JP2019172649A - Photocurable artificial nail composition - Google Patents

Abstract

To provide a photocurable artificial nail composition that, when cured with an ultraviolet irradiation machine such as an LED light source, has excellent photocurability, while showing a type D durometer hardness of D30 or more, but keeping the highest exothermic temperature at the time of curing in a range of less than 55°C.SOLUTION: A photocurable artificial nail composition has a urethane (meth) acrylate resin (A) having a polytetramethylene glycol skeleton with the number of functional groups being 2-5, a (meth) acrylate monomer (B), and a photopolymerization initiator (C), with the weight ratio of the (A) and (B) being (A):(B)=95/5-25/75.SELECTED DRAWING: None

Description

  The present invention relates to a photocurable artificial nail composition.

  In recent years, gel nails in which a resin composition is applied to the surface of the nail have become widespread as a cosmetic agent for decorating the surface of the nail. Usually, it consists of three layers, a base layer, a color layer, and a top layer. After the resin composition is applied, it is photocured in a short time by ultraviolet irradiation. The cured film has hardness, glossiness, and adhesion to the ground. Various properties are required, such as property, durability, slipperiness, and releasability when removed.

As a specific composition, for example, by containing a specific photopolymerization initiator such as an alkylphenone type, a composition for forming an artificial nail that cures even with UVA (499 to 315 nm) safe for the human body (Patent Document 1) In addition, an artificial nail raw material composition (Patent Document 2), which is made of urethane-modified methacrylate and methacrylate having an ethylene oxide / propylene oxide copolymer and removable with ethanol, has been proposed.

By the way, since the artificial nail composition is directly applied to the human body and photocured, it is desirable that it can be cured at a low temperature as much as possible in terms of safety, but in the case of a composition that can be cured at a low temperature, the hardness of the cured product tends to be low Therefore, there is room for improvement in order to achieve both conflicting characteristics of maintaining the hardness of the cured product high and lowering the maximum temperature during curing.

JP 2010-105967 A JP 2016-141634 A

  The problem of the present invention is that when cured by an ultraviolet irradiator such as an LED light source, it has a good photocurability and has a type D durometer hardness of D30 or higher and a maximum exothermic temperature during curing of 55. It is to provide a less than a which is photocurable artificial nail composition ° C..

  The invention described in claim 1 includes a urethane (meth) acrylate resin (A) having a polytetramethylene glycol skeleton and having 2 to 5 functional groups, a (meth) acrylate monomer (B), and a photopolymerization initiator (C And a weight blending ratio of (A) and (B) is (A) :( B) = 95/5 to 25/75. .

The invention according to claim 2 provides the photocurable artificial nail composition according to claim 1, wherein the weight average molecular weight of (A) is 1,000 to 30,000.

Invention of Claim 3 contains the plasticizer (D) further in the photocurable artificial nail composition of the said Claim 1, The photocurable artificial nail of Claim 1 or 2 characterized by the above-mentioned. A composition is provided.

The invention described in claim 4 is characterized in that the plasticizer (D) is selected from the group consisting of aliphatic ester-based, alicyclic ester-based, phthalate ester-based, and polyalkylene polyol-based. The photocurable artificial nail composition according to any one of 1 to 3 is provided.

The invention according to claim 5 is characterized in that the photocurable artificial nail composition according to claim 1 further includes a polyether-modified polysiloxane copolymer (E). A curable artificial nail composition is provided.

The invention according to claim 6 has a shape of 15 mm × 30 mm × t 0.2 mm, and is a cured product when cured by irradiation with LED light (405 nm, 40 mW / cm 2) from a height of 5 cm from the resin surface for 20 seconds. The photocurable artificial nail composition according to any one of claims 1 to 5, wherein the maximum temperature is less than 55 ° C.

The composition of the present invention has good photocurability when cured by an ultraviolet irradiator such as an LED light source, and the maximum exothermic temperature during curing is high while the type D durometer hardness is D30 or higher. It is useful as an artificial nail composition having a temperature of less than 55 ° C., particularly as an artificial nail composition used for the top layer.

The composition of the ultraviolet curable resin composition of the present invention is a urethane (meth) acrylate resin (A) having 2 to 5 functional groups, a (meth) acrylate monomer (B), and a photopolymerization initiator (C). In the present specification, (meth) acrylate includes both acrylate and methacrylate.

The urethane (meth) acrylate resin (A) used in the present invention is one of the main components constituting the cured film and has 2 to 5 (meth) acryloyl groups, and is excellent in wear resistance and flexibility at low temperatures. a photoreactive resin having polytetramethylene glycol skeleton. For example, in the case of a bifunctional urethane acrylate, a compound obtained by the addition reaction of polytetramethylene glycol (hereinafter referred to as PTMG) and diisocyanate is subjected to a condensation reaction of a monofunctional (meth) acrylate having a hydroxyl group. In the case of urethane acrylate, a reaction product of PTMG and diisocyanate can be exemplified by a condensation reaction of a bifunctional (meth) acrylate having a hydroxyl group. The reaction method may be a known method using a tin-based compound as a catalyst. By setting the number of functional groups to 2 to 5, appropriate reactivity and hardness after curing can be achieved. If the number of functional groups is one, the reactivity at the time of polymerization is low and the molecular weight does not increase.

The weight average molecular weight (hereinafter referred to as Mw) of (A) is preferably 1,000 to 30,000, more preferably 1,500 to 10,000, and particularly preferably 2,000 to 6,000. By setting it to 1,000 or more, sufficient cohesive force can be secured, and by setting it to 30,000 or less, it is easy to control the viscosity to be easy to handle. In addition, Mw measured and calculated the molecular weight of standard polystyrene conversion using the tetrahydrofuran hydrosolvent with the column of a styrene divinylbenzene base material by the gel permeation chromatography.

As a compounding quantity of (A) with respect to the whole composition, 25 to 95 weight% is preferable and 28 to 90 weight% is still more preferable. When it is 25% by weight or more, sufficient curability and hardness can be secured, and when it is 95% by weight or less, it becomes easy to control the viscosity suitable for workability.

The (meth) acrylate monomer (B) used in the present invention plays a role of improving the reactivity while reducing the viscosity of the (A) and improving workability. The number of functional groups may be either monofunctional or polyfunctional, can be used alone or in combination of two or more.

As an example of the (B), as the monofunctional (meth) acrylate monomer, alkyl (methyl) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate Cyclohexyl (meth) acrylate, octyl (meth) acrylate, ethylhexyl (meth) acrylate, benzyl (meth) acrylate as an aromatic system, phenoxyethyl acrylate as a hydroxyl group containing 2-hydroxyethyl (meth) Acrylates, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate are those containing amino groups (meth) acrylamide, N, N- Methyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and acryloylmorpholine are dicyclopentenyl (meth) acrylate and dicyclopentenyloxyethyl (meth) as aliphatic cyclic groups. Examples include acrylate, dicyclopentanyl (meth) acrylate, and isobornyl (meth) acrylate. Among these, surface hardness in terms of good 2-hydroxypropyl methacrylate are preferred.

Moreover, as a bifunctional (meth) acrylate monomer, (poly) ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1.4-butanediol di (meth) acrylate, 4.6-hexanediol di (meth) acrylate, 1.9-nonanediol di ( And (meth) acrylate, 1.10-decanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, and the like. Among these, (poly) ethylene glycol diacrylate having good compatibility with (A) and having a flexible skeleton is preferable.

Further, trifunctional or higher (meth) acrylate monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, isocyanuric acid EO-modified triacrylate, glycerin triacrylate, Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, (EO modified) diglycerin tetraacrylate, (EO modified) dipentaerythritol penta (meth) acrylate, (EO-modified) dipentaerythritol hexa (meth) acrylate and the like. Among these, glycerin triacrylate, EO-modified diglycerin triacrylate, EO-modified dipentaerythritol pentaacrylate, EO-modified dipentaerythritol hexaacrylate, etc., in terms of good compatibility with (A) and good surface hardness. Is preferred.

  The weight blending ratio of (B) to (A) is (A) :( B) = 95 / 5-25 / 75, and preferably 90 / 10-30 / 70. If the ratio of (A) exceeds 95, the viscosity will be too high, and if it is less than 25, the hardness of the cured product will be low and unsuitable.

The photopolymerization initiator (C) used in the present invention generates radicals upon irradiation with ultraviolet rays or electron beams, and the radicals trigger the polymerization reaction. The benzyl ketal series, acetophenone series, phosphine oxide series For example, a general-purpose photopolymerization initiator can be used. By arbitrarily selecting the light absorption wavelength of the polymerization initiator, curability can be imparted over a wide wavelength range from the ultraviolet region to the visible light region. Specifically, 2.2-dimethoxy-1.2-diphenylethan-1-one as benzyl ketal system and 1-hydroxy-cyclohexyl-phenyl-ketone and 1- [4- (2- Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one as the α-aminoacetophenone series is 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -On includes acylphosphine oxide as 2.4.6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2.4.6-trimethylbenzoyl) -phenylphosphine oxide, either alone or in combination Can be used in combination. In these, it is preferable that the acyl phenphine oxide type | system | group excellent in internal curability is included.

The blending amount is preferably 0.3 to 10 parts by weight with respect to 100 parts by weight of the radical polymerizable component, and more preferably 0.5 to 3 parts by weight for the base layer and the color layer which are the undercoat. 3-6 parts by weight in the top layer is the top layer is more preferred. By blending in this range, it is possible to cure the composition efficiently. Commercially available products include phosphine oxide and Omnirad TPOH (trade name: manufactured by iGM).

  By further blending the plasticizer (D) with the photocurable artificial nail composition of the present invention, the slipperiness on the surface of the cured product can be greatly improved. Plasticizer is a general term for additives that improve the flexibility of thermoplastic resins. It penetrates between polymer molecules to weaken the intermolecular force of the polymer and makes the molecular chain easier to move, thereby making the glass transition point of the polymer easier to move. Can be lowered to give the polymer flexibility.

Examples of the (D) include aliphatic ester, alicyclic ester, phthalate ester, aliphatic dibasic ester, polyalkylene polyol, phosphate ester, polyester, and paraffin. It can be used alone or in combination of two or more.

Of these, aliphatic ester, alicyclic ester, phthalate, and polyalkylene polyols are preferred. In particular, 2-ethylhexyl stearate is used for aliphatic ester, and 1. 2-cyclohexanedicarboxylic acid isononyl ester, diallyl phthalate in the phthalate ester system, polypropylene glycol in the polyalkylene polyol system are very compatible with (A), and greatly improves the slippage of the cured product surface. It is particularly preferable in terms of improvement.

The blending amount of (D) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, and more preferably 0.8 to 7 parts per 100 parts by weight of the total of (A) and (B). Part by weight is particularly preferred. By making it 0.1 parts by weight or more, slipperiness can be improved, and by making it 10 parts by weight or less, sufficient curability can be secured.

By further blending the polyether-modified polysiloxane copolymer (E) with the photocurable artificial nail composition of the present invention, the slipping property on the surface of the cured product can be greatly improved as in the case of (D). Even if it has a polysiloxane skeleton, if it has a polar functional group such as an acrylic group or a phenyl group, the compatibility with (A) is lowered, which is not suitable.

The blending amount of (E) is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.5 part by weight with respect to 100 parts by weight in total of (A) and (B), and 0.08. -0.3 parts by weight are particularly preferred. By making it 0.01 parts by weight or more, the sliding property can be improved, and by making it 1 parts by weight or less, sufficient curability can be secured.

In the composition of the present invention, an antioxidant, a white pigment, a color pigment, a fragrance, a dye, a light stabilizer, a photosensitizer, an ultraviolet absorber, a silane coupling agent, if necessary, as long as the performance is not impaired. Various additives such as antibacterial agents, antifungal agents, surfactants, decorative powders and strips may be contained.

An artificial nail is generally composed of a three-layer structure of a base layer, a color layer, and a top layer, but any one of the layers may be omitted, or an arbitrary layer may be formed into multiple layers. The base layer improves the adhesion between the nail and the color layer, and the color layer can be decorated with various colors and various powders, and the top layer is the outermost layer that enhances the durability of the artificial nail and gives gloss Improve the appearance of etc. Among these, the photocurable artificial nail composition of the present invention is particularly suitable for the top layer, but may be used for the base layer and the color layer. In particular, when used for the top layer, it is preferable to blend a plasticizer or a polyether-modified polysiloxane copolymer in order to improve the slipperiness.

The viscosity of this composition at 25 ° C. is preferably 300 to 100,000 mPa · s, and more preferably 500 to 70,000 mPa · s. When it is set to 300 mPa · s or more, it is difficult to sag on the skin or the like during work, and when it is set to 100,000 mPa · s or less, the coating workability is improved.

Cured product when this composition is made into a shape of 15 mm × 30 mm × t 0.2 mm and cured by irradiation with a pressed LED light (405 nm, 40 mW / cm 2) manufactured by Nail Lab Co., Ltd. for 20 seconds from a height of 5 cm from the resin surface. The maximum temperature is preferably less than 55 ° C., and more preferably 50 ° C. or less. When the maximum temperature exceeds 55 ° C. in this shape, even when it is actually applied thinly on the nail, it feels hot. The illuminance was measured with a UIT-250 (receiver: UVD-C405) manufactured by USHIO.

The cured product obtained by irradiating the composition with a thickness of 4 mm at 40 mW / cm 2 (405 nm) with an LED light irradiator for 1 minute has a type D durometer hardness of preferably D30 or more, and more preferably D50 or more. By setting it to D30 or more, appearance deterioration due to scratches or the like of the artificial nail can be suppressed, and durability can be improved.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and demonstrated in detail about this invention, a specific example is shown and it does not specifically limit to these. In the case there is no notation is room temperature was measured under the conditions of 25 ° C. and 65% relative humidity.

Example 1
In the light-shielding bottle, urethane acrylate (hereinafter referred to as ureac) 1 (PTMG skeleton, tetrafunctional, Mw4300) is used as (A), and Aronix M-245 (trade name: manufactured by Toagosei Co., Ltd., PEG # 400 diacrylate) is used as (B). ) And OmniradTPOH (trade name: manufactured by iGM, 2.4.6-trimethylbenzoyl-diphenyl-phosphine oxide) are added in the amount shown in Table 1 and uniform using a stirring deaerator. And the resin composition of Example 1 was prepared. The unit of the recipe is part by weight.

Examples 2-19
In addition to the materials used in Example 1, ureac 2 (PTMG skeleton, tetrafunctional, Mw3200) and ureac 3 (PTMG skeleton, bifunctional, Mw2600) were used as (A), and light ester HOP (N ) (Trade name: manufactured by Kyoeisha Chemical Co., Ltd., 2-hydroxypropyl methacrylate) and Aronix MT-3547 (trade name: manufactured by Toagosei Co., Ltd., glycerin triacrylate) and Aronix MT-3553 (trade name: manufactured by Toagosei Co., Ltd., EO modified) Diglycerin tetraacrylate) and Aronix M-240 (trade name: manufactured by Toagosei Co., Ltd., PEG # 200 diacrylate) and New Frontier MF-001 (trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., dipentaerythritol EO adduct hexa / Pentaacrylate) as Hexamol as (D) DINCH (trade name: manufactured by BASF Japan, 1.2-cyclohexanedicarboxylic acid diisononyl ester) and Exepearl ES-H (trade name: manufactured by Kao Corporation, 2-ethylhexyl stearate) and Daisodap monomer (trade name: Osaka) Soda, diallyl phthalate monomer) and P-400 (trade name: ADEKA, polypropylene glycol) are used as (E), and TEGO Glide ZD400 (trade name: EVONIK, polyether-modified polysiloxane copolymer) is used. The resin compositions of Examples 2 to 19 were prepared by stirring until uniform using a stirring defoaming machine with the formulation shown in Table 1.

Comparative Examples 1-7
In addition to the materials used in the examples, ureac 4 (PTMG skeleton, hexafunctional, Mw3700) and epoxy ester 3000A (trade name: manufactured by Kyoeisha Chemical Co., Ltd., bifunctional, epoxy acrylate) and UN-9200A (trade name) are used as acrylate oligomers. : Negami Industrial Co., Ltd., bifunctional, polycarbonate-based ureac) and TE-2000 (Brand name: Nippon Soda Co., Ltd., bifunctional, polybutadiene-based ureak) and RUA-049X (trade name: manufactured by Asia Industrial Co., Ltd., trifunctional, isocyania The resin compositions of Comparative Examples 1 to 7 were prepared by stirring until uniform using a stirring defoamer with the formulation shown in Table 2 using a urelate type ureak).

Production of cured product (for hardness measurement)
2 g of room temperature ultraviolet curable resin is put into a silicone mold (Φ26 mm, depth 10 mm), and about 1 cm from a height of about 4 cm from the resin surface with an LED irradiator (Nail Lab Presto LED Light 405 nm, 40 mW / cm2). Irradiated to cure. Thereafter, the cured product was taken out from the silicone mold and left at 23 ± 2 ° C. for 30 minutes to prepare.

Table 1

Table 2

The evaluation method was as follows.

Viscosity: Using an E-type viscometer RE-215R manufactured by Toki Sangyo Co., Ltd., with a cone angle of 3 ° R17.65 and 25 ± 1 ° C. 2000 to 5000 mPa · s was measured at 10 rpm, 5000 to 10,000 mPa · s was measured at 5 rpm, 10000 mPa · s to 50000 mPa · s was 1 rpm, and 50000 mPa · s was measured at 0.5 rpm.

  Hardness: The irradiated surface of the cured product was measured with a D-type hardness meter (5 kg weighted).

  Exothermic temperature: A 0.5 mm thick vinyl tape is applied to both ends of a 26 mm x 76 mm glass slide with a 0.3 mm thick thermo label (trade name: NOF Corporation), between the tapes. 15 mm × 30 mm × t0 by pouring the resin composition into a thickness of 0.5 mm and irradiating with an LED irradiator (manufactured by Nail Lab, 40 mW / cm2, 405 nm) for 20 seconds from a height of about 5 cm from the resin surface. The case where the maximum temperature (thermo label display temperature) when cured to a shape of 2 mm was less than 55 ° C. was evaluated as “◯”, and 55 ° C. or more was evaluated as “X”.

Curability: A vinyl tape with a thickness of 0.1 mm is pasted on both ends of a 26 mm × 76 mm slide glass, and a resin composition is poured so that the thickness is 0.1 mm between the tapes. From the height, when it is cured by irradiation for 2 minutes with an LED irradiator (manufactured by Nail Lab Co., 40 mW / cm2, 405 nm) and left until the cured product reaches room temperature, the presence or absence of tack is evaluated by finger touch, and there is no tack Was marked with ◯, and in some cases with x. In addition, evaluation evaluated only Examples 13-19 which mix | blend (D) and (E) and are preferable to use for a top layer.

Compatibility: The resin composition was confirmed by visual observation, and the case where it was transparent was marked with ◯, and the case where it was cloudy was marked with ×.

Appearance: Using a sample that was evaluated for curability, visually observing the surface of the cured product, ○ when the surface is flat, and × when there are small dots like a dodd pattern or a wavy pattern did.

Sliding property: About Examples 13-19 which mix | blended said (D) and (E), using the sample which evaluated hardenability, with the automatic friction abrasion analyzer TS-501 by Kyowa Interface Science Co., Ltd., the load of 100g, The dynamic friction coefficient was measured twice under the measurement conditions of a speed of 5 mm / second and a measurement distance of 20 mm.

The evaluation results of the examples are shown in Table 3.
Table 3

Table 4 shows the evaluation results of the comparative examples.
Table 4

  Resin compositions of the examples were good none of the evaluation results.

 On the other hand, Comparative Example 1 in which (B) is not blended has a high viscosity, Comparative Example 2 in which the blending ratio of (A) is low has a low hardness, and Comparative Example 3 in which a ureak having a large number of functional groups is blended has a high exothermic temperature. Comparative Examples 4 to 7 containing other than ureac were unsuitable for evaluation of any of viscosity, hardness and exothermic temperature, and none of them was suitable for the present invention.

When the resin composition of the present invention is cured by an ultraviolet irradiator such as an LED light source, the resin composition has good photocurability, and the maximum heat generation temperature upon curing is 55 ° C. while the type D durometer hardness is D30 or more. Therefore, it is useful as an artificial nail composition, particularly an artificial nail composition used for a top layer.

Claims (6)

A urethane (meth) acrylate resin (A) having a polytetramethylene glycol skeleton and having 2 to 5 functional groups, a (meth) acrylate monomer (B), and a photopolymerization initiator (C), ) And (B) in a weight blending ratio of (A) :( B) = 95/5 to 25/75.   The photocurable artificial nail composition according to claim 1, wherein the weight average molecular weight of (A) is 1,000 to 30,000. 3. The photocurable artificial nail composition according to claim 1, further comprising a plasticizer (D) in the photocurable artificial nail composition according to claim 1. The light according to any one of claims 1 to 3, wherein the plasticizer (D) is selected from the group consisting of aliphatic ester series, alicyclic ester series, phthalate ester series, and polyalkylene polyol series. Curable artificial nail composition. 3. The photocurable artificial nail composition according to claim 1, further comprising a polyether-modified polysiloxane copolymer (E) in the photocurable artificial nail composition according to claim 1. The maximum temperature of the cured product when it is cured by irradiation for 20 seconds from a height of 5 cm from the resin surface with an LED light (405 nm, 40 mW / cm 2) in a shape of 15 mm × 30 mm × t 0.2 mm. The photocurable artificial nail composition according to any one of claims 1 to 5, wherein