WO2016152545A1

WO2016152545A1 - Nail cosmetic preparation and nail-art kit

Info

Publication number: WO2016152545A1
Application number: PCT/JP2016/057498
Authority: WO
Inventors: 大橋　秀和
Original assignee: 富士フイルム株式会社
Priority date: 2015-03-24
Filing date: 2016-03-10
Publication date: 2016-09-29

Abstract

The purpose of the present invention is to provide: a nail cosmetic preparation which lasts longer and is reduced in the burden to finger tips and nails; and a nail-art kit including the nail cosmetic preparation. The nail cosmetic preparation according to the present invention is characterized by containing particles that each have polymerizable groups, include a three-dimensionally crosslinked structure having at least one kind of bonds selected from the group consisting of urethane bonds, thiourethane bonds, dithiourethane bonds, urea bonds, and thiourea bonds, and contain a photopolymerization initiator inside. The nail-art kit according to the present invention is characterized by including the nail cosmetic preparation.

Description

Nail cosmetics and nail art kits

The present invention relates to a nail cosmetic and a nail art kit.

In recent years, the popularity of nail art for designing hands and toenails has increased, and technology for forming synthetic resin artificial nails (fake nails, nail tips, etc.) on nails (self nails) has been developed (Patent Literature). 1). In particular, a nail decoration called gel nail that has been cured by irradiation with ultraviolet rays after applying a gel-like decorative curable composition containing a urethane-based resin and a photopolymerizable monomer to the nail has a clear finish. It has attracted attention for some reasons, such as high adhesion with nails and long-lasting, no odor like acrylic resin (see Patent Document 2).
Also, a nail or artificial nail containing an aqueous emulsion of a polymer containing a functional group capable of undergoing a polymerization reaction upon irradiation with active energy rays, polyethylene glycol, and a photo radical initiator (except for those containing a nitrogen atom in the molecule) An aqueous composition such as a curable resin composition for coating is also known (see Patent Document 3).

JP 2004-275736 A Special Table 2002-505915 JP 2011-121867 A

An object of the present invention is to provide a nail cosmetic and a nail art kit including the nail cosmetic, which have improved durability and reduce the burden on fingertips and nails.

As a result of intensive studies to solve the above problems, the present inventor has found that the above object can be achieved by means described in the following <1> or <12>, although the reason is not clear. It is described below together with <2> to <11>, which are preferred embodiments.
<1> having a polymerizable group, including a three-dimensional crosslinked structure having at least one bond selected from the group consisting of a urethane bond, a thiourethane bond, a dithiourethane bond, a urea bond, and a thiourea bond, A nail cosmetic characterized by containing particles containing a photopolymerization initiator in
<2> The nail cosmetic according to <1>, wherein the particle has a structure represented by the following formula 1 as the three-dimensional crosslinked structure:

In formula 1, ^one of X ¹ and X ² represents NH, the other represents O, NH, or S, Y represents O or S, n represents an integer of 3 or more, and R represents An n-valent organic group is represented, and * represents a bonding position with another structure.

<3> The nail cosmetic according to <1> or <2>, wherein the particles have a structure represented by the following formula 2 as the three-dimensional crosslinked structure:

In Formula 2, R ¹ represents an n-valent organic group, R ² represents a divalent organic group, n represents an integer of 3 or more, and * represents a bonding position with another structure.

<4> The nail cosmetic according to any one of <1> to <3>, wherein the particles have a dispersion-stable group,
<5> The nail cosmetic according to <4>, wherein the dispersion-stable group is at least one of a group having a polyether structure and an ionic group.
<6> The nail cosmetic according to any one of <1> to <5>, wherein the particle further contains a polymerizable compound inside the particle,
<7> The nail cosmetic according to <6>, wherein the polymerizable compound is a (meth) acrylate compound,
<8> The nail cosmetic according to <7>, wherein the (meth) acrylate compound is an acrylate compound having three or more functions.
<9> The nail cosmetic according to any one of <1> to <8>, further comprising a polymerizable compound,
<10> The nail cosmetic according to any one of <1> to <9>, further comprising a polymer compound,
<11> The nail cosmetic according to any one of <1> to <10>, further comprising a solvent,
<12> A nail art kit comprising the nail cosmetic according to any one of <1> to <11>.

According to the present invention, a nail cosmetic with improved durability and a reduced burden on fingertips and nails and a nail art kit including the nail cosmetic are provided.

Hereinafter, the nail cosmetic of the present invention will be described in detail.
In this specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In this specification, (meth) acrylate means at least one of acrylate and methacrylate.
In the present specification, “mass%” and “part by mass” have the same meanings as “% by weight” and “part by weight”, respectively. In the following description, part of the chemical formula is described with H and C omitted.
Further, unless otherwise specified, the group means not only an unsubstituted substituent but also a case having a substituent. For example, the description of an alkyl group means not only an unsubstituted alkyl group but also an alkyl group having a substituent.
In the following description, a combination of preferred embodiments is a more preferred embodiment.

1. Nail cosmetic The nail cosmetic of the present invention has a polymerizable group and has at least one bond selected from the group consisting of a urethane bond, a thiourethane bond, a dithiourethane bond, a urea bond, and a thiourea bond. It contains particles containing a three-dimensional crosslinked structure and containing a photopolymerization initiator inside.
Details of the mechanism of action in the present invention are unknown, but are presumed as follows.
The nail cosmetic of the present invention has a polymerizable group in the particle containing the photopolymerization initiator inside, so that the active species generated from the photopolymerization initiator act on the surface or inside of the particle by irradiation with active energy rays. An existing polymerizable group is bonded to a polymerizable group of an adjacent particle to form a crosslinked structure. At this time, since both the photopolymerization initiator and the polymerizable group are present in the particles, it is considered that a cured film having high sensitivity and excellent strength can be obtained. Moreover, it is thought that the film | membrane excellent in film | membrane strengths, such as water resistance and solvent resistance, is formed because particle | grains have a three-dimensional crosslinked structure.
In addition, since the particles have a three-dimensional cross-linking structure, voids are formed in the particles or between the particles, and the removal liquid can quickly permeate through the voids, so that it is considered that the removal of the cured film is accelerated.
Furthermore, since it is possible to impart water dispersibility to the particles themselves by having a three-dimensional cross-linking structure having a specific bond, it is possible to produce an aqueous nail cosmetic, which is a burden on the nails. It is not necessary to use an organic solvent having a large size.
Hereinafter, the nail cosmetic used in the present invention will be described.

(particle)
The nail cosmetic of the present invention has a polymerizable group and has a three-dimensional crosslink having at least one bond selected from the group consisting of a urethane bond, a thiourethane bond, a dithiourethane bond, a urea bond, and a thiourea bond. It contains particles (hereinafter also referred to as “specific particles”) containing a structure and containing a photopolymerization initiator inside. That is, the specific particles contained in the nail cosmetic of the present invention have a polymerizable group. Further, the specific particle has a three-dimensional crosslinked structure, and is selected from the group consisting of a urethane bond, a thiourethane bond, a dithiourethane bond, a urea bond, and a thiourea bond in the three-dimensional crosslinked structure. It has a species bond. That is, it is preferable that a three-dimensional crosslinked structure is formed by a urethane bond, a thiourethane bond, a dithiourethane bond, a urea bond, and a thiourea bond. Furthermore, the specific particles contain a photopolymerization initiator inside.
In the present invention, the inside of the particle means a void of a three-dimensional cross-linked structure, and the specific particle contains a photopolymerization initiator inside, the photopolymerization initiator is in a three-dimensional cross-linked structure It is said that it exists without being combined. In the present specification, the term “particle” includes a photopolymerization initiator and the like present in the voids of the three-dimensional crosslinked structure.
The specific particles contain a photopolymerization initiator therein, so that a film with high sensitivity and a high crosslinkability is formed.

The specific particle in the present invention having a polymerizable group means that the polymerizable group in the particle is present at a position where it can react with the polymerizable group of the adjacent particle. For example, in the case of an aspect existing on the surface of the particle or an aspect existing inside the particle, it can be said that the particle exists in a position where it can react with the polymerizable group of the adjacent particle. The aspect which exists in the surface of particle | grains or the particle | grain surface and surface vicinity at least is preferable.
The polymerizable group in the specific particle is preferably an ethylenically unsaturated group, more preferably an acryloyl group, a methacryloyl group, an acrylamide group, a methacrylamide group, a vinylphenyl group, a vinyl group, and / or an allyl group, and an acryloyl group. A methacryloyl group, an acrylamide group, a methacrylamide group, a vinylphenyl group, and / or an allyl group are more preferable, and an acryloyl group, a methacryloyl group, an acrylamide group, and / or a methacrylamide group are particularly preferable.

The particles having a three-dimensional cross-linking structure having at least one type of bond selected from the group consisting of a urethane bond, a thiourethane bond, a dithiourethane bond, a urea bond, and a thiourea bond are structures represented by the following formula 1. It means that the particles have.

In Formula 1, it is preferable that any one of X ¹ and X ² represents NH and the other represents O or NH. Y is preferably O.
In addition, when ^one of X ¹ and X ² is NH, the other is O, and Y is O, it means a urethane bond. When ^one of X ¹ and X ² is NH and the other is O and Y is S, and when ^one of X ¹ and X ² is NH, the other is S and Y is O, Means a thiourethane bond. That is, a thiourethane bond means a case where one of two Os of a urethane bond is S. Furthermore, when ^one of X ¹ and X ² is NH, the other is S and Y is S, it means a dithiourethane bond.
When both X ¹ and X ² are NH and Y is O, it means a urea bond, and when both X ¹ and X ² are NH and Y is S, it means a thiourea bond. .
n X ¹ , X ² , and Y may be the same or different.

n represents an integer of 3 or more, preferably an integer of 3 or more, 10 or less, more preferably an integer of 3 or more and 8 or less, and still more preferably an integer of 3 or more and 6 or less.
* Represents a site that binds to another structural part.

R represents an n-valent organic group. The organic group represented by R is an organic group composed of an element selected from the group consisting of oxygen, nitrogen, halogen, phosphorus, sulfur, silicon and boron as essential elements, with carbon and hydrogen as essential elements. Preferably, carbon and hydrogen are essential elements, and as an optional element, an organic group composed of an element selected from the group consisting of oxygen, nitrogen, halogen, phosphorus, and sulfur is more preferable, and carbon and hydrogen are essential. More preferably, the element is an organic group composed of an element selected from the group consisting of oxygen, nitrogen, and sulfur. Organic groups composed only of carbon atoms and hydrogen atoms are also preferred.

Specific examples (R-1) to (R-22) of the organic group represented by R are shown below. The present invention is not limited to these.

Particles having a three-dimensional cross-linking structure having at least one bond selected from the group consisting of a urethane bond, a thiourethane bond, a dithiourethane bond, a urea bond, and a thiourea bond have a structure represented by the following formula 2. More preferably, the particles have.

In Formula 2, n represents an integer of 3 or more, preferably an integer of 3 or more and 10 or less, more preferably an integer of 3 or more and 8 or less, and still more preferably an integer of 3 or more and 6 or less.
n R ^{2 s} may be the same or different.
* Represents a site that binds to another structural part. In addition, it is preferable to couple | bond with another structure part through S, NH, or O, it is more preferable to couple | bond through NH or O, and it is still more preferable to couple | bond through NH. In the case of bonding through NH, the site forms a urea bond, and in the case of bonding through O, the site forms a urethane bond.
R ¹ represents an n-valent organic group, and is preferably an n-valent organic group bonded to the carbonyl carbon via NH, O, or S, and is an n-valent organic group bonded via NH or O. It is more preferable that it is an n-valent organic group bonded through O. The organic group represented by R ¹ is an organic group composed of an element selected from the group consisting of oxygen, nitrogen, halogen, phosphorus, sulfur, silicon, and boron, with carbon and hydrogen as essential elements and optional elements. Preferably, carbon and hydrogen are essential elements, and as an optional element, an organic group composed of an element selected from the group consisting of oxygen, nitrogen, halogen, phosphorus, and sulfur is more preferable. More preferably, the essential element is an organic group composed of an element selected from the group consisting of oxygen, nitrogen and sulfur. Organic groups composed only of carbon atoms and hydrogen atoms are also preferred.

As the n-valent organic group represented by R ¹ , a compound having three or more functional groups selected from an OH group, an NHR group (where R represents a hydrogen atom, an alkyl group, and an aryl group) and an SH group Therefore, a residue obtained by removing H present in the OH group, NHR group, and SH group is preferable. Specific examples of the n-valent organic group represented by R ¹ are preferably (R1-1) to (R1-83) shown below, more preferably (R1-1) to (R1-77), R1-1) to (R1-37) are particularly preferred. By setting it as the said structure, the intensity | strength of a film is high and an external appearance becomes favorable.

In (R1-32) to (R1-36), a to d each independently represents an integer of 1 to 20.

R ² represents a divalent organic group. The divalent organic group represented by R ² includes carbon and hydrogen as essential elements, and is composed of an element selected from the group consisting of oxygen, nitrogen, halogen, phosphorus, sulfur, silicon, and boron as an optional element. It is preferably a divalent organic group, and is a divalent organic group composed of elements selected from the group consisting of oxygen, nitrogen, halogen, phosphorus, and sulfur as essential elements, with carbon and hydrogen as essential elements. More preferably, it is more preferably a divalent organic group composed of an element selected from the group consisting of oxygen, nitrogen and sulfur with carbon and hydrogen as essential elements. A divalent organic group composed only of carbon atoms and hydrogen atoms is also preferred.
The divalent organic group represented by R ² is preferably a residue obtained by removing an NCO group from a compound having two NCO groups. Specific examples of the divalent organic group represented by R ² are preferably (R2-1) to (R2-34) shown below, more preferably (R2-1) to (R2-25), R2-1) to (R2-8) are more preferable. By setting it as the said structure, the intensity | strength of a film is high and an external appearance becomes favorable.

In (R2-8), one of R ³ and R ⁴ is a hydrogen atom, and the other is a methyl group. Me represents a methyl group.

As a method for introducing a polymerizable group into particles, for example, (1) when a three-dimensional crosslinked structure is formed, a trifunctional or higher functional isocyanate compound or a thioisocyanate compound and water or two or more active hydrogen groups are included. A method of reacting a compound with a polymerizable compound having an active hydrogen group, (2) when producing a trifunctional or higher functional isocyanate compound or thioisocyanate compound, a trifunctional isocyanate compound or thioisocyanate, and an active hydrogen group After forming an isocyanate compound or thioisocyanate to which a polymerizable group has been added in advance to form a three-dimensional cross-linked structure by reacting with water or a compound having two or more active hydrogen groups. Method (3) When producing particles, a polymerizable compound is used as an oil phase component together with the components constituting the particles. It is a solution, adding the aqueous phase component in the oil phase component, mixing, and a method of emulsification. As a method for introducing a polymerizable group into the particles in the present invention, the above (1) or (2) is preferable, and (2) is more preferable. These three methods can be used in combination as a method for introducing a polymerizable group.
When the specific particles have a polymerizable group, adjacent particles can be crosslinked and a film can be formed.

Since the particles in the present invention contain at least one compound having three or more reactive groups (isocyanate group, thioisocyanate group or active hydrogen group) as a raw material for producing the particles, the crosslinking reaction is three-dimensional. It proceeds to form a three-dimensional network structure.
The particles are excellent in mechanical strength by including a three-dimensional crosslinked structure having at least one bond selected from the group consisting of urethane bond, thiourethane bond, dithiourethane bond, urea bond, and thiourea bond. A film is obtained.
Hereinafter, a: a trifunctional or higher functional isocyanate compound, b: water or a compound having two or more active hydrogen groups (which forms a trifunctional or higher functional isocyanate compound), which is a component for forming particles used in the present invention. Different from water or a compound having two or more active hydrogen groups), c: a polymerizable compound having an active hydrogen group, d: a bifunctional or higher functional isocyanate compound and a polymerizable compound having an active hydrogen group. An isocyanate compound to which a polymerizable group has been added in advance (hereinafter referred to as a polymerizable isocyanate compound), e: a polymerizable compound, f: a photopolymerization initiator, and g: a compound having a dispersion stability group will be described.
In addition, as a particle formation method, a trifunctional or higher functional isocyanate compound, a thioisocyanate compound, or a compound having an active hydrogen group, and a bifunctional or higher functional compound reactive with the above trifunctional or higher functional compound (including water). And a compound for introducing a polymerizable group (a polymerizable compound having an active hydrogen group, a polymerizable isocyanate compound, or a polymerizable compound) and a photopolymerization initiator are preferably used as raw materials.
Specifically, as a method for forming particles, (i) a, b, c, and f (optionally, at least one selected from the group consisting of d, e, and g may be added thereto) And (ii) adding at least one selected from the group consisting of a, b, d, and f (optionally consisting of c, e, and g). And (iii) a, b, e, and f (optionally selected from the group consisting of c, d, and g). The method of forming particles by reacting may be preferably exemplified, but the present invention is not limited thereto.
The three-dimensional crosslinked structure in the particles is preferably a product formed by the reaction of a trifunctional or higher functional isocyanate compound and water.
In the following description, an isocyanate compound will be described, but the present invention can be similarly applied to a thioisocyanate compound in which an isocyanate group is replaced with a thioisocyanate group.

a: Trifunctional or higher functional isocyanate compound The trifunctional or higher functional isocyanate compound is a compound having three or more isocyanate groups in the molecule, preferably a compound having 3 to 10 isocyanate groups in the molecule. A compound having an isocyanate group is more preferable, and a compound having 3 to 6 isocyanate groups is still more preferable. As the trifunctional or higher functional isocyanate compound used in the present invention, a known compound and a compound synthesized by the method described later can be used.
Known compounds include, for example, compounds described in “Polyurethane Resin Handbook” (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987)).

As trifunctional or higher functional isocyanate compounds, (1) bifunctional or higher functional isocyanate compounds (compounds having two or more isocyanate groups in the molecule) and trifunctional or higher functional polyols, polyamines, polythiols, etc. Triad or higher isocyanate compound (adduct type) as an adduct (adduct) with the compound having the above active hydrogen group, (2) Trimer of bifunctional or higher isocyanate compound (biuret type or isocyanurate type) And (3) compounds having three or more isocyanate groups in the molecule such as formalin condensate of benzene isocyanate are preferably exemplified.
These trifunctional or higher functional isocyanate compounds may be a mixture containing a plurality of compounds, and the compound of the preferred embodiment shown below is preferably the main component of the mixture, and may contain other components. .

(1) Adduct Type The adduct type trifunctional or higher functional isocyanate compound is preferably a compound represented by the following formula 3.

In Formula 3, R ³¹ represents an n3 valent organic group, n3 represents an integer of 3 or more, and R ³² represents a divalent organic group.
R ³¹ is preferably an n3 valent organic group bonded to the carbonyl carbon via NH, O or S, more preferably an n3 valent organic group bonded via NH or O, It is further more preferable that it is an n3 valent organic group couple | bonded through this. The organic group represented by R ³¹ is an organic group composed of an element selected from the group consisting of oxygen, nitrogen, halogen, phosphorus, sulfur, silicon, and boron, with carbon and hydrogen as essential elements and optional elements. Preferably, carbon and hydrogen are essential elements, and as an optional element, an organic group composed of an element selected from the group consisting of oxygen, nitrogen, halogen, phosphorus, and sulfur is more preferable. More preferably, the essential element is an organic group composed of an element selected from the group consisting of oxygen, nitrogen and sulfur. Organic groups composed only of carbon atoms and hydrogen atoms are also preferred.
As an n3-valent organic group represented by R ³¹ , a compound having three or more functional groups selected from an OH group, an NHR group (where R represents a hydrogen atom, an alkyl group, and an aryl group) and an SH group Therefore, a residue obtained by removing H present in the OH group, NHR group, and SH group is preferable.
Specific examples of the n3-valent organic group represented by R ³¹ are preferably the above-described (R1-1) to (R1-83), more preferably (R1-1) to (R1-77), and (R1 -1) to (R1-37) are particularly preferable. By setting it as the said structure, the intensity | strength of a film is high and an external appearance becomes favorable.
n3 is preferably an integer of 3 to 10, more preferably an integer of 3 to 8, and still more preferably an integer of 3 to 6.

The divalent organic group represented by R ³² includes carbon and hydrogen as essential elements, and is composed of an element selected from the group consisting of oxygen, nitrogen, halogen, phosphorus, sulfur, silicon and boron as an optional element. It is preferably a divalent organic group, and is a divalent organic group composed of elements selected from the group consisting of oxygen, nitrogen, halogen, phosphorus, and sulfur as essential elements, with carbon and hydrogen as essential elements. More preferably, it is more preferably a divalent organic group composed of an element selected from the group consisting of oxygen, nitrogen and sulfur with carbon and hydrogen as essential elements. A divalent organic group composed only of carbon atoms and hydrogen atoms is also preferred.
The divalent organic group represented by R ³² is preferably a residue obtained by removing an NCO group from a compound having two NCO groups.
Specific examples of the divalent organic group represented by R ³² are preferably the aforementioned (R2-1) to (R2-34), more preferably (R2-1) to (R2-25), and (R2 -1) to (R2-8) are more preferable. By setting it as the said structure, the intensity | strength of a film is high and an external appearance becomes favorable.

An adduct-type trifunctional or higher functional isocyanate compound can be synthesized by reacting a compound having three or more active hydrogen groups in a molecule described later with a bifunctional or higher functional isocyanate compound described later. The active hydrogen group means a hydroxyl group, a primary amino group, a secondary amino group, and a mercapto group.
The adduct-type trifunctional or higher functional isocyanate compound is, for example, heated (50 ° C. to 100 ° C.) while stirring a compound having three or more active hydrogen groups in the molecule and a bifunctional or higher functional isocyanate compound in an organic solvent. Or by stirring at a low temperature (0 ° C. to 70 ° C.) while adding a catalyst such as stannous octylate. The trifunctional or higher functional isocyanate compound is prepared by synthesizing an adduct (prepolymer) of a compound having two active hydrogen groups in the molecule and a bifunctional or higher functional isocyanate compound. It can also be obtained by reacting a compound having an active hydrogen group.

Generally, the number of moles (number of molecules) of a bifunctional or higher functional isocyanate compound to be reacted with a compound having three or more active hydrogen groups in the molecule is the active hydrogen group in the compound having three or more active hydrogen groups in the molecule. A bifunctional or higher functional isocyanate compound having a mole number (number of molecules) of 0.6 times or more is used with respect to the number of moles (equivalent number of active hydrogen groups). The number of moles of the bifunctional or higher functional isocyanate compound is preferably 0.6 to 5 times, more preferably 0.6 to 3 times, more preferably 0.8 to 2 times the number of moles of the active hydrogen group. preferable.

Specific examples of adduct-type trifunctional or higher functional isocyanate compounds in the present invention are shown in Table 1 below. The present invention is not limited to these. In Table 1, compounds having trifunctional or higher functional active hydrogen groups and diisocyanate compounds are described, and further, molar equivalents at the time of addition reaction of these compounds are described.

The adduct-type trifunctional or higher functional isocyanate compound in the present invention is more preferably NCO102 to NCO105, NCO107, NCO108, NCO111, and NCO113 among the compounds shown in Table 1 above.

As the adduct type trifunctional or higher functional isocyanate compound in the present invention, commercially available products may be used. For example, D-102, D-103, D-103H, D-103M2, P49-75S, D -110, D-120N, D-140N, D-160N (Mitsui Chemicals Co., Ltd.), Death Module (registered trademark) L75, UL57SP (manufactured by Sumika Bayer Urethane Co., Ltd.), Coronate (registered trademark) HL, HX, L (manufactured by Nippon Polyurethane Co., Ltd.), P301-75E (manufactured by Asahi Kasei Co., Ltd.) and the like.
Among these adduct-type trifunctional or higher functional isocyanate compounds, D-110, D-120N, D-140N, and D-160N (manufactured by Mitsui Chemicals, Inc.) are more preferable.

(2) Biuret type or isocyanurate type The biuret type or isocyanurate type trifunctional or higher functional isocyanate compound is preferably a compound represented by the following formula 5 or formula 6.

In Formula 5 and Formula 6, R ⁵¹ to R ⁵³ and R ⁶¹ to R ⁶³ each independently represent a divalent organic group. The divalent organic groups represented by R ⁵¹ to R ⁵³ and R ⁶¹ to R ⁶³ have carbon and hydrogen as essential elements, and as optional elements, oxygen, nitrogen, halogen, phosphorus, sulfur, silicon and boron Preferably, it is a divalent organic group composed of an element selected from the group consisting of carbon and hydrogen as essential elements, and as an optional element selected from an element selected from the group consisting of oxygen, nitrogen, halogen, phosphorus and sulfur More preferably, it is a divalent organic group, more preferably a divalent organic group composed of an element selected from the group consisting of oxygen, nitrogen and sulfur with carbon and hydrogen as essential elements. . A divalent organic group composed only of carbon atoms and hydrogen atoms is also preferred.
The divalent organic group represented by R ⁵¹ to R ⁵³ and R ⁶¹ to R ⁶³ is preferably a residue obtained by removing an NCO group from a compound having two NCO groups.
Specific examples of the divalent organic group represented by R ⁵¹ to R ⁵³ and R ⁶¹ to R ⁶³ are preferably the aforementioned (R2-1) to (R2-34), and (R2-1) to (R2-25) is more preferable, and (R2-1) to (R2-8) are particularly preferable. By setting it as the said structure, the intensity | strength of a film is high and an external appearance becomes favorable.

As the biuret-type trifunctional or higher functional isocyanate compound in the present invention, commercially available products may be used. For example, D-165N, NP1100 (manufactured by Mitsui Chemicals), Desmodur (registered trademark) N3200 (Manufactured by Sumika Bayer Urethane Co., Ltd.), Duranate (registered trademark) 24A-100 (manufactured by Asahi Kasei Co., Ltd.), and the like.
In addition, as the isocyanurate type trifunctional or higher functional isocyanate compound in the present invention, commercially available products may be used. For example, D-127, D-170N, D-170HN, D-172N, D- 177N (manufactured by Mitsui Chemicals), Sumidur N3300, Death Module (registered trademark) N3600, N3900, Z4470BA (manufactured by Sumika Bayer Urethane Co., Ltd.), Coronate (registered trademark) HX, HK (Nippon Polyurethane Co., Ltd.) Manufactured), Duranate (registered trademark) TPA-100, TKA-100, TSA-100, TSS-100, TLA-100, TSE-100 (manufactured by Asahi Kasei Corporation).
Among these biuret-type and isocyanurate-type trifunctional or higher isocyanate compounds, Duranate (registered trademark) 24A-100 (manufactured by Asahi Kasei Co., Ltd.), D-127 (manufactured by Mitsui Chemicals, Inc.), TKA-100, TSE-100 (manufactured by Asahi Kasei Co., Ltd.) is more preferable.

b: Water or a compound having two or more active hydrogen groups The particles (specific particles) in the present invention have the above-described trifunctional or higher functional isocyanate compound or thioisocyanate compound and water or two or more active hydrogen groups. It is preferably produced by reacting a compound.
As a compound to be reacted with a trifunctional or higher functional isocyanate compound, water is generally used. By reacting the trifunctional or higher functional isocyanate compound with water, a three-dimensional crosslinked structure having a urea bond is formed.
In addition to water, a compound having two or more active hydrogen groups is exemplified as a compound to be reacted with a trifunctional or higher functional isocyanate compound. Examples of the compound having two or more active hydrogen groups include 3 in the molecule described above. Examples thereof include compounds having one or more active hydrogen groups and compounds having two active hydrogen groups in the molecule. Examples of the compound having two active hydrogen groups in the molecule include compounds having two groups selected from the group consisting of a hydroxyl group, a primary amino group, a secondary amino group, and a mercapto group in the molecule.

Specific examples of the compound having two active hydrogen groups in the molecule include propylene glycol, 1,4-butanediol, 1,3-butanediol, pinacol, triethylene glycol, dipropylene glycol, and 1,3-cyclohexanediol. N-butyldiethanolamine, diethyl tartrate, N, N′-bis (2-hydroxyethyl) oxamide, 2,2′-sulfonyldiethanol, 1,3-benzenedimethanol, 2-mercaptoethyl ether, 1,3-propane Dithiol, 3-mercapto-1-propanol, hexamethylenediamine, trimethylhexamethylenediamine, 1,3-cyclohexanebis (methylamine), isophoronediamine, 4,4'-methylenebis (cyclohexylamine), ethanolamine, 6-amino - -Hexanol, ethylene glycol bis (2-mercaptoacetate), hydroquinone, resorcinol, 1,5-dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bisphenol A, 2,2-bis (4-hydroxyphenyl) hexafluoropropane 1,3-benzenedimethanethiol, 4,4′-thiodiphenol, 4,4′-thiobisbenzenethiol, 4,4′-methylenedianiline, 4,4′-oxydianiline, and o -Toridine and the like.
These compounds may be used individually by 1 type, and may use 2 or more types together.

c: Polymerizable compound having an active hydrogen group The polymerizable compound having an active hydrogen group is used to introduce a polymerizable group into the three-dimensional crosslinked structure of the particles. For example, (1) when forming a three-dimensional crosslinked structure having at least one type of bond selected from the group consisting of a urethane bond, a thiourethane bond, a dithiourethane bond, a urea bond, and a thiourea bond. (2) a trifunctional or higher functional isocyanate compound or thioisocyanate, a method of reacting an isocyanate compound or a thioisocyanate compound, water, a compound having two or more active hydrogen groups, and a polymerizable compound having an active hydrogen group Is produced by reacting a bifunctional or higher functional isocyanate compound or thioisocyanate compound with a polymerizable compound having an active hydrogen group to form an isocyanate compound or thioisocyanate compound to which a polymerizable group has been added in advance. Reaction with a compound having two or more active hydrogen groups Used in.
Examples of the polymerizable compound having an active hydrogen group include compounds having at least one active hydrogen group and at least one ethylenically unsaturated bond.
The compound having at least one active hydrogen group and at least one ethylenically unsaturated bond can be represented by the following formula a.
L ¹ Lc _m Z _n (a)
In Formula a, L ¹ represents an m + n-valent linking group, m and n are each independently 1 to 100, Lc represents a monovalent ethylenically unsaturated group, and Z represents an active hydrogen group. To express.
L ¹ is a divalent or higher aliphatic group, a divalent or higher aromatic group, a divalent or higher heterocyclic group, —O—, —S—, —NH—, —N <, —CO—, —SO. It is preferably —, —SO ₂ — or a combination thereof.
m and n are each independently preferably from 1 to 50, more preferably from 2 to 20, still more preferably from 3 to 10, and particularly preferably from 3 to 5.
As the monovalent ethylenically unsaturated group represented by Lc, an allyl group, a vinyl group, an acryloyl group, a methacryloyl group, or a vinylphenyl group is preferable, and an acryloyl group or a methacryloyl group is particularly preferable.
Z is preferably OH, SH, NHR (R represents a monovalent organic group) or NH ₂ , more preferably OH or NH ₂ , and still more preferably OH.

Examples of compounds having at least one active hydrogen group and at least one ethylenically unsaturated bond are shown below, but are not limited to this structure.

As the compound having at least one active hydrogen group and at least one ethylenically unsaturated bond in the present invention, a commercially available product may be used. For example, hydroxyethyl acrylate (Osaka Organic Chemical Co., Ltd.) ), 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate (manufactured by Nippon Kasei Co., Ltd.), Bremer AE-90U (polyethylene glycol monoacrylate, n = 2), AE-200 (polyethylene glycol monoacrylate) , N = 4.5), AE-400 (polyethylene glycol monoacrylate, n = 10), AP-150 (polypropylene glycol monoacrylate, n = 3), AP-400 (polypropylene glycol monoacrylate, n = 6), AP-550 Polypropylene glycol monoacrylate, n = 9), AP-800 (polypropylene glycol monoacrylate, n = 13) (manufactured by NOF Corporation), DENACOL ACRYLATE DA-212, DA-250, DA-314, DA-721, Acrylate such as DA-722, DA-911M, DA-920, DA-931 (above, epoxy acrylate, manufactured by Nagase ChemteX Corp.), 2-hydroxyethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PE- 90 (polyethylene glycol monomethacrylate, n = 2), PE-200 (polyethylene glycol monomethacrylate, n = 4.5), PE-350 (polyethylene glycol monomethacrylate, n = 8), PP-1000 (polypropylene glycol model) Methacrylate, nN = 4-6), PP-500 (polypropylene glycol monomethacrylate, n = 9), PP-800 (polypropylene glycol monomethacrylate, n = 13) (manufactured by NOF Corporation), 2 -Hydroxyethyl acrylamide (manufactured by KJ Chemicals).
Among these compounds having at least one active hydrogen group and at least one ethylenically unsaturated bond, hydroxyethyl acrylate, BLEMMER AE-90U, AE-200, AE-400, AP-150, AP-400, AP- 550, AP-800, DENACOL ACRYLATE DA-212, DA-250, DA-314, DA-721, DA-722, DA-911M, DA-920, DA-931,2-hydroxyethyl methacrylate, BLEMMER PE-90 , PE-200, PE-350, PP-1000, PP-500, PP-800 and other methacrylates, preferably 2-hydroxyethylacrylamide, hydroxyethyl acrylate, Blemmer AE-90U, AE-200, AE-400, AP -15 AP-400, AP-550, AP-800, 2-hydroxyethyl methacrylate, BLEMMER PE-90, PE-200, PE-350, PP-1000, PP-500, PP-800 and other methacrylates, 2-hydroxy Ethylacrylamide is more preferable, 2-hydroxyethyl methacrylate, methacrylates such as Bremer PE-90, PE-200, PE-350, PP-1000, PP-500, PP-800, and 2-hydroxyethylacrylamide are particularly preferable.

d: Polymerizable isocyanate compound The polymerizable isocyanate compound includes, for example, an isocyanate group of the above-described trifunctional or higher isocyanate compound, at least one active hydrogen group, and at least one ethylenic group as shown in Synthesis Scheme 3 below. It can be prepared by reacting an active hydrogen group of a compound having an unsaturated bond.

Among the synthetic scheme 3, X ⁷¹ represents a n7 monovalent organic group, Z ⁷¹ represents O or NH, R ⁷¹ represents a hydrogen atom or a methyl group, X ⁷² represents a divalent organic group. n7 represents an integer of 3 or more.

As the polymerizable isocyanate compound in the present invention, any of the above compounds can be suitably used, but at least one active hydrogen group and at least one ethylenically unsaturated bond are combined in the combinations shown in Table 2 below. It is preferable to use a compound obtained by reacting a compound having a compound (indicated as a polymerizable group-introducing monomer in Table 2) with a trifunctional or higher functional isocyanate compound (indicated in Table 2 as polyisocyanate).

In the table, “active hydrogen group / NCO group” represents the molar ratio of the active hydrogen group in the polymerizable group-introduced monomer to the NCO group in the polyisocyanate.

In Table 2, DA-212 and DA-920 are the following compounds.

These trifunctional or higher functional isocyanate compounds may be used singly or in combination of two or more.
These compounds having at least one active hydrogen group and at least one ethylenically unsaturated bond may be one kind or a combination of two or more kinds.
A compound having an isocyanate group, at least one active hydrogen group and at least one ethylenically unsaturated bond of a tri- or higher functional isocyanate compound (indicated as polyisocyanate in Table 2) (indicated as a polymerizable group-introducing monomer in Table 2) The active hydrogen group is preferably reacted in an amount such that the number of moles of active hydrogen groups / the number of moles of isocyanate groups = 0.01 to 0.3, preferably in an amount of 0.02 to 0.25. It is more preferable that the reaction is carried out in an amount of 0.03 to 0.2.
The compound obtained by the reaction of the trifunctional or higher functional isocyanate compound and the compound having at least one active hydrogen group and at least one ethylenically unsaturated bond has an average functional group number of isocyanate groups in the compound of 3 or less. Although a trifunctional or higher functional isocyanate group is contained in the compound, a three-dimensional crosslinked structure can be formed when the particles are produced.

e: Polymerizable compound The polymerizable compound is a compound used in (3) of the method for introducing a polymerizable group into particles, and the polymerizable compound is present inside the particles (voids of a three-dimensional cross-linked structure). It is a compound used when manufacturing this particle | grain. The polymerizable compound present inside the particles is also referred to as “encapsulated polymerizable compound”. As said compound, polymeric compounds other than the polymeric compound which has the above-mentioned active hydrogen group are mentioned.
As these polymerizable compounds, known polymerizable compounds can be used. As the above compound, a compound having an acryloyl group, a methacryloyl group, a vinylphenyl group, a vinyl group, and / or an allyl group as a polymerizable group is preferable, and an acryloyl group, a methacryloyl group, a vinylphenyl group, and / or a vinyl group. A compound having an acryloyl group and / or a compound having a methacryloyl group ((meth) acrylate compound) is particularly preferable.
As the polymerizable compound used in the present invention, any compound having at least one polymerizable group in the molecule can be suitably used.
The polymerizable compound used in the present invention may be any one having a chemical form such as a monomer, an oligomer, or a polymer.

The CLogP value of the polymerizable compound used in the present invention is preferably 0 or more. By using the compound having the CLogP value, it is possible to keep the compound in the particle during the production of the particle. Here, the CLogP value is an estimated value of a water / octanol partition coefficient, and is a value calculated by Chem Bio Draw Ultra Version 12.0.2.1076 (manufactured by Cambridge Soft).

The boiling point of the polymerizable compound used in the present invention is preferably 130 ° C or higher, more preferably 140 ° C or higher, and further preferably 150 ° C or higher. By using the compound having the above boiling point, it is possible to suppress volatilization at the time of particle production and storage of particles and cosmetics. The upper limit of the boiling point of the polymerizable compound is not particularly limited.

Specific examples of the polymerizable compound used in the present invention include butoxyethyl acrylate, ethyl carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, tridecyl acrylate, 2-phenoxyethyl acrylate, bis (4-acryloxy) Polyethoxyphenyl) propane, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate (for example, A-TMPT manufactured by Shin-Nakamura Chemical Co., Ltd.), ditrimethylolpropane tetraacrylate (for example, Shin-Nakamura Chemical Co., Ltd. AD-TMP), dipentaerythritol hexaacrylate, diacetone acrylic And acrylate compounds such as isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, neopentyl glycol propylene oxide adduct diacrylate (NPGPODA); n-butyl methacrylate, allyl methacrylate, Examples thereof include benzyl methacrylate, dimethylaminomethyl methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, and methacrylate compounds such as 2,2-bis (4-methacryloxypolyethoxyphenyl) propane.
Among these (meth) acrylate compounds, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, and / or neopentyl glycol propylene oxide adduct diacrylate are preferable.
The inclusion polymerizable compound is preferably a polyfunctional polymerizable compound, more preferably a trifunctional or higher functional polymerizable compound, and even more preferably a tetrafunctional or higher functional polymerizable compound from the viewpoint of crosslinkability and film strength. The inclusion polymerizable compound is preferably a methacrylate compound or an acrylate compound.
The encapsulated polymerizable compound used in the present invention is preferably a (meth) acrylate compound, more preferably a trifunctional or higher functional (meth) acrylate compound, and even more preferably a trifunctional or higher functional acrylate compound.

In addition to the encapsulated polymerizable compounds listed above, Shinzo Yamashita, “Crosslinker Handbook”, (1981 Taiseisha); Kiyoto Kato, “UV / EB Curing Handbook (raw material)” (1985, Polymer Publications); Radtech Study Group, “Application and Market of UV / EB Curing Technology”, 79 pages, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo) Commercially available products described in newspapers) or the like, or radically polymerizable or crosslinkable monomers, oligomers and polymers known in the industry can be used.
Examples of the encapsulating polymerizable compound include, for example, JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-9-134011, and JP-T-2004. Photocurable polymerizable compounds used in the photopolymerizable composition described in each publication such as 5114014 are known, and these can also be applied to the particles in the present invention.

In addition, as the encapsulated polymerizable compound, commercially available products may be used. For example, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G DAUA-167 (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-6300B, UV-7550B, UV7600B, UV-7605B, UV-7620EA, UV-7630B, UV-7650B, UV-7650B, UV-6630B , UV7000B, UV-7510B, UV-7461TE, UV-2000B, UV-2750B, UV-3000B, UV-3200B, UV-3210EA, UV-3300B, UV-3310B, UV-3500BA, UV-3520TL, UV-3700B , UV-6640B ( Urethane acrylate such as SR415, SR454, SR492, SR499, CD501, SR502, SR9020, CD9021, SR9035, SR494 (manufactured by Sartomer) and the like, A-9300 And isocyanuric monomers such as A-9300-1CL (manufactured by Shin-Nakamura Chemical Co., Ltd.).

The encapsulated polymerizable compound in the present invention is prepared by dissolving the encapsulated polymerizable compound as an oil phase component together with the components constituting the particle, and adding, mixing, and emulsifying the water phase component to the oil phase component. And can be contained inside the particles.

The molecular weight of the encapsulated polymerizable compound in the present invention is preferably 100 to 100,000, more preferably 200 to 30,000, and still more preferably 250 to 10,000 as a weight average molecular weight. .
In the total solid content of the particles (specific particles) in the present invention, the content of the encapsulating polymerizable compound is preferably 0.1% by mass to 75% by mass, more preferably 0.5% by mass to 60% by mass. More preferably, it is 1% by mass to 50% by mass. By setting the content in the above range, a cured film having good crosslinkability and strength can be obtained.
These polymerizable compounds may be used alone or in combination of two or more.

f: Photopolymerization initiator The particles (specific particles) in the present invention contain at least one photopolymerization initiator inside the particles (voids having a three-dimensional crosslinked structure). Hereinafter, the photopolymerization initiator included in the particles of the specific particles is also referred to as “encapsulated photopolymerization initiator”.
When the particles contain a photopolymerization initiator inside, the sensitivity to active energy rays is increased, and a film having excellent strength can be obtained. In addition, since the particle contains a photopolymerization initiator inside, it is possible to use a photopolymerization initiator that has been conventionally difficult to use because of its high sensitivity but low dispersibility or low solubility in water. Compared with conventional nail cosmetics, a highly sensitive nail cosmetic can be realized.
As the photopolymerization initiator contained in the particles (hereinafter also referred to as an encapsulated photopolymerization initiator), a known photopolymerization initiator may be appropriately selected and used according to the purpose of use of the nail cosmetic. Can do.
The encapsulated photopolymerization initiator is a compound that absorbs active energy rays and generates radicals that are polymerization initiation species. Examples of active energy rays include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays. Among these, ultraviolet rays and / or visible rays are preferably used as active energy rays.

As the encapsulated photopolymerization initiator, known compounds can be used, but preferred encapsulated photopolymerization initiators usable in the present invention include the following compounds.
Acetophenone derivatives (eg, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 1- [ 4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, benzoin methyl ether, etc.);
Benzophenone derivatives (for example, 4,4′-bis (dimethylamino) benzophenone, 3,3-dimethyl-4-methoxy-benzophenone, etc.);
Anthraquinone derivatives (eg, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, tert-butylanthraquinone, etc.);
Thioxanthone derivatives (for example, 2-chlorothioxanthone, diethylthioxanthone, isopropylthioxanthone, diisopropylthioxanthone, etc.);
Trihaloalkyl compounds (eg, 2,4,6- (trichloromethyl) triazine, 2,4-trichloromethyl-6- (4-methoxyphenyl) triazine, tribromomethylphenylsulfone, etc.);
Lophine dimer derivatives (eg 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer);
Acridine derivatives (eg, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, 1,3-bis (9-acridinyl) pronopane);
Phosphine oxide derivatives (eg, trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide);
Metallocene derivatives (eg biscyclopentadienylbis (difluoropyrylphenyl) titanium, etc.);
Onium salts (for example, bis (4-tert-butylphenyl) iodonium tosylate, triphenylsulfonium tosylate, etc.).

The photopolymerization initiator can be appropriately selected according to the wavelength of light emitted from the light source used for exposure. Derivatives are preferred, and acetophenone derivatives, benzophenone derivatives, thioxanthone derivatives, and / or phosphine oxide derivatives are more preferred.
These photopolymerization initiators may use the above compounds alone or in combination of two or more.

The encapsulated photopolymerization initiator in the present invention, when producing particles, dissolves the encapsulated photopolymerization initiator as an oil phase component together with the components constituting the particles, and adds, mixes, and emulsifies the water phase component to the oil phase component. By doing so, it can be included inside the particles. Accordingly, the ClogP value of the photopolymerization initiator is preferably 0 or more.

The content of the encapsulated photopolymerization initiator in the present invention is preferably 0.1% by mass to 25% by mass, more preferably 0.5% by mass to 20% by mass with respect to the total mass of the specific particles. The content is preferably 1% by mass to 15% by mass.

g: Compound having a dispersion-stable group The particles (specific particles) in the present invention preferably have a dispersion-stable group on the surface.
The particles have a dispersion-stable group on the surface thereof, so that the dispersibility in the medium is further improved. Therefore, the dispersibility of the particles in the nail cosmetic can be further improved.
Examples of the dispersion-stable group added to the surface of the particle include a group having a polyether structure and an ionic group, and examples of the ionic group include a carboxylic acid (salt) group, a phosphonic acid (salt) group, Examples thereof include a phosphoric acid (salt) group, a sulfonic acid (salt) group, a sulfuric monoester (salt) group, and a group having a betaine structure.
Moreover, a dispersion stability group may be used individually by 1 type, and may use 2 or more types together.
The dispersion stability group added to the surface of the particle is more preferably at least one of a group having a polyether structure and a carboxylic acid group.

The addition of the dispersion stability group to the surface of the particle is performed by reacting the above-described trifunctional or higher functional isocyanate compound and the above-described compound having two or more active hydrogen groups with the compound having the dispersion stability group. Can be done. Further, when the above-described trifunctional or higher functional isocyanate compound is produced, the bifunctional or higher functional isocyanate compound is reacted with a compound having a dispersion stability group, and the above-described isocyanate compound having a dispersion stability group added in advance is described. It can also be performed by reacting with a compound having two or more active hydrogen groups.
Examples of the compound having a dispersion stability group used for addition of the dispersion stability group to the surface of the particle include compounds having the above dispersion stability group.

As the compound having a dispersion stability group, a compound having a group having a polyether structure and a compound having a carboxylic acid group are preferable.
Examples of the compound having a group having a polyether structure include a compound having a polyoxyalkylene chain. Specific examples include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polystyrene oxide, polycyclohexylene oxide, polyethylene oxide-polypropylene oxide-block copolymer, polyethylene oxide-polypropylene oxide random copolymer, and the like.
Among these compounds having a polyoxyalkylene chain, polyethylene oxide, polypropylene oxide, and polyethylene oxide-polypropylene oxide block copolymers are preferable, and polyethylene oxide is more preferable.
Examples of the compound having a group having a polyether structure include polyethylene oxide monoethers (monoethers include monomethyl ether, monoethyl ether, etc.), polyethylene oxide monoesters (monoesters include monoesters). Acetic acid ester, mono (meth) acrylic acid ester, etc. are mentioned).

Specific examples of the compound having a carboxylic acid group or other ionic dispersion stability group include the following. The compound having a carboxylic acid group or other ionic dispersion-stable group may be partially neutralized with an inorganic salt machine such as sodium hydroxide and an organic base such as triethylamine.

When using an isocyanate compound with a dispersion stability group added to the surface of the particles, trimethylolpropane (TMP), xylene diisocyanate (XDI), and polyethylene glycol monomethyl ether (EO) are added. Adduct (Mitsui Chemicals, Takenate (registered trademark) D-116N) and / or reaction product of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and isophorone diisocyanate (IPDI) (carvone It is preferable to use an isocyanate compound containing an acid group.

The amount of the compound having a dispersion-stable group used for addition of the dispersion-stable group to the surface of the particle is preferably 0.1% by mass to 40% by mass with respect to the mass of the particle, and 1% by mass to 35% by mass. Is more preferable, and 3% by mass to 30% by mass is even more preferable.

~ Particle manufacturing method ~
The method for producing the specific particles in the present invention is not particularly limited, but the trifunctional or higher functional isocyanate compound and / or the thioisocyanate compound (or the trifunctional or higher functional isocyanate compound to which a polymerizable group is added and / or the oil phase component). Thioisocyanate compound), a photopolymerization initiator, and optionally a polymerizable compound, using water or a compound having two or more active hydrogen groups as the aqueous phase component, and preparing an oil phase component and an aqueous phase component, It can manufacture by performing well-known operation applied to the manufacturing method of the general polymer fine particle which mixes both and produces an emulsified dispersion.
As described above, as a method for introducing a polymerizable group into particles, (1) a method using a polymerizable compound having an active hydrogen group when forming a three-dimensional cross-linked structure, and (2) preliminarily polymerizable. Examples thereof include a method using an isocyanate compound or a thioisocyanate compound to which a group is added, and (3) a method using a polymerizable compound together with components constituting the particles, and any of these may be selected.
Specifically, the trifunctional or higher functional isocyanate compound and / or thioisocyanate compound (or trifunctional or higher functional isocyanate compound and / or thioisocyanate compound to which a polymerizable group is added) as described above as an oil phase component, photopolymerization. Prepare an oil phase component and an aqueous phase component using an initiator and, if necessary, a polymerizable compound, water as an aqueous phase component, mix both, and prepare an emulsified dispersion using an emulsifier such as a homogenizer. By removing the organic solvent by heating or the like, an aqueous dispersion containing particles can be obtained. In this case, the isocyanate groups (and / or thioisocyanate groups) are cross-linked by the reaction of the isocyanate groups (and / or thioisocyanate groups) of the trifunctional or higher functional isocyanate compound (and / or thioisocyanate compound) with water. Having a three-dimensional cross-linking structure including at least one bond selected from the group consisting of a urethane bond, a thiourethane bond, a dithiourethane bond, a urea bond, and a thiourea bond, and a polymerizable group. Particles containing a polymerization initiator are formed.
In the present invention, preferred embodiments of particle formation include (1) an oil phase component containing a trifunctional or higher functional isocyanate compound to which a polymerizable group is added and a photopolymerization initiator, and water as an aqueous phase component. (2) A method of using a trifunctional or higher functional isocyanate compound to which a polymerizable group has been added, a polymerizable compound, and an oil phase component containing a photopolymerization initiator, and water as an aqueous phase component, (3 ) Preferred examples include a trifunctional or higher functional isocyanate compound, a polymerizable compound, and an oil phase component containing a photopolymerization initiator and water as the aqueous phase component. In the above (1) to (3), it is preferable that the oil phase component further contains an isocyanate compound to which a dispersion stability group has been added. The isocyanate group reacts with water to produce an amine, and the produced amine reacts with the isocyanate group to form a urea bond.

Three-dimensionally crosslinked particles having at least one bond selected from the group consisting of a urethane bond, a thiourethane bond, a dithiourethane bond, a urea bond, and a thiourea bond by reaction with an isocyanate group and / or a thioisocyanate group In addition to water, the above-mentioned polyfunctional alcohols, polyfunctional phenols, polyfunctional amines having a hydrogen atom on the nitrogen atom, polyfunctional thiols, and the like are used as the compound that forms.
These compounds may be used individually by 1 type, and may use 2 or more types together.
Specifically, polyfunctional alcohols such as water, propylene glycol, glycerin and trimethylolpropane, polyfunctional amines such as bis (hexamethylene) triamine, ethylenediamine and diethylenetriamine, and pentaerythritol tetra (3-mercaptopropionate) And polyfunctional thiol.
Among these, it is preferable to use water and / or a polyfunctional alcohol from the viewpoint of production stability, and it is more preferable to use water.

In addition, during the production of the particles in the present invention, the above trifunctional or higher functional isocyanate compound and / or the trifunctional or higher functional thioisocyanate compound, water, polyfunctional alcohol, polyfunctional phenol, polyfunctional amine having a hydrogen atom on the nitrogen atom, In addition to the polyfunctional thiol, it is preferable to include a compound having the dispersion stability group described above. By including a compound having a dispersion-stable group as a raw material during the production of the particles, the dispersion-stable group can be added to the surface of the particles.

In the production of the particles in the present invention, in addition to the above raw materials, a dispersant, a surfactant and the like may be added. The dispersant and the surfactant are added to the oil phase component and / or the aqueous phase component depending on the solubility thereof.
In the production of the particles in the present invention, it is preferable to add a surfactant in order to improve the stability of the emulsified dispersion. The surfactant may be added to either the oil phase or the aqueous phase, but it is usually preferable to add it to the aqueous phase because of its low solubility in organic solvents. The addition amount is preferably 0.1% by mass to 5% by mass and more preferably 0.5% by mass to 3% by mass with respect to the total solid content of the oil phase. In general, surfactants used for emulsification and dispersion are considered to be excellent surfactants having a relatively long-chain hydrophobic group. For example, “Surfactant Handbook” (Nishiichiro et al., Published in industrial books (1980)). ), Specifically, alkali metal salts such as alkyl sulfates, alkyl sulfonic acids, and alkyl benzene sulfonic acids can be used. In the present invention, alkyl sulfate salts are preferred.

-Physical properties of particles-
The average particle diameter of the specific particles is preferably 0.01 μm to 10.0 μm from the viewpoint of dispersibility, more preferably 0.01 μm to 5 μm, and still more preferably 0.05 μm to 1 μm.
The average particle diameter of the particles can be measured by a light scattering method. The average particle diameter in this specification is a value measured by LA-910 (manufactured by Horiba, Ltd.).

The specific particles are preferably contained in the nail cosmetic from 1% by mass to 90% by mass, more preferably from 3% by mass to 85% by mass from the viewpoint of dispersibility and crosslinkability, and more preferably 5% by mass. More preferably, the content is from 80% to 80% by mass.
The content of the particles is a value including a compound such as a photopolymerization initiator existing inside the particles (voids having a three-dimensional crosslinked structure).
The particles (specific particles) used in the nail cosmetic of the present invention may be added to the nail cosmetic in the form of an aqueous solution after production. After the production, water is removed by evaporation to obtain a particle aqueous solution having a desired concentration. It may be added to the material. In addition, after the production, water may be completely removed by evaporation or centrifugation, and then added to the nail cosmetic and redispersed.

(Other ingredients)
Next, components other than the specific particles used in the nail cosmetic of the present invention will be described.
A: Photopolymerization initiator In the nail cosmetic of the present invention, a photopolymerization initiator may be added to the outside of the specific particles in addition to the photopolymerization initiator contained in the specific particles. As said photoinitiator, the thing similar to the above-mentioned photoinitiator (encapsulated photoinitiator) is mentioned.

B: Polymer and / or oligomer In the nail cosmetic of the present invention, a polymer and / or oligomer may be added outside the specific particles.
The weight average molecular weight of the polymer and / or oligomer used in the nail cosmetic of the present invention is preferably 2,000 or more and 300,000 or less, more preferably 3,000 or more and 200,000 or less. Is more preferably from 5,000 to 150,000, and particularly preferably from 5,000 to 100,000. It is excellent in the adhesiveness and temporal stability of the hardened | cured material as it is the said range.
The weight average molecular weight (Mw) of the polymer and oligomer in the present invention is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
There is no restriction | limiting in particular about the structure of the said polymer and / or oligomer, What is necessary is just an arbitrary structure. Examples thereof include a chain structure, a branched (branched) structure, a star structure, a crosslinked structure, and a network structure.
The type of the polymer and / or oligomer is not particularly limited, and known polymer species (poly (meth) acrylic acid ester, poly (meth) acrylic acid amide, polyurethane, polyester, polyether, polyurea, polycarbonate, polyamide, Polystyrene, polyolefin, polyvinyl alcohol, polyvinyl butyral, vinyl resin, etc.) can be used.
The polymer and / or oligomer preferably has an ethylenically unsaturated group capable of radical polymerization.

Among the above polymers and / or oligomers, polymers and / or oligomers having a structure represented by the following formula A are preferable, and polymers and / or oligomers having a structure represented by formula A in the polymer main chain. It is particularly preferred. By having this structure, adhesion is particularly excellent.

In formula A, the wavy line represents the position of coupling with another structure.

Specific examples (P-16 to P-22) of polymers and / or oligomers used in the present invention are shown below. The present invention is not limited to these.

In the above table, Unit-1 to Unit-5 indicate the isocyanate compound used in the synthesis of the polymer, the compound having an active hydrogen group, and the like, and the polymerization reaction is performed so that the respective molar ratios are obtained. Went.
The abbreviations in the table are as follows.
TDI: Tolylene diisocyanate Diol-9: 2,2-bis (4-hydroxycyclohexyl) propane Diol-5: Polytetrabutylene glycol (Mw: 2,000)
HEMA: 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate MDI: bis (4-isocyanatophenyl) methane HDI: hexamethylene diisocyanate Diol-6: polypropylene glycol (Mw: 1,000)
Diol-10: Glycerin monomethacrylate MMA: Methyl methacrylate BMA: n-Butyl methacrylate ADPA: Adipic acid dichloride Nitrocellulose: DHX40-70 (manufactured by Inabata Sangyo Co., Ltd.)
Diamin-2: Polypropylene glycol diamine (Mw: 2,000)

The polymer and / or oligomer used in the present invention is preferably a polymer and / or oligomer having an amino group. As the amino group, any of primary, secondary, and tertiary amino groups can be used. From the viewpoint of ease of production of the polymer and / or oligomer, adhesion and removability, and stability over time. A tertiary amino group is preferred.
The amino group in the polymer and / or oligomer may be introduced at any of the side chain, inside the main chain, and at the end of the main chain, and may be introduced at two or more positions.
The amino group is preferably a group represented by the following formulas B and C.

In Formula B, R ^b1 and R ^b2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, L ^b1 represents a single bond or a divalent linking group, R ^b1 , R ^b2 , and At least two members selected from the group consisting of L ^b1 may be connected to each other to form a ring, and the wavy line portion represents a bonding position with another structure.
In formula C, R ^c1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, L ^c1 and L ^c2 each independently represents a single bond or a divalent linking group, R ^c1 , L ^c1 , And at least two members selected from the group consisting of L ^c2 may be linked to each other to form a ring, and the wavy line portion represents a bonding position with another structure.

R ^b1 and R ^b2 in Formula B are preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 6 carbon atoms from the viewpoint of the balance between solubility in an aqueous acid solution and water resistance. The alkyl group having 1 to 4 carbon atoms is more preferable, and the alkyl group having 1 to 2 carbon atoms is particularly preferable.
Specific examples of L ^b1 in Formula B include a single bond, an alkylene group having 1 to 20 carbon atoms (which may have a substituent, and part of the carbon atoms may be replaced by a hetero atom), carbon number And an arylene group having 6 to 20 (which may have a substituent and a part of carbon atoms may be replaced by a heteroatom), a single bond, an alkylene group having 1 to 20 carbon atoms, a carbon number of 2 It is preferably an oxyalkylene group having 20 to 20 carbon atoms or a polyoxyalkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms or a polyoxyalkylene group having 2 to 20 carbon atoms. An alkylene group having 1 to 20 carbon atoms is particularly preferable, and an alkylene group having 1 to 10 carbon atoms is most preferable.
In the formula B, at least two selected from the group consisting of R ^b1 , R ^b2 and L ^b1 may be connected to each other to form a ring.

In formula C, R ^c1 is preferably an alkyl group having 1 to 10 carbon atoms, and preferably an alkyl group having 1 to 6 carbon atoms, from the viewpoint of the balance between solubility in an aqueous acid solution and water resistance. More preferred is an alkyl group having 1 to 4 carbon atoms.
In formula C, specific examples of L ^c1 and L ^c2 include a single bond and an alkylene group having 1 to 20 carbon atoms (which may have a substituent, and some of the carbon atoms may be replaced with a hetero atom. ), An arylene group having 1 to 20 carbon atoms (which may have a substituent, and part of the carbon atoms may be replaced by a hetero atom), a single bond, an alkylene group having 1 to 20 carbon atoms And preferably an oxyalkylene group having 2 to 20 carbon atoms or a polyoxyalkylene group having 2 to 20 carbon atoms, preferably an alkylene group having 1 to 20 carbon atoms or a polyoxyalkylene group having 2 to 20 carbon atoms. More preferred is an alkylene group having 1 to 20 carbon atoms, and most preferred is an alkylene group having 1 to 10 carbon atoms.
In formula C, at least two selected from the group consisting of R ^c1 , L ^c1 and L ^c2 may be linked to each other to form a ring.

The amine value of the polymer and / or oligomer used in the present invention is preferably 0.1 to 10 mmol / g, more preferably 0.25 to 9 mmol / g, and 0.5 to 8 mmol / g. More preferably it is. It is excellent in adhesiveness and removability as it is the said range. As a method for measuring the amine value, for example, a sample is placed in a beaker, acetic acid is added, and the mixture is stirred and dissolved. And can be obtained by titrating with a titration apparatus. The amine value is the amount of perchloric acid consumed when titrated, expressed as the number of moles per gram of sample (solid content).

Specific examples of the polymer and / or oligomer having an amino group used in the present invention are shown below. The present invention is not limited to these. The polymers and / or oligomers in the table are obtained by polymerizing the compounds shown in the units in the table at the molar ratio in the table.

Each component in the table is as follows.
IPDI: isophorone diisocyanate TDI: tolylene diisocyanate HDI: hexamethylene diisocyanate MDI: bis (4-isocyanatophenyl) methane Diol-1: 3-dimethylamino-1,2-propanediol Diol-2: as diol monomer Polycarbonate diol using 1,5-pentanediol and 1,6-hexanediol (Mw: 2,000)
Diol-3: N-butyldiethanolamine Diol-4: 1,5-pentanediol Diol-5: Polytetrabutylene glycol (Mw: 2,000)
Diol-6: Polypropylene glycol (Mw: 1,000)
Diol-7: 3-diethylamino-1,2-propanediol Diol-8: 1,4-butanediol Diamin-1: 3,3-diamino-N-methyldipropylamine Diamine-2: polypropylene glycol diamine (Mw: 2,000)
ADPA: adipic acid dichloride DMAPAm: 3-dimethylaminopropyl acrylamide CHAm: N-cyclohexyl acrylamide DMAEM: 2-dimethylaminoethyl methacrylate BMA: n-butyl methacrylate HEMA: 2-hydroxyethyl methacrylate IPA: 2-hydroxypropane DMPA: 3- Dimethylaminopropylamine

As the polymer and / or oligomer used in the present invention, a water-soluble polymer and / or oligomer can also be suitably used. The water-soluble polymer and / or oligomer is preferably a polymer and / or oligomer that dissolves by 0.1 g or more with respect to 100 g of distilled water, more preferably a polymer and / or oligomer that dissolves by 0.2 g or more, and 0.5 g or more. Soluble polymers and / or oligomers are particularly preferred. By having water solubility in the above range, it becomes easy to produce nail cosmetics using water.
Examples of the water-soluble polymer and / or oligomer used in the present invention include a carboxylic acid (salt) group, a sulfonic acid (salt) group, a phosphoric acid (salt) group, a phosphonic acid (salt) group, a quaternary ammonium base, and a hydroxyl group. , A polymer and / or an oligomer having a functional group selected from the group consisting of a carboxylic acid amide group and a polyethylene glycol chain. The counter cation of the carboxylic acid (salt) group, sulfonic acid (salt) group, phosphoric acid (salt) group, phosphonic acid (salt) group is an alkali metal cation such as sodium or potassium, or an alkaline earth such as calcium or magnesium. Metal cations, ammonium cations, or phosphonium cations are preferred, and alkali metal cations such as sodium and potassium are particularly preferred. The alkyl group of the ammonium group of the quaternary ammonium base is preferably a methyl group or an ethyl group. The counter anion is preferably a halide ion such as chloride ion or bromide ion, sulfate anion, nitrate anion, phosphate anion, sulfonate anion, carboxylate anion, carbonate anion, halide ion, sulfonate anion, Carboxylic acid anions are particularly preferred. The substituent on the nitrogen atom of the carboxylic acid amide group is preferably an alkyl group having 8 or less carbon atoms, and particularly preferably an alkyl group having 6 or less carbon atoms. The connecting chain length (the number of repeating ethyleneoxy units) of the polyethylene glycol chain is preferably 2 or more, and particularly preferably 4 or more.

Specific examples of the water-soluble polymer and / or oligomer used in the present invention are shown below. The present invention is not limited to these. The polymers and / or oligomers in the table are obtained by polymerizing the compounds shown in the units in the table at the molar ratio in the table.

Each component in the table is as follows. Further, in the polymer represented by the formula (P-25), the suffix of the constitutional repeating unit indicates the molar ratio.
MDI: Bis (4-isocyanatophenyl) methane Diol-6: Polypropylene glycol (Mw: 1,000)
Diol-11: 2,2-bis (hydroxymethyl) propionic acid Na
Diol-10: Glycerin monomethacrylate TDI: Tolylene diisocyanate Diol-12: Polyethylene glycol (Mw: 2,000)
Diol-9: 2,2-bis (4-hydroxycyclohexyl) propane HEMA: 2-hydroxyethyl methacrylate

The polymer and / or oligomer used in the present invention can be produced by a known method (eg, radical polymerization, polycondensation, etc.).
These polymers and / or oligomers may be used alone or in combination of two or more.
The content of the polymer and / or oligomer in the nail cosmetic used in the present invention is preferably 0 to 90% by mass, more preferably 5 to 80% by mass, and particularly preferably 10 to 70% by mass. In this range, the adhesion and removability of the cured product are improved.

C: Polymerizable compound In the nail cosmetic of the present invention, a polymerizable compound may be added to the outside of the particle in addition to the polymerizable compound contained in the particle. Examples of the polymerizable compound include compounds having an ethylenically unsaturated group, acrylonitrile, styrene, and various radically polymerizable compounds such as various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes. Among these, a compound having an ethylenically unsaturated group is preferable, and a compound having a (meth) acryl group is particularly preferable.

One of the ethylenically unsaturated compounds used in the present invention is a radically polymerizable monomer having an amino group. As the amino group, any of primary, secondary, and tertiary amino groups can be used, but it is a tertiary amino group from the viewpoint of temporal stability, adhesion and removability of the radical polymerizable monomer. It is preferable.
The amino group is preferably a group represented by the following formula B or C.

Among radical polymerizable monomers having an amino group, a radical polymerizable monomer having a structure represented by the following formula A is more preferable. By having this structure, adhesion and removability with an aqueous solution are particularly excellent.

Specific examples of the radical polymerizable monomer having an amino group used in the present invention include 2-dimethylaminoethyl methacrylate, 3-dimethylaminopropyl acrylamide, 2-diethylaminoethyl methacrylate, 4-dimethylaminomethylstyrene, N-butylbis ( 2-methacryloyloxyethyl) amine, 1,2,2,6,6-pentamethyl-4-piperidine methacrylate and the like. However, the present invention is not limited to these.

Another example of the ethylenically unsaturated compound used in the present invention is a radical polymerizable monomer having no amino group. Specific examples of the radical polymerizable monomer having no amino group include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Monofunctional (meth) acrylic acid esters such as 2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylamide, N, N-dimethylacrylamide, N , N-diethylacrylamide, isopropylacrylamide, morpholineacrylamide, and other monofunctional (meth) acrylamides; N-vinylpyrrolidone, N-vinylcaprolactam, and other N-vinylamides; styrene, 4-acetoxystyrene Styrenes such as 4-carboxystyrene; ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cardo Polyfunctional (meth) acrylic acid esters such as epoxy di (meth) acrylate and neopentyl glycol di (meth) acrylate; N- [Tris (3-acryloyl (Minopropyloxymethylene) methyl] acrylamide, polyfunctional (meth) acrylamides such as diethylene glycol bis (3-acryloylaminoproyl) ether; urethane (meta) containing diisocyanate, hydroxyl-containing (meth) acrylic acid derivative and optionally diol ) Acrylate and the like. Among these, radical polymerizable monomers having no amino group are (meth) acrylic acid, N, N-dimethylacrylamide, N, N-diethylacrylamide, morpholine acrylamide, N-2-hydroxyethyl (meth) acrylamide, N -Vinylpyrrolidone, N-vinylcaprolactam, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerin monomethacrylate, N- [tris (3-acryloylaminopropyl) Oxymethylene) methyl] acrylamide, diethylene glycol bis (3-acryloylaminoproyl) ether, polyethylene glycol di (meth) acrylate, or polypropylene glycol di (meth) a Relate is preferably contained, and (meth) acrylic acid, N, N-dimethylacrylamide, N-2-hydroxyethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, glycerol monomethacrylate, N- [tris (3 -Acrylylaminopropyloxymethylene) methyl] acrylamide, diethylene glycol bis (3-acryloylaminoproyl) ether, polyethylene glycol di (meth) acrylate or polypropylene glycol di (meth) acrylate is particularly preferred.

These radical polymerizable monomers may be used alone or in combination of two or more.
The content of the polymerizable compound in the nail cosmetic of the present invention is preferably 0 to 90% by mass, more preferably 5 to 80% by mass, and particularly preferably 10 to 70% by mass. In this range, the adhesion and removability of the cured product are improved.

D: Solvent In the nail cosmetic of the present invention, a solvent may be used for dissolving each component or adjusting the ease of application of the nail cosmetic. Among the solvents, a solvent having a boiling point of 50 to 150 ° C. at 1 atm is preferable, and a solvent having a boiling point of 60 to 140 ° C. is particularly preferable. By using a solvent having a boiling point in the above range, the concentration fluctuation of the nail cosmetic can be suppressed, and drying after application becomes good. Examples of the solvent include water; alcohols such as methanol, ethanol, isopropyl alcohol, 1-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 2-methyl-1-propanol, and 1-methoxy-2-propyl alcohol. Hydrocarbons such as hexane, heptane, toluene and xylene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane and diphenyl ether; esters such as methyl acetate, ethyl acetate, butyl acetate and γ-butyrolactone; acetone , Ketones such as methyl ethyl ketone and cyclohexanone; amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and N-ethylpyrrolidone; dimethyl carbonate, die Carbonates such as carbonate and propylene carbonate; ureas such as tetramethylurea and 1,3-dimethyl-2-imidazolidinone; halogenated hydrocarbons such as chloroform, dichloromethane and chlorobenzene; triethylamine, acetic acid, acetonitrile and nitromethane And known solvents such as dimethyl sulfoxide. Among these solvents, water, methanol, ethanol, isopropyl alcohol, 1-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 2-methyl-1-propanol, 1-methoxy-2-propyl alcohol, acetic acid, And / or acetonitrile is preferable, and water, ethanol, isopropyl alcohol, and / or acetic acid are more preferable. By using the above-mentioned solvent, each component is easily dissolved and / or dispersed, and the production of the nail cosmetic is facilitated.

The content of the solvent in the nail cosmetic of the present invention is preferably 0 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass. In this range, the applicability and drying properties of the nail cosmetic are improved.

E: Others In addition to the above components, known compounds can be added to the nail cosmetic of the present invention as necessary. Specifically, other polymer particles (emulsions, etc.), sensitizing dyes, polymerization inhibitors, pigments, dyes, fragrances, ultraviolet (UV) absorbers, antioxidants, fillers, various elastomers, plasticizers, thickeners , Additives such as thixotropy imparting agent, silane coupling agent, titanate coupling agent, chelating agent, flame retardant, and surfactant.
The nail cosmetic of the present invention can be produced by mixing the above ingredients by a known method. As a combination of each component of the nail cosmetic of the present invention, [Particle], [Particle] + (A), [Particle] + (B), [Particle] + (C), [Particle] + (D), [Particle] + (A) + (B), [Particle] + (A) + (C), [Particle] + (A) + (D), [Particle] + (B) + (C), [Particle] ] + (B) + (D), [Particle] + (C) + (D), [Particle] + (A) + (B) + (D), [Particle] + (A) + (B) + (C), [Particle] + (A) + (C) + (D), [Particle] + (B) + (C) + (D), [Particle] + (A) + (B) + (C ) + (D), [Particle], [Particle] + (B), [Particle] + (C), [Particle] + (D), [Particle] + (B) + (C), [ [Particle] + (B) + (D), [Particle] + (C) + (D), and [Particle] + (B) + (C) + (D) are more preferable. Even when other components are added, they are preferably added to the above combination. This combination facilitates the production of nail cosmetics, improves the applicability, increases the strength of the formed cured film, and improves the sustainability.
In the above, [Particle] represents a specific particle, (A) represents a photopolymerization initiator, (B) represents a polymer and / or oligomer, (C) represents a polymerizable compound, (D) Represents a solvent.

<Nail cosmetic treatment method>
A method for producing nail makeup using the nail cosmetic of the present invention is to apply a nail cosmetic on an object such as a nail, nail cosmetic, or artificial nail by a known method, and then irradiate with light to form a cured product. The method of forming is mentioned.
The method for applying the nail cosmetic of the present invention onto an object is not particularly limited and may be carried out by a known method, but a method using a brush or brush, spray coating, ink jet coating, bar Examples include coater coating, spin coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.
The coating thickness on the object of the nail cosmetic of the present invention varies depending on the application, but is preferably 1 nm to 1 mm, more preferably 10 nm to 0.5 mm, and particularly preferably 100 nm to 0.4 mm. Within this range, good adhesion and removability are realized.
The method of applying light after applying the nail cosmetic of the present invention to an object is not particularly limited, and is a known light source (for example, sunlight, high-pressure mercury lamp, fluorescent lamp, UV lamp, light-emitting diode (LED) lamp, A known light irradiation method using an LED laser or the like (for example, full surface exposure, scanning exposure, etc.) can be used. The light irradiation time is not particularly limited as long as the photocurable composition is cured.
As a method of forming a cured product of the nail cosmetic on the object, the above method can be repeated.

The nail makeup using the nail cosmetic of the present invention can be removed by a known method. Specifically, a method of polishing with a file, a method of cutting with a sword or knife, a method of covering with nail makeup with cotton dampened with acetone, leaving it embrittled for a few minutes, embrittled with a stick, etc. Examples thereof include a method of immersing in an aqueous solution having a pH for several minutes, embrittlement and then peeling with a tweezers or the like or peeling with a stick, and a method of combining them.

<Nail Art Kit>
The nail art kit of the present invention includes the nail cosmetic of the present invention and tools necessary for applying them to the nails.
The preferred embodiments of the nail cosmetic of the present invention in the nail art kit of the present invention are the same as those described above.
Specific examples of tools necessary for performing nail surgery include nail cosmetics other than the nail cosmetic of the present invention for color or top use, nail files such as files, and flats for applying nail cosmetics. Brushes and brushes such as brushes, exposure devices such as UV light, wiping or cleaning liquids, wiping wipes, nail brushes, dust brushes, nail foam used for lengthening nails, acrylic resin, glass, metal Or decorative stones made of natural stone, nail seals, decorative powders such as glitter and holograms, cutters, spatulas, sticks, tweezers, separators that increase finger spacing to prevent contact between nails, etc. Not limited.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples unless the gist of the present invention is exceeded. Unless otherwise specified, “part” is based on mass.

[Synthesis of trifunctional or higher isocyanate compound NCO104]
Trimethylolpropane (TMP) 10 g, 1,3-bis (isocyanatomethyl) cyclohexane (HXDI) 57.91 g, and ethyl acetate (AcOEt) 126.11 g are added to a three-necked flask and heated to 50 ° C. 0.194 g of 600 (manufactured by Nitto Kasei Co., Ltd., inorganic bismuth catalyst) was added and reacted for 3 hours to obtain an isocyanate compound NCO104.

[Synthesis of polymerizable isocyanate compound NCO202]
Trimethylolpropane (TMP) 10 g, 1,3-bis (isocyanatemethyl) cyclohexane (HXDI) 57.91 g, and ethyl acetate (AcOEt) 169.62 g were added to a three-necked flask and heated to 50 ° C. 0.261 g of 600 was added and reacted for 3 hours. After the reaction, 23.43 g of Bremer AP-400 (manufactured by NOF Corporation) and 0.04 g of di-t-butylhydroxytoluene (BHT) were added thereto, and further reacted at 50 ° C. for 3 hours to obtain a polymerizable isocyanate compound NCO202. Obtained.

[Synthesis of Isocyanate Compound 2 with Added Dispersion Stabilization Group]
To a three-necked flask, 45 g of 2,2-bis (hydroxymethyl) propionic acid (DMPA), 223.72 g of isophorone diisocyanate (IPDI), and 499.05 g of ethyl acetate (AcOEt) were added and heated to 50 ° C. Then, 0.7677 g of 600 was added and reacted for 3 hours to obtain an ethyl acetate solution (solid content 35% by mass) of isocyanate compound 2 (an isocyanate compound having a carboxylic acid group) to which a dispersion-stable group was added.

[Synthesis of NCO101 to NCO103, NCO105 to NCO119, NCO201, NCO203 to NCO222]
NCO101 to NCO103 and NCO105 to NCO119 in Table 6 below were produced in the same manner as NCO104.
Further, NCO 201 and NCO 203 to NCO 222 shown in Table 7 below were produced in the same manner as NCO 202.

(Synthesis of particle 1 dispersion)
As an oil phase component, NCO202 (solid content 35% by mass) 39 g (a trifunctional or higher functional isocyanate compound with a polymerizable group added), an adduct of trimethylolpropane, xylene diisocyanate and polyethylene glycol monomethyl ether (Mitsui Chemicals ( Co., Ltd., Takenate D-116N 50% ethyl acetate solution, 3.5 g of isocyanate compound to which a dispersion stability group was added, 1 g of Irgacure (registered trademark) 184 (manufactured by BASF) (encapsulated photopolymerization initiator) Dissolved in 5 g of ethyl.
As an aqueous phase component, 0.4 g of sodium dodecyl sulfate was dissolved in 50 g of distilled water.
The aqueous phase component was added to the oil phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer.
The obtained emulsion was added to 25 g of distilled water, stirred for 30 minutes at room temperature (23 ° C., the same applies hereinafter), and then stirred for 3 hours at 50 ° C. to distill off ethyl acetate.
Thereafter, stirring was continued while distilling off water at 50 ° C., and when the solid content concentration of the dispersion liquid of particles 1 was about 40% by mass, the stirring was stopped to obtain a dispersion liquid of particles 1. The average particle diameter of the particles measured by the light scattering method was 0.20 μm. Note that LA-910 (manufactured by Horiba, Ltd.) was used for measurement of the average particle size.
In addition, “NCO202 (solid content 35% by mass) 39 g” means that 39 g of NCO202 having a solid content of 35% by mass was used, and the trifunctional or more functional group to which a polymerizable group as an active ingredient was added. The amount of the isocyanate compound used is 39 g × 0.35 = 13.65 g. The same applies to the following examples.

(Synthesis of particle 2 to particle 3 dispersion)
Dispersions of Particles 2 to 3 were prepared in the same manner as Particle 1, except that the trifunctional isocyanate compound (NCO202) used in Particle 1 was changed to the isocyanate compound shown in Table 8 below.

(Synthesis of particle 4 dispersion)
As an oil phase component, 19 g of NCO202 (solid content 35% by mass) (a trifunctional or higher functional isocyanate compound having a polymerizable group added), an adduct of trimethylolpropane, xylene diisocyanate, and polyethylene glycol monomethyl ether (Mitsui Chemical ( Co., Ltd., Takenate D-116N ethyl acetate 50% solution, dispersion compound added isocyanate compound 1) 3.5 g, dipentaerythritol hexaacrylate 6.5 g (encapsulated polymerizable compound), Irgacure (registered trademark) 819 1 g (included photopolymerization initiator) (manufactured by BASF) was dissolved in 18 g of ethyl acetate.
As an aqueous phase component, 0.4 g of sodium dodecyl sulfate was dissolved in 50 g of distilled water.
The aqueous phase component was added to the oil phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate.
Subsequently, stirring was continued while distilling off water at 50 ° C., and stirring was stopped when the solid content concentration of the dispersion liquid of particles 4 reached about 40% by mass, whereby a dispersion liquid of particles 1 was obtained. The average particle diameter of the particles measured by the light scattering method was 0.21 μm.

(Synthesis of particle 5 to particle 7 dispersion)
Particles 5 to 7 are the same as Particle 4 except that the trifunctional isocyanate compound (NCO202) and dipentaerythritol hexaacrylate used in Particle 4 are changed to the isocyanate compounds and inclusion polymerizable compounds shown in Table 8 below. A dispersion was prepared.

(Synthesis of particle 8 dispersion)
1. As an oil phase component, 39 g of NCO202 (solid content 35% by mass) (a trifunctional or higher functional isocyanate compound with a polymerizable group added), and isocyanate compound 2 with a dispersion stability group added (solid content concentration 35% by mass) 51 g and 1 g of TPO (BASF) (encapsulated photopolymerization initiator) were dissolved in 5 g of ethyl acetate.
As an aqueous phase component, 0.4 g of sodium dodecyl sulfate and 0.033 g of sodium hydroxide were dissolved in 50 g of distilled water.
The aqueous phase component was added to the oil phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer.
The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate.
Subsequently, stirring was continued while distilling off water at 50 ° C., and stirring was stopped when the solid content concentration of the dispersion liquid of particles 8 reached about 40% by mass to obtain a dispersion liquid of particles 8. The average particle diameter of the particles measured by the light scattering method was 0.19 μm.

(Synthesis of particle 9 to particle 10 dispersion)
Dispersions of Particles 9 to 10 were prepared in the same manner as Particle 8, except that the trifunctional isocyanate compound (NCO202) used in Particle 8 was changed to the isocyanate compound shown in Table 8 below.

(Synthesis of particle 11 dispersion)
As an oil phase component, 19 g of NCO 202 (solid content 35% by mass) (a trifunctional or higher functional isocyanate compound with a polymerizable group added), 2.51 g of isocyanate compound 2 with a dispersion stability group added, UA-306T (Kyoeisha Chemical) (Inc.) 6.5 g (encapsulated polymerizable compound) and TPO (BASF) 1 g (encapsulated photopolymerization initiator) were dissolved in 18 g of ethyl acetate.
As an aqueous phase component, 0.4 g of sodium dodecyl sulfate and 0.033 g of sodium hydroxide were dissolved in 50 g of distilled water.
The aqueous phase component was added to the oil phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate.
Thereafter, stirring was continued while distilling off water at 50 ° C., and when the solid content concentration of the dispersion liquid of particles 11 reached about 40% by mass, the stirring was stopped to obtain a dispersion liquid of particles 11. The average particle diameter of the particles measured by the light scattering method was 0.15 μm.

(Synthesis of particle 12 to particle 13 dispersion)
Dispersions of particles 12 to 13 were prepared in the same manner as the particles 11 except that the trifunctional isocyanate compound (NCO202) used in the particles 11 was changed to the isocyanate compounds shown in Table 8 below.

(Synthesis of particle 14 dispersion)
As an oil phase component, NCO202 (solid content 35% by mass) 39 g (a trifunctional or higher functional isocyanate compound having a polymerizable group added), trimethylolpropane, xylene diisocyanate and polyethylene glycol monomethyl ether adduct (Mitsui Chemicals ( Co., Ltd., Takenate D-116N 50% ethyl acetate solution, 3.5 g isocyanate compound added with a dispersion-stable group, isocyanate compound 2 added with a dispersion-stable group (ethyl acetate solution, solid content 35% by mass) 2.51 g, Irgacure (registered trademark) 819 (manufactured by BASF) 1 g (encapsulated photopolymerization initiator) was dissolved in 5 g of ethyl acetate.
As an aqueous phase component, 0.4 g of sodium dodecyl sulfate and 0.033 g of sodium hydroxide were dissolved in 50 g of distilled water.
The aqueous phase component was added to the oil phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer.
The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate.
Thereafter, stirring was continued while distilling off water at 50 ° C., and stirring was stopped when the solid content concentration of the dispersion liquid of particles 14 was about 40% by mass to obtain a dispersion liquid of particles 14. The average particle size of the particles measured by the light scattering method was 0.16 μm.

(Synthesis of particle 15 to particle 16 dispersion)
Dispersions of particles 15 to 16 were prepared in the same manner as particles 14 except that the trifunctional isocyanate compound (NCO202) used in particles 14 was changed to the isocyanate compounds shown in Table 8 below.

(Synthesis of particle 17 dispersion)
As an oil phase component, 19 g of NCO202 (solid content 35% by mass) (a trifunctional or higher functional isocyanate compound having a polymerizable group added), an adduct of trimethylolpropane, xylene diisocyanate, and polyethylene glycol monomethyl ether (Mitsui Chemical ( Co., Ltd., Takenate D-116N 50% ethyl acetate solution, 3.5 g isocyanate compound added with a dispersion-stable group, isocyanate compound 2 added with a dispersion-stable group (ethyl acetate solution, solid content 35% by mass) 2.51 g, 6.5 g of dipentaerythritol hexaacrylate (encapsulated polymerizable compound), and 1 g of Irgacure (registered trademark) 819 (manufactured by BASF) (encapsulated photopolymerization initiator) were dissolved in 18 g of ethyl acetate.
As an aqueous phase component, 0.4 g of sodium dodecyl sulfate and 0.033 g of sodium hydroxide were dissolved in 50 g of distilled water.
The aqueous phase component was added to the oil phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate.
Subsequently, stirring was continued while distilling off water at 50 ° C., and when the solid content concentration of the dispersion liquid of particles 17 reached about 40% by mass, the stirring was stopped to obtain a dispersion liquid of particles 17. The average particle diameter of the particles measured by the light scattering method was 0.17 μm.

(Synthesis of particle 18 dispersion)
As oil phase components, NCO101 (solid content 35% by mass) 19 g (trifunctional or higher isocyanate compound), trimethylolpropane, xylene diisocyanate and polyethylene glycol monomethyl ether adduct (Mitsui Chemicals, Takenate D- 116N ethyl acetate 50% solution, 3.5 g of isocyanate compound 1 with added dispersion stability group, neopentylglycol propylene oxide adduct diacrylate (manufactured by Sartomer, NPGPODA) 6.5 g (encapsulated polymerizable compound), Irgacure ( 1 g (registered photopolymerization initiator) of registered trademark 819 (manufactured by BASF) was dissolved in 18 g of ethyl acetate.
As an aqueous phase component, 0.4 g of sodium dodecyl sulfate was dissolved in 50 g of distilled water.
The aqueous phase component was added to the oil phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate.
Then, stirring was further continued while distilling off water at 50 ° C., and the stirring was stopped when the solid content concentration of the dispersion liquid of particles 18 reached about 40% by mass to obtain a dispersion liquid of particles 18. The average particle diameter of the particles measured by the light scattering method was 0.19 μm.

In Table 8, the isocyanate compound 1 to which the dispersion stability group was added and the isocyanate compound 2 to which the dispersion stability group was added are compounds having the following structures. TPO represents Lucirin (registered trademark) TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by BASF). Irgacure® 184 is 1-hydroxycyclohexyl phenyl ketone manufactured by BASF. Irgacure (registered trademark) 819 is bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide manufactured by BASF. UA-306T is manufactured by Kyoeisha Chemical Co., Ltd. (pentaerythritol triacrylate, toluene diisocyanate, urethane prepolymer).

(Examples 1 to 3, Comparative Examples 1 and 2)
In a brown glass bottle, the components (parts by mass) shown in Table 9 were weighed out, and then sufficiently stirred and mixed at room temperature to obtain a composition. The obtained composition was evaluated by carrying out the following tests. Table 9 shows the evaluation results. In addition, the description of “-” in the table means that the above component is not contained.

Test methods used in Examples and Comparative Examples are as follows.
<Storage stability>
Each composition obtained in Examples and Comparative Examples was allowed to stand at 23 ° C. for 24 hours, and then evaluated by visually observing the presence or absence of separation and sedimentation. The evaluation criteria are shown below.
A: No change was observed B: Separation and sedimentation were observed

<Water resistance>
Each composition obtained in Examples and Comparative Examples was applied to a false nail made of polypropylene and photocured. Here, the photocuring was performed by irradiating for 2 minutes using a 36 watt (9 watt × 4) ultraviolet irradiation device (all the same in the following test methods). Next, after being immersed in warm water at 40 ° C. for 24 hours, the presence or absence of peeling and dissolution of the cured product was visually evaluated. The evaluation criteria are shown below.
A: No change was observed. B: Peeling and dissolution were observed even in part.

<Abrasion resistance>
Each composition obtained in Examples and Comparative Examples was photocured in the same procedure as water resistance. Next, the surface of the cured product was rubbed with various pencils, and the hardness of the pencils with scratches was evaluated.

<Odor after curing>
Each composition obtained in Examples and Comparative Examples was cured in the same procedure as water resistance. The odor after curing was evaluated by human olfaction. The evaluation criteria are shown below.
A: There is no or almost no odor B: There is a weak odor C: There is an odor D: There is a very strong odor

<Damage to nails>
Each composition obtained in Examples and Comparative Examples was applied to a size of about 1 mmφ on a human nail and photocured. After leaving for 30 minutes, the cured product was peeled off from the nail, and the peeled nail portion was visually observed. The evaluation criteria are shown below.
A: No change on nail surface B: Nail surface slightly whitened C: Nail surface whitened

<Appearance after curing>
Each composition obtained in the examples and comparative examples was applied onto a human nail and the appearance before curing was determined. Next, each composition was photocured to determine the appearance after curing. The evaluation criteria are shown below. Moreover, what did not correspond to the following evaluation criteria and the colored thing showed the coloring state. For the following examples and comparative examples, only the evaluation results of the appearance after curing were described.
A: Gloss clearly remained on the surface, and the fluorescent lamp on the ceiling was clearly reflected B: Some gloss remained on the surface, and a fluorescent lamp on the ceiling was projected C: Slight gloss was observed on the surface D: Coating film The surface was not glossy

<Nail persistence and removability (removal time from nail) and nail surface after removal>
Each composition obtained in the examples and comparative examples was applied on the nails of 10 humans and cured in the same manner as in the water resistance test. The thickness of the cured coating was about 150 μm (± 10 μm). Next, a commercially available calgel # CG-03 fresh pink (manufactured by Mogabrook Co., Ltd.) was applied as a color layer on the formed film with a brush and irradiated with an ultraviolet lamp (36 W) for 1 minute. Thereafter, a commercially available top gel (manufactured by Mogabrook Co., Ltd.) was applied as a top layer with a brush and similarly irradiated with an ultraviolet lamp (36 W) for 2 minutes. In this way, nail makeup was made on the nails of 10 people. When the formed gel nail layer was visually observed, it was completely solidified. The total film thickness of the color layer and the top layer was about 250 μm. Ten people who applied nail makeup were allowed to live their daily lives as they were, and the number of days until the appearance of the nail makeup was poor (floating from the nail, lacking nail makeup, scratching, etc.) was measured. Table 9 shows the number of days until appearance failure occurs in the nail makeup of five people.
On the other hand, the nail cosmetic produced in the same manner was covered with a cotton soaked with acetone after 1 day from the production, and further covered with aluminum foil over the cotton and left for 15 minutes. Thereafter, after removing the aluminum foil and cotton, the removal was carried out by gradually removing the nail cosmetic using an orange stick. Table 9 shows the time required for removal with an orange stick and the result of visual observation of the nail surface after removal.
A: No change on nail surface B: Nail surface slightly whitened C: Nail surface whitened

The components used in Table 9 are as follows. The same applies to the components in the table described later.
Aqueous emulsion (1): acrylic self-crosslinkable photocurable emulsion, functional group: acryloyl group, solid content: about 40% by mass, number average molecular weight of polymer: about 100,000, manufactured by Cray Valley, CRAYMUL -2717 (trademark)
Aqueous emulsion (2): urethane-based non-self-crosslinking photocurable emulsion, functional group: acryloyl group, solid content: about 40% by mass, number average molecular weight of polymer: about 100,000, manufactured by Albertingk, LUX -2411 (trademark)
Polyethylene glycol: manufactured by Sasol, LIPOXOL 1500 (trademark), weight average molecular weight: about 1,500
Carnauba wax: Carnaubawax (trademark) manufactured by Toa Kasei Co., Ltd.
Leveling agent: foam-breaking polysiloxane, BYK Chemie, BYK028 ™, foam-breaking polysiloxane, hydrophobic particles and polyglycol mixture

From the results of Table 9, it was revealed that the nail cosmetic of the present invention has high water resistance and scratch resistance and high durability.

(Examples 4 to 8)
Each component of the amount (part by mass) shown in Table 10 was weighed into a brown glass bottle, and then sufficiently stirred and mixed at room temperature to obtain a composition. With respect to the obtained composition, the above tests were performed and evaluated. Table 10 shows the evaluation results.

From the results in Table 10, it was revealed that the nail cosmetic of the present invention using particles containing a polymerizable compound therein has high durability while maintaining storage stability and water resistance.

(Examples 9 to 11)
Each component in an amount (parts by mass) shown in Table 11 was weighed into a brown glass bottle, and then sufficiently stirred and mixed at room temperature to obtain a composition. With respect to the obtained composition, the above tests were performed and evaluated. The evaluation results are shown in Table 11.

From the results in Table 11, it was revealed that the nail cosmetic of the present invention using the particles having a carboxylic acid group as a dispersion stability group has high durability while maintaining storage stability and water resistance.

(Examples 12 to 15)
Each component of the amount (part by mass) shown in Table 12 was weighed into a brown glass bottle, and then sufficiently stirred and mixed at room temperature to obtain a composition. With respect to the obtained composition, the above tests were performed and evaluated. The evaluation results are shown in Table 12.

From the results of Table 12, it was revealed that the nail cosmetic of the present invention using particles containing a polymerizable compound therein has high durability while maintaining storage stability and water resistance.

(Examples 16 to 18)
Each component of the amount (part by mass) shown in Table 13 was weighed into a brown glass bottle, and then sufficiently stirred and mixed at room temperature to obtain a composition. With respect to the obtained composition, the above tests were performed and evaluated. The evaluation results are shown in Table 13.

Monomer (1) in Table 13 has the following structure.

From the results in Table 13, it is clear that the nail cosmetic of the present invention using particles having a carboxylic acid group and an ethylene oxide group as a dispersion stability group has high durability while maintaining storage stability and water resistance. It became.

(Examples 19 to 21, Comparative Example 3)
The dispersion liquid of particles 1 obtained as described above was subjected to centrifugal separation at 14,500 rpm for 30 minutes to precipitate the solid particles. The separated supernatant was removed by decantation, and the remaining solid was spread thinly on an unbaked plate and dried at room temperature at 23 ° C. for 3 days. In this way, a solid of particles 1 (particle 1D) was obtained.
Similarly, solid particles 8D and particles 14D were obtained from the dispersion of particles 8 and the dispersion of particles 14, respectively.
In accordance with the formulation shown in Table 14, each component was weighed into a glass container, added with glass beads, and mixed for 1 hour in a paint shaker. Thus, a nail cosmetic was prepared.
The obtained nail cosmetic was applied onto the nails of 10 humans and cured by irradiation with an ultraviolet lamp (36 W) for 2 minutes. The thickness of the cured coating was about 150 μm (± 10 μm). Next, a commercially available calgel # CG-03 fresh pink (manufactured by Mogabrook Co., Ltd.) was applied as a color layer on the formed film with a brush and irradiated with an ultraviolet lamp (36 W) for 1 minute. Thereafter, a commercially available top gel (manufactured by Mogabrook Co., Ltd.) was applied as a top layer with a brush and similarly irradiated with an ultraviolet lamp (36 W) for 2 minutes. In this way, nail makeup was made on the nails of 10 people. When the formed gel nail layer was visually observed, it was completely solidified. The total film thickness of the color layer and the top layer was about 250 μm. Ten people who applied nail makeup were allowed to live their daily lives as they were, and the number of days until the appearance of the nail makeup was poor (floating from the nail, lacking nail makeup, scratching, etc.) was measured. Table 14 shows the number of days until appearance defects occur in the nail makeup of five people.
On the other hand, a nail makeup consisting of the same three layers as described above was produced on a nail made of polypropylene with a sanded surface. One day after the preparation, an artificial nail having nail makeup was wrapped in acetone-impregnated cotton, left for a certain period of time, and then peeled off with an orange stick. Acetone removability was evaluated by wrapping time with acetone-impregnated cotton necessary for peeling. The results are shown in Table 14.

From the results of Table 14, it was revealed that the nail cosmetic of the present invention has high durability and high removability.

(Examples 22 to 24)
According to the formulation shown in Table 15, each component was weighed into a brown polyethylene bottle and mixed at 40 ° C. for 24 hours. Thus, a nail cosmetic was prepared.
The obtained nail cosmetic was applied onto the nails of 10 humans and cured by irradiation with an ultraviolet lamp (36 W) for 2 minutes. The thickness of the cured coating was about 150 μm (± 10 μm). Next, a commercially available calgel # CG-03 fresh pink (manufactured by Mogabrook Co., Ltd.) was applied as a color layer on the formed film with a brush and irradiated with an ultraviolet lamp (36 W) for 1 minute. Thereafter, a commercially available top gel (manufactured by Mogabrook Co., Ltd.) was applied as a top layer with a brush and similarly irradiated with an ultraviolet lamp (36 W) for 2 minutes. In this way, nail makeup was made on the nails of 10 people. When the formed gel nail layer was visually observed, it was completely solidified. The total film thickness of the color layer and the top layer was about 250 μm. Ten people who applied nail makeup left their daily lives as they were, and the number of days until the appearance of the nail makeup deteriorated (floating from nails, lack of nail makeup, scratches, etc.) was measured. Table 15 shows the number of days until a poor appearance occurs in the nail makeup of five people.
On the other hand, a nail makeup consisting of the same three layers as described above was produced on a nail made of polypropylene with a sanded surface. One day after the preparation, an artificial nail having nail makeup was immersed in an aqueous solution (liquid temperature 40 ° C.) having the following composition, left for a certain period of time, and then peeled off with an orange stick. The removability was evaluated by the required liquid immersion time until peeling. The results are shown in Table 15.
(Aqueous solution) (pH = 2.6)
・ Citric acid: 2.7 g
・ 1,3-Butylene glycol: 1.0 g
・ Water: 297g

From the results of Table 15, it was revealed that the nail cosmetic of the present invention has high durability and high acid aqueous solution removability.

Claims

Contains a three-dimensional cross-linked structure having a polymerizable group and having at least one type selected from the group consisting of urethane bond, thiourethane bond, dithiourethane bond, urea bond, and thiourea bond, and is internally photopolymerized A nail cosmetic comprising particles containing an initiator.
The nail cosmetic according to claim 1, wherein the particles have a structure represented by the following formula 1 as the three-dimensional crosslinked structure.

In formula 1, one of X 1 and X 2 represents NH, the other represents O, NH, or S, Y represents O or S, n represents an integer of 3 or more, and R represents An n-valent organic group is represented, and * represents a bonding position with another structure.
The nail cosmetic according to claim 1 or 2, wherein the particles have a structure represented by the following formula 2 as the three-dimensional crosslinked structure.
In Formula 2, R 1 represents an n-valent organic group, R 2 represents a divalent organic group, n represents an integer of 3 or more, and * represents a bonding position with another structure.
The nail cosmetic according to any one of claims 1 to 3, wherein the particles have a dispersion-stable group.
The nail cosmetic according to claim 4, wherein the dispersion-stable group is at least one of a group having a polyether structure and an ionic group.
The nail cosmetic according to any one of claims 1 to 5, wherein the particles further contain a polymerizable compound inside the particles.
The nail cosmetic according to claim 6, wherein the polymerizable compound is a (meth) acrylate compound.
The nail cosmetic according to claim 7, wherein the (meth) acrylate compound is a tri- or higher functional (meth) acrylate compound.
The nail cosmetic according to any one of claims 1 to 8, further comprising a polymerizable compound.
The nail cosmetic according to any one of claims 1 to 9, further comprising a polymer compound.
The nail cosmetic according to any one of claims 1 to 10, further comprising a solvent.
A nail art kit comprising the nail cosmetic according to any one of claims 1 to 11.