Curable resin composition and its cured product

Abstract

The present invention provides a curable composition that can form a cured layer with excellent wear resistance, surface impact strength, and chemical resistance. [Solution] The composition comprises a urethane (meth)acrylate obtained from (meth)acrylates with a specific range of hydroxyl values ​​and polyvalent isocyanates, a mixture of (meth)acrylates having a different specific range of alkylene oxides as structural units, and an inorganic filler.

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition and a cured product thereof, comprising a urethane acrylate obtained from specific hydroxylated acrylates and polyvalent isocyanates, a mixture of polyfunctional acrylates having different numbers of alkylene oxide units, and an inorganic filler. [Background technology]

[0002] In recent years, resin films and molded products made from polyethylene terephthalate (PET), polycarbonate (PC), and poly(meth)methyl acrylate (PMA or PMMA) resins have been widely used in many devices and their components, such as LCD televisions, mobile phones, communication equipment, office equipment, and household appliances, replacing glass substrates and molded products. While these resins are lighter and easier to process than glass, their surfaces are easily scratched, so protective layers are commonly applied. Therefore, these protective layers are required to have scratch resistance or abrasion resistance. However, devices with such protective layers are now expected to be used in a variety of environments, and consequently, a variety of properties are required of the protective layers.

[0003] In this context, various curable resin compositions have been conventionally proposed as coating agents for resin substrates.

[0004] For example, an active energy ray curable coating agent has been proposed that includes a mixture of urethane acrylates synthesized from pentaerythritol acrylates (PETA) with different hydroxyl values, and inorganic fine particles, with the aim of providing a coating agent that can form a coating layer that achieves both high hardness and high flexibility (Patent Document 1).

[0005] Furthermore, with the aim of providing a curable composition that has a viscosity suitable for spray coating even with a high solids content, suppresses the precipitation of ultraviolet absorbers, and yields a cured product with excellent weather resistance and hot water resistance, a curable composition has been proposed that contains a multi-branched acrylate, a bifunctional urethane acrylate, an ultraviolet absorber, and a photopolymerization initiator in predetermined proportions (Patent Document 2).

[0006] Furthermore, with the aim of providing a curable resin composition that can form a hard coat layer with high hardness without causing curling or cracking during the formation or processing of the hard coat layer, a curable resin composition has been provided that contains, in a predetermined proportion, a urethane (meth)acrylate (A), which is a reaction product of norbornane diisocyanate (a1) and a compound (a2) having a hydroxyl group and a (meth)acryloyl group, and a bifunctional (meth)acrylate monomer (B) in which an ethoxy structure is introduced between terminal (meth)acryloyl groups (Patent Document 3).

[0007] Furthermore, with the aim of providing a coating material composition that can form a cross-linked cured coating on the substrate surface that has improved abrasion resistance, particularly abrasion resistance as measured by the Taber abrasion test, and at the same time has excellent weather resistance, a coating material composition has been provided that mainly comprises a (iso)cyanurate compound having a polyfunctional (meth)acryloyl group, polypentaerythritol having a (meth)acryloyl group, a urethane poly(meth)acrylate compound having a radically polymerizable unsaturated double bond, cyanurate having a (meth)acryloyl group, an ultraviolet absorber, a hindered amine-based light stabilizer, and a photopolymerization initiator (Patent Document 4).

[0008] However, none of these coating agents or curable compositions were intended to improve surface impact strength or chemical resistance, and the resulting cured products were insufficient in terms of surface impact strength and chemical resistance. Therefore, there is still a demand for a curable composition that can form cured products that are excellent in surface impact strength and chemical resistance, in addition to abrasion resistance. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent No. 6845586 [Patent Document 2] Japanese Patent No. 7452588 [Patent Document 3] Japanese Patent No. 6481302 [Patent Document 4] U.S. Patent No. 4204106 [Summary of the Invention] [Problems to be Solved by the Invention]

[0010] Therefore, an object of the present invention is to provide, in one embodiment thereof, a curable composition capable of forming a cured layer excellent in surface impact strength and chemical resistance in addition to wear resistance. Another object of the present invention is to provide, in another embodiment, a cured product excellent in surface impact strength and chemical resistance in addition to wear resistance in a cured layer, or a product having the same. [Means for Solving the Problems]

[0011] The present inventors have variously studied the composition of the curable composition to achieve the above object, and a mixture of (meth)acrylates having a hydroxyl value within a specific range, more preferably (meth)acrylates having different hydroxyl values within a specific range, and urethane (meth)acrylate obtained from polyisocyanate, and a mixture of (meth)acrylates having a different specific number of alkylene oxides as structural units, and an inorganic filler (C) were cured on a resin substrate. As a result, it was found that the obtained cured product was excellent not only in wear resistance but also in surface impact strength and chemical resistance, and the present invention was thus achieved.

[0012] That is, the present invention provides, in one embodiment thereof, the following curable resin composition, cured layer, method for forming the same, and product having the same. [1] A urethane (meth)acrylate (A) obtained by reacting a (meth)acrylate (a1) having a polyhydric alcohol with a hydroxyl value of 90 to 300 mgKOH / g as a structural unit, a polyisocyanate (a2), and optionally a polyol (a3), an alkylene oxide-modified (meth)acrylate (B), an inorganic filler (C), and wherein the alkylene oxide-modified (meth)acrylate (B) comprises a (meth)acrylate (B1) having an average number of repeating units of alkylene oxide of 0 to 2.0, optionally, a (meth)acrylate (B2) having an average number of repeating units of alkylene oxide of 3.0 to 5.0, and a (meth)acrylate (B3) having an average number of repeating units of alkylene oxide of 6.0 to 8.0, a curable resin composition. [2] The alkylene oxide-modified (meth)acrylate (B) is represented by the following formula (1): [Chemical formula] (In the formula, R 1 is hydrogen or a methyl group, A is selected from hydrogen, trimethylolpropane residue, pentaerythritol residue, ethylhexyl carbitol residue, glycerin residue, nonylphenol residue, paracumylphenol residue, bisphenol A residue, styrene oxide residue, isocyanuric acid residue, bisphenol F residue, phthalic acid residue, phenoxy residue, silicone residue, fluorine, urethane residue, amide group, phosphate group, tetramethylene glycol residue, and butadiene residue, m is an integer of 1 to 4, and n is an integer of 0 to 8.) has a structure represented by a (meth)acrylate (B1) of formula (1) having an average of n of 0 to 2.0, optionally, a (meth)acrylate (B2) of formula (1) having an average of n of 3.0 to 5.0, and a (meth)acrylate (B3) of formula (1) having an average of n of 6.0 to 8.0 A curable resin composition according to [1], comprising the above. [3] The alkylene oxide modified (meth)acrylate (B) is The (meth)acrylate (B1) is prepared in an amount of 25 to 75% by mass. The (meth)acrylate (B2) is used in an amount of 0 to 50% by mass, and The (meth)acrylate (B3) is 25-75% by mass. A curable resin composition as described in [1] or [2]. [4] The alkylene oxide modified (meth)acrylate (B) is The (meth)acrylate (B1) is prepared in an amount of 25-50% by mass. The (meth)acrylate (B2) is used in a quantity of 25-50% by mass, and The (meth)acrylate (B3) is used in a quantity of 25-50% by mass. The curable resin composition described in [3]. [5] The urethane (meth)acrylate (A) is Urethane (meth)acrylate (A1) obtained by the reaction of (meth)acrylate (a1-1) with a hydroxyl value of 90-180 mgKOH / g, polyhydric isocyanate (a2), and optionally polyol (a3), and / or Urethane (meth)acrylate (A2) obtained by the reaction of (meth)acrylate (a1-2) with a hydroxyl value of 200-300 mgKOH / g, polyhydric isocyanate (a2), and optionally polyol (a3). A curable resin composition according to any one of [1] to [4], comprising the above. [6] The urethane (meth)acrylate (A) is A urethane (meth)acrylate (A1) obtained by the reaction of a (meth)acrylate (a1-1) with a hydroxyl value of 90-180 mgKOH / g, a polyhydric isocyanate (a2), and optionally a polyol (a3), Urethane (meth)acrylate (A2) obtained by the reaction of (meth)acrylate (a1-2) with a hydroxyl value of 200-300 mgKOH / g, polyhydric isocyanate (a2), and optionally polyol (a3) A curable resin composition according to [5], comprising the above. [7] The urethane (meth)acrylate (A) is A urethane (meth)acrylate (A1) obtained by the reaction of a (meth)acrylate (a1-1) with a hydroxyl value of 90-180 mgKOH / g, a polyhydric isocyanate (a2), and optionally a polyol (a3) ​​is used in an amount of 10% to 90% by mass. Urethane (meth)acrylate (A2) obtained by the reaction of (meth)acrylate (a1-2) with a hydroxyl value of 200-300 mgKOH / g, polyhydric isocyanate (a2), and optionally low molecular weight polyol (a3) ​​is used in a concentration of 10% to 90% by mass. A curable resin composition according to [6], comprising the above. [8] The urethane (meth)acrylate (A) is A urethane (meth)acrylate (A1) obtained by the reaction of a (meth)acrylate (a1-1) with a hydroxyl value of 90-180 mgKOH / g, a polyhydric isocyanate (a2), and optionally a polyol (a3) ​​is used in an amount of 25% to 75% by mass. A urethane (meth)acrylate (A2) obtained by the reaction of (meth)acrylates (a1-2) with a hydroxyl value of 200-300 mgKOH / g, polyhydric isocyanate (a2), and optionally polyol (a3) ​​is used in a concentration of 25% to 75% by mass. A curable resin composition according to [7], comprising the above. [9] The curable resin composition according to any one of [1] to [8], wherein the mass ratio of urethane (meth)acrylate (A1) to urethane (meth)acrylate (A2) is 10:1 to 1:10.

[10] The curable resin composition according to [9], wherein the mass ratio of urethane (meth)acrylate (A1) to urethane (meth)acrylate (A2) is 6:1 to 1:6.

[11] The curable resin composition according to any one of [1] to

[10] , wherein the (meth)acrylates (a1), (a1-1), and (a1-2) each independently have a structure derived from at least one polyhydric alcohol selected from the group consisting of glycerin, pentaerythritol, dipentaerythritol, and tripentaerythritol.

[12] The curable resin composition according to

[11] , wherein each of the (meth)acrylates (a1), (a1-1), and (a1-2) independently has a structure derived from either or both dipentaerythritol and tripentaerythritol.

[13] The curable resin composition according to any one of [1] to

[12] , wherein the polyvalent isocyanate (a2) is an aliphatic isocyanate, an alicyclic isocyanate (especially an alicyclic isocyanate without a crosslinking structure), an aromatic isocyanate, or a hydrogenated version thereof.

[14] The curable resin composition according to

[13] , wherein the polyvalent isocyanate (a2) is an alicyclic isocyanate that does not have a crosslinking structure.

[15] The curable resin composition according to

[14] , wherein the alicyclic isocyanate is isophorone diisocyanate or dicyclohexylmethane diisocyanate.

[16] The curable resin composition according to any one of [1] to

[15] , wherein the alkylene oxide-modified (meth)acrylate (B) comprises one or more selected from the group consisting of alkylene oxide-modified pentaerythritol di(meth)acrylate, pentaerythritol di(meth)acrylate, alkylene oxide-modified pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, alkylene oxide-modified pentaerythritol tetra(meth)acrylate, pentaerythritol (meth)tetraacrylate, alkylene oxide-modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkylene oxide-modified pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkylene oxide-modified bisphenol A di(meth)acrylate, and bisphenol A di(meth)acrylate.

[17] The curable resin composition according to any one of [1] to

[16] , wherein the hydroxyl value of the urethane (meth)acrylate (A) is 20 to 50 mg KOH / g. The curable resin composition described in (c).

[18] The curable resin composition according to any one of [1] to

[17] , wherein the inorganic filler (C) is composed of silica, titanium dioxide, zirconia, alumina, zinc oxide, cerium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, or a mixture thereof.

[19] The curable resin composition according to any one of [1] to

[18] , wherein the inorganic filler (C) is a particle with an average particle size of 5 to 200 nm.

[20] The curable resin composition according to

[19] , wherein the inorganic filler (C) is a particle with an average particle size of 10 to 50 nm.

[21] The curable resin composition according to any one of

[18] to

[20] , wherein the inorganic filler (C) is silica particles.

[22] The curable resin composition according to

[21] , wherein the inorganic filler (C) is silica particles surface-treated with a silane coupling agent comprising an alkoxysilane having a (meth)acryloyl group.

[23] Inorganic filler (C) is given by the following formula [ka] (In the formula, m is an integer from 0 to 2, n is an integer from 1 to 3, and m+n is 3, C 1-10 Alkylene refers to alkylene with 1 to 10 carbon atoms, R 1 R is an alkyl group having 1 to 4 carbon atoms. 2 R is a hydrogen or methyl group. 3 (These are alkyl groups with 1 to 4 carbon atoms.) The curable resin composition according to

[22] , wherein silica particles are surface-treated with a silane coupling agent comprising an alkoxysilane represented by

[22] .

[24] The curable resin composition according to

[23] , wherein the alkoxysilane is selected from the group consisting of 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

[25] The curable resin composition according to any one of [1] to

[24] , wherein the mass ratio of the inorganic filler (C) to the total mass (A+B) of the urethane (meth)acrylate (A) and the alkylene oxide-modified (meth)acrylate (B) is 2:98 to 55:45 (A+B:C).

[26] The curable resin composition according to

[25] , wherein the mass ratio of the inorganic filler (C) to the total mass (A+B) of the urethane (meth)acrylate (A) and the alkylene oxide-modified (meth)acrylate (B) is 5:95 to 50:50 (A+B:C).

[27] The curable resin composition according to

[25] , wherein the mass ratio of the urethane (meth)acrylate (A) and the alkylene oxide-modified (meth)acrylate (B) to the inorganic filler (C) is 15:85 to 40:60 (A+B:C).

[28] The curable resin composition according to

[25] , wherein the mass ratio of the inorganic filler (C) to the total mass (A+B) of the urethane (meth)acrylate (A) and the alkylene oxide-modified (meth)acrylate (B) is 20:80 to 30:70 (A+B:C).

[29] A curable resin composition according to any one of [1] to

[28] , comprising 0.01 to 10 parts by mass of a polymerization initiator per 100 parts by mass of the urethane (meth)acrylate (A) and the (meth)acrylate (B) in total.

[30] The curable resin composition according to

[29] , wherein the polymerization initiator is one or more thermal polymerization initiators selected from azo compound-based polymerization initiators and organic peroxide-based polymerization initiators.

[30] The curable resin composition according to

[29] , wherein the polymerization initiator is one or more photopolymerization initiators selected from the group consisting of acetophenone-based polymerization initiators, benzophenone-based polymerization initiators, thioxanthone-based polymerization initiators, and acylphosphine-based polymerization initiators.

[31] The curable resin composition according to

[29] , wherein the polymerization initiator is a thermal and light-activated polymerization initiator selected from azo compound-based polymerization initiators and organic peroxides.

[32] The curable resin composition according to

[29] , comprising 0.1 to 15 parts by mass in total of one or more of the group consisting of a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and a hindered amine-based light stabilizer, per 100 parts by mass in total of the urethane (meth)acrylate (A) and the (meth)acrylate (B).

[33] A cured layer obtained by curing any of the curable resin compositions described in [1] to

[32] .

[34] An article having the cured layer described in

[33] on all, one, or part of an inorganic or organic substrate.

[35] A method for forming a coating layer, comprising applying a curable resin composition described in any of [1] to

[32] onto a substrate, irradiating the curable resin composition with active energy rays, or heating the curable resin composition to cure it. [Effects of the Invention]

[0013] In one embodiment of the present invention, a curable resin composition is obtained on a resin substrate that exhibits not only excellent abrasion resistance but also superior surface impact strength and chemical resistance.

[0014] Here, we define the main terms used in this specification. In this specification, "hydroxyl value" refers to the number of mg of potassium hydroxide equivalent to the hydroxyl groups in 1 g of sample, and is determined by esterifying the sample with a pyridine solution of phthalic anhydride and titrating the excess reagent with a potassium hydroxide solution, according to the polyether test method for polyurethanes described in Japanese Industrial Standard (JIS) K1557. Furthermore, in this specification, "hydroxyl value" means the hydroxyl value as an average value. Therefore, for example, "(meth)acrylate with a hydroxyl value of 90 mg KOH / g" means a mixture of (meth)acrylates with an average hydroxyl value of 90 mg KOH / g. Furthermore, in this specification, the term "(meth)acrylic" is used to encompass both acrylic and methacrylic. Therefore, for example, the term "(meth)acrylic acid" means both or either acrylic acid and methacrylic acid. Similarly, the term "(meth)acrylate" means both or either acrylate and methacrylate. In this specification, the term "pentaerythritol (meth)acrylate" is used collectively to refer to pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate, and includes any one of these compounds or a mixture of two or more of them. Furthermore, the term "dipentaerythritol (meth)acrylate" as used herein is used collectively to refer to dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, and includes any one of these compounds or a mixture of two or more of them. The term "tripentaerythritol (meth)acrylate" is understood in the same way. Furthermore, the term "glycerin (meth)acrylate" in this specification is used collectively to refer to glycerin mono(meth)acrylate, glycerin di(meth)acrylate, and glycerin tri(meth)acrylate, and includes any one of these compounds or a mixture of two or more of them.

[0015] Furthermore, "polyvalent isocyanate" refers to a compound that has two or more isocyanate groups in one molecule. Furthermore, in this specification, "isocyanate (NCO) content" refers to the value measured by a potentiometric measuring device in accordance with JIS K 1603-1 B method. Furthermore, in this specification, "polyhydric alcohol" means a compound having two or more hydroxyl groups, and "(meth)acrylate having a structure derived from a polyhydric alcohol" means a (meth)acrylate obtained by the reaction of a polyhydric alcohol with acrylic acid, methacrylic acid, or their respective chloride compounds, and having a structure partially derived from the polyhydric alcohol as a result of this reaction. For example, pentaerythritol is a "polyhydric alcohol," and in this case, "(meth)acrylate having a structure derived from a polyhydric alcohol" includes pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Furthermore, in this specification, "alkylene oxide-modified (meth)acrylate (B)" means a mixture of (meth)acrylates that includes at least alkylene oxide-modified (meth)acrylate and optionally also includes unmodified alkylene oxide (meth)acrylate.

[0016] Furthermore, "molecular weight" as used herein refers to the weight-average molecular weight, and in this specification, it refers to the value measured by gel permeation chromatography (GPC). Furthermore, unless otherwise specified, "molecular weight" in this specification means weight-average molecular weight (measured by GPC method using SHODEX KF-806M manufactured by Showa Denko). Furthermore, in this specification, "particle size" refers to the volume-average particle size (Dv), and in this specification, it refers to the value measured by a light scattering particle size distribution analyzer. Furthermore, in this specification, "viscosity" refers to the value measured with a BM-type viscometer in accordance with JIS Z 8803. Unless otherwise specified, all operations and measurements of physical properties are performed under room temperature (20-25°C) and relative humidity of 40-60%. [Modes for carrying out the invention]

[0017] Embodiments of the present invention are described below. However, the present invention is not limited to the following embodiments.

[0018] 1. Curable resin composition In one embodiment, the present invention relates to a curable resin composition comprising a urethane (meth)acrylate (A), an alkylene oxide-modified (meth)acrylate (B), and an inorganic filler (C).

[0019] 1-1. Urethane (meth)acrylate (A) Urethane (meth)acrylate (A) can be obtained by the reaction of (meth)acrylate (a1) with a hydroxyl value of 90-300 mgKOH / g, a polyvalent isocyanate (a2), and optionally a polyol (a3). In the reaction of (meth)acrylate (a1) with such a hydroxyl value and polyvalent isocyanate (a2), the proportion of urethane bonds per molecule and the molecular weight of urethane (meth)acrylate (A) remain within a certain range, and a cured product with excellent impact resistance and abrasion resistance can be obtained.

[0020] Examples of (meth)acrylates (a1) having a hydroxyl value of 90-300 mgKOH / g include (meth)acrylates whose hydroxyl value is 90-300 mgKOH / g due to structural units derived from polyhydric alcohols. There are no particular restrictions on the structural units derived from polyhydric alcohols, but structural units derived from at least one selected from the group consisting of glycerin, pentaerythritol, dipentaerythritol, and tripentaerythritol are preferred. In particular, (meth)acrylates containing either or both structural units derived from dipentaerythritol and tripentaerythritol are preferred in that they impart excellent abrasion resistance to the cured product of the resin composition.

[0021] (Meth)acrylate (a1) is, for example, Mono(meth)acrylate compounds having hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethylphthalic acid, 2-hydroxy-3-phenoxypropyl (meth)acrylate, aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate. Aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate, Polyoxyalkylene-modified di(meth)acrylate compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the various di(meth)acrylate compounds mentioned above, Lactone-modified di(meth)acrylate compounds obtained by introducing a (poly)lactone structure into the molecular structure of the various di(meth)acrylate compounds mentioned above, Aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate, Aliphatic poly(meth)acrylate compounds with four or more functions, such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. A poly(meth)acrylate compound with four or more functions, wherein a poly(oxyalkylene) chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound, and Four- or more lactone-modified poly(meth)acrylate compounds having a (poly)lactone structure introduced into the molecular structure of the aliphatic poly(meth)acrylate compound. These are some examples. The various (meth)acrylate compounds (b1) mentioned above can be used individually or in combination of two or more.

[0022] (Meth)acrylate (a1) can be selected from a variety of hydroxyl values ​​within the range of 90 to 300 mgKOH / g. For example, (meth)acrylate with a hydroxyl value of 90 to 180 mgKOH / g, preferably 100 to 150 mgKOH / g, or (meth)acrylate with a hydroxyl value of 200 to 300 mgKOH / g, preferably 250 to 300 mgKOH / g.

[0023] In (meth)acrylate (a1), a (meth)acrylate (mixture) having a desired hydroxyl value can be obtained, for example, by mixing the same or different types of (meth)acrylates and determining the mixing ratio considering the hydroxyl value of each compound. For example, when a (meth)acrylate (b1) with a hydroxyl value of 90-180 mgKOH / g is composed of pentaerythritol polyacrylate, for instance, a mixture of pentaerythritol triacrylate containing one hydroxyl group (hydroxyl value 188 mgKOH / g) and one or more of pentaerythritol monoacrylate, pentaerythritol diacrylate, and pentaerythritol tetraacrylate can be used, resulting in a (meth)acrylate mixture containing pentaerythritol triacrylate in the range of 30-70%. Furthermore, when using glycerin polyacrylate, for example, a mixture of glycerin diacrylate containing one hydroxyl group (hydroxyl value 280 mg KOH / g), glycerin monoacrylate, and glycerin triacrylate, or a (meth)acrylate mixture containing glycerin diacrylate in the range of 20-55%, may be used. Furthermore, when composed of dipentaerythritol polyacrylate, for example, a mixture of dipentaerythritol pentaacrylate containing one hydroxyl group (hydroxyl value 106 mg KOH / g), dipentaerythritol tetraacrylate containing two hydroxyl groups (hydroxyl value 238 mg KOH / g), and one or more of the following: dipentaerythritol monoacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate, can be used, resulting in a (meth)acrylate mixture containing 5-85% dipentaerythritol pentaacrylate and 5-75% dipentaerythritol tetraacrylate. Furthermore, when composed of tripentaerythritol polyacrylate, for example, a mixture of tripentaerythritol hexaacrylate (hydroxyl value 161 mg KOH / g) containing two hydroxyl groups and one or more of the following: tripentaerythritol monoacrylate, tripentaerythritol diacrylate, tripentaerythritol triacrylate, tripentaerythritol tetraacrylate, tripentaerythritol pentaacrylate, tripentaerythritol heptaacrylate, and tripentaerythritol octaacrylate, can be used, resulting in a (meth)acrylate mixture containing tripentaerythritol hexaacrylate in the range of 5-55%.

[0024] Similarly, when a (meth)acrylate (b2) with a hydroxyl value of 200-300 mgKOH / g is composed of pentaerythritol polyacrylate, for example, a mixture of pentaerythritol diacrylate containing two hydroxyl groups (hydroxyl value 459 mgKOH / g) and one or more of pentaerythritol monoacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate may be used, resulting in a (meth)acrylate mixture containing pentaerythritol diacrylate in the range of 20-50%. Furthermore, when using glycerin polyacrylate, for example, a mixture of glycerin diacrylate containing one hydroxyl group (hydroxyl value 280 mg KOH / g), glycerin monoacrylate, and glycerin triacrylate, or a (meth)acrylate mixture containing glycerin diacrylate in the range of 50-80%, may be used. Furthermore, when using dipentaerythritol polyacrylate, for example, a mixture of dipentaerythritol tetraacrylate (hydroxyl value 238 mg KOH / g) containing two hydroxyl groups and one or more of the following: dipentaerythritol monoacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate, can be used, resulting in a (meth)acrylate mixture containing 50-85% dipentaerythritol tetraacrylate. Furthermore, when composed of tripentaerythritol polyacrylate, for example, a mixture of tripentaerythritol pentaacrylate (hydroxyl value 262 mg KOH / g) containing two hydroxyl groups and one or more of the following: tripentaerythritol monoacrylate, tripentaerythritol diacrylate, tripentaerythritol triacrylate, tripentaerythritol tetraacrylate, tripentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, and tripentaerythritol octaacrylate may be used, resulting in a (meth)acrylate mixture containing tripentaerythritol pentaacrylate in the range of 40-85%.

[0025] There are no particular restrictions on the polyvalent isocyanate (a2), and examples include aliphatic, alicyclic, or aromatic isocyanates and polyisocyanates, as well as hydrogenated versions thereof. Alicyclic isocyanates without crosslinking structures or their hydrogenated versions are preferred because they yield cured products with high impact resistance and chemical resistance.

[0026] Examples of polyvalent isocyanates (a2) include isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, triene diisocyanate, polymeric MDI, naphthalene diisocyanate, tetramethyl xylylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, diphenylmethane diisocyanate, methylenebis(4,1-cyclohexylene)-diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, and tolylene diisocyanate (e.g., 2,4-tolyene). Examples include diisocyanates, phenylenediisocyanates (1,4-phenylenediisocyanate), diphenyl diisocyanates (e.g., 4,4-diphenyldiisocyanate, 3,3-dimethyl-4,4-diphenylenediisocyanate), diphenylmethane diisocyanate (4,4-diphenylmethanediisocyanate), dicyclohexylmethane diisocyanate, naphthalenediisocyanates (e.g., 1,5-naphthalenediisocyanate), xylylene diisocyanate, adducts of diisocyanate compounds with polyol compounds such as trimethylolpropane, and isocyanate derivatives such as biuret and isocyanurate forms of diisocyanate compounds. Among these, isophorone diisocyanate or dicyclohexylmethane diisocyanate are preferred in terms of impact resistance and chemical resistance of the cured product, with dicyclohexylmethane diisocyanate being more preferred. Commercially available products include Vestanat IPDI (registered trademark) and Vestanat H12MDI (registered trademark) from Evonik, Duranate D-201, TPA-100, TKA-100, 24A-100, 22A-75P, P301-75E, etc. from Asahi Kasei Corporation, Coronate HX, 2715, etc. from Tosoh Corporation, HDI from Tosoh Corporation, and Takenate (registered trademark) D160N, D-170N, D-170HN, D-172N, D-177N, 600, etc. from Mitsui Chemicals, Inc. These may be used individually or in combination of two or more.

[0027] Urethane (meth)acrylate (A) may also be synthesized by reacting (meth)acrylate (a1) and polyvalent isocyanate (a2) with polyol (a3) ​​as needed. The polyol is preferably one that has a solubility of 3.0 g / L or more in water at 25°C, more preferably 3.5 g / L or more, even more preferably 4.0 g / L or more, and is particularly preferably one that can dissolve in water in any ratio. Examples of polyols include alkylene glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, and 1,3-butanediol; polyalkylene glycols such as diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; glycerin and glycerin condensates such as glycerin, diglycerin, and triglycerin; and triols such as 1,2,4-butanetriol, 1,2,5-pentanetriol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane. Furthermore, the average molecular weight of the polyalkylene glycol (e.g., polyethylene glycol and polypropylene glycol) is preferably 2000 or less, more preferably 1000 or less, and even more preferably 400 or less. Among the polyols listed above, ethylene glycol, propylene glycol, 1,3-butanediol, dipropylene glycol, polyethylene glycol (molecular weight 400 or less), glycerin, and diglycerin are more preferred, and propylene glycol, 1,3-butanediol, dipropylene glycol, polyethylene glycol (molecular weight 400 or less), and glycerin are even more preferred. Furthermore, polyols with low molecular weight (specifically, molecular weight 100 or less, preferably molecular weight 50 to 100) are preferred because they have little effect on the heat resistance and moisture-heat resistance hardness of the cured product. The content of low molecular weight polyol (a3) ​​in the reaction composition should typically be in the range of 0 to 10.

[0028] It is preferable to mix (meth)acrylate (a1) having a hydroxyl value of 90 to 300 mgKOH / g, polyvalent isocyanate (a2), and polyol (a3) ​​in a ratio such that the hydroxyl value of the resulting urethane (meth)acrylate (A) is within a predetermined range, and the cured resin composition can be given properties such as impact strength, chemical resistance, and abrasion resistance. Specifically, it is preferable to mix (meth)acrylate (a1), polyvalent isocyanate (a2), and polyol (a3) ​​in a ratio such that the ratio of the number of moles of isocyanate groups to the sum of the number of moles of hydroxyl groups (moles of isocyanate groups / sum of moles of hydroxyl groups), as determined by the following formulas (1) and (2), is 0.1 to 0.9, and more preferably 0.2 to 0.8. Total number of moles of hydroxyl groups = (Amount of (a1) / Hydroxyl equivalent of (a1)) + (Amount of (a3) ​​ / Hydroxyl equivalent of (a3)) ... (1) (In the formula, hydroxyl value equivalent means molecular weight / number of hydroxyl groups.) Moles of isocyanate groups = Amount of (a2) / Equivalent amount of isocyanate in (a2) ... (2) (In the formula, the isocyanate equivalent in (a2) means molecular weight / number of isocyanate groups.)

[0029] The reaction between (meth)acrylate (a1), polyvalent isocyanate (a2), and optionally polyol (a3) ​​can be carried out under the conditions of a normal urethane reaction. For example, these compounds can be dissolved in an organic solvent, and then a catalyst and polymerization inhibitor can be added as appropriate, followed by heating to carry out the reaction.

[0030] Examples of organic solvents include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; esters or ether esters such as ethyl acetate, butyl acetate, and methoxybutyl acetate; ethers such as diethyl ether, tetrahydrofuran, monoethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monomethyl ether of propylene glycol, and monoethyl ether of diethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and sulfoxides such as dimethyl sulfoxide.

[0031] Examples of catalysts include inorganic bismuth; organotin compounds such as dioctyl tin, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyl tin oxide, tributyltin chloride, tributyltin trichloroacetate, and 2-ethylhexanoate tin; and tertiary amine compounds such as triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU). Among these, inorganic bismuth is particularly preferred because it does not contain tin.

[0032] From the viewpoint of preventing the C=C bond from reacting and gelling, polymerization inhibitors may be added. For example, polymerization inhibitors such as phenothiazine, tri-p-nitrophenylmethyl, di-p-fluorophenylamine, diphenylpicrylhydrazyl, N-(3-N-oxyanilino-1,3-dimethylbutylidene)aniline oxide, benzoquinone, hydroquinone, methoquinone, butylcatechol, nitrosobenzene, picric acid, dithiobenzoyl disulfide, cuperone, and copper(II) chloride can be used. From the viewpoint of polymerization inhibiting effect, methoquinone is preferred. These polymerization inhibitors may be used alone or in combination of two or more. The reaction temperature varies depending on the catalyst, but it is usually sufficient to carry it out at 50-120°C.

[0033] The obtained urethane (meth)acrylate (A) is preferably one having a hydroxyl value of 20 to 50 mg KOH / g, from the viewpoint of impact resistance, chemical resistance, and abrasion resistance of the resulting cured product.

[0034] Furthermore, the molecular weight of urethane (meth)acrylate (A2) is preferably 2,000 to 20,000, and more preferably 3,000 to 18,000, from the viewpoint of adhesion under high temperature and high humidity heat conditions of the cured product. Furthermore, in terms of compatibility with urethane acrylate (A1), as well as adhesion and transparency under high humidity and heat conditions, the molecular weight of urethane (meth)acrylate (A2) is preferably 1,000 to 5,000, and more preferably 1,200 to 4,000.

[0035] The curable composition preferably contains urethane (meth)acrylate (A1) and urethane (meth)acrylate (A2) in that it can improve the impact resistance and chemical resistance of the cured product. In particular, it contains (meth)acrylate (a1) having a hydroxyl value of 90 to 300 mgKOH / g and having a structure derived from at least one selected from glycerin, pentaerythritol, dipentaerythritol, and tripentaerythritol, preferably dipentaerythritol and tripentaerythritol or both, and alicyclic isocyanate without a crosslinking structure, preferably polyvalent isocyanate (a2) which is dicyclohexylmethane diisocyanate or a hydrogenated thereof, and urethane (meth)acrylate (A1) obtained by reaction with polyol (a3), and glycerin, penta The material preferably contains a (meth)acrylate (a2) with a hydroxyl value of 200-300 mgKOH / g having a structure derived from at least one selected from erythritol, dipentaerythritol, and tripentaerythritol, preferably dipentaerythritol and tripentaerythritol or both, and a polyhydric isocyanate (a2) which is a cyclohexylmethane diisocyanate or its hydrogenated derivative that does not have a crosslinking structure, preferably dicyclohexylmethane diisocyanate or its hydrogenated derivative, and optionally a urethane (meth)acrylate (A2) obtained by reaction with a polyol (a3). The reason why this composition provides excellent impact resistance and chemical resistance is not clear, but it is thought that urethane acrylates made from acrylates with different hydroxyl values ​​have different hydrophilicity and hydrophobicity (the higher the urethane group content, the more hydrophilic they are), and the resulting cured product forms a minute phase separation state that is not visible, and that this phase separation interface exhibits resistance to external forces such as impacts. Furthermore, regarding chemical resistance, this is thought to be because physical deformation such as swelling due to chemical exposure is suppressed for the reasons mentioned above. In addition, alicyclic isocyanates without crosslinking structures, particularly dicyclohexylmethane diisocyanate, are thought to have an advantage in exhibiting impact resistance because their alicyclic structure without crosslinking provides appropriate hydrophobicity and flexibility.

[0036] The mass ratio (A1 / A2) of urethane (meth)acrylate (A1) and urethane (meth)acrylate (A2) is not particularly limited and can be combined in the range of 10:1 to 1:10, preferably 6:1 to 1:6, more preferably 2:1 to 1:4, and particularly preferably 1:1 to 1:3.

[0037] The content of urethane (meth)acrylate (A) in the curable resin composition is not particularly limited and can vary over a relatively wide range. The curable resin composition can usually contain urethane (meth)acrylate (A) in the range of 5 to 60% by mass, preferably in the range of 10 to 40% by mass, more preferably in the range of 15 to 35% by mass, and particularly preferably in the range of 20 to 30% by mass. Furthermore, the coating film component (A+B) of the curable resin composition can usually contain urethane (meth)acrylate (A) in a range of 10 to 95% by mass, preferably in a range of 20 to 90% by mass, more preferably in a range of 30 to 86% by mass, even more preferably in a range of 35 to 80% by mass, and particularly preferably in a range of 40 to 70% by mass.

[0038] 1-2. Alkylene oxide modified (meth)acrylate (B) A curable resin composition according to one embodiment of the present invention includes alkylene oxide-modified (meth)acrylate (B) along with the urethane (meth)acrylate (A) described above. In the curable resin composition according to this embodiment, (meth)acrylate (B) comprises (meth)acrylate (B1) having an average number of alkylene oxide repeating units of 0 to 2.0, optionally (meth)acrylate (B2) having an average number of alkylene oxide repeating units of 3.0 to 5.0, and (meth)acrylate (B3) having an average number of alkylene oxide repeating units of 6.0 to 8.0, and preferably has structural units selected from trimethylolpropane residues, pentaerythritol residues, ethylhexylcarbitol residues, glycerin residues, nonylphenol residues, paracumylphenol residues, bisphenol A residues, styrene oxide residues, isocyanuric acid residues, bisphenol F residues, phthalic acid residues, phenoxy groups, silicone residues, fluorine, urethane residues, amide groups, phosphate groups, tetramethylene glycol residues, and butadiene residues.

[0039] (Meth)acrylate (B) is preferably the following formula (1): [ka] It is a mixture of (meth)acrylates having the structure shown.

[0040] In the formula, R 1 It is either a hydrogen atom or a methyl group. In the formula, A is selected from hydrogen, trimethylolpropane residue, pentaerythritol residue, ethylhexylcarbitol residue, glycerin residue, nonylphenol residue, paracumylphenol residue, bisphenol A residue, styrene oxide residue, isocyanuric acid residue, bisphenol F residue, phthalic acid residue, phenoxy residue, silicone residue, fluorine, urethane residue, amide group, phosphate group, tetramethylene glycol residue, and butadiene residue, preferably selected from trimethylolpropane residue, pentaerythritol residue, glycerin residue, and bisphenol A residue, and particularly preferably selected from trimethylolpropane residue, pentaerythritol residue, and bisphenol A residue. In the formula, m is an integer from 1 to 4, preferably an integer of 2 or 3, and more preferably 2. In the formula, n is an integer from 0 to 8, preferably an integer from 1 to 4, and more preferably an integer of 1 or 2.

[0041] Examples of the (meth)acrylate (B) include alkylene oxide-modified (preferably C 1-4 alkylene oxide)(meth)acrylate or (meth)acrylate such as 2-ethylhexyl ethylene oxide-modified acrylate and butoxyethylene oxide-modified acrylate; alkylene oxide (preferably C 1-4 alkylene oxide)-modified cresol acrylate or cresol acrylate such as ethylene oxide-modified cresol acrylate; alkylene oxide (preferably C 1-4 alkylene oxide)-modified pentaerythritol di(meth)acrylate, pentaerythritol di(meth)acrylate, alkylene oxide (preferably C 1-4 alkylene oxide)-modified pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, alkylene oxide (preferably C 1-4 alkylene oxide)-modified pentaerythritol tetra(meth)acrylate, pentaerythritol (meth)tetraacrylate, alkylene oxide (preferably C 1-4 alkylene oxide)-modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkylene oxide (preferably C 1-4 alkylene oxide)-modified pentaerythritol tetra(meth)acrylate, or pentaerythritol tetra(meth)acrylate; Alkylene oxides such as alkylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, alkylene oxide-modified ditrimethylolpropanetetra(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, etc. (preferably C 1-4 Alkylene oxide-modified trimethylolpropane (meth)acrylate, or trimethylolpropane (meth)acrylate; Alkylene oxide (preferably C 1-4 Alkylene oxide-modified glyceryl tri(meth)acrylate, glyceryl tri(meth)acrylate, alkylene oxide-modified polyglycerin (meth)acrylate, or polyglycerin (meth)acrylate; Alkylene oxides such as ethylene oxide-modified bisphenol A di(meth)acrylate and propylene oxide-modified bisphenol A di(meth)acrylate (preferably C 1-4 Alkylene oxide-modified bisphenol A di(meth)acrylate, or bisphenol A di(meth)acrylate; Phenoxyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenol ethylene oxide modified (meth)acrylate; and Alkylene oxides such as methoxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethoxyethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, etc. (preferably C 1-4 Alkylene oxide) modified polyethylene glycol (meth)acrylate, or alkylene oxide (preferably C 1-4 Alkylene oxide-modified polypropylene glycol (meth)acrylate These are some examples. Among these, those having about 2 to 3 (meth)acrylate groups are preferred in that they improve water resistance without worsening adhesion due to curing shrinkage, and in particular, trimethylolpropane tri(meth)acrylate and its alkylene oxide (preferably C 1-4 Alkylene oxide) modified product, bisphenol A di(meth)acrylate and its alkylene oxide (preferably C 1-4 Alkylene oxide-modified products are more preferable.

[0042] (Meth)acrylate (B1) is selected from the above-mentioned (meth)acrylate (B) such that the number of repeating alkylene oxide units averages 0 to 2.0. Preferably, (meth)acrylate (B1) is bisphenol A di(meth)acrylate, bisphenol A di(meth)acrylate with 1 mol of ethylene oxide, bisphenol A di(meth)acrylate with 2 mol of ethylene oxide, trimethylolpropane tri(meth)acrylate, or trimethylolpropane tri(meth)acrylate with 1 mol of ethylene oxide. The following are selected: trimethylolpropane tri(meth)acrylate with ethylene oxide (2 mol) added, pentaerythritol tri and tetra(meth)acrylate, pentaerythritol tri and tetra(meth)acrylate with ethylene oxide (1 mol) added, pentaerythritol tri and tetra(meth)acrylate with ethylene oxide (2 mol) added, glycerin tri(meth)acrylate, glycerin tri(meth)acrylate with ethylene oxide (1 mol) added, and glycerin tri(meth)acrylate with ethylene oxide (2 mol) added. Among these, bisphenol A di(meth)acrylate and its ethylene oxide adduct, and trimethylolpropane tri(meth)acrylate and its ethylene oxide adduct are preferred due to their excellent heat resistance and moisture-heat resistance.

[0043] (Meth)acrylate (B2) is selected from the above-mentioned (meth)acrylate (B) such that the number of repeating alkylene oxide units averages 3.0 to 5.0. Preferably, (meth)acrylate (B2) is ethylene oxide (3 mol) added bisphenol A di(meth)acrylate, ethylene oxide (4 mol) added bisphenol A di(meth)acrylate, ethylene oxide (5 mol) added bisphenol A di(meth)acrylate, ethylene oxide (3 mol) added glycerin tri(meth)acrylate, ethylene oxide (4 mol) added glycerin tri(meth)acrylate, ethylene oxide (5 mol) added glycerin tri(meth)acrylate, ethylene oxide (3 mol) added trimethylolpropane tri(meth)acrylate The following are selected: bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate with ethylene oxide (4 mol) added, trimethylolpropane tri(meth)acrylate with ethylene oxide (5 mol) added, pentaerythritol tri and tetra(meth)acrylate with ethylene oxide (3 mol) added, pentaerythritol tri and tetra(meth)acrylate with ethylene oxide (4 mol) added, pentaerythritol tri and tetra(meth)acrylate with ethylene oxide (5 mol) added, dipentaerythritol hexaacrylate with ethylene oxide (3 mol) added, dipentaerythritol hexaacrylate with ethylene oxide (4 mol) added, and dipentaerythritol hexaacrylate with ethylene oxide (5 mol) added. Among these, bisphenol A di(meth)acrylate and its ethylene oxide adducts, trimethylolpropane tri(meth)acrylate and its ethylene oxide adducts are preferred due to their excellent heat resistance and moisture resistance.

[0044] (Meth)acrylate (B3) is selected from the above-mentioned (meth)acrylate (B) such that the number of repeating alkylene oxide units averages 6.0 to 8.0. (Meth)acrylate (B3) is preferably ethylene oxide (6 mol) added bisphenol A di(meth)acrylate, ethylene oxide (7 mol) added bisphenol A di(meth)acrylate, ethylene oxide (8 mol) added bisphenol A di(meth)acrylate, ethylene oxide (6 mol) added glycerin tri(meth)acrylate, ethylene oxide (7 mol) added glycerin tri(meth)acrylate, ethylene oxide (8 mol) added glycerin tri(meth)acrylate, ethylene oxide (6 mol) added trimethylolpropane tri( The following are selected: meth)acrylate, trimethylolpropane tri(meth)acrylate with ethylene oxide (7 mol), trimethylolpropane tri(meth)acrylate with ethylene oxide (8 mol), pentaerythritol tri and tetra(meth)acrylate with ethylene oxide (6 mol), pentaerythritol tri and tetra(meth)acrylate with ethylene oxide (7 mol), pentaerythritol tri and tetra(meth)acrylate with ethylene oxide (8 mol), dipentaerythritol hexaacrylate with ethylene oxide (6 mol), dipentaerythritol hexaacrylate with ethylene oxide (7 mol), and dipentaerythritol hexaacrylate with ethylene oxide (8 mol). Among these, bisphenol A di(meth)acrylate and its ethylene oxide adducts, and trimethylolpropane tri(meth)acrylate and its ethylene oxide adducts are preferred due to their excellent heat resistance and moisture-heat resistance.

[0045] The alkylene oxide-modified (meth)acrylate (B) preferably contains (meth)acrylate (B1), (meth)acrylate (B2), and (meth)acrylate (B3) on average in terms of the number of repeating alkylene oxide units, in order to further improve chemical resistance and abrasion resistance.

[0046] The alkylene oxide-modified (meth)acrylate (B) preferably comprises 25 to 75% by mass of (meth)acrylate (B1), 0 to 50% by mass of (meth)acrylate (B2), and 25 to 75% by mass of (meth)acrylate (B3), more preferably comprising 25 to 50% by mass of (meth)acrylate (B1), 25 to 50% by mass of (meth)acrylate (B2), and 25 to 50% by mass of (meth)acrylate (B3), and particularly preferably comprising 25 to 40% by mass of (meth)acrylate (B1), 35 to 50% by mass of (meth)acrylate (B2), and 25 to 40% by mass of (meth)acrylate (B3).

[0047] There are no particular restrictions on the content of alkylene oxide-modified (meth)acrylate (B) in the curable resin composition, and it can be varied over a wide range. The curable resin composition can usually contain alkylene oxide-modified (meth)acrylate (B) in the range of 5 to 60% by mass, preferably in the range of 10 to 40% by mass, more preferably in the range of 13 to 35% by mass, and particularly preferably in the range of 15 to 30% by mass. Furthermore, the coating film component (A+B) of the curable resin composition can typically contain 5 to 90% by mass of alkylene oxide-modified (meth)acrylate (B), preferably 10 to 80% by mass of alkylene oxide-modified (meth)acrylate (B), more preferably 14 to 70% by mass of alkylene oxide-modified (meth)acrylate (B), even more preferably 20 to 65% by mass of alkylene oxide-modified (meth)acrylate (B), and particularly preferably 30 to 60% by mass of alkylene oxide-modified (meth)acrylate (B).

[0048] 1-3. Inorganic fillers (C) The curable resin composition preferably contains an inorganic filler (C) from the viewpoint of further improving impact resistance, chemical resistance, and abrasion resistance. Examples of inorganic fillers (C) include silica, titanium oxide, zirconia, alumina, zinc oxide, cerium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and mixtures thereof. From the viewpoint of impact resistance, chemical resistance, and abrasion resistance, fillers made of silica, zirconia, or alumina are preferred, fillers made of silica or alumina are more preferred, and fillers made of silica are particularly preferred.

[0049] The inorganic filler (C) is preferably reactive inorganic particles, particularly reactive silica particles, that have been surface-treated with a silane coupling agent having a (meth)acryloyl group. Such reactive inorganic particles, especially reactive silica particles, polymerize and chemically bond with urethane (meth)acrylate, which can further improve impact resistance and abrasion resistance.

[0050] Such silane coupling agents include, for example, the following formula [ka] (In the formula, m is an integer from 0 to 2, n is an integer from 1 to 3, and m+n is 3, C 1-10 Alkylene refers to alkylene with 1 to 10 carbon atoms, R 1 R is an alkyl group having 1 to 4 carbon atoms. 2 R is a hydrogen or methyl group. 3 (These are alkyl groups with 1 to 4 carbon atoms.) These are alkoxysilanes represented by [formula]. Specifically, examples include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane. These silane coupling agents may be used individually or in combination of two or more.

[0051] Commercially available reactive silica nanoparticles include organosilica sols from Nissan Chemical Industries (MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, MEK-AC-5340Z, PGM-AC-2140Y, PGM-AC-3140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIBK-SD-L, etc.), Adelite AT from ADEKA Corporation, and ELCOM V-8802 and V-8804 from JGC Catalysts & Chemicals Ltd. A commercially available reactive organosilicate compound particle is, for example, TSUV-011A from Taisei Fine Chemicals Co., Ltd. (a condensate of tetraethyl orthosilicate (TEOS) and 3-acryloxypropyltrimethoxysilane).

[0052] There are no particular restrictions on the shape of the inorganic filler (C), but examples include particulate, needle-shaped, fibrous, and plate-shaped inorganic fillers, with particulate inorganic fillers being preferred. Furthermore, there are no particular limitations on the particle size (volume average particle diameter (Dv)) of the particulate inorganic filler (C). Typically, an average particle diameter is selected in the range of 1 nm to 10 μm. However, from the viewpoint of impact resistance and abrasion resistance, an average particle diameter of 5 to 200 nm is preferred, more preferably 5 to 150 nm, and even more preferably 10 to 50 nm. From the viewpoint of further improvement of impact resistance, an average particle diameter of 10 to 20 nm is particularly preferred.

[0053] The content of inorganic filler (C) in the curable resin composition can vary over a relatively wide range, but from the viewpoint of impact resistance and chemical resistance, it is usually 2 to 30% by mass, preferably 8 to 21% by mass, and particularly preferably 10 to 18% by mass. Similarly, the content of inorganic fine particles (C) in the total solid components of the curable resin composition is usually 3% to 55% by mass, preferably 7% to 50% by mass, more preferably 10% to 42% by mass, and particularly preferably 17% to 35% by mass. Furthermore, the mass ratio (C:A+B) of the inorganic filler (C) to the total mass (A+B) of the urethane (meth)acrylate (A) and alkylene oxide-modified (meth)acrylate (B) is typically 2:98 to 55:45, preferably 5:95 to 50:50, more preferably 15:85 to 40:60 (A+B:C), and particularly preferably 20:80 to 30:70 (A+B:C).

[0054] 1-4. Other ingredients The curable resin composition may optionally contain other components such as coating components, solvents, polymerization initiators, antioxidants, UV absorbers, light stabilizers, leveling agents, thickeners, plasticizers, lubricants, antioxidants, colorants such as pigments and dyes, flame retardants, antistatic agents, and organic particles.

[0055] Other coating components include, for example, urethane acrylates other than urethane (meth)acrylate (A), polyester resins, polyamide resins, styrene resins, olefin resins, tackifiers, and epoxy resins.

[0056] However, the content of other urethane acrylates is 30 parts by mass or less, preferably 20 parts by mass or less, per 100 parts by mass of the total mass of the urethane (meth)acrylate (A) and the alkylene oxide modified (meth)acrylate (B), and is 25% by mass or less, preferably 15% by mass or less, in the curable resin composition.

[0057] Depending on the polymerization method, the polymerization initiator may include a thermal polymerization initiator, a photopolymerization initiator, or a thermal / photopolymerization initiator. Examples of thermal polymerization initiators include azo compound polymerization initiators, organic peroxide polymerization initiators, and inorganic peroxide polymerization initiators, with azo compound polymerization initiators and organic peroxide polymerization initiators being preferred, and organic peroxide polymerization initiators being more preferred. Examples of photopolymerization initiators include acetophenone polymerization initiators, benzophenone polymerization initiators, alkylphenone polymerization initiators, thioxanthone polymerization initiators, xanthone photopolymerization initiators, acylphosphine polymerization initiators, oxime polymerization initiators, benzoin compound polymerization initiators, anthracene compound polymerization initiators, and quinone compound polymerization initiators, with acetophenone polymerization initiators, benzophenone polymerization initiators, thioxanthone polymerization initiators, and acylphosphine polymerization initiators being preferred. Examples of thermal and light-activated polymerization initiators include azo compound polymerization initiators and organic peroxides. These polymerization initiators can be used individually or in combination of two or more. For example, combinations of an acetophenone-based photopolymerization initiator and a benzophenone-based photopolymerization initiator, and combinations of an acetophenone-based photopolymerization initiator and a thioxanthone-based photopolymerization initiator are preferred.

[0058] Examples of azo compound-based thermal polymerization initiators include 2,2-azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN), azobiscyanovaleric acid, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl2,2'-azobis(2-methylpropionate), 1,1'-azobis(cyclohexane-1-carbonitride), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis[2-(2-imidazoline-2-i Examples include 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(1-imino-1-pyrrolidino-2-methylpropane)dihydrochloride, and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], which may be used alone or in combination of two or more. Among these, 2,2-azobisisobutyronitrile (AIBN) is preferred.

[0059] Examples of organic peroxide polymerization initiators include organic peroxides such as tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, and tert-butyl hydroperoxide, which may be used alone or in combination of two or more. Examples of inorganic peroxide polymerization initiators include inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate, which may be used alone or in combination of two or more. Among these, benzoyl peroxide is preferred.

[0060] Examples of acetophenone-based photopolymerization initiators include α-aminoacetophenone-based photopolymerization initiators such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, as well as 1-hydroxy-cyclohexyl-phenyl- Examples of α-hydroxyacetophenone-based photopolymerization initiators include ton, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl]-2-methyl-propan-1-one, which may be used alone or in combination of two or more. Among these, α-hydroxyacetophenone-based photopolymerization initiators are preferred.

[0061] Examples of benzophenone-based polymerization initiators include benzophenone, 4-methylbenzophenone, o-benzoyl methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylic benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, and 2,4-dihydrobenzophenone. Examples include xybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-propoxybenzophenone, benzophenone, o-methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-di(N,N'-dimethylamino)-benzophenone, which may be used alone or in combination of two or more. Among these, benzophenone is preferred.

[0062] Examples of alkylphenone compound polymerization initiators include benzyl methyl ketal compounds such as 2,2'-dimethoxy-1,2-diphenylethane-1-one, α-hydroxyalkylphenone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, as well as aminoalkylphenone compounds such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one and 2-benzylmethyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone. These may be used alone or in combination of two or more.

[0063] Examples of thioxanthone-based photopolymerization initiators include thioxanthone, dimethylthioxanthone (e.g., 2,4-dimethylthioxanthone), diethylthioxanthone (e.g., 2,4-diethylthioxanthone), isopropylthioxanthone (e.g., 2-isopropylthioxanthone), chlorothioxanthone (e.g., 2,4-dichlorothioxanthone-9, mercaptothioxanthone), and the like. Examples of xanthone-based photopolymerization initiators include xanthone, 2-isopropylxanthone, 2,4-dimethylxanthone, 2,4-diethylxanthone, and 2,4-dichloroxanthone, which may be used alone or in combination of two or more.

[0064] Examples of acylphosphine-based photopolymerization initiators include bisacylphosphine oxide-based photopolymerization initiators and monoacylphosphine oxide-based photopolymerization initiators. Specifically, examples include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide. Examples include fin oxides, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine methyl ester, 2-methylbenzoyldiphenylphosphine oxide, isopropyl pivaloylphenylphosphine ester, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphine, (2,6-dimethoxybenzoyl)-2,4,4-pentylphosphine oxide, etc., which may be used alone or in combination of two or more. Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide is particularly preferred.

[0065] Examples of O-acyloxime compound-based photopolymerization initiators include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazole Examples include -3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propane-1-one-2-imine, and N-acetyloxy-1-[4-(1-methyl-2-methoxyethoxy)-2-methylphenyl]-1-(9-ethyl-6-nitro-9H-carbazole-3-yl)methane-1-imine.

[0066] Examples of benzoin compound polymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0067] Examples of anthracene compound polymerization initiators include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. Examples of quinone compound polymerization initiators include 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone.

[0068] The content of the polymerization initiator is preferably 0.01 to 10 parts by mass per 100 parts by mass of the total of components (A) and (B). More preferably, the content of the polymerization initiator is 2 to 8 parts by mass. When combining multiple polymerization initiators, the total content should be in the above mass ratio. For example, in a combination of an acetophenone-based photopolymerization initiator and a benzophenone-based photopolymerization initiator, or a combination of an acetophenone-based photopolymerization initiator and a thioxanthone-based photopolymerization initiator, the mass ratio of the acetophenone-based photopolymerization initiator to the benzophenone-based photopolymerization initiator or thioxanthone-based photopolymerization initiator is preferably 3:1 to 1:2, and more preferably 2:1 to 1:1.

[0069] There are no particular restrictions on the ultraviolet absorbers, but examples include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers, which may be used individually or in combination of two or more.

[0070] Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)benzotriazole, 2-(3,5-di-t-pentyl-2-hydroxyphenyl-2-benzotriazole, 2-(2-benzotriazole-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol, and 2-(2-hydroxy-4-octylox (Ciphenyl)-2-benzotriazole, 2-(2-hydroxy-5-t-octylphenyl)-2-benzotriazole, 2-(2-hydroxy-5-methyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-t-butylphenyl) 2-(2-hydroxy-3,5-t-butylphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2-hydroxy-3,5-t-pentylbenzotriazole, 2-[2-hydroxy-5-(1,1,3,3,-tetramethylbutyl)]benzotriazole, 2-(2-hydroxy-3-s-butyl-5-t-butylbenzotriazole, 2-(2-hydroxy) Examples include xy-3-dodecyl-5-methylbenzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)]-6-(2H-benzotriazole-2-yl)phenol], and 3-[3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl]propionate.

[0071] Examples of triazine-based UV absorbers include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, and 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl) Examples include triazines such as 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, and 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine.

[0072] Examples of cyanoacrylate-based ultraviolet absorbers include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate.

[0073] The UV absorber is preferably included in the curable resin composition in an amount of 0 to 2.0% by mass, and more preferably in an amount of 0.1 to 1.0% by mass. Furthermore, the UV absorber is preferably included in a total amount of 0 to 20 parts by mass, preferably in an amount of 5 to 16 parts by mass, and preferably in an amount of 8 to 14 parts by mass, per 100 parts by mass of the total of the urethane (meth)acrylate (A) and alkylene oxide-modified (meth)acrylate (B).

[0074] There are no particular restrictions on the light stabilizer, but hindered amine light stabilizers can be used as an example.

[0075] Examples of hindered amine-based light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, and bis(1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate. Bis(1-pentyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-heptyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-nonyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-decanyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate aminomethyl group-containing compounds such as tetrakis(1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(4-methoxy-benzylidene) malonate, tetrakis(2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6 A condensate of ,6-pentamethyl-4-piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol, a condensate of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-pentamethyl-4-piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol, a diester compound of decanedicarboxylic acid and 2,2,6,6-tetramethyl-1-octoxy-4-piperidinol and 1,Examples of amino ether group-containing compounds include the reaction product of 1-dimethylethyl hydroperoxide and octane (BASF, trade name Tinuvin 123) and bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1,dimethylethyl)-4-hydroxyphenyl]methyl] (BASF, trade name Tinuvin 144).

[0076] The light stabilizer is preferably included in the curable resin composition in an amount of 0 to 0.3% by mass, and more preferably in an amount of 0.05 to 0.2% by mass. Furthermore, the light stabilizer is preferably included in a total amount of 0 to 2.5 parts by mass, more preferably in an amount of 0.6 to 2 parts by mass, and more preferably in an amount of 1 to 1.8 parts by mass, per 100 parts by mass of the total of the urethane (meth)acrylate (A) and alkylene oxide-modified (meth)acrylate (B). It is also preferable to combine the light stabilizer with the above-mentioned ultraviolet absorber, in which case the mass ratio of the ultraviolet absorber to the stabilizer (ultraviolet absorber:stabilizer) is preferably in the range of 1:2 to 30:1, and more preferably in the range of 1:1 to 14:1.

[0077] Examples of leveling agents include silicone-based leveling agents such as polydimethylsiloxane, its copolymers, acrylic polymers having a polydimethylsiloxane skeleton, urethane polymers having a polydimethylsiloxane skeleton, and compounds obtained by introducing acryloyl groups or methacryloyl groups to these to impart active energy ray reactivity, or fluorine-based leveling agents such as perfluoroalkyl sulfonic acid, perfluoroalkyl carboxylic acid, fluorine telomer alcohol, or derivatives thereof. A commercially available example is Futergent 602A manufactured by Neos Corporation. The leveling agent is preferably included in the curable resin composition of the present invention in an amount of 0 to 0.5% by mass, and more preferably in an amount of 0.01 to 0.3% by mass.

[0078] Examples of antioxidants include di-t-butylhydroxytoluene, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], and 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]. Examples include pioneate, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, octylated diphenylamine, 2,4-bis[(octylthio)methyl]-O-cresol, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and dibutylhydroxytoluene. The antioxidant is preferably included in the curable resin composition of the present invention in an amount of 0 to 2% by mass.

[0079] Examples of thickening agents include associated nonionic urethane thickeners, alkali swelling thickeners, inorganic intercalation compounds such as bentonite, cellulose thickeners, (meth)acrylic acid thickeners, polyurethane thickeners, polyacrylamide thickeners, vinyl ether thickeners, mineral thickeners, or polysaccharide thickeners. The thickening agent is preferably included in the curable resin composition of the present invention in an amount of 0 to 5% by mass.

[0080] Examples of plasticizers include phthalate esters, non-aromatic dibasic acid esters, aliphatic esters, polyalkylene glycol esters, phosphate esters, trimellitic acid esters, chlorinated paraffin, hydrocarbon oils, process oils, polyethers, epoxy plasticizers, polyester plasticizers, etc., with phthalate esters being preferred. Specific examples of the plasticizers include dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, tricresyl phosphate, tributyl phosphate, epoxidized soybean oil, and benzyl epoxy stearate. The plasticizer is preferably included in the curable resin composition of the present invention in an amount of 0 to 10% by mass.

[0081] Examples of lubricants include hydrocarbon-based, fatty acid-based, higher alcohol-based, aliphatic amide-based, metal soap-based, ester-based, amide-based lubricants, silicone compounds, and perfluoroalkyl compounds. The lubricant is preferably included in the curable resin composition of the present invention in an amount of 0 to 1% by mass.

[0082] Examples of colorants include dyes such as direct dyes, acid dyes, basic dyes, and metal complex dyes; inorganic pigments such as carbon black, titanium dioxide, zinc oxide, iron oxide, and mica; and organic pigments such as coupling azos, condensation azos, anthraquinones, thioindigos, dioxazones, and phthalocyanines. The coloring agent is preferably included in the curable resin composition of the present invention in an amount of 0 to 2% by mass.

[0083] Examples of flame retardants include additives and reactive flame retardants such as phosphorus and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, and antimony oxide. The flame retardant is preferably included in the curable resin composition of the present invention in an amount of 0 to 20% by mass.

[0084] Examples of antistatic agents include quaternary ammonium salt cationic antistatic agents, aliphatic sulfonates, higher alcohol sulfate esters, higher alcohol alkylene oxide adduct sulfate esters, higher alcohol phosphate esters, higher alcohol alkylene oxide adduct phosphate esters, higher alcohol alkylene oxide adduct phosphate esters, higher alcohol alkylene oxide adducts, polyalkylene glycol fatty acid esters, and the like. The antistatic agent is preferably included in the curable resin composition of the present invention in an amount of 0 to 5% by mass.

[0085] Examples of organic particles include particles formed from polyacrylate resins, polymethacrylate resins, polyolefin resins, polystyrene resins, polyamide resins, polyamino acid resins, polyester resins, polyurethane resins, polyvinyl chloride resins, cellulose resins, melamine resins, urea resins, epoxy resins, fluororesins, and mixtures thereof. The organic particles are preferably included in the curable resin composition of the present invention in an amount of 0 to 30% by mass.

[0086] The curable resin composition of the present invention typically contains the above-mentioned components in a solvent. The solvent is not particularly limited as long as it can dissolve each monomer to be polymerized, the polymer precursor to be produced, and, if necessary, polymerization initiators and other additives. Examples of solvents that can be used include methanol, ethanol, isopropanol, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, toluene, ethyl acetate, ethyl lactate, methyl lactate, dimethyl sulfoxide, water, etc. These may be used alone or in combination of two or more. Methyl ethyl ketone, 1-methoxy-2-propanol (PGM), and 1-methoxy-2-propyl acetate are preferred because they have high solubility for urethane (meth)acrylate (A) and alkylene oxide-modified (meth)acrylate (B), are less likely to dissolve resin substrates such as polycarbonate, and have appropriate volatility, making application and drying easy.

[0087] There are no particular restrictions on the solvent content in the curable composition, but typically 10% to 80% by mass of solvent can be incorporated into the curable composition, and in many cases, 30% to 70% by mass of solvent, preferably 30% to 60% by mass of solvent, is incorporated into the curable composition. Furthermore, the amount of the organic coating component is usually 10 to 500 parts by mass, preferably 50 to 300 parts by mass, per 100 parts by mass of the organic coating component. The viscosity of the curable resin composition is usually 5 to 500 mPa·s, preferably 10 to 100 mPa·s, at the temperature during use (usually 15 to 30°C). The curable resin composition may be diluted with a solvent to adjust it to an appropriate viscosity during coating. The solvent content after dilution is typically 55 to 85% by mass of the curable resin composition, preferably 70 to 80% by mass.

[0088] A curable composition can be applied to a substrate, for example, and a cured material (cured layer) can be formed on all, one, or part of an inorganic or organic substrate by irradiating the curable composition with active energy rays or by heating. Both irradiation with active energy rays and heating may be performed for curing.

[0089] The curable composition can be applied to a substrate by means of, for example, a bar coater, applicator, die coater, spin coater, spray coater, curtain coater, roll coater, screen printing, dipping, etc.

[0090] The amount of curable composition applied to the substrate is not particularly limited and can be adjusted according to the thickness of the cured layer to be formed. As a guideline, an amount that results in a cured layer thickness of 1 to 1,000 μm after curing by active energy ray irradiation and / or heating is preferably 10 to 800 μm.

[0091] There are no particular restrictions on the type of active energy ray, but examples include ultraviolet rays and electron beams. When irradiating with ultraviolet light, an ultraviolet irradiation device equipped with a light source such as a high-pressure mercury lamp or a metal halide lamp can be used. The amount of ultraviolet irradiation is preferably 30 to 2,000 mW / cm². 2 The cumulative light intensity is 100-1000 mJ / cm². 2 The curing atmosphere may be either an air atmosphere or an inert gas atmosphere (e.g., nitrogen, argon). When irradiating with an electron beam, a commercially available electron beam irradiation device can be used, and the electron beam irradiation dose is preferably 1 to 10 Mrad.

[0092] After curing by irradiation with active energy rays, further curing may be advanced by heat treatment (annealing) as needed. The heating temperature is preferably in the range of 80 to 220°C. The heating time is preferably in the range of 10 to 60 minutes.

[0093] When curing a curable composition by thermal polymerization, the heating temperature is preferably in the range of 80 to 200°C, and more preferably in the range of 100 to 150°C. If the heating temperature is lower than 80°C, the heating time needs to be longer, which tends to be economically uneconomical. If the heating temperature is higher than 200°C, the energy cost is high, and the heating and cooling times are also long, which also tends to be economically uneconomical. Polymerization conditions are not particularly limited and can be adjusted as appropriate depending on the type of polymerization initiator used, but for example, the reaction can be carried out under an inert gas (preferably nitrogen) atmosphere at a polymerization temperature of 60 to 90°C for 3 to 10 hours.

[0094] The curing resin composition can be used on various substrates, such as polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, polycycloolefin, polyimide, epoxy resin, melamine resin, triacetylcellulose resin, ABS resin, AS resin, norbornene-based resin, etc.

[0095] As described above, the thickness of the formed hardened layer can be adjusted by the amount applied, and is usually less than 15 μm, preferably 10 μm or less, and more preferably 7 μm or less.

[0096] The resulting cured product exhibits excellent transparency, heat resistance, and moisture resistance, making it suitable for use as a coating material for various applications, such as personal computer materials (pen-input computers, touch panels, display covers, etc.), home appliances (televisions, radio cassette players, stereos, computer game console cases and displays, etc.), mobile phones and smartphones (touch panels, displays and housing covers, etc.), automotive materials (headlights, glazing, instrument covers, interior components, etc.), optical discs, optical lenses (cameras, video cameras, magnifying glasses, etc.), eyeglass lenses (corrective lenses, sunglasses, fashion glasses, etc.), sporting goods (skis, tennis rackets, etc.), organic plate glass, signs, traffic signs, nameplates, decorative cases, watch lenses, cosmetic containers, housing components, transfer foils, transfer films, dry film resists, and mirrors. [Examples]

[0097] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, parts and percentages in each example are by mass, and the room temperature storage conditions are all 23°C / 55%RH.

[0098] 1. Manufacturing of urethane (meth)acrylate (A) [Synthesis Example 1] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 169.4 g of hexamethylene diisocyanate (HDI, manufactured by Tosoh Corporation, isocyanate content 50%) and pentaerythritol acrylate (PEA, Aronics M-305, manufactured by Toagosei Co., Ltd., with a hydroxyl value of 115 mg KOH / g, containing 0% pentaerythritol diacrylate, 0% pentaerythritol monoacrylate, and 0% pentaerythritol triacrylate) were added. 1428.7g of a mixture containing 60% isocyanate and 40% pentaerythritol tetraacrylate, 399.5g of methyl ethyl ketone as a solvent, 0.8g of methoquinone as a polymerization inhibitor, and 1.6g of inorganic bismuth (Nitto Kasei Co., Ltd., Neostan U-600) as a reaction catalyst were charged together and reacted at 70°C with uniform stirring until the residual isocyanate group reached 0.1%, at which point the reaction was terminated to obtain urethane acrylate (A-1). The obtained urethane acrylate (A-1) had a solid content of 80%, a viscosity of approximately 100 mPa·s at 25°C, a weight-average molecular weight of 800, and a hydroxyl value of 29.2 mgKOH / g when calculated based on solid content.

[0099] [Synthesis Example 2] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 249.3 g of dicyclohexylmethane 4,4-diisocyanate (H12MDI, VESTANT® manufactured by Evonik) and pentaerythritol acrylate (PEA, Aronics M-305 manufactured by Toagosei Co., Ltd., with a hydroxyl value of 115 mg KOH / g, containing 0% pentaerythritol diacrylate and 0% pentaerythritol monoacrylate) were added. 1348.8 g of a mixture containing 60% urethane acrylate and 40% pentaerythritol tetraacrylate, 399.5 g of methyl ethyl ketone as a solvent, 0.8 g of methoquinone as a polymerization inhibitor, and 1.6 g of inorganic bismuth (Nitto Kasei Co., Ltd., Neostan U-600) as a reaction catalyst were charged together and reacted at 70°C with uniform stirring until the residual isocyanate group reached 0.1%, at which point the reaction was terminated to obtain urethane acrylate (A-2). The obtained urethane acrylate (A-2) had a solid content of 80%, a viscosity of approximately 80 mPa·s at 25°C, a weight-average molecular weight of 1,000, and a hydroxyl value of 27.3 mgKOH / g when calculated based on solid content.

[0100] [Synthesis Example 3] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 568.9 g of dicyclohexylmethane 4,4-diisocyanate (H12MDI, VESTANT®, manufactured by Evonik, isocyanate content 32%) and pentaerythritol acrylate (Aronics M-933, manufactured by Toagosei Co., Ltd., pentaerythritol diacrylate content 30%, pentaerythritol monoacrylate content 5%, pentaerythritol) with a hydroxyl value of 280 mgKOH / g were added. 1029.2g of a mixture containing 50% erythritol triacrylate and 15% pentaerythritol tetraacrylate, 399.5g of methyl ethyl ketone as a solvent, 0.8g of methoquinone as a polymerization inhibitor, and 1.6g of inorganic bismuth (Neostan U-600, Nitto Kasei Co., Ltd.) as a reaction catalyst were charged together and reacted at 70°C with uniform stirring until the residual isocyanate group reached 0.1%, at which point the reaction was terminated to obtain urethane acrylate (A-3). The obtained urethane acrylate (A-3) had a solid content of 80%, a viscosity of approximately 350 mPa·s at 25°C, a weight-average molecular weight of 3,000, and a hydroxyl value of 28.5 mgKOH / g when calculated based on solid content.

[0101] [Synthesis Example 4] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 217.3 g of isophorone diisocyanate (IPDI, VESTANT® manufactured by Evonik, isocyanate content 37.7%) and pentaerythritol acrylate (PEA, Aronics M-305 manufactured by Toagosei Co., Ltd., hydroxyl value 115 mg KOH / g, pentaerythritol diacrylate content 0%, pentaerythritol monoacrylate content 0%, pentaerythritol 1380.7 g of a mixture containing 60% urethane triacrylate and 40% pentaerythritol tetraacrylate, 399.5 g of methyl ethyl ketone as a solvent, 0.8 g of methoquinone as a polymerization inhibitor, and 1.6 g of inorganic bismuth (Nitto Kasei Co., Ltd., Neostan U-600) as a reaction catalyst were charged together and reacted at 70°C with uniform stirring until the residual isocyanate group reached 0.1%, at which point the reaction was terminated to obtain urethane acrylate (A-4). The obtained urethane acrylate (A-4) had a solid content of 80%, a viscosity of approximately 110 mPa·s at 25°C, a weight-average molecular weight of 900, and a hydroxyl value of 27.6 mgKOH / g when calculated based on solid content.

[0102] [Synthesis Example 5] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 511.4 g of isophorone diisocyanate (IPDI, VESTANT® manufactured by Evonik, isocyanate content 37.7%) and pentaerythritol acrylate (Aronics M-933, manufactured by Toagosei Co., Ltd., pentaerythritol diacrylate content 30%, pentaerythritol monoacrylate content 5%, pentaerythritol) with a hydroxyl value of 280 mg KOH / g were added. 1086.7g of a mixture containing 50% urethane acrylate and 15% pentaerythritol tetraacrylate, 399.5g of methyl ethyl ketone as a solvent, 0.8g of methoquinone as a polymerization inhibitor, and 1.6g of inorganic bismuth (Nitto Kasei Co., Ltd., Neostan U-600) as a reaction catalyst were charged together and reacted at 70°C with uniform stirring until the residual isocyanate group reached 0.1%, at which point the reaction was terminated to obtain urethane acrylate (A-5). The obtained urethane acrylate (A-5) had a solid content of 80%, a viscosity of approximately 400 mPa·s at 25°C, a weight-average molecular weight of 3,000, and a hydroxyl value of 40.8 mgKOH / g when calculated based on solid content.

[0103] [Comparative Synthesis Example 1] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 127.8 g of dicyclohexylmethane 4,4-diisocyanate (H12MDI, VESTANT® manufactured by Evonik, isocyanate content 32%), 1470.2 g of dipentaerythritol acrylate (DPHA, NK ester A-9550 manufactured by Shin Nakamura Chemical Industry Co., Ltd.) with a hydroxyl value of 50 mg KOH / g, 399.5 g of methyl ethyl ketone as a solvent, 0.8 g of methoquinone as a polymerization inhibitor, and 1.6 g of inorganic bismuth (Neostan U-600 manufactured by Nitto Kasei Co., Ltd.) as a reaction catalyst were charged. The reaction was carried out at 70°C with uniform stirring, and the reaction was stopped when the remaining isocyanate groups reached 0.1%, yielding urethane acrylate (A-6). The obtained urethane acrylate (A-6) had a solid content of 80%, a viscosity of approximately 110 mPa·s at 25°C, a weight-average molecular weight of 1,100, and a hydroxyl value of 13.7 mgKOH / g when calculated based on solid content.

[0104] [Comparative Synthesis Example 2] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 535.4 g of dicyclohexylmethane 4,4-diisocyanate (H12MDI, VESTANT® manufactured by Evonik, isocyanate content 32%), 1062.7 g of pentaerythritol acrylate (Aronics M-926 manufactured by Toagosei Co., Ltd.) with a hydroxyl value of 310 mg KOH / g, 399.5 g of methyl ethyl ketone as a solvent, 0.8 g of methoquinone as a polymerization inhibitor, and 1.6 g of inorganic bismuth (Neostan U-600 manufactured by Nitto Kasei Co., Ltd.) as a reaction catalyst were charged. The reaction was carried out at 70°C with uniform stirring, and the reaction was terminated when the remaining isocyanate group was 0.1%, yielding urethane acrylate (A-7). The obtained urethane acrylate (A-7) had a solid content of 80%, a viscosity of approximately 4800 mPa·s at 25°C, and a hydroxyl value of 64.2 mgKOH / g when calculated based on solid content.

[0105] The following outlines the synthesis conditions for each urethane acrylate and the hydroxyl value of each obtained urethane acrylate. [Table 1]

[0106] 2. Production of alkylene oxide-modified (meth)acrylate (B) [Synthesis Example 6] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 134 g of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 134.2), 0.3 g of caustic potassium, and 134 g of toluene as a solvent were charged. The reaction was carried out at 140°C while uniformly stirring, and 44 g of ethylene oxide (molecular weight 44) was gradually blown into the reaction vessel. After the reaction, the mixture was neutralized with acetic acid to obtain ethylene oxide-modified trimethylolpropane. 178 g of the obtained ethylene oxide-modified trimethylolpropane, 288 g of acrylic acid, 30 g of p-toluenesulfonic acid, 0.45 g of hydroquinone, and 400 g of toluene as a solvent were placed in a separate reaction vessel and heated to 110°C while blowing in air to carry out the reaction. Water produced in the dehydration reaction was removed as needed during the reaction. After the reaction, alkaline washing and water washing were performed, and toluene was recovered under reduced pressure while blowing in air to obtain ethylene oxide-modified trimethylolpropane triacrylate (B-1). The obtained ethylene oxide-modified trimethylolpropane triacrylate (B-1) was prepared under the following conditions. 1 H-HMR, 13 Analysis by 13C-NMR and HPLC revealed that the number of ethylene oxide additions was 0.9.

[0107] 1 Conditions for H-HMR analysis Equipment: JEOL ECX-400 Measurement solvent: Deuterated chloroform Measured concentration: 1% by weight Measurement temperature 50℃ Total number of times: 16

[0108] 13 Conditions for 1C-NMR analysis Equipment: JEOL ECX-400 Measurement solvent: Deuterated chloroform Measured concentration: 5% by weight Measurement temperature: room temperature Total number of times: 4096

[0109] Conditions for HPLC analysis outfit Placement: SHIMADZU LC-10A Detector: UV 254nm Column: GL Science Inertsil ODS-2 (4.6 x 150 mm) Column temperature: 40℃ Eluent: Acetonitrile / 0.1% phosphoric acid = 60 / 40 Flow rate: 0.6ml / min Sample injection volume: 2 μl Sample concentration: 1 wt%

[0110] [Synthesis Example 7] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 134 g of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 134.2), 0.3 g of caustic potassium, and 134 g of toluene as a solvent were charged. The reaction was carried out at 140°C while uniformly stirring, and 176 g of ethylene oxide (molecular weight 44) was gradually blown into the reaction vessel. After the reaction, the mixture was neutralized with acetic acid to obtain ethylene oxide-modified trimethylolpropane. 310 g of the obtained ethylene oxide-modified trimethylolpropane, 288 g of acrylic acid, 30 g of p-toluenesulfonic acid, 0.45 g of hydroquinone, and 600 g of toluene as a solvent were placed in a separate reaction vessel and heated to 110°C while blowing in air to carry out the reaction. Water produced in the dehydration reaction was removed as needed during the reaction. After the reaction, alkaline washing and water washing were performed, and toluene was recovered under reduced pressure while blowing in air to obtain ethylene oxide-modified trimethylolpropane triacrylate (B-2). The obtained ethylene oxide-modified trimethylolpropane triacrylate (B-2) was prepared under the conditions described above. 1 H-HMR, 13 Analysis by 13C-NMR and HPLC revealed that the number of ethylene oxide additions was 3.7.

[0111] [Synthesis Example 8] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 134 g of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 134.2), 0.3 g of caustic potassium, and 134 g of toluene as a solvent were charged. The reaction was carried out at 140°C while uniformly stirring, and 308 g of ethylene oxide (molecular weight 44) was gradually blown into the reaction vessel. After the reaction, the mixture was neutralized with acetic acid to obtain ethylene oxide-modified trimethylolpropane. 442 g of the obtained ethylene oxide-modified trimethylolpropane, 288 g of acrylic acid, 30 g of p-toluenesulfonic acid, 0.45 g of hydroquinone, and 800 g of toluene as a solvent were placed in a separate reaction vessel and heated to 110°C while blowing in air to carry out the reaction. Water produced in the dehydration reaction was removed as needed during the reaction. After the reaction, alkaline washing and water washing were performed, and toluene was recovered under reduced pressure while blowing in air to obtain ethylene oxide-modified trimethylolpropane triacrylate (B-3). Regarding the obtained ethylene oxide-modified trimethylolpropane triacrylate (B-3), 1 H-HMR, 13 Analysis by 13C-NMR and HPLC revealed that the number of ethylene oxide additions was 6.4.

[0112] The number of ethylene oxide groups added to the obtained ethylene oxide-modified trimethylolpropane triacrylates B-1 to B-3 is summarized below. [Table 2]

[0113] 3. Preparation of curable resin composition [Example 1] 35.0 g of urethane acrylate (A-1) obtained in Synthesis Example 1 (synthesized from hexamethylene diisocyanate (HDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g; hydroxyl value is 29.2 mg KOH / g), 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-1) obtained in Synthesis Example 6 (number of ethylene oxide additions: 0.9), 15.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) obtained in Synthesis Example 7 (number of ethylene oxide additions: 3.7), 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) obtained in Synthesis Example 8 (number of ethylene oxide additions: 6.4), and silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition with a solid content of 50% was prepared by mixing and stirring 75.0g of "MEK-ST-40" (particle size 12nm, active ingredient 40%) (30.0g as active ingredient), 8.0g of a triazine-based UV absorber (Tinuvin 479, manufactured by BASF), 1.0g of a hindered amine-based light stabilizer ("ADEKA Stab LA-87," manufactured by ADEKA Corporation), and 5.0g of a monoacylphosphine oxide-based photopolymerization initiator ("Omnirad TPO," manufactured by IGM RESINS). 60.0g of 1-methoxy-2-propanol (PGM) was added as a diluent.

[0114] [Example 2] A curable composition was prepared in the same manner as in Example 1, except that 100.0 g of silica particle dispersion (C-2) (Snowtex MEK-ST-L, manufactured by Nissan Chemical Corporation, with a particle size of 45 nm and an active ingredient of 30%) was added instead of silica particle dispersion (C-1) (Snowtex MEK-ST-40, manufactured by Nissan Chemical Corporation, with a particle size of 12 nm and an active ingredient of 40%), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0115] [Example 3] A curable composition was prepared in the same manner as in Example 1, except that 100.0 g of silica particle dispersion (C-3) (Snowtex MEK-ST-ZL, manufactured by Nissan Chemical Corporation, with a particle size of 80 nm and an active ingredient of 30%) was added instead of silica particle dispersion (C-1) (Snowtex MEK-ST-40, manufactured by Nissan Chemical Corporation, with a particle size of 12 nm and an active ingredient of 40%), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0116] [Example 4] A curable composition was prepared in the same manner as in Example 1, except that 80.0 g (30.0 g as active ingredient) of alumina particle dispersion (C-4) (NANOBYK-3610, BYK, particle size 23 nm, methoxypropyl acetate solvent, active ingredient 37%) was added instead of silica particle dispersion (C-1) ("Snowtex MEK-ST-40" manufactured by Nissan Chemical Corporation, particle size 12 nm, active ingredient 40%), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0117] [Example 5] A curable composition was prepared in the same manner as in Example 1, except that 43.0 g (30.0 g as active ingredient) of zirconia particle dispersion (C-5) (ZP-153

[0118] [Example 6] A curable composition was prepared in the same manner as in Example 1, except that 75.0 g of zinc oxide particle dispersion (C-6) (manufactured by Sigma-Aldrich, particle size 110 nm, ethanol solvent, 40% active ingredient) was added instead of silica particle dispersion (C-1) ("Snowtex MEK-ST-40" manufactured by Nissan Chemical Corporation, particle size 12 nm, active ingredient 40%) (30.0 g as active ingredient), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0119] [Example 7] A curable composition was prepared in the same manner as in Example 1, except that 75.0 g (30.0 g as active ingredient) of methacrylate silane coupling agent treated silica particle dispersion (C-7) (Nissan Chemical Corporation's "Snowtex MEK-AC-2140Z", particle size 12 nm, methyl ethyl ketone solvent, 40% active ingredient) was added instead of silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex MEK-ST-40", particle size 12 nm, active ingredient 40%), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0120] [Example 8] A curable composition was prepared in the same manner as in Example 1, except that 100.0 g (30.0 g as active ingredient) of methacrylate silane coupling agent treated silica fine particle dispersion (C-8) (Nissan Chemical Corporation's "Snowtex MEK-AC-4130Y", particle size 45 nm, methyl ethyl ketone solvent, active ingredient 30%) was added instead of silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex MEK-ST-40", particle size 12 nm, active ingredient 40%), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0121] [Example 9] A curable composition was prepared in the same manner as in Example 1, except that 75.0 g (30.0 g as active ingredient) of methacrylate silane coupling agent treated silica fine particle dispersion (C-9) (Nissan Chemical Corporation's "Snowtex PGM-AC-5140Z", particle size 80 nm, methyl ethyl ketone solvent, 40% active ingredient) was added instead of silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex MEK-ST-40", particle size 12 nm, active ingredient 40%), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0122] The following is a summary of the compositions of the curable compositions in Examples 1 to 9. [Table 3]

[0123] [Example 10] A curable composition was prepared in the same manner as in Example 1, except that urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, and a hydroxyl value of 27.3 mg KOH / g) was used instead of urethane acrylate (A-1), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0124] [Example 11] A curable composition was prepared in the same manner as in Example 1, except that urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, with a hydroxyl value of 28.5 mg KOH / g) was used instead of urethane acrylate (A-1), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0125] [Example 12] A curable composition was prepared in the same manner as in Example 1, except that urethane acrylate (A-4) (synthesized from isophorone diisocyanate (IPDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, with a hydroxyl value of 27.6 mg KOH / g) was used instead of urethane acrylate (A-1), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0126] [Example 13] A curable composition was prepared in the same manner as in Example 1, except that urethane acrylate (A-5) (synthesized from isophorone diisocyanate (IPDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, with a hydroxyl value of 40.8 mg KOH / g) was used instead of urethane acrylate (A-1), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0127] [Example 14] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 35 g of urethane acrylate (A-1), 20 g of urethane acrylate (A-1) (synthesized from hexamethylene diisocyanate (HDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 29.2 mg KOH / g) and 15 g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 28.5 mg KOH / g) were mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0128] [Example 15] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 35 g of urethane acrylate (A-1), 20 g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 27.3 mg KOH / g) and 15 g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 28.5 mg KOH / g) were mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0129] [Example 16] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 35 g of urethane acrylate (A-1), 15 g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 28.5 mg KOH / g) and 20 g of urethane acrylate (A-4) (synthesized from isophorone diisocyanate (IPDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 27.6 mg KOH / g) were mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0130] [Example 17] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 35 g of urethane acrylate (A-1), 20 g of urethane acrylate (A-1) (synthesized from hexamethylene diisocyanate (HDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 29.2 mg KOH / g) and 15 g of urethane acrylate (A-5) (synthesized from isophorone diisocyanate (IPDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 40.8 mg KOH / g) were mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0131] [Example 18] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 35 g of urethane acrylate (A-1), 20 g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 27.3 mg KOH / g) and 15 g of urethane acrylate (A-5) (synthesized from isophorone diisocyanate (IPDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 40.8 mg KOH / g) were mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0132] [Example 19] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 35 g of urethane acrylate (A-1), 20 g of urethane acrylate (A-4) (synthesized from isophorone diisocyanate (IPDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 27.6 mg KOH / g) and 15 g of urethane acrylate (A-5) (synthesized from isophorone diisocyanate (IPDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 40.8 mg KOH / g) were mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0133] The following is a summary of the compositions of the curable compositions in Examples 1, 10-19. [Table 4]

[0134] [Example 20] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 35 g of urethane acrylate (A-1), 5 g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 27.3 mg KOH / g) and 30 g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 28.5 mg KOH / g) were mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0135] [Example 21] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 35 g of urethane acrylate (A-1), 10 g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 27.3 mg KOH / g) and 25 g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 28.5 mg KOH / g) were mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0136] [Example 22] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 35 g of urethane acrylate (A-1), 30 g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 27.3 mg KOH / g) and 5 g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 28.5 mg KOH / g) were mixed.

[0137] [Example 23] Instead of mixing 35g of urethane acrylate (A-1), mix 25g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g; hydroxyl value is 27.3mgKOH / g) and 20g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g; hydroxyl value is 28.5mgKOH / g) to make ethylene oxide-modified trimethylolpropane triacrylate (B-1). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 10.0 g of (ethylene oxide addition number 0.9), 15.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) (ethylene oxide addition number 3.7), and 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) (ethylene oxide addition number 6.4), 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-1) and 15.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) were mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0138] [Example 24] Instead of mixing 35g of urethane acrylate (A-1), mix 30g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g, hydroxyl value of 27.3mgKOH / g) and 30g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g, hydroxyl value of 28.5mgKOH / g), and then mix ethylene oxide-modified trimethylolpropane triacrylate (B-1 A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) (with 0.9 ethylene oxide additions), 15.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) (with 3.7 ethylene oxide additions), and 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) (with 6.4 ethylene oxide additions), 5.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-1) and 5.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) were mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0139] [Example 25] Instead of mixing 35g of urethane acrylate (A-1), mix 20g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g; hydroxyl value is 27.3mgKOH / g) and 15g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g; hydroxyl value is 28.5mgKOH / g) to make ethylene oxide-modified trimethylolpropane triacrylate (B-1). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 10.0 g of (ethylene oxide addition number 0.9), 15.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) (ethylene oxide addition number 3.7), and 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) (ethylene oxide addition number 6.4), 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-1) and 25.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-3), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0140] [Example 26] Instead of mixing 35g of urethane acrylate (A-1), mix 30g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g, hydroxyl value of 27.3mgKOH / g) and 30g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g, hydroxyl value of 28.5mgKOH / g), and add silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 75.0 g (30.0 g as active ingredient) of "MEK-ST-40" (particle size 12 nm, active ingredient 40%), 12.5 g (5.0 g as active ingredient) of silica particle dispersion (C-1) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%. [Example 27] Instead of mixing 35g of urethane acrylate (A-1), mix 25g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, with a hydroxyl value of 27.3 mg KOH / g) and 25g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, with a hydroxyl value of 28.5 mg KOH / g), and add silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 75.0 g (30.0 g as active ingredient) of "MEK-ST-40" (particle size 12 nm, active ingredient 40%), 37.5 g (15.0 g as active ingredient) of silica particle dispersion (C-1) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%. [Example 28] Instead of mixing 35g of urethane acrylate (A-1), mix 25g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g, hydroxyl value of 27.3mgKOH / g) and 20g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g, hydroxyl value of 28.5mgKOH / g), and then mix with silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 75.0 g (30.0 g as active ingredient) of "MEK-ST-40" (particle size 12 nm, active ingredient 40%), 50.0 g (20.0 g as active ingredient) of silica particle dispersion (C-1) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%. [Example 29] Instead of mixing 35g of urethane acrylate (A-1), mix 15g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g, hydroxyl value of 27.3mgKOH / g) and 10g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g, hydroxyl value of 28.5mgKOH / g), and then mix with silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 75.0 g (30.0 g as active ingredient) of "MEK-ST-40" (particle size 12 nm, active ingredient 40%), 100.0 g (40.0 g as active ingredient) of silica particle dispersion (C-1) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%. [Example 30] Instead of mixing 35g of urethane acrylate (A-1), mix 10g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g, hydroxyl value of 27.3mgKOH / g) and 5g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g, hydroxyl value of 28.5mgKOH / g), and add silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 75.0 g (30.0 g as active ingredient) of "MEK-ST-40" (particle size 12 nm, active ingredient 40%), 125.0 g (50.0 g as active ingredient) of silica particle dispersion (C-1) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0141] [Example 31] Instead of mixing 35g of urethane acrylate (A-1), mix 30g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g, hydroxyl value of 27.3mgKOH / g) and 30g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g, hydroxyl value of 28.5mgKOH / g), and add silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 75.0 g (30.0 g as active ingredient) of "MEK-ST-40" (particle size 12 nm, active ingredient 40%), 12.5 g (5.0 g as active ingredient) of methacrylate silane coupling agent treated silica particle dispersion (C-7) (Nissan Chemical Corporation's "Snowtex MEK-AC-2140Z", particle size 12 nm, methyl ethyl ketone solvent, active ingredient 40%) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0142] [Example 32] Instead of mixing 35g of urethane acrylate (A-1), mix 25g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, with a hydroxyl value of 27.3 mg KOH / g) and 25g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, with a hydroxyl value of 28.5 mg KOH / g), and add silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 75.0 g (30.0 g as active ingredient) of "MEK-ST-40" (particle size 12 nm, active ingredient 40%), 37.5 g (15.0 g as active ingredient) of methacrylate silane coupling agent treated silica particle dispersion (C-7) (Nissan Chemical Corporation's "Snowtex MEK-AC-2140Z", particle size 12 nm, methyl ethyl ketone solvent, active ingredient 40%) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0143] [Example 33] Instead of mixing 35g of urethane acrylate (A-1), mix 25g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g, hydroxyl value of 27.3mgKOH / g) and 20g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g, hydroxyl value of 28.5mgKOH / g), and then mix with silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 75.0 g (30.0 g as active ingredient) of "MEK-ST-40" (particle size 12 nm, active ingredient 40%), 50.0 g (20.0 g as active ingredient) of methacrylate silane coupling agent treated silica particle dispersion (C-7) (Nissan Chemical Corporation's "Snowtex MEK-AC-2140Z", particle size 12 nm, methyl ethyl ketone solvent, active ingredient 40%) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0144] [Example 34] Instead of mixing 35g of urethane acrylate (A-1), mix 20g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g, hydroxyl value of 27.3mgKOH / g) and 15g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g, hydroxyl value of 28.5mgKOH / g), and then mix with silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 75.0 g (30.0 g as active ingredient) of "MEK-ST-40" (particle size 12 nm, active ingredient 40%), 75.0 g (30.0 g as active ingredient) of methacrylate silane coupling agent treated silica particle dispersion (C-7) (Nissan Chemical Corporation's "Snowtex MEK-AC-2140Z", particle size 12 nm, methyl ethyl ketone solvent, active ingredient 40%) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0145] [Example 35] Instead of mixing 35g of urethane acrylate (A-1), mix 15g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g, hydroxyl value of 27.3mgKOH / g) and 10g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g, hydroxyl value of 28.5mgKOH / g), and then mix with silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 75.0 g (30.0 g as active ingredient) of "MEK-ST-40" (particle size 12 nm, active ingredient 40%), 100.0 g (40.0 g as active ingredient) of methacrylate silane coupling agent treated silica particle dispersion (C-7) (Nissan Chemical Corporation's "Snowtex MEK-AC-2140Z", particle size 12 nm, methyl ethyl ketone solvent, active ingredient 40%) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0146] [Example 36] Instead of mixing 35g of urethane acrylate (A-1), mix 10g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g, hydroxyl value of 27.3mgKOH / g) and 5g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g, hydroxyl value of 28.5mgKOH / g), and add silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 75.0 g (30.0 g as active ingredient) of "MEK-ST-40" (particle size 12 nm, active ingredient 40%), 125.0 g (50.0 g as active ingredient) of methacrylate silane coupling agent treated silica particle dispersion (C-7) (Nissan Chemical Corporation's "Snowtex MEK-AC-2140Z", particle size 12 nm, methyl ethyl ketone solvent, active ingredient 40%) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0147] The compositions of the curable compositions in Examples 20 to 36 are summarized below. [Table 5]

[0148] [Comparative Example 1] A curable composition was prepared in the same manner as in Example 1, except that 20 g of ethylene oxide-modified trimethylolpropane triacrylate B-1 (number of added ethylene oxides: 0.9), 30 g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (number of added ethylene oxides: 3.7), and 20 g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (number of added ethylene oxides: 6.4) were mixed without mixing urethane acrylate (A-1), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0149] [Comparative Example 2] Instead of mixing 35g of urethane acrylate (A-1), use 35g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g. The hydroxyl value is 27.3 mg KOH / g) and urethane acrylate (A-3) (dicyclohexylmethane 4,4-diisocyanate ( Synthesized from H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g. A curable composition was prepared in the same manner as in Example 1, except that 35 g of (with a hydroxyl value of 28.5 mg KOH / g) was mixed, ethylene oxide-modified trimethylolpropane triacrylate (B-1), (B-2), and (B-3) were not mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0150] [Comparative Example 3] Instead of mixing 35g of urethane acrylate (A-1), mix 20g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g; hydroxyl value is 27.3mgKOH / g) and 15g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g; hydroxyl value is 28.5mgKOH / g) to make ethylene oxide-modified trimethylolpropane triacrylate (B-1). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 10.0 g of (ethylene oxide addition number 0.9), 15.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) (ethylene oxide addition number 3.7), and 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) (ethylene oxide addition number 6.4), 15.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) and 20.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) were mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0151] [Comparative Example 4] Instead of mixing 35g of urethane acrylate (A-1), mix 20g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g; hydroxyl value is 27.3mgKOH / g) and 15g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g; hydroxyl value is 28.5mgKOH / g) to make ethylene oxide-modified trimethylolpropane triacrylate (B-1). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 10.0 g of (ethylene oxide addition number 0.9), 15.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) (ethylene oxide addition number 3.7), and 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) (ethylene oxide addition number 6.4), 20.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-1) and 15.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) were mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0152] [Comparative Example 5] Instead of mixing 35g of urethane acrylate (A-1), mix 20g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g; hydroxyl value is 27.3mgKOH / g) and 15g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g; hydroxyl value is 28.5mgKOH / g) and ethylene oxide modified trim A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 10.0 g of styrene propane triacrylate (B-1) (number of added ethylene oxides: 0.9), 15.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) (number of added ethylene oxides: 3.7), and 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) (number of added ethylene oxides: 6.4), 35.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%. Oxide oxide oxide oxide oxide oxide oxide oxide oxide

[0153] [Comparative Example 6] Instead of mixing 35g of urethane acrylate (A-1), mix 25g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 27.3 mg KOH / g) and 25g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 28.5 mg KOH / g), and ethylene oxide modified trimethylolpropane triacrylate (B-1) (ethylene oxide Instead of mixing 10.0g of (0.9) ethylene oxide-modified trimethylolpropane triacrylate (B-2) (3.7 ethylene oxide additions) and 10.0g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) (6.4 ethylene oxide additions), mix 15.0g of ethylene oxide-modified trimethylolpropane triacrylate (B-1), 20.0g of ethylene oxide-modified trimethylolpropane triacrylate (B-2), and 15.0g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) to form a silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that 75.0 g (30.0 g as active ingredient) of "MEK-ST-40" (particle size 12 nm, active ingredient 40%) was not mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0154] [Comparative Example 7] A curable composition was prepared in the same manner as in Example 1, except that urethane acrylate (A-6) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 50 mg KOH / g, with a hydroxyl value of 13.7 mg KOH / g) was used instead of urethane acrylate (A-1), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0155] [Comparative Example 8] A curable composition was prepared in the same manner as in Example 1, except that urethane acrylate (A-7) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 310 mg KOH / g, with a hydroxyl value of 64.2 mg KOH / g) was used instead of urethane acrylate (A-1), and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0156] [Comparative Example 9] Instead of mixing 35g of urethane acrylate (A-1), mix 35g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, with a hydroxyl value of 27.3 mg KOH / g) and 35g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, with a hydroxyl value of 28.5 mg KOH / g), without mixing ethylene oxide-modified trimethylolpropane triacrylate (B-1), (B-2), and (B-3), and use silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 30 g of "MEK-ST-40" (particle size 12 nm, active ingredient 40%) as the active ingredient, 75.0 g of methacrylate silane coupling agent treated silica particle dispersion (C-7) (Nissan Chemical Corporation's "Snowtex MEK-AC-2140Z", particle size 12 nm, methyl ethyl ketone solvent, active ingredient 40%) (30.0 g as the active ingredient) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0157] [Comparative Example 10] Instead of mixing 35g of urethane acrylate (A-1), mix 20g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g; hydroxyl value is 27.3mgKOH / g) and 15g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g; hydroxyl value is 28.5mgKOH / g) and ethylene oxide modified trimethylolpropane Instead of mixing 10.0g of acrylate (B-1) (ethylene oxide addition number: 0.9), 15.0g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) (ethylene oxide addition number: 3.7), and 10.0g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) (ethylene oxide addition number: 6.4), mix 25.0g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) and 10.0g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) and use silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 30 g of "MEK-ST-40" (particle size 12 nm, active ingredient 40%) as the active ingredient, 75.0 g of methacrylate silane coupling agent treated silica particle dispersion (C-7) (Nissan Chemical Corporation's "Snowtex MEK-AC-2140Z", particle size 12 nm, methyl ethyl ketone solvent, active ingredient 40%) (30.0 g as the active ingredient) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0158] [Comparative Example 11] Instead of mixing 35g of urethane acrylate (A-1), mix 20g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g; hydroxyl value is 27.3mgKOH / g) and 15g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g; hydroxyl value is 28.5mgKOH / g) and ethylene oxide modified trimethylolpropane Instead of mixing 10.0g of acrylate (B-1) (ethylene oxide addition number: 0.9), 15.0g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) (ethylene oxide addition number: 3.7), and 10.0g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) (ethylene oxide addition number: 6.4), mix 10.0g of ethylene oxide-modified trimethylolpropane triacrylate (B-1) and 25.0g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) and use silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 30 g of "MEK-ST-40" (particle size 12 nm, active ingredient 40%) as the active ingredient, 75.0 g of methacrylate silane coupling agent treated silica particle dispersion (C-7) (Nissan Chemical Corporation's "Snowtex MEK-AC-2140Z", particle size 12 nm, methyl ethyl ketone solvent, active ingredient 40%) (30.0 g as the active ingredient) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0159] [Comparative Example 12] Instead of mixing 35g of urethane acrylate (A-1), mix 20g of urethane acrylate (A-2) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115mgKOH / g, hydroxyl value of 27.3mgKOH / g) and 15g of urethane acrylate (A-3) (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280mgKOH / g, hydroxyl value of 28.5mgKOH / g), and eth Instead of mixing 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-1) (ethylene oxide addition number: 0.9), 15.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) (ethylene oxide addition number: 3.7), and 10.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-3) (ethylene oxide addition number: 6.4), mix 35.0 g of ethylene oxide-modified trimethylolpropane triacrylate (B-2) and silica particle dispersion (C-1) (Nissan Chemical Corporation's "Snowtex"). A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 30 g of "MEK-ST-40" (particle size 12 nm, active ingredient 40%) as the active ingredient, 75.0 g of methacrylate silane coupling agent treated silica particle dispersion (C-7) (Nissan Chemical Corporation's "Snowtex MEK-AC-2140Z", particle size 12 nm, methyl ethyl ketone solvent, active ingredient 40%) (30.0 g as the active ingredient) was mixed, and the amount of diluent PGM was appropriately adjusted so that the solid content was 50%.

[0160] The following is a summary of the compositions of the curable compositions of Comparative Examples 1 to 12. [Table 6]

[0161] 4. Performance evaluation of curable resin compositions [Sample preparation method] The resin compositions prepared in the examples and comparative examples were coated onto an acrylic film substrate (product name: "Acryprene HBA-007P", manufactured by Mitsubishi Chemical Corporation, 125 μm thick) using a bar coater to a dry thickness of 3 μm, and then dried in an oven at 80°C for 1 minute to evaporate the solvent. After that, they were heated with a high-pressure mercury lamp at an output of 1300 mW / cm². 2 A multilayer article with a cured layer was fabricated by irradiating it with ultraviolet light so that the cumulative light intensity was 200 mJ.

[0162] [Surface Impact Test Method] In accordance with JIS K7124-1, a dart impact tester (manufactured by Toyo Seiki Co., Ltd.) was used to drop an aluminum dart (φ38mm, 32g) with a weight attached from a height of 0.66m onto a multilayer film. The appearance of the multilayer structure after dropping the dart was visually inspected, and the maximum weight mass at which no damage was observed was defined as the dart impact strength of the multilayer structure [unit: gf], and was judged according to the following criteria. A:150gf or more B: 100gf or more, less than 150gf C: 50gf or more, less than 100gf D: Less than 50gf

[0163] [Chemical resistance] Hand cream (product name "Neutrogena SPF45", manufactured by Johnson & Johnson) was applied to the hardened layer of the molded product prepared as described above, and it was left in a 60°C oven for 6 hours. After returning to room temperature, the surface of the hardened layer was observed visually and under an optical microscope (100x magnification) after wiping off the hand cream, and judged according to the following criteria. A: No changes were observed visually or under an optical microscope. B: No changes are visible to the naked eye, but changes are observed under an optical microscope. C: Slight surface changes (traces) are visible to the naked eye. D: Clear surface changes (marks) are visible to the naked eye.

[0164] [Taber wear test] Regarding the above-prepared molded product, in accordance with JIS K6264-2(2005), using a Taber abrasion tester manufactured by Toyo Seiki Co., Ltd., the abrasion wheel CS-10 was rotated 100 times at a load of 4.9 N and a rotational speed of 60 rpm. The haze values before and after the test were measured, and the haze difference was calculated using the following formula (1) and judged according to the following criteria. Haze difference [%] = Haze value after the test [%] - Haze value before the test [%] (1) A: Haze difference is less than 10 B: Haze difference is 10 or more and less than 20 C: Haze difference is 20 or more and less than 30 D: Haze difference is 30 or more

[0165] The test results are summarized and shown below.

Table 7

Table 8

Table 9

Table 10

Industrial Applicability

[0166] According to the present invention, there is provided a curable composition capable of forming a hard coat layer excellent in heat resistance and hygrothermal resistance. The curable composition according to the present invention can be used to form a hard coat layer on many resin films and molded products such as polyethylene terephthalate (PET) resin, polycarbonate (PC) resin, poly(meth)acrylate (PMA or PMMA) resin, etc. In particular, since it is used outdoors such as equipment mounted on automobiles and portable devices, it is useful for forming a hard coat layer of equipment that requires higher heat resistance and hygrothermal resistance.

Claims

1. A urethane (meth)acrylate (A) obtained by the reaction of a (meth)acrylate (a1) with a hydroxyl value of 90 to 300 mg KOH / g, a polyhydric isocyanate (a2), and optionally a polyol (a3), Alkylene oxide-modified tri(meth)acrylate (B), Inorganic filler (C) and The alkylene oxide-modified tri(meth)acrylate (B) is, (Meth)acrylate (B1), in which the number of repeating units of alkylene oxide is, on average, 0 to 2.

0. (Meth)acrylate (B3), in which the number of repeating units of alkylene oxide is, on average, 6.0 to 8.0, and (Meth)acrylate (B2) having an average of 3.0 to 5.0 repeating units of alkylene oxide. A curable resin composition containing [the specified ingredient].

2. The alkylene oxide-modified tri(meth)acrylate (B) is, The (meth)acrylate (B1) is 25 to 75% by mass. The (meth)acrylate (B2) is used in an amount of 0 to 50% by mass, and The curable resin composition according to claim 1, comprising 25 to 75% by mass of the (meth)acrylate (B3).

3. The alkylene oxide-modified tri(meth)acrylate (B) is, The (meth)acrylate (B1) is 25 to 50% by mass. The (meth)acrylate (B2) is used in an amount of 25 to 50% by mass, and The (meth)acrylate (B3) is 25 to 50% by mass. A curable resin composition according to claim 2, including the one described in claim 2.

4. The aforementioned urethane (meth)acrylate (A) is Urethane (meth)acrylate (A1) obtained by the reaction of (meth)acrylate (a1-1) with a hydroxyl value of 90-180 mgKOH / g, polyhydric isocyanate (a2), and optionally polyol (a3), and / or A urethane (meth)acrylate (A2) obtained by the reaction of (meth)acrylate (a1-2) with a hydroxyl value of 200-300 mgKOH / g, polyhydric isocyanate (a2), and optionally a polyol (a3). A curable resin composition according to claim 1, comprising the above.

5. The aforementioned urethane (meth)acrylate (A) A urethane (meth)acrylate (A1) obtained by the reaction of a (meth)acrylate (a1-1) with a hydroxyl value of 90-180 mgKOH / g, a polyhydric isocyanate (a2), and optionally a polyol (a3), A urethane (meth)acrylate (A2) obtained by the reaction of (meth)acrylate (a1-2) with a hydroxyl value of 200-300 mgKOH / g, polyhydric isocyanate (a2), and optionally polyol (a3) ​​and A curable resin composition according to claim 4, comprising:

6. The aforementioned urethane (meth)acrylate (A) is A urethane (meth)acrylate (A1) obtained by the reaction of a (meth)acrylate (a1-1) with a hydroxyl value of 90 to 180 mg KOH / g, a polyvalent isocyanate (a2), and optionally a polyol (a3) ​​is used in an amount of 10% to 90% by mass. A urethane (meth)acrylate (A2) obtained by the reaction of (meth)acrylate (a1-2) with a hydroxyl value of 200-300 mgKOH / g, polyhydric isocyanate (a2), and optionally polyol (a3) ​​is used in a concentration of 10% to 90% by mass. A curable resin composition according to claim 5, comprising the above.

7. The aforementioned urethane (meth)acrylate (A) is A urethane (meth)acrylate (A1) obtained by the reaction of a (meth)acrylate (a1-1) with a hydroxyl value of 90 to 180 mg KOH / g, a polyvalent isocyanate (a2), and optionally a polyol (a3) ​​is used in an amount of 25% to 75% by mass. A urethane (meth)acrylate (A2) obtained by the reaction of (meth)acrylate (a1-2) with a hydroxyl value of 200-300 mgKOH / g, polyhydric isocyanate (a2), and optionally polyol (a3) ​​is used in a concentration of 25% to 75% by mass. A curable resin composition according to claim 6, comprising the above.

8. The curable resin composition according to claim 4, wherein the mass ratio of the urethane (meth)acrylate (A1) to the urethane (meth)acrylate (A2) is 10:1 to 1:

10.

9. The curable resin composition according to claim 8, wherein the mass ratio of the urethane (meth)acrylate (A1) to the urethane (meth)acrylate (A2) is 6:1 to 1:

6.

10. The curable resin composition according to claim 1, wherein the (meth)acrylate (a1) has a structure derived from at least one polyhydric alcohol selected from the group consisting of glycerin, pentaerythritol, dipentaerythritol, and tripentaerythritol.

11. The curable resin composition according to claim 10, wherein the (meth)acrylate (a1) has a structure derived from either dipentaerythritol or tripentaerythritol, or both.

12. The curable resin composition according to claim 4, wherein the (meth)acrylates (a1-1) and (a1-2) each independently have a structure derived from at least one polyhydric alcohol selected from the group consisting of glycerin, pentaerythritol, dipentaerythritol, and tripentaerythritol.

13. The curable resin composition according to claim 12, wherein the (meth)acrylates (a1-1) and (a1-2) have structures derived from either or both dipentaerythritol and tripentaerythritol.

14. The curable resin composition according to claim 1, wherein the polyvalent isocyanate (a2) is an aliphatic isocyanate, an alicyclic isocyanate, an aromatic isocyanate, or a hydrogenated product thereof.

15. The curable resin composition according to claim 14, wherein the polyvalent isocyanate (a2) is an alicyclic isocyanate that does not have a crosslinking structure.

16. The curable resin composition according to claim 15, wherein the alicyclic isocyanate is isophorone diisocyanate or dicyclohexylmethane diisocyanate.

17. The curable resin composition according to claim 1, wherein the alkylene oxide-modified (meth)acrylate (B) comprises ethylene oxide-modified trimethylolpropane triacrylate or alkylene oxide-modified pentaerythritol tri(meth)acrylate.

18. The curable resin composition according to claim 1, wherein the hydroxyl value of the urethane (meth)acrylate (A) is 20 to 50 mg KOH / g.

19. The curable resin composition according to claim 1, wherein the inorganic filler (C) is composed of silica, titanium oxide, zirconia, alumina, zinc oxide, cerium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, or a mixture thereof.

20. The curable resin composition according to claim 1, wherein the inorganic filler (C) is a particle with an average particle diameter of 5 to 200 nm.

21. The curable resin composition according to claim 20, wherein the inorganic filler (C) is a particle with an average particle diameter of 10 to 50 nm.

22. The curable resin composition according to claim 19, wherein the inorganic filler (C) is silica particles.

23. The curable resin composition according to claim 22, wherein the inorganic filler (C) is silica particles surface-treated with a silane coupling agent comprising an alkoxysilane having a (meth)acryloyl group.

24. The inorganic filler (C) is defined by the following formula 【Chemistry 2】 (In the formula, m is an integer from 0 to 2, n is an integer from 1 to 3, and m + n is 3, C １－１０ Alkylene refers to alkylene with 1 to 10 carbon atoms, R １ R is an alkyl group having 1 to 4 carbon atoms. ２ is hydrogen or a methyl group, R ３ (These are alkyl groups with 1 to 4 carbon atoms.) The curable resin composition according to claim 23, wherein silica particles are surface-treated with a silane coupling agent comprising an alkoxysilane represented by [formula].

25. The curable resin composition according to claim 24, wherein the alkoxysilane is selected from the group consisting of 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

26. The curable resin composition according to claim 1, wherein the mass ratio of the inorganic filler (C) to the total mass (A + B) of the urethane (meth)acrylate (A) and the alkylene oxide-modified tri(meth)acrylate (B) is 2:98 to 55:45 (C:A + B).

27. The curable resin composition according to claim 26, wherein the mass ratio of the inorganic filler (C) to the total mass (A + B) of the urethane (meth)acrylate (A) and the alkylene oxide-modified tri(meth)acrylate (B) is 5:95 to 50:50 (A + B:C).

28. The curable resin composition according to claim 26, wherein the mass ratio of the inorganic filler (C) to the total mass (A + B) of the urethane (meth)acrylate (A) and the alkylene oxide-modified tri(meth)acrylate (B) is 15:85 to 40:60 (A + B:C).

29. The curable resin composition according to claim 26, wherein the mass ratio of the inorganic filler (C) to the total mass (A + B) of the urethane (meth)acrylate (A) and the alkylene oxide-modified tri(meth)acrylate (B) is 20:80 to 30:70 (A + B:C).

30. A cured layer obtained by curing the curable resin composition according to any one of claims 1 to 29.

31. An article having the cured layer described in claim 30 on the entire surface, one side, or part of the substrate.

32. A method for forming a coating layer, comprising applying a curable resin composition according to any one of claims 1 to 29 onto a substrate, irradiating the curable resin composition with active energy rays, or heating the curable resin composition to cure the curable resin composition.

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