Curable resin composition and its cured product

Abstract

The present invention provides a curable composition capable of forming a hard coat layer with excellent heat resistance and moisture resistance. [Solution] The composition comprises a mixture of (meth)acrylates having a specific range of hydroxyl values ​​and a structure derived from a polyhydric alcohol, and urethane (meth)acrylates obtained from specific polyhydric isocyanates, and (meth)acrylates having a different specific range of alkylene oxide structural units.

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition and a cured product thereof, comprising a urethane (meth)acrylate obtained from a specific hydroxyl value (meth)acrylate having a structure derived from a polyhydric alcohol and a specific polyhydric isocyanate, and a mixture of polyfunctional (meth)acrylates having different numbers of alkylene oxide units. [Background technology]

[0002] In recent years, resin films and molded products made from polyethylene terephthalate (PET), polycarbonate (PC), and poly(meth)methyl (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, they have poor weather resistance and their surfaces are easily scratched, so protective layers are generally applied. For this reason, the protective layer needs to have hardness and scratch resistance, but it is also used in molded products and the curved parts of displays, and in recent years, its use has begun in foldable or rollable portable display devices, so high flexibility is required. Furthermore, when applying a coating agent to the film and curing it, it is also required that curling and cracking due to curing shrinkage do not occur.

[0003] In addition, equipment used outdoors, such as devices installed in automobiles and portable devices, is increasingly required to have higher heat resistance and heat / humidity resistance.

[0004] In response to these requirements, various curable resin compositions have been conventionally proposed as coating agents for resin substrates.

[0005] 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).

[0006] 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).

[0007] 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).

[0008] 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).

[0009] However, none of these coating agents or curable compositions aimed to improve heat resistance or heat- and humidity resistance, and the resulting cured products were insufficient in terms of adhesion and transparency under high heat or high-humidity heat conditions. Therefore, there is still a demand for curable compositions that can impart high heat resistance and heat- and humidity resistance. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Patent No. 6845586 [Patent Document 2] Patent No. 7452588 [Patent Document 3] Patent No. 6481302 [Patent Document 4] Publication No. 4204106 [Overview of the project] [Problems that the invention aims to solve]

[0011] In one embodiment, the present invention aims to provide a curable composition capable of forming a hard coat layer with excellent heat resistance and moisture resistance, in response to such requirements. In another embodiment, the present invention also aims to provide a cured product, or a product having the same, with excellent heat resistance and moisture resistance. [Means for solving the problem]

[0012] The present inventors have variously studied the composition of the curable composition to achieve the above object, and have found that (meth)acrylates having a hydroxyl value within a specific range having a structure derived from a polyhydric alcohol, more preferably a mixture of (meth)acrylates having a hydroxyl value within different specific ranges having a structure derived from a polyhydric alcohol, and urethane (meth)acrylate obtained from a specific polyisocyanate and a mixture of (meth)acrylates having a different specific number of alkylene oxide structural units. When the composition was cured on a resin substrate, it was found that the obtained cured product maintained adhesion and transparency even after being exposed to high heat conditions or high humidity and heat conditions for a long time, leading to the present invention.

[0013] That is, in one embodiment, the present invention provides the following curable resin composition, cured layer, method for forming the same, and article having the same. [1] A urethane (meth)acrylate (A) obtained by reacting a (meth)acrylate (a1) having a hydroxyl value of 90 to 300 mgKOH / g having a structure derived from a polyhydric alcohol, an aliphatic isocyanate, an alicyclic isocyanate having no crosslinked structure, an aromatic isocyanate, and a hydrogenated product thereof, a polyisocyanate (a2) selected therefrom, and optionally a polyol (a3), and an alkylene oxide-modified (meth)acrylate (B) The alkylene oxide-modified (meth)acrylate (B) includes a (meth)acrylate (B1) in which the average number of repeating units of alkylene oxide is 0 to 2.0, optionally, a (meth)acrylate (B2) in which the average number of repeating units of alkylene oxide is 3.0 to 5.0, and a (meth)acrylate (B3) in which the average number of repeating units of alkylene oxide is 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

[10] The curable resin composition according to any one of [1] to [9], wherein the polyvalent isocyanate (a2) is an alicyclic isocyanate that does not have a crosslinking structure.

[11] The curable resin composition according to

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

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

[11] , wherein the hydroxyl value of the urethane (meth)acrylate (A) is 0.1 to 10 mg KOH / g.

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

[12] , wherein the alkylene oxide-modified (meth)acrylate (B) is selected from ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, ethylene oxide-modified bisphenol A diacrylate, propylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified pentaerythritol tetraacrylate, and propylene oxide-modified pentaerythritol tetraacrylate.

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

[13] , 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.

[15] The curable resin composition according to

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

[16] The curable resin composition according to

[14] , 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.

[17] The curable resin composition according to

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

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

[17] , comprising 0.1 to 15 parts by mass in total of one or more of the group consisting of a benzotriazole-based light stabilizer, a triazine-based light stabilizer, a cyanoacrylate-based light stabilizer, 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).

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

[18] .

[20] An article having the cured layer described in

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

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

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

[0014] In a curable resin composition according to one embodiment of the present invention, the cured product obtained by curing on a resin substrate maintains adhesion and transparency even after being exposed to high heat conditions or high humidity heat conditions for a long period of time.

[0015] 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 mgKOH / g" means a mixture of (meth)acrylates having the same or different hydroxyl values, with an average hydroxyl value of 90 mgKOH / g. 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 or methacrylic acid, etc., and having a part of the structure of the said polyhydric alcohol. 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. On the other hand, for example, "lactone" is not a "polyhydric alcohol," and "lactone-modified (meth)acrylate" is not a "(meth)acrylate having a structure derived from a polyhydric alcohol." 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. Furthermore, the term "pentaerythritol (meth)acrylate" in this specification 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" in this specification 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 same applies to the term "tripentaerythritol (meth)acrylate." 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. 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, "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. 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, "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]

[0016] Embodiments of the present invention are described below. However, the present invention is not limited to the following embodiments.

[0017] 1. Curable resin composition In one embodiment, the present invention relates to a curable resin composition comprising a urethane (meth)acrylate (A) with a specific hydroxyl value and a specific alkylene oxide-modified (meth)acrylate (B).

[0018] 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 low molecular weight 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 heat resistance and moisture resistance can be obtained.

[0019] As the (meth)acrylate (a1) with a hydroxyl value of 90 to 300 mgKOH / g, a (meth)acrylate with a hydroxyl value of 90 to 300 mgKOH / g due to a structure derived from a polyhydric alcohol is preferred. Furthermore, there are no particular restrictions on the structure derived from the polyhydric alcohol, but a structure derived from at least one selected from the group consisting of glycerin, pentaerythritol, dipentaerythritol, and tripentaerythritol is preferred. In particular, a (meth)acrylate having either or both of the structures derived from dipentaerythritol and tripentaerythritol is preferred in terms of the moisture and heat resistance of the cured product.

[0020] Examples of (meth)acrylate (a1) include glycerin mono(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, and other glycerin (meth)acrylates; pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and other pentaerythritol (meth)acrylates; dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, and di Examples of tripentaerythritol (meth)acrylates include pentaerythritol tetra(meth)acrylate and dipentaerythritol penta(meth)acrylate; tripentaerythritol mono(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, and tripentaerythritol hepta(meth)acrylate.

[0021] Regarding (meth)acrylate (a1), in terms of the heat and humidity resistance of the cured product, (meth)acrylate with a hydroxyl value of 90 to 180 mgKOH / g is preferred, and (meth)acrylate with a hydroxyl value of 100 to 150 mgKOH / g is more preferred. On the other hand, in terms of the heat resistance of the cured product, (meth)acrylate with a hydroxyl value of 200 to 300 mgKOH / g is preferred, and (meth)acrylate with a hydroxyl value of 250 to 300 mgKOH / g is more preferred.

[0022] 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%.

[0023] 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%.

[0024] 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. Aliphatic isocyanates, alicyclic isocyanates without crosslinking structures, aromatic isocyanates or their hydrogenated versions are preferred in that they yield cured products with high resistance to moisture and heat, and alicyclic isocyanates without crosslinking structures are particularly preferred.

[0025] Examples of polyvalent isocyanates (a2) include isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, polymeric MDI, tetramethylxylylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, methylenebis(4,1-cyclohexylene)-diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, tolylene diisocyanate (e.g., 2,4-tolylene diisocyanate), and phenylene diisocyanate (1,4-phenylene diisocyanate). Examples include anates, diphenyl diisocyanates (e.g., 4,4-diphenyl diisocyanate, 3,3-dimethyl-4,4-diphenyl diisocyanate), diphenylmethane diisocyanate (4,4-diphenylmethane diisocyanate), naphthalene diisocyanates (e.g., 1,5-naphthalene diisocyanate), 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, 1,3-bis(isocyanate methyl)cyclohexane, isophorone diisocyanate, or dicyclohexylmethane diisocyanate are preferred from the viewpoint of improving the moisture and heat resistance of the cured product, and dicyclohexylmethane diisocyanate is more preferred. Commercially available products that can be used include Evonik's VESTANAT® IPDI, Evonik's VESTANAT® H12MDI, Asahi Kasei Corporation's Duranate D-201, TPA-100, TKA-100, 24A-100, 22A-75P, P301-75E, etc., Tosoh Corporation's Coronate HX, 2715, etc., Tosoh Corporation's HDI, and Mitsui Chemicals, Inc.'s Takenate® D160N, D-170N, D-170HN, D-172N, D-177N, 600, etc. These may be used individually or in combination of two or more.

[0026] 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 dihydric alcohols, trihydric alcohols, and their condensates. Specifically, examples 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 polyalkylene glycols such as 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, with propylene glycol, 1,3-butanediol, dipropylene glycol, polyethylene glycol (molecular weight 400 or less), and glycerin being 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.

[0027] By efficiently reacting (meth)acrylate (a1) with polyvalent isocyanate (a2) and reducing the residual hydroxyl groups in the resulting urethane (meth)acrylate (A), the heat resistance and moisture resistance of the cured product can be significantly improved. From this perspective, it is more preferable to mix (meth)acrylate (a1) with a hydroxyl value of 90-300 mgKOH / g, polyvalent isocyanate (a2), and polyol (a3) ​​in a ratio such that the ratio of the total number of moles of isocyanate groups to the total number of moles of hydroxyl groups (moles of isocyanate groups / total number of moles of hydroxyl groups), as determined by the following formulas (1) and (2), is 0.95-1.05. Total number of moles of hydroxyl groups = (Amount of (a1) / Equivalent amount of hydroxyl groups in (a1)) + (Amount of (a3) ​​ / Equivalent amount of hydroxyl groups in (a3)) ... (1) (In the formula, hydroxyl group 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.)

[0028] The reaction between (meth)acrylate (a1), polyvalent isocyanate (a2), and optionally low molecular weight 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] The resulting urethane (meth)acrylate (A) has a low residual hydroxyl value, which allows for the production of urethane (meth)acrylate with a higher number of functional groups and molecular weight. Furthermore, by reducing the number of hydrophilic residual hydroxyl groups, the heat resistance and moisture resistance of the cured product can be significantly improved. For this reason, it is preferable that urethane (meth)acrylate (A) has a low residual hydroxyl group value. Specifically, a hydroxyl value of 15 mgKOH / g or less is preferred, urethane (meth)acrylate (A) with a hydroxyl value of 0.1 to 10 mgKOH / g is more preferred, and urethane (meth)acrylate (A) with a hydroxyl value of 0.1 to 7 mgKOH / g is particularly preferred.

[0033] Furthermore, from the viewpoint of adhesion of the cured product under high temperature and high humidity heat conditions, the molecular weight of the urethane (meth)acrylate (A) is preferably 2,000 to 20,000, and more preferably 3,000 to 18,000. Furthermore, in terms of compatibility with urethane (meth)acrylate (A1), as well as adhesion and transparency under high humidity and heat conditions, the molecular weight of urethane (meth)acrylate (A1) is preferably 1,000 to 5,000, and more preferably 1,200 to 4,000.

[0034] In a preferred embodiment, the coating agent comprises a mixture of urethane (meth)acrylate (A1) and urethane (meth)acrylate (A2). Urethane (meth)acrylate (A2), which has a high molecular weight and many urethane bonds per molecule, can reduce curing shrinkage of the coating film, resulting in excellent adhesion of the cured product at high temperatures. On the other hand, urethane (meth)acrylate (A1), which has a low molecular weight, improves the crosslinking density of the cured coating film, preventing the penetration of moisture into the cured product and substrate interface, and preventing deterioration of adhesion and transparency under high humidity and heat conditions. By combining such urethane (meth)acrylates, a cured product with excellent adhesion and transparency under high temperature and high humidity and heat conditions can be obtained. The mass ratio (A / B) of urethane (meth)acrylate (A1) and urethane (meth)acrylate (A2) is not particularly limited and can be combined in the range of 1 / 5 to 9 / 1, preferably 1 / 3 to 8 / 1, more preferably 1 / 2 to 7 / 1, and particularly preferably 1 / 1 to 5 / 1.

[0035] The content of urethane (meth)acrylate (A) in the coating agent can vary over a relatively wide range. Typically, the coating film component in the coating agent can contain urethane (meth)acrylate (A) in the range of 5 to 95% by mass, preferably in the range of 10 to 90% by mass, more preferably in the range of 20 to 80% by mass, and particularly preferably in the range of 40 to 70% by mass.

[0036] 1-2. Alkylene oxide modified (meth)acrylate (B) A curable resin composition according to one embodiment of the present invention includes, together with the above-described urethane (meth)acrylate (A), an alkylene oxide-modified (meth)acrylate (B), wherein the alkylene oxide-modified (meth)acrylate (B) includes (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. The reason why using (meth)acrylates with a specific range of alkylene oxide addition numbers results in good heat-resistant adhesion, moisture-resistant heat-resistant adhesion, and moisture-resistant heat-transparency is not entirely clear. However, it is thought that (meth)acrylates with fewer alkylene oxide addition numbers penetrate the substrate and improve adhesion durability through an anchoring effect, while (meth)acrylates with more addition numbers improve adhesion by reducing the internal stress of the cured product after active energy ray curing.

[0037] (Meth)acrylate (B) is preferably the following formula (1): [ka] It is a mixture of (meth)acrylates, as shown by [formula]. In the formula, R1 is a hydrogen atom or a methyl group. In the formula, A is a trimethylolpropane residue, a bisphenol A residue, or a pentaerythritol residue, preferably a trimethylolpropane residue. In the formula, m is an integer between 2 and 3, preferably 2. In the formula, n is an integer between 0 and 8, preferably 0 and 7.

[0038] The alkylene oxide modified (meth)acrylate (B) is preferably an alkylene oxide (C 2-3Alkylene oxide) Modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkylene oxide (preferably, C 2-3 Alkylene oxide) Modified pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkylene oxide (preferably, C 2-3 Alkylene oxide) Modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, alkylene oxide (preferably, C 2-3 Alkylene oxide) Modified glyceryl tri(meth)acrylate, glyceryl tri(meth)acrylate, alkylene oxide (preferably C 2-3 Examples include alkylene oxide-modified bisphenol A di(meth)acrylate and bisphenol A di(meth)acrylate. 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 especially in that they have superior water resistance and improve adhesion to the substrate, trimethylolpropane tri(meth)acrylate and its alkylene oxide (preferably C 2-3 Alkylene oxide) modified product, bisphenol A di(meth)acrylate and its alkylene oxide (preferably C 2-3 Alkylene oxide-modified products are more preferable.

[0039] (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 particularly preferred due to their excellent heat resistance and moisture resistance.

[0040] (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. (Meth)acrylate (B2) is preferably 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( The following are selected: 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 adduct, and trimethylolpropane tri(meth)acrylate and its ethylene oxide adduct are particularly preferred due to their excellent heat resistance and moisture resistance.

[0041] (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 particularly preferred due to their excellent heat resistance and moisture-heat resistance.

[0042] The alkylene oxide-modified (meth)acrylate (B) is preferably a mixture containing (meth)acrylate (B1) with an average number of repeating alkylene oxide units (n in formula (1)) of 0 to 2.0, (meth)acrylate (B2) with an average number of repeating alkylene oxide units (n in formula (1)) of 3.0 to 5.0, and (meth)acrylate (B3) with an average number of repeating alkylene oxide units (n in formula (1)) of 6.0 to 8.0.

[0043] In terms of improving both heat resistance and moisture heat resistance, alkylene oxide-modified (meth)acrylate (B) preferably contains 5 to 50% by mass of (meth)acrylate (B1), 20 to 90% by mass of (meth)acrylate (B2), and 5 to 30% by mass of (meth)acrylate (B3), and more preferably, alkylene oxide-modified (meth)acrylate (B) contains 10 to 45% by mass of (meth)acrylate (B1), 30 to 80% by mass of (meth)acrylate (B2) having n in formula (1) of 3.0 to 5.0, and 10 to 25% by mass of (meth)acrylate (B3) having n in formula (1) of 6.0 to 8.0.

[0044] There are no particular restrictions on the content of (meth)acrylate(B) in the coating agent, and it can be varied over a wide range. Typically, the coating film component of the coating agent can contain (meth)acrylate(B) in the range of 5 to 95% by mass, preferably in the range of 10 to 90% by mass, more preferably in the range of 20 to 80% by mass, and particularly preferably in the range of 40 to 70% by mass. 1-3. Other ingredients

[0045] The curable resin composition may optionally contain other components such as polymerization initiators, light stabilizers, solvents, thickeners, flame retardants, UV absorbers, leveling agents, and antioxidants.

[0046] Depending on the polymerization method, either a thermal polymerization initiator or a photopolymerization initiator may be used as the polymerization 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 photopolymerization 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] Examples of benzoin compound polymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] Examples of cyanoacrylate-based UV absorbers include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate.

[0062] 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).

[0063] There are no particular restrictions on the light stabilizer, but hindered amine light stabilizers can be used as an example.

[0064] 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).

[0065] 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.

[0066] 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 coating agent 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.

[0067] 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 coating agent of the present invention in an amount of 0 to 2% by mass.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] The coating agent of the present invention typically contains the above-mentioned components in a polymerization solvent. The polymerization 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 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. 1-methoxy-2-propanol (PGM) is preferred because it has moderate solubility and does not easily dissolve substrates such as polycarbonate.

[0076] There are no particular restrictions on the content of polymerization solvent in the curable composition, but typically 10% to 80% by mass of polymerization solvent can be incorporated into the curable composition, and in many cases, 30% to 70% by mass of polymerization solvent, preferably 30% to 60% by mass of polymerization solvent, is incorporated into the curable composition. Furthermore, the amount of the coating agent is typically 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 coating agent is typically 5 to 500 mPa·s, preferably 10 to 100 mPa·s, at the temperature during use (typically 15 to 30°C). The coating agent may be diluted with a solvent to adjust its viscosity to an appropriate level during application. The solvent content after dilution is typically 55-85% by mass of the coating agent, preferably 70-80% by mass.

[0077] A curable composition can be applied to a substrate, for example, and a cured product 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.

[0078] 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.

[0079] 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.

[0080] There are no particular restrictions on the type of active energy ray, but examples include ultraviolet rays and electron beams. When irradiating with ultraviolet rays, 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 irradiation amount of ultraviolet rays is preferably an illuminance of 30 to 2,000 mW / cm 2 and, as an integrated light amount, 100 to 1000 mJ / cm 2 . The curing atmosphere may be either an air atmosphere or an inert gas (e.g., nitrogen, argon) atmosphere. When irradiating with an electron beam, a commercially available electron beam irradiation device can also be used, and the irradiation amount of the electron beam is preferably 1 to 10 Mrad.

[0081] After irradiating with active energy rays for curing, if necessary, heat treatment (annealing treatment) may be performed to further promote curing. The heating temperature at that time is preferably in the range of 80 to 220°C. The heating time is preferably in the range of 10 minutes to 60 minutes.

[0082] When curing the curable composition by thermal polymerization, the heating temperature is preferably in the range of 80 to 200°C, more preferably in the range of 100 to 150°C. If the heating temperature is lower than 80°C, it is necessary to extend the heating time and there is a tendency to lack economic efficiency. If the heating temperature is higher than 200°C, not only is the energy cost high, but also the heating temperature rise time and the cooling time are long, so there is a tendency to lack economic efficiency. The polymerization conditions are not particularly limited and can be appropriately adjusted according to the type of polymerization initiator used, etc. For example, it can be carried out by reacting at a polymerization temperature of 60 to 90°C for 3 to 10 hours under an inert gas (preferably nitrogen) atmosphere.

[0083] The cured resin composition can be used for various substrates, for example, it can be used for polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, polycycloolefin, polyimide, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin, etc.

[0084] 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.

[0085] The resulting cured product exhibits excellent transparency, heat resistance, and moisture resistance, making it suitable for use as a coating material for outdoor displays such as digital signage, and for automotive resin substrates. [Examples]

[0086] 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.

[0087] 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% ylene 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, and a hydroxyl value of 29.2 mgKOH / g when calculated based on solid content.

[0088] [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 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-2. The obtained urethane acrylate A-2 had a solid content of 80%, a viscosity of approximately 80 mPa·s at 25°C, and a hydroxyl value of 27.3 mgKOH / g when calculated based on solid content.

[0089] [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, and a hydroxyl value of 28.5 mgKOH / g when calculated based on solid content.

[0090] [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, and a hydroxyl value of 27.6 mgKOH / g when calculated based on solid content.

[0091] [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, and a hydroxyl value of 40.8 mgKOH / g when calculated based on solid content.

[0092] [Synthesis Example 6] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 127.8 g of isophorone diisocyanate (IPDI, VESTANT® manufactured by Evonik, isocyanate content 37.7%), 1470.2 g of dipentaerythritol acrylate (DPHA, Aronics M-403 manufactured by Toagosei Co., Ltd.) with a hydroxyl value of 95 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 until the residual isocyanate groups reached 0.1%, at which point the reaction was terminated to obtain 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, and a hydroxyl value of 13.7 mgKOH / g when calculated based on solid content.

[0093] [Synthesis Example 7] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 321.2 g of dicyclohexylmethane 4,4-diisocyanate (H12MDI, VESTANT® manufactured by Evonik, isocyanate content 32%) 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%) were added. 1276.9g of a mixture containing 60% erythritol triacrylate 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-7. The obtained urethane acrylate A-7 had a solid content of 80%, a viscosity of approximately 140 mPa·s at 25°C, and a hydroxyl value of 5.2 mgKOH / g when calculated based on solid content.

[0094] [Synthesis Example 8] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 615.3 g of dicyclohexylmethane 4,4-diisocyanate (H12MDI, VESTANT® manufactured by Evonik, isocyanate content 32%) was added, along with pentaerythritol acrylate (PEA, Aronics M-933 manufactured by Toagosei Co., Ltd., with a hydroxyl value of 280 mg KOH / g, containing 30% pentaerythritol diacrylate and 5% pentaerythritol monoacrylate). 982.8 g of a mixture containing 50% taerythritol triacrylate and 15% 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-8. The obtained urethane acrylate A-8 had a solid content of 80%, a viscosity of approximately 500 mPa·s at 25°C, and a hydroxyl value of 6.7 mgKOH / g when calculated based on solid content.

[0095] [Comparative Synthesis Example 1] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 595.5 g of dicyclohexylmethane 4,4-diisocyanate (H12MDI, VESTANT® manufactured by Evonik, isocyanate content 32%), 738.7 g of polytetramethylene ether glycol (PTMEG, PTMG650 manufactured by Mitsubishi Chemical Corporation, molecular weight 650), 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, and the mixture was reacted at 70°C for 2 hours with uniform stirring. Subsequently, 263.9 g of 2-hydroxyethyl acrylate (2HEA, manufactured by Osaka Organic Industry Co., Ltd., hydroxyl value 483 mg KOH / g) was added and the reaction was allowed to proceed for 3 hours. The reaction was terminated when the remaining isocyanate group was reduced to 0.1%, yielding urethane acrylate A-9. The obtained urethane acrylate A-9 had a solid content of 80%, a viscosity of approximately 2000 mPa·s at 25°C, and a hydroxyl value of 15 mg KOH / g when calculated based on solid content. Note that urethane acrylate A-9 is the same urethane acrylate used in the example of Japanese Patent No. 4204106.

[0096] [Comparative Synthesis Example 2] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 645.6 g of a bifunctional hexamethylene diisocyanate prepolymer (HDI prepolymer, Duranate A201H, manufactured by Asahi Kasei Corporation, isocyanate content 15.8%), 952.5 g of lactone-modified acrylate (LA, Praxel FA2D, manufactured by Daicel Corporation) with a hydroxyl value of 163 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, and the reaction was carried out at 70°C with uniform stirring. The reaction was terminated when the remaining isocyanate groups reached 0.1%, yielding urethane acrylate A-10. The obtained urethane acrylate A-10 had a solid content of 80%, a viscosity of approximately 1200 mPa·s at 25°C, and a hydroxyl value of 11.3 mgKOH / g when calculated based on solid content. Note that urethane acrylate A-10 is the same urethane acrylate used in the examples of Japanese Patent No. 7452588.

[0097] [Comparative Synthesis Example 3] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 210.9 g of norbornene diisocyanate (synthesized by Taisei Fine Chemical Co., Ltd., isocyanate content 47.1%) and pentaerythritol acrylate (PEA, manufactured by Toagosei Co., Ltd., Aronics M-305, hydroxyl value 115 mg KOH / g, pentaerythritol diacrylate content 0%, pentaerythritol monoacrylate content 0%, pentaerythritol triacrylate) were added. 1387.1g of a mixture containing 60% acrylate 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-11. The obtained urethane acrylate A-11 had a solid content of 80%, a viscosity of approximately 110 mPa·s at 25°C, and a hydroxyl value of 15.3 mgKOH / g when calculated based on solid content. Note that urethane acrylate A-11 is the same urethane acrylate used in the examples of Patent 6481302.

[0098] [Comparative Synthesis Example 4] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 303.6 g of 1,3,bis(isocyanatomethyl)cyclohexane (H6XDI, Takenate® 600 manufactured by Mitsui Chemicals, Inc., isocyanate content 43.3%) and pentaerythritol acrylate (PEA, Aronics M-933 manufactured by Toagosei Co., Ltd., with a hydroxyl value of 280 mg KOH / g, containing 30% pentaerythritol diacrylate, 5% pentaerythritol monoacrylate, and 50% pentaerythritol triacrylate) were added. 567.3g of 15% litol tetraacrylate, 727.1g of dipentaerythritol acrylate (DPHA, Aronics M-403, manufactured by Toagosei Co., Ltd.) with a hydroxyl value of 95mgKOH / g, 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, manufactured by 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-12. The obtained urethane acrylate A-12 had a solid content of 80%, a viscosity of approximately 400 mPa·s at 25°C, and a hydroxyl value of 16.4 mgKOH / g when calculated based on solid content. Note that urethane acrylate A-12 is the same urethane acrylate used in the examples of Patent 7024558.

[0099] [Comparative Synthesis Example 5] 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 until the residual isocyanate group reached 0.1%, at which point the reaction was terminated to obtain urethane acrylate A-13. The obtained urethane acrylate A-13 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.

[0100] [Comparative Synthesis Example 6] 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 until the residual isocyanate groups reached 0.1%, at which point the reaction was terminated to obtain urethane acrylate A-14. The obtained urethane acrylate A-14 had a solid content of 80%, a viscosity of approximately 110 mPa·s at 25°C, and a hydroxyl value of 13.7 mgKOH / g when calculated based on solid content.

[0101] The following outlines the synthesis conditions for each urethane acrylate and the hydroxyl value of each obtained urethane acrylate. [Table 1] [Table 2] UA: Urethane acrylate PEA: Pentaerythritol acrylate DPHA: Dipentaerythritol acrylate HDI: Hexamethylene diisocyanate H12MDI: Dicyclohexylmethane diisocyanate H6XDI:1,3,Bis(isocyanatomethyl)cyclohexane IPDI: Isophorone diisocyanate LA: Lactone-modified acrylate HEA: 2-hydroxyethyl acrylate NBDI: norbornene diisocyanate SEA: Sorbitol EO-modified acrylate OH value 50 mg KOH / g DPHA: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK Ester A-9550 OH value 95 mg KOH / g DPHA: Aronics M-403 manufactured by Toagosei Co., Ltd. OH value 115 mg KOH / g PEA: Aronics M-305 manufactured by Toagosei Co., Ltd. OH value 280 mg KOH / g PEA: Aronics M-933 manufactured by Toagosei Co., Ltd. OH value 310 mg KOH / g SEA: Aronics M-926, manufactured by Toagosei Co., Ltd. PTMEG: Polytetramethylene ether glycol (PTMG650, manufactured by Mitsubishi Chemical Corporation, molecular weight 650) OH value 163 mgKOH / g LA: Daicel Corporation's Praxel FA2D OH value 483 mg KOH / g HEA: 2-hydroxyethyl acrylate manufactured by Osaka Organic Industry Co., Ltd., hydroxyl value 483 mg KOH / g HDI (NCO%: 50%): HDI manufactured by Tosoh Corporation (isocyanate content 50%) H12MDI (NCO%:32): Vestanat® (registered trademark) manufactured by Evonik (isocyanate content 32%) IPDI (NCO%: 37.7%): Vestanat® manufactured by Evonik (isocyanate content 37.7%) H6XDI (NCO%: 43.8%): Takenate® 600 (Isocyanate content 43.8%) manufactured by Mitsui Chemicals, Inc. Bifunctional HDI (NCO%: 15.8): Bifunctional hexamethylene diisocyanate (HDI) prepolymer (manufactured by Asahi Kasei Corporation, Duranate A-201H) NBDI (NCO%: 47.1%): Synthesized by Taisei Fine Co., Ltd. (Isocyanate content 47.1%)

[0102] 2. Manufacture of alkylene oxide-modified or unmodified (meth)acrylate (B) [Synthesis Example 9] 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, 216 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 B-1 is subject to the following conditions: 1 H-HMR, 13 Analysis by 13C-NMR and HPLC revealed that the number of ethylene oxide additions was 0.9.

[0103] 1 Conditions for H-HMR analysis Equipment: JEOL Ltd. ECX-400 Measurement solvent: Deuterated chloroform Measured concentration: 1% by weight Measurement temperature 50℃ Total number of times: 16

[0104] 13 Conditions for 1C-NMR analysis Equipment: JEOL Ltd. ECX-400 Measurement solvent: Deuterated chloroform Measured concentration: 5% by weight Measurement temperature: room temperature Total number of times: 4096

[0105] 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%

[0106] [Synthesis Example 10] 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, 216 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. Regarding the obtained B-2, 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.

[0107] [Synthesis Example 11] 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, 216 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 B-3, 1 H-HMR, 13 Analysis by 13C-NMR and HPLC revealed that the number of ethylene oxide additions was 6.4.

[0108] [Synthesis Example 12] In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel, etc., 178 g of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 134.2), 216 g of acrylic acid, 30 g of p-toluenesulfonic acid, 0.45 g of hydroquinone, and 400 g of toluene as a solvent were added, and the reaction was carried out by heating to 110°C while blowing in air. 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 unmodified trimethylolpropane triacrylate B-4. The number of ethylene oxide groups added to the resulting B-4 is 0.

[0109] The number of ethylene oxide molecules added (moles) to the obtained ethylene oxide-modified trimethylolpropane triacrylates B-1 to B-3 are summarized below. [Table 3] EO-modified TMPTA: Ethylene oxide-modified trimethylolpropane triacrylate

[0110] 3. Preparation of curable resin composition [Example 1] 60g 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 is 29.2 mg KOH / g), 10g of ethylene oxide-modified trimethylolpropane triacrylate B-1 (0.9 ethylene oxide additions), 25g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (3.7 ethylene oxide additions), 5g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (6.4 ethylene oxide additions), 8g of benzotriazole-based UV absorber (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber, 1g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA LA-87) as a light stabilizer, and a monoacylphosphine oxide-based photopolymerization initiator (IGM) as a photopolymerization initiator. 5 g of OmniradTPO) manufactured by RESINS was mixed and stirred, and 114 g of 1-methoxy-2-propanol (PGM) was added as a diluent to prepare a curable composition with a solid content of 50.0%.

[0111] [Example 2] 80g 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 is 29.2 mg KOH / g), 5g of ethylene oxide-modified trimethylolpropane triacrylate B-1 (0.9 ethylene oxide additions), 12.5g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (3.7 ethylene oxide additions), 2.5g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (6.4 ethylene oxide additions), 8g of benzotriazole-based UV absorber (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber, 1g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA LA-87) as a light stabilizer, and a monoacylphosphine oxide-based photopolymerization initiator (IGM) as a photopolymerization initiator. 5 g of OmniradTPO) manufactured by RESINS was mixed and stirred, and 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0112] [Example 3] 20g 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 is 29.2 mg KOH / g), 20g of ethylene oxide-modified trimethylolpropane triacrylate B-1 (0.9 ethylene oxide additions), 50g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (3.7 ethylene oxide additions), 10g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (6.4 ethylene oxide additions), 8g of benzotriazole-based UV absorber (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber, 1g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA LA-87) as a light stabilizer, and a monoacylphosphine oxide-based photopolymerization initiator (IGM) as a photopolymerization initiator. 5 g of OmniradTPO) manufactured by RESINS was mixed and stirred, and 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%. .

[0113] [Example 4] 60g 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 is 29.2 mg KOH / g), 18g of ethylene oxide-modified trimethylolpropane triacrylate B-1 (0.9 ethylene oxide additions), 12g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (3.7 ethylene oxide additions), 10g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (6.4 ethylene oxide additions), 8g of benzotriazole-based UV absorber (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber, 1g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA LA-87) as a light stabilizer, and a monoacylphosphine oxide-based photopolymerization initiator (IGM) as a photopolymerization initiator. 5 g of OmniradTPO) manufactured by RESINS was mixed and stirred, and 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0114] [Example 5] 60g 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 is 29.2 mg KOH / g), 4g of ethylene oxide-modified trimethylolpropane triacrylate B-1 (0.9 ethylene oxide additions), 32g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (3.7 ethylene oxide additions), 4g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (6.4 ethylene oxide additions), 8g of benzotriazole-based UV absorber (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber, 1g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA LA-87) as a light stabilizer, and a monoacylphosphine oxide-based photopolymerization initiator (IGM) as a photopolymerization initiator. 5 g of OmniradTPO) manufactured by RESINS was mixed and stirred, and 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0115] [Example 6] 60g 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 is 29.2 mg KOH / g), 4g of ethylene oxide-modified trimethylolpropane triacrylate B-1 (0.9 ethylene oxide additions), 26g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (3.7 ethylene oxide additions), 10g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (6.4 ethylene oxide additions), 8g of benzotriazole-based UV absorber (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber, 1g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA LA-87) as a light stabilizer, and a monoacylphosphine oxide-based photopolymerization initiator (IGM) as a photopolymerization initiator. 5 g of OmniradTPO) manufactured by RESINS was mixed and stirred, and 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0116] [Example 7] 60g 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 is 29.2 mg KOH / g), 18g of ethylene oxide-modified trimethylolpropane triacrylate B-1 (0.9 ethylene oxide additions), 18g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (3.7 ethylene oxide additions), 4g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (6.4 ethylene oxide additions), 8g of benzotriazole-based UV absorber (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber, 1g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA LA-87) as a light stabilizer, and a monoacylphosphine oxide-based photopolymerization initiator (IGM) as a photopolymerization initiator. 5 g of OmniradTPO) manufactured by RESINS was mixed and stirred, and 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0117] [Comparative Example 1] 100 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) was mixed and stirred with 8 g of a benzotriazole-based UV absorber (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber, 1 g of a hindered amine-based light stabilizer (ADEKA Corporation's ADEKA Stab LA-87) as a light stabilizer, and 5 g of a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator. 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0118] [Comparative Example 2] 30 g of ethylene oxide-modified trimethylolpropane triacrylate B-1 (0.9 ethylene oxide additions), 60 g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (3.7 ethylene oxide additions), and 10 g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (6.4 ethylene oxide additions) were mixed and stirred. 8 g of a benzotriazole-based UV absorber (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber, 1 g of a hindered amine-based light stabilizer (ADEKA Corporation's ADEKA Stab LA-87) as a light stabilizer, and 5 g of a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator. 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0119] [Comparative Example 3] 60g 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 is 29.2 mg KOH / g), 10g of ethylene oxide-modified trimethylolpropane triacrylate B-1 (0.9 ethylene oxide additions), 30g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (3.7 ethylene oxide additions), 8g of benzotriazole-based UV absorber (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber, 1g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA LA-87) as a light stabilizer, and a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator. 5g was mixed and stirred, and 114g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0120] [Comparative Example 4] 60g 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 is 29.2 mg KOH / g), 30g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (3.7 ethylene oxide additions), 10g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (6.4 ethylene oxide additions), 8g of benzotriazole-based UV absorber (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber, 1g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA Stab LA-87) as a light stabilizer, and a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator. 5g was mixed and stirred, and 114g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0121] [Comparative Example 5] 60g 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 is 29.2 mg KOH / g), 24g of ethylene oxide-modified trimethylolpropane triacrylate B-1 (0.9 ethylene oxide additions), 16g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (6.4 ethylene oxide additions), 8g of benzotriazole-based UV absorber (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber, 1g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA Stab LA-87) as a light stabilizer, and a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator. 5g was mixed and stirred, and 114g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0122] The following is a summary of the compositions of the curable compositions in Examples 1-7 and Comparative Examples 1-5. [Table 4] Unless otherwise specified, the units of the values ​​in the table are grams (g).

[0123] [Example 8] 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, with a hydroxyl value of 27.3 mg KOH / g) was used instead of urethane acrylate A-1.

[0124] [Example 9] 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; hydroxyl value of 28.5 mg KOH / g) was used instead of urethane acrylate A-1.

[0125] [Example 10] 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.

[0126] [Example 11] 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.

[0127] [Example 12] A curable composition was prepared in the same manner as in Example 1, except that 60 g of urethane acrylate A-6 (synthesized from isophorone diisocyanate (IPDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 95 mg KOH / g, and a hydroxyl value of 13.7 mg KOH / g) was mixed instead of 60 g of urethane acrylate A-1.

[0128] [Example 13] A curable composition was prepared in the same manner as in Example 1, except that 60 g of urethane acrylate A-7 (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 5.2 mg KOH / g) was mixed instead of 60 g of urethane acrylate A-1.

[0129] [Example 14] A curable composition was prepared in the same manner as in Example 1, except that 60 g of urethane acrylate A-8 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, and a hydroxyl value of 6.7 mg KOH / g) was mixed instead of 60 g of urethane acrylate A-1.

[0130] [Example 15] A curable composition was prepared in the same manner as in Example 1, except that 10 g of unmodified alkylene oxide (meth)acrylate B-4 was mixed instead of 10 g of ethylene oxide-modified trimethylolpropane triacrylate B-1 (with 0.9 ethylene oxide additions).

[0131] [Comparative Example 6] A curable composition was prepared in the same manner as in Example 1, except that urethane acrylate A-9 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI), polytetramethylene ether glycol (PTMEG), and 2-hydroxyethyl acrylate (2HEA), with a hydroxyl value of 483 mgKOH / g) was used instead of urethane acrylate A-1.

[0132] [Comparative Example 7] A curable composition was prepared in the same manner as in Example 1, except that urethane acrylate A-10 (synthesized from a hexamethylene diisocyanate (HDI)-based prepolymer and a lactone-modified acrylate; hydroxyl value 11.3 mg KOH / g) was used instead of urethane acrylate A-1.

[0133] [Comparative Example 8] A curable composition was prepared in the same manner as in Example 1, except that urethane acrylate A-11 (synthesized from norbornene diisocyanate and pentaerythritol acrylate with a hydroxyl value of 115 mg KOH / g, with a hydroxyl value of 15.3 mg KOH / g) was used instead of urethane acrylate A-1.

[0134] [Comparative Example 9] 100 g of urethane acrylate A-12 (synthesized from 1,3,bis(isocyanatomethyl)cyclohexane (H6XDI), pentaerythritol acrylate with a hydroxyl value of 280 mg KOH / g, and dipentaerythritol acrylate with a hydroxyl value of 95 mg KOH / g; hydroxyl value of 16.4 mg KOH / g) was mixed and stirred with 8 g of a benzotriazole-based light stabilizer (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as an ultraviolet absorber, 1 g of a hindered amine-based light stabilizer (ADEKA Corporation's ADEKA Stab LA-87) as a light stabilizer, and 5 g of a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator. 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0135] The compositions of the curable compositions of Examples 1, 8-15, and Comparative Examples 6-9 are summarized below. [Table 5] Unless otherwise specified, the units of the values ​​in the table are grams (g).

[0136] [Example 16] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 30 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 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.

[0137] [Example 17] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 54 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 6 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.

[0138] [Example 18] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 6 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 54 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.

[0139] [Example 19] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 40 g of urethane acrylate A-1 (synthesized from hexamethylene diisocyanate (HDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, with a hydroxyl value of 29.2 mg KOH / g) and 40 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, with a hydroxyl value of 28.5 mg KOH / g) were mixed.

[0140] [Example 20] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 10 g of urethane acrylate A-1 (synthesized from hexamethylene diisocyanate (HDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, with a hydroxyl value of 29.2 mg KOH / g) and 10 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, with a hydroxyl value of 28.5 mg KOH / g) were mixed.

[0141] [Example 21] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 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 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.

[0142] [Example 22] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 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) and 30 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.

[0143] [Example 23] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 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 30 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.

[0144] [Example 24] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 30 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 30 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.

[0145] [Example 25] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 30 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) and 30 g of urethane acrylate A-6 (synthesized from isophorone diisocyanate (IPDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 95 mg KOH / g, hydroxyl value of 13.7 mg KOH / g) were mixed.

[0146] [Example 26] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 50 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) and 10 g of urethane acrylate A-6 (synthesized from isophorone diisocyanate (IPDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 95 mg KOH / g, hydroxyl value of 13.7 mg KOH / g) were mixed.

[0147] [Example 27] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 10 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) and 50 g of urethane acrylate A-6 (synthesized from isophorone diisocyanate (IPDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 95 mg KOH / g, hydroxyl value of 13.7 mg KOH / g) were mixed.

[0148] [Example 28] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 30 g of urethane acrylate A-7 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 5.2 mg KOH / g) and 30 g of urethane acrylate A-8 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 6.7 mg KOH / g) were mixed.

[0149] [Example 29] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 10 g of urethane acrylate A-7 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 5.2 mg KOH / g) and 50 g of urethane acrylate A-8 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 6.7 mg KOH / g) were mixed.

[0150] [Example 30] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 50 g of urethane acrylate A-7 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 5.2 mg KOH / g) and 10 g of urethane acrylate A-8 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 6.7 mg KOH / g) were mixed.

[0151] [Example 31] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 30 g of urethane acrylate A-7 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 115 mg KOH / g, hydroxyl value of 5.2 mg KOH / g) was mixed, and 30 g of urethane acrylate A-8 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and pentaerythritol acrylate (PEA) with a hydroxyl value of 280 mg KOH / g, hydroxyl value of 6.7 mg KOH / g) was mixed, and instead of ethylene oxide-modified trimethylolpropane triacrylate B-1 (ethylene oxide addition number: 0.9), alkylene oxide-unmodified (meth)acrylate B-4 was mixed.

[0152] The compositions of the curable compositions in Examples 16 to 31 are summarized below. [Table 6]

[0153] [Comparative Example 10] 50g 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 is 27.3 mg KOH / g), 50g 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 is 28.5 mg KOH / g), 8g of benzotriazole-based light stabilizer (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as an ultraviolet absorber, 1g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA stab LA-87) as a light stabilizer, and a monoacylphosphine oxide-based photopolymerization initiator (IGM) as a photopolymerization initiator. 5 g of OmniradTPO) manufactured by RESINS was mixed and stirred, and 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0154] [Comparative Example 11] 40g 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 is 27.6 mg KOH / g), 20g 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 is 40.8 mg KOH / g), and ethylene oxide modified trimethylolpropane triacrylate B-1 (the number of ethylene oxide additions) 28 g of (0.9), 8 g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (3.7 ethylene oxide additions), 4 g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (6.4 ethylene oxide additions), 8 g of benzotriazole-based light stabilizer (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as an ultraviolet absorber, 1 g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA Stab LA-87) as a light stabilizer, and 5 g of monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator were mixed and stirred, and 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0155] [Comparative Example 12] 40g 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 is 27.6 mg KOH / g), 20g 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 is 40.8 mg KOH / g), and ethylene oxide modified trimethylolpropane triacrylate B-1 (the number of ethylene oxide additions is 0.9) 22g, ethylene oxide-modified trimethylolpropane triacrylate B-2 (ethylene oxide addition number 3.7), ethylene oxide-modified trimethylolpropane triacrylate B-3 (ethylene oxide addition number 6.4), 8g of benzotriazole-based light stabilizer (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as an ultraviolet absorber, 1g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA Stab LA-87) as a light stabilizer, and 5g of monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator were mixed and stirred, and 114g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0156] [Comparative Example 13] 40g 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 is 27.6 mg KOH / g), 20g 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 is 40.8 mg KOH / g), and ethylene oxide modified trimethylolpropane triacrylate B-1 (the number of ethylene oxide additions is A curable composition with a solid content of 50.0% was prepared by mixing and stirring 4g of 0.9), 12g of ethylene oxide-modified trimethylolpropane triacrylate B-2 (ethylene oxide addition number 3.7), 24g of ethylene oxide-modified trimethylolpropane triacrylate B-3 (ethylene oxide addition number 6.4), 8g of a benzotriazole-based light stabilizer (RUVA-93 manufactured by Otsuka Chemical Co., Ltd.) as an ultraviolet absorber, 1g of a hindered amine-based light stabilizer (ADEKA Corporation's ADEKA Stab LA-87) as a light stabilizer, and 5g of a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO manufactured by IGM RESINS). Then, 114g of 1-methoxy-2-propanol (PGM) was added.

[0157] [Comparative Example 14] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 30 g of urethane acrylate A-13 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and sorbitol EO-modified acrylate with a hydroxyl value of 310 mg KOH / g, hydroxyl value of 64.2 mg KOH / g) and 30 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.

[0158] [Comparative Example 15] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 60 g of urethane acrylate A-1, 30 g of urethane acrylate A-14 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and dipentaerythritol acrylate (PEA) with a hydroxyl value of 50 mg KOH / g; hydroxyl value of mg KOH / g) and 30 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 13.7 mg KOH / g) were mixed.

[0159] [Comparative Example 16] Instead of mixing 60g of urethane acrylate A-1, use urethane acrylate A-13 (dicyclohexylmethane 4,4-diisocyanate (H 12 A curable composition was prepared in the same manner as in Example 1, except that 30 g of urethane acrylate A-14 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and dipentaerythritol acrylate (PEA) with a hydroxyl value of 50 mgKOH / g, with a hydroxyl value of 11.8 mgKOH / g) was mixed with 30 g of urethane acrylate A-14 (synthesized from dicyclohexylmethane 4,4-diisocyanate (H12MDI) and dipentaerythritol acrylate (PEA) with a hydroxyl value of 50 mgKOH / g, with a hydroxyl value of 11.8 mgKOH / g).

[0160] [Comparative Example 17] Preparation Example of Patent 4204106 Urethane acrylate A-9 (dicyclohexylmethane 4,4-diisocyanate (H 12Synthesized from MDI (methyl dimethylcellulose), polytetramethylene ether glycol (PTMEG), and 2-hydroxyethyl acrylate (2HEA). (Hydroxyl value: 483 mgKOH / g) 24 g of this mixture, 25 g of dipentaerythritol hexaacrylate (DPHA) B-5, 62 g of tris(2-acryloyloxyethyl) isocyanurate (TAIC) B-6, 8 g of benzotriazole-based light stabilizer (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as an ultraviolet absorber, 1 g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA LA-87) as a light stabilizer, and 5 g of monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator were mixed and stirred, and 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0161] [Comparative Example 18] Preparation example of Patent No. 6481302 91 g of urethane acrylate A-11 (synthesized from norbornene diisocyanate and pentaerythritol acrylate with a hydroxyl value of 115 mg KOH / g; hydroxyl value of 15.3 mg KOH / g), 9 g of ethylene oxide (10 mol)-added bisphenol A diacrylate B-10, 8 g of benzotriazole-based light stabilizer (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as an ultraviolet absorber, 1 g of hindered amine-based light stabilizer (ADEKA Corporation's ADEKA Stab LA-87) as a light stabilizer, and 5 g of monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator were mixed and stirred, and 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0162] [Comparative Example 19] Preparation example of Patent 7024558 100 g of urethane acrylate A-12 (synthesized from 1,3,bis(isocyanatomethyl)cyclohexane (H6XDI), pentaerythritol acrylate with a hydroxyl value of 280 mg KOH / g, and dipentaerythritol acrylate with a hydroxyl value of 95 mg KOH / g; hydroxyl value of 16.4 mg KOH / g) was mixed and stirred with 8 g of a benzotriazole-based light stabilizer (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as an ultraviolet absorber, 1 g of a hindered amine-based light stabilizer (ADEKA Corporation's ADEKA Stab LA-87) as a light stabilizer, and 5 g of a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator. 114 g of 1-methoxy-2-propanol (PGM) was added to prepare a curable composition with a solid content of 50.0%.

[0163] The following is a summary of the compositions of the curable compositions of Comparative Examples 10 to 19. [Table 7] DPHA: Dipentaerythritol hexaacrylate TAIC: Tris(2-acryloyloxyethyl) isocyanurate EO10.0 BPADA: Ethylene oxide (10 mol) added bisphenol A diacrylate

[0164] [Example 32] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 5 g of a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator, 5 g of 2,2'-azobis(isobutyronyl), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was mixed.

[0165] [Example 33] A curable composition was prepared in the same manner as in Example 1, except that 5 g of benzoyl peroxide (Nipper BO, NOF Corporation) was mixed instead of 5 g of a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, IGM RESINS) as the photopolymerization initiator.

[0166] [Example 34] A curable composition was prepared in the same manner as in Example 1, except that 5 g of α-hydroxyalkylphenone (Omnirad184, manufactured by IGM RESINS) was mixed instead of 5 g of a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as the photopolymerization initiator.

[0167] [Example 35] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 5 g of a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator, 4 g of α-hydroxyalkylphenone (Omnirad184, manufactured by IGM RESINS) and 2 g of benzophenone (manufactured by Matsugaki Pharmaceutical Co., Ltd.) were mixed.

[0168] [Example 36] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 5 g of a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) as a photopolymerization initiator, 4 g of α-hydroxyalkylphenone (Omnirad184, manufactured by IGM RESINS) and 2 g of thioxatone (Omnirad DETX, manufactured by IGM RESINS) were mixed.

[0169] [Example 37] A curable composition was prepared in the same manner as in Example 1, except that 8 g of a monoacylphosphine oxide-based photopolymerization initiator (OmniradTPO, manufactured by IGM RESINS) was mixed in as a photopolymerization initiator.

[0170] [Example 38] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 8 g of a benzotriazole-based UV absorber (RUVA-93 manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber and 1 g of a hindered amine-based light stabilizer (ADEKA Corporation's Adekastab LA-87) as a light stabilizer, 6 g of a triazine-based UV absorber (BASF's Tinuvin 400) and 1 g of a hindered amine-based light stabilizer (ADEKA Corporation's Adekastab LA-87) were mixed together.

[0171] [Example 39] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 8 g of a benzotriazole-based UV absorber (RUVA-93 manufactured by Otsuka Chemical Co., Ltd.) as a UV absorber and 1 g of a hindered amine-based light stabilizer (ADEKA Corporation's Adekastab LA-87) as a light stabilizer, 6 g of a cyanoacrylate-based light stabilizer (BASF's Uvinul3035) and 1 g of a hindered amine-based light stabilizer (ADEKA Corporation's Adekastab LA-87) were mixed together.

[0172] [Example 40] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 8 g of a benzotriazole-based ultraviolet absorber (RUVA-93 manufactured by Otsuka Chemical Co., Ltd.) as an ultraviolet absorber and 1 g of a hindered amine-based light stabilizer (ADEKA Corporation's Adekastab LA-87) as a light stabilizer, 1 g of a benzotriazole-based ultraviolet absorber (RUVA-93 manufactured by Otsuka Chemical Co., Ltd.) and 1 g of a hindered amine-based light stabilizer (ADEKA Corporation's Adekastab LA-87) were mixed together.

[0173] [Example 41] A curable composition was prepared in the same manner as in Example 1, except that instead of mixing 8 g of a benzotriazole-based ultraviolet absorber (RUVA-93 manufactured by Otsuka Chemical Co., Ltd.) as an ultraviolet absorber and 1 g of a hindered amine-based light stabilizer (ADEKA Corporation's Adekastab LA-87) as a light stabilizer, 14 g of a benzotriazole-based ultraviolet absorber (RUVA-93 manufactured by Otsuka Chemical Co., Ltd.) and 1 g of a hindered amine-based light stabilizer (ADEKA Corporation's Adekastab LA-87) were mixed.

[0174] The compositions of the curable compositions in Examples 32 to 41 are summarized below. [Table 8]

[0175] 4. Performance evaluation of curable resin compositions [Sample preparation method] The resin compositions prepared in the examples and comparative examples were coated onto a PET film (Cosmoshine A4360, manufactured by Toyobo Co., Ltd.; thickness 100 μm) using a bar coater and pre-dried at 80°C for 1 minute. Next, ultraviolet irradiation was performed under air conditions using an ultraviolet irradiation device (Lighthammer 10, manufactured by Heraeus K.K.) to an irradiation dose of 500 mJ / cm2 (illuminance 1,500 mW / cm2) to produce a coating layer with a thickness of 5 μm.

[0176] [Heat resistance test: Adhesion] A 100mm x 150mm test specimen was prepared from the multilayer material manufactured as described above. The test specimen was then placed in a constant temperature and humidity testing chamber set to 120°C for 500 hours before being removed. After the test, 100 grid squares measuring 1mm x 1mm were created on the surface of the hardened film using a utility knife. Cellophane tape was then applied to the grid and peeled off. The number of grid squares that remained without peeling off the hardened film was used to evaluate the hardened film according to the following criteria. A: No peeling of the hardened film. B: Number of grid squares that did not peel off: "70-99 / 100" C: Number of grid squares that did not peel off: "30-69 / 100" D: Number of unpeeled grid squares less than 30

[0177] [Humid heat resistance test: Transparency] For the coating layer manufactured above, a test piece of 100 mm × 150 mm was prepared. Subsequently, the test piece was left standing in a thermo-hygrostat (manufactured by Isuzu Manufacturing Co., Ltd., HPCF-288-40) set at a temperature of 85°C and a humidity of 85%RH for 1000 hours, and then the test piece was taken out. For the test piece after the humid heat resistance test, haze measurement was performed using a haze meter (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the haze before and after the test was evaluated according to the following criteria. A: ΔHAZE = 2 or less B: ΔHAZE = 2 - 4 C: ΔHAZE = 4 - 6 D: ΔHAZE = 6 or more

[0178] [Humid heat resistance test: Adhesion] For the test piece subjected to the humid heat resistance test under the same test conditions as in the transparency test, 100 squares of 1 mm × 1 mm in size were made on the surface of the cured film using a cutter knife, and after sticking cellophane tape on the grid squares and then peeling it off, the evaluation was performed according to the following evaluation criteria based on the number of grid squares that remained without the cured film peeling off. A: No peeling of the cured film B: Number of unpeeled grid squares "70 - 99 / 100" C: Number of unpeeled grid squares "30 - 69 / 100" D: Number of unpeeled grid squares less than 30

[0179] The test results are summarized and shown below.

Table 9

Table 10

Table 11

Table 12

[0180] The present invention provides a curable composition capable of forming a hard coat layer with excellent heat resistance and moisture resistance. The curable composition according to the present invention can be used to form hard coat layers on many resin films and molded products such as polyethylene terephthalate (PET) resin, polycarbonate (PC) resin, and poly(meth)acrylate (PMA or PMMA) resin. In particular, it is useful for forming hard coat layers on equipment that is used outdoors, such as equipment mounted on automobiles and portable devices, and therefore requires higher heat resistance and moisture resistance.

Claims

1. A (meth)acrylate (A) obtained by reaction with a polyol (a3), optionally, a polyhydric isocyanate (a2) selected from a polyhydric isocyanate (a1) having a hydroxyl value of 90 to 300 mg KOH / g and a structure derived from a polyhydric alcohol, aliphatic isocyanate, alicyclic isocyanate without a cross-linking structure, aromatic isocyanate, and hydrogenated versions thereof, and a urethane (meth)acrylate (A), Alkylene oxide modified (meth)acrylate (B) and The alkylene oxide modified (meth)acrylate (B) is, (Meth)acrylate (B1), in which the number of repeating units of alkylene oxide is, on average, 0 to 2.

0. Optionally, (meth)acrylate (B2), in which the number of repeating units of alkylene oxide is 3.0 to 5.0 on average, and A curable resin composition comprising (meth)acrylate (B3) having an average of 6.0 to 8.0 repeating units of alkylene oxide.

2. The alkylene oxide-modified (meth)acrylate (B) is given by the following formula (1): 【Chemistry 1】 (In the formula, R １ (where is a hydrogen or methyl group, A is a trimethylolpropane residue, a bisphenol A residue, or an erythritol residue, m is an integer between 2 and 3, and n is an integer between 0 and 8.) It comprises an alkylene oxide-modified (meth)acrylate having the structure shown, The average of n is 0 to 2.0, and the (meth)acrylate (B1) of formula (1) is 5 to 50% by mass. The average of n is 3.0 to 5.0, and the (meth)acrylate (B2) of formula (1) is used in a quantity of 20 to 90% by mass, and The curable resin composition according to claim 1, comprising 5 to 30% by mass of (meth)acrylate (B3) of formula (1), wherein the average of n is 6.0 to 8.

0.

3. The curable resin composition according to claim 1, wherein the urethane (meth)acrylate (A) comprises (meth)acrylates (a1-2) having a hydroxyl value of 200 to 300 mg KOH / g and a structure derived from a polyhydric alcohol, a polyhydric isocyanate (a2) selected from aliphatic isocyanates, alicyclic isocyanates without crosslinking structures, aromatic isocyanates, and hydrogenated versions thereof, and optionally a urethane (meth)acrylate (A2) obtained by reaction with a polyol (a3).

4. The aforementioned urethane (meth)acrylate (A) The curable resin composition according to claim 1, comprising (meth)acrylate (a1-1) having a hydroxyl value of 110 to 180 mg KOH / g and a structure derived from a polyhydric alcohol, polyhydric isocyanate (a2) selected from aliphatic isocyanates, alicyclic isocyanates without crosslinking structures, aromatic isocyanates, and hydrogenated versions thereof, and optionally urethane (meth)acrylate (A1) obtained by reaction with a polyol (a3).

5. The aforementioned urethane (meth)acrylate (A) A (meth)acrylate (a1-1) having a hydroxyl value of 90-180 mgKOH / g and a structure derived from a polyhydric alcohol, a polyhydric isocyanate (a2) selected from aliphatic isocyanates, alicyclic isocyanates without crosslinking structures, aromatic isocyanates, and hydrogenated versions thereof, and a urethane (meth)acrylate (A1) obtained by reaction with a polyol (a3), (Meth)acrylates (a1-2) having a hydroxyl value of 200-300 mgKOH / g and a structure derived from polyhydric alcohols, polyhydric isocyanates (a2) selected from aliphatic isocyanates, alicyclic isocyanates without crosslinking structures, aromatic isocyanates, and hydrogenated versions thereof, and optionally urethane (meth)acrylate (A2) obtained by reaction with polyol (a3) A curable resin composition according to claim 1, comprising the above.

6. The aforementioned urethane (meth)acrylate (A) (Meth)acrylate (a1-1) having a hydroxyl value of 110-180 mgKOH / g and a structure derived from a polyhydric alcohol, polyhydric isocyanate (a2) selected from aliphatic isocyanates, alicyclic isocyanates without crosslinking structures, aromatic isocyanates, and hydrogenated versions thereof, and urethane (meth)acrylate (A1) obtained by reaction with a polyol (a3) ​​optionally. (Meth)acrylates (a1-2) having a hydroxyl value of 200-300 mgKOH / g and a structure derived from polyhydric alcohols, polyhydric isocyanates (a2) selected from aliphatic isocyanates, alicyclic isocyanates without crosslinking structures, aromatic isocyanates, and hydrogenated versions thereof, and optionally urethane (meth)acrylate (A2) obtained by reaction with polyol (a3) A curable resin composition according to claim 1, comprising the above.

7. The curable resin composition according to claim 5, wherein the mass ratio of the urethane (meth)acrylate (A1) to the urethane (meth)acrylate (A2) is 10:1 to 1:

2.

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

9. The curable resin composition according to claim 8, wherein the urethane (meth)acrylate (A) has a structure derived from either dipentaerythritol or tripentaerythritol, or both.

10. The curable resin composition according to claim 1, wherein the polyvalent isocyanate (a2) is an alicyclic isocyanate that does not have a crosslinking structure.

11. The curable resin composition according to claim 10, wherein the alicyclic isocyanate is isophorone diisocyanate or dicyclohexylmethane diisocyanate.

12. The curable resin composition according to claim 1, wherein the hydroxyl value of the urethane (meth)acrylate (A) is 0.1 to 10 mg KOH / g.

13. The curable resin composition according to claim 1, wherein the alkylene oxide-modified (meth)acrylate (B) is selected from ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, ethylene oxide-modified bisphenol A diacrylate, propylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified pentaerythritol tetraacrylate, and propylene oxide-modified pentaerythritol tetraacrylate.

14. A cured layer obtained by curing the curable resin composition according to any one of claims 1 to 13.

15. An article having the cured layer described in claim 14 on the entire surface, one side, or part of the substrate.

16. A method for forming a coating layer, comprising applying a curable resin composition according to any one of claims 1 to 13 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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