JP7084255B2 - Beautiful nails - Google Patents

Description

The present invention relates to a nail-beautifying agent, and more specifically, contains a specific polyurethane gel composition, a film-forming agent and a volatile oil agent, and has excellent restorability and thickness of a decorative film immediately after application and before drying. Regarding nail polish that has a cosmetic film, is easy to apply, and has a long-lasting makeup.

Functions required for beautiful nails include ease of application, quick-drying, and long-lasting makeup. Recently, there is a tendency to enjoy nail art by applying a beautiful nail agent using an ultraviolet curable resin called gel nail, and a beautiful nail agent having a very high thickness and gloss of a decorative film is preferred. However, the UV curable resin used in gel nails is difficult for individual consumers to handle, and it is necessary to remove it at a specialty store. One of the reasons why gel nails are preferred is not only the aesthetic appearance, the thickness of the film, and the glossiness, but also the hassle-free. On the other hand, when a solvent-based nail polish is used, the user must be careful so that the coating film is completely dried and does not damage the coating film until it is cured. If the coating film is damaged before drying, it is difficult to restore the decorative film, and the surface may not be finished uniformly.

Therefore, various studies have been conducted to shorten the drying time of the coating film and improve its usability. For example, Patent Document 1 has a beautiful nail agent using a solvent having a high evaporation rate such as ethanol or propylene glycol monomethyl ether, but there is a problem that it is difficult to obtain a uniform coating film. In addition, Patent Document 2 has developed a method of immersing a nail polish in water and sucking out the solvent in the coating film to increase the drying speed of the coating film. There was a problem that it was also limited.

Japanese Unexamined Patent Publication No. 2012-72123 JP-A-2002-201115

Even if a solvent with a high volatilization rate is selected as in Patent Document 1, although it is excellent in quick-drying property, care must be taken not to touch the cosmetic film for a certain period of time after application, and if the cosmetic film is damaged, it is uniform. In some cases, it was not possible to obtain a good cosmetic film. Further, the method of immersing in water as in Patent Document 2 is also excellent in quick-drying property, but it cannot be said that the convenience is sufficient. Furthermore, in pursuit of quick-drying and when a large amount of volatile solvent is contained, it is necessary to apply multiple coats in order to obtain a thick decorative film. If a large amount of the component forming the above is contained, the ease of application may be impaired. In other words, in solvent-based nail polish, we have developed a nail polish that is easy to apply without relying on quick-drying, it is difficult to achieve both film thickness, and even if the cosmetic film before drying is damaged, it has resilience. However, it has been desired to solve the above-mentioned problems and to develop a beautiful nail agent that has a thickness like a gel nail, is easy to use, and has a long-lasting makeup. Therefore, it is a main object of the present invention to provide a nail enamel that has a restorative property of a makeup film before drying, has a thick makeup film, is easy to apply, and has a long-lasting makeup.

In view of such circumstances, the present inventor has diligently studied and, as a result, by using a polyurethane gel composition, a film forming agent, and a volatile oil agent in combination as a beautiful nail agent, the coating film before drying can be restored even if it is damaged. It was found that the cosmetic film is thick, easy to apply, and has excellent long-lasting makeup. Furthermore, it has been found that the effect of the present invention can be further enhanced by using the polyurethane gel composition and the film forming agent in a specific ratio, and it is a big problem that even if it is damaged after application, it can be restored, which has been strongly desired in the past. We have succeeded in developing a beautiful nail agent that solves the above problems, and have completed the present invention.

That is, in the present invention, the following components (A) to (C);
Ingredient (A) Polyurethane gel composition,
Ingredient (B) film forming agent,
Ingredient (C) A beautiful nail agent containing a volatile oil agent.
The component (A) is a gel composition containing the polyurethane (i) or (ii) below the component (A-1) and the oil agent (A-2).
(I) (a) Hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO-R ³ -OH (in the formula, R ³ may have an ether bond, linear or branched C2-C6 alkylene). Polyurethane obtained by reaction with glycol represented by (representing a group), or
(Ii) (c) Hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) Diisocyanate compound, and (b) HO-R ³ -OH (R ³ in the formula may have an ether bond. It is intended to provide a beautiful nail agent which is a polyurethane obtained by a reaction with a glycol represented by (representing a C2-C6 alkylene group).

It is intended to provide the nail enamel agent in which the component (B) is one or more selected from the group consisting of nitrocellulose, (styrene / acrylates) copolymer, and trimethylsiloxysilicic acid.

It provides the nail enamel agent in which the component (C) is one or more selected from the group consisting of ethyl acetate, butyl acetate and thinner.

It provides the nail enamel agent in which the content mass ratio of the component (A) and the component (B) is (A) / (B) = 0.01 to 1.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a nail enamel that has a restorative coating film before drying, has a thick cosmetic film, is easy to apply, and has a long-lasting makeup.

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

Details of the present invention will be described below. In addition, in this specification, "-" shall mean the range including the numerical values before and after it.

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. The polyurethane gel composition can be obtained by producing the polyurethane gel composition by using the raw material of the polyurethane component (A-1) in the presence of the oil component (A-2).

Here, the component (A-1) polyurethane is represented by HO-R ³ -OH (in the formula, R ³ represents a linear or branched C2-C6 alkylene group which may have an ether bond). It is a polyurethane that uses glycol.
Further, the polyurethane component (A-1) preferably contains at least the following polyurethane (i) or (ii).
More preferably, the component (A-1) polyurethane has (i) a hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO-R ³ -OH (in the formula, R ³ has an ether bond. It may be a polyurethane obtained by reaction with a glycol represented by a linear or branched C2-C6 alkylene group), or (ii) (c) with a hydrogenated polybutadiene having a hydroxyl group at the terminal. d) Reaction of the diisocyanate compound with (b) a glycol represented by HO-R ³ -OH (where R ³ in the formula represents a linear or branched C2-C6 alkylene group which may have an ether bond). It is a polyurethane obtained by.

Examples of the glycol represented by (b) HO-R ³ -OH in the component (A-1) include ethylene glycol, propylene glycol, 1,3-butylene glycol, 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 the gel material in order to obtain a cosmetic film of an oil-soluble gel having high gloss, elasticity and resilience. The gel composition.

The inventor has been conducting research using silicone rubber, polysaccharides, and water-based polyurethane as restorative materials. However, these materials had advantages as well as drawbacks to be solved. Specifically, silicone rubber has the disadvantage of lacking luster and lacking restoring force; polysaccharides have the disadvantage of having weak restoring and restoring force; water-based polyurethane has a limited color gamut because it is water-based, and has sufficient luster. It had the serious drawback of not being;
However, as a result of diligent studies, the inventor found that in the presence of an oil agent, HO-R ³ -OH (in the formula, R ³ may have an ether bond is a linear or branched C2-C6 alkylene group. When polyurethane synthesis was carried out using the glycol represented by), a new gel material was obtained by chance. The novel gel material had a special function of high gloss, elasticity, and restoring force, as shown in Examples described later. This was an unpredictable effect for the inventor.
It is known that polyurethane is obtained by reacting diisocyanate with a polyol. However, there is no example of using polyurethane as an oil-soluble gelling agent, and the polyurethane gel composition of the present invention was found by a new idea of producing in the presence of an oil agent.

The concept of the polyurethane gel composition used in the present invention is still under intense study, but at the present time, the inventor thinks as follows. (1) The polyurethane in the polyurethane composition forms a plurality of ring-shaped clusters (bunches) by associating the hydrophilic parts in the molecule with each other, and is hydrophilic by contacting the oil agent at the hydrophobic part in the molecule. The inventor believes that it has a basic association thickening mechanism. (2) The polyurethane imparts flexibility and oil solubility because the hydrophobic part in the molecule is a low crystalline hydrocarbon; the polar groups of the hydrophilic part in the molecule interact with each other. The inventor thinks that it imparts gelling power and restoring power. (3) The inventor thinks that a three-dimensional structure is formed into a transparent gel by finely taking a three-dimensional structure by a hydrophilic group-associating thickening mechanism. The polyurethane is preferably an oil-soluble polyurethane, and the oil-soluble polyurethane is more preferably soluble in cetyl 2-ethylhexanoate at least 1% by mass or more at 30 ° C.

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

Composition 1: Polyurethane gel composition 1 containing component (A-1) (i) polyurethane and component (A-2) oil.
As the component (A-1) polyurethane, (i) (a) hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO-R ³ -OH (in the formula, R ³ may have an ether bond). A composition containing a polyurethane obtained by reaction with a glycol represented by (representing a linear or branched C2-C6 alkylene group) and a component (A-2) oil.
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) hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) a diisocyanate compound, and (b) HO-R ³ -OH (R ³ in the formula has an ether bond). Polyurethane obtained by reaction with glycol represented by (representing a linear or branched C2-C6 alkylene group) which may be used.
In the present invention, "terminal" means "both ends".

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

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

R ¹ and R ² each independently represent the same or different C1 to C6 alkylene groups, and the alkylene may be a straight chain or a branched chain. Examples of the C1 to C6 alkylene group include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene and the like. The alkylene group of R ¹ is preferably a C1 to C2 alkylene group. The alkylene group of ^R2 is preferably a C5 to C6 alkylene group. The alkylene group is preferably linear.
n represents an integer of 10 to 100, and a more preferable range of n is 15 to 55.
n ₁ and n ₂ are independently the same or different, and represent 0 or 1.

The structure of the repeating unit "C ₄ H ₈ " in the hydrogenated polybutadiene moiety of the general formula (1) (the following general formula (6)) is various as shown in the following general formulas (7a) to (7d), for example. There are types. It is preferable to use the compound from the viewpoint of the effect of the present invention.

The hydrogenated polybutadiene moiety in the hydrogenated polybutadiene having an isocyanate group at the terminal used in the present invention may consist of only one of the repeating units as exemplified above, or two or more repeating units. May be included regularly or randomly.
In the present invention, the three-dimensional structure of the repeating unit " _C4 H ₈ " constituting the hydrogenated polybutadiene moiety of the general formula (1) (the above general formula (6)) may be the same or different, and the hydrogenated polybutadiene may be different. All the structures whose parts are represented by the general formula (6) are included in the present invention.
As the hydrogenated polybutadiene having an isocyanate group at the terminal represented by the general formula (1), for example, a compound represented by the following general formula (2) is exemplified, and using the compound is from the viewpoint of the effect of the present invention. Suitable.

(Here, in the equation (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 end of the general formula (1) when R ¹ is an ethylene group, R ² is a hexamethylene group, and n ₁ = n ₂ = 1. Equivalent to.

(B): Component (A) Polyurethane gel composition (preferably compositions 1 and 2) component (A-1) Used in polyurethane (b) HO-R ³ -OH (in the formula, R ³ is Examples of glycols represented by linear or branched C2-C6 alkylene groups which may have an ether bond are, for example, ethylene glycol (HOCH ₂ CH ₂ OH), propylene glycol (HOCH ₂ CH (HOCH 2 CH)). OH) CH ₃ ), 1,3-butylene glycol (HOCH ₂ CH ₂ CH (OH) CH ₃ ), diethylene glycol (HOCH ₂ CH ₂ OCH ₂ CH ₂ OH) and the like can be mentioned. It is preferable to use the compound from the viewpoint of the effect of the present invention.
As the (b) HO-R ³ -OH, a compound represented by the following general formula (5) is shown, and the compound is suitable from the viewpoint of the effect of the present invention.

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

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

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

Examples of the (d) diisocyanate compound used in the component (d): polyurethane (preferably composition 2) include hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) benzene, and 1 , 3-Bis (isocyanatomethyl) cyclohexane, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and the like. 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 the terminal 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) is added in layers to produce a polyurethane, the molar ratio (a): (b) = 1. It is preferably carried out at a ratio of 4: 4 to 4: 1, more preferably at a molar ratio (a): (b) = 2: 3 to 3: 2, still more preferably 4: 5 to 4: 3, and even more preferably. Is from 9:10 to 10: 9. In this case, the weight average molecular weight (Mw) of (a) is preferably 1000 to 3000. It is more preferable to set the range within this range from the viewpoint that the effect 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 the terminal, (d) a diisocyanate compound, and (b) HO-R ³ -OH (b). In the formula, R ³ represents a linear or branched C2-C6 alkylene group which may have an ether bond), and when polyurethane is produced by reaction with a glycol represented by a glycol, the molar ratio (c): (b). ) = 1: 4 to 4: 1, more preferably a molar ratio (c): (b) = 2: 3 to 3: 2, and even more preferably 4: 5 to 4: 3. Even more preferably, it is 9:10 to 10: 9. Within this range, the effect of the present invention can be remarkably obtained, which is more preferable.

The weight average molecular weight (Mw) of the polyurethane obtained in (i) or (ii) is preferably 10,000 to 100,000, more preferably 20,000 to 80,000, and even more preferably 30,000 to 70,000. It is more preferable to set the range within this range from the viewpoint that the effect 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 (polystyrene conversion).

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, still more preferably 10 to 30% by mass. be.
The content of the component (A-2) oil in the component (A) polyurethane gel composition is preferably 65 to 99% by mass, more preferably 70 to 95% by mass, and further preferably 70 to 90% by mass. be.
It is more preferable to set the range within this range from the viewpoint that the effect of the present invention can be remarkably obtained.

Ingredient (A) The ingredient (A-2) oil used in the polyurethane gel composition is not particularly limited as long as it is usually used in cosmetics. The properties are not particularly limited, but it is preferably an oil agent that is liquid at 25 ° C. Further, 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, for example, a hydrocarbon oil or an ester oil (particularly, the number of hydroxyl groups is 0) regardless of the origin of animal oil, vegetable oil, synthetic oil and the like. Alternatively, one ester oil), fatty acids, silicone oils, fluorine-based oils and the like can be mentioned.

Of these, the lower the polarity, the higher the strength of the polyurethane gel composition tends to be. Therefore, from hydrocarbon oils, ester oils having 0 or 1 hydroxyl groups, and silicone oils containing phenyl groups. It is exemplified to use one or more selected ones, and it is preferable to include these one or two or more in the component (A-2) oil.
One or more selected from these hydrocarbon oils, ester oils and silicone oils may be contained in the component (A-2) oil preferably in an amount of 90% by mass or more, more preferably 95% by mass or more. Suitable.
Further, it is preferable to use the component (A-2) oil as a solvent in the production. By using the oil agent in the production, the characteristics of the produced polyurethane gel composition are improved. Further, the hardness of the composition can be adjusted by appropriately using an oil agent in the produced polyurethane gel composition.

Ingredients (A) Ingredients used in polyurethane gel compositions (A-2) More specifically, hydrocarbons such as liquid paraffin, squalane, polybutene and polyisobutylene; olive oil, castor oil, mink oil, etc. Fats and oils such as macadamian nut oil; jojoba oil, cetyl isooctanoate (cetyl 2-ethylhexanate), isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl isostearate, Esters such as diisostearyl malate, glyceryl tribehenate, pentaerythrit rosinate, neopentylglycol dioctanoate; silicones such as methylphenylpolysiloxane and diphenylpolysiloxane, and these may be one or two. More than seeds can be used.

The component (A) polyurethane gel composition used in the present invention has the advantages of not only transparency and gloss but also extremely high elasticity and restoring force.
As a result of measuring the load value with a needle, 30 parts of this polyurethane gel composition and 70 parts of liquid paraffin (kinematic viscosity at 40 ° C. by the ASTM D445 measurement method is 8 mm ² / s) were heated and melted at 85 ° C. to 30 ° C. The gel obtained by cooling the gel showed excellent characteristics with a load value of 0.2 to 10 N when a 2 cmφ spherical adapter was inserted into the needle at 2 cm / min by 10 mm. This hardness property 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 of 90% or more at a wavelength of 700 nm. 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 to produce polyurethane in the presence of the oil agent (A-2). Further, it is more preferable to use the specific polyol in the component (A-1) as a polyurethane raw material and to produce polyurethane in the presence of the oil agent (A-2). The polyurethane gel composition of the component (A) of the present invention can be produced with reference to a known polyurethane production method.

For example, the polyurethane gel composition 1 used in the present invention contains hydrogenated polybutadiene having an isocyanate group at the terminal (a) of A and (b) HO-R ³ -OH (in the formula) in the oil agent of the component (A-2). , R ³ represents a linear or branched C2-C6 alkylene group which may have an ether bond) and is obtained by carrying out a hydrogenation reaction.
For example, the polyurethane gel composition 2 of the present invention has (c) hydrogenated polybutadiene having a hydroxyl group at the terminal, and (b) HO-R ³ -OH (in the formula, R ³ may have an ether bond. It can be produced by charging a glycol represented by (representing a C2-C6 alkylene group of a chain or a branch) and a component (A-2) oil agent, mixing them uniformly, and adding (d) a diisocyanate compound to react. can.

In addition to the above components (A-1) and (A-2), the polyurethane gel composition of the present invention may appropriately contain any component that can be used in the pharmaceutical field or the cosmetic field as long as the effects of the present invention are not impaired. It may be contained. Optional ingredients include, for example, volatile ingredients, surfactants, oily ingredients, powders, water-soluble polymers, UV absorbers, moisturizers, anti-fading agents, antioxidants, defoamers, beauty ingredients, preservatives, etc. Other ingredients usually used in cosmetics can be appropriately used to impart various effects such as fragrances.

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 "%") with respect to the total amount of the nail polish, preferably 1 to 30%. 5 to 25% is particularly preferable. Within this range, it is suitable from the viewpoint of excellent resilience of the coating film before drying and the thickness of the decorative film. 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% with respect to the total amount of the nail polish. Within this range, it is suitable from the viewpoint of excellent resilience of the coating film before drying and the thickness of the decorative film.

The component (B) film-forming agent used in the present invention is a component that forms a flexible cosmetic film and improves the long-lasting makeup against physical stimuli. The component (B) film-forming agent of the present invention is not particularly limited, but an oil-soluble film-forming agent is preferable 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 in which a component corresponding to component (B) is dissolved in a soluble solvent at 40% is applied to a glass plate with a 400 μm-thick applicator, and a film is formed after drying at room temperature for 24 hours. It means that it is. The film-forming agent in the present invention is not particularly limited as long as it is usually used in cosmetics, and for example, nitrocellulose, phthalic acid-based alkyd resin, toluenesulfonamide resin, acrylic acid / alkyl copolymer, and the like. Benzoic acid sucrose ester, alkyl-styrene copolymer acrylate, silicone resin such as trimethylsiloxysilicate, polymethylsilsesquioxane, toluenesulfonamide epoxy resin, polyvinyl alcohol, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate co-weight Coalescence and the like can be mentioned. Of these, nitrocellulose, phthalic acid-based alkyd resin, toluenesulfonamide resin, acrylate / alkyl copolymer, benzoic acid sucrose ester, alkyl acrylate / styrene copolymer, and trimethyl, which are oil-soluble film-forming agents. One or more selected from the group consisting of silicone resins such as siloxysilicic acid and polymethylsilsesquioxane, and toluenesulfonamide epoxy resins is preferable, and more preferably, nitrocellulose, (styrene / acrylate) copolymer, and trimethyl. One or more selected from the group consisting of syroxysilicic acid, and in particular, nitrocellulose acts as a plasticizer for the cosmetic film to impart flexibility to the cosmetic film, and the cosmetic film is peeled off by physical stimulation. It is preferable because it has an excellent effect of suppressing chipping and chipping and improving the longevity of makeup. Examples of commercially available products of nitrocellulose include nitrified cotton H1 / 2, H1 / 4, H1 / 8 (all manufactured by Asahi Kasei Kogyo Co., Ltd.) and the like.

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% with respect to the total amount of the nail polish. Within this range, it is suitable from the viewpoint of excellent makeup retention and ease of application.

The component (C) volatile oil agent used in the present invention is an oil agent having volatile properties at 25 ° C. The ingredient (C) of the present invention can be used without particular limitation as long as it is usually used for cosmetics. Specific examples thereof include volatile hydrocarbon oils, volatile silicone oils, organic solvents and the like. 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 these may contain one or more. Among these, it is preferable to use an organic solvent from the viewpoint of long-lasting makeup, and in particular, the effect of the present application can be remarkably obtained by using one or more selected from the group consisting of ethyl acetate, butyl acetate and thinner. It is preferable in that it can be used. In particular, it is more preferable to use ethyl acetate, butyl acetate and thinner in combination in that the effect of the present application can be remarkably obtained, and it is further preferable to use all three types 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 polish. Within this range, it is suitable from the viewpoint of excellent makeup retention.

In addition to the above-mentioned components (A) to (C), the cosmetological agent of the present invention contains components normally used in cosmetics, oily components, powders, surfactants, fibers, polyhydric alcohols, and highly water-soluble components. Aqueous components such as molecules and moisturizers, sugars, ultraviolet absorbers, anti-fading agents, antioxidants, antifoaming agents, beauty ingredients, preservatives, fragrances and the like can be contained within a range that does not interfere with the effects of the present invention. ..

The oily components other than the component (A) and the component (C) are not particularly limited as long as they are usually used in cosmetics, and the origins of animal oils, vegetable oils, synthetic oils, etc., solid oils, semi-solid oils, liquid oils, etc. Regardless of the properties such as, hydrocarbons, oils and fats, cured oils, ester oils, fatty acids, higher alcohols, silicone oils, fluorooils, lanolin derivatives, etc. can be mentioned. Specifically, hydrocarbons such as liquid paraffin, squalane, polyisobutylene and polybutene, fats and oils such as olive oil, castor oil, mink oil and macadamian nut oil, jojoba oil, cetyl 2-ethylhexanoate and isostearyl lactate. , Octyldodecyl lactate, oleyl lactate, stearyl lactate, diisostearyl malate, tritridecyl trimeritoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, pentaerythrit ester loginate, neopentyl glycol dioctanoate, dioctanoic acid Esters such as neopentyl glycol, cholesterol fatty acid ester, phytosterol fatty acid ester, fatty acids such as stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid, oleic acid, stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, Examples thereof include higher alcohols such as isostearyl alcohol and behenyl alcohol, fluorohydric oils such as perfluorodecane, perfluorooctane and perfluoropolyether, and lanolin derivatives such as lanolin, lanolin acetate, lanolin fatty acid isopropyl and lanolin alcohol. One or two or more of these can be used.

As the powder, if it is a powder usually used for cosmetics, it has a plate-like or needle-like shape, a fumes-like, fine particles, a particle size such as a pigment grade, a porous or non-porous particle structure, etc. The present invention is not particularly limited, and examples thereof include inorganic powders, glittering powders, organic powders, dye powders, metal powders, and composite powders. Specifically, for example, white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide, barium sulfate, iron oxide, carbon black, titanium / titanium oxide sintered body, chromium oxide, chromium hydroxide, dark blue, ultramarine, etc. Colored inorganic pigments, white mica, gold mica, red mica, black mica, synthetic mica, silk mica (serisite), synthetic sericite, silicon carbide, bentonite, smectite, aluminum oxide, magnesium oxide, zirconium oxide, antimony oxide, silica White constitution powder such as soybean soil, aluminum silicate, aluminum magnesium metasilicate, calcium silicate, barium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, hydroxyapatite, boron nitride, titanium oxide-coated mica, titanium oxide-coated Oxychloride bismuth, iron oxide mica titanium, navy blue treated mica titanium, carmine treated mica titanium, oxychloride bismuth, fish scale foil, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polyolefin laminated film powder, polyethylene terephthalate / polymethylmethacrylate laminated Glittering powder such as film powder, copolymer resin such as fluororesin and cellulose resin, organic low molecular weight powder such as zinc stearate and N-acyllysine, silk powder, cellulose powder, natural organic powder such as dextrin powder. Body, Red 201, Red 202, Red 205, Red 226, Red 228, Orange 203, Orange 204, Blue 404, Yellow 401, etc., Red 3, Red 104, Red 106, etc. Organic pigment powder such as zirconium, barium or aluminum lake such as No., orange 205, yellow 4, yellow 5, green 3 and blue 1, or metal powder such as aluminum powder, gold powder and silver powder, fine particles. Examples thereof include composite powders such as titanium oxide-coated mica titanium, fine particle zinc oxide-coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing silicon dioxide and zinc oxide-containing silicon dioxide, and fibers such as polyester, rayon and cellulose. These may be surface-treated with a fluorine compound, a silicone oil, a powder, an oil agent, a gelling agent, an emulsion polymer, a surfactant or the like. One kind or two or more kinds of these can be used, and a further compounded one may be used.

As the surfactant, any surfactant usually used for cosmetics can be used, and a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, etc. can be used. Can be mentioned.

The aqueous component may be any component soluble in water, for example, propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerin, diglycerin, polyglycerin, aloe vera, witch hazel, hamamelis, cucumber. , Lemon, lavender, rose water and other plant extracts.

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, diethylaminohydroxybenzoylhexylbenzoate, bisethylhexyloxyphenol methoxyphenyltriazine and the like can be mentioned.

Examples of the antioxidant include tocopherol and ascorbic acid, examples of the beauty ingredient include vitamins, anti-inflammatory agents and crude drugs, and examples of the preservative include paraoxybenzoic acid ester, phenoxyethanol and 1,2-pentadiol. ..

The method for producing the beautiful nail agent of the present invention is not particularly limited, and can be obtained by a general production method. For example, the component (A), the component (B) and the component (C) can be uniformly mixed and dispersed and filled in a container to obtain the product. Further, each component may be mixed at the same time, or other components may be added at the time of mixing.

The beautiful nail preparation of the present invention is not particularly limited and may be in various dosage forms. Examples thereof include an oil-based type, a water-in-oil type, and an oil-in-water type. From the viewpoint of dispersibility of the constituent elements of the present invention, the oil-based type and the water-in-oil type are preferable, and the oil-based type is particularly preferable. The properties are not particularly limited and can be applied to any of them, but they can be solid, liquid, creamy or the like, and can be applied without limitation as long as they are used for nails. For example, manicure, 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. It should be noted that these do not limit the present invention in any way.

[Production Example 1 of Polyurethane Gel Composition of Component (A)]
899 parts of hydroxyl-terminated polybutadiene (molecular weight 2200), 2450 parts of cetyl 2-ethylhexaneate and 128 parts of hexamethylene diisocyanate were charged in a 3 L three-necked flask and mixed uniformly.
0.9 part of dibutyltin dilaurate was added while controlling to 60 ° C., 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 5 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of 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 melted by heating at 85 ° C. with 70 parts of liquid paraffin, and the load value of the gel cooled to 30 ° C. was determined by a load measuring machine (manufactured by FUDOH), 2 cmφ spherical adapter, 2 cm /. In the case of min and 10 mm needle insertion conditions, it was 2.5 N.

[Production Example 2 of Polyurethane Gel Composition of Component (A)]
899 parts of hydroxyl-terminated polybutadiene (molecular weight 2200), 2450 parts of cetyl 2-ethylhexaneate and 128 parts of hexamethylene diisocyanate were charged in a 3 L three-necked flask and mixed uniformly.
0.9 part of dibutyltin dilaurate was added while controlling to 60 ° C., 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 polyurethane in the obtained polyurethane gel was 50,000 as measured by GPC (in terms of polystyrene). Further, 30 parts of the obtained gel was melted by heating at 85 ° C. with 70 parts of liquid paraffin, and the load value of the gel cooled to 30 ° C. was determined by a load measuring machine (manufactured by FUDOH), 2 cmφ spherical adapter, 2 cm /. In the case of min and 10 mm needle insertion conditions, it was 5N.

[Production Example 3 of Polyurethane Gel Composition of Component (A)]
899 parts of hydroxyl-terminated polybutadiene (molecular weight 2200), 2450 parts of jojoba oil and 128 parts of hexamethylene diisocyanate were charged into a 3 L three-necked flask and mixed uniformly.
0.9 part of dibutyltin dilaurate was added while controlling to 60 ° C., 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 then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of polyurethane in the obtained polyurethane gel was 100,000 as measured by GPC (in terms of polystyrene). Further, 30 parts of the obtained gel was melted by heating at 85 ° C. with 70 parts of liquid paraffin, and the load value of the gel cooled to 30 ° C. was determined by a load measuring machine (manufactured by FUDOH), 2 cmφ spherical adapter, 2 cm /. In the case of min and 10 mm needle insertion conditions, it was 7.5 N.

[Production Example 4 of Polyurethane Gel Composition of Component (A)]
899 parts of hydroxyl-terminated polybutadiene (molecular weight 2200), 24 parts of ethylene glycol, 0.9 part of dibutyltin dilaurate, and 2450 parts of squalane were placed in a 3 L three-necked flask and mixed uniformly.
128 parts of hexaethylene diisocyanate was added while controlling to 60 ° C., and 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 polyurethane in the obtained polyurethane gel was 50,000 as measured by GPC (in terms of polystyrene). Further, 30 parts of the obtained gel was melted by heating at 85 ° C. with 70 parts of liquid paraffin, and the load value of the gel cooled to 30 ° C. was determined by a load measuring machine (manufactured by FUDOH), 2 cmφ spherical adapter, 2 cm /. In the case of min and 10 mm needle insertion conditions, it was 3N.

[Production Example 5 of Polyurethane Gel Composition of Component (A)]
899 parts of hydroxyl-terminated polybutadiene (molecular weight 2200), 24 parts of ethylene glycol, 0.9 part of dibutyltin dilaurate, and 2450 parts of diisostearyl malate were charged in a 3 L three-necked flask and mixed uniformly.
While controlling the temperature to 60 ° C., 128 parts of hexaethylene diisocyanate was added, and after the addition was completed, the mixture was stirred at 80 ° C. for 15 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of polyurethane in the obtained polyurethane gel was 100,000 as measured by GPC (in terms of polystyrene). Further, 30 parts of the obtained gel was melted by heating at 85 ° C. with 70 parts of liquid paraffin, and the load value of the gel cooled to 30 ° C. was determined by a load measuring machine (manufactured by FUDOH), 2 cmφ spherical adapter, 2 cm /. In the case of min and 10 mm needle insertion conditions, it was 4.5 N.

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

[Evaluation of gel]
From the polyurethane gels obtained by the above-mentioned production method, the polyurethane gel composition of Production Example 2 was evaluated with respect to the gel load value for various oils commonly used in cosmetics and the transparency of the gel (Test Example 1). ~ 6). The results are shown in Table 1. In addition, various evaluation methods are as follows. 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 dissolved at 85 ° C. and cooled to 30 ° C. to prepare an elastic gel (Test Examples 1 to 6). The load value of the gel was measured using a load measuring machine (manufactured by FUDOH) under the conditions of a 2 cmφ spherical adapter, 2 cm / min, and a 10 mm needle. The gel strength was evaluated by this. As a result of Test Examples 1 to 4, it was confirmed that the load value tends to be higher as the oil agent has a smaller number of hydroxyl groups in the molecule. It is considered that this is because the hydroxyl group in the oil agent affects the hydrophilic group portion in the hydrophilic group-associating thickening mechanism of the polyurethane gel, resulting in a decrease in thickening.

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

[Measurement and evaluation of self-restoring force]
The self-restoring force was evaluated using the polyurethane gel composition of Production Example 2 and the dextrin fatty acid ester gel of Production Comparative Example 2. Each measurement sample is diluted with cetyl 2-ethylhexanoate so that the pure content becomes 10.5% by mass, heated at 85 ° C., poured into a jar, and cooled to 30 ° C. to make it elastic. A gel was prepared. From the time when a load of 5 g was applied to the prepared sample using a texture analyzer (manufactured by Ei Seiki Co., Ltd.) with a 2 cmφ spherical adapter, 7 times at a speed of 1 mm / min and under the condition of inserting a 5 mm needle. By repeating the same operation, it was confirmed that the gel structure was not destroyed by the load and that it had a restoring force. A schematic diagram of the measurement is shown in FIG.
As a result, in the dextrin fatty acid ester gel of Production Comparative Example 2, the gel structure was destroyed by repeated loading and the same curve was not obtained, whereas in the polyurethane gel composition of Production Example 2, the gel was formed by repeated loading. By following the same curve without collapsing, it was found that the gel has high resilience. Further, since the value of the load value itself was also 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 studies, it was found that the component (A) polyurethane gel composition used in the present invention is a highly novel gel having excellent transparency, high elasticity, and excellent self-restoring force.

Examples 1 to 10 and Comparative Examples 1 to 4: Beautiful nail preparation The beautiful 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, and the results were also combined. It is shown in Table 1. As the component (A) polyurethane gel composition, the polyurethane gel composition of Production Example 2 produced above was used.

※１：固形分２０％
※２：チミロンスーパーシーン ＭＰ－１００１（メルク社製）

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

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

〔evaluation〕
How to evaluate the stability of the coating film before drying:
1 g of the beautiful nail agent of the above-mentioned Example and Comparative Example was dropped onto the glass plate, and a coating film of 200 micrometers was applied. Immediately after that, a toothpick was dropped on the coating film and lifted 10 seconds later. After 5 minutes (after the coating film was dried), the coating film was observed again, and the presence or absence of toothpick marks was visually evaluated by 20 cosmetic evaluation specialist panels.
<Judgment criteria>
More than 15 panels answered that they don't mind the marks at all: ◎
10 or more and less than 15 panels responding that they do not care about the marks at all: 〇 5 or more and less than 10 panels responding that they do not care about the marks at all: △
Less than 5 panels answered that they didn't mind the marks at all: ×

Sensory evaluation method: We asked 20 cosmetics evaluation panel to use the cosmetics of the above example and comparative example, and each of them had the following criteria for "thickness of dry film", "makeup retention", and "ease of application". According to the above, the evaluation was made on a 5-point scale, a score was given for each beauty nail agent, and the average score of the scores of all the panels was judged according to the following criteria.
<Evaluation criteria>
(Evaluation result): (Score)
Very good: 5 points Good: 4 points Normal: 3 points Slightly defective: 2 points Defective: 1 point <Judgment criteria>
(Average score): (Judgment)
4 points or more: ◎
3 points or more and less than 4 points: 〇 2 points or more and less than 3 points: △
Less than 2 points: ×
The higher the score, the better.

The nail polishes of Examples 1 to 10 have a synergistic effect with the component (A) polyurethane gel composition, the component (B) film forming agent, and the component (C) volatile oil agent, and the restoration property of the coating film before drying is obtained. A beautiful nail agent was obtained, which was excellent, had a good thickness on the film after drying, and had better makeup retention and ease of application. On the other hand, Comparative Examples 1 and 2 containing no component (A) did not satisfy the resilience of the coating film before drying and the thickness of the decorative film, and Comparative Example 3 containing no component (B) was not satisfied. Comparative Example 4, which contained powdered polyurethane instead of the component (A), was satisfied with the restorability of the film before drying, the thickness of the makeup film, and the makeup retention. I didn't get anything.
Further, the amount of the component (A) polyurethane gel composition used in this technique was in a wide range of 0.5 to 50% by mass, and a good nail polish was obtained. By increasing the content of the component (A) in the nail polish, there was a tendency to improve the resilience of the film before drying and the thickness of the film. In addition, even when various types of film forming agents used in this technique such as nitrocellulose, (styrene / acrylate) copolymer and trimethylsiloxysilicic acid were used, good nail polish was obtained. There was a tendency to improve the longevity of makeup by increasing the content of the component (B) in the nail polish. Further, even when the component (A) / component (B) had a wide content mass ratio of 0.025 to 10, a good nail polish was obtained. In addition, a good nail polish was obtained in the range of component (A-1) / component (B) of 0.005 to 2.

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

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

The nail polish obtained as described above was excellent in the restorability of the coating film before drying, had a thick film, and was satisfactory in terms of longevity and ease of application.

Example 12: Top coat (ingredient) (%)
1. 1. Polyurethane gel composition of Production Example 3 10
2. 2. Polyurethane gel composition of Production Example 2 10
3. 3. Trimethylsiloxysilicic acid 10
4. Isopropyl alcohol 7
5. Ethyl acetate 20
6. Butyl acetate 30
7. Remaining thinner 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)
Ingredients (1) to (12) are uniformly mixed with a disper.

The top coat obtained as described above was excellent in the restorability of the coating film before drying, had a thick film, and was satisfactory in terms of longevity and ease of application.

Example 13: Base coat (ingredient) (%)
1. 1. Polyurethane gel composition of Production Example 4 15
2. 2. (Styrene / Acrylate) Copolymer 5
3. 3. Isopropyl alcohol 7
4. Ethyl acetate 30
5. Butyl acetate 30
6. Thinner remaining amount 7. Acetyl tributyl citrate 5
8. Silicic acid anhydride 2
9. Bengala 0.1
10. Yellow iron oxide 0.1

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

The base coat obtained as described above was excellent in the restorability of the coating film before drying, had a thick film, and was satisfactory in terms of longevity and ease of application.

Example 14: Nail oil (ingredient) (%)
1. 1. Polyurethane gel composition 15 of Production Example 5
2. 2. Nitrocellulose 1
3. 3. Isopropyl alcohol 7
4. Remaining thinner 5. Mineral oil 10
6. Polyglyceryl triisostearate-2 20
7. Glyceryl tri2-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. Rosehip extract 0.01
20. Squalene 0.1
21. Meadowfoam oil 0.1
22. Almond oil 0.1
23. Avocado oil 0.1
24. Astaxanthin solution 0.001

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

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

Claims (7)

The following components (A) to (C);
Ingredient (A) Polyurethane gel composition,
Ingredient (B) film forming agent,
Ingredient (C) A beautiful nail agent containing a volatile oil agent.
The component (A) is a gel composition containing the polyurethane (i) or (ii) below the component (A-1) and the oil agent (A-2).
(I) (a) Hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO-R ³ -OH (in the formula, R ³ may have an ether bond, linear or branched C2-C6 alkylene). Polyurethane obtained by reaction with glycol represented by (representing a group), or
(Ii) (c) Hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) Diisocyanate compound, and (b) HO-R ³ -OH (R ³ in the formula may have an ether bond. Polyurethane obtained by reaction with a glycol represented by (representing a C2-C6 alkylene group). The beautiful nail agent according to claim 1, wherein the polyurethane (A-1) is an oil-soluble polyurethane. The nail polish 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 beautiful 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 / acrylicite) copolymer, and trimethylsiloxysilicic acid. Fee The nail polish 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 isopropyl alcohol . The beauty nail agent 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.

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