitting to the movement of facial expressions. Patent Document 3 also has the same function, but the effect is insufficient and the sustainability is also lacking. Further, since Patent Document 4 uses stearyl stearate and a hydrocarbon oil, it is difficult to obtain a firm tension feeling, and the lift-up effect is not satisfactory.
Therefore, there is a demand for a method capable of imparting excellent firmness to the skin and maintaining the effect for a long time, and an object of the present invention is to provide such a skin care cosmetic.

In such a situation, the present inventors have conducted intensive research to solve the above problems, and as a result, the cation-modified (meth) acryl silicone graft copolymer adheres to the skin surface by ionic interaction, It has been found that a uniform film can be formed, and the cosmetic effect over time is continuously exhibited. In addition, when used together with a hard acrylic polymer in the core, a urethane polymer with flexibility in the shell, and a composite resin emulsion containing a polymer with a different specific structure, the film is flexible and non-sticky, and has a uniform and high elasticity. It was found that the lift-up effect was also significantly improved, and the present invention was completed.

That is, the present invention includes the following components (A) and (B):
(A) A composite resin emulsion obtained by the following steps (1) to (4);
(1) A polymerization monomer that contains an ester group-containing (meth) acrylic acid monomer, and a polymer obtained by polymerizing the monomer has a glass transition temperature of 95 ° C. or higher and 105 ° C. or lower. Prepolymer containing an isocyanate group and a carboxyl group by reacting polypropylene glycol, dimethylolpropionic acid and an aliphatic or alicyclic polyvalent isocyanate in the presence of a functional monomer (component (a2)) Producing (component (a1)) and obtaining a mixture of component (a1) and component (a2),
(2) Neutralizing the carboxyl group contained in the component (a1) in the mixed solution obtained in (1) with an equivalent amount of triethanolamine, the neutralized product of the component (a1) and the component (a2) Obtaining a mixture of
(3) A step of emulsifying and dispersing the mixed liquid obtained in (2) in an aqueous medium to obtain an emulsion.
(4) It is obtained by polymerizing the component (a2) in the emulsion obtained in (3) and sequentially performing each step of obtaining a composite resin emulsion. In step (1), as polypropylene glycol, Two types of polypropylene glycol having a number average molecular weight of 1000 and polypropylene glycol having a number average molecular weight of 2000 are used in a ratio of 94: 6 to 92: 8 (mass ratio), and the components (a1) and (a2) in the mixed solution The ratio of (a1) component: (a2) component (pure mass ratio) = 50: 50-60: 40 composite resin emulsion (B) cation-modified (meth) acryl silicone-based graft copolymer The present invention relates to a skin care cosmetic.

Furthermore, the component (B) is a polymer obtained by reacting the radically polymerizable monomers of the following components (b1), (b2), (b3) and (b4), and 99.5 at 25 ° C. (Meth) acryl silicone graft copolymer that dissolves in 50% by weight or more in% ethanol.
(B1) The following general formula (I)
(In the formula, Me is a methyl group, R 1 is a hydrogen atom or a methyl group, R 2 is a linear or branched C 1-10 divalent divalent alkyl group which may contain 1 or 2 ether bonds. A saturated hydrocarbon group, R3 is a saturated hydrocarbon group having 1 to 10 carbon atoms, and m is an integer of 5 to 100.) (b2) The following general formula (II)
(In the formula, R4 may be a hydrogen atom or a methyl group, R5, R6 and R7 may be the same or different, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is -O-, -NH-, -O. -CH2- or -O-CH2CH (OH)-, Y is a linear or branched divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and Z- is a counter anion. Compound and formula (III)
(In the formula, R8 and R9 may be the same or different, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R10 and R11 may be the same or different, and a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Group, Z- represents a counter anion.) At least one selected from compounds represented by (b3) the following general formula (IV)
(Wherein R12 represents a hydrogen atom or a methyl group, R13 represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms) (b4) The following general formula (V )
In the formula, R14 represents a hydrogen atom or a methyl group, and R15 represents a hydroxyalkyl group having 1 to 4 carbon atoms.

  Furthermore, it is related with the skin care cosmetics characterized by containing a polyhydric alcohol as a component (C).

The product of the present invention has no stickiness during and after use, and is excellent in sustainability because it is uniformly adsorbed on the skin surface by ionic interaction and a flexible and elastic film is formed. No protective film gives skin firmness and provides a skin care cosmetic excellent in lift-up effect.

Next, the present invention will be described in detail. In the present specification, “to” indicates a range including numerical values before and after.

  The component (A) used in the present invention is a composite resin emulsion in which a urethane polymer and an acrylic polymer are combined. This composite resin emulsion comprises a urethane prepolymer (a1) containing an isocyanate group and a carboxyl group (hereinafter sometimes referred to as “(a1) component”) and a specific polymerizable monomer (a2) (hereinafter referred to as “ An aqueous emulsion obtained by emulsifying and dispersing a mixed solution with (a2) component ”) in an aqueous medium and polymerizing the (a2) component in the emulsion.

The component (A) can be obtained by sequentially performing the following steps (1) to (4).
(1) A polymerization monomer that contains an ester group-containing (meth) acrylic acid monomer, and a polymer obtained by polymerizing the monomer has a glass transition temperature of 95 ° C. or higher and 105 ° C. or lower. Prepolymer containing an isocyanate group and a carboxyl group by reacting polypropylene glycol, dimethylolpropionic acid and an aliphatic or alicyclic polyvalent isocyanate in the presence of a functional monomer (component (a2)) Producing (component (a1)) and obtaining a mixture of component (a1) and component (a2),
(2) Neutralizing the carboxyl group contained in the component (a1) in the mixed solution obtained in (1) with an equivalent amount of triethanolamine, the neutralized product of the component (a1) and the component (a2) Obtaining a mixture of
(3) A step of emulsifying and dispersing the mixed liquid obtained in (2) in an aqueous medium to obtain an emulsion.
(4) A step of polymerizing the component (a2) in the emulsion obtained in (3) to obtain a composite resin emulsion

  Each step will be described below. First, the carboxyl group-containing urethane prepolymer of component (a1) obtained in step (1) is a urethane prepolymer containing an isocyanate group and a carboxyl group, and includes polypropylene glycol, dimethylolpropionic acid, aliphatic or It is a polymer obtained by reacting an alicyclic polyvalent isocyanate.

  As polypropylene glycol, two kinds of polypropylene glycol (PPG1000) having a number average molecular weight of about 1000 and polypropylene glycol (PPG2000) having a number average molecular weight of about 2000 are used in a ratio of PPG1000: PPG2000 = 94: 6 to 92: 8 (mass ratio). To do.

  The aliphatic or alicyclic polyvalent isocyanate compound has at least two isocyanate groups in one molecule. Specific examples thereof include dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 1, Examples include 3-cyclohexylene diisocyanate and 1,4-cyclohexylene diisocyanate.

  The acid value of the component (a1) is preferably 15 mgKOH / g or more, and more preferably 20 mgKOH / g or more. If it is less than 15 mgKOH / g, the dispersion state in the aqueous solvent may be deteriorated. On the other hand, the upper limit is preferably 70 mgKOH / g, and more preferably 60 mgKOH / g or less. What is necessary is just to adjust the usage-amount of dimethylol propionic acid so that the acid value of (a1) component formed by superposition | polymerization may become said range.

  A desirable use ratio of dimethylolpropionic acid is preferably 30 mol% or more and more preferably 50 mol% or more in the total of polypropylene glycol and dimethylolpropionic acid. On the other hand, it is preferably 90 mol% or less, and more preferably 80 mol% or less. By setting it within this range, the above acid value range can be satisfied.

  On the other hand, the use ratio of polypropylene glycol and dimethylolpropionic acid and the aliphatic or alicyclic polyvalent isocyanate compound is an equivalent ratio, and polypropylene glycol and dimethylolpropionic acid: polyvalent isocyanate compound = 1: 1.2 to 2 is preferable, and 1: 1.5 to 1.9 is more preferable. In this way, by reacting the diol component polypropylene glycol and dimethylolpropionic acid with a stoichiometric excess of the aliphatic or alicyclic polyvalent isocyanate compound, the component (a1) Isocyanate groups are introduced.

  The urethane formation reaction for producing the component (a1) is performed in the presence of the component (a2). The reaction system is diluted with the component (a2), and the reaction can be performed uniformly.

The polymerizable monomer as component (a2) is a monomer having a polymerizable double bond containing an ester group-containing (meth) acrylic acid monomer, and is particularly reactive with an isocyanate group. Preferred is a polymerizable monomer having no active hydrogen group.

Examples of such a component (a2), particularly a polymerizable monomer containing no active hydrogen group, are (meth) acrylic acid alkyl esters having 1 to 24 carbon atoms, ester group-containing vinyl monomers, styrene. Derivatives, vinyl ether monomers and the like.

  Examples of the (meth) acrylic acid alkyl ester having 1 to 24 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, ( (Meth) butyl acrylate, (meth) acrylate isobutyl, (meth) acrylate s-butyl, (meth) acrylate t-butyl, (meth) acrylate pentyl, (meth) acrylate s-pentyl, (meth) 1-ethylpropyl acrylate, 2-methylbutyl (meth) acrylate, isopentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, neopentyl (meth) acrylate, (meta ) Hexyl acrylate, 2-methylpentyl (meth) acrylate, 4-methylpentyl (meth) acrylate Ruthel, 2-ethylbutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-heptyl (meth) acrylate, 3-heptyl (meth) acrylate, Octyl (meth) acrylate, 2-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, (3,3,5-acrylic acid) Trimethylhexyl, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, (meth) acrylic acid Docosyl, Tetracosyl (meth) acrylate, Methylsic (meth) acrylate Hexyl, (meth) acrylic acid isobornyl (meth) norbornyl acrylate, (meth) acrylate, benzyl (meth) phenethyl acrylate are exemplified. Among these, (meth) acrylic acid alkyl esters having 1 to 24 carbon atoms, particularly (meth) acrylic acid alkyl esters having 1 to 8 carbon atoms are preferable. “(Meth) acryl” means “acryl or methacryl”.

  Specific examples of the ester group-containing vinyl monomer include hydrophobic vinyl monomers such as vinyl acetate, diethyl maleate, dibutyl maleate, vinyl (meth) acrylate, fluoroalkyl esters of (meth) acrylic acid, radical polymerization Examples thereof include unsaturated group-containing macromonomers such as an unsaturated group-containing silicon macromonomer.

  Examples of the styrene derivative include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene and the like. Specific examples of the vinyl ether monomer include vinyl methyl ether and vinyl cyclohexyl ether.

  These (a2) components may use only 1 type, and may mix and use multiple types. In the case of consisting of one kind, the homopolymer thereof, and in the case of comprising a plurality of kinds, the glass transition temperature of the copolymer in the composition ratio is 95 ° C. or more and 105 ° C. or less. If it is less than 95 ° C., the film strength is insufficient, the sustainability is lowered, and problems such as distorting may occur, and the lift-up effect may be impaired. On the other hand, when it exceeds 105 ° C., the minimum film-forming temperature increases, and a uniform film may not be formed on the skin.

In addition, when it is a copolymer, the calculation method of the glass transition temperature is based on following formula (A). Here, Tg is the glass transition temperature (K) of the copolymer, Tga, Tgb, Tgc, etc. are the glass transition temperatures (K) of the homopolymers of the respective monomers a, b, c, etc. Wa, Wb, Wc, etc. indicate the weight fraction of each monomer a, b, c in the copolymer.
1 / Tg = (Wa / Tga) + (Wb / Tgb) + (Wc / Tgc) + (B)
The glass transition temperature of each homopolymer is described in POLYMER HANDBOOK (Polymer Handbook), 3rd edition, Chapter 6, page 209, and the like.

  In the presence of the component (a2), urethanization reaction of polypropylene glycol, dimethylolpropionic acid, aliphatic or alicyclic polyvalent isocyanate produces the component (a1). The urethanization reaction may be performed at about 50 to 100 ° C. for about 0.5 to 20 hours. Thereby, the component (a1) containing an isocyanate group at the carboxyl group and the terminal can be obtained.

  (A1) As a catalyst used for manufacture of a component, the catalyst generally used for a urethanation reaction can be used. Specific examples include dibutyltin dilaurate.

  The number average molecular weight of the component (a1) is preferably 800 to 10,000, more preferably 1000 to 9000. When the number average molecular weight is less than 800, the resulting film becomes hard, and problems such as a feeling of stickiness may occur when used as a cosmetic. On the other hand, if it is greater than 10,000, the viscosity of the prepolymer itself becomes high, and gelation may occur or a stable emulsion may not be obtained.

  After the urethanization reaction, a mixture of the produced (a1) component and (a2) component is obtained. The mixing ratio of the component (a1) and the component (a2) in the mixed solution is (a1) :( a2) = 50: 50 to 60:40 in terms of a pure weight ratio. When the proportion of the component (a2) is larger than this, the film becomes hard and a uniform film may not be formed on the skin. On the other hand, when the amount of the component (a2) is small, the film is too soft and nonuniform, which causes a problem that the film is likely to be twisted.

  In step (2), the carboxyl group contained in component (a1) in the mixture of component (a1) and component (a2) obtained in step (1) above is neutralized using an equivalent amount of triethanolamine. Thus, a neutralized product of the component (a1) and a mixed solution of the component (a2) are obtained. Thus, the dispersibility in the aqueous medium of (a1) component can be improved by neutralizing the carboxyl group which (a1) component contains.

  Next, in step (3), the neutralized product of component (a1) obtained in step (2) and the mixture of component (a2) are emulsified and dispersed in an aqueous medium to obtain an emulsion. As a method of adding an aqueous medium to the mixture of the neutralized product of the component (a1) and the component (a2), a method in which the aqueous medium is dropped and dispersed in the mixed solution, and a mixture is dropped and dispersed in the aqueous medium. Either method may be used. Examples of the aqueous medium include water and a mixed solution of water and an organic solvent compatible with water such as methanol and ethanol. Among these, water is preferable from the environmental aspect. The temperature during emulsification dispersion is preferably 0 ° C. or higher, more preferably 10 ° C. or higher. On the other hand, 80 degrees C or less is preferable and 60 degrees C or less is more preferable. If the temperature is too high, the component (a1) may be denatured.

Further, in step (4), the component (a2) in the emulsion obtained in step (3) is polymerized to obtain a composite resin emulsion. The polymerization reaction when polymerizing the component (a2) can be performed by a general polymerization method according to the component (a2). For example, the polymerization reaction can be performed by adding a radical polymerization initiator to the mixed solution. it can.

  As the radical polymerization initiator, a conventional radical polymerization initiator may be used. For example, azo initiators such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyanovaleric acid, sodium persulfate Persulfate initiators such as potassium persulfate and ammonium persulfate, t-butyl hydroperoxide, dilauroyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, etc. Organic peroxide initiators can be used. A redox polymerization initiator in which an organic peroxide initiator or persulfate initiator is combined with a reducing agent such as ascorbic acid, Rongalite or metal sulfite is also preferably used. The amount of the radical polymerization initiator used may be about 0.1 to 5% by mass, preferably about 0.5 to 2% by mass with respect to the polymerizable monomer (a2).

The polymerization of the component (a2) is preferably performed at a polymerization temperature of 10 to 80 ° C, more preferably 30 to 60 ° C. The polymerization is usually almost completed by maintaining the temperature at about 40 to 90 ° C. for about 30 minutes to 3 hours after the end of heat generation. Thereby, a component (A) polymer emulsion is obtained. This polymer is considered to have a structure in which a urethane polymer is a core and an acrylic polymer is a shell.

The minimum film-forming temperature of the component (A) polymer emulsion is preferably + 20 ° C. or lower, more preferably + 15 ° C. or lower. If it exceeds + 20 ° C., defects such as cracks are likely to occur in the resulting film. On the other hand, the minimum film forming temperature is preferably −10 ° C. or higher, and more preferably 0 ° C. or higher. If it is less than -10 degreeC, the sustainability of the film obtained may deteriorate.

The solid content concentration of the component (A) polymer emulsion thus obtained is not particularly limited, but is preferably 20 to 50% by mass. The component (A) polymer emulsion can be produced according to the production method described in JP-A-2007-001969.

The content of the component (A) in the skin care cosmetic of the present invention is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass in terms of solid content. If it is such a range, since a membrane | film | coat will become a flexible thing, there is no feeling of burden in a makeup part, and it can maintain the firmness which was excellent in elasticity.

The component (B) cation-modified (meth) acryl silicone graft copolymer used in the skin care cosmetic of the present invention is at least of the following components (b1), (b2), (b3) and (b4) It is a polymer obtained by reacting a radically polymerizable monomer, and includes a polymer obtained by adding and reacting a copolymerizable monomer other than the components (b1) to (b4).
In the present invention, (meth) acryl means to include acrylic and methacrylic.
The (meth) acryl silicone graft copolymer of the present invention dissolves in an amount of 50% by mass or more in 99.5% ethanol at 25 ° C.
The charging ratio of each monomer is not limited as long as the effects of the present invention are exhibited, but (b1) component = 20 to 50% by mass, (b2) with respect to the total amount of monomers of component (b1) to component (b4). Component = 0.5-4 mass%, (b3) component and (b4) component = 46-79.5 mass%, and (b3) component / (b4) component = 0.5-1.5. Is preferred.
When a copolymerizable monomer other than the component (b3) and the component (b4) is used, the total of the monomers of the component (b3) and the component (b4) is preferably 66.5% by mass or more based on the total amount. .
In addition, in this invention, the preparation ratio of a monomer is substantially synonymous with those composition ratios in a copolymer.
The (meth) acryl silicone graft copolymer of the present invention is a B-type rotational viscometer at 25 ° C. of an ethanol solution obtained by dissolving the copolymer in 99.5% ethanol so that the copolymer becomes 20% by mass. The viscosity (unit mPa · s = CS) measured by using is 50 to 250, preferably 70 to 150.
The Tg of the (meth) acryl silicone graft copolymer of the present invention is preferably −10 to 40 ° C., more preferably 0 to 30 ° C. Here, Tg is similarly calculated by the method described in paragraph 0027.
Furthermore, the (meth) acryl silicone graft copolymer of the present invention includes various forms such as a random copolymer and a block copolymer.

Below, the monomer which is a raw material of a copolymer is demonstrated.
(B1): radically polymerizable monomer represented by the general formula (I)

In the formula, Me represents a methyl group, and R1 represents a hydrogen atom or a methyl group.
R2 represents a linear or branched divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and may contain one or two ether bonds. Specifically, -CH2-,-(CH2) 2,-(CH2) 5-,-(CH2) 10-, -CH2-CH (CH3) -CH2-, -CH2CH2OCH2CH2CH2-, -CH2CH2OCH2 (CH3) CH2 -, -CH2CH2OCH2CH2CH2OCH2CH2CH2- and the like are exemplified.
R3 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group. , T-butyl group, n-pentyl group, n-hexyl group, n-nonyl group, isononyl group, n-decyl group and other alkyl groups having 1 to 10 carbon atoms; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclo A cycloalkyl group having 1 to 10 carbon atoms such as hexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group; cyclopropylmethyl group, 2-cyclopropylethyl group, cyclobutylmethyl group, cyclopentylmethyl group, 3- 1 carbon number such as cyclopentylpropyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, cycloheptylmethyl group, cyclooctylmethyl group, etc. To 10 cycloalkylalkyl groups.
m represents an integer of 5 to 100.

  The monomer represented by the formula (I) is, for example, the formula (Ia)

(Meth) acrylate substituted chlorosilane compound represented by formula (Ib)

Can be obtained by dehydrochlorination reaction according to a conventional method, but the synthesis method is not limited thereto.

  Specific examples of the monomer represented by the formula (I) include the following. In the following formulae, Me represents a methyl group, and n-Bu represents an n-butyl group.

(B2): The radically polymerizable monomer (b2) component represented by the formula (II) or the formula (III) is at least one selected from the cationic compounds represented by the following formula (II) or the formula (III) It is.

In formula (II), R4 represents a hydrogen atom or a methyl group.
R5, R6 and R7 may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, Examples include i-propyl group, n-butyl group, s-butyl group, i-butyl group, and t-butyl group.
X represents -O-, -NH-, -O-CH2- or -O-CH2CH (OH)-.
Y represents a linear or branched divalent saturated hydrocarbon group having 1 to 4 carbon atoms, -CH2-,-(CH2) 2,-(CH2) 3-,-(CH2) 4-, -CH2-CH (CH3) -CH2- etc. are illustrated.
Z- is a counter anion, and examples thereof include chlorine ion, bromine ion, hydrogen sulfate ion, nitrate ion, perchlorate ion, boron tetrafluoride ion, and phosphorus hexafluoride ion.

In formula (III), R8 and R9 may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and n- Examples are propyl, i-propyl, n-butyl, s-butyl, i-butyl and t-butyl.
R10 and R11 may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, an n-propyl group, i- Propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-nonyl group, isononyl group, n-decyl group, lauryl group, tridecyl Group, myristyl group, n-pentadecyl group, palmityl group, heptadecyl group, stearyl group and the like.

(B3) Radical polymerizable monomer represented by formula (IV)

In the formula, R12 represents a hydrogen atom or a methyl group.
R13 represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and examples of the linear or branched alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and n -Propyl group and i-propyl group are exemplified.

(B4) Radical polymerizable monomer represented by formula (V)

In the formula, R14 represents a hydrogen atom or a methyl group.
R15 represents a hydroxyalkyl group having 1 to 4 carbon atoms, and examples thereof include a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group.

(B5) Other copolymerizable monomers
Examples of other copolymerizable monomers include the following.
((Meth) acrylic monomer)
N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acryl N-octyl acid, cyclohexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, ( Pentadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, oleyl (meth) acrylate, behenyl (meth) acrylate, (Meth) acrylic acid ester having a linear, branched or alicyclic hydrocarbon group; acrylo Tolyl; (meth) acrylamide such as acrylamide, diacetone acrylamide, N, N-dimethylacrylamide, Nt-butylacrylamide, N-octylacrylamide, Nt-octylacrylamide; 2- (meth) acrylamide-2-methyl Sulfonic acid group-containing (meth) acrylamides such as propanesulfonic acid; alkylaminoalkyl (meth) acrylates such as aminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, methylaminoethyl (meth) acrylate; dimethylaminoethyl (meta) ) Acrylates, dialkylaminoalkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate; dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylate Dialkylaminoalkyl (meth) methacrylamides such as ruamide; esters of cyclic compounds and meth) acrylic acid, such as tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate; (Meth) acrylic acid alkoxyalkyl esters such as ethoxyethyl methacrylate and methoxyethyl (meth) acrylate; polyalkylene glycols such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate and (meth) acrylic Monoesters with acids; sulfonic acid group-containing (meth) acrylic esters; methacryloyloxyalkyl phosphate monoesters such as (meth) acryloyloxyethyl phosphate; glyceryl (meth) acrylate, 2 -Methacryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, β-carboxyethyl acrylate, acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid, 2- (meth) acryloyloxy Ethylhexahydrophthalic acid; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene (n = 2-50) glycol di (meth) ) Acrylate, propylene glycol di (meth) acrylate, polypropylene (n = 2-50) glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dipentyl glycol di (meth) acrylate, Opentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, methylenebisacrylamide, bisphenol F EO modified (n = 2-50) di (meth) acrylate, bisphenol A EO modified (n = 2-50) Diacrylate, bisphenol S EO modified (n = 2-50) di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate , Trimethylol hexane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diglycerin tetra (meth) acrylate, ditrimethylol Propanetetra (meth) acrylate, ditrimethylolpropanetetracaprolactonate, tetra (meth) acrylate, ditrimethylolethanetetra (meth) acrylate, ditrimethylolbutanetetra (meth) acrylate, ditrimethylolhexanetetra (meth) acrylate, di Ethylenically unsaturated dimers such as pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, etc. Examples include (meth) acrylate having two or more heavy bonds.

(Monomers other than (meth) acrylic)
Unsaturated monocarboxylic acids such as crotonic acid; Aromatic vinyl compounds such as styrene; Unsaturated dicarboxylic acids such as itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic acid; monoalkyl maleate, monoalkyl fumarate Monoalkyl esters of unsaturated dicarboxylic acids such as esters and itaconic acid monoalkyl esters; examples of sulfonic acid group-containing monomers include alkene sulfonic acids such as vinyl sulfonic acid and (meth) allyl sulfonic acid; α-methylstyrene sulfone Aromatic vinyl group-containing sulfonic acids such as acids; primary to tertiary amino group-containing unsaturated compounds such as (meth) allylamine; amino group-containing aromatic vinyl compounds such as N, N-dimethylaminostyrene; divinylbenzene, di Ethylenic unsaturation such as isopropenylbenzene and trivinylbenzene Compounds having a double bond two or more; ethylenically unsaturated double bond of a silicone compound having two or more; ethylenically unsaturated double bond urethane oligomer having two or more vinyl acetate, vinyl pyrrolidone, and the like.

  Although content of the component (B) in the skin care cosmetics of this invention is not specifically limited, Preferably it is 0.1-10 mass%, More preferably, it is 1-7.5 mass%, and skin by an ionic interaction The present invention relates to a skin care cosmetic that is excellent in sustainability because it is uniformly adsorbed on the surface, and a protective film that does not feel stiff or dry gives the skin firmness.

In the present invention, when the component (C) polyhydric alcohol is further contained, the uniformity of the film formed by the components (A) and (B) is further improved, and the firmness and the sustainability of the lift-up effect are improved. .
As a component (C), it does not restrict | limit in particular, The polyhydric alcohol used for normal cosmetics can be used arbitrarily. For example, divalent alcohols (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2- Butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trivalent alcohol (for example, glycerin, trimethylolpropane, etc.); tetravalent alcohol (for example, pentane, such as 1,2,6-hexanetriol, etc.) Erythritol, etc.); pentavalent alcohol (eg, xylitol, etc.); hexavalent alcohol (eg, sorbitol, mannitol, etc.); polyhydric alcohol polymer (eg, diethylene glycol, dipropylene glycol, triethylene glycol, poly) Lopylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); sugar alcohols (eg, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch) Degraded sugar, maltose, xylitol, starch-degraded sugar reducing alcohol, etc.); polyglycerin and the like can be mentioned, and one or more can be used.

Although content of a component (C) is not specifically limited, 0.1 to 10% is preferable and especially 1 to 5% is more preferable. If it is this range, the uniformity of a film | membrane will improve further and the sustainability of a flexible firm feeling will be especially excellent.

In addition to the components described above, the skin care cosmetics of the present invention are usually used in cosmetics, for example, surfactants, oily components, water-soluble polymers, emulsion polymers other than component (A), and powders. Components, aqueous components, ultraviolet absorbers, humectants, antioxidants, cosmetic components, preservatives, fragrances, and the like can be appropriately blended within a range that does not impair the effects of the present invention.

  Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. For example, glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol adduct, sucrose fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene alkyl co-modified Examples thereof include organopolysiloxane, polyether-modified organopolysiloxane, and lecithin, and one or more can be used.

Oily components include hydrocarbons, oils and fats, waxes, hardened oils, ester oils, regardless of the origin, such as animal oils, vegetable oils, synthetic oils, and solid oils, semisolid oils, liquid oils, etc. , Fatty acids, higher alcohols, silicone oils, fluorine oils, lanolin derivatives, oily gelling agents, oil-soluble resins, volatile oils and the like. Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, paraffin wax, ceresin wax, microcrystalline wax, ethylene propylene copolymer, montan wax, fisher trops wax, molasses, olive oil, castor oil, mink oil, macadamia Fats such as peanut oil, beeswax, carnauba wax, candelilla wax, waxes such as gay wax, jojoba oil, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, diisostearate Polyglyceryl acid, diglyceryl triisostearate, glyceryl tribehenate, diisostearyl malate, neopentyl glycol dioctanoate, cholesterol fat Acid esters, esters such as N-lauroyl-L-glutamate di (cholesteryl, behenyl, octyldodecyl), stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol and other higher alcohols, methylphenyl poly Silicones such as siloxane and fluorine-modified organopolysiloxane, fluorinated oils such as perfluorodecane, perfluorooctane and perfluoropolyether, lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin derivatives such as lanolin alcohol, dextrin octoate , Dextrin laurate, dextrin palmitate, dextrin myristate, dextrin stearate, dextrin behenate, coconut oil Fatty acid dextrin, (palmitic acid / octanoic acid) dextrin, sucrose fatty acid ester, starch fatty acid ester, 12-hydroxystearic acid, calcium stearate and other oily gelling agents, hydrogenated rosin acid pentaerythrityl, specific alkyl acrylate Volatilization of oil-soluble resins such as methylpolysiloxane esters, hydrocarbon oils such as light liquid isoparaffin and isododecane, silicones such as decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, methyltrimethicone, and low polymerization degree dimethylpolysiloxane Natural oil agent etc. are mentioned, 1 type (s) or 2 or more types can be used.

Water-soluble polymers include gum arabic, tragacanth, galactan, carob gum, guar gum, cationized guar gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), starch (rice, corn, potato, wheat), alge colloid ( Plant-based polymers such as brown alga extract), microbial polymers such as dextran, succinoglucan, and pullulan, animal-based polymers such as collagen, casein, albumin, and gelatin, and starch-based compounds such as carboxymethyl starch and methylhydroxypropyl starch Polymer, methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, cationization Cellulose polymers such as droxyethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, alginic acid polymers such as sodium alginate and propylene glycol alginate, polyvinyl methyl ether, carboxyvinyl polymer (CARBOPOL (trade name), etc.), Vinyl polymers such as alkyl-modified carboxylic vinyl polymers (such as PEMULEN (trade name)), polyoxyethylene polymers, polyoxyethylene polyoxypropylene copolymer polymers, sodium polyacrylate, polyethyl acrylate, polyacrylamide Acrylic polymers such as polyethyleneimine, organic water-soluble polymers such as cationic polymers, bentonite, magnesium aluminum silicate, laponite, hectorite, silicic anhydride Inorganic water-soluble polymers and the like, and can be used either alone or in combination.

  Examples of emulsion polymers other than component (A) include alkyl acrylate copolymer emulsions, alkyl acrylate copolymer emulsions, alkyl methacrylate copolymer emulsions, alkyl methacrylate copolymer emulsions, organopolysiloxane polymer emulsions, and polyvinyl acetate polymer emulsions. 1 type, or 2 or more types can be used.

  The powder component is not particularly limited as long as it is used in cosmetics, and is particularly limited by the shape of a plate, spindle, needle, etc., particle size, particle structure such as porous, nonporous, etc. Inorganic powders, glitter powders, organic powders, composite powders, and the like are included. Specifically, titanium oxide, zinc oxide, aluminum oxide, cerium oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, chromium oxide, chromium hydroxide, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica , Synthetic mica, synthetic sericite, sericite, talc, kaolin, silicon carbide, barium sulfate, bentonite, smectite, boron nitride and other inorganic powders, bismuth oxychloride, mica titanium, silicic anhydride coated mica titanium, titanium oxide Coated glass powder, titanium oxide / iron oxide coated glass powder, titanium oxide / silicic acid-coated glass powder, aluminum powder and other bright powders, magnesium stearate, zinc stearate, N-acyl lysine, nylon and other organic powders Body, fine particle titanium oxide Titanium-coated mica, fine-particle zinc oxide-coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing silicon dioxide, zinc oxide-containing silicon dioxide composite powder, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polyolefin laminated film powder , Polyethylene terephthalate / polymethylmethacrylate laminated film powder, and the like, and one or more of them can be used. These powders may be used alone or in combination of two or more, and are known using fluorine compounds, silicone oils, metal soaps, waxes, surfactants, oils and fats, hydrocarbons, etc. It may be subjected to a surface treatment by a method.

The aqueous component may be any component that is soluble in water, for example, lower alcohols such as ethyl alcohol and butyl alcohol, plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender and rose. Can be mentioned. Examples of water-soluble polymers include guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan and other semi-synthetic compounds such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyvinyl polymer, Synthetic compounds such as alkyl-added carboxyvinyl polymer and sodium polyacrylate can be mentioned. Other moisturizing agents such as protein, mucopolysaccharide, collagen, elastin, keratin and the like can also be contained.

  Examples of ultraviolet absorbers include benzophenone-based, PABA-based, cinnamic acid-based, salicylic acid-based, 4-tert-butyl-4'-methoxydibenzoylmethane, and oxybenzone. Examples of humectants include protein, mucopolysaccharide, and collagen. , Elastin, keratin, etc., antioxidants such as α-tocopherol, ascorbic acid, etc., cosmetic ingredients such as vitamins, anti-inflammatory agents, herbal medicines, etc., antiseptics such as paraoxybenzoic acid esters, phenoxyethanol, 1 , 2-pentanediol and the like.

The form of the skin care cosmetic of the present invention is not particularly limited, and examples thereof include solid, semi-solid, and liquid, and can be used as transparent, translucent, and opaque skin care cosmetics. The dosage form is not particularly limited, and examples thereof include water-based, oil-based, emulsified (water-in-oil, oil-in-water, etc.), powder, and solvent systems, and can be appropriately selected according to the purpose and application.
The skin care cosmetics of the present invention are, for example, face wash, hand soap, body soap, cleansing agent, point makeup remover, lotion, milky lotion, cream, massage agent, beauty essence, lip balm, pack, peel off pack, sunscreen Etc.

  Hereinafter, the present invention will be described in more detail with reference to examples. Note that these do not limit the present invention.

[Component (A) Production Example 1]
In a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 19.7 parts by weight of methyl methacrylate and 0.8 part by weight of n-butyl acrylate, which are polymerizable monomers (a2), are used as a reaction solvent. Polypropylene glycol (7.7 parts by weight of number average molecular weight 1000 (* 1) and 0.6 parts by weight of number average molecular weight 2000 (* 2)) and 2.0 parts by weight of dimethylolpropionic acid were added, and the internal temperature Then, 10.2 parts by weight of isophorone diisocyanate was added, and the mixture was heated to 90 ° C. and reacted at this temperature for 5 hours to obtain a urethane prepolymer (a1) containing an isocyanate group and a carboxyl group.
While maintaining the obtained urethane prepolymer (a1) solution at 50 ° C., 2.3 parts by weight of triethanolamine was added to neutralize the carboxyl group in the urethane prepolymer (a1). Subsequently, 56.6 parts by weight of purified water was added dropwise to this solution at 50 ° C. over 15 minutes to obtain a milky white transparent dispersion.
Thereafter, this dispersion was kept at 50 ° C., and at this temperature, 0.15 part by weight of a 7% by weight aqueous solution of t-butyl hydroperoxide and 0.05 part by weight of an aqueous 1% by weight ascorbic acid were used as a radical polymerization catalyst. Was added to initiate polymerization of the polymerizable monomer (a2). After the end of heat generation, the temperature was further raised to 70 ° C. and maintained for 3 hours to obtain polymer emulsion 1.
(In the polymer emulsion 1, the glass transition temperature of the copolymer obtained by polymerizing the component (a2) is about 95 ° C., and the mixing ratio of the urethane prepolymer (a1) and the polymerizable monomer (a2) is 50:50. )
* 1: Polypropylene glycol, diol type, 1000 (hydroxyl value: 111 mgKOH / g, manufactured by Wako Pure Chemical Industries, Ltd.)
* 2: Polypropylene glycol, diol type, 2000 (manufactured by Wako Pure Chemical Industries, Ltd., hydroxyl value: 56 mgKOH / g)

[Component (A) Production Example 2]
Into a four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, 20.2 parts by weight of methyl methacrylate as a polymerizable monomer (a2) and 0.2 part by weight of n-butyl acrylate were added, and Polypropylene glycol (7.2 parts by weight of the above * 1, 0.58 parts by weight of the above * 2) and 2.6 parts by weight of dimethylolpropionic acid were added to bring the internal temperature to 50 ° C. Then, isophorone diisocyanate was added to 10.1 parts. Part by weight was added, and the mixture was heated to 90 ° C. and reacted at this temperature for 5 hours to obtain a urethane prepolymer (a1) containing an isocyanate group and a carboxyl group.
While maintaining the obtained urethane prepolymer (a1) solution at 50 ° C., 2.8 parts by weight of triethanolamine was added to neutralize all the carboxyl groups in the urethane prepolymer (a1). Next, 56.3 parts by weight of an aqueous medium was added dropwise to the solution at 50 ° C. over 15 minutes to obtain a milky white transparent dispersion.
Thereafter, this dispersion was kept at 50 ° C., and at this temperature, 0.14 parts by weight of a 7% by weight aqueous solution of t-butyl hydroperoxide as a radical polymerization catalyst and 0.06 parts by weight of an aqueous 1% by weight ascorbic acid solution were obtained. Was added to initiate polymerization of the polymerizable monomer (a2). After the end of heat generation, the temperature was further raised to 70 ° C. and maintained for 3 hours to obtain polymer emulsion 2.
(In the polymer emulsion 2, the glass transition temperature of the copolymer obtained by polymerizing the component (a2) is about 102 ° C., and the mixing ratio of the urethane prepolymer (a1) and the polymerizable monomer (a2) is 50:50. )

[Component (A) Production Example 3]
Into a four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, 19.6 parts by weight of methyl methacrylate as the polymerizable monomer (a2) and 0.8 part by weight of n-butyl acrylate were added, and Polypropylene glycol (8.7 parts by weight of the above * 1 and 0.6 parts by weight of the above * 2) and 2.3 parts by weight of dimethylolpropionic acid were added to an internal temperature of 50 ° C., and then 8.9% of isophorone diisocyanate Part by weight was added, and the mixture was heated to 90 ° C. and reacted at this temperature for 5 hours to obtain a urethane prepolymer (a1) containing an isocyanate group and a carboxyl group.
While maintaining the obtained urethane prepolymer (a1) solution at 50 ° C., 2.6 parts by weight of triethanolamine was added to neutralize all the carboxyl groups in the urethane prepolymer (a1). Next, 56.5 parts by weight of an aqueous medium was added dropwise to this solution at 50 ° C. over 15 minutes to obtain a milky white transparent dispersion.
Thereafter, this dispersion was kept at 50 ° C., and at this temperature, 0.07 part by weight of a 7% by weight aqueous solution of t-butyl hydroperoxide as a radical polymerization catalyst and 0.02 part by weight of an aqueous 1% by weight ascorbic acid solution were obtained. Was added to initiate polymerization of the polymerizable monomer (a2). After the end of heat generation, the temperature was further raised to 70 ° C. and maintained for 3 hours to obtain polymer emulsion 3.
(In the polymer emulsion 3, the glass transition temperature of the copolymer obtained by polymerizing the component (a2) is about 95 ° C., and the mixing ratio of the urethane prepolymer (a1) and the polymerizable monomer (a1) is 50:50. )

[Component (A) Production Example 4]
To a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 14.8 parts by weight of methyl methacrylate as a polymerizable monomer (a2) and 0.6 part by weight of n-butyl acrylate were added, and Polypropylene glycol (9.8 parts by weight of the above * 1 and 0.7 parts by weight of the above * 2) and 2.6 parts by weight of dimethylolpropionic acid were added to an internal temperature of 50 ° C. Then, isophorone diisocyanate was added to 10.1 parts. Part by weight was added, and the mixture was heated to 90 ° C. and reacted at this temperature for 5 hours to obtain a urethane prepolymer (a1) containing an isocyanate group and a carboxyl group.
While maintaining the obtained urethane prepolymer (a1) solution at 50 ° C., 2.9 parts by weight of triethanolamine was added to neutralize all the carboxyl groups in the urethane prepolymer (a1). Next, 53.2 parts by weight of an aqueous medium was added dropwise to the solution at 50 ° C. over 15 minutes to obtain a milky white transparent dispersion.
Thereafter, this dispersion was kept at 50 ° C., and at this temperature, 0.11 part by weight of a 7% by weight aqueous solution of t-butyl hydroperoxide as a radical polymerization catalyst and 0.04 part by weight of an aqueous 1% by weight ascorbic acid solution were obtained. Was added to initiate polymerization of the polymerizable monomer (a2). After the end of heat generation, the temperature was further raised to 70 ° C. and maintained for 3 hours to obtain polymer emulsion 4.
(In the polymer emulsion 4, the glass transition temperature of the copolymer obtained by polymerizing the component (a2) is about 95 ° C., and the mixing ratio of the urethane prepolymer (a1) and the polymerizable monomer (a2) is 60:40. )

[Component (B) Production Example 1]
In a three-necked flask, under a nitrogen atmosphere, 100 g of isopropanol (IPA) (* 3) is stirred at 70 to 80 ° C., and dimethyl 2,2-azobis (2-methylpropionate) (V-601) (* 4) 4 g, single-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (* 5) 40 g, ethyl acrylate (EA) (* 6) 31 g, 2-hydroxyethyl methacrylate (HEMA) (* 7) 27 g 4-trimethylammoniumpropylmethacrylamide chloride (MAPTAC) (* 8) 4 g and isopropanol (* 3) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (* 4) dissolved in isopropanol was added and reacted for 5 hours within a temperature range of 70 to 80 ° C. to obtain a viscous solution. . This solution was poured into purified water to precipitate the graft polymer, and then the precipitate was filtered off and dried under reduced pressure at 80 ° C. to obtain 87 g of a transparent rubber-like product.
It was confirmed by infrared absorption spectrum that the obtained rubber-like product was the desired (meth) acryl silicone graft copolymer (this product was dimethylpolysiloxane, amide bond by infrared absorption spectrum. And a polymer having an ester bond, an alkyl group, and a hydroxyl group).
The monomer charge ratio is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 2: 31: 27: 40
* 3: IPA Kanto Chemical Co., Ltd. * 4: V-601 Wako Pure Chemical Industries, Ltd. * 5: X-24-8201 Shin-Etsu Chemical Co., Ltd.
* 6: EA manufactured by Kanto Chemical Co., Ltd. * 7: HEMA manufactured by Kanto Chemical Co., Ltd. * 8: MAPTAC manufactured by Evonik Degussa Japan Co., Ltd., 50% aqueous solution

[Component (B) Production Example 2]
In a three-necked flask, under nitrogen atmosphere, 50 g of isopropanol (* 3) is stirred at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (* 4), one end Methacrylate-substituted dimethylpolysiloxane (X-22-174DX) (* 9) 40 g, ethyl acrylate (* 6) 31 g, 2-hydroxyethyl methacrylate (* 7) 27 g, 3-trimethylammoniumpropyl methacrylamide chloride (* 8) 4 g Then, 170 g of isopropanol (* 3) was added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (* 4) dissolved in isopropanol was added and reacted for 5 hours within a temperature range of 70 to 80 ° C. to obtain a viscous solution. . This solution was poured into purified water to precipitate the graft polymer, and then the precipitate was filtered off and dried under reduced pressure at 80 ° C. to obtain 90 g of a transparent rubber-like product.
From the infrared absorption spectrum, it was confirmed that the obtained rubber-like product was the intended (meth) acryl silicone graft copolymer.
The monomer charge ratio is as follows.
MAPTAC: EA: HEMA: X-22-174DX = 2: 31: 27: 40
* 9: X-22-174DX Shin-Etsu Chemical Co., Ltd.

[Component (B) Production Example 3]
In a three-necked flask, under a nitrogen atmosphere, 100 g of isopropanol (* 3) is stirred at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (* 4), one end Methacrylate-substituted dimethylpolysiloxane (X-22-174ASX) (* 10) 40 g, ethyl acrylate (* 6) 31 g, 2-hydroxyethyl methacrylate (* 7) 27 g, 3-trimethylammoniumpropyl methacrylamide chloride (* 8) 4 g Then, 50 g of isopropanol (* 3) was added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (* 4) dissolved in isopropanol was added and reacted for 5 hours within a temperature range of 70 to 80 ° C. to obtain a viscous solution. . This solution was poured into purified water to precipitate the graft polymer, and then the precipitate was filtered and dried under reduced pressure at 80 ° C. to obtain 83 g of a transparent rubber-like product.
From the infrared absorption spectrum, it was confirmed that the obtained rubber-like product was the intended (meth) acryl silicone graft copolymer.
The monomer charge ratio is as follows.
MAPTAC: EA: HEMA: X-22-174ASX = 2: 31: 27: 40
* 10: X-22-174ASX Shin-Etsu Chemical Co., Ltd.

[Component (B) Production Example 4]
In a three-necked flask, under a nitrogen atmosphere, 100 g of isopropanol (* 3) is stirred at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (* 4), one end Methacrylate-substituted dimethylpolysiloxane (X-24-8201) (* 5) 40.4 g, ethyl acrylate (* 6) 27.3 g, 2-hydroxyethyl methacrylate (* 7) 31.3 g, 3-trimethylammoniumpropyl methacrylamide 2 g of chloride (* 8) and 50 g of isopropanol (* 3) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (* 4) dissolved in isopropanol was added and reacted for 5 hours within a temperature range of 70 to 80 ° C. to obtain a viscous solution. . This solution was poured into purified water to precipitate the graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 86 g of a transparent rubber-like material.
From the infrared absorption spectrum, it was confirmed that the obtained rubber-like product was the intended (meth) acryl silicone graft copolymer.
The monomer charge ratio is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 1: 27.3: 31.3: 40.4

Examples 1 to 9 and Comparative Examples 1 to 7: Emulsions The emulsions shown in Tables 1 and 2 below were prepared, and the skin “softness (flexibility)”, “harshness (elasticity)” immediately after application, and The “continuity of firmness” over time was evaluated by the following method. The results are also shown in Tables 1 and 2.

(Production method)
(1) No. 1 to 6 were dissolved by heating at 70 ° C. Add 7 and emulsify.
(2) Cool (1) to 35 ° C. Add 8-22 and mix evenly.
(3) (2) was filled in a container to obtain an evaluation emulsion.

(Evaluation method)
20 cosmetic panel evaluation specialists used the emulsions of Examples 1-9 and Comparative Examples 1-7, and immediately after use, “softness (flexibility)”, “harness (elasticity)”, from use 3 Each of the “continuity of firmness” after time was evaluated on a 7-point scale according to the following criteria and given a score for each emulsion, and the average score of all panels was determined according to the following criteria.
(Evaluation criteria)
(Score): (Evaluation)
6: Very good 5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad 0: Very bad (judgment criteria)
(Judgment): (Average score)
◎: 4.5 points or more
○: 3.5 or more and less than 4.5
△: 1 point or more and less than 3.5 point
×: Less than 1 point

As is clear from the results of Tables 1 and 2, the emulsions of Examples 1 to 9 of the present invention are more flexible and elastic than the emulsions of Comparative Examples 1 to 8, and the film Since it is uniform and flexible, the firmness without stickiness persists and the lift-up effect is excellent.
On the other hand, the comparative example 1 which does not contain a component (A) did not have the softness | flexibility of a membrane | film | coat, and was feeling stiff. In Comparative Example 2 using a commercially available product in which the theoretical Tg of the component (a2) of the composite resin emulsion of the component (A) was 6 ° C., the film strength was insufficient and sufficient firmness was not obtained. Further, in Comparative Example 3 in which a urethane / acrylic mixed polymer was used instead of the composite resin emulsion of component (A), the durability of the film was poor, and a sustained firmness was not obtained. In Comparative Example 4 in which an alkyl acrylate copolymer emulsion polymer was used instead of the composite resin emulsion of component (A), the film was hard and lacked flexibility, and the film was twisted over time, and a lift-up effect was not obtained. .
On the other hand, in Comparative Example 5 which does not contain a cation-modified (meth) acryl silicone graft copolymer, flexibility and firmness can be felt immediately after coating, but since a uniform film is not formed, a sustained effect cannot be obtained. It was. Comparative Examples 6 and 7 using cellulose or guar gum having a cation-modified group instead of a cation-modified (meth) acryl silicone graft copolymer have weak film-forming ability itself and impair the effect of the composite resin emulsion. It lacked flexibility and elasticity. Further, in Comparative Example 8 containing a (meth) acryl silicone graft copolymer having no cation-modified group, since there is no ionic interaction, the adsorptive power to the skin is weak and the effect of the composite resin emulsion is not sufficiently exhibited. It was inferior to suppleness and elasticity.

Example 10: lotion
(Ingredient) (%)
1. Hydrogenated soybean phospholipid (Note 10) 0.65
2. Cholesterol (Note 11) 0.15
3. Glycerin 4
4. 1,3-Butylene glycol 5
5. Sorbitan sesquioleate (Note 12) 0.1
6). Polyoxyethylene (10 mol) cholesteryl ether (Note 13)
0.04
7). Glyceryl tri-2-ethylhexanoate 0.02
8). Cetostearyl alcohol (Note 14) 0.02
9. Perfume 0.03
10. Purified water 20
11. Sodium lactate 50% aqueous solution 0.2
12 Polyethylene glycol 20000 (Note 15) 0.3
13. Purified water balance
14 Composite resin emulsion (Note 1) 3
15. (Meth) acrylic silicone graft copolymer (Note 16) 5
16.1,3-butylene glycol 6
17. Dipropylene glycol 5
18. Edetic acid disodium 0.05
19. Glycerin 2
20. Methylparaben 0.15
21. Ethanol 3
(Note 10) Resinol S-10 (Nikko Chemicals)
(Note 11) Nissui Marine Cholesterol (Nippon Suisan Co., Ltd.)
(Note 12) Rheodor AO-15V (manufactured by Kao Corporation)
(Note 13) EMALEX CS-10 (Nippon Emulsion Co., Ltd.)
(Note 14) Higher alcohol NAA 45 (manufactured by NOF Corporation)
(Note 15) PEG-400 (manufactured by NOF Corporation)
(Note 16) Component B Production Example 3 (Meth) acrylic silicone graft copolymer

(Production method)
(1) No. Heat 1-9 to 70 ° C. and mix uniformly.
(2) No. Heat 10-12 to 70 ° C and mix uniformly.
(3) Add (2) to (1) and emulsify.
(4) Cool (3) to 35 ° C. and perform high-pressure emulsification treatment.
(5) No. 15 No. No. 21 after dissolution in part. 13-21 were mixed and dissolved, and further added to (4) and mixed uniformly to obtain a skin lotion.

 The lotion of Example 10 was a lotion excellent in flexibility, elasticity, and elasticity over time.

Example 11: Cream (ingredient) (%)
1. Hydrogenated egg yolk phospholipids (Note 17) 5
2. Stearic acid 1
3. Behenyl alcohol 3
4). Vaseline 1.5
5. Tri (capryl / capric acid) glyceryl 10
6). Liquid paraffin 5
7). Dimethylpolysiloxane (Note 18) 2
8). Phytosterol 1.5
9. 1,3-butylene glycol 10
10. Glycerin 10
11. Sodium lactate 2
12 Xanthan gum 0.4
13. Triethanolamine 0.5
14 Methylparaben 0.15
15. Fragrance 0.05
16. Composite resin emulsion (Note 19) 6
17. (Meth) acrylic silicone graft copolymer (Note 6) 3
18. Ethanol 2
19. Purified water balance
(Note 17) Egg yolk lecithin PL-100P (manufactured by Kewpie)
(Note 18) Silicon KF-96 (10CS) (Shin-Etsu Chemical Co., Ltd.)
(Note 19) Composite resin emulsion of Component A Production Example 4 ((a) component: (b) component mass ratio = 60: 40, (b) component theory Tg = 95 ° C., solid content 40%)

(Production method)
(1) No. Heat 1-8 to 70 ° C and mix uniformly.
(2) No. Heat 9-15 and 19 to 70 ° C. and mix uniformly.
(3) Add (2) to (1) and emulsify and mix at 70 ° C.
(4) No. 17 No. No. 18 was dissolved and then No. 18 was dissolved. 16-18 was added and mixed to obtain a cream.

 The cream of Example 11 was a cream having a smooth feeling of use and excellent in flexibility, elasticity, and lift-up effect.

Example 12 Sunscreen Latex
(Ingredient) (%)
1. Soy phospholipid 2
2. Polyoxyalkylene-modified organopolysiloxane (Note 20) 5
3. Octamethylcyclotetrasiloxane 20
4). Dioctyl succinate 5
5. Paramethoxycinnamic acid-2-ethylhexyl 5
6). Glyceryl monolinoleate (iodine value 123) 1
7). Methyl paraoxybenzoate 0.1
8). Silicone-treated fine particle titanium oxide 10
9. Silicone-treated fine particle zinc oxide 10
10. Polystyrene powder 3
11. Trimethylsiloxysilicate 0.5
12 Dipropylene glycol 3
13. Ethyl alcohol 10
14 Purified water remaining amount 15. L-sodium ascorbate phosphate 2
16. Sodium chloride 0.2
17. Composite resin emulsion (Note 1) 5
18. (Meth) acrylic silicone-based graft copolymer (Note 21) 2
19. Sulphite 1
20. Perfume appropriate amount 21. Ethanol 4
(Note 20) ABIL EM-90 (manufactured by Degussa)
(Note 21) Component B Production Example 4 (meth) acryl silicone graft copolymer

(Production method)
(1) No. 1 to 11 are heated to 70 ° C. and mixed uniformly.
(2) No. Heat 12-16 to 70 ° C and mix uniformly.
(3) Add (2) to (1) and emulsify and mix at 70 ° C.
(4) No. No. 18 No. 21 after dissolution in part. 17 to 21 were mixed and dissolved, and added to (3) to obtain a sunscreen emulsion.

The sunscreen emulsion of Example 12 was a sunscreen emulsion excellent in flexibility, firmness and sustained firmness.

Example 13 Cosmetic liquid
(Prescription) (%)
1. Hydrogenated soybean phospholipid 5
2. Cholesterol 0.5
3. Glyceryl monolinoleate (iodine value 123) 1
4). Liquid paraffin 10
5. Cyclomethicone 5
6). Hydroxy stearic acid hydrogenated castor oil 2
7). Glycerin 10
8). Dipropylene glycol 5
9. Vitamin E 0.1
10. Phenoxyethanol 0.1
11. (Na-acrylate / acryloyldimethyltaurine) copolymer 0.1
12 Carboxyvinyl polymer 0.1
14 Ethyl alcohol 5
15. Purified water remaining
16. Catechin 0.1
17. Composite resin emulsion (Note 22) 1
18. (Meth) acrylic silicone-based graft copolymer (Note 21) 3
19. Ethanol 4
(Note 22) Composite resin emulsion of Component A Production Example 3 (mass ratio of (a) component: (b) component = 50: 50, theoretical Tg of component (b) = 95 ° C., solid content 40%)

(Production method)
(1) No. A part of 11, 12, 15 is heated to 70 ° C. and mixed uniformly.
(2) No. Heat 1-10 to 70 ° C. and mix uniformly.
(3) No. 2 in (2). Add 15 and mix uniformly to emulsify.
(4) In (3), (1), No. Add 13 and mix evenly.
(5) After cooling (4), No. 14, no. 16-19 were added and mixed uniformly to obtain a serum. The component 18 is pre- After being dissolved in 19, it was added and mixed.

The essence of Example 13 was an essence excellent in flexibility, elasticity, and sustained elasticity.

Example 14 Body Soap
(Ingredient) (%)
1. Sodium tetradecenesulfonate 10
2. Polyoxyethylene (3E.O.) sodium lauryl sulfate 5
3. Lauryldimethylaminoacetic acid betaine 5
4). Guar hydroxypropyltrimonium chloride 0.2
5. Hydroxypropyl methylcellulose 0.3
6). Sorbitol 1
7). Perfume appropriate amount 8. Palm oil fatty acid isopropanolamide 0.5
9. Citric acid 0.5
10. Sodium benzoate 0.5
11. Purified water remaining amount 12. Composite resin emulsion (Note 1) 10
13. (Meth) acrylic silicone graft copolymer (Note 7) 4
14 Ethanol 4

(Production method)
(1) No. 1-5 and 8-11 are heated and dissolved uniformly.
(2) Cool (1).
(3) No. 2 in (2). 6, 7, 12-14 were added and mixed to obtain a body soap. In addition, No. No. 13 in advance Then, the mixture was added and mixed.

The body soap of Example 14 was a body soap excellent in the softness of the back skin, firmness, and sustained firmness after washing.

Claims (5)

The following components (A) and (B);
(A) The following steps (1) to (4);
(1) A polymerization monomer that contains an ester group-containing (meth) acrylic acid monomer, and a polymer obtained by polymerizing the monomer has a glass transition temperature of 95 ° C. or higher and 105 ° C. or lower. Prepolymer containing an isocyanate group and a carboxyl group by reacting polypropylene glycol, dimethylolpropionic acid and an aliphatic or alicyclic polyvalent isocyanate in the presence of a functional monomer (component (a2)) Producing (component (a1)) and obtaining a mixture of component (a1) and component (a2),
(2) The carboxyl group contained in the component (a1) in the mixture of the component (a1) and the component (a2) obtained in (1) is neutralized with an equivalent amount of triethanolamine, and (a1) Obtaining a neutralized product of the component and a mixture of the component (a2),
(3) A step of emulsifying and dispersing the mixed solution of the (a1) component obtained in (2) and the (a2) component in an aqueous medium to obtain an emulsion,
(4) It is obtained by polymerizing the component (a2) in the emulsion obtained in (3) and sequentially performing each step of obtaining a composite resin emulsion. In step (1), as polypropylene glycol, Two types of polypropylene glycol having a number average molecular weight of 1000 and polypropylene glycol having a number average molecular weight of 2000 are used in a ratio of 94: 6 to 92: 8 (mass ratio), and the components (a1) and (a2) in the mixed solution The ratio of (a1) component: (a2) component (pure mass ratio) = 50: 50-60: 40 composite resin emulsion (B) cation-modified (meth) acryl silicone-based graft copolymer Skin care cosmetics characterized by The component (B) is
A polymer obtained by reacting the following radically polymerizable monomers (b1), (b2), (b3) and (b4), and is dissolved in 99.5% ethanol at 50% by mass or more at 25 ° C. ( (Meth) acrylic silicone graft copolymer (b1)

(In the formula, Me is a methyl group, R 1 is a hydrogen atom or a methyl group, R 2 is a linear or branched C 1-10 divalent divalent alkyl group which may contain 1 or 2 ether bonds. A saturated hydrocarbon group, R3 is a saturated hydrocarbon group having 1 to 10 carbon atoms, and m is an integer of 5 to 100.) (b2) The following general formula (II)

(In the formula, R4 may be a hydrogen atom or a methyl group, R5, R6 and R7 may be the same or different, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is -O-, -NH-, -O. -CH2- or -O-CH2CH (OH)-, Y is a linear or branched divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and Z- is a counter anion. Compound and formula (III)

(In the formula, R8 and R9 may be the same or different, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R10 and R11 may be the same or different, and a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Group, Z- represents a counter anion.) At least one selected from the compounds represented by (b3) the following general formula (IV)

(Wherein R12 represents a hydrogen atom or a methyl group, R13 represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms) (b4) The following general formula (V )

The skin care cosmetic according to claim 1, wherein R14 is a hydrogen atom or a methyl group, and R15 is a hydroxyalkyl group having 1 to 4 carbon atoms.   Furthermore, polyhydric alcohol is contained as a component (C), The skin care cosmetics of Claim 1 or 2 characterized by the above-mentioned. The following steps (1) to (4);
(1) A polymerization monomer that contains an ester group-containing (meth) acrylic acid monomer, and a polymer obtained by polymerizing the monomer has a glass transition temperature of 95 ° C. or higher and 105 ° C. or lower. Prepolymer containing an isocyanate group and a carboxyl group by reacting polypropylene glycol, dimethylolpropionic acid and an aliphatic or alicyclic polyvalent isocyanate in the presence of a functional monomer (component (a2)) Producing (component (a1)) and obtaining a mixture of component (a1) and component (a2),
(2) The carboxyl group contained in the component (a1) in the mixture of the component (a1) and the component (a2) obtained in (1) is neutralized with an equivalent amount of triethanolamine, and (a1) Obtaining a neutralized product of the component and a mixture of the component (a2),
(3) A step of emulsifying and dispersing the mixed solution of the (a1) component obtained in (2) and the (a2) component in an aqueous medium to obtain an emulsion,
(4) A step of polymerizing the component (a2) in the emulsion obtained in (3) to obtain a composite resin emulsion
The component (A) composite resin emulsion is obtained by sequentially performing each step of
At this time, in the step (1), as the polypropylene glycol, two kinds of polypropylene glycol having a number average molecular weight of 1000 and polypropylene glycol having a number average molecular weight of 2000 are used in a ratio of 94: 6 to 92: 8 (mass ratio) and mixed. The ratio of the (a1) component and the (a2) component in the liquid is (a1) component: (a2) component (pure mass ratio) = 50: 50-60: 40,
A method for producing a skin care cosmetic, comprising mixing the component (A) and the component (B) cation-modified (meth) acryl silicone graft copolymer. Furthermore, the manufacturing method of the skin care cosmetics of Claim 4 including mixing a polyhydric alcohol as a component (C).