Claws are light-cured resin compositions used for artificial claws.

Abstract

A photocurable resin composition for nails or artificial nails is provided from which cured objects having a gloss can be formed. The photocurable resin composition for nails or artificial nails comprises the following (A) to (D) components, wherein the (C) component is contained in an amount of 0.01-3.0 parts by mass per 100 parts by mass of the compound having (meth)acryloyl groups. (A) component: A urethane (meth)acrylate oligomer (B) component: A compound having three or more (meth)acryloyl functional groups (the (A) component is excluded) (C) component: A polyfunctional thiol compound (D) component: A photoinitiator

Description

Technical Field

[0001] The present invention relates to a photocurable resin composition suitable for coating nails or artificial nails.

Background Art

[0002] Conventionally, in the nail field, photocurable resin compositions (UV gel nails) containing a photopolymerizable monomer and / or oligomer are known. These UV gel nails are used to decorate and make up nails by applying the resin to the nails using a brush or the like and then irradiating with light to cure them. A nail makeup film with beautiful gloss and high adhesion to the nails can be obtained. These UV gel nails are formed of multiple layers including a base coat layer, a color layer, and a top coat layer. Among them, the top coat layer is most important for showing the beauty of the underlying decoration, and thus a colorless and transparent appearance with gloss is required, and hardness for protecting and coating the decoration is also required.

[0003] [[ID=1,6]]JP 2019-6689 A discloses an artificial nail composition excellent in surface glossiness, which contains a urethane (meth)acrylate oligomer, a polyfunctional thiol compound having two or more thiol groups in one molecule, and a radically polymerizable compound having one or more radically polymerizable unsaturated bonds in one molecule.

[0004] JP 2017-210475 A discloses a glossy photocurable artificial nail composition containing a urethane (meth)acrylate oligomer, a (meth)acrylic monomer, a polyfunctional thiol, and a photoinitiator.

Summary of the Invention

[0005] However, it has been difficult for the cured products of the compositions described in JP 2019-6689 A and JP 2017-210475 A to satisfy high glossiness.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a photocurable resin composition for nails or artificial nails that can form a cured product having excellent gloss. [Means for solving the problem]

[0007] The gist of this invention is described below. [1] A photocurable resin composition for nails or artificial nails comprising the following components (A) to (D), wherein the composition contains a compound having a (meth)acryloyl group or a compound having a (meth)acryloyl group comprising component (A) and component (B), and component (C) is present in an amount of 0.01 parts by mass to 3 (3.0) parts by mass: (A) Ingredients: Urethane (meth)acrylate oligomer; (B) Component: A compound having three or more (meth)acryloyl groups (excluding component (A)); (C) Component: polyfunctional thiol compound; and (D) Component: Photoinitiator. [2] The photocurable resin composition for nails or artificial nails according to [1], wherein the (C) component is a polyfunctional thiol compound having a trimethylolpropane skeleton. [3] The photocurable resin composition for nails or artificial nails according to [1] or [2], wherein component (B) is a compound having a trifunctional group of (meth)acryloyl groups. [4] A photocurable resin composition for nails or artificial nails according to any one of [1] to [3], further comprising a polyether-based plasticizer as component (F). [5] A photocurable resin composition for nails or artificial nails according to any one of [1] to [4], further comprising (meth)acryloyl groups other than components (A) and (B) as component (E). [6] The photocurable resin composition for nails or artificial nails is applied to a thickness of 0.1 mm, and the integrated light intensity is 7.5 kJ / m 2 A photocurable resin composition for nails or artificial nails according to any one of [1] to [5], wherein the gloss of the cured surface is 67 to 88 at 20° when cured with a solvent. [7] The photocurable resin composition for nails or artificial nails according to any one of [1] to [6], wherein the photocurable resin composition for nails or artificial nails is for forming a top coat layer. A cured product obtained by curing a photocurable resin composition for nails or artificial nails described in any of [8][1] to [6]. A method for coating a nail or artificial nail, comprising applying a photocurable resin composition for nails or artificial nails described in any of [9][1] to [6] to the nail or artificial nail to form a coating film, and then curing the coating film by irradiating it with energy rays. [Modes for carrying out the invention]

[0008] The details of the invention are described below. In this specification, "X~Y" means that the numerical values ​​(X and Y) described before and after it are included as the lower and upper limits. Unless otherwise specified, the operation and measurement of physical properties are performed under room temperature (20~25°C) / relative humidity 40~50%RH conditions.

[0009] One embodiment of the present invention is a photocurable resin composition for nails or artificial nails comprising the following components (A) to (D), wherein component (C) is present in an amount of 0.01 parts by mass to 3.0 parts by mass per 100 parts by mass of a compound having a (meth)acryloyl group: (A) Ingredients: Urethane (meth)acrylate oligomer; (B) Component: A compound having three or more (meth)acryloyl groups (excluding component (A)); (C) Component: polyfunctional thiol compound; and (D) Component: Photoinitiator.

[0010] According to a photocurable resin composition for nails or artificial nails according to one embodiment of the present invention, it is possible to form a cured product having excellent gloss.

[0011] <(A) component> Component (A) in the photocurable resin composition according to the present invention is a urethane (meth)acrylate oligomer, and any oligomer having one or more urethane bonds and one or more (meth)acryloyl groups can be used as component (A). Adding a urethane (meth)acrylate oligomer improves adhesion to nails or artificial nails, and improves the curability and strength of the photocurable resin composition (coating film). Furthermore, "oligomer" refers to a polymer in which monomer units (including monomer units other than (meth)acrylate monomers) are repeated about 2 to several dozen times. In this specification, a compound having a (meth)acryloyl group refers to (meth)acrylate. The (meth)acryloyl group may also be in the form of a (meth)acryloyloxy group. Furthermore, the term "(meth)acryloyl" includes both acryloyl and methacryloyl. Therefore, for example, the term "(meth)acryloyl group" encompasses both the acryloyl group (H2C=CH-C(=O)-) and the methacryloyl group (H2C=C(CH3)-C(=O)-). Similarly, the term "(meth)acrylate" encompasses both acrylate and methacrylate, and the term "(meth)acrylic" encompasses both acrylic and methacrylic.

[0012] Component (A) is not particularly limited as long as it is an oligomer having one or more urethane bonds and (meth)acryloyl groups, but it is preferable to have 2 to 6 (meth)acryloyl groups, and more preferably to have 2 to 3 (meth)acryloyl groups. 、( It is most preferable to have two meth)acryloyl groups. Furthermore, it is preferable that the (meth)acryloyl group in component (A) is an acryloyl group. In addition to the urethane bond and (meth)acryloyl group, it may also have other functional groups such as a carboxyl group, a phosphate group, a hydroxyl group, etc.

[0013] The weight-average molecular weight of the oligomer of component (A) is preferably 1,000 to 100,000, more preferably 1,200 to 30,000, and particularly preferably 1,500 to 20,000. Within this range, good curability of the cured product can be achieved while maintaining a viscosity that is easy to work with. In this specification, the weight-average molecular weight is the value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0014] Component (A) can be synthesized by forming a urethane bond through the reaction of a polyol and a polyisocyanate, and then adding a compound having a hydroxyl group and a (meth)acryloyl group in the molecule, or (meth)acrylic acid, to the unreacted isocyanate group; however, the method of synthesizing the urethane (meth)acrylate oligomer is not limited to this method.

[0015] Particularly from the viewpoint of adhesion, it is preferable to use a polyether-backed urethane (meth)acrylate oligomer using a polyether polyol or an aromatic polyether polyol such as bisphenol as the polyol. Component (A) is preferably a polyether-backed bifunctional urethane (meth)acrylate oligomer. However, other urethane (meth)acrylate oligomers, such as polyester-backed urethane (meth)acrylate oligomers, polycaprolactone-backed urethane (meth)acrylate oligomers, polycarbonate-backed urethane (meth)acrylate oligomers, etc., can also be used in combination.

[0016] Examples of commercially available products include AH-600, UA-510H (manufactured by Kyoeisha Chemical Co., Ltd.), SUA-008, SUA-023 (manufactured by Asia Chemical Industry Co., Ltd.), UN-6060S, UN-6060PTM, UN-6200, UN-6207, UN-6303, UN-6304, UN-6305, UN-6306 (manufactured by Negami Kogyo Co., Ltd.), but are not limited to these. (A) Component can be used individually or in combination of two or more.

[0017] <(B) component> Component (B) in the photocurable resin composition according to the present invention is a compound having three or more (meth)acryloyl groups (excluding component (A)). The number of (meth)acryloyl groups contained in one molecule is not particularly limited as long as there are three or more functional groups, but for the purpose of obtaining a cured product with good hardness, it is preferably 3 to 8 functional groups, more preferably 3 to 6 functional groups, and most preferably 3 functional groups. In a preferred embodiment, component (B) is a compound having three (meth)acryloyl groups.

[0018] Specific examples of component (B) contained in the photocurable resin composition according to the present invention include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, ethoxylated trimethylolpropane (meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, ECH-modified trimethylolpropane tri(meth)acrylate, ECH-modified glycerol tri(meth)acrylate, tris(acryloyloxyethyl) isocyanurate, pentaerythritol tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified pentaerythritol penta(meth)acrylate, and the like. Among these, ethoxylated trimethylolpropane tri(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, and / or trimethylolpropane tri(meth)acrylate are preferable from the viewpoint of obtaining appropriate hardness and excellent glossiness. Component (B) can be used alone or in combination of two or more kinds.

[0019] In the present invention, the content of component (B) is 3 to 50 parts by mass, more preferably 5 to 40 parts by mass, and still more preferably 10 to 30 parts by mass with respect to 100 parts by mass of component (A). When component (B) is 3 parts by mass or more, the hardness of the cured product can be maintained. On the other hand, when (B) is 50 parts by mass or less, the transparency of the cured product can be maintained.

[0020] <(C) component> Component (C) contained in the photocurable resin composition according to the present invention is a polyfunctional thiol compound. The content of component (C) is, for example, 0.01 to 4.0 parts by mass, 0.01 to 3 (3.0) parts by mass, more preferably 0.1 to 2.8 parts by mass, and even more preferably 1 to 2.5 parts by mass, based on 100 parts by mass of the compound having a (meth)acryloyl group contained in the photocurable resin composition or the compound having a (meth)acryloyl group containing the above-mentioned component (A) and component (B). By including the polyfunctional thiol compound within the above range, a cured product having excellent gloss can be obtained. As the polyfunctional thiol compound, any compound having two or more thiol groups in one molecule can be used, but from the viewpoint of glossiness, it is preferable that the thiol group is a 3- to 6-functional group, and most preferably a 3-functional group. Also, the functional group ratio of the (meth)acryloyl group to the thiol group is preferably such that (meth)acryloyl group number / thiol group number is 9 or more, and more preferably 11 or more. Although there is no particular limitation, the upper limit value is such that (meth)acryloyl group number / thiol group number is 1000. Note that the "100 parts by mass of the compound having a (meth)acryloyl group" means 100 parts by mass considering the blending amount of component (E) in the case of a composition containing component (E) described later, and the "functional group ratio of the (meth)acryloyl group to the thiol group" means the ratio considering the (meth)acryloyl group of component (E) in the case of a composition containing component (E) described later. Also, the content of component (C) is, for example, 0.01 to 4.0 parts by mass, preferably 0.1 to 3.9 parts by mass, and more preferably 1 to 3.8 parts by mass, based on 100 parts by mass of the total of component (A) and component (B).

[0021] (The functional group ratio of the (meth)acryloyl group to the thiol group can be calculated from the (meth)acryloyl group equivalent and the thiol group equivalent determined, for example, by the following method.)

[0022] (As a method for measuring the (meth)acryloyl group equivalent, the following method can be used.)

[0023] Dissolve 1-2 g of a compound containing a (meth)acryloyl group in 20 ml of acetone, and add 10 ml of a 20% by mass methanol solution of morpholine. Then add 1 ml of a 75% by mass aqueous solution of acetic acid and react for 30 minutes. After the reaction is complete, add 25 ml of a 40% by mass acetonitrile solution of acetic anhydride, stir, and titrate with a 0.5 mol / L methanol solution of hydrogen chloride (titration volume: A1). As a blank, titrate with a 0.5 mol / L methanol solution of hydrogen chloride in the same manner as above, except that a compound containing a (meth)acryloyl group is not used (titration volume: A0). Calculate the equivalent amount of (meth)acryloyl group from the following formula: (meth)acryloyl group equivalent (g / eq) = 2000 × S / [(A0 - A) × f] In the formula, S is the mass (g) of the compound having a (meth)acryloyl group, and f is the titer of a 0.5 mol / L hydrogen chloride methanol solution.

[0024] The following method (iodine titration) can be used to measure the thiol group equivalent.

[0025] Prepare a sample solution by adding 20 mL of chloroform to 0.2 g of a polyfunctional thiol compound. As a starch indicator, dissolve 0.275 g of soluble starch in 30 g of pure water. Add 20 mL of pure water, 10 mL of isopropyl alcohol, and 1 mL of starch indicator to the sample solution and stir with a stirrer. Add iodine solution dropwise, and the endpoint is reached when the chloroform layer turns green. Calculate the thiol group equivalent using the following formula: Thiol group equivalent (g / eq) = Mass of polyfunctional thiol compound (g) × 10000 / Titration volume of iodine solution (mL) × Factor of iodine solution.

[0026] Furthermore, the equivalent amounts of the (meth)acryloyl group and the thiol group may be calculated from the chemical structure.

[0027] Specific examples of component (C) included in the photocurable resin composition according to the present invention include 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,3-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 3,6-dichloro-1,2-benzenedithiol, and toluene-3,4-dithiol. L, 1,5-naphthalenedithiol, ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bisthioglycolate, tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(thioglycolate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)-ethyl]isocyanurate, pentaerythritol 1,4-Bis(3-mercaptobutyryloxy)butane, Pentaerythritol tetrakis(3-mercaptopropionate), Dipentaerythritol hexakis(3-mercaptopropionate), 1,4-Bis(3-mercaptobutyryloxy)butane, Pentaerythritol tetrakis(3-mercaptobutyrate), Pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-Tris(3-mercaptobutyloxyethyl)-1,3,5-Triadine-2,4,6(1H,3H,5H)-Trion, Dimercaptodiethyl sulfide, 1 ,8-dimercapto-3,6-dithiaoctane, 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, tetrakis(7-mercapto-2,5-dithiaheptyl)methane, trithiocyanuric acid, 1,2-benzenedimethane, thiol, 4,4'-thiobisbenzenethiol, 2-di-n-butylamino-4,6-dimercapto-s-triazine, 2-di-n-butylamino-4,6-dimercapto-s-triazine, 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6-dioxaoctane, 1,5-Dimercapto-3-thiapentane, Tris(2-hydroxyethyl)isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, bis(4-(2-mercaptopropoxy)phenyl)methane, 1,1-bis(4-(2-mercaptopropoxy)phenyl)ethane, 2,2-bis(4-(2-mercaptopropoxy)phenyl)propane, 2,2-bis(4-(2-mercaptopropoxy)phenyl)butane, 1,1-bis(4-(2-mercaptopropoxy)phenyl)isobutane, 2,2-bis(4-(2-mercaptopropoxy)phenyl)isobutane (Ptopropoxy)-3-methylphenyl)propane, 2,2-bis(4-(2-mercaptopropoxy)-5-methylphenyl)propane, bis(2-(2-mercaptopropoxy)-5-methylphenyl)methane, 2,2-bis(4-(2-mercaptopropoxy)-3-t-butylphenyl)propane, tris(4-(2-mercaptopropoxy)phenyl)methane, 1,1,1-tris(4-(2-mercaptopropoxy)phenyl)ethane, bis(4-(2-mercaptobutoxy)phenyl)methane, 2,2-bis(4-(2-mercaptobutoxy)phenyl)propane, tris(4-(2-mercaptobutoxy)phenyl)methane, 1,3,5-triazine-2,4,Examples include 6-trithiol. Preferably, polyfunctional thiol compounds include polyfunctional thiol compounds having a trimethylolpropane skeleton, a pentaerythritol skeleton and a dipentaerythritol skeleton, and particularly preferably trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionyl) Examples include (C), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptobutyrate), and more preferably polyfunctional thiols having a trimethylolpropane skeleton, most preferably trimethylolpropanetris(3-mercaptopropionate) and trimethylolpropanetris(3-mercaptobutyrate). Having these skeletons allows for the production of cured products with superior gloss. In preferred embodiments, component (C) is a polyfunctional thiol compound having a trimethylolpropane skeleton. Component (C) can be used alone or in combination of two or more.

[0028] <(D) component> Component (D) contained in the photocurable resin composition according to the present invention is a photoinitiator. Examples of component (D) include radical-type photoinitiators that generate radical species in response to energy rays such as visible light, ultraviolet light, X-rays, and electron beams, cationic-type photoinitiators that generate cationic species, and anionic-type photogenerators that generate anionic species. Among these, radical-type photoinitiators are preferred from the viewpoint of reactivity, and it is preferable to use a combination of a visible light radical-type photoinitiator and an ultraviolet radical-type photoinitiator. Furthermore, from the viewpoint of long-term storage stability, it is preferable that the ultraviolet radical-type photoinitiator and the visible light radical-type photoinitiator are included in a ratio (mass ratio) of 5:5 to 7:3.

[0029] Examples of radical photoinitiators include acetophenone-based radical initiators, benzoin-based radical initiators, thioxanthone-based radical initiators, acylphosphine oxide-based radical initiators, and titanocene-based radical initiators. Among these, acetophenone-based radical initiators and acylphosphine oxide-based radical initiators are preferred from the viewpoint of excellent photocuring properties. These may be used individually or in combination of two or more. Acetophenone-based radical initiators are classified as ultraviolet radical photoinitiators, and acylphosphine oxide-based radical initiators are classified as visible light radical photoinitiators.

[0030] Examples of acetophenone-based radical initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl-ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer. Examples of acylphosphine oxide-based radical initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Component (D) can be used alone or in combination of two or more. Furthermore, from the viewpoint of achieving both gloss and curability, it is preferable to use an acetophenone-based radical initiator and an acylphosphine oxide-based radical initiator in combination. Specifically, it is more preferable to use 1-hydroxycyclohexyl-phenyl-ketone and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide in combination.

[0031] In the present invention, the content of component (D) is, for example, 0.1 to 15 parts by mass, more preferably 1 to 12 parts by mass, and even more preferably 3 to 9 parts by mass, per 100 parts by mass of a compound having a (meth)acryloyl group contained in the photocurable resin composition or a compound having a (meth)acryloyl group containing component (A) and component (B). When component (D) is 0.1 parts by mass or more, the glossiness of the cured product can be maintained. On the other hand, when component (D) is 15 parts by mass or less, the transparency of the cured product can be maintained. The above "100 parts by mass of a compound having a (meth)acryloyl group" means 100 parts by mass, taking into account the amount of component (E) that will be described later, in the case of a composition containing component (E). Furthermore, the content of component (D) is preferably 3 to 10 parts by mass per 100 parts by mass of the total of component (A) and component (B).

[0032] <Optional ingredients> In addition to the present invention, additives such as compounds having (meth)acryloyl groups other than components (A) and (B), fillers, conductive fillers, silane coupling agents, plasticizers, adhesives, defoamers, pigments, rust inhibitors, leveling agents, dispersants, rheology modifiers, and flame retardants can be used, to the extent that the objectives of the present invention are not impaired. Furthermore, the photocurable resin composition according to the present invention is preferably solvent-free from the viewpoint of adhesion to nails.

[0033] A compound having a (meth)acryloyl group other than components (A) and (B) may be added as component (E) to the photocurable resin composition according to the present invention. By adding component (E), adhesion to the nail can be improved and the fluidity of the photocurable resin composition can be improved. In a preferred embodiment, the photocurable resin composition according to the present invention further comprises a compound having a (meth)acryloyl group other than components (A) and (B) as component (E). The mass ratio of the sum of components (A) and (B) to component (E) (component (A) + component (B) : component (E)) is preferably 7:3 to 5:5.

[0034] Specific examples of compounds having one (meth)acryloyl group other than components (A) and (B) include lauryl (meth)acrylate, stearyl (meth)acrylate, ethyl carbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, and phenyl (meth)acrylate. Phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, nonylphenoxyethyl (meth)acrylate, nonylphenoxytetraethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxyethyl (meth)acrylate, butoxytriethylene glycol (meth)acrylate, 2-ethylhexyl Examples include, but are not limited to, polyethylene glycol (meth)acrylate, 4-hydroxybutyl (meth)acrylate, nonylphenyl polypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid, hydroxybutyl (meth)acrylate, 3-hydroxy-3-methylbutyl (meth)acrylate, hydroxypentyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyheptyl (meth)acrylate, hydroxyoctyl (meth)acrylate, glycerol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, epichlorohydrin-modified butyl (meth)acrylate, epichlorohydrin-modified phenoxy (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and N,N-diethylaminoethyl (meth)acrylate.In particular, it is preferable to add 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl methacrylate, and / or hydroxybutyl (meth)acrylate. Adding these makes it possible to reduce the fluidity of the photocurable resin composition without reducing its reactivity.

[0035] Specific examples of compounds having two (meth)acryloyl groups other than components (A) and (B) include 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, ethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and ethylene oxide-modified neopentyl glycol di(meth)acrylate. Examples of suitable materials include, but are not limited to, propylene oxide-modified neopentyl glycol di(meth)acrylate, bisphenol A ethoxylate di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, epichlorohydrin-modified bisphenol A di(meth)acrylate, ethylene oxide-modified bisphenol S di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, dicyclopentenyl di(meth)acrylate, ethylene oxide-modified dicyclopentenyl di(meth)acrylate, di(meth)acryloyl isocyanurate, and isocyanuric acid EO-modified di(meth)acrylate. In particular, the addition of bisphenol A ethoxylate di(meth)acrylate and / or isocyanuric acid EO-modified di(meth)acrylate is preferable. Adding these can improve adhesion to the nail. Component (E) can be used alone or in combination of two or more types.

[0036] To improve the elastic modulus, fluidity, and other properties of the cured product, fillers may be added to the photocurable resin composition according to the present invention, to the extent that the objectives of the present invention are not impaired. Specifically, examples include inorganic powders and organic powders.

[0037] Examples of inorganic powder fillers include, but are not limited to, glass, fumed silica, alumina, mica, ceramics, silicone rubber powder, calcium carbonate, aluminum nitride, carbon powder, kaolin clay, dried clay minerals, dried diatomaceous earth, and kaolin. These can be used individually or in combination of two or more. The amount of inorganic powder to be blended is preferably about 0.1 to 200 parts by mass per 100 parts by mass of component (A).

[0038] Fumed silica is added to photocurable resin compositions for the purpose of adjusting the viscosity or improving the mechanical strength of the cured product. Preferably, fumed silica surface-treated with dimethylsilane, trimethylsilane, alkylsilane, methacryloxysilane, organochlorosilane, polydimethylsiloxane, hexamethyldisilazane, etc. is used. Examples of commercially available fumed silica include, but are not limited to, Aerosil R972, R972V, R972CF, R974, R976, R976S, R9200, RX50, NAX50, NX90, RX200, RX300, R812, R812S, R8200, RY50, NY50, RY200S, RY200, RY300, R104, R106, R202, R805, R816, T805, R711, R7200, etc. (manufactured by Nippon Aerosil Co., Ltd.). These can be used individually or in combination of two or more types.

[0039] Examples of organic powder fillers include, but are not limited to, polyethylene, polypropylene, polystyrene, nylon, polyester, polyvinyl alcohol, polyvinyl butyral, polycarbonate, and polymethyl (meth)acrylate. These may be used individually or in combination of two or more. The amount of organic powder blended is preferably about 0.1 to 200 parts by mass per 100 parts by mass of component (A).

[0040] A conductive filler may be added to the photocurable resin composition according to the present invention. Examples of conductive fillers include, but are not limited to, gold, silver, platinum, nickel, palladium, and plated particles obtained by coating organic polymer particles with a thin metal film. These may be used individually or in combination of two or more.

[0041] A silane coupling agent may be added to the photocurable resin composition according to the present invention. Examples of silane coupling agents include, but are not limited to, γ-chloropropyltrimethoxysilane, octenyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, and p-styryltrimethoxysilane. These may be used individually or in combination of two or more.

[0042] In the photocurable resin composition according to the present invention, it is preferable to add a plasticizer as component (F) from the viewpoint of fluidity. Component (F) is not particularly limited, but for example, as a polyether-based plasticizer, a compound having a polyether skeleton can be mentioned. The polyether skeleton refers to a skeleton having alkylene oxides such as polypropylene glycol, polyethylene glycol, and polybutylene glycol. The number of alkylene oxide repeats is not particularly limited, but for example, it is in the range of 3 to 300, more preferably 5 to 100, and particularly preferably 10 to 60. Also, as polycarboxylic acid ester-based plasticizers, aromatic polycarboxylic acid esters such as dioctyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and butyl benzyl phthalate (BBP) can be mentioned, as well as trimellitic acid esters such as trioctyl trimellitic acid (TOTM) and triisodecyl trimellitic acid (TITM), and pyromellitic acid esters such as pyromellitic acid tetra Examples of aliphatic polycarboxylic acid esters such as laoctyl include di2-ethylhexyl adipate (DOA), isodecyl adipate (DIDA), di2-ethylhexyl sebacate (DOS), dibutyl sebacate (DBS), di2-ethylhexyl maleate (DOM), dibutyl fumarate (DBF), di2-ethylhexyl azelaate (DOZ), di2-ethylhexyl epoxyhexahydrophthalate, trioctyl citrate, and glycerol triacetate, but are not limited to these. Examples of phosphate ester plasticizers include, but are not limited to, trimethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, alkylallyl phosphate, triethyl phosphate, tri(chloroethyl) phosphate, trisdichloropropyl phosphate, tris(β-chloropropyl) phosphate, octyldiphenyl phosphate, tris(isopropylphenyl) phosphate, and cresylphenyl phosphate.Furthermore, multiple plasticizers can be used in combination.

[0043] As component (F), a polyether-based plasticizer is preferred, and polypropylene glycol is even more preferred. By using a polyether-based plasticizer, the fluidity of the photocurable composition can be optimized without reducing the gloss of the cured product. In a preferred embodiment, the photocurable resin composition according to the present invention further comprises a polyether-based plasticizer as component (F).

[0044] The number-average molecular weight of component (F) is not particularly limited, but is, for example, in the range of 200 to 30,000, preferably in the range of 350 to 10,000, and particularly preferably in the range of 500 to 5,000. Unless otherwise specified, the number-average molecular weight is calculated by the standard polystyrene equivalent method using size exclusion chromatography (SEC). By being within the above range, it is possible to obtain a radical-curable thermally conductive resin composition in which a cured product with excellent tensile strength and elongation is obtained while maintaining thermal conductivity.

[0045] There are no particular limitations on commercially available polyether-based plasticizers of component (F) mentioned above, but examples include PEG#300, PEG#400, PEG#600, PEG#1000, PEG#1500, PEG#15400, PEG#2000, PEG#4000, PEG#6000, PEG#1100, PEG#2000, Uniol D-700, D-1000, D-1200, D-2000, D-4000, PB-500, PB-700, PB-1000, and PB-2000 (manufactured by NOF Corporation).

[0046] The amount of component (F) is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, and particularly preferably 5 to 13 parts by mass, per 100 parts by mass of a compound having a (meth)acryloyl group contained in the photocurable resin composition or a compound having a (meth)acryloyl group containing component (A) and component (B). Adding 1 part by mass or more of component (F) can lower the viscosity, and adding 20 parts by mass or less of component (F) can maintain the gloss of the cured product. Note that "100 parts by mass of a compound having a (meth)acryloyl group" means 100 parts by mass, taking into account the amount of component (E) in the composition containing component (E). Furthermore, the content of component (F) is preferably 5 to 18 parts by mass per 100 parts by mass of the total of component (A) and component (B).

[0047] As described above, the photocurable resin composition for nails or artificial nails according to the present invention makes it possible to form a cured product with excellent gloss.

[0048] In one embodiment of the present invention, the photocurable resin composition for nails or artificial nails according to the present invention is applied to a film thickness of 0.1 mm, and the integrated light intensity is 7.5 kJ / m 2 When cured and the uncured material on the surface of the cured material is wiped off with a solvent, the gloss level of the cured material surface is between 67 and 88 at a 20° angle.

[0049] One embodiment of the present invention is a cured product obtained by curing a photocurable resin composition for nails or artificial nails according to the present invention.

[0050] In this invention, "artificial nail" refers to a layer formed on a human or animal nail for decorative and / or protective purposes. Other examples of artificial nails include resin base materials (false nails) of any shape intended for decorative and / or protective purposes. The shape of the artificial nail is not particularly limited; it may be formed to cover the nail, or it may be formed in a shape larger than the nail for the purpose of extending the nail. It may also be formed for the purpose of adhering items such as stones to the nail to improve its appearance.

[0051] Artificial nails are generally constructed by forming a base coat layer (a layer intended to provide adhesion to the nail, prevent color transfer, etc.) on the surface of the nail by curing a photocurable resin composition for base coats, then forming a color layer (a layer containing colorants, etc., for decorative purposes) on top of that by curing a photocurable resin composition for color, and finally forming a top coat layer (a layer intended for coating, providing gloss, and improving aesthetics) on top of that by curing a photocurable resin composition for top coats. The photocurable resin composition of the present invention is not particularly limited as long as it is used for the purpose of forming layers on nails or artificial nails, but it is preferable to use it as a photocurable resin composition for forming a top coat layer because it has gloss. In a preferred embodiment, the photocurable resin composition of the present invention is for forming a top coat layer.

[0052] Before applying the photocurable resin composition according to the present invention, if applying it directly to the nail, sand the nail surface with a file or the like to improve adhesion, and then remove dust, oil, moisture, etc. with a nail-specific solvent mainly composed of ethanol. When applying the photocurable resin composition according to the present invention, a coating film with a thickness of 50 to 300 μm in the pre-curing state is formed with a brush or the like. Alternatively, the photocurable resin composition according to the present invention may be applied directly on a cured film such as a base coat resin or a color resin. A primer may be used beforehand when applying. When curing, the photocurable composition is cured by irradiating it with energy rays. Energy rays here refer to all light in a broad sense, including radiation such as alpha rays and beta rays, electromagnetic waves such as gamma rays and X-rays, electron beams (EB), ultraviolet rays with a wavelength of about 100 to 380 nm, and visible light with a wavelength of about 381 to 800 nm, and preferably ultraviolet rays and visible light. A commercially available nail UV lamp or nail LED lamp is used as the irradiation device for curing. The irradiation time is 15 to 120 seconds, but considering the effect on the fingers, it is preferably 20 to 70 seconds. The cumulative light intensity is 3 to 15 kJ / m². 2 Preferably, it is 5-10 kJ / m³ 2It is more preferable that this is the case. Furthermore, it is preferable to wipe the surface of the cured product of the photocurable resin composition of the present invention with a nail-specific wiping solvent. Doing so will allow for a better gloss to be exhibited. The nail-specific wiping solvent may be, but is not limited to, one whose main components are ethanol, isopropyl alcohol, methyl ethyl ketone, acetone, etc.

[0053] Another embodiment of the present invention is a method for coating a nail or artificial nail, comprising applying a photocurable resin composition according to the present invention to a nail or artificial nail to form a coating film, and then curing the coating film by irradiating it with energy rays.

[0054] The photocurable resin composition of the present invention can be manufactured by conventionally known methods. For example, it can be manufactured by blending predetermined amounts of components (A) to (D) and other components as needed, and mixing them using a mixing means such as a planetary mixer under light-shielding conditions at a temperature preferably of 10 to 50°C for preferably 0.1 to 5 hours. [Examples]

[0055] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Hereafter, the photocurable resin composition will also be simply referred to as resin.

[0056] <Preparation of photocurable resin composition> Each component was collected in parts by mass as shown in Table 1 and mixed for 60 minutes in a planetary mixer under light-shielding conditions at 25°C to prepare a photocurable resin composition.

[0057] <(A) component> a1: Polyether skeleton bifunctional urethane acrylate (ART RESIN UN-6303, manufactured by Negami Kogyo Co., Ltd., weight-average molecular weight: 4000) <(B) component> b1: Isocyanuric acid EO-modified triacrylate (Aronics M-313 (65% by mass), manufactured by Toagosei Co., Ltd.) b2: Trimethylolpropane triacrylate (NK ester A-TMPT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) b3: Trimethylolpropane trimethacrylate (NK ester TMPT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) b4: Ethoxylated trimethylolpropane triacrylate (Sartomer SR502, manufactured by Sartomer Corporation) <(C) component> c1: Trimethylolpropanetris (3-mercaptopropionate) (TMMP-20P, manufactured by SC Organic Chemicals Co., Ltd.) c2: Trimethylolpropanetris(3-mercaptobutyrate) (Kalenz MT TPMB, manufactured by Showa Denko Corporation) c3: Dipentaerythritol hexakis (3-mercaptopropionate) (DPMP, manufactured by SC Organic Chemicals Co., Ltd.) c4: Pentaerythritol tetrakis(3-mercaptopropionate) (PEMPII-20P, manufactured by SC Organic Chemicals Co., Ltd.) c5: Pentaerythritol tetrakis(3-mercaptobutyrate) (Kalenz MT PE1, manufactured by Showa Denko Corporation) <(D) component> d1: 1-Hydroxycyclohexylphenyl ketone (DOUBLECURE 184, manufactured by Double Bond Chemical) d2: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (DOUBLECURE TPO, manufactured by Double Bond Chemical) <(E) component> e1: Isocyanuric acid EO-modified diacrylate (Aronics M-313 (35% by mass), manufactured by Toagosei Co., Ltd.) e2: Bisphenol A ethoxylate dimethacrylate (NK ester BPE-80N, manufactured by Shin-Nakamura Chemical Co., Ltd.) e3: 4-Hydroxybutyl acrylate (4-HBA, Osaka Organic Chemical Co., Ltd.) e4:2-Hydroxypropyl methacrylate (Acrylic ester HP, Mitsubishi Rayon Co., Ltd.) <(F) component> f1: Polypropylene glycol (Uniol D-700, NOF Corporation).

[0058] The test methods used in the examples and comparative examples in Table 1 are as follows:

[0059] <Glossiness Measurement> A 0.8 x 70 x 150 mm black test piece (one side with electrodeposited amino alkyd clear coating, material: SPCC-SD) was degreased and cleaned. A spacer was set to ensure a film thickness of 0.1 mm, and approximately 2-3 ml of resin was applied. The resin was then squeegeeed using a glass rod. The piece was then cured using a nail LED lamp (Lexia EX 30W, wavelength 395-405 nm; manufactured by PriAnfa Co., Ltd.) to prepare a cured sample for measurement (curing conditions: irradiation time 30 seconds, integrated light intensity 7.5 kJ / m²). 2 ). Afterwards, it was wiped with cotton soaked in plenty of acetone. The 60° and 20° values ​​were measured using a gloss meter (Gloss Checker, manufactured by Horiba, Ltd.). From the perspective of superior gloss, a ○ is preferable, and a ◎ is even preferable, according to the following evaluation criteria. ≪Evaluation Criteria≫ ◎: 67-88 when 20° ○: 81-90 when 60° ×: 80 or less when at 60°.

[0060] <Viscosity measurement> 0.5 mL of each of the photocurable resin compositions shown in Table 1 was taken and dispensed into a measuring cup. Viscosity was measured using an EHD type viscometer (manufactured by Toki Sangyo Co., Ltd.) under the following conditions. The results were defined as "viscosity (Pa·s)". When coating (decorating) nails, from the viewpoint of workability such as suppression of resin flow and ease of application, a ○ is preferable, and a ◎ is even preferable, according to the following evaluation criteria. ≪Evaluation Criteria≫ ◎: 0.5~50 Pa·s ○: 49~150 Pa·s ×: Less than 0.5 Pa·s or greater than 150 Pa·s <Measurement Conditions> Cone rotor: 3° × R14 Rotation speed: 1 rpm Measurement time: 3 minutes Measurement temperature: 25°C (temperature controlled by a chiller).

[0061] <Hardness measurement> A 1mm thick spacer was placed on a 1.0 x 150 x 150mm blue glass plate, and a photocurable resin composition was applied. A PET film was placed on top, and then another blue glass plate was placed on top, sandwiching the photocurable resin composition between them. Curing conditions: integrated light intensity 30kJ / m². 2 Using a UV meter, two sheets of blue glass were irradiated twice from the front and back surfaces to create a 1mm thick cured material (the UV light passing through the PET film and blue glass was adjusted to meet the above curing conditions). Three cured materials were created in the same manner and left for 2 hours. After that, the blue glass and PET film were peeled off, and the three 1mm thick sheet-like cured materials were stacked with the side where the PET film was attached facing upwards. The hardness of the stacked sheet-like cured materials was measured on a smooth surface using a Type D durometer tester. Five measurements were taken, and the average of the three measurements excluding the maximum and minimum values ​​was calculated. For materials to be resistant to scratches and peeling in daily life, it is preferable that they meet the following evaluation criteria (○). ≪Evaluation Criteria≫ ○: D70~100 ×: Less than D70 <Measurement Conditions> Durometer pressing speed: 3.0 mm / sec Numerical reading method: The maximum value within 1 second after the tip of the durometer's measuring part comes into close contact with the object being measured.

[0062] [Table 1]

[0063] According to the examples in Table 1, it can be seen that the photocurable resin composition can form cured products with excellent gloss. Although component (C) differs between Example 1 and Examples 3-6, all cured products have excellent gloss, and although component (B) differs between Example 1 and Examples 7-9, all cured products have excellent gloss.

[0064] According to the comparative examples in Table 1, Comparative Example 1 does not contain component (C), so the gloss of the cured product is inferior. In Comparative Example 2, the amount of component (C) added exceeds 3 parts by mass (3.0) per 100 parts by mass of components (A), (B), and (E), so the gloss of the cured product is inferior. In Comparative Examples 3 and 4, component (B) is replaced with component (E), but the gloss of the cured product is still not good. In Comparative Example 5, component (B) is not included, so the gloss of the cured product is inferior. [Industrial applicability]

[0065] The photocurable resin composition of the present invention is a photocurable resin composition for nails or artificial nails that has the hardness necessary for coating during curing and can form a glossy cured product, and therefore can be widely used in the nail industry.

[0066] This application is based on Japanese Patent Application No. 2021-095549, filed on June 8, 2021, the disclosures of which are referenced and incorporated in whole.

Claims

1. It contains the following components (A) to (F): The compound comprising 100 parts by mass of a compound having a (meth)acryloyl group contains 0.01 parts by mass or more and 3.0 parts by mass of component (C), 0.1 to 15 parts by mass of component (D), and 1 to 20 parts by mass of component (F), The above-mentioned (A) component comprises 10 to 40 parts by mass of component (B) with respect to 100 parts by mass of component (A). A photocurable resin composition for nails or artificial nails, wherein the mass ratio of the sum of components (A) and (B) to component (E) is 7:3 to 5:5: (A) Component: Urethane (meth)acrylate oligomer containing 2 to 6 (meth)acryloyl groups; (B) Component: A compound having 3 to 6 functional groups of (meth)acryloyl groups (excluding component (A) above); (C) Component: A polyfunctional thiol compound having 3 to 6 thiol groups; (D) Component: Radical photoinitiator; (E) Component: Compounds having one or two (meth)acryloyl groups as functional groups, other than the above components (A) and (B); and (F) Component: Polyether-based plasticizer.

2. The photocurable resin composition for nails or artificial nails according to claim 1, wherein component (C) is a polyfunctional thiol compound having a trimethylolpropane skeleton.

3. The photocurable resin composition for nails or artificial nails according to claim 1, wherein component (B) is a compound having a trifunctional group of (meth)acryloyl groups.

4. The aforementioned photocurable resin composition for nails or artificial nails is applied to a film thickness of 0.1 mm, and the integrated light intensity is 7.5 kJ / m². ２ The photocurable resin composition for nails or artificial nails according to claim 1, wherein the gloss of the cured surface is 67 to 88 at 20° when cured with a solvent and the uncured material on the cured surface is wiped off.

5. The photocurable resin composition for nails or artificial nails according to claim 1, wherein the photocurable resin composition for nails or artificial nails is for forming a top coat layer.

6. A cured product obtained by curing a photocurable resin composition for nails or artificial nails according to any one of claims 1 to 4.

7. A method for coating a nail or artificial nail, comprising applying a photocurable resin composition for nails or artificial nails according to any one of claims 1 to 4 to a nail or artificial nail to form a coating film, and then curing the coating film by irradiating it with energy rays.

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