JP2020029443A - Nail polish - Google Patents

Abstract

To provide nail polishes having restorability of the cosmetic film before drying and a thick cosmetic film, being easy to apply, and having good makeup retention.SOLUTION: Provided is a nail polish containing a component (A-1): a polyurethane (i) obtained by reacting a hydrogenated polybutadiene (a) having an isocyanate group at the terminal with a glycol (b) represented by HO-R-OH, or a polyurethane (ii) obtained by reacting a hydrogenated polybutadiene (c) having a hydroxyl group at a terminal with a diisocyanate compound (d) and a glycol (b) represented by HO-R-OH, a component (A-2): a gel composition containing oil, a component (B): a film forming agent, and a component (C): a volatile oil.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a nail pill, and in particular, contains a specific polyurethane gel composition, a film-forming agent and a volatile oil agent, has excellent restorability of a decorative film immediately after application and before drying, and has a thickness. The present invention relates to a beautiful nail material which has a cosmetic film, is easy to apply, and has a long lasting makeup.

  The functions required for the nail polish include ease of application, quick-drying, long-lasting makeup, and the like. Also, recently, there is a tendency to enjoy nail art by applying a nail varnish using an ultraviolet curable resin called gel nail, and a nail varnish having an extremely high thickness and luster of a makeup film is preferred. However, ultraviolet curable resins used in gel nails are difficult to handle by consumers individually and need to be removed at specialized stores to remove them. One of the reasons that gel nails are preferred is that they are not only aesthetically pleasing in appearance, the thickness of the film, and a glossy feeling, but also require little effort. On the other hand, when using a solvent-based nail polish, the user must be careful not to damage the coating until the coating is completely dried and cured. If the coating film is damaged before drying, it is difficult to restore the decorative film, and the surface may not be uniformly finished.

  Therefore, various studies have been made to shorten the drying time of the coating film and to enhance the usability. For example, Patent Document 1 has a nail polish using a solvent having a high evaporation rate such as ethanol or propylene glycol monomethyl ether, but has a problem that it is difficult to obtain a uniform coating film. In addition, Patent Literature 2 discloses a method in which a nail polish is immersed in water and a solvent in the coating film is sucked out into water to increase the drying speed of the coating film. Was also limited.

JP 2012-72123 A JP-A-2002-201115

  Even if a solvent having a high volatilization rate is selected as in Patent Literature 1, it is excellent in quick drying, but care must be taken not to touch the decorative film for a certain period of time after application. In some cases, a perfect cosmetic film could not be obtained. Further, a method of immersing in water as in Patent Document 2 is also excellent in quick-drying, but is not simple enough. Furthermore, in the case of purifying quick drying and containing a lot of volatile solvents, it is necessary to repeatedly apply to obtain a thick decorative film. When a large amount of a component is formed, easy coating may be impaired. In other words, in the case of solvent-based nail polish, it is easy to apply without relying on quick-drying, it is difficult to achieve both film thickness, and in addition, if the cosmetic film before drying is damaged, it has been developed to have a restoring property. It has been desired to solve the above-mentioned problem and to develop a nail varnish having a thickness like a gel nail, good usability, and a long lasting makeup. Therefore, an object of the present invention is to provide a cosmetic nail that has a restoring property of a cosmetic film before drying and has a thick cosmetic film, is easy to apply, and has good makeup durability.

  In view of such circumstances, the present inventors have conducted intensive studies, and as a result, by using a polyurethane gel composition and a film forming agent and a volatile oil agent in combination as a beauty nail preparation, even if the coating film before drying is damaged, it has resilience. Further, the present inventors have found that the decorative film has a large thickness, is easy to apply, and has excellent makeup durability. Furthermore, it has been found that by using the polyurethane gel composition and the film-forming agent in a specific ratio, the effect of the present invention can be further enhanced. Succeeded in the development of a beautiful nail material that solved the above, and completed the present invention.

That is, the present invention provides the following components (A) to (C);
Component (A) a polyurethane gel composition,
Component (B) a film-forming agent,
It is a beautiful nail filler containing the component (C) volatile oil agent,
The nail ingredient, wherein the component (A) is a gel composition containing the polyurethane of the component (A-1) or lower (i) or (ii) and an oil agent of the component (A-2).
(I) (a) hydrogenated polybutadiene and ^{(b) HO-R 3 -OH} ( wherein having a terminal isocyanate group, ^{R 3} is optionally straight or branched C2~C6 alkylene which may have an ether bond A polyurethane obtained by reaction with a glycol represented by
(Ii) (c) a hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) a diisocyanate compound, and (b) HO—R ³ —OH (wherein R ³ is a linear or branched linear group which may have an ether bond. The present invention provides a beauty nail preparation which is a polyurethane obtained by a reaction with a glycol represented by a C2 to C6 alkylene group).

  The present invention provides the nail enamel wherein the component (B) is one or more selected from the group consisting of nitrocellulose, (styrene / acrylates) copolymer, and trimethylsiloxysilicic acid.

  An object of the present invention is to provide the nail enamel wherein the component (C) is one or more selected from the group consisting of ethyl acetate, butyl acetate, and thinner.

  An object of the present invention is to provide the nail enamel wherein the content ratio of the component (A) and the component (B) is (A) / (B) = 0.01 to 1.

  ADVANTAGE OF THE INVENTION By this invention, the coating film before drying has a restoring property, the cosmetic film has a thickness, it is easy to apply | coat, and it can provide the cosmetics with good makeup durability.

It is a schematic diagram which shows the method of measuring the self-restoring force in the present invention.

  The details of the present invention will be described below. In the present specification, “to” means a range including numerical values before and after that.

  The component (A) polyurethane gel composition used in the present invention is a polyurethane gel composition containing the component (A-1) polyurethane and the component (A-2) oil agent. The polyurethane gel composition can be obtained by producing the polyurethane gel composition using the raw material of the component (A-1) polyurethane in the presence of the component (A-2) oil agent.

Here, the component (A-1) polyurethane, (wherein, ^{R 3} represents a C2~C6 alkylene group which may linear or branched have an ether bond) ^HO-R 3 -OH is represented by This is a polyurethane that uses a glycol.
Further, the component (A-1) polyurethane preferably contains at least the following polyurethane (i) or (ii).
More preferably, the component (A-1) polyurethane, (i) at the end and hydrogenated polybutadiene having an isocyanate group ^{(b) HO-R 3 -OH} ( wherein, ^{R 3} is have an ether bond (Representing a linear or branched C2-C6 alkylene group which may be substituted), or (ii) (c) a hydrogenated polybutadiene having a hydroxyl group at the terminal (c). d) Reaction of diisocyanate compound with (b) glycol represented by HO—R ³ —OH (wherein R ³ represents a linear or branched C2-C6 alkylene group optionally having an ether bond) Is a polyurethane obtained by

As glycol represented by (b) ^HO-R 3 -OH in the component (A-1), such as ethylene glycol, propylene glycol, 1,3-butylene glycol, and diethylene glycol, and the like.

  The novel polyurethane gel composition used in the present invention was found as a result of intensive research and development on gel materials in order to obtain a cosmetic film of an oil-soluble gel having high gloss, elasticity, and resilience. It is a gel composition.

The inventor has repeatedly studied using a silicone rubber, a polysaccharide, and an aqueous polyurethane as a restorable material. However, these materials have disadvantages to be solved along with advantages. Specifically, silicone rubber has a disadvantage that it lacks luster and lacks restoring power; polysaccharides have a disadvantage that they have poor restoring / restoring power; water-based polyurethane has a limited color gamut due to its water-based properties. No serious disadvantage;
However, extensive studies were carried out the results, the inventors under oil presence, ^HO-R 3 -OH (wherein, ^{R 3} is optionally straight or branched C2~C6 alkylene group which may have an ether bond When a polyurethane was synthesized using the glycol represented by the formula (1), a novel gel material was obtained by accident. The new gel material had a special function of high gloss, elasticity, and resilience, as described in Examples below. This was an unexpected effect for the inventor.
It is known that polyurethane is obtained by reacting a diisocyanate with a polyol. However, there is no example in which polyurethane is used as an oil-soluble gelling agent, and the polyurethane gel composition of the present invention has been found by a new idea of manufacturing in the presence of an oiling agent.

  The concept of the polyurethane gel composition used in the present invention is still under intensive study, but at present, the present inventors consider as follows. (1) The polyurethane in the polyurethane composition forms a plurality of ring-shaped clusters (bunches) by associating with hydrophilic portions in the molecule, and becomes hydrophilic by contacting the oil agent with the hydrophobic portion in the molecule. The inventor believes that it has a group-associative thickening mechanism. (2) The polyurethane imparts flexibility and oil solubility because the hydrophobic portion in the molecule is a low-crystalline hydrocarbon; the polar group of the hydrophilic portion in the molecule interacts with the polyurethane. The inventor believes that the gelling / restoring force is provided. (3) The inventor considers that the three-dimensional three-dimensional structure is finely formed into a transparent gel by a hydrophilic group associative thickening mechanism. The polyurethane is preferably an oil-soluble polyurethane, and more preferably the oil-soluble polyurethane can be dissolved in cetyl 2-ethylhexanoate at 30% at least 1% by mass or more.

  The component (A) polyurethane gel composition used in the present invention includes the following composition 1 and composition 2. Of these, compositions 1 and 2 are preferred.

Composition 1: polyurethane gel composition 1 containing component (A-1) (i) polyurethane and component (A-2) oil agent;
As component (A-1) a polyurethane, (i) (a) at the end and hydrogenated polybutadiene having an isocyanate group ^{(b) HO-R 3 -OH} ( wherein, ^{R 3} may have an ether bond A composition comprising a polyurethane obtained by reaction with a glycol represented by a linear or branched C2 to C6 alkylene group), and a component (A-2) an oil agent.
Composition 2: polyurethane gel composition 2 containing component (A-1) (ii) polyurethane and component (A-2) oil agent;
As the component (A-1) polyurethane, (ii) (c) a hydrogenated polybutadiene having a hydroxyl group at a terminal, (d) a diisocyanate compound, and (b) HO—R ³ —OH (where R ³ has an ether bond) Which represents a linear or branched C2-C6 alkylene group which may be substituted.
In the present invention, “terminal” means “both terminals”.

  (A): Component (A) The (a) used in the component (A-1) polyurethane of the polyurethane gel composition (preferably the composition 1) is a hydrogenated polybutadiene having an isocyanate group at a terminal. Is not particularly limited. For example, a compound represented by the following general formula (1) is shown, and it is preferable to use the compound from the viewpoint of the effects of the present invention.

(In the formula, R ¹ and R ² each independently represent a C1 to C6 alkylene group, n represents an integer of 10 to 100, and n ₁ and n ₂ each independently represent 0 or 1.)

R ¹ and R ² each independently represent the same or different and represent a C1 to C6 alkylene group, and the alkylene may be linear or branched. Examples of the C1-C6 alkylene group include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene and the like. The alkylene group for R ¹ is preferably a C1-C2 alkylene group. The alkylene group for R ² is preferably a C5-C6 alkylene group. The alkylene group is preferably straight-chain.
n represents an integer of 10 to 100, and a more preferable range of n is 15 to 55.
n ₁ and n ₂ each independently represent the same or different and represent 0 or 1.

The structure of the repeating unit “C ₄ H ₈ ” in the hydrogenated polybutadiene portion of the general formula (1) (the following general formula (6)) may be, for example, various as shown in the following general formulas (7a) to (7d). There are types. Use of the compound is preferable from the viewpoint of the effects of the present invention.

The hydrogenated polybutadiene part in the hydrogenated polybutadiene having an isocyanate group at the terminal used in the present invention may be composed of only one kind of the repeating unit as exemplified above, or two or more kinds of the repeating unit May be included regularly or randomly.
In the present invention, the three-dimensional structure of the repeating unit “C ₄ H ₈ ” constituting the hydrogenated polybutadiene portion of the general formula (1) (the above general formula (6)) may be the same or different. All the structures represented by the general formula (6) are included in the present invention.
As the hydrogenated polybutadiene having a terminal isocyanate group represented by the general formula (1), for example, a compound represented by the following general formula (2) is exemplified, and the use of the compound is from the viewpoint of the effects of the present invention. It is suitable.

(Here, in the formula (2), n represents an integer of 10 to 100)
The compound of the general formula (2) is a hydrogenated polybutadiene having an isocyanate group at the terminal of the general formula (1), wherein R ¹ is an ethylene group, R ² is a hexamethylene group, and n ₁ = n ₂ = 1. Equivalent to.

(B): Component (A) HO—R ³ —OH used in component (A-1) polyurethane of component (A-1) polyurethane gel composition (preferably compositions 1 and 2), wherein R ³ is Examples of the glycol represented by a linear or branched C2-C6 alkylene group which may have an ether bond include, for example, ethylene glycol (HOCH ₂ CH ₂ OH), propylene glycol (HOCH ₂ CH ( _OH) CH _3), 1,3- butylene glycol _{(HOCH 2 CH 2 CH (OH} ) CH 3), and diethylene glycol _{(HOCH 2 CH 2 OCH 2 CH} 2 OH) , and the like. Use of the compound is preferable from the viewpoint of the effects of the present invention.
Wherein (b) HO-R 3 ^-OH, a compound represented by the following general formula (5) is shown, the compound are preferred from the viewpoint of the effect of the present invention.

  (C): Component (A) The hydrogenated polybutadiene having a hydroxyl group at a terminal used in the component (A-1) polyurethane of the polyurethane gel composition (preferably composition 2) is not particularly limited. For example, a compound represented by the following general formula (3) is shown, and the compound is suitable from the viewpoint of the effects of the present invention.

(In the formula, n represents an integer of 10 to 100)

  In the general formula (3), the hydrogenated polybutadiene moiety (general formula (6)) has the same meaning as described above. Use of the compound is preferable from the viewpoint of the effects of the present invention.

  (D): Component (A-1) Examples of the (d) diisocyanate compound used in the polyurethane (preferably composition 2) include hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) benzene, , 3-bis (isocyanatomethyl) cyclohexane, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate. Of these, hexamethylene diisocyanate represented by the following general formula (4) is preferable.

In the component (A) polyurethane gel composition (preferably composition 1), (i): (a) hydrogenated polybutadiene having an isocyanate group at a terminal and (b) HO—R ³ —OH (wherein R ³ Represents a linear or branched C2-C6 alkylene group which may have an ether bond) to produce a polyurethane, the molar ratio (a) :( b) = 1 : 4 to 4: 1, preferably at a molar ratio of (a) :( b) = 2: 3 to 3: 2, more preferably 4: 5 to 4: 3, and still more preferably. Is 9:10 to 10: 9. In this case, the weight average molecular weight (Mw) of (a) is preferably from 1,000 to 3,000. It is more preferable that the content be in such a range since the effects of the present invention can be remarkably obtained.

In the component (A) polyurethane gel composition (preferably composition 2), (ii): (c) a hydrogenated polybutadiene having a hydroxyl group at a terminal, (d) a diisocyanate compound, and (b) HO—R ³ —OH ( In the formula, R ³ represents a linear or branched C2-C6 alkylene group which may have an ether bond, and the reaction with a glycol represented by the following formula (c) :( b) ) = 1: 4 to 4: 1, preferably at a molar ratio of (c) :( b) = 2: 3 to 3: 2, more preferably 4: 5 to 4: 3, Even more preferably, it is 9:10 to 10: 9. It is more preferable that the content be in such a range since the effects of the present invention can be remarkably obtained.

  The weight average molecular weight (Mw) of the polyurethane obtained in the above (i) or (ii) is preferably 10,000 to 100,000, more preferably 20,000 to 80,000, and further preferably 30,000 to 70,000. It is more preferable that the content be in such a range since the effects of the present invention can be remarkably obtained. The weight average molecular weight (Mw) of the polyurethane of the present invention is measured by GPC measurement (in terms of polystyrene).

The content of the component (A-1) polyurethane in the component (A) polyurethane gel composition is preferably 1 to 35% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 30% by mass. is there.
The content of the component (A-2) oil agent in the component (A) polyurethane gel composition is preferably 65 to 99% by mass, more preferably 70 to 95% by mass, and still more preferably 70 to 90% by mass. is there.
It is more preferable that the content be in such a range since the effects of the present invention can be remarkably obtained.

The component (A-2) oil used in the component (A) polyurethane gel composition can be used without any particular limitation as long as it is generally used in cosmetics. The property is not particularly limited, but an oil agent that is liquid at 25 ° C. is preferable. Moreover, it is preferable to use it as a solvent when producing the polyurethane gel composition of the present invention.
Component (A) The component (A-2) oil used in the polyurethane gel composition may be any of oils such as animal oils, vegetable oils, and synthetic oils. Or one ester oil), fatty acids, silicone oil, fluorinated oils and the like.

Of these, since the lower polarity tends to increase the strength of the polyurethane gel composition, hydrocarbon oils, ester oils in which the number of hydroxyl groups is 0 or 1, and silicone oils containing phenyl groups are used. The use of one or more selected ones is exemplified, and it is preferable to include one or more of these in the component (A-2) oil agent.
One or more selected from these hydrocarbon oils, ester oils and silicone oils may be contained in the component (A-2) oil agent preferably at least 90% by mass, more preferably at least 95% by mass. It is suitable.
In the production, it is preferable to use the component (A-2) oil as a solvent. The properties of the polyurethane gel composition produced by using the oil agent during production are improved. The hardness of the polyurethane gel composition can be adjusted by using an oil agent as appropriate.

  As the component (A-2) oil agent used in the component (A) polyurethane gel composition, more specifically, hydrocarbons such as liquid paraffin, squalane, polybutene, polyisobutylene; olive oil, castor oil, mink oil, Fats and oils such as macadamian nut oil; jojoba oil, cetyl isooctanoate (cetyl 2-ethylhexanoate), isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl isostearate, Esters such as diisostearyl malate, glyceryl tribehenate, pentaerythritol rosinate and neopentyl glycol dioctanoate; silicones such as methylphenylpolysiloxane and diphenylpolysiloxane The recited, these can be used alone or in combination.

The component (A) polyurethane gel composition used in the present invention has an advantage that not only transparency and gloss but also elasticity and restoring force are extremely high.
As a result of the penetration load measurement, 30 parts of this polyurethane gel composition and 70 parts of liquid paraffin (kinematic viscosity at 40 ° C. according to ASTM D445 measurement method at 40 ° C. of 8 mm ² / s) were heated and melted at 85 ° C. The gel obtained by cooling at a pressure of 0.2 cm to 10 N exhibited excellent characteristics when a 2 cmφ spherical adapter was inserted at a rate of 10 mm at 2 cm / min. This hardness characteristic indicates that the component (A) polyurethane gel composition used in the present invention has a gel restoring force.
Regarding transparency, the component (A) polyurethane gel composition used in the present invention has a transmittance at a wavelength of 700 nm of 90% or more. This high permeability indicates that the component (A) polyurethane gel composition used in the present invention has extremely high transparency.

  In the method for producing the component (A) polyurethane gel composition of the present invention, it is preferable that the polyurethane is produced in the presence of the oil agent (A-2). Further, it is more preferable to use a specific polyol as the polyurethane raw material in the component (A-1) and to produce a polyurethane in the presence of the oil agent (A-2). The component (A) polyurethane gel composition of the present invention can be produced by referring to a known polyurethane production method.

For example, polyurethane gel composition 1 used in the present invention, component (A-2) in a oil, hydrogenated polybutadiene and ^{(b) HO-R 3 -OH} ( wherein having an isocyanate group (a) end of A , R ³ represents a linear or branched C2 to C6 alkylene group which may have an ether bond) and a polyaddition reaction is performed.
For example, the polyurethane gel composition 2 of the present invention comprises (c) a hydrogenated polybutadiene having a hydroxyl group at a terminal, and (b) HO—R ³ —OH (where R ³ may have an ether bond. (Representing a chain or branched C2-C6 alkylene group), a component (A-2) an oil agent, and uniformly mixing the resulting mixture. it can.

  In addition, the polyurethane gel composition of the present invention may optionally contain, in addition to the above-mentioned components (A-1) and (A-2), optional components that can be used in the pharmaceutical field or the cosmetic field as long as the effects of the present invention are not impaired. You may make it contain. As optional components, for example, volatile components, surfactants, oil components, powders, water-soluble polymers, ultraviolet absorbers, humectants, anti-fading agents, antioxidants, defoamers, beauty components, preservatives, Other components usually used in cosmetics for imparting various effects, such as fragrances, can be appropriately used.

  In the present invention, the content of the component (A) is not particularly limited, but is 0.1 to 50% by mass (hereinafter, simply abbreviated as “%”) based on the total amount of the nail enamel, and preferably 1 to 30%. , 5 to 25% are particularly preferred. This range is preferable from the viewpoint of excellent resilience of the coating film before drying and excellent thickness of the decorative film. In addition, the content of (A-1) is not particularly limited, but is 0.02 to 10%, preferably 0.2 to 6%, and particularly preferably 1 to 5% based on the total amount of the nail enamel. This range is preferable from the viewpoint of excellent resilience of the coating film before drying and excellent thickness of the decorative film.

  The component (B) film-forming agent used in the present invention is a component that forms a cosmetic film having flexibility and improves cosmetic durability against physical stimulation. The component (B) film-forming agent of the present invention is not particularly limited, but an oil-soluble film-forming agent is preferred from the viewpoint of compatibility with the components to be combined in the present invention. In the present invention, film formation means that a solution obtained by dissolving 40% of a component corresponding to the component (B) in a solvent is applied to a glass plate with an applicator having a thickness of 400 μm, and the film is formed after drying at room temperature for 24 hours. I mean. The film-forming agent in the present invention is not particularly limited as long as it is commonly used in cosmetics.Examples include nitrocellulose, phthalic alkyd resin, toluenesulfonamide resin, acrylic acid / alkyl copolymer, Silicone resin such as benzoic acid sucrose ester, alkyl acrylate / styrene copolymer, trimethylsiloxysilicic acid, polymethylsilsesquioxane, toluenesulfonamide epoxy resin, polyvinyl alcohol, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer Coalescence and the like. Among them, nitrocellulose, phthalic acid alkyd resin, toluenesulfonamide resin, acrylic acid / alkyl copolymer, sucrose benzoate, alkyl acrylate / styrene copolymer, trimethyl One or more selected from the group consisting of silicone resins such as siloxysilicic acid and polymethylsilsesquioxane, and toluenesulfonamide epoxy resin are preferable, and nitrocellulose, (styrene / acrylates) copolymer, and trimethyl are more preferable. One or two or more selected from the group consisting of siloxysilicic acid, in particular, nitrocellulose acts as a plasticizer for the decorative film, thereby imparting flexibility to the decorative film and peeling of the decorative film due to physical stimulation. Effect of suppressing makeup and chipping, and improving makeup durability Preferred in order to be. Examples of commercially available nitrocellulose include nitrified cotton H1 / 2, H1 / 4, H1 / 8 (all manufactured by Asahi Kasei Kogyo Co., Ltd.).

  In the present invention, the content of the component (B) is not particularly limited, but is preferably 1 to 50%, more preferably 5 to 40%, and particularly preferably 10 to 25% based on the total amount of the nail enamel. This range is preferable from the viewpoint of excellent durability and ease of application.

  The component (C) volatile oil used in the present invention is an oil having volatility at 25 ° C. The component (C) of the present invention can be used without any particular limitation as long as it is usually used for cosmetics. Specific examples include volatile hydrocarbon oils, volatile silicone oils, and organic solvents. More specifically, isododecane, light liquid isoparaffin, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, methyltrimethicone, caprylyltrimethicone, dimethylpolysiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, ethyltrisiloxane Butyl acetate, isobutyl acetate, ethyl acetate, thinner, methyl ethyl ketone, acetone, n-butanol, isopropyl alcohol, ethyl alcohol and the like, and one or more of these can be contained. Among these, it is preferable to use an organic solvent from the viewpoint of long-lasting cosmetics. Particularly, by using one or more selected from the group consisting of ethyl acetate, butyl acetate, and thinner, the effect of the present invention is remarkably obtained. Is preferred. In particular, using ethyl acetate, butyl acetate and thinner in combination is more preferable because the effect of the present invention is remarkably obtained, and it is more preferable to use all three of ethyl acetate, butyl acetate and thinner in combination.

  The content of the component (C) of the present invention is not particularly limited, but is preferably 30 to 90%, more preferably 40 to 80%, based on the total amount of the nail enamel. This range is suitable from the viewpoint of excellent durability.

  In addition to the above components (A) to (C), the nail polish of the present invention may contain components commonly used in cosmetics, oily components, powders, surfactants, fibers, polyhydric alcohols, and high water solubility. Molecules, aqueous components such as humectants, saccharides, ultraviolet absorbers, anti-fading agents, antioxidants, defoamers, cosmetic ingredients, preservatives, fragrances, etc. can be contained as long as the effects of the present invention are not impaired. .

  The oily component other than the component (A) and the component (C) is not particularly limited as long as it is generally used in cosmetics, and includes oils such as animal oils, vegetable oils, synthetic oils, solid oils, semi-solid oils, and liquid oils. Irrespective of properties such as hydrocarbons, oils and fats, hardened oils, ester oils, fatty acids, higher alcohols, silicone oils, fluorine-based oils, lanolin derivatives, and the like. Specifically, hydrocarbons such as liquid paraffin, squalane, polyisobutylene and polybutene; oils and fats such as olive oil, castor oil, mink oil, macadamian nut oil, jojoba oil, cetyl 2-ethylhexanoate, and isostearyl lactate Octyldodecyl lactate, oleyl lactate, stearyl lactate, diisostearyl malate, tritridecyl trimellitate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, pentaerythritol rosinate, neopentyl glycol dioctanoate, dioctanoic acid Esters such as neopentyl glycol, cholesterol fatty acid ester and phytosterol fatty acid ester, and fats such as stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid and oleic acid , Higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol, fluorine oils such as perfluorodecane, perfluorooctane, perfluoropolyether, lanolin, lanolin acetate, lanolin Examples thereof include lanolin derivatives such as fatty acid isopropyl and lanolin alcohol, and one or more of these can be used.

  As the powder, if it is a powder commonly used in cosmetics, it may be in the form of a plate, a needle, or the like, a fume, a particle size such as a fine particle, a pigment grade, or a particle structure such as a porous or nonporous. Are not particularly limited, and include inorganic powders, glitter powders, organic powders, pigment powders, metal powders, composite powders, and the like. Specifically, for example, titanium oxide, zinc oxide, cerium oxide, white inorganic pigments such as barium sulfate, iron oxide, carbon black, titanium / titanium oxide sintered product, chromium oxide, chromium hydroxide, navy blue, ultramarine, etc. Colored inorganic pigments, muscovite, phlogopite, mica, biotite, synthetic mica, sericite (sericite), synthetic sericite, silicon carbide, bentonite, smectite, aluminum oxide, magnesium oxide, zirconium oxide, antimony oxide, silica Sodium earth, aluminum silicate, magnesium aluminum metasilicate, calcium silicate, barium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, hydroxyapatite, white powder such as boron nitride, titanium oxide coated mica, titanium oxide coated Bismuth oxychloride, iron oxide mica titanium, navy blue treated cloud Luminous powders such as titanium, carmine-treated mica titanium, bismuth oxychloride, fish scale foil, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polyolefin laminated film powder, polyethylene terephthalate / polymethyl methacrylate laminated film powder, fluorine resin , A copolymer resin such as a cellulose resin, a low-molecular organic powder such as zinc stearate and N-acyl lysine, a natural organic powder such as a silk powder, a cellulose powder and a dextrin powder, Red No. 201, Red No. 202 and Red 205 No., Red No. 226, Red No. 228, Orange No. 203, Orange No. 204, Blue No. 404, Yellow No. 401, Red No. 3, Red No. 104, Red No. 106, Orange No. 205, Yellow No. 4, Yellow No. 5 No. 3, green No. 3, blue No. 1, etc. zirconium, Organic pigment powders such as lium or aluminum lake or further metal powders such as aluminum powder, gold powder, silver powder, fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium, barium sulfate coated mica titanium, titanium oxide containing silicon dioxide, Examples include composite powders such as zinc oxide-containing silicon dioxide, fibers such as polyester, rayon, and cellulose. These may be surface-treated with a fluorine compound, silicone oil, powder, oil agent, gelling agent, emulsion polymer, surfactant or the like. One or two or more of these can be used, and a composite of these may be used.

  As the surfactant, any surfactant can be used as long as it is a surfactant usually used in cosmetics, such as a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. Is mentioned.

  The aqueous component may be any component soluble in water, such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerin, diglycerin, polyglycerin, aloe vera, witch hazel, hamamelis, and cucumber. , Lemon, lavender, rose water and the like.

  Examples of the ultraviolet absorber include benzophenone-based, PABA-based, cinnamic acid-based, salicylic acid-based, and the like, for example, 4-tert-butyl-4′-methoxydibenzoylmethane, oxybenzone, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, hexyl diethylaminohydroxybenzoylbenzoate, bisethylhexyloxyphenol methoxyphenyl triazine and the like.

  Antioxidants include, for example, tocopherol and ascorbic acid; cosmetics include, for example, vitamins, anti-inflammatory agents, crude drugs; and preservatives include, for example, parahydroxybenzoate, phenoxyethanol, 1,2-pentadiol, and the like. .

  The method for producing the nail enamel of the present invention is not particularly limited, and it can be obtained by a general production method. For example, it can be obtained by uniformly mixing and dispersing the component (A), the component (B) and the component (C), and filling the mixture in a container. The components may be mixed at the same time, or other components may be added at the time of mixing.

  The nail polish of the present invention is not particularly limited and can be in various dosage forms. For example, an oil type, a water-in-oil type, and an oil-in-water type can be mentioned, and from the viewpoint of dispersibility of the components of the present invention, an oil type, a water-in-oil type is preferable, and an oil type is particularly preferable. In addition, the properties are not particularly limited and can be applied to any one of them. However, they can be solid, liquid, creamy, and the like, and are not limited as long as they are used for nails. For example, nail polish, base coat, top coat, nail oil and the like can be mentioned.

  Hereinafter, the present invention will be described in detail with reference to examples. These do not limit the present invention at all.

[Production Example 1 of polyurethane gel composition of component (A)]
A 3 L three-necked flask was charged with 899 parts of a hydroxyl-terminated polybutadiene (molecular weight: 2200), 2450 parts of cetyl 2-ethylhexanoate, and 128 parts of hexamethylene diisocyanate, and uniformly mixed.
While controlling the temperature at 60 ° C., 0.9 parts of dibutyltin dilaurate was added, and after stirring for 3 hours, 24 parts of ethylene glycol was added.
After completion of the addition, the mixture was stirred at 80 ° C. for 5 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of the polyurethane in the obtained polyurethane gel was 10,000 as measured by GPC (in terms of polystyrene). Further, 30 parts of the obtained gel was dissolved in 70 parts of liquid paraffin by heating at 85 ° C. and cooled to 30 ° C. The load value of the gel was measured using a load measuring machine (manufactured by FUDOH). min, 2.5 N in the case of 10 mm penetration.

[Production Example 2 of polyurethane gel composition of component (A)]
A 3 L three-necked flask was charged with 899 parts of a hydroxyl-terminated polybutadiene (molecular weight: 2200), 2450 parts of cetyl 2-ethylhexanoate, and 128 parts of hexamethylene diisocyanate, and uniformly mixed.
While controlling the temperature at 60 ° C., 0.9 parts of dibutyltin dilaurate was added, and after stirring for 3 hours, 24 parts of ethylene glycol was added.
After the addition was completed, the mixture was stirred at 80 ° C. for 10 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of the polyurethane in the obtained polyurethane gel was 50,000 by GPC measurement (in terms of polystyrene). Further, 30 parts of the obtained gel was dissolved in 70 parts of liquid paraffin by heating at 85 ° C. and cooled to 30 ° C. The load value of the gel was measured using a load measuring machine (manufactured by FUDOH). min, 5N in the case of 10 mm penetration.

[Production Example 3 of polyurethane gel composition of component (A)]
A 3 L three-necked flask was charged with 899 parts of a hydroxyl-terminated polybutadiene (molecular weight: 2200), 2450 parts of jojoba oil, and 128 parts of hexamethylene diisocyanate, and uniformly mixed.
While controlling at 60 ° C., 0.9 part of dibutyltin dilaurate was added, and after stirring for 3 hours, 24 parts of ethylene glycol was added while diluting with cetyl 2-ethylhexanoate.
After the addition was completed, the mixture was stirred at 80 ° C. for 15 hours, and 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of the polyurethane in the obtained polyurethane gel was 100,000 by GPC measurement (in terms of polystyrene). Further, 30 parts of the obtained gel was dissolved in 70 parts of liquid paraffin by heating at 85 ° C. and cooled to 30 ° C. The load value of the gel was measured using a load measuring machine (manufactured by FUDOH). In the case of min and 10 mm penetration conditions, it was 7.5N.

[Production Example 4 of polyurethane gel composition of component (A)]
A 3-L three-necked flask was charged with 899 parts of a hydroxyl-terminated polybutadiene (molecular weight: 2200), 24 parts of ethylene glycol, 0.9 parts of dibutyltin dilaurate, and 2450 parts of squalane, and uniformly mixed.
While controlling at 60 ° C., 128 parts of hexaethylene diisocyanate were charged, and after completion of the charging, the mixture was stirred at 80 ° C. for 10 hours. Thereafter, 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of the polyurethane in the obtained polyurethane gel was 50,000 by GPC measurement (in terms of polystyrene). Further, 30 parts of the obtained gel was dissolved in 70 parts of liquid paraffin by heating at 85 ° C. and cooled to 30 ° C. The load value of the gel was measured using a load measuring machine (manufactured by FUDOH). min, 3N in the case of 10 mm penetration condition.

[Production Example 5 of polyurethane gel composition of component (A)]
A 3 L three-necked flask was charged with 899 parts of hydroxyl-terminated polybutadiene (molecular weight: 2200), 24 parts of ethylene glycol, 0.9 parts of dibutyltin dilaurate, and 2450 parts of diisostearyl malate, and uniformly mixed.
While controlling the temperature at 60 ° C., 128 parts of hexaethylene diisocyanate was charged, and after the completion of the charging, the mixture was stirred at 80 ° C. for 15 hours. Thereafter, 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of the polyurethane in the obtained polyurethane gel was 100,000 by GPC measurement (in terms of polystyrene). Further, 30 parts of the obtained gel was dissolved in 70 parts of liquid paraffin by heating at 85 ° C. and cooled to 30 ° C. The load value of the gel was measured using a load measuring machine (manufactured by FUDOH). In the case of min and 10 mm penetration conditions, it was 4.5N.

[Production Comparative Example 1]
100 parts of a crosslinkable silicone gel (KSG-43 manufactured by Shin-Etsu Chemical Co., Ltd.) is used.
[Production Comparative Example 2]
35 parts of dextrin fatty acid ester (Leopearl ISK, manufactured by Chiba Flour Milling Co., Ltd.) and 65 parts of cetyl 2-ethylhexanoate were heated and cooled at 90 ° C. to prepare a polysaccharide gel.
[Production Comparative Example 3]
35 parts of crystalline polyethylene wax (PERFORMALENE 655, manufactured by New Phase Technology) and 65 parts of cetyl 2-ethylhexanoate were heated and cooled at 90 ° C. to prepare a wax oil gel.
The silicone gel of Production Comparative Example 1 lacks luster and lacks restoring force. The polysaccharide gel of Production Comparative Example 2 has poor restorability and restoring power. The wax oil gel of Production Comparative Example 3 is insufficient in luster.

[Evaluation of gel]
Among the polyurethane gels obtained by the above-mentioned production method, the polyurethane gel composition of Production Example 2 was evaluated with respect to gel load values for various oil agents widely used in cosmetics and gel transparency (Test Example 1). ~ 6). Table 1 shows the results. Various evaluation methods are as follows. In addition, the gel load value of the component (A) polyurethane gel composition of Production Examples 1 to 5 was 2.5 to 7.5 N, and the weight average molecular weight was 10,000 to 100,000.

[Measurement of load value and evaluation of gel strength]
The polyurethane gel composition of Production Example 2 and various oils shown in Table 1 were heated and melted at 85 ° C and cooled to 30 ° C to prepare elastic gels (Test Examples 1 to 6). The load value of the gel was measured using a load measuring device (manufactured by FUDOH) under the conditions of a 2 cmφ spherical adapter, 2 cm / min, and 10 mm needle insertion. Thereby, the gel strength was evaluated. As a result of Test Examples 1 to 4, it was confirmed that the oil agent having a smaller number of hydroxyl groups in the molecule had a higher load value. This is considered to be due to the effect of the hydroxyl group in the oil agent on the hydrophilic group portion in the hydrophilic group associative thickening mechanism of the polyurethane gel, resulting in a decrease in thickening.

[Measurement and evaluation of transparency]
For the transparency to various gels (Test Examples 1 to 6) described in Table 1, the transmittance at 700 nm was measured using a transmittance meter (manufactured by Shimadzu Corporation). As a result, all of the gels in Test Examples 1 to 6 exhibited good transparency (◎) of 90% or more.

[Measurement and evaluation of self-restoring force]
The self-restoring power was evaluated using the polyurethane gel composition of Production Example 2 and the dextrin fatty acid ester gel of Production Comparative Example 2. Each of the measurement samples was diluted with cetyl 2-ethylhexanoate to a pure content of 10.5% by mass, heated at 85 ° C, poured into a jar, and cooled to 30 ° C to obtain an elasticity. A gel was prepared. Using a texture analyzer (manufactured by Eisei Seiki Co., Ltd.), a 5 cm load was applied to the prepared sample with a 2 cmφ spherical adapter, at a speed of 1 mm / min and at a condition of 5 mm needle insertion, 7 times. By repeating the same operation, the gel structure was not destroyed by the load, and it was confirmed whether the gel structure had a restoring force. FIG. 1 shows a schematic diagram of the measurement.
As a result, the gel structure of the dextrin fatty acid ester gel of Production Comparative Example 2 was destroyed by repeated loading and did not become the same curve, whereas the polyurethane gel composition of Production Example 2 was gelated by repeated loading. By following the same curve without collapse, it was found that the gel was highly resilient. Further, since the value of the load value itself was higher than that of the dextrin fatty acid ester gel of Production Comparative Example 2, it was found that the elasticity was excellent.

  From the above study, it was found that the component (A) polyurethane gel composition used in the present invention was a novel gel having excellent transparency, high elasticity, and excellent self-restoring force.

Examples 1 to 10 and Comparative Examples 1 to 4: Nail preparations A nail preparation having the composition shown in Table 1 was produced by the following production method, and each sample was evaluated by the following evaluation method. The results are shown in Table 1. As the polyurethane gel composition of the component (A), the polyurethane gel composition of Production Example 2 produced above was used.

* 1: Solid content 20%
* 2: Cimilon Super Scene MP-1001 (Merck)

〔Production method〕
No. 1 to 14 were mixed with a disper.

[Evaluation]
Evaluation method of restoring property of coating film before drying:
1 g of the nail polish of Examples and Comparative Examples was dropped on a glass plate, and a 200-micrometer coating film was applied. Immediately thereafter, a toothpick was dropped on the coating film and lifted 10 seconds later. Five minutes later (after drying of the coating film), the coating film was observed again, and the presence or absence of a toothpick mark was visually evaluated by 20 cosmetic evaluation panels.
<Judgment criteria>
Fifteen or more panels answered that they were not worried about any marks: ◎
10 or more and less than 15 panelists who answered that they did not care at all: ５ 5 or more and less than 10 panels who answered that they did not care at all: △
Less than 5 panels answered that they were not bothered by any marks: ×

Sensory evaluation method: 20 panelists specializing in cosmetics evaluation use the cosmetics of the above examples and comparative examples. Were evaluated according to the following criteria, and a score was given for each beauty nail material, and the average score of the scores of all panels was determined according to the following criteria.
<Evaluation criteria>
(Evaluation result): (Score)
Very good: 5 points Good: 4 points Normal: 3 points Slightly poor: 2 points Bad: 1 point <Judgment criteria>
(Average score): (Judgment)
4 points or more: ◎
3 or more and less than 4 points: 〇 2 or more and less than 3 points: △
Less than 2 points: ×
The higher the score, the better.

The nail polish of Examples 1 to 10 is based on the synergistic effect of the component (A) polyurethane gel composition, the component (B) film-forming agent, and the component (C) volatile oil, and thus the restoring property of the coating film before drying. The nail polish was excellent, had a good thickness on the film after drying, and had better cosmetic durability and ease of application. On the other hand, Comparative Examples 1 and 2, which do not contain the component (A), did not provide satisfactory resilience of the coating film before drying and the thickness of the decorative film, and Comparative Example 3, which did not contain the component (B), Comparative Example 4 containing powdered polyurethane instead of component (A) was not able to obtain a satisfactory cosmetic durability, and the film had satisfactory restorability before drying, thickness of the decorative film, and cosmetic durability. I couldn't get anything.
In addition, the amount of the component (A) polyurethane gel composition used in the present technology was in a wide range of 0.5 to 50% by mass, and good nail polish was obtained. By increasing the content of the component (A) in the nail polish, there was a tendency that the resilience of the film before drying and the thickness of the film were improved. In addition, even when various kinds of film forming agents such as nitrocellulose, (styrene / acrylates) copolymer and trimethylsiloxysilicic acid were used as the film forming agent used in the present technology, good nail polish was obtained. There was a tendency for the cosmetic durability to be improved by increasing the content of the component (B) in the nail polish. Furthermore, even when component (A) / component (B) had a wide content mass ratio of 0.025 to 10, good nail polish was obtained. In addition, when component (A-1) / component (B) was in the range of 0.005 to 2, good nail polish was obtained.

Example 11: Nail polish (component) (%)
1. Polyurethane gel composition of Production Example 1 10
2. Nitrocellulose 15
3. Organic modified bentonite 1
4. Isopropyl alcohol 5
5. Ethyl acetate 10
6. Butyl acetate 30
7. Thinner Remaining 8. Butanol 3
9. Heptane 0.1
10. Perfluorooctyltriethoxysilane 3% treatment Red No. 202 0.2
11. Perfluorooctyltriethoxysilane 3% treated yellow No. 4 0.2
12. Perfluorooctyltriethoxysilane 3% treated titanium oxide 1
13. Perfluorooctyltriethoxysilane 3% treated black iron oxide 0.1
14． 3% silicone treated mica titanium (average particle size 21 μm) 1
15. Polyethylene terephthalate / aluminum / epoxy laminated powder 2
16. Plate-like aluminum powder (average particle diameter 20 μm) 2
17． Perfluorooctyltriethoxysilane 2% treatment Borosilicate (Ca / Al) 2
18. Oxybenzone-3 0.5

(Production method)
Components (1) to (18) are uniformly mixed with a disper.

  The nail polish obtained as described above was excellent in restoring property of the coating film before drying, had a thick film, and was satisfactory in all aspects such as long-lasting makeup and ease of application.

Example 12: Top coat (component) (%)
1. Polyurethane gel composition of Production Example 3 10
2. Polyurethane gel composition of Production Example 2 10
3. Trimethylsiloxysilicic acid 10
4. Isopropyl alcohol 7
5. Ethyl acetate 20
6. Butyl acetate 30
7. Thinner Remaining 8. Benzoic acid sucrose ester 5
9. Dextrin isostearate 2
10. Camphor 1
11. (PET / Al) laminate 0.5
12. Titanium oxide coated synthetic phlogopite 0.3
13. Octocrylene 0.5

(Production method)
Components (1) to (12) are uniformly mixed with a disper.

The topcoat obtained as described above was excellent in restorability of the coating film before drying, had a thick film, and was satisfactory in all aspects of makeup durability and ease of application.

Example 13: Base coat (component) (%)
1. Polyurethane gel composition of Production Example 4 15
2. (Styrene / Acrylates) Copolymer 5
3. Isopropyl alcohol 7
4. Ethyl acetate 30
5. Butyl acetate 30
6. Thinner Remaining 7. Acetyltributyl citrate 5
8. Silicic anhydride 2
9. Bengala 0.1
10. Yellow iron oxide 0.1

(Production method)
Components (1) to (10) are uniformly mixed with a disper.

  The base coat obtained as described above was excellent in the restoring property of the coating film before drying, had a thick film, was long-lasting and easy to apply, and was satisfactory in all respects.

Example 14: Nail oil (component) (%)
1. Polyurethane gel composition of Production Example 5 15
2. Nitrocellulose 1
3. Isopropyl alcohol 7
4. Thinner Remaining amount5. Mineral oil 10
6. Polyglyceryl triisostearate-2 20
7. Glyceryl tri-2-ethylhexanoate 10
8. Purified water 5
9. Glycerin 5
10. Butanol 3
11. Heptane 0.1
12. Bengala 0.1
13. Yellow iron oxide 0.1
14． Fragrance 0.1
15. Argan oil 0.1
16. Lavender oil 0.05
17． Camellia oil 0.05
18. Panthenol 0.01
19. Rose hip extract 0.01
20. Squalane 0.1
21. Meadowfoam oil 0.1
22. Almond oil 0.1
23. Avocado oil 0.1
24. Astaxanthin solution 0.001

(Production method)
Components (1) to (24) are uniformly mixed with a disper.

The nail oil obtained as described above was excellent in restorability of the coating film before drying, had a thick film, and was satisfactory in all aspects in terms of makeup durability and ease of application.

Claims (7)

The following components (A) to (C):
Component (A) a polyurethane gel composition,
Component (B) a film-forming agent,
It is a beautiful nail filler containing the component (C) volatile oil agent,
The nail ingredient, wherein the component (A) is a gel composition containing the polyurethane of the component (A-1) or lower (i) or (ii) and an oil agent of the component (A-2).
(I) (a) hydrogenated polybutadiene and ^{(b) HO-R 3 -OH} ( wherein having a terminal isocyanate group, ^{R 3} is optionally straight or branched C2~C6 alkylene which may have an ether bond A polyurethane obtained by reaction with a glycol represented by
(Ii) (c) a hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) a diisocyanate compound, and (b) HO—R ³ —OH (wherein R ³ is a linear or branched linear group which may have an ether bond. (Representing a C2-C6 alkylene group).   The nail enamel according to claim 1, wherein the (A-1) polyurethane is an oil-soluble polyurethane.   The nail enamel according to claim 1 or 2, wherein the component (A-1) polyurethane has an average molecular weight (Mw) of 10,000 to 100,000.   The nail polish according to any one of claims 1 to 3, wherein the component (A-2) oil is a liquid oil at 25 ° C.   The nail according to any one of claims 1 to 4, wherein the component (B) is one or more selected from the group consisting of nitrocellulose, (styrene / acrylates) copolymer, and trimethylsiloxysilicic acid. Fee   The nail enamel according to any one of claims 1 to 5, wherein the component (C) is one or more selected from the group consisting of ethyl acetate, butyl acetate, and thinner. The nail enamel according to any one of claims 1 to 6, wherein the content mass ratio of the component (A) and the component (B) is (A) / (B) = 0.01 to 1.