JP2019085330A - Photocurable nail cosmetics - Google Patents

Abstract

To provide curable photocurable nail cosmetics that have excellent coatability, curability, safety and storage stability, and have sufficient curability in a thin coating, and a gel nail, a nail seal and a nail chip that are obtained from the nail cosmetics, and have excellent glossiness and durability, and also flexibility and tenacity, and can be easily repaired and removed.SOLUTION: The photocurable nail cosmetics contain polyrotaxane (A) having an unsaturated group.

Description

  The present invention relates to a photocurable nail cosmetic and a gel nail, a nail sheet and a nail tip obtained by curing the same.

  With the increasing popularity of nail art, such as decorating small artificial gems on nails, drawing patterns, pasting stickers, putting nails on them, nail cosmetics and nail art technology using them are rapidly increasing Has developed into Typical nail cosmetic products are nail polishes and enamels composed of nitrocellulose, alkyd resin, and solvents such as ethyl acetate and butyl acetate, and these are base coat (underlayer) on the nail surface, color polish (intermediate layer) And a top coat (top layer) are applied in the order of three layers to form a film, but using organic solvents, the drying time is long, the inside is hard to be dried, and thick coating is difficult. was there. Furthermore, since an organic solvent such as acetone, ethyl acetate, butyl acetate or the like is used as a peeling agent for peeling off the film (off) due to the elongation of the nail, an organic solvent by direct suction by the user or absorption from the skin There was a risk of causing health problems such as poisoning.

  Recently, a nail cosmetic using a photocurable resin composition called gel nail does not contain an organic solvent, can be cured in a short time, and is excellent in thick coating and glossing properties, so it is noted became. The gel nail is mainly composed of a polymer or oligomer, a monomer and a photopolymerization initiator, which is applied to the surface of the nail and irradiated with an ultraviolet (UV) exposure device or a light emitting diode (LED) exposure device as a light source A film is formed.

    As nail cosmetics for gel nails, what was indicated in patent documents 1-5 is known. Patent Document 1 proposes an artificial nail composition characterized in that it comprises a polyfunctional urethane (meth) acrylate oligomer, a radically polymerizable monomer, and a photopolymerization initiator. Patent Document 2 proposes an artificial nail composition characterized in that it contains polyurethane (meth) acrylate having a weight average molecular weight of 8,000 or more, a radically polymerizable monomer and a photopolymerization initiator. Although these compositions were excellent in coating properties and stability over time, and the durability of the resulting artificial nail was reported to be good, with regard to removability, they are removed by swelling with a remover containing a conventional organic solvent. A method and a method for removing by contacting with an acidic aqueous solution have been proposed, and there is a risk of causing health hazard due to the organic solvent and acid of the user.

  Patent Document 3 is characterized in that it contains hydroxyethyl acrylamide as the essential component 1 and at least one compound selected from the group consisting of dimethyl acrylamide, diethyl acrylamide, acryloyl morpholine and butoxy diethyl glycol methacrylate as the essential component 2. Nail cosmetics were proposed. Patent Document 4 discloses at least one compound selected from the group consisting of methacrylamide as the essential component 1 and isobornyl methacrylate, dimethyl acrylamide, diethyl acrylamide, acryloyl morpholine and butoxy diethyl glycol methacrylate as the essential component 2. A nail cosmetic characterized in that it contains is proposed. These nail cosmetics were reported to be excellent in adhesion of the cured product and also excellent in removability (removability). However, with regard to removability, the removal method proposed in these documents was still a method of rubbing with a stick after swelling with an organic solvent. In addition, in some cases, the above-mentioned swelling and rubbing cycles are required 2-3 times until completely removed, and there is also a problem that the user's own nail is damaged by these operations.

  Moreover, the usage methods of the nail cosmetics proposed by these patent documents 1-4 are all the formation of a base layer (base layer), and top layers which are required to have higher performance such as glossiness, scratch resistance, durability, etc. It has not been mentioned that it is used as a one-pack type gel nail which can serve as an underlayer, an intermediate layer and a top layer.

  On the other hand, Patent Document 5 proposes a photocurable artificial nail composition which can be used as an underlayer, or as an intermediate layer, and further as a top layer, that is, a one-part gel nail. This composition is characterized by containing a urethane (meth) acrylate oligomer having a weight average molecular weight of 1,000 or less, a hydroxyl group-containing (meth) acrylate monomer, and a photopolymerization initiator, and having sufficient curability for visible light. However, uncured monomers and the like remained on the film surface after curing, and it was necessary to wipe them off in order to obtain gloss. Even if oligomers and monomers with low skin irritation are used, there is a risk of harm to the human body such as neurotoxicity and carcinogenicity of these chemicals, so chronic poisoning, allergy onset, etc. may be caused by direct contact with the user. There was a risk. Furthermore, no mention was made of the method for removing the gel nail after curing or the removability.

JP 2017-141176 A JP, 2017-141177, A WO 2016/194730 WO 2016/194732 JP, 2017-171633, A

  The present invention provides a photocurable nail cosmetic which is excellent in coatability, curability, safety and storage stability and which can be used as an undercoat, an intermediate layer, a top layer or any one-component gel. It will be an issue. In addition, the present invention provides a gel nail, a nail seal and a nail chip that have flexibility and toughness obtained by applying, laminating and curing the photocurable nail cosmetic, and can be easily repaired and removed. It will be an issue.

  As a result of intensive studies to solve the above problems, the present inventors have found that coating property, curability, safety and storage stability can be achieved by containing polyrotaxane (A) having an unsaturated group as an essential component. The photocurable nail cosmetic having excellent properties, and the gel nail, the nail seal and the nail tip having both the flexibility and the toughness obtained by curing the nail cosmetic have been observed, and the present invention has been achieved.

That is, the present invention relates to (1) a photocurable nail cosmetic comprising a polyrotaxane (A) having an unsaturated group,
(2) The polyrotaxane (A) having an unsaturated group is composed of a cyclic molecule, a linear molecule which clathrates the cyclic molecule and the blocking group at both ends of the linear molecule, and the cyclic molecule is unsaturated A photocurable nail cosmetic according to the above (1), which is a compound having a group,
(3) Polyrotaxane (A) having an unsaturated group is, as an unsaturated group, (meth) acrylate group, (meth) acrylamide group, vinyl group, vinyl ether group, methyl vinyl ether group, allyl group, (meth) allyl ether group and The photocurable nail cosmetic according to (1) or (2), which is a functional group having at least one unsaturated bond selected from the group consisting of maleimide groups,
(4) The photocurable nail cosmetic according to any one of the above (1) to (3), which contains 1.0% by mass or more of a polyrotaxane (A) having an unsaturated group.
(5) The photocurable nail cosmetic according to any one of the above (1) to (4), which contains 1.0 to 60% by mass of polyrotaxane (A) having an unsaturated group.
(6) The compound (B) having an ethylenic unsaturated group (excluding (A)) is contained in an amount of 5 to 99% by mass, described in any one of the above (1) to (5) Photocurable nail cosmetic,
(7) The compound (B) having an ethylenically unsaturated group is characterized in that it is at least one compound selected from the group consisting of methacrylate monomers, acrylate monomers, methacrylamide monomers and acrylamide monomers. The photocurable nail cosmetic according to any one of the above (1) to (6),
(8) Compound (B) having an ethylenically unsaturated group is a compound represented by the general formula [1] (wherein, R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represent a hydrogen atom or a carbon number) Introduction of 1 to 18 linear or branched alkyl group, alkyl ether group, alicyclic hydrocarbon and aromatic hydrocarbon, linear, branched or cyclic alkyl group having 1 to 6 carbon atoms R ₂ and R represent an alkoxy group, a hydroxyalkyl group, a 4-hydroxyphenyl group, an alkylsulfonic acid group, an aminoalkyl group, an N'-alkylaminoalkyl group, and an N ', N'-dialkylaminoalkyl group. ₃ represents a saturated 5- to 7-membered ring (including one having an oxygen atom) together with the nitrogen atom supporting them. Or N) -substituted (meth) acrylamide and N, N-disubstituted (meth) acrylamide, diacetone (meth) acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, or more selected from the group consisting of The photocurable nail cosmetic according to any one of the above (1) to (7), which is a compound,
(9) The compound (B) having an ethylenically unsaturated group is N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylamino Propyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methyl-N-hydroxyethyl (meth) acrylamide, N- (meth) acryloyl morpholine, diacetone (meth) acrylamide, N-vinyl pyrrolidone, N -Photocurable nail cosmetic as described in any one of the above (1) to (8), which is one or more compounds selected from the group consisting of vinylcaprolactam and methoxybutyl (meth) acrylamide. ,
(10) The photocurable nail cosmetic according to any one of the above (1) to (9), further comprising 0.1 to 10% by mass of a photopolymerization initiator (C).
(11) A gel nail obtained by curing the photocurable nail cosmetic according to any one of (1) to (10) with light.
(12) A nail seal characterized in that the photocurable nail cosmetic composition according to any one of the above (1) to (10) is coated on a substrate and then cured by light.
(13) A nail chip characterized in that the photocurable nail cosmetic composition according to any one of the above (1) to (10) is coated on a substrate and then cured by light. .

  According to the present invention, by containing the polyrotaxane (A) having an unsaturated group, it is possible to obtain a nail cosmetic which is excellent in photocurability, which is excellent in coatability, curability, safety and storage stability, In addition, by curing the cosmetic with light, it has gel nails, nail seals and nail tips that have good hardness, scratch resistance, and durability, have both flexibility and toughness, and can be easily repaired and removed. it can.

Hereinafter, the present invention will be described in detail.
The polyrotaxane (A) having an unsaturated group used in the present invention comprises a cyclic molecule, a linear molecule penetrating the opening of the cyclic molecule in a skewered manner, and the cyclic molecule at both ends of the linear molecule. It is a polyrotaxane comprising a blocking group which prevents desorption and an unsaturated group introduced to the cyclic molecule. A cross-linked structure is formed via a cyclic molecule by the polymerization reaction of unsaturated groups between molecules of the polyrotaxane having unsaturated groups or with compounds having other unsaturated groups, and cyclic molecules are formed on linear molecules. By sliding movement, it is possible to obtain an annular material in which the bridging point moves like a pulley. The present inventors speculate that the formation of such a structure is the reason why a material having both flexibility and toughness can be obtained. In addition, these polyrotaxanes (A) may be used alone or in combination of two or more.

  The linear molecule of the polyrotaxane (A) used in the present invention is not particularly limited as long as it can be included in the opening of the cyclic molecule in a skewed manner. Specific examples of the linear molecule include polyethylene glycol, polypropylene glycol, polytetraethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethylene imine, casein, gelatin, starch and / or these. Copolymers, cellulose resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose etc.), polyethylene, polypropylene, and other polyolefin resins such as copolymer resins with other olefin monomers, polyester resins, polyvinyl chloride resins , Polystyrene based resins such as polystyrene and copolymer resin of acrylonitrile-styrene, poly (meth) acrylic acid, polyacrylamide, poly And acrylic resins such as (meth) acrylic acid ester copolymer, acrylonitrile-methyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, etc., and derivatives thereof Or modified products, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polydienes such as polyisoprene, polybutadiene, polysiloxanes such as polydimethylsiloxane , Polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and these Derivatives of and the like. It is preferably selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polyisoprene, polyisobutylene, polybutadiene, polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether, and polydimethylsiloxane, and more preferably polyethylene glycol. These linear molecules may be used alone or in combination of two or more. The molecular weight of the linear molecule is, on average, 1,000 to 1,000,000, preferably 2,000 to 100,000, and more preferably 3,000 to 80,000.

  The cyclic molecule of the polyrotaxane (A) used in the present invention is preferably a cyclic molecule having a hydroxyl group, and specific examples thereof include α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, etc. Particular preference is given to cyclodextrin. In addition, part of the hydroxyl groups of the cyclic molecule may be substituted by another group. Examples of other groups include hydrophilic groups for hydrophilizing the polyrotaxane of the present invention, and hydrophobic groups for hydrophobizing. These cyclic molecules may be used alone or in combination of two or more.

  In the polyrotaxane (A) used in the present invention, when the amount of cyclic molecule included at the maximum when the cyclic molecule is included in a skewed manner by a linear molecule is 1.0, the cyclic molecule is Is preferably included in a skewed manner in a linear molecule in an amount of 0.001 to 0.6, more preferably 0.01 to 0.5, and 0.05 to 0.4. Is more preferred. The maximum inclusion amount of the cyclic molecule can be determined by the length of the linear molecule and the thickness of the cyclic molecule.

  The blocking group of the polyrotaxane (A) used in the present invention is not particularly limited as long as it is a group disposed at both ends of the pseudo-polyrotaxane and acting so as not to release cyclic molecules. Examples of blocking groups include adamantane groups, norbornane groups, trityl groups, dinitrophenyl groups, cyclodextrins, fluoresceins, silsesquioxanes, pyrenes, steroids, substituted benzenes (as a substituent And alkyl groups, alkyloxy groups, hydroxy groups, halogen groups, cyano groups, sulfonyl groups, carboxyl groups, amino groups, phenyl groups and the like, and one or more substituents may be present), Polynuclear aromatics which may be substituted (as a substituent, an alkyl group, an alkyloxy group, a hydroxy group, a halogen group, a cyano group, a sulfonyl group, a carboxyl group, an amino group, a phenyl group, etc. can be mentioned; One or more groups may be present) and the like. These blocking groups may be used alone or in combination of two or more. The adamantane group or trityl group is preferably selected from the group consisting of adamantane groups, norbornane groups, trityl groups, dinitrophenyl groups, cyclodextrins, fluoresceins, silsesquioxanes, and pyrenes. More preferred are groups.

The unsaturated group of the polyrotaxane (A) used in the present invention is bonded to a cyclic molecule directly or via a chain molecule. The unsaturated group is not particularly limited as long as it has radical polymerizability, and specifically, (meth) acrylate group, (meth) acrylamide group, vinyl group, vinyl ether group, methyl vinyl ether group, allyl group, (meth) allyl ether Groups, maleimide groups and the like. These unsaturated groups may be used alone or in combination of two or more. Note
When a visible light source or LED light is used, a (meth) acrylate group or a (meth) acrylamide group is preferable in order to maintain sufficient curability, and a methacrylate group or a (meth) acrylamide group in order to ensure safety. Is more preferred.

  Further, the chain molecule is not particularly limited as long as it is bonded to the hydroxyl group of the cyclic molecule. Specific examples of chain molecules include alkylenes, alkenylenes, alkylene glycols, polycaprolactones, polycarbonates, polyesters, polyamides, polyurethanes and the like. One of these chain molecules may be used alone, or two or more of them may be used in combination, or two or more chain molecules may be combined and used as a single chain molecule.

  Examples of the alkylenes and alkenylenes include a linear alkylene group having 1 to 8 carbon atoms or a linear alkenylene group, and a branched alkylene group having 3 to 20 carbon atoms or a branched alkenylene group.

  The alkylene glycols include linear or branched alkylene glycols having 1 to 20 carbon atoms, dialkylene glycols, trialkylene glycols, polyalkylene glycols and the like.

  The polycaprolactones are ring-opened polymers of lactone monomers, and the number average molecular weight is preferably 200 to 10,000. Examples of lactone monomers include 4-membered ring lactones such as β-propiolactone, β-methylpropiolactone and L-serine-β-lactone derivatives, γ-butyrolactone, γ-hexanolactone, γ-heptanolactone, γ -Octanolactone, γ-decanolactone, γ-dodecanolactone, α-hexyl-γ-butyrolactone, α-heptyl-γ-butyrolactone, α-hydroxy-γ-butyrolactone, γ-methyl-γ-decanolactone, α-methylene -Γ-butyrolactone, α, α-dimethyl-γ-butyrolactone, D-erythronolactone, α-methyl-γ-butyrolactone, γ-nonanolactone, DL-pantolactone, γ-phenyl γ-butyrolactone, γ-undecanolactone Γ-valerolactone, 2,2-pentamethylene-1,3-dioxolane-4- 5-membered ring lactones such as .alpha.-bromo-.gamma.-butyrolactone, .gamma.-crotonolactone, .alpha.-methylene-.gamma.-butyrolactone, .alpha.-methacryloyloxy-.gamma.-butyrolactone, .beta.-methacryloyloxy-.gamma.-butyrolactone, .delta.- Valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, δ-tridecanolactone, δ-tetradecanolactone, DL- Examples thereof include 6-membered ring lactones such as mevalonolactone and 4-hydroxy-1-cyclohexanecarboxylic acid δ-lactone, 7-membered ring lactones such as ε-caprolactone, lactide and 1,5-dioxepane-2-one. As lactone monomers, ε-caprolactone, γ-butyl lactone, α-methyl-γ-butyl lactone, δ-valerolactone, lactide and the like can be mentioned.

  The polycarbonates are polycarbonates comprising a diol component and a carbonyl component, and the number average molecular weight is preferably 200 to 10,000. Examples of the carbonyl component include phosgene, chloroformate, dialkyl carbonate, diaryl carbonate and alkylene carbonate, and examples of the diol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, neopentyl glycol, 2-ethyl-2-one And butyl 1,3-propanediol and the like.

  The polyesters are compounds obtained by polycondensation of a diol component and a polyvalent carboxylic acid, and the number average molecular weight is preferably 200 to 10,000. Examples of the polyvalent carboxylic acid component include terephthalic acid, isophthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and the like, and as the diol component, ethylene glycol, 1,2-propylene glycol, 1,1 3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,9-nonane Diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol and the like can be mentioned.

  Polyamides are ring-opened polymers of compounds obtained by polycondensation of a diamine component and a polyvalent carboxylic acid or lactam monomers, and as polyvalent carboxylic acid components, terephthalic acid, isophthalic acid, succinic acid, adipic acid , Azelaic acid, sebacic acid, dodecanedioic acid, etc., and as the diamine component, ethylene diamine, 1,2-propylene diamine, 1,3-propylene diamine, 1,4-butane diamine, pentamethylene diamine, hexamethylene diamine 1,4-cyclohexanediamine and the like, and as the lactam monomer, β-propiolactam, γ-butyrolactam, ε-caprolactam, undecalactam, lauryl lactam and the like can be mentioned. The number average molecular weight is preferably 200 to 10,000.

  The polyurethanes are compounds obtained by the addition reaction of a diol and a polyisocyanate compound having two or more isocyanate groups in one molecule, and the number average molecular weight is preferably 200 to 10,000. As the diol component, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol And 3-methyl-1,5-pentanediol, 1,9-nonanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, etc., and having two or more isocyanate groups. As a polyisocyanate compound, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butadiene Aliphatic isocyanates such as toluene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tridiisocyanate Aromatic isocyanates such as diethylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, xylylene diisocyanate, etc., cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, 4, 4'-dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate, 2,5-norbornane diisocyanate, 2 Alicyclic isocyanates such as 6-norbornane diisocyanate, or, these adduct type, isocyanurate type, multimers such as biuret type and the like.

  It does not specifically limit as a synthesis method of polyrotaxane (A) used for this invention, It can obtain by a well-known method using said various raw material compounds. For example, first, the opening of the cyclic molecule is encapsulated in a skewed manner by a linear molecule, and a blocking group is disposed at both ends of the linear molecule so that the cyclic molecule is not detached, and unmodified polyrotaxane (a1 Get). Second, using a part or all of the hydroxyl groups of the cyclic molecule of polyrotaxane (a1), a chain molecule is introduced through ether bond, ester bond, urethane bond, carbonate bond, etc. by known synthesis reaction, and modification is performed Polyrotaxane (a2) is obtained. Third, polyrotaxane (A) can be obtained by introducing an unsaturated group using a reactive group such as a hydroxyl group possessed in the chain molecule of the modified polyrotaxane (a2).

  In addition, regardless of the above synthesis method, an unsaturated group and a cyclic molecule can be directly introduced to the unmodified polyrotaxane (a1) through an ether bond, an ester bond, a urethane bond, a silyl ether bond or the like.

  In order to introduce an unsaturated group into polyrotaxane (A), a compound having both an unsaturated group and another reactive group can be used. Specifically, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, (meth) acrylamide 2-carboxyethyl, carboxylic acids having unsaturated groups such as maleic acid and itaconic acid, maleic anhydride, anhydride Carboxylic acid anhydrides having an unsaturated group such as (meth) acrylic acid, (meth) acrylic acid chloride, carboxylic acid halides having an unsaturated group such as 3- (acryloyloxy) propionic acid chloride, (meth) acro Isocyanates having an unsaturated group such as yloxyethyl isocyanate, glycidyl (meth) acrylate, vinyl glycidyl ether, epoxy having an unsaturated group such as 4-hydroxybutyl (meth) acrylate glycidyl ether, vinyltrimethoxysilane, vinyl Triethoxysilane, p-styryl tri Alkoxysilanes having unsaturated groups such as toxilsilane, p-styryltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, hydroxyethyl (meth) acrylate, Alcohols having unsaturated groups such as hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, N- (2-hydroxyethyl) acrylamide, 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples include oxazolines having an unsaturated group such as 2-allyl-2-oxazoline, 2- [2- (acryloylamino) phenyl] -4-methyl-2-oxazoline and the like.

  In addition, the polyrotaxane (A) used in the present invention may have a step of binding a functional group other than the unsaturated group directly to the cyclic molecule or via a chain molecule independently of the above synthesis method.

  In producing the polyrotaxane (A) used in the present invention, an organic solvent is generally used, and as the type of the organic solvent, a linear molecule, a blocking group, a chain molecule to be introduced, an unsaturated group For example, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, methylene chloride, N, N'-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, etc. -Pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like can be mentioned.

  The content of the polyrotaxane (A) having an unsaturated group used in the present invention can be suitably varied depending on its structure and molecular weight, but it is 0.1 mass to the entire photocurable nail cosmetic (D) %, The flexibility and toughness of the cured film can be improved. Moreover, the case where it is 1.0-60 mass% is more preferable. When the content is 1.0% by mass or more, the cured film obtained by polymerizing the photocurable nail cosmetic (D) by light irradiation has good hardness and durability, and scratch resistance is also good. When it is 60% by mass or less, the photocurable property The liquid viscosity of the nail cosmetic (D) is easy to control, and the coating property on the nail can be sufficiently satisfied. Furthermore, it is particularly preferable that the gel nail after curing be 3.0 to 50% by mass in order to combine flexibility and toughness as a decorative film of nails.

  The compound (B) having an ethylenically unsaturated group (except for the polyrotaxane (A) having an unsaturated group) used in the present invention comprises a monofunctional unsaturated compound (b1) and a bifunctional or higher unsaturated compound (polyfunctional Composed of unsaturated compound) (b2). Depending on the molecular weight of the polyrotaxane (A) having an unsaturated group and the structure and number of the unsaturated group contained, only (b1) may be used as the compound (B) having an ethylenically unsaturated group, but with (b1) By using (b2) in combination, the hardness and durability of the resulting cured product can be further improved. Moreover, it is preferable that content of the compound (B) which has an ethylenically unsaturated group is 5-99 mass% with respect to the whole photocurable nail cosmetics (D). If the content of (B) is within this range, adjustment of the compounding ratio with the polyrotaxane (A) having an unsaturated group results in a cured film with a good balance of flexibility and toughness.

  The monofunctional unsaturated compound (b1) is not particularly limited as long as it is a monomer having one ethylenically unsaturated group in the molecule. In addition, the ethylenically unsaturated group is not particularly limited as long as it has radical polymerizability, and specifically, (meth) acrylate group, (meth) acrylamide group, vinyl group, vinyl ether group, methyl vinyl ether group, allyl group, Meta) allyl ether group etc. are mentioned. It is preferable that content of (b1) is 50-100 mass% with respect to the whole (B). The strength and flexibility of the photocured film obtained by blending in proportion to this proportion are good, and the durability and removability of the formed gel nail, nail sheet and nail tip can both be improved.

  Among the monofunctional unsaturated compounds (b1), as a compound containing a (meth) acrylate group, for example, (meth) acrylic acid, and a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms are introduced Alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates having a linear, branched or cyclic hydroxyalkyl group having 1 to 18 carbon atoms, (meth) acrylic acid and hydroxyalkyl carboxylic acids (meth) (Meth) acrylic acid alkyl carboxylic acids such as acrylic acid ethyl carboxylic acid, (meth) acrylic acid ethyl succinic acid, (meth) acrylic acid ethyl phthalic acid, ethyl (meth) acrylic acid hexahydrophthalic acid, etc., having 1 to 18 carbon atoms (Meth) acrylic acid alkyl sulfonic acids introduced with linear, branched or cyclic alkyl sulfonic acid group, carbon number is (Meth) acrylic acid alkyl phosphoric acids having a linear, branched or cyclic alkyl phosphoric acid group of ̃18, a functional group comprising an alkyl group having 1 to 18 carbon atoms and an alkylene glycol group having 1 to 4 carbon atoms Alkoxy alkylene glycol (meth) acrylates introduced, alkoxy dialkylene glycol (meth) acrylates, alkoxy trialkylene glycol (meth) acrylates, alkoxy polyalkylene glycol (meth) acrylates, phenoxy group and 1 to 4 carbon atoms Phenoxy alkylene glycol (meth) acrylates, phenoxy dialkylene glycol (meth) acrylates, phenoxy trialkylene glycol (meth) acrylates, phenoxy polyal introduced with a functional group consisting of an alkylene glycol group of Kylene glycol (meth) acrylate, N-alkylamino (meth) acrylate in which an aminoalkyl group having 1 to 6 carbon atoms is introduced, or an aminoalkyl group having 1 to 6 carbon atoms and an alkyl having 1 to 6 carbon atoms N-alkylaminoalkyl (meth) acrylates into which an N-alkylaminoalkyl group consisting of a group is introduced, and N, N-dialkyl consisting of an aminoalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms N, N-dialkylaminoalkyl (meth) acrylates into which an aminoalkyl group has been introduced, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth ) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (Meth) acrylates having a cyclic structure such as oxyethyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, etc. The (meth) acrylates which introduce | transduced epoxy groups, such as a glycidyl (meth) acrylate and 4-hydroxy butyl (meth) acrylate glycidyl ether, are mentioned.

  Among the monofunctional unsaturated compounds (b1), examples of the compound containing a (meth) acrylamide group include (meth) acrylamide, mono- or di-substituted (meth) acrylamide, (meth) acroyl morpholine, etc. As mono- or di-substituted (meth) acrylamide, for example, N-alkyl (meth) acrylamide, N, N- dialkyl (meth) acrylamide, carbon having a linear, branched or cyclic alkyl group of 1 to 18 carbon atoms introduced N-hydroxyalkyl (meth) acrylamide which introduce | transduced the hydroxyalkyl group of number 1-6, N, N- di (hydroxyalkyl) (meth) acrylamide, N-hydroxyalkyl N- (4-hydroxy) Phenyl) (meth) acrylamide, C 1 -C 6 hydroxyalkyl group and C 1 -C 6 al Group-introduced N-alkyl-N-hydroxyalkyl (meth) acrylamide, N-alkyl-N- (4-hydroxyphenyl) (meth) acrylamide, 4-hydroxyphenyl (meth) acrylamide, N, N -Di (4-hydroxyphenyl) (meth) acrylamide, N-alkoxyalkyl (meth) acrylamide introduced with an alkoxyalkyl group consisting of an alkoxy group having 1 to 6 carbon atoms and an alkylene group having 1 to 6 carbon atoms, N, N-di (alkoxyalkyl) (meth) acrylamide, an alkoxyalkyl group consisting of an alkoxy group having 1 to 6 carbon atoms and an alkylene group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms introduced Alkyl-N-alkoxyalkyl (meth) acrylamide, alkyl sulfonate having 1 to 6 carbon atoms N-sulfoalkyl acrylamide introduced, N-alkylamino (meth) acrylamide introduced an aminoalkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms N-alkylaminoalkyl (meth) acrylamide introduced with an N-alkylaminoalkyl group, an N, N-dialkylaminoalkyl group consisting of an aminoalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms The introduced N, N-dialkylaminoalkyl (meth) acrylamide etc. are mentioned.

  Among the monofunctional unsaturated compounds (b1), as the compound containing a vinyl group, carboxylic acid vinyl esters introduced with carboxylic acids having 1 to 22 carbon atoms, linear, branched or cyclic ones having 1 to 22 carbon atoms Alkyl vinyl ether, vinyl chloride, N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl oxazoline, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, carbon number is 1 to 1 22 linear, branched, cyclic alkyl group-introduced maleic acid monoalkyl esters, maleic acid dialkyl esters, maleic acid monoalkyl amides, maleic acid dialkyl amides, maleic acid alkylimides, fumaric acid monoalkyl esters, dialkyl fumarates Ester, fumaric acid monoalkylamide, fumaric acid di Rukiruamido, itaconic acid monoalkyl esters, itaconic acid dialkyl esters, itaconic acid monoalkyl amides, itaconic acid dialkyl amides, itaconic acid alkyl imide, vinyl carboxylic acids, vinyl sulfonic acid, vinyl phosphoric acid.

  Among the monofunctional unsaturated compounds (b1), as a compound containing an allyl group, carboxylic acid allyl esters into which a carboxylic acid having 1 to 22 carbon atoms has been introduced, linear, branched or cyclic ones having 1 to 22 carbon atoms And alkyl aryl ethers in which an alkyl group is introduced, phenyl allyl ether, alkyl phenyl allyl ether, allyl amine, and mono- or dialkyl allyl amines in which a branched or cyclic alkyl group is introduced.

  These monofunctional unsaturated compounds (b1) may be used alone or in combination of two or more.

  The polyfunctional unsaturated compound (b2) is not particularly limited as long as it is a monomer or oligomer having two or more ethylenic unsaturated groups in the molecule. In addition, the ethylenically unsaturated group is not particularly limited as long as it has radical polymerizability, and specifically, (meth) acrylate group, (meth) acrylamide group, vinyl group, vinyl ether group, methyl vinyl ether group, allyl group, Meta) allyl ether group etc. are mentioned. In addition, those ethylenically unsaturated groups in the molecule may have two or more identical functional groups, or may be a combination of two or more different functional groups that can be arbitrarily selected. It is preferable that content of (b2) is 0-50 mass% with respect to the whole (B). If the content of (b2) exceeds 50% by mass with respect to the whole of (B), the viscosity of the photocurable nail cosmetic to be prepared is high, so that the coating property and the adhesion to the nail surface can not be sufficiently satisfied There is sex. Also. The flexibility of the resulting light-cured film is insufficient, and cracking of the formed gel nails, nail sheets, and nail tips tends to occur, resulting in insufficient durability.

  Among the polyfunctional unsaturated compounds (b2), for example, (di) ethylene glycol di (meth) acrylate, (tri) propylene glycol di (meth) acrylate, ditetraethylene glycol di (meth) acrylate, polyalkylene (carbon 1 to 4) Glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3 (or 1,4) -butanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, cyclohexane dimethanol di (meth) acrylate, acrylate ester (dioxane glycol diacrylate), alkoxylated (cyclo) hexanediol di (meth) acrylate, epoxy di (meth) acrylate, dicyclopentanyl di (meth) acrylate, Lolactone modified dicyclopentenyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polyester di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate Polyurethane di (meth) acrylate, allyl (meth) acrylate, methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, polyurethane di (meth) acrylamide, allyl (meth) acrylamide, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerys Lytol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxy tri Methylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide Modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol Rutetora (meth) acrylate, and succinic acid-modified pentaerythritol tri (meth) acrylate. These polyfunctional unsaturated compounds (b2) may be used alone or in combination of two or more.

  In the compound (B) having an ethylenically unsaturated group used in the present invention, the monofunctional unsaturated compound (b1) is a methacrylate monomer, a methacrylamide monomer and an acrylamide from the viewpoint of safety such as skin irritation and odor. The monomers are preferred, and from the viewpoint of curing, acrylamide monomers are more preferred. Furthermore, in order to control the calorific value at the time of curing, it is most preferable to use an acrylamide monomer and a methacrylate monomer in combination.

  The photocurable nail cosmetic (D) of the present invention can be sufficiently cured by visible light or ultraviolet irradiation. Usually, although it is necessary to contain a photopolymerization initiator, the unsaturated group of the polyrotaxane (A) having an unsaturated group is a group consisting of a vinyl ether group, a methyl vinyl ether group, an allyl group, a (meth) allyl ether group and a maleimide group. In the case of a functional group having one or more types of unsaturated bonds selected from these, these unsaturated groups produce active radicals upon irradiation with light, so a photopolymerization initiator is used in the photocurable nail cosmetic (D). It may not be contained.

  As the photopolymerization initiator (C) used in the present invention, acetophenone type, benzoin type, benzophenone type, α-amino ketone type, xanthone type, anthraquinone type, acyl phosphine oxide type, polymer photopolymerization initiator type, etc. What is necessary is just to select from things suitably. For example, as acetophenones, diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4- (4 Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- 1- (4-methylthiophenyl) -2-morpholinopropane-1, as benzoins, benzoin, α-methylbenzoin, α-phenylbenzoin, α-allylbenzoin, α-benzoylbenzoin, benzoin methyl ether, benzoin ethyl ether , Benzoin isopropyl ether, Zoin isobutyl ether, benzyl dimethyl ketal, as benzophenones, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, as alpha amino ketones, 2-methyl-1- (4-methylthiophenyl) -2- (4-morpholinyl) ) -Propanone, 2-benzyl-2- (dimethylamino) -1- (4- (4-morpholinyl) phenyl) -1-butanone, 2- (dimethylamino) -2- (4-methylphenyl) methyl -1- (4- (4-morpholinyl) phenyl) -1-butanone, as xanthones, as xanthone, thioxanthone, as anthraquinones, as anthraquinone, 2-methylanthraquinone, 2-ethyl anthraquinone, acylphosphine oxides The bis (2,4,6-tri (Tyl benzoyl) -phenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, and as a polymer photopolymerization initiator, 2-hydroxy-2-methyl-1- (4- (1- (methyl)) Polymers of vinyl) phenyl) propan-1-one and the like can be mentioned. These photopolymerization initiators can be used alone or in combination of two or more.

  The content of the photopolymerization initiator (C) is preferably 0.1 to 10% by mass with respect to the entire photocurable nail cosmetic (D). When the content is 0.1% by mass or more, even thin coating has sufficient curability, and the strength and durability of the resulting cured film are good. When the content is 10% by mass or less, the pot life of the photocurable nail cosmetic (D) is sufficiently long, and troubles such as gelation during storage do not occur. Furthermore, 0.5-5 mass% is more preferable.

  The photocurable nail cosmetic of the present invention can be used without containing a solvent. In addition, water or an organic solvent may be contained, as necessary, in order to obtain special products that require higher precision patterns, shapes, gloss, hardness and the like. As an organic solvent, it is preferable that the boiling point in normal pressure is 50-120 degreeC, and it is more preferable that a boiling point is 55-100 degreeC. Further, from the viewpoint of safety, water, acetone, ethyl acetate, butyl acetate, ethanol, isopropanol and the like are particularly preferable as a solvent used for ordinary nail polish, enamel and the like. These solvents may be contained alone or in combination of two or more. Moreover, it is preferable that it is 1.0-50 mass% with respect to the whole photocurable nail cosmetics (D), and content in the case of containing a solvent is 5-30 mass% more. preferable. Within this range, it is easy to manufacture a photocurable nail cosmetic and there is no risk of adversely affecting the expected properties of the cured film.

  Various additives can be blended with the photocurable nail cosmetic of the present invention as required. Specifically, the additive includes, for example, a thermal polymerization inhibitor, an antioxidant, an ultraviolet sensitizer, an antiseptic, a phosphate ester type and other flame retardants, a surfactant, an antistatic agent, a pigment, a dye, etc. Colorants, flavors, antifoaming agents, fillers, silane coupling agents, surface tension regulators, plasticizers, surface lubricants, leveling agents, softeners, organic fillers, inorganic fillers and the like can be added. The addition amount of these other components is not particularly limited as long as it does not adversely affect the properties of the photocurable nail cosmetic (D) according to the present invention. A range is preferred.

  The photocurable nail cosmetic of the present invention can be used as an object of the user's own nails (ground nails) or artificial nails attached to or kneaded with the nails. Specifically, the photocurable nail cosmetic composition of the present invention is applied to the surface of these objects and cured by light irradiation to obtain a gel nail, a nail sheet or a nail chip as a cured film. The photocurable nail cosmetic composition of the present invention is excellent in adhesion to both self-nails and to an acrylic resin which is a material of artificial nails, and therefore, can be used as a base cording agent. In this case, although the durability is further improved by performing pretreatment such as polishing the surface of the nail and wiping with alcohol, sufficiently satisfactory adhesion, durability and the like can be obtained without performing pretreatment. In addition, since the cured film of the photocurable nail cosmetic has both flexibility and toughness, the number of times of off by a solvent such as acetone is small, and no gel is used. It can also be peeled off towards your fingertips. Furthermore, since the photocurable nail cosmetic composition of the present invention is composed of components with low odor and low or no skin irritation, it is highly safe and can be used as a nail protectant.

  The photocurable nail cosmetic composition of the present invention has many polar functional groups such as ester groups, amide groups and urethane bonds, and is uniform with organic or inorganic colorants such as general-purpose pigments, brightening agents and dyes. Easy to mix with In addition, since the photocuring property is good, deep layer curing of a thick film and extreme surface curing of a thin film can be completed in a short time, and it can be used as a color gel by adding a coloring agent and the like. In this case, it may be applied and cured on the base cord after curing, or it may be applied directly to the surface of a self-nail or artificial nail as a nail cosmetic that achieves two effects of the base cord and the color code. It can be cured. It may be a single-layer coating of a thick film or a multilayer coating of a thin film.

  The curability of the photocurable nail cosmetic of the present invention is high, the hardness of the cured film can be adjusted by the compounding ratio of the constituent components, and it can be suitably used as a top cord agent. In particular, since an uncured material does not remain on the surface of the electrode, sufficient gloss can be obtained even if the wiping operation with ethanol or water is omitted. Since the cured film of the photocurable nail cosmetic of the present invention has both flexibility and toughness, it has excellent hardness as well as scratch resistance and durability while having sufficient hardness on the surface of the gel nail to be formed. When a transparent gel nail is required, it may be applied and cured on the base cord after curing, and the surface such as a self-nail or an artificial nail as a nail cosmetic which achieves two effects of the base cord and the top cord Can be applied directly and cured. When a gel nail modified in color or pattern is required, it may be applied and cured on a laminated cured film of a base code and a color code or a single layer cured film of a base code and a color code. . Furthermore, it can be directly applied to the surface of a self-nail, artificial nail or the like as a one-component nail cosmetic that achieves the three effects of a base code, a color code and a top code, and can be cured. It may be a single-layer coating of a thick film or a multilayer coating of a thin film.

  The method for applying the photocurable nail cosmetic composition of the present invention to a base material such as acrylic resin chips, films and sheets of self-nails and artificial nails is not particularly limited and can be carried out by known methods. For example, a method of coating with a small brush (brush), a method of embossing with a sponge or the like, a spray coating method, an inkjet coating method, a bar coater coating method, a spin coating method, an air knife coating method, a roll coating method, etc. may be mentioned.

  When water or an organic solvent is contained in the photocurable nail cosmetic of the present invention, it is preferable to apply on the above-mentioned various base materials, evaporate the solvent and the like and then carry out the photocuring. The thickness of the cured film is different depending on the application such as base coat, color code, top code or 1-component type of these 2 roles or 3 roles, but it differs according to the difference of coated substrates such as self-nails, films, sheets, chips The film thickness is preferably in the range of 1 nm to 1 mm, more preferably 10 nm to 0.7 mm, and particularly preferably 100 nm to 0.5 mm. If the film thickness is in the range of 1 nm to 1 mm, the adhesion of the cured product to the substrate, the durability of the gel nail, and the scratch resistance as the top layer are both good.

  The light source used for the photocuring of the photocurable nail cosmetic of the present invention is not particularly limited as long as it can be irradiated with light. For example, as a known light source, sunlight, fluorescent lamp, high pressure mercury lamp, metal halide lamp, ultraviolet (UV) lamp, light emitting diode (LED) lamp, ultraviolet light emitting diode (UV-LED) lamp, ultraviolet laser diode (UV-LD) ) Lamps and the like. Further, from the viewpoints of small size, long life, high efficiency, low cost and safety, UV irradiation type using a fluorescent tube of 365 nm and visible light irradiation type having an LED light source of 405 nm are becoming mainstream.

Although the irradiation energy required for the photocuring of the photocurable nail cosmetic of the present invention varies somewhat depending on the application and light source, the irradiation energy (integrated light quantity) is preferably in the range of 5-1000 mJ / cm ² , 10-500 mJ / cm ² is more preferable. Within this range, the nail cosmetic composition can be sufficiently cured and health problems do not occur. The specific irradiation conditions depend on the preference of the user, but when curing nail cosmetics by UV, using a commercially available gel nail UV lamp (Beauty Nailer, 36 W) as a light source for 1 to 2 minutes In the case of curing a cosmetic by visible light, it is preferable to use 0.5 to 1 minute of irradiation using a commercially available gel nail LED lamp (Beauty Nailer, 40 W) as a light source. preferable.

  The cured film (gel nail) obtained by photocuring the photocurable nail cosmetic of the present invention (gel nail) is removed from the nail (off) The method depends on the application, but it is impregnated with a peeling solution containing a solvent such as acetone. A method of swelling and peeling off the cured film by covering an elastic cloth or cotton on the cured film for several minutes, or a method of peeling the gel of the cuticle of the nail at the toe and peeling it toward the fingertip. Also, after swelling with a peeling solution, a method of rubbing and dropping lightly with a rod-like or stick-like material, or a method of rubbing completely with a stick-like material to completely peel it off is also used. In addition, when it is used as a base cord, only the top layer and the color layer are turned off by a method such as swelling and rubbing, and the extended base portion of the remaining base cord is repaired and cured. It is possible to apply and cure a color layer, a top layer, or a two-part / one-part nail cosmetic. Furthermore, when gel nails are formed by lamination, there is a method in which the gel nails are peeled off one by one in order, adjustment of the consistency with the portion stretched by repair, etc., and then laminated and cured again. The method of peeling off the gel with a toe without using a peeling solution is preferable because it does not damage its own nail.

  EXAMPLES The present invention will be more specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following, "parts" and "%" are all based on mass unless otherwise specified.

  Table 1 shows molecular weights of polyrotaxanes (A-1) to (A-6) having unsaturated groups and types and equivalent weights of unsaturated groups.

The monofunctional unsaturated compound (b1) used for an Example and a comparative example is shown below.
b1-1: Isobornyl acrylate (IBOA)
b1-2: 2-hydroxyethyl methacrylate (HEMA)
b1-3: 2-hydroxyethyl acrylate (HEA)
b1-4: 2-hydroxypropyl methacrylate (2 HPMA)
b1-5: 4-hydroxybutyl acrylate (4HBA)
b1-6: Ethoxydiethylene glycol acrylate (ECA)
b1-7: BA: butyl acrylate b1-8: acroyl morpholine (registered trademark of KJ Chemicals, Inc. "ACMO")
b1-9: Dimethylacrylamide (registered trademark "DMAA" of KJ Chemicals, Inc.)
b1-10: Diethyl acrylamide (registered trademark "DEAA" of KJ Chemicals, Inc.)
b1-11: N- (2-hydroxyethyl) acrylamide (registered trademark "HEAA" of KJ Chemicals, Inc.)
b1-12: Isopropyl acrylamide (registered trademark "NIPAM" of KJ Chemicals, Inc.)
b1-13: Dimethylaminopropyl acrylamide (a registered trademark of KJ Chemicals, Inc. “DMAPAA”)
b1-14: Diacetone acrylamide (DAAM)
b1-15: N-vinyl pyrrolidone (NVP)
b1-16: N-vinylcaprolactam NVC)

Multifunctional unsaturated compounds (b2) used in Examples and Comparative Examples are shown below.
b2-1: triethylene glycol diacrylate (TEGDA)
b2-2: triethylene glycol dimethacrylate (TEGDMA)
b2-3: trimethylol prohan triacrylate (TMPAT)
b2-4: tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.)
b2-5: Urethane diacrylate (UA, molecular weight 5000)

The photoinitiator (C) used for an Example and a comparative example is shown below.
C-1: 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184, manufactured by BASF Japan Ltd.)
C-2: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (IRGACURE-TPO, manufactured by BASF Japan Ltd.)
C-3: 1-hydroxycyclohexyl phenyl ketone / benzophenone = 1/1 mixture (IRGACURE-500, manufactured by BASF Japan Ltd.)

Example 1 Preparation of photocurable nail cosmetic (D-1) 20.0 parts by mass of a methacryloyl group-introduced polyrotaxane (A1-1) as (A), isobornyl acrylate (b1-1) 65 as (B) .0 parts by mass, 12.0 parts by mass of "ACMO" (b1-8), and 3.0 parts by mass of 1-hydroxycyclohexyl phenyl ketone (C-1, IRGACURE 184) as (C) are added to the container, respectively, The mixture was stirred for 1 hour to obtain a uniformly transparent photocurable nail cosmetic (D-1) of Example 1.

Examples 2 to 10 Preparation of Photocurable Nail Cosmetics (D-2) to (D-10) The compositions shown in Table 2 correspond to Examples 2 to 9 by performing the same operation as Example 1. Photocurable nail cosmetics (D-2) to (D-9) were obtained.

Comparative Examples 1 to 3 Preparation of Photocurable Resin Compositions (E-1) to (E-3) The compositions shown in Table 2 correspond to Comparative Examples 1 to 3 by performing the same operation as in Example 1. Photocurable resin compositions (E-1) to (E-4) were obtained.

  The photocurable nail cosmetics obtained in Examples 1 to 10 and the photocurable resin compositions obtained in Comparative Examples 1 to 3 were evaluated by the following method, and the results are shown in Table 3. . In addition, all evaluation represents the average value implemented 10 times.

Apply a commercially available gel nail to the photocurable nail cosmetic obtained in Examples 1 to 10 and the photocurable resin composition obtained in Comparative Examples 1 to 3 uniformly using a flat brush on the nail; The coating properties were evaluated visually according to the following criteria, and the results are shown in Table 3.
1. Coatability 性: There was no stringing at the time of coating, no handwriting after coating, and a smooth coating film was formed.
:: Slight writing was slightly observed after coating or application, but after leaving for 30 seconds, the writing was lost and a smooth coating was formed.
[Delta]: Some stringing during application or some handwriting after application was confirmed, and remaining of the handwriting was also confirmed after standing for 30 seconds.
X: Stringing or coating after application was confirmed, and a uniform coating was not obtained.
2. Curability The photocurable nail cosmetic obtained in Examples 1 to 10 and the photocurable resin compositions obtained in Comparative Examples 1 to 3 were uniformly coated on commercially available gel nails using a flat brush on the nails. After irradiating for 1 minute using a UV lamp for gel nails (manufactured by BEAUTY NAILER, 36 W), the surface of the cured film was touched with a finger to evaluate stickiness, and the presence or absence of an uncured component was confirmed.
◎: no stickiness (complete cure).
○: Slight stickiness, but no finger marks are left on the surface (almost completely cured, wiping of uncured components is unnecessary).
Δ: Sticky, finger marks on the surface (incomplete curing, wiping of uncured components is necessary).
X: Stickiness is bad and a finger sticks on the surface (A lot of uncured components remain, and it can not be used as a cured film).
3. Glossiness The cured film (gel nail) obtained in the above-mentioned curability evaluation was visually observed to confirm the glossiness.
◎: There is surface gloss.
○: The reflection of light can be confirmed, but slightly cloudy.
Δ: The surface is slightly cloudy as a whole.
X: The surface becomes cloudy.
4. Durability In the cured film (gel nail) obtained by the above-mentioned curability evaluation, the appearance change of the film was visually confirmed after two weeks of daily life.
◎: No change in appearance.
○: Slightly damaged but still in intimate contact with nails.
Δ: There was a damaged part or a part peeled slightly from the nail.
X: There was significant damage or peeling.
5. Solvent Removability A cotton-containing acetone was placed so as to cover the cured film (gel nail) obtained in the above curing evaluation. Then cover the entire nail with aluminum foil, put on a sanitary glove and leave it in warm water for 10 minutes. Remove the aluminum foil and cotton, and rub gently with a cloth.
:: The nail decoration could be easily peeled off without using a cloth.
:: The nail decoration could be easily peeled off by rubbing lightly with a cloth.
Δ: The nail decoration could be peeled off by continuing rubbing with a cloth for about 1 minute.
X: The acetone is not swollen and can not be peeled off even with a cloth.
6. Removability by Toe Peeling In the case of the one-component type cured film (gel nail) obtained in the above-mentioned hardenability evaluation, gel of the cuticle of the nail was raised at the toe and slowly peeled off toward the fingertip.
◎: The gel nail could be easily peeled off without the cured film remaining on the nail.
○: The cured film slightly remained on the nail but could be easily peeled off by lightly rubbing it with the toe.
Fair: A cured film remained on the nail and after immersion in warm water, it could be dropped while being lightly rubbed with a toe, a rod-like or stick-like thing.
X: The cured film hardly peels off, and after immersion in warm water, it can not be scraped off with a toe, rod or stick.
7. Storage stability The photocurable nail cosmetic obtained in Examples 1 to 10 and the photocurable resin compositions obtained in Comparative Examples 1 to 3 were put in a light shielding screw tube, the lid was closed, and 1 at 40 ° C. It stored on 2 conditions of two weeks at month and 80 degreeC. The presence or absence of increase in liquid viscosity after storage was confirmed, and storage stability was evaluated.
○: The two conditions of 1 month at 40 ° C. and 2 weeks at 80 ° C. had no increase in viscosity after storage.
Fair: An increase in viscosity after storage at 40 ° C. for one month or at 80 ° C. for 2 weeks was confirmed.
X: Both of the two conditions of 1 month at 40 ° C. and 2 weeks at 80 ° C. confirmed an increase in viscosity after storage.

Table 3

  As shown in the results of Examples and Comparative Examples, when the polyrotaxane (A) having an unsaturated group of the present invention is contained, a photocurable nail cosmetic which can satisfy all of coating properties, curability and storage stability It can be acquired. In addition, by blending the polyrotaxane (A) having an unsaturated group, a cured film (gel nail) having both flexibility and toughness can be formed, and while being excellent in glossiness and durability, peeling due to solvent swelling can also be performed. The method of peeling with a toe made it possible to remove the nail easily without damaging the nail.

  As described above, the photocurable nail cosmetic of the present invention is excellent in coatability, curability, safety and storage stability, and photocurable nail cosmetic having sufficient curability even in thin coating and thick coating. It can be suitably used as a charge. In addition, adhesion to nails, compatibility with pigments, glossiness of the resulting cured film, and durability are good, and it can be used as a base layer, an intermediate layer, a top layer or any one-component gel. In the photocurable nail cosmetic composition of the present invention, a liquid having the same or different composition is formed into a single layer or a laminate and has flexibility and toughness, and the cured film can be easily repaired and removed, and gel nails and nail seals It can be widely used as a nail chip.

Claims (13)

A photocurable nail cosmetic containing a polyrotaxane (A) having an unsaturated group. The polyrotaxane (A) having an unsaturated group is composed of a cyclic molecule, a linear molecule which clathrates the cyclic molecule in a skewered manner, and a blocking group at both ends of the linear molecule, and the cyclic molecule has an unsaturated group The photocurable nail cosmetic according to claim 1, which is a compound. Polyrotaxane (A) having an unsaturated group is an unsaturated group having a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, a (meth) allyl ether group and a maleimide group It is a functional group which has a 1 or more types of unsaturated bond selected from the group which consists of, The photocurable nail cosmetics of Claim 1 or Claim 2 characterized by the above-mentioned. The photocurable nail cosmetic according to any one of claims 1 to 3, containing 1.0% by mass or more of a polyrotaxane (A) having an unsaturated group. The photocurable nail cosmetic according to any one of claims 1 to 4, which contains 1.0 to 60% by mass of polyrotaxane (A) having an unsaturated group. The photocurable nail cosmetic according to any one of claims 1 to 5, containing 5 to 99% by mass of the compound (B) (excluding (A)) having an ethylenically unsaturated group. . The compound (B) having an ethylenically unsaturated group is one or more compounds selected from the group consisting of methacrylate monomers, acrylate monomers, methacrylamide monomers and acrylamide monomers. Photocurable nail cosmetics as described in any one of 1-6. The compound (B) having an ethylenically unsaturated group is a compound represented by the general formula [1] (wherein, R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represent a hydrogen atom or C 1-18 carbon atoms) A linear or branched alkyl group, an alkyl ether group, an alkoxy group introduced with an alicyclic hydrocarbon and an aromatic hydrocarbon, and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms And R ₂ and R ₃ each represents a hydroxyalkyl group, a 4-hydroxyphenyl group, an alkylsulfonic acid group, an aminoalkyl group, an N′-alkylaminoalkyl group, or an N ′, N′-dialkylaminoalkyl group. They represent a saturated 5- to 7-membered ring (including one having an oxygen atom) together with the nitrogen atom supporting them. Or N) -substituted (meth) acrylamide and N, N-disubstituted (meth) acrylamide, diacetone (meth) acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, or more selected from the group consisting of The photocurable nail cosmetic according to any one of claims 1 to 7, which is a compound.
The compound (B) having an ethylenically unsaturated group is N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) ) Acrylamide, N-hydroxyethyl (meth) acrylamide, N-methyl-N-hydroxyethyl (meth) acrylamide, N- (meth) acryloyl morpholine, diacetone (meth) acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam The photocurable nail cosmetic according to any one of claims 1 to 8, which is one or more compounds selected from the group consisting of methoxybutyl (meth) acrylamide. The photocurable nail cosmetic according to any one of claims 1 to 9, further comprising 0.1 to 10% by mass of a photopolymerization initiator (C). A gel nail obtained by curing the photocurable nail cosmetic according to claim 1 with light. A nail seal formed by coating the photocurable nail cosmetic according to any one of claims 1 to 10 on a substrate and then curing with light. After coating the photocurable nail cosmetic according to any one of claims 1 to 10 on a substrate, the nail chip is formed by curing with light.