JP2009120520A - Cosmetics - Google Patents

Abstract

An object of the present invention is to provide a water-based cosmetic that has quick drying properties, such as organic solvent-based cosmetics, and provides good gloss, film-forming properties, water resistance, and the like.
A cosmetic comprising a crosslinked polymer emulsion and a hydrazine derivative (B) having at least two hydrazide groups in one molecule,
The crosslinked polymer emulsion is obtained by emulsion polymerization of an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer (a1) having at least one aldo group or keto group in one molecule. Features cosmetics.
[Selection figure] None

Description

  The present invention relates to a cosmetic, and more particularly, to a cosmetic for skin, lips, and hair that has a fast drying property and excellent gloss, water resistance, and film-forming properties.

  Conventionally, water-soluble or oil-soluble film-forming polymers are blended in cosmetics for hair, makeup, and medicinal use.

  However, when a water-soluble polymer is blended in cosmetics, the water resistance is inferior, so that the cosmetics are easily removed by sweat or water. On the other hand, when an oil-soluble polymer is blended, the cosmetic has a drawback that it is easily removed by sebum.

  In order to solve these drawbacks, conventionally, cosmetics containing a polymer emulsion have been proposed. Patent Document 1 discloses a cosmetic comprising an acrylic aqueous polymer emulsion, but it is not yet satisfactory in terms of drying, gloss, film-forming properties, water resistance, and adhesion.

Therefore, development of various cosmetics that provide excellent drying properties, gloss, film-forming properties, water resistance and the like has been desired.
Japanese Patent Laid-Open No. 6-80537

  An object of the present invention is to provide a water-based cosmetic that has a fast drying property such as an organic solvent-based cosmetic and provides good gloss, film-forming properties, water resistance, and the like.

  As a result of intensive studies, the present inventors have found that a cosmetic containing a specific cross-linked polymer emulsion and a hydrazine derivative solves the above problems, and has completed the present invention.

That is, the first invention is a cosmetic comprising a crosslinked polymer emulsion (A) and a hydrazine derivative (B) having at least two hydrazide groups in one molecule,
The crosslinked polymer emulsion (A) is obtained by emulsion polymerization of an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer (a1) having at least one aldo group or keto group in one molecule. It is related with the cosmetics characterized by becoming.

  In the second invention, the ethylenically unsaturated monomer (a1) having at least one aldo group or keto group in one molecule in a total of 100% by weight of the ethylenically unsaturated monomer is 0.1. The cosmetic composition according to the first invention is characterized by containing 1 to 20% by weight.

  The third invention relates to the cosmetic according to the first invention or the second invention, wherein the cross-linked polymer emulsion (A) is emulsion-polymerized in the presence of a hydrolyzable silane.

  The fourth invention relates to the cosmetic according to any one of the first to third inventions, wherein the average particle size of the dispersed particles of the crosslinked polymer emulsion (A) is 10 nm to 1 μm.

  The fifth invention relates to the cosmetic according to any one of the first to fourth inventions, which is a makeup or care composition for skin, lips, and hair.

  The sixth invention is a group consisting of foundation, blusher, face powder, eye shadow, eyeliner, eyebrow, mascara, concealer, lipstick, lip gloss, lip pencil, hair mousse, hair foam, hair spray and hair gel. The present invention relates to a cosmetic according to any one of the first to fifth inventions, characterized by being used for at least one of the uses.

  The cosmetic of the present invention has a quick drying property like an organic solvent-based cosmetic by using an aqueous dispersion containing a cross-linked polymer emulsion (A) and a hydrazine derivative (B), and It has become possible to provide water-based cosmetics that provide good gloss, film-forming properties, water resistance, and the like.

  Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following descriptions.

  The cosmetic of the present invention is characterized by containing a crosslinked polymer emulsion (A) and a hydrazine derivative (B) having at least two hydrazide groups in one molecule.

  First, the crosslinked polymer emulsion (A) will be described. The cross-linked polymer emulsion (A) is obtained by emulsion polymerization of an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer (a1) having at least one aldo group or keto group in one molecule. An aqueous dispersion of an acrylic polymer.

  Examples of the ethylenically unsaturated monomer (a1) having at least one aldo group or keto group used in the present invention include diacetone acrylamide, diacetone methacrylamide, acrolein, N-vinylformamide, Selection from one or more of vinyl methyl ketone, vinyl ethyl ketone, acetoacetoxyethyl acrylate, acetoacetoxypropyl acrylate, acetoacetoxybutyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, etc. it can.

In the present invention, the ethylenically unsaturated monomer (a1) having at least one aldo group or keto group in one molecule is used as the ethylenically unsaturated monomer in obtaining the crosslinked polymer emulsion (A). ) Other than the ethylenically unsaturated monomer (a2) can be used. Examples of the ethylenically unsaturated monomer (a2) include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, and isoamyl acrylate. Alkyl acrylates such as n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, dodecyl acrylate, and isobornyl acrylate;
Methyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n methacrylate -Alkyl methacrylates such as octyl, decyl methacrylate, dodecyl methacrylate, isobornyl methacrylate;
Styrene unsaturated monomers such as styrene, vinyltoluene, 2-methylstyrene, t-butylstyrene, chlorostyrene;
Carboxyl group-containing unsaturated monomers such as polymerizable unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid, and anhydrides thereof;
Hydroxy group-containing unsaturated monomers such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate;
N-substituted acrylic and methacrylic unsaturated monomers such as N-methylol acrylamide, N-butoxymethyl acrylamide, N-methylol methacrylamide, N-butoxymethyl methacrylamide;
It can be selected from one or more of epoxy group-containing unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate; and acrylonitrile.

  In the present invention, among the ethylenically unsaturated monomers (a2), carboxyl group-containing unsaturated monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid are used. Is preferred. The carboxyl group-containing unsaturated monomer is 0.1 to 5% by weight in the radically polymerizable ethylenically unsaturated monomer used [total of monomer (a1) and monomer (a2)]. It is preferable to use it. If the carboxyl group-containing unsaturated monomer is less than 0.1% by weight, the stability over time of the resulting crosslinked polymer emulsion (A) may be lowered. On the other hand, when the amount is more than 5% by weight, the viscosity at the time of neutralization increases, and when used as a cosmetic, the water resistance of the coating film may be deteriorated.

  The ethylenically unsaturated monomer (a1) having at least one aldo group or keto group in one molecule is a radically polymerizable ethylenically unsaturated monomer [monomer (a1) and monomer ( The total content of a2) is preferably 0.1 to 20% by weight. If the monomer (a1) is less than 0.1% by weight, the drying effect of the resulting cosmetic may be reduced. On the other hand, when it is more than 20% by weight, the polymerization stability and the storage stability may be deteriorated.

  Furthermore, the cross-linked polymer emulsion (A) is preferably obtained by emulsion polymerization in the presence of a hydrolyzable silane. Examples of the hydrolyzable silane that can be used in the present invention include alkoxysilyl group-containing compounds to which an alkoxyl group having 1 to 14 carbon atoms is bonded. The cosmetic of the present invention has excellent properties even when it does not contain the alkoxysilyl group-containing compound, but when it contains the alkoxysilyl group-containing compound, the resulting film has excellent water resistance and gloss retention. Properties, temperature change resistance and the like can be further imparted.

  The alkoxysilyl group-containing compound is not particularly limited as long as it is a compound containing an alkoxysilyl group having an alkoxyl group having 1 to 14 carbon atoms, and the alkoxyl group having 1 to 14 carbon atoms is linear or branched. It may be. The alkoxyl group may be bonded to 1 to 4 silicon atoms constituting the alkoxysilyl group.

  The alkoxysilyl group-containing compound is not particularly limited. For example, tetramethoxysilane, trimethoxymethylsilane, dimethoxydimethylsilane, methoxytrimethylsilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane , Γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-actyl Liloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ -Aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane and the like. These may be used alone or in combination of two or more. Of these, tetramethoxysilane, trimethoxymethylsilane, dimethoxydimethylsilane, methoxytrimethylsilane, and γ-glycidoxypropyltrimethoxysilane are particularly preferable. In addition, when using the compound which has an ethylenically unsaturated bond as an alkoxy silyl group containing compound, the said compound shall not be handled as a monomer used for calculation of the glass transition temperature of a polymer.

  The alkoxysilyl group-containing compound is preferably used in an amount of 0.1 to 10% by weight based on the total of ethylenically unsaturated monomers. If the alkoxysilyl group-containing compound is less than 0.1% by weight, crosslinking or high molecular weight based on the siloxane bond is insufficient, and the effect of addition is poor. If the compound exceeds 10% by weight, stable production during polymerization is achieved. It can be difficult. More preferably, it is 0.5 to 8% by weight, and particularly preferably 1 to 7% by weight.

  The average particle diameter of the dispersed particles of the crosslinked polymer emulsion (A) will be described. The average particle size of the dispersed particles of the crosslinked polymer emulsion (A) of the present invention is important because it has a great influence on the appearance, viscosity and viscosity of the cosmetic. That is, the average particle size of the dispersed particles of the crosslinked polymer emulsion (A) is preferably 10 nm to 1 μm, and more preferably 30 nm to 200 nm. Further, when a large amount of coarse particles having a particle diameter exceeding 10 μm is contained, the transparency is remarkably deteriorated and the appearance is deteriorated. When the solution viscosity of the cosmetic is low, the particles are precipitated and hard caked and re-appeared. Since it may not be possible to disperse, coarse particles exceeding 10 μm are preferably at most 5% by weight in the total 100% by weight of the dispersed particles. Further, if the average particle size of the dispersed particles is larger than 1 μm, the reproducibility may be slightly lowered when a high appearance is required as a cosmetic, but it is used depending on the required reproducibility of the appearance. Of course it is also possible. When the average particle size of the dispersed particles is smaller than 10 nm, the viscosity of the dispersion itself increases, which may affect the storage stability as a cosmetic and the ease of use in use. The average particle diameter can be measured by a dynamic light scattering method.

  A chain transfer agent can be used to adjust the molecular weight of the resin constituting the cross-linked polymer emulsion (A). Among chain transfer agents, chain transfer agents having a mercapto group (thiol group) generally have a very unpleasant odor and cannot be used in applications such as cosmetics. However, the mercaptopropionic acid derivative (c) represented by the following general formula (1) is odorless and can be preferably used in the cosmetic of the present invention.

General formula (1)
(HS-CH ₂ —CH ₂ —COO—) _n R
When n = 1, R represents an alkyl group having 4 or more carbon atoms or an alkoxyalkyl group having 4 or more carbon atoms. In the case of n = 2 to 4, R represents an n-valent organic residue, and preferably represents a hydrocarbon group having 2 to 8 carbon atoms, an isocyanurate ring or an aromatic ring.

  In addition, from the viewpoint of odor suppression, it is possible to use a very small amount of a chain transfer agent other than the mercaptopropionic acid derivative (c). However, considering the practical odor level, other chain transfer agents alone cannot exert an effect on molecular weight adjustment.

  In the present invention, it is preferable to use 0.1 to 10.0 parts by weight of the mercaptopropionic acid derivative (c) with respect to 100 parts by weight of the total of ethylenically unsaturated monomers, and 0.5 to 5.0 More preferably, parts by weight are used. If the mercaptopropionic acid derivative (c) is less than 0.1 parts by weight, the weight-average molecular weight of the resin constituting the cross-linked polymer emulsion (A) exceeds 100,000, resulting in poor film removability. May end up. On the other hand, when the amount of mercaptopropionic acid derivative (c) is more than 10.0 parts by weight, the weight average molecular weight of the resin constituting the cross-linked polymer emulsion (A) becomes less than 5,000, and the mechanical properties of the film are lowered. There is a case.

  Among the mercaptopropionic acid derivatives (c) used in the present invention, those with n = 1 include, for example, mercaptopropionic acid alkyl such as octyl mercaptopropionic acid, n-butyl-3-mercaptopropionic acid, tridecyl mercaptopropionic acid, and the like. And an alkoxyalkyl mercaptopropionate such as methoxybutyl mercaptopropionate. The alkyl group of alkyl mercaptopropionate may be either linear or branched. For example, octyl mercaptopropionate is preferred, either mercaptopropionate-n-octyl or 2-ethylhexyl mercaptopropionate may be used together. Examples of n = 2 to 4 include ethylene glycol bisthiopropionate, butanediol bisthiopropionate, totimethylolpropane tristhiopropionate, tris (2-hydroxyethyl) isocyanurate tris (β- Mercaptopropionate) and the like. In this invention, these well-known things can be used 1 type or more or in mixture of many types. Among these derivatives, in particular, when a monomer is polymerized in the presence of octyl mercaptopropionate, there is no odor that causes problems when used as a cosmetic, and a cross-linked polymer emulsion having a molecular weight suitably adjusted ( A) can be provided.

  The glass transition temperature (hereinafter also referred to as Tg) of the resin constituting the crosslinked polymer emulsion (A) is preferably 0 to 100 ° C, more preferably 30 to 80 ° C. When Tg is lower than 0 ° C., the mechanical properties at room temperature tend to decrease. Moreover, when Tg exceeds 100 degreeC, there exists a tendency for a film to become weak. It is more preferable that Tg is in the range of 0 to 100 ° C., since the mechanical properties at room temperature when used as a cosmetic and the mechanical durability due to the mechanical properties under warm water are further improved. Tg in the present specification can be obtained from the following formula described in Kyozo Kitaoka, “Introduction to Synthetic Resins for Paints” (Polymer Publications).

1 / Tg = (W1 / Tg1) + (W2 / Tg2)... + (Wn / Tgn)
Here, Tg is the glass transition temperature (K) of the resin obtained by copolymerization, Tg1, Tg2, etc. are the glass transition temperatures (K) of homopolymers that can be formed from the respective monomers, W1, W2, etc. It represents the weight ratio (W1 + W2 +... + Wn = 1) of each monomer.

  In addition, when using what has an ethylenically unsaturated group as an emulsifier in the case of emulsion polymerization, the emulsifier which has an ethylenically unsaturated group shall not be handled as a monomer used for calculation of said Tg. .

  In the present invention, the particle structure of the cross-linked polymer emulsion (A) may be a multi-layer structure so-called core-shell particles. For example, drying property and film-forming property can be improved by localizing the monomer (a1) in the shell portion which is the particle surface layer or by providing a difference in Tg and composition between the core and the shell. .

  The crosslinked polymer emulsion (A) of the present invention is synthesized by a conventionally known emulsion polymerization method. By synthesizing by an emulsion polymerization method, it is easy to adjust the average particle diameter, molecular weight, etc. of the dispersed particles of the resulting crosslinked polymer emulsion (A), and it is excellent in stability when used as a cosmetic.

  As the emulsifier used in the emulsion polymerization in the present invention, a conventionally known one such as a reactive emulsifier having an ethylenically unsaturated group and / or a non-reactive emulsifier having no ethylenically unsaturated group is arbitrarily used. can do.

  Reactive emulsifiers having an ethylenically unsaturated group can be further broadly classified into anionic and nonionic nonionic ones. In particular, when an anionic reactive emulsifier having an ethylenically unsaturated group is used alone, the dispersed particle size of the copolymer becomes fine and the particle size distribution becomes narrow. It is preferable for improving dramatically. This anionic reactive emulsifier having an ethylenically unsaturated group may be used alone or in combination of two or more.

Specific examples of the anionic reactive emulsifier having an ethylenically unsaturated group are illustrated below, but the emulsifiers that can be used in the present invention are not limited to those described below. Examples of the emulsifier include alkyl ethers (commercially available products include, for example, Aqualon KH-05, KH-10, KH-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap SR-10N, SR manufactured by Asahi Denka Kogyo Co., Ltd. -20N, LATEMUL PD-104 manufactured by Kao Corporation);
Sulfosuccinic acid ester-based (for example, Latmul S-120, S-120A, S-180P, S-180A, Sanyo Chemical Co., Ltd., Elemiol JS-2, etc., manufactured by Kao Corporation);
Alkyl phenyl ether type or alkyl phenyl ester type (commercially available products include, for example, Aqualon H-2855A, H-3855B, H-3855C, H-3856, HS-05, HS-10, HS, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. -20, HS-30, Adeka Soap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, SE-, etc. manufactured by Asahi Denka Kogyo Co., Ltd.);
(Meth) acrylate sulfate ester (commercially available products such as Antox MS-60, MS-2N, Sanyo Kasei Kogyo Co., Ltd. Elminol RS-30 manufactured by Nippon Emulsifier Co., Ltd.);
Examples of the phosphoric acid ester type (commercially available products include H-3330PL manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap PP-70 manufactured by Asahi Denka Kogyo Co., Ltd., etc.).

When the crosslinked polymer emulsion (A) of the present invention is prepared by emulsion polymerization, a nonionic reactive emulsifier can be used alone or together with the anionic reactive emulsifier as necessary. Nonionic reactive emulsifiers that can be used in the present invention include, for example, alkyl ether-based (commercially available products include, for example, Adeka Soap ER-10, ER-20, ER-30, ER- manufactured by Asahi Denka Kogyo Co., Ltd. 40, Latemu PD-420, PD-430, PD-450, etc. manufactured by Kao Corporation);
Alkylphenyl ether or alkylphenyl ester (commercially available products include, for example, Aqualon RN-10, RN-20, RN-30, RN-50, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap manufactured by Asahi Denka Kogyo Co., Ltd. NE-10, NE-20, NE-30, NE-40, etc.);
(Meth) acrylate sulfate-based (as commercial products, for example, RMA-564, RMA-568, RMA-1114, etc. manufactured by Nippon Emulsifier Co., Ltd.) can be mentioned.

  When the crosslinked polymer emulsion (A) of the present invention is obtained by emulsion polymerization, it is necessary together with the reactive emulsifier having an ethylenically unsaturated group, as long as the performance of the resulting aqueous dispersion is not adversely affected. Accordingly, a non-reactive emulsifier having no ethylenically unsaturated group can be used in combination. Non-reactive emulsifiers can be broadly classified into non-reactive anionic emulsifiers and non-reactive nonionic emulsifiers.

Examples of non-reactive nonionic emulsifiers include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether;
Polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether;
Sorbitan higher fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate;
Polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate;
Polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate;
Glycerin higher fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride;
Examples thereof include polyoxyethylene / polyoxypropylene / block copolymer and polyoxyethylene distyrenated phenyl ether.

Examples of non-reactive anionic emulsifiers include higher fatty acid salts such as sodium oleate;
Alkylaryl sulfonates such as sodium dodecylbenzenesulfonate;
Alkyl sulfate salts such as sodium lauryl sulfate;
Polyoxyethylene alkyl ether sulfate ester salts such as sodium polyoxyethylene lauryl ether sulfate;
Polyoxyethylene alkylaryl ether sulfate salts such as sodium polyoxyethylene nonylphenyl ether sulfate;
Alkyl sulfosuccinic acid ester salts such as sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof;
Examples thereof include polyoxyethylene distyrenated phenyl ether sulfate salts.

  The usage-amount of the emulsifier used in this invention is not necessarily limited, According to the physical property calculated | required when a crosslinkable polymer emulsion (A) is finally used as cosmetics, it can select suitably. For example, the amount of the emulsifier is usually preferably 0.1 to 30 parts by weight, more preferably 0.3 to 20 parts by weight, based on 100 parts by weight of the total of ethylenically unsaturated monomers. More preferably, it is in the range of 5 to 10 parts by weight.

In the emulsion polymerization for obtaining the crosslinked polymer emulsion (A) of the present invention, a water-soluble protective colloid can be used in combination as long as the performance of the resulting aqueous resin dispersion is not adversely affected. Examples of the water-soluble protective colloid include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol;
Cellulose derivatives such as hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose salts;
Natural polysaccharides such as guar gum; and the like, and these can be used singly or in combination. The amount of the water-soluble protective colloid used is 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the total amount of ethylenically unsaturated monomers.

  Examples of the aqueous medium used in the emulsion polymerization for obtaining the cross-linked polymer emulsion (A) of the present invention include water, and a hydrophilic organic solvent can be used as long as the object of the present invention is not impaired. .

  The polymerization initiator used for obtaining the cross-linked polymer emulsion (A) of the present invention is not particularly limited as long as it has the ability to initiate radical polymerization, and is a known oil-soluble polymerization initiator or water-soluble polymerization. Initiators can be used. The oil-soluble polymerization initiator is not particularly limited, and examples thereof include benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, tert-butyl peroxy (2-ethylhexanoate), and tert-butyl peroxide. Organic peroxides such as oxy-3,5,5-trimethylhexanoate, di-tert-butyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4- Examples thereof include azobis compounds such as dimethylvaleronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobiscyclohexane-1-carbonitrile and the like. These may be used alone or in combination of two or more. These polymerization initiators are preferably used in an amount of 0.1 to 10.0 parts by weight with respect to 100 parts by weight of the total of ethylenically unsaturated monomers.

In the present invention, it is preferable to use a water-soluble polymerization initiator. For example, ammonium persulfate, potassium persulfate, hydrogen peroxide, 2,2′-azobis (2-methylpropionamidine) dihydrochloride and the like are conventionally known. A thing can be used conveniently. Moreover, when performing emulsion polymerization, a reducing agent can be used together with a polymerization initiator if desired. Thereby, it becomes easy to accelerate the emulsion polymerization rate or to perform the emulsion polymerization at a low temperature. Examples of such a reducing agent include reducing organic compounds such as metal salts such as ascorbic acid, ersorbic acid, tartaric acid, citric acid, glucose, and formaldehyde sulfoxylate;
Reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite;
Other examples include ferrous chloride, Rongalite, and thiourea dioxide. These reducing agents are preferably used in an amount of 0.05 to 5.0 parts by weight based on 100 parts by weight of the total of ethylenically unsaturated monomers. In addition, it can superpose | polymerize by a photochemical reaction, radiation irradiation, etc. irrespective of an above described polymerization initiator. The polymerization temperature is equal to or higher than the polymerization start temperature of each polymerization initiator. For example, in the case of a peroxide-based polymerization initiator, it may be usually about 70 ° C. The polymerization time is not particularly limited, but is usually 2 to 24 hours.

When a monomer having an acidic functional group such as a carboxyl group-containing unsaturated monomer is used as a monomer for obtaining the cross-linked polymer emulsion (A), a basic compound is used before or after polymerization. Can be summed. When neutralizing, ammonia or alkylamines such as trimethylamine, triethylamine, butylamine;
Alcohol amines such as 2-dimethylaminoethanol, diethanolamine, triethanolamine, aminomethylpropanol;
It can be neutralized with a base such as morpholine. However, it is a highly volatile base that has a high effect on drying properties, and preferred bases are aminomethylpropanol and ammonia.

  Next, the hydrazine derivative (B) will be described. The hydrazine derivative of the present invention is a compound having at least two hydrazide groups in one molecule, and is a compound capable of reacting with the aldo group or keto group of the resin present in the crosslinked polymer emulsion (A). . As a method for adding the hydrazine derivative (B) and the cross-linked polymer emulsion (A), the water-soluble hydrazine derivative (B) is added as it is or diluted with water. When the hydrazine derivative (B) is oil-soluble, it is not preferable in view of the form of the present invention. However, when used, it is better to emulsify with a surfactant if necessary.

  Examples of the hydrazine derivative (B) having at least two hydrazide groups in one molecule of the present invention include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide and the like. In addition to aliphatic dihydrazide, carbonated polyhydrazide, aliphatic, alicyclic, aromatic bissemicarbazide, aromatic dicarboxylic acid dihydrazide, polyacrylic acid polyhydrazide, aromatic hydrocarbon dihydrazide, hydrazine-pyridine derivative and maleic acid dihydrazide And dihydrazide of unsaturated dicarboxylic acid.

  The blending amount of the hydrazide derivative (B) is 0.1 to 1 with respect to 1 equivalent of the hydrazide group in the hydrazide derivative (B) and the aldo group or keto group of the resin present in the crosslinked polymer emulsion (A). It is preferable to mix them at a ratio so as to be 0.0 equivalent. When the hydrazide group is less than 0.1 equivalent, the effect of drying of the cosmetic is poor. On the other hand, when it exceeds 1.0 equivalent, the water resistance of the coating film obtained may be inferior.

  In the cross-linked polymer emulsion (A) of the present invention, a polyvalent metal can be blended as a cross-linking agent. As an addition method, the polyvalent metal salt is dissolved in water and then added. More preferably, a basic substance is added to the aqueous polyvalent metal salt solution and added as a metal complex. Further, it is preferable that the pH of the resin solution before the addition of the polyvalent metal is also increased in advance.

  As the polyvalent metal, copper, silver, beryllium, zinc, aluminum, cobalt, nickel, lead, calcium, strontium, barium, titanium, vanadium, chromium, manganese, iron, tin, zirconium, molybdenum, magnesium and the like can be used. These metals can be used in the form of oxides, hydroxides, carbonates, chlorides or the like that can be dissolved in water or basic water.

  The addition amount of the polyvalent metal is 0.05 to 0.5 mol of metal with respect to 1 mol in total of the aldo group or keto group of the resin contained in the cross-linked polymer emulsion (A) and the carboxyl group. Added. If it is less than 0.05 mol, the drying effect may not be remarkably exhibited. On the other hand, when the amount exceeds 0.5 mol, the stability of the cosmetic is deteriorated and the water resistance of the coating film may be deteriorated.

  For the present invention, cosmetically acceptable oils, more generally physiologically acceptable lipophilic media, can be used, especially carbon-based oils of mineral, animal, vegetable or synthetic origin. , Hydrocarbon base oils, fluoro oils and / or silicone oils, alone or as a mixture provided that they form a stable and homogeneous mixture and are compatible with the intended use. The oil may be a non-volatile oil or a volatile oil, preferably a volatile oil.

Accordingly, examples of oils that can be used in the present invention include hydrocarbon-based oils such as liquid paraffin and liquid petrolatum;
Mink oil, turtle oil, soybean oil, perhydrosqualene, sweet almond oil, Terihaboku (beauty leaf) oil, palm oil, grape seed oil, sesame seed oil, corn oil, parleam oil, arara oil Cereal germ oils such as rapeseed oil, sunflower oil, cottonseed oil, apricot oil, castor oil, avocado oil, jojoba oil, and olive oil;
Lanolinic acid esters, oleic acid esters, lauric acid esters, or stearic acid esters; isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate 2-octyldecyl laurate, 2-octyldecyl palmitate, 2-octyldecyl myristate, 2-octyldecyl lactate, 2-diethylhexyl succinate, diisostearyl malate, glyceryl triisostearate, and triisostearic acid Fatty acid esters such as diglyceryl;
Higher fatty acids such as myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid;
Higher aliphatic alcohols such as cetanol, stearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, isostearyl alcohol and octyldodecanol;
Silicone oils such as polydimethylsiloxanes (PDMS), which are optionally phenylated, such as phenyltrimethicones, or aliphatic and / or aromatic groups that are optionally fluorinated Substituted with functional groups such as hydroxy groups, thiol groups, and amine groups).
Mention may be made of fatty acids, fatty alcohols, polysiloxanes modified with polyoxyalkylenes, fluorosilicones and perfluoro oils.

The cosmetic of the present invention may contain one or more oils that are volatile at room temperature. Here, the volatile oil includes oils having a vapor pressure in the range of 0.13 to 40000 Pa (10 ^{−3 to} 300 mmHg) at room temperature and atmospheric pressure. These volatile oils particularly facilitate the application of the composition to the skin. These oils can be hydrocarbon-based oils, silicone oils (including oils having an alkyl or alkoxyl group in the side chain or terminal of the silicone), and fluoro oils.

  Volatile silicone oils can include linear or cyclic silicones containing 2 to 7 silicon atoms, these silicones optionally being alkyl containing 1 to 10 carbon atoms. Group or alkoxy group. Thus, mention may be made in particular of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexadecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, and mixtures thereof.

  Examples of volatile hydrocarbon-based oils include C8-C16 isoparaffins such as Isopar (manufactured by ExxonMobil) and Permethyl (manufactured by EC Eldorchemie, Nippon Koken Kogyo), especially isododecane, isooctane, and isodecane. , Isohexadecane, and mixtures thereof.

  The cosmetic of the present invention can contain an oil or the like corresponding to 5 to 97.5% by weight with respect to the total weight of the cosmetic, and corresponds to 20 to 75% by weight of the oil, particularly volatile oil. It is even more preferred to include one.

  The cosmetic of the present invention can contain at least one colorant. The colorant can be selected from dyes, pigments, pearlescent pigments, and mixtures thereof commonly used in cosmetics. The colorant is generally blended in a proportion of 0.01 to 50% by weight, preferably 1 to 30% by weight, based on the total weight of the cosmetic.

  Examples of the dye include Sudan Red, D & C Red 17, D & C Green 6, β-carotene, soybean oil, Sudan Brown, D & C Yellow 11, D & C Violet 2, D & C Orange 5, Quinoline Yellow, Anato, and mixtures thereof. It is done.

  The pigment may be white or colored, inorganic and / or organic, coated or uncoated, normal size or nanometer size. Examples of inorganic pigments include titanium dioxide, optionally surface-treated titanium dioxide, zirconium oxide, cerium oxide, iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydroxide, ferric blue, and the like There is a mixture of Examples of organic pigments include carbon black, D & C type pigments, cochineal carmine, barium, strontium, calcium and aluminum based lakes, and mixtures thereof. Said pigments can in particular be coated with at least one silicone compound and / or polymers, in particular polydimethylsiloxanes, in particular polyethylenes and / or at least one fluoro compound and / or at least one amino acid. Mention may also be made of “SI oxides” which are polymethylhydrogenosiloxane-coated pigments sold by the company Miyoshi.

  Examples of the pearlescent pigment include white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, titanium mica coated with iron oxides, titanium mica coated with ferric blue or chromium oxide, and the organic materials described above It can be selected from colored pearlescent pigments such as titanium mica coated with pigment, bismuth oxychloride based pearlescent pigments, and mixtures thereof.

  Among the cosmetics according to the invention, at least one filler can be included, in particular in order to obtain a matte product particularly desired for foundations, especially for foundations with individuals with oily skin or desired for day creams. . The term “filler” is any particle that is solid, at room temperature and atmospheric pressure, used alone or in combination, at a temperature at which the components of the composition exceed room temperature, in particular their softening point or their melting point. Even so, the filler means particles that do not chemically react with the various components of the composition and are insoluble in these components. These inert fillers have a melting point of at least higher than 170 ° C, more preferably higher than 200 ° C. They can be absorbable or non-absorbable. That is, it can also absorb especially the oils of the composition and biological materials secreted by the skin. These fillers preferably have an apparent diameter in the range of 0.01 to 150 μm, preferably 0.5 to 120 μm, more preferably 1 to 80 μm. The apparent diameter corresponds to the diameter of the circumference where the basic particles are inscribed in the smallest dimension (lamellar thickness).

  Fillers that can be used in the present invention can be inorganic or organic, lamellar, spherical or elliptical. For example, talc, mica, silica, kaolin, polyamide powder [Nylon®, Orgasol® from Atochem], poly-β-alanine powder, polyethylene powder, acrylic polymer powder, especially polymethacrylic Methyl acid (PMMA) powder [reference Covabead LH-85 (product sold by Wackherr with particle size 10-12 μm)], acrylic acid copolymer powder [Dow Corning Polytrap®], polytetrafluoroethylene powder Body [Teflon®], lauroyl lysine, boron nitride, starch, polyvinylidene chloride / acrylonitrile hollow polymer microspheres, [Expancel® (Nobel Industry)], precipitated calcium carbonate , Carbonates such as magnesium carbonate and magnesium hydrogen carbonate, hydroxyapatite, hollow silica microspheres [Maplicos Silica Beads®], glass microcapsules, ceramic microcapsules, polyester particles, and mixtures thereof . These fillers can be surface-treated to make them particularly lipophilic.

  The cosmetic of the present invention can contain one or more kinds of waxes. In the present invention, the wax has a reversible solid / liquid state change and is solid at room temperature (25 ° C.) and has a melting point higher than 45 ° C., more preferably higher than 55 ° C. and up to 200 ° C. It is a lipophilic aliphatic compound having an anisotropic crystal structure in the state. In the present invention, the waxes are generally used for cosmetics. These are of particular natural origin, for example beeswax, carnauba wax, candelilla wax, cucumber wax, wood wax, cork fiber wax, sugar cane wax, paraffin wax, lignite wax, microcrystalline wax, lanolin wax, montan wax , Ozokerite, and hydrogenated oils (eg, hydrogenated jojoba oil). Examples of the waxes of synthetic origin include, for example, polyethylene waxes derived from ethylene polymerization, waxes obtained by Fischer-Tropsch synthesis, solid fatty acid and glyceride esters at 40 ° C., and silicone waxes [for example, Alkyl and / or alkoxy esters of poly (di) methylsiloxane that are solid at 40 ° C. Synthetic waxes are preferably used because they are more reproducible than natural waxes.

  The cosmetics of the present invention include antioxidants, essential oils, preservatives, fragrances, neutralizing agents, fat-soluble or dispersible polymers (for example, emollients), wetting agents, vitamins, essential fatty acids, sunscreen agents. , Including any additive commonly used in the field selected from cosmetic active agents, such as free radical scavengers, dispersants [eg poly (12-hydroxystearic acid)], and mixtures thereof. You can also. These additives can be present in a proportion of 0.01 to 30% by weight, more preferably 0.01 to 10% by weight, based on the total weight of the cosmetic. Advantageously, the cosmetic contains at least one active agent.

  It goes without saying that the person skilled in the art may optionally add additional additives and / or amounts thereof so that the advantageous properties of the cosmetics according to the invention are not adversely affected or substantially adversely affected by the intended addition. You will pay attention to choose.

  Cosmetics according to the invention are simple or multiple emulsions containing an oily or aqueous continuous phase, oily dispersions in aqueous phase, suspensions, water or aqueous containing vesicles containing ionic and / or nonionic lipids. It may be in the form of a dispersion or solution in an alcoholic medium, a mousse, and a vesicle dispersion of ionic or nonionic lipids.

  Said cosmetics are creams, gels, pastes, solids (especially sticks), solid emulsions cast into dishes, aqueous or aqueous-alcoholic gels, hydrophilic mousses, emulsifying gels, biphasic or multiphasic lotions, and Can have the appearance of a spray.

  On the one hand, the nature of the components used, in particular the solubility in the support, on the other hand, taking into account the intended use of the composition, an appropriate provisional form based on general knowledge, and a method for preparing it It is possible for those skilled in the art to select.

  Next, the characteristics when the cosmetic according to the present invention is used for each application will be described.

  When the cosmetic according to the present invention is a lip makeup product such as a lipstick, lip gloss or lip pencil, or other lip care product, the odor at the time of application, gloss after application, water resistance, oil resistance, adhesion It is excellent in properties, and in particular, it has good gloss in makeup, and at the same time, it cannot be transferred to a coffee cup, clothing or the like.

  In addition, the cosmetic according to the present invention is a foundation, blusher, face powder, eye shadow, eyeliner, eyebrow, mascara, concealer product, odor when applied, gloss after application, water resistance, oil resistance, It has excellent adhesion, and in particular, it does not lose its makeup due to sweat, tears, swimming, sebum, etc., and it can exhibit an extremely excellent effect on makeup.

  When the cosmetic according to the present invention is made of a hair styling cosmetic such as a hair mousse, a hair foam, a hair spray, a hair gel, etc., it is excellent in gloss, setting effect, combing, color and smell, and further in cleaning properties. It can be effective.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively.

[Production Example 1] (Production of polymer emulsion)
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 265.0 parts of ion-exchanged water and 5.9 parts by weight of Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) as a reactive emulsifier. Separately, 11.7 parts by weight of diacetone acrylamide, 39.4 parts by weight of styrene, 204.2 parts by weight of methyl methacrylate, 129.6 parts by weight of 2-ethylhexyl acrylate, 3.9 parts by weight of acrylic acid, 2-methacrylic acid 2- 3.9 parts by weight of hydroxyethyl, 1.9 parts by weight of γ-methacryloxypropyltrimethoxysilane (S-710, manufactured by Chisso Corporation), 263.7 parts of ion-exchanged water, and Aqualon KH-10 as a reactive emulsifier 5% by weight of the pre-emulsion obtained by premixing 5.9 parts by weight of Ichi Kogyo Seiyaku Co., Ltd. was further added.

  After raising the internal temperature to 60 ° C. and sufficiently purging with nitrogen, 6.0 parts of a 5% aqueous solution of potassium persulfate and 14.7 parts by weight of a 1% aqueous solution of sodium metabisulfite were added to initiate polymerization. After maintaining the reaction system at 70 ° C. for 5 minutes, while maintaining the internal temperature at 70 ° C., the rest of the pre-emulsion, 9.8 parts of a 5% aqueous solution of potassium persulfate, and 24.6 wt. Of a 1% aqueous solution of sodium metabisulfite The portion was added dropwise over 3 hours, and stirring was further continued for 3 hours. During the emulsion polymerization, the pH of the polymerization reaction solution was kept at 3.0. After completion of the reaction, the temperature was cooled to 30 ° C., and 3.9 parts by weight of 25% aqueous ammonia was added to obtain a polymer emulsion. The resulting polymer emulsion had a pH of 8.5 and a nonvolatile content concentration of 40.5%. The non-volatile content concentration was determined from the baking residue at 150 ° C. for 20 minutes. The glass transition temperature (calculated value) of the resin in the obtained polymer emulsion was 30 ° C. The average particle diameter of the dispersed particles of the obtained polymer emulsion was 60 nm. The average particle size was measured by a dynamic light scattering type particle size distribution measuring device.

  Further, a predetermined amount of adipic acid dihydrazide (0.5 equivalent to 1 equivalent of contained aldo group or keto group) was added thereto to obtain an aqueous dispersion (1).

[Production Examples 2 and 3]
In the same manner as in Production Example 1, the polymer emulsion was prepared by reacting at the ratio of “Table 1”. Further, in Production Example 2, an aqueous dispersion (2) was obtained by adding adipic acid dihydrazide. In addition, Production Example 3 is an aqueous dispersion (3) that does not contain a hydrazine derivative.

[Example 1] (Eye Shadow)
Using the aqueous dispersion (1) obtained in Production Example 1, an eye shadow having the composition shown below was produced by the following production method.

Composition (wt%)
(1) Microcrystalline wax 3.0
(2) Stearic acid 3.0
(3) Liquid paraffin 8.5
(4) Lanolin 1.0
(5) Sorbitan monostearate 1.5
(6) Glycerin 5.5
(7) Triethanolamine 1.5
(8) Methylcellulose 0.5
(9) Aqueous dispersion (1) 10.0
(10) Pearl pigment 10.0
(11) Ultramarine 2.0
(12) Remaining amount of ion-exchanged water (13) Trace amount of perfume (14) Preservative amount

  Methyl cellulose, glycerin and triethanolamine are dissolved in ion-exchanged water, and then heated to uniformly disperse the pearl pigment and ultramarine blue. Next, an oil phase component such as microcrystalline wax is heated and dissolved, and added to the aqueous phase with stirring to emulsify. After cooling, the aqueous dispersion (1) obtained in Production Example 1, a fragrance, and a preservative were added to obtain a blue cream type eye shadow.

[Comparative Examples 1 and 2] (Eye Shadow)
In the same manner as in Example 1, except that the aqueous dispersions (2) and (3) obtained in Production Examples 2 and 3 were used in place of the aqueous dispersion (1) obtained in Production Example 1, respectively. A shadow was produced.

[Eye shadow evaluation]
(1) Speed of drying, gloss after drying, and makeup feeling Example 1 and Comparative Examples 1 and 2 were used as samples, and the speed of drying, gloss after drying and makeup feeling (durability of makeup effect) panel 10 Evaluation by use test by name. The evaluation criteria were determined as follows.

"Evaluation criteria"
☆: All 10 people were extremely good.
A: 8 or more out of 10 were considered good.
○: 6 or more out of 10 people were good.
(Triangle | delta): 4 or more out of 10 persons considered favorable.
X: 3 or less out of 10 were considered good.

(2) Water resistance The sample eye shadows of Example 1 and Comparative Examples 1 and 2 were uniformly applied to a nylon plate having a length of 5 cm, a width of 1 cm, and a thickness of 1 cm, and after drying, 10 ml of ion-exchanged water was added. The sample was set in a 20 ml glass sample tube, shaken for 10 minutes with a shaker, and the state of peeling of the coating film and the like was compared and evaluated for each sample.

(3) Oil resistance Prepare a sample by the same method as in (2), set it in a 20 ml glass sample tube containing 10 ml of oil (triglyceride), and shake as in (2). Each sample was evaluated for peeling of the coating film, rubbing strength when touched with a finger, and color transfer to the fingertip.

(4) Adhesion A sample was made in the same manner as in (2), set in a 20 ml glass sample tube containing 10 g of rice granular Duracon resin, and shaken as in (2). The adhesion state such as peeling of the coating film was evaluated for each sample. The evaluation criteria (2) to (4) were determined as follows.

"Evaluation criteria"
◎: Extremely good ○: Good △: Poor ×: Extremely bad

[Example 2] (mascara)
Using the aqueous dispersion (1) obtained in Production Example 1, a mascara having the following composition was produced by the following production method.

Composition (wt%)
(1) Aqueous dispersion (1) 45.0
(2) Black iron oxide 15.0
(3) Talc 10.0
(4) Methyl hydroxypropyl cellulose 2.0
(5) Polyoxyethylene sorbitan monooleate 1.5
(6) Glycerin 5.0
(7) Remaining amount of ion-exchanged water (8) Trace amount of perfume (9) Preservative amount

  Add methylhydroxypropylcellulose, talc and aqueous dispersion (1) to ion-exchanged water, mix uniformly with stirring, and then add colored paste consisting of black iron oxide, glycerin and polyoxyethylene sorbitan monooleate Mix and add a fragrance and preservative to make a black mascara.

[Comparative Examples 3 and 4] (Mascara)
A mascara in the same manner as in Example 2 except that the aqueous dispersions (2) and (3) obtained in Production Examples 2 and 3 were used in place of the aqueous dispersion (1) obtained in Production Example 1, respectively. Manufactured.

[Evaluation of mascara]
(1) Speed of drying after application and gloss and makeup after drying Using Example 2 and Comparative Examples 3 and 4 as samples, odor during application, gloss after drying and makeup feeling (persistence of makeup effect) ) Was evaluated by a use test with 10 panelists. The evaluation criteria were the same as in the case of the eye shadow.

(2) Water resistance, (3) Oil resistance, (4) Adhesion Evaluation was performed by the same method and evaluation criteria as in the case of the eye shadow.

[Example 3] (Eyeliner)
Using the aqueous dispersion obtained in Production Example 1, a liquid film type eyeliner having the following composition was produced by the following production method.

Composition (wt%)
(1) Aqueous dispersion (1) 58.0
(2) Carbon black 6.0
(3) Titanium dioxide 3.0
(4) Polyoxyethylene sorbitan monostearate 1.0
(5) Glycerin 3.0
(6) Methylcellulose 1.0
(7) Remaining amount of ion-exchanged water (8) Trace amount of perfume (9) Preservative amount

  Polyoxyethylene sorbitan monostearate is dissolved in ion-exchanged water, and carbon black and titanium dioxide are mixed therein and uniformly dispersed using a colloid mill. Glycerin, methylcellulose and the aqueous dispersion (1) were added and mixed uniformly. Finally, a fragrance and a preservative were added to obtain a black film type eyeliner.

[Comparative Examples 5 and 6] (Eyeliner)
In the same manner as in Example 3, except that the aqueous dispersions (2) and (3) obtained in Production Examples 2 and 3 were used in place of the aqueous dispersion (1) obtained in Production Example 1, respectively. A liner was produced.

[Eyeliner evaluation]
(1) Speed of drying after application, gloss and makeup after drying Using Example 3 and Comparative Examples 5 and 6 as samples, odor during application, gloss after drying, and makeup feeling (persistence of makeup effect) The panel was evaluated by a use test with 10 panelists. The evaluation criteria were the same as in the case of the eye shadow.

(2) Water resistance, (3) Oil resistance, (4) Adhesion Evaluation was performed by the same method and evaluation criteria as in the case of the eye shadow.

[Example 4] (O / W emulsified foundation)
Using the aqueous dispersion (1) obtained in Production Example 1, a liquid film type O / W emulsion type foundation having the following composition was produced by the following production method.

Compounding ingredients Compounding amount (% by weight)
(1) Talc 3.0
(2) Titanium dioxide 5.0
(3) Bengala 0.5
(4) Yellow iron oxide 1.4
(5) Black iron oxide 0.1
(6) Bentonite 0.5
(7) Polyoxyethylene sorbitan monostearate 0.9
(8) Triethanolamine 1.0
(9) Propylene glycol 10.0
(10) Aqueous dispersion (1) 5.0
(11) Ion-exchanged water Remainder (12) Stearic acid 2.2
(13) Isohexadecyl alcohol 7.0
(14) Glycerol monostearate 2.0
(15) Liquid lanolin 2.0
(16) Liquid paraffin 8.0
(17) Ethylparaben 0.1
(18) Perfume appropriate amount

  (9), in which (6) is dispersed, is added to (11) and subjected to a homomixer treatment at 70 ° C., and then the remaining aqueous phase components (7), (8) and (10) are added and sufficiently stirred. The powder part sufficiently mixed and pulverized is added to this while stirring, and homomixed at 70 ° C. Next, the oil phases (12) to (16) and (17) dissolved by heating at 70 to 80 ° C are gradually added and homotreated at 70 ° C. This is cooled with stirring, (18) is added at 45 ° C. and cooled to room temperature. Finally degassed and filled into containers. The obtained emulsified foundation was moist, smooth and long-lasting.

[Comparative Examples 7 and 8] (O / W emulsified foundation)
O in the same manner as in Example 4 except that the aqueous dispersions (2) and (3) obtained in Production Examples 2 and 3 were used in place of the aqueous dispersion (1) obtained in Production Example 1. A / W emulsified foundation was produced.

[Evaluation of O / W emulsion type foundation]
(1) Drying speed after application and makeup feeling Example 4 and Comparative Examples 7 and 8 were used as samples, and the drying speed after application and makeup feeling (continuity of makeup effect) were used by 10 panelists. Evaluation by testing was performed. The evaluation criteria were the same as those for the eyeliner.

(2) Water resistance, (3) Oil resistance, (4) Adhesion Evaluation was carried out by the same method and evaluation criteria as in the case of the above eyeliner.

[Example 5] (Hair gel)
A hair gel having the following composition was produced by the following production method using the aqueous dispersion (1) obtained in Production Example 1.

Compounding ingredients Compounding amount (% by weight)
(1) Carboxyvinyl polymer 0.7
(2) Aqueous dispersion (1) 5.0
(3) Glycerin 2.5
(4) 1,3-butylene glycol 2.5
(5) Polyoxyethylene hydrogenated castor oil (40EO) 0.5
(6) Dimethylpolysiloxane 100cs 5.0
(7) Polyether-modified silicone 1.0
(Product name: KF6011, manufactured by Shin-Etsu Chemical Co., Ltd.)
(8) Sodium hydroxide appropriate amount (adjusted to pH 7.5)
(9) Ethanol 20.0
(10) Polyoxyethylene octyldodecyl ether 0.1
(11) Fragrance 0.1
(12) Edetate trisodium 0.03
(13) Residual ion exchange water

  (4), (5), (6), (8), (7) is added to a part of (14) and emulsified with a homomixer. Next, a part of (14) is added to form an emulsifying part. On the other hand, (1), (2), (3), (9), (10), (11), (12), (13) are uniformly dissolved in the remaining (14), and the previous emulsifying part Was added to obtain an emulsified hair gel.

[Comparative Examples 9 and 10] (hair gel)
A hair gel in the same manner as in Example 5 except that the aqueous dispersions (2) and (3) obtained in Production Examples 2 and 3 were used in place of the aqueous dispersion (1) obtained in Production Example 1. Manufactured.

[Evaluation of hair gel]
(1) Set effect Each sample of Example 5 and Comparative Examples 9 and 10 was uniformly sprayed on each of 12 bundles of hair having a length of 18 cm and a weight of 1 g, and was naturally dried by winding on a rod having a diameter of 2 cm. . After drying, the rod was removed, and the curled hair bundle was suspended in a high humidity environment at a temperature of 25 ° C. and a humidity of 90%, and the extent of curling was evaluated. Evaluation is the length of the hair bundle immediately after being suspended in a high humidity environment a (cm), the length of the hair bundle after 30 minutes b (cm), the length of the original uncurled hair bundle As h (cm), the curl retention ratio R (%) was calculated according to the equation (1), and (b) was determined in four stages according to the evaluation criteria.

Curling retention ratio: R (%) = (h−b) / (ha−) × 100 (1)
Length of hair bundle immediately after hanging: a (cm)
Hair bundle length 30 minutes after hanging: b (cm)
Length of original uncurled hair bundle: h (cm)

(I) Evaluation criteria A: 76 to 100% (very good)
○: 51-75% (good)
Δ: 26-50% (slightly bad)
X: 0 to 25% (bad)

(2) Polishing: Evaluation was performed by a use test with 10 panelists.
(3) Comb: Evaluation by use test with 10 panelists.
(4) Detergency: Evaluation was performed by a use test with 10 panelists.

  As the 10 evaluation panels, a five-step evaluation was performed using (b) absolute evaluation criteria for each of the glossiness, combing and detergency by actual use.

(B) Absolute evaluation criteria 4: Very good 3: Good 2: Unchanged 1: Somewhat bad 0: Bad

  As shown in Table 2, each of the cosmetics of Examples 1 to 5 had good dryness, gloss, makeup, and the like.

Claims (6)

A cosmetic comprising a crosslinked polymer emulsion (A) and a hydrazine derivative (B) having at least two hydrazide groups in one molecule,
The crosslinked polymer emulsion (A) is obtained by emulsion polymerization of an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer (a1) having at least one aldo group or keto group in one molecule. Cosmetics characterized by   It contains 0.1 to 20% by weight of ethylenically unsaturated monomer (a1) having at least one aldo group or keto group in one molecule in a total of 100% by weight of ethylenically unsaturated monomers. The cosmetic according to claim 1, characterized in that:   The cosmetic according to claim 1 or 2, wherein the cross-linked polymer emulsion (A) is obtained by emulsion polymerization in the presence of a hydrolyzable silane.   The cosmetic according to any one of claims 1 to 3, wherein the average particle size of the dispersed particles of the crosslinked polymer emulsion (A) is 10 nm to 1 µm.   The cosmetic according to any one of claims 1 to 4, which is a makeup or care composition for skin, lips, and hair.   Used in at least one of the group consisting of foundation, blusher, face powder, eye shadow, eyeliner, eyebrow, mascara, concealer, lipstick, lip gloss, lip pencil, hair mousse, hair foam, hair spray and hair gel The cosmetic according to any one of claims 1 to 5, wherein: