JP2022041419A - Curable composition for nail coating - Google Patents

Abstract

To provide a curable composition for nail coating having excellent wettability to a base coat, coating film hardness, and storage stability, while exhibiting good curability.SOLUTION: A curable composition for nail coating comprises: a polycaprolactone-based urethane (meth) acrylate oligomer (A); a polycaprolactone-based urethane(meth)acrylate oligomer (B); trimethylolpropane tri(meth)acrylate (C), and a polyfunctional thiol compound (D). The content of the polyfunctional thiol compound (D) is 1 to 8% by weight. Further, a photopolymerization initiator (F) may be contained.SELECTED DRAWING: None

Description

The present invention relates to a curable composition for nail coating that can be suitably used as a non-wipe type top coat.

As a beautiful nail agent used for the beauty of nails, it is known that a resin layer is formed on the nail by applying it on the nail and then irradiating it with energy rays such as ultraviolet rays and visible light to cure it. There is. These are used not only for protecting nails and imparting luster, but also for nail art and the like.
Among the beautiful nail agents, a non-wipe type top gel that does not require wiping of the uncured gel after curing is known.
Patent Document 1 describes an artificial nail raw material composition containing a radically polymerizable compound such as a urethane acrylate oligomer, a polyfunctional thiol compound, and a photopolymerization initiator.

Japanese Unexamined Patent Publication No. 2014-5260

According to the composition containing the urethane acrylate oligomer and the polyfunctional thiol compound as disclosed in Patent Document 1, the curability is good, and a non-wipe type top gel can be provided.
However, in the composition disclosed in Patent Document 1, the wettability to the base (base layer, nail polish layer, or nail) is low, the problem of cissing after application to the base, and the hardness of the coating film are lowered. There was a problem that it was insufficient as a top coat and the storage stability before use was insufficient.

Therefore, an object of the present invention is to provide a curable composition for nail coating, which is excellent in wettability to a substrate, coating film hardness, and storage stability while exhibiting good curability.

The present invention relates to an aliphatic polyfunctional urethane (meth) acrylate oligomer (A), a polycaprolactone-based urethane (meth) acrylate oligomer (B), a trimethylolpropane tri (meth) acrylate (C), and a polyfunctional thiol compound. The present invention relates to a curable composition for nail coating, which contains (D) and has a content of the polyfunctional thiol compound (D) of 1 to 8% by weight.
Preferably, the content of the aliphatic polyfunctional urethane (meth) acrylate oligomer (A) is 30 to 50% by weight, and the content of the polycaprolactone-based urethane (meth) acrylate oligomer (B) is 20 to 30% by weight. The content of trimethylolpropane tri (meth) acrylate (C) is 5 to 35% by weight.
Preferably, the curable composition for nail coating further contains a hydroxyl group-containing (meth) acrylate (E).
Preferably, the curable composition for nail coating further contains a photopolymerization initiator (F).
Preferably, the curable composition for nail coating is intended for use as a non-wipe topcoat.

According to the present invention, it is possible to provide a curable composition for nail coating, which is excellent in wettability to a substrate, coating film hardness, and storage stability while exhibiting good curability.
According to a preferred embodiment of the present invention, it is possible to form a cured coating film which is smooth and glossy with less friction, and is less likely to generate heat during curing, and is suitable as a non-wipe type top coat. It is possible to provide a curable composition for nail coating that can be used in Japan.

Hereinafter, embodiments of the present invention will be described in detail.
The curable composition for claw coating according to the present embodiment includes an aliphatic polyfunctional urethane (meth) acrylate oligomer (A), a polycaprolactone-based urethane (meth) acrylate oligomer (B), and a trimethylolpropane tri (meth) acrylate. (C) and the polyfunctional thiol compound (D) are contained, and the content of the polyfunctional thiol compound (D) is 1 to 8% by weight.

The aliphatic polyfunctional urethane (meth) acrylate oligomer (A) is a compound having a urethane bond, a (meth) acryloyl group, and an aliphatic hydrocarbon skeleton, and has a (meth) acryloyl group in one molecule. It is a compound having three or more. By blending this compound, the curability of the curable composition for nail coating can be improved, and the storage stability of the composition can also be improved. The aliphatic hydrocarbon skeleton preferably refers to a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

The aliphatic polyfunctional urethane (meth) acrylate oligomer (A) is not particularly limited, but by reacting one molecule of the aliphatic polyfunctional isocyanate compound with three or more molecules of the (meth) acryloyl monomer having a hydroxyl group. The resulting compound is preferred.

The (meth) acryloyl monomer having a hydroxyl group is not particularly limited, and is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 1,3-butanediol. (Meta) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta ( Meta) Acrylate and the like can be mentioned. These may be used alone or in combination of two or more.

The aliphatic polyfunctional isocyanate compound is a compound having three or more isocyanate groups in one molecule and an aliphatic hydrocarbon skeleton. Specific examples thereof are not particularly limited, and examples thereof include isocyanurates of aliphatic diisocyanates. The isocyanurate form is a compound in which three isocyanate molecules are bonded to form a cyclic compound. The isocyanurate form of diisocyanate is a cyclic compound having three isocyanate groups in one molecule.

Specific examples of the isocyanurate form of the aliphatic diisocyanate include an isocyanurate form of hexamethylene diisocyanate, an isocyanurate form of trimethylhexamethylene diisocyanate, and an isocyanurate form of isopropylene diisocyanate.

A catalyst can be appropriately used in synthesizing the aliphatic polyfunctional urethane (meth) acrylate oligomer (A). Examples of such a catalyst include amine-based catalysts and organometallic catalysts. Examples of the amine-based catalyst include triethylenediamine, diethanolamine, dimethylaminomorpholine, N-ethylmorpholine and the like. Examples of the organometallic catalyst include sternas octoate, dibutyltin dilaurate, lead octenoate, potassium octylate and the like. These various catalysts may be used alone or in combination of two or more.

In the curable composition for nail coating according to the present embodiment, the content of the polyfunctional urethane (meth) acrylate oligomer (A) in the entire composition can be appropriately set in consideration of the effect, but 30 It is preferably ~ 50% by weight, more preferably 35 ~ 45% by weight.

The polycaprolactone-based urethane (meth) acrylate oligomer (B) is a compound having a urethane bond, a (meth) acryloyl group, and a polycaprolactone skeleton, and preferably has two (meth) acryloyl groups in one molecule. It is a compound. By blending this compound, in addition to improving the hardness of the coating film obtained by curing the curable composition for nail coating, it is applied to the base layer (base layer, nail polish layer, or nail) of the composition. The wettability is improved, and the storage stability of the composition can be improved.

The polycaprolactone-based urethane (meth) acrylate oligomer (B) is not particularly limited, but one molecule of polycaprolactone diol and two molecules of a diisocyanate compound are reacted to produce a polycaprolactone-based urethane diisocyanate, and then the polycaprolactone-based urethane. A compound obtained by reacting one molecule of diisocyanate with two molecules of (meth) acryloyl monomer having a hydroxyl group is preferable.

The polycaprolactone diol is a polymer obtained by ring-opening polymerization of ε-caprolactone.

The diisocyanate compound is not particularly limited, and examples thereof include aromatic isocyanates, aliphatic isocyanates, and alicyclic isocyanates.

Examples of the aromatic isocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethylene diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,5-naphthalene diisocyanate and the like. Will be. Examples of the aliphatic isocyanate include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isopropylene diisocyanate. Examples of the alicyclic isocyanate include o-hydrogenated xylenedi isocyanate, m-hydrogenated xylenediocyanate, p-hydrogenated xylenediocyanate, methylene bis (cyclohexamethylene), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1, Examples thereof include 4-dimethylene diisocyanate, isophorone diisocyanate, and dicyclohexammethane diisocyanate. These diisocyanate compounds may be used alone or in combination of two or more.

As the (meth) acryloyl monomer having a hydroxyl group, the above-mentioned compound for the component (A) can be used.

In synthesizing the polycaprolactone-based urethane (meth) acrylate oligomer (B), a catalyst can be appropriately used. As such a catalyst, the catalyst described above for the component (B) can be used.

In the curable composition for nail coating according to the present embodiment, the content of the polycaprolactone-based urethane (meth) acrylate oligomer (B) in the entire composition can be appropriately set in consideration of the effect. It is preferably 20 to 30% by weight.

Trimethylolpropane Tri (meth) acrylate (C) is a compound in which three (meth) acryloyl groups are bonded to the trimethylolpropane skeleton. The compound may be trimethylolpropane triacrylate or trimethylolpropane trimethacrylate. Moreover, you may use both compounds together. By blending this compound, the wettability of the nail-coating curable composition to the base (base layer, nail polish layer, or nail) was particularly improved, and the nail-coating curable composition was applied to the base surface. It is less likely that repelling will occur later.

In the curable composition for nail coating according to the present embodiment, the content of trimethylolpropane tri (meth) acrylate (C) in the entire composition can be appropriately set in consideration of the effect. It is preferably to 35% by weight, more preferably 10 to 30% by weight, still more preferably 15 to 25% by weight.

The polyfunctional thiol compound (D) is a compound in which two or more thiol groups, preferably three or more thiol groups, are present in one molecule. By blending the polyfunctional thiol compound (D), the curability of the nail coating curable composition can be improved, and the nail coating curable composition is suitably used as a non-wipe type top coat. It will be possible to do.

The polyfunctional thiol compound (D) is not particularly limited, but a compound having a trimethylolpropane skeleton, a pentaerythritol skeleton, or a dipentaerythritol skeleton is preferable. Specifically, trimethylolpropane tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] -isosyanurate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa. Examples thereof include kiss (3-mercaptopropionate), pentaerythritol hexakis (3-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptobutyrate).

In the curable composition for nail coating according to the present embodiment, the content of the polyfunctional thiol compound (D) in the entire composition is 1 to 8% by weight. If more polyfunctional thiol compound (D) is used than in this range, the wettability to the substrate, the hardness of the coating film, and the storage stability tend to be lowered. In addition, there is a tendency that heat generation is likely to occur during curing. The content of the polyfunctional thiol compound (D) is preferably 3 to 8% by weight, more preferably 5 to 8% by weight.

The curable composition for nail coating according to this embodiment preferably contains a hydroxyl group-containing (meth) acrylate (E) in addition to the components (A) to (D). By containing the hydroxyl group-containing (meth) acrylate (E), the wettability of the composition to the base (base layer, nail polish layer, or nail) is improved, and heat generation and shrinkage during further curing are alleviated. ..

The hydroxyl group-containing (meth) acrylate (E) refers to a hydroxyl group-containing monofunctional (meth) acrylate monomer, and is not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate And so on. These may be used alone or in combination of two or more.

In the curable composition for nail coating according to the present embodiment, the content of the hydroxyl group-containing (meth) acrylate (E) in the entire composition can be appropriately set in consideration of the effect, but is 0 to 20. It is preferably by weight%, more preferably 1 to 10% by weight, still more preferably 2 to 5% by weight.

The curable composition for nail coating according to the present embodiment preferably further contains a photopolymerization initiator (F) in addition to the components (A) to (D) and any component (E). Thereby, by irradiating the coating film formed by applying the curable composition with energy rays such as ultraviolet rays and visible light, the coating film can be cured in a short time. Therefore, the curable composition for nail coating according to the present embodiment can be an energy ray curable curable composition.

The photopolymerization initiator (F) is not particularly limited, and for example, benzoin ethers, benzyl ketals, acid esters, α-aminoalkylphenones, acylphosphine oxides, benzophenones, thioxanthones, titanosen and the like. Can be mentioned.

More specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylacetic acid, α-oxo-, oxydi-2,1-ethanediyl ester, oxy-phenyl-acetic acid 2- [2-oxo -2-Phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetylic acid 2- [2-hydroxy-ethoxy] -ethyl ester, mixtures of these compounds, 2,4-diethylthioxanthone, 2-isopropylthioxanthone , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, bis (2,4,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, Bis (2,4,6-trimethylbenzoyl) -phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, oligo (2-hydroxy-2-methyl- 1- (4- (1-Methylvinyl) phenyl) propanone), 4-benzoyl-4'-methyl-diphenylsulfide, 1,2-octanedione, 1- (4- (phenylthio) -2,2- (O) -Benzoyloxime)) 1-hydroxycyclohexylphenylketone, benzoin ethyl ether, benzyldimethylketal, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenylketone, 1- (4-isopropyl) Phenyl) -2-hydroxy-2-methylpropane-1-one, 2-hydroxy-1-{4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl} -2-methylpropane- 1-on, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4- [4- (2-hydroxy) -2-Methylpropionyl) -benzyl] phenyl} -2-methylpropane, benzophenone, 4-phenylbenzophenone, isophthalphenone and the like. Of these, 1-hydroxycyclohexylphenylketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable.

In the curable composition for nail coating according to the present embodiment, the content of the photopolymerization initiator (F) in the entire composition can be appropriately set in consideration of the curing time and the like, but is 0.5. It is preferably from 20% by weight, more preferably from 1 to 5% by weight.

Various additives can be added to the curable composition for nail coating according to the present embodiment as long as the glossiness, viscosity, transparency, curability and the like are not adversely affected. Examples of such additives include polyols, silicone-based and fluorine-based defoamers, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, fillers, surface tension modifiers, flame retardants, and the like. Examples thereof include antioxidants, ion adsorbents, colorants, pigments, low stress agents, antibacterial agents, polymerization inhibitors, flexibility-imparting agents, waxes, halogen trapping agents, leveling agents, wetting improvers and the like.

As the colorant, known pigments, bright materials, dyes and the like can be used, and in particular, inorganic pigments used for nail coating, bright material organic pigments, dyes and the like can be used. Further, by adding no of these colorants, adding a pigment in an amount sufficient to ensure transparency, or adding a dye, a transparent curable composition for nail coating shall be obtained. You can also. In addition, resin particles, decorative materials, and the like may be added to the curable composition for covering nails according to the present embodiment.

In general, when applying a nail polish, it is often practiced to form a nail layer composed of a plurality of layers by a multi-layer composition. In this case, layers such as a base layer, a nail polish layer, and a top coat layer are formed.

The curable composition for nail coating according to the present embodiment can be suitably used as a composition for forming a top coat layer among the above layers. When the curable composition for nail coating according to the present embodiment is used as a top coat, the top coat is preferably applied on the base layer and / or the nail polish layer, but the base layer and the nail polish layer are formed. Instead, it may be applied directly to the nail.

Like the top coat layer, the base layer and / or the nail polish layer may be formed from the nail coating curable composition according to the present embodiment, and does not fall under the nail coating curable composition according to the present embodiment. It may be formed from a nail polish having another composition. The nail polish having another composition is not particularly limited, and any known nail polish can be used, and commercially available nail polishes can also be preferably used. The base layer and / or the nail polish layer are also preferably of the energy ray curable type.

The curable composition for nail coating according to the present embodiment may be applied to the nail surface (including the nail surface coated with the base layer and / or the nail polish layer; the same applies hereinafter) with a coating tool such as a brush. Further, after applying to the surface of the nail and before curing the composition, a small decoration, powder or the like may be attached to the surface of the coating film. The target claw may be either the claw of a human hand or the claw of a toe, or the claw of an animal such as a dog or a cat.

A cured coating film can be formed by forming a coating film made of the curable composition for nail coating according to the present embodiment on the surface of the nail and then curing the coating film by irradiating it with energy rays. The light source is not particularly limited, and examples thereof include a mercury lamp, a metal halide lamp, an ultraviolet light emitting diode (UV-LED), and an ultraviolet laser diode (UV-LD).

The curable composition for nail coating according to the present embodiment has good curability, and uncured gel does not easily remain after curing. Therefore, the curable composition for nail coating according to the present embodiment can be suitably used as a non-wipe type top coat that does not require wiping work of the uncured gel after curing.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1) Synthesis of aliphatic trifunctional urethane acrylate oligomer First, 1 mol of an isocyanurate form of hexamethylene diisocyanate (HDI) (that is, a compound having 3 isocyanate groups), 3 mol of hydroxyethyl acrylate, and butyl hydroxytoluene. 200 ppm and 200 ppm of methquinone were put into a flask and stirred at 80 ° C. for 5 hours. After cooling to 60 ° C. or lower, 200 ppm of dibutyltin dilaurate was added and stirred at 80 ° C. for 1 hour to obtain an aliphatic trifunctional urethane acrylate oligomer.

(Synthesis Example 2) Synthesis of polycaprolactone-based urethane acrylate oligomer First, 1 mol of polycaprolactone diol (molecular weight 500), 2 mol of isophorone diisocyanate, 200 ppm of butyl hydroxytoluene, 200 ppm of methquinone, and 200 ppm of dibutyltin dilaurate are put into a flask. , 40 ° C. for 1 hour, then 80 ° C. for 1 hour. Then, 2 mol of hydroxyethyl acrylate was added and stirred at 80 ° C. for 2 hours to obtain a polycaprolactone-based urethane acrylate oligomer.

(Examples 1 to 3 and Comparative Examples 1 to 14)
Each component shown in each table was mixed to obtain a curable composition. The curable composition was applied to a slide glass (Matsunami Glass Ind. No. 1 S1125) using a bar coater # 20, and then an LED was used as a light source for 40 seconds under the conditions of a wavelength of 405 nm and 32 W. It was irradiated with energy rays and photocured.
The obtained cured coating film was evaluated for curability, hardness, coating film friction, and gloss according to the methods shown below. In addition, the heat of curing, wettability, and storage stability were evaluated according to the methods shown below. The obtained results are shown in Tables 1 to 3.

(Curability)
The formed coating film was touched with a finger, and the curability was judged based on the following criteria.
⊚: No adhesion due to uncured coating film ○: Some adhesion due to uncured coating film △: Adhesive due to uncured coating film ×: Not cured and liquid

(hardness)
The hardness of the formed coating film was measured by a pencil hardness test (based on JIS K 5600 5-4).

(Coating film friction)
The formed coating film was touched with a finger, and the coating film friction was judged based on the following criteria.
◎: There is no friction (tightness) and it is smooth ○: Friction (tightness) is felt a little, but it is generally smooth △: Friction (tightness) is felt and it cannot be said to be smooth ×: Friction (tightness) (Tightness) is strong and not smooth at all

(Gloss)
The gloss of the formed coating film was visually judged based on the following criteria.
◎: Strong gloss and looks shining ○: Glossy but looks a little dull △: Not so glossy ×: No gloss

(Curing heat)
When each curable composition was applied directly to the nail using a face-to-face brush and photo-cured under the above photo-curing conditions, the heat of curing was determined based on the following criteria.
◎: No heat generated by curing ○: Heat generated by curing is slightly warm △: Heat generated by curing is felt but tolerable ×: Heat generated by curing is strongly felt

(Wetability)
Each curable composition was applied directly to the nail using a face-to-face brush, and the wettability of the coating film was judged based on the following criteria.
⊚: No repellency of the coating film is seen when left on the nail for 2 minutes or more ○: No repellency of the coating film is seen when left on the nail for 1 minute or more △: On the nail for 30 seconds or more No repelling of the coating film is seen when it is left to stand in. ×: Repulsion of the coating film is seen within a few seconds after application.

(Storage stability)
The storage stability was evaluated by observing the presence or absence of curing when each curable composition was allowed to stand in a constant temperature bath at 50 ° C. for 24 hours.

From Table 1, in Examples 1 and 2 in which the content of the polyfunctional thiol compound (D) was 8% by weight or less, excellent results were obtained in all the evaluation items, whereas the polyfunctional thiol compound was obtained. Comparative Examples 1 to 3 having a content of (D) of more than 8% by weight are inferior to Examples 1 and 2 in terms of coating film hardness, heat of curing, wettability, or storage stability. I understand.

From Table 2, in Example 3 in which trimethylolpropane tri (meth) acrylate (C) was blended, excellent results were obtained in evaluation items other than the heat of curing, whereas trimethylolpropane tri (meth) acrylate was obtained. It can be seen that Comparative Examples 4 to 7 containing the acrylate monomer not corresponding to (C) are inferior to Example 3 in at least in terms of wettability.

Comparative Examples 8 to 14 in Table 3 do not contain trimethylolpropane tri (meth) acrylate (C), and Comparative Examples 8 to 13 are inferior to each example in at least in terms of wettability. Comparative Example 14 is inferior to each Example at least in terms of curability. However, in Comparative Example 9 in which the aliphatic polyfunctional urethane (meth) acrylate oligomer (A) and the polycaprolactone-based urethane (meth) acrylate oligomer (B) are used in combination, they are generally compared with other comparative examples. Good evaluation results were obtained. From this, it can be seen that the combined use of the aliphatic polyfunctional urethane (meth) acrylate oligomer (A) and the polycaprolactone-based urethane (meth) acrylate oligomer (B) is preferable.

Claims (5)

Aliphatic polyfunctional urethane (meth) acrylate oligomer (A),
Polycaprolactone urethane (meth) acrylate oligomer (B),
Trimethylolpropane Tri (meth) acrylate (C), and
Contains the polyfunctional thiol compound (D),
A curable composition for nail coating, wherein the content of the polyfunctional thiol compound (D) is 1 to 8% by weight. The content of the aliphatic polyfunctional urethane (meth) acrylate oligomer (A) is 30 to 50% by weight.
The content of the polycaprolactone-based urethane (meth) acrylate oligomer (B) is 20 to 30% by weight.
The curable composition for nail coating according to claim 1, wherein the content of trimethylolpropane tri (meth) acrylate (C) is 5 to 35% by weight. The curable composition for nail coating according to claim 1 or 2, further containing a hydroxyl group-containing (meth) acrylate (E). The curable composition for nail coating according to any one of claims 1 to 3, further comprising a photopolymerization initiator (F). The curable composition for nail coating according to any one of claims 1 to 4, which is used as a non-wipe type top coat.