Active energy ray-curable composition, cured product, and laminate

Abstract

To provide an active energy ray-curable composition that can form a cured product having high wear resistance and high adhesion to a substrate and also having resistance to cracking during its molding process and a cured product of the composition, and a laminate having the cured product.SOLUTION: An active energy ray-curable composition contains a resin with a radical-polymerizable double bond equivalent of 100-10000 g / mol and a hydroxyl value of 5-500 mgKOH / g.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable composition, a cured product of the active energy ray-curable composition, and a laminate having a layer made of the cured product. [Background technology]

[0002] For the surface protection and decoration of resin molding materials such as automotive interior and exterior parts, electronic devices, miscellaneous goods, and building materials, methods of hard coating or adhering a film to the surface are known. Known decoration methods include insert methods, thermal lamination methods, and transfer methods. Furthermore, a hard coat layer is generally known that is formed by curing a curable composition containing a compound having a radical polymerizable group and a photopolymerization initiator through radical polymerization. However, when a hard coat layer is used to protect the surface, although abrasion resistance and scratch resistance are improved, extensibility during molding processing may be deteriorated, making it unsuitable for decorative applications. Another issue is the adhesion between the substrate and the hard coat layer to prevent peeling during processing.

[0003] Patent Document 1 describes an insert film for in-mold labels, Patent Document 2 describes a hard coating agent for decorative molding, Patent Document 3 describes a decorative sheet for automobile interiors, and Patent Document 4 describes a decorative hard coat film that is printed directly onto a hard coat layer by a thermal transfer printing method using a thermal transfer printer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-288720 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-180082 [Patent Document 3] Japanese Patent Application Publication No. 2019-189043 [Patent Document 4] Japanese Patent Application Laid-Open No. 2011-110903 Summary of the Invention [Problem to be solved by the invention]

[0005] The hard coat layer described in Patent Document 1 has excellent abrasion resistance, but does not necessarily have satisfactory elongation during molding processing, and is difficult to conform to the surface shape of the molding material, which can lead to peeling or cracking of the hard coat layer. The hard coat agent described in Patent Document 2 also has excellent abrasion resistance, but does not necessarily have satisfactory elongation or adhesion to the substrate. The sheet described in Patent Document 3 does not fully satisfy the abrasion resistance of the surface protection layer, and the hard coat film described in Patent Document 4 has difficulty in ensuring elongation. The present invention aims to provide an active energy ray-curable composition capable of forming a hard coat layer that has excellent abrasion resistance, extensibility during molding (suppressing the occurrence of cracks), and adhesion to a substrate; a cured product of the active energy ray-curable composition; and a laminate having a layer made of the cured product. [Means for solving the problem]

[0006] The present invention has the following aspects. That is, the above object of the present invention can be achieved by the following means [1] to

[10] . [1] An active energy ray-curable composition containing a resin having a radically polymerizable double bond equivalent of 100 to 10,000 g / mol and a hydroxyl value of 5 to 500 mgKOH / g. [2] The active energy ray-curable composition according to [1], which contains an active energy ray-curable compound other than the resin. [3] The active energy ray-curable composition according to [2], wherein the active energy ray-curable compound other than the resin is a (meth)acrylate. [4] The active energy ray-curable composition according to [3], wherein the (meth)acrylate is a tri- or higher functional (meth)acrylate. [5] The active energy ray-curable composition according to any one of [1] to [4], which contains a leveling agent. [6] The active energy ray-curable composition according to any one of [1] to [5], which contains an ultraviolet absorber. [7] A cured product of the active energy ray-curable composition according to any one of [1] to [6]. [8] A cured product of [7] that has an elongation of 5% or more in a tensile test at 140°C. [9] A laminate in which the cured product according to [7] or [8] is laminated on a substrate.

[10] The laminate of [9], which has a transmittance of 80% or less at a wavelength of 360 nm. DETAILED DESCRIPTION OF THE INVENTION

[0007] In this specification, "(meth)acrylic" is a general term for "acrylic" and "methacrylic", and "(meth)acrylate" is a general term for "acrylate" and "methacrylate". "(meth)acryloyl group" is a general term for "acryloyl group" and "methacryloyl group", and CH2=C(R 1 )-C(=O)-(R 1 is a group represented by a hydrogen atom or a methyl group). Furthermore, "monofunctional" means having one radically polymerizable double bond. "polyfunctional" means having two or more radically polymerizable double bonds, for example, "bifunctional" means having two radically polymerizable double bonds.

[0008] <Active energy ray-curable composition> The active energy ray-curable composition of the present invention contains a resin having a radical polymerizable double bond equivalent of 100 to 10,000 g / mol and a hydroxyl value of 5 to 500 mgKOH / g.

[0009] The radical polymerizable double bond equivalent of the resin is typically in the range of 100 to 10,000 g / mol, preferably 150 to 6,000 g / mol, more preferably 200 to 3,500 g / mol, even more preferably 250 to 2,500 g / mol, particularly preferably 300 to 1,500 g / mol, and most preferably 400 to 1,000 g / mol. Using a resin within this range enables both abrasion resistance and extensibility during molding when a cured film (hard coat layer) is formed. The radical polymerizable double bond equivalent can be measured, for example, by reacting a resin composition with a mixed solution of sodium bromide and potassium bromate, adding a potassium iodide solution, and then measuring the resultant mixture with a sodium thiosulfate solution using a starch solution as an indicator.

[0010] The hydroxyl value of the resin is typically 5 to 500 mgKOH / g, preferably 10 to 300 mgKOH / g, more preferably 15 to 250 mgKOH / g, even more preferably 25 to 220 mgKOH / g, particularly preferably 40 to 170 mgKOH / g, and most preferably 60 to 150 mgKOH / g. Using a resin within this range improves adhesion to the substrate. The hydroxyl value can be measured, for example, by reacting the resin composition with excess acetic anhydride in pyridine and titrating the liberated acetic acid with potassium hydroxide.

[0011] Resins that satisfy the above requirements include (meth)acrylic resins, polyester resins, and urethane resins. Among these, (meth)acrylic resins are preferred because they allow for easy adjustment of the radical polymerizable double bond equivalent and hydroxyl value, and allow for the formation of a hard coat layer with appropriate properties.

[0012] Methods for introducing a radically polymerizable double bond into a (meth)acrylic resin include reacting an acrylic resin having an epoxy group with a compound having a double bond and a carboxyl group (Method 1), reacting an acrylic resin having a carboxyl group with a compound having a double bond and an epoxy group (Method 2), reacting an acrylic resin having a hydroxyl group with a compound having a double bond and a carboxyl group (Method 3), reacting an acrylic resin having a carboxyl group with a compound having a double bond and a hydroxyl group (Method 4), reacting an acrylic resin having an isocyanate group with a compound having a double bond and a hydroxyl group (Method 5), and reacting an acrylic resin having a hydroxyl group with a compound having a double bond and an isocyanate group (Method 6). These methods may also be used in combination. In the following, a monomer having a radically polymerizable double bond may be referred to as a vinyl monomer.

[0013] In the above-mentioned method 1, examples of the vinyl monomer having an epoxy group used to obtain an acrylic resin having an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred, and glycidyl methacrylate is particularly preferred, in consideration of good reactivity and ease of use of the material. These may be used alone or in combination of two or more.

[0014] Examples of the compound having a double bond and a carboxyl group in Method 1 include (meth)acrylic acid, carboxyethyl (meth)acrylate, an adduct of glycerin di(meth)acrylate and succinic anhydride, an adduct of pentaerythritol tri(meth)acrylate and succinic anhydride, and an adduct of pentaerythritol tri(meth)acrylate and phthalic anhydride. Among these, (meth)acrylic acid and an adduct of pentaerythritol tri(meth)acrylate and succinic anhydride are preferred, (meth)acrylic acid is more preferred, and acrylic acid is even more preferred. The compound having a double bond and a carboxyl group may be used alone or in combination of two or more.

[0015] In the method 2, examples of the vinyl monomer having a carboxyl group used to obtain the acrylic resin having a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, and polybasic acid-modified (meth)acrylate. Among these, (meth)acrylic acid is preferred, and acrylic acid is more preferred. These may be used alone or in combination of two or more.

[0016] In the method 2, examples of the compound having a double bond and an epoxy group include glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether. Among these, glycidyl (meth)acrylate is preferred. These compounds may be used alone or in combination of two or more.

[0017] In the method 3, examples of the vinyl monomer having a hydroxyl group used to obtain the acrylic resin having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0018] In the method 3, the compound having a double bond and a carboxyl group may be the same as the compound in the method 1.

[0019] In the method 4, the same acrylic resin having a carboxyl group as in the method 2 can be used.

[0020] In the method 4, examples of the compound having a double bond and a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0021] In the above-mentioned method 5, examples of the vinyl monomer having an isocyanate group used to obtain the acrylic resin having an isocyanate group include isocyanate ethyl (meth)acrylate.

[0022] In the method 5, the compound having a double bond and a hydroxyl group may be, for example, the same compound as that mentioned in the method 4.

[0023] In the method 6, the same compounds as those in the method 3 can be used as the acrylic resin having a hydroxyl group.

[0024] In the method 6, examples of the compound having a double bond and an isocyanate group include isocyanate ethyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0025] Among the above methods, Method 1 or Method 2 are preferred because hydroxyl groups can also be introduced at the same time. Method 1 is more preferred because the reaction is easier to control. In Method 1, the double bond is introduced by a ring-opening addition reaction between the epoxy group of the acrylic resin having an epoxy group and the carboxyl group of the compound having a double bond and a carboxyl group.

[0026] In the above-mentioned method 1, the amount of the epoxy group-containing monomer in the epoxy group-containing acrylic resin is preferably 2% by weight or more, more preferably 5% by weight or more, even more preferably 10% by weight or more, and particularly preferably 15% by weight or more, based on the total amount of the monomers constituting the epoxy group-containing acrylic resin. There is no particular upper limit, but the amount is preferably 99.9% by weight or less, more preferably 80% by weight or less, even more preferably 70% by weight or less, and particularly preferably 50% by weight or less. By using the epoxy group-containing monomer in this range, not only can the cured film have improved adhesion to the substrate, scratch resistance, and hardness, but also stretchability that prevents cracks from occurring due to stress during decorative molding can be achieved.

[0027] In the method 1, the ratio of the compound having a double bond and a carboxyl group to the epoxy groups in the acrylic resin having an epoxy group is preferably 10 to 150 mol %, more preferably 30 to 130 mol %, even more preferably 50 to 120 mol %, and particularly preferably 100 to 110 mol %, which is an amount that allows the reaction to proceed just right. By using the compound in this range, radically polymerizable double bonds can be effectively introduced.

[0028] It is also possible to introduce a hydroxyl group by a method other than the above-mentioned Method 1 or Method 2. For example, there is a method in which a compound having a hydroxyl group is copolymerized as a monomer during the production of the (meth)acrylic resin.

[0029] Examples of monomers having a hydroxyl group include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, and hydroxylauryl (meth)acrylate. Among these, hydroxyethyl (meth)acrylate is preferred from the viewpoints of ease of introduction and ability to efficiently adjust the hydroxyl value.

[0030] Furthermore, (meth)acrylic resins such as the above-mentioned (meth)acrylic resins having an epoxy group may be copolymerized with (meth)acrylates other than those mentioned above or other vinyl monomers. The polymerization reaction of these raw materials is usually radical polymerization, and can be carried out under conventionally known conditions.

[0031] Monomers that can be used in combination as raw materials include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, methoxy(poly)ethylene glycol (meth)acrylate, methoxy(poly)propylene glycol (meth)acrylate, methoxy(poly)ethylene glycol (poly)propylene glycol (meth)acrylate, octoxy(poly)ethylene glycol (meth)acrylate, octoxy(poly)propylene glycol (meth)acrylate, (meth)acrylates such as octoxytetramethylene glycol (meth)acrylate, lauroxy(poly)ethylene glycol (meth)acrylate, and stearoxy(poly)ethylene glycol (meth)acrylate; acrylamides such as ethyl(meth)acrylamide, n-butyl(meth)acrylamide, i-butyl(meth)acrylamide, t-butyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-hydroxypropyl(meth)acrylamide, and N,N-dihydroxyethyl(meth)acrylamide; and styrene-based monomers such as styrene, p-chlorostyrene, and p-bromostyrene. These may be used alone or in combination of two or more.

[0032] The (meth)acrylic resin can be produced by radical polymerization using the above-mentioned vinyl monomer as the raw material, which is preferably carried out in an organic solvent in the presence of a radical polymerization initiator.

[0033] Examples of organic solvents used in radical polymerization include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, and 2-ethoxyethyl acetate; and aromatic hydrocarbon solvents such as toluene. These organic solvents may be used alone or in combination of two or more.

[0034] Examples of radical polymerization initiators used in radical polymerization include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; and azo compounds such as 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more. The radical polymerization initiator is preferably used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the total of the vinyl monomers used as raw materials.

[0035] In addition, during radical polymerization, a chain transfer agent can be used for the purpose of controlling the weight average molecular weight of the (meth)acrylic resin, etc. Examples of the chain transfer agent include butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-ethylhexyl thioglycolate, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, 2,2-(ethylenediaminetetraacetic acid)-2-methylpropanol, methyl-3-mercaptopropionate ... Examples of the thiol-based compounds include (oxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decantrithiol, dodecyl mercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccinic acid, and 2-mercaptoethanesulfonic acid. These may be used alone or in combination of two or more.

[0036] The amount of the chain transfer agent used is preferably 0.1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, and even more preferably 1.0 to 15 parts by weight, per 100 parts by weight of the total of the vinyl monomers as raw materials.

[0037] The reaction time for radical polymerization is preferably 1 to 20 hours, more preferably 3 to 12 hours, and the reaction temperature is preferably 40 to 120°C, more preferably 50 to 100°C.

[0038] To react a compound having a double bond and a carboxyl group with a (meth)acrylic resin, the compound having a double bond and a carboxyl group is added to the (meth)acrylic resin obtained as described above, and the reaction is carried out in the presence of one or more catalysts, such as triphenylphosphine, tetrabutylammonium bromide, tetramethylammonium chloride, and triethylamine, typically at a temperature of 90 to 140°C, preferably 100 to 120°C, for typically 3 to 9 hours. The catalyst is preferably used in an amount of approximately 0.5 to 3 parts by weight per 100 parts by weight of the combined raw materials (meth)acrylic acid ester polymer and the compound having a double bond and a carboxyl group. This reaction may be carried out immediately after the (meth)acrylic resin is produced by polymerization, or the (meth)acrylic resin may be separated from the reaction system and then the compound having a double bond and a carboxyl group may be added.

[0039] The weight-average molecular weight of the resin should be selected appropriately depending on the application of the curable composition. It is preferably in the range of 1,000 to 200,000, more preferably 5,000 to 100,000, even more preferably 8,000 to 80,000, and particularly preferably 10,000 to 60,000. Use within this range improves abrasion resistance, improves adhesion to the substrate, and ensures good extensibility during molding. Furthermore, the viscosity of the composition can be easily adjusted to an appropriate range, resulting in excellent coatability. The weight-average molecular weight (Mw) of the resin can be determined using gel permeation chromatography (GPC) as a polystyrene-based conversion value. Specific measurement conditions are described in the Examples below.

[0040] The content of the above-mentioned resin in the active energy ray-curable composition cannot be generalized because it varies depending on the application and the required properties of the cured film, but it is preferably in the range of 5 to 100 mass%, more preferably 10 to 90 mass%, even more preferably 20 to 85 mass%, particularly preferably 30 to 80 mass%, and most preferably 40 to 75 mass% of the nonvolatile content. By using it in this range, it is possible to ensure abrasion resistance while achieving good elongation during molding and adhesion to the substrate. In applications where elongation is particularly important, the range is preferably 50 to 100% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 90% by mass. The nonvolatile content is the total mass of components other than the solvent, such as the organic solvent. The nonvolatile content of the active energy ray-curable composition can be measured by a conventionally known method, for example, by measuring the change in weight when 1 g of the composition is spread and heated at 100°C for 1 hour to volatilize the organic solvent.

[0041] <Activated energy ray-curable compounds other than resins> Furthermore, it is preferable to use an active energy ray-curable compound other than the above-mentioned resins in the active energy ray-curable composition in order to improve or adjust the abrasion resistance and hardness of the cured film formed therefrom.

[0042] As the active energy ray-curable compound other than resin, conventionally known materials can be used, but (meth)acrylates are a suitable example. The (meth)acrylate is not particularly limited and may be a monofunctional (meth)acrylate, a bifunctional (meth)acrylate, or a trifunctional or higher polyfunctional (meth)acrylate. Commercially available (meth)acrylates as curable resin materials can also be used. The (meth)acrylate may contain other components as long as the objectives of the present invention are not impaired. Among these, bifunctional or trifunctional or higher polyfunctional (meth)acrylates are preferred because of their particularly excellent abrasion resistance, and trifunctional or higher functional (meth)acrylates are particularly preferred. Furthermore, epoxy (meth)acrylates, urethane (meth)acrylates, silicone (meth)acrylates, etc. can also be used as the (meth)acrylate.

[0043] Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, morpholyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethyl mono(meth)acrylates such as methylaminoethyl (meth)acrylate, tricyclodecane (meth)acrylate, polyethylene glycol mono(meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenyl (meth)acrylate; and mono(meth)acrylate compounds such as an adduct of phthalic anhydride and 2-hydroxyethyl (meth)acrylate.

[0044] Examples of difunctional polyfunctional (meth)acrylates include alkanediol di(meth)acrylates such as 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and tricyclodecanedimethylol di(meth)acrylate; bisphenol-modified di(meth)acrylates such as bisphenol A ethylene oxide-modified di(meth)acrylate and bisphenol F ethylene oxide-modified di(meth)acrylate; polyethylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; urethane di(meth)acrylate; and epoxy di(meth)acrylate.

[0045] Examples of trifunctional or higher polyfunctional (meth)acrylates include dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol hexa(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Examples of the urethane (meth)acrylate include ethylene oxide-modified (meth)acrylates such as erythritol tetra(meth)acrylate, isocyanuric acid-modified tri(meth)acrylates such as ethylene oxide isocyanuric acid-modified tri(meth)acrylate and ε-caprolactone-modified tris(acryloxyethyl)isocyanurate, and urethane (meth)acrylates such as pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer. Among these, tetrafunctional or higher (meth)acrylates are preferred because they have particularly good abrasion resistance, and hexafunctional or higher (meth)acrylates are even more preferred. Furthermore, taking into consideration compatibility with elongation during molding, polyfunctional (meth)acrylates with extended alkyl chains, particularly tetrafunctional or higher (meth)acrylates with extended alkyl chains, are preferred, and hexafunctional or higher (meth)acrylates with extended alkyl chains are even more preferred. For example, caprolactone-modified dipentaerythritol hexa(meth)acrylate is an optimal material. In particular, two or more caprolactone modifications per (meth)acrylate molecule are preferred for elongation, and six or more is more preferred for applications where elongation is particularly important.

[0046] The content of the active energy ray-curable compound other than the resins described above in the active energy ray-curable composition cannot be generalized because it varies depending on the application and the required properties of the cured film, but it is preferably 90% by mass or less, more preferably 3 to 80% by mass, even more preferably 5 to 70% by mass, particularly preferably 10 to 60% by mass, and most preferably 15 to 50% by mass, based on the nonvolatile content. By using it in this range, it is possible to improve abrasion resistance while ensuring elongation during molding processing. In applications where elongation is particularly important, the content is preferably 50% by mass or less, more preferably 3 to 30% by mass, and even more preferably in the range of 5 to 20% by mass.

[0047] <Leveling agent> In order to improve the appearance of the cured product, a leveling agent can be blended into the active energy ray-curable composition. Examples of leveling agents include acrylic leveling agents, silicone leveling agents, and fluorine leveling agents. Among these, silicone leveling agents are more preferred from the viewpoint of improving abrasion resistance, which is one of the objectives of the present invention. Furthermore, silicone leveling agents having a radical polymerizable functional group are particularly preferred from the viewpoint of preventing bleed-out of the leveling agent after forming a hard coat layer during molding, etc. Silicone leveling agents impart slip properties to the cured product and can achieve high abrasion resistance. Silicone leveling agents having a radical polymerizable functional group are very useful because they are incorporated into the cured product by reacting with the active energy ray-curable composition, and can achieve slip properties, abrasion resistance, and chemical resistance over a long period of time.

[0048] The content of the leveling agent in the active energy ray-curable composition is preferably 20% by mass or less, more preferably 0.01 to 10% by mass, even more preferably 0.1 to 5% by mass, particularly preferably 0.2 to 4% by mass, and most preferably 0.3 to 3% by mass, based on the nonvolatile content. By using the leveling agent in this range, not only can the appearance of the cured film be improved, but also the abrasion resistance can be improved.

[0049] <UV absorber> To improve the weather resistance of the cured product, an ultraviolet absorber can be blended into the active energy ray-curable composition. From the viewpoint of heat resistance, one with a molecular weight of 500 or more is preferred. From the viewpoint of good solubility in the composition and improved weather resistance, the ultraviolet absorber is preferably an ultraviolet absorber derived from a triazine-based, benzophenone-based, benzotriazole-based, cyclic imino ester-based, salicylic acid ester-based, or cyanoacrylate-based compound, and has a maximum absorption wavelength in the range of 240 to 380 nm. Among these, triazine-based and benzotriazole-based compounds are more preferred, and triazine-based compounds are even more preferred, from the viewpoint of particularly good ultraviolet absorption and excellent appearance when formed into a hard coat layer.

[0050] Examples of triazine-based ultraviolet absorbers include, but are not limited to, 2-[4-([2-hydroxy-3-dodecyloxypropyl]oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-([2-hydroxy-3-tridecyloxypropyl]oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (Tinuvin® 400). BASF), 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol), reaction products of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester (Tinuvin® 405, BASF), 2,4-bis[2-hydroxy-4- butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3-5-triazine (Tinuvin (registered trademark) 460, manufactured by BASF), 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol (Tinuvin (registered trademark) 1577, manufactured by BASF), 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]-phenol (ADK STAB LA46, manufactured by ADEKA), and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (Tinuvin (registered trademark) 479, manufactured by BASF).

[0051] Examples of benzotriazole-based ultraviolet absorbers include, but are not limited to, 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxypropyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyhexyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-tert-butyl- 3'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole, and the like.

[0052] Examples of cyclic imino ester-based ultraviolet absorbers include, but are not limited to, 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2-(1- or 2-naphthyl)-3,1-benzoxazin-4-one, 2-(4-biphenyl)-3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2-p-benzoylphenyl phenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2-p-(or m-)phthalimidophenyl-3,1-benzoxazin-4-one, N-phenyl-4-(3,1-benzoxazin-4-one-2-yl)phthalimide, N-benzoyl-4-(3,1-benzoxazin-4-one-2-yl)aniline, N-benzoyl-N-methyl-4-( 3,1-benzoxazin-4-one-2-yl)aniline, 2-(p-(N-methylcarbonyl)phenyl)-3,1-benzoxazin-4-one, 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-ethylenebis(3,1-benzoxazin-4-one), 2,2'-tetramethylenebis(3,1-benzoxazin-4-one), 2,2'-decamethylenebis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one) benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2,6- or 1,5-naphthylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(1,4-cyclohexylene)bis(3,1-benzoxazin-4-one), 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)benzene, 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)naphthalene, 2,4,6-tri(3,1-benzoxazin-4-one-2-yl)naphthalene, 2,8-dimethyl-4H,6H-benzo(1,2-d;5,4-d')bis(1,3)-oxazine-4,6-dione, 2,7-dimethyl-4H,9H-benzo(1,2-d;4,5-d')bis(1,3)-oxazine-4,9-dione, 2,8-diphenyl 4H,8H-benzo(1,2-d;5,4-d')bis(1,3)-oxazine-4,6-dione, 2,7-diphenyl-4H,9H-benzo(1,2-d;4,5-d')bis(1,3)-oxazine-4,6-dione, 6,6'-bis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-bis(2-ethyl-4H,3,1-benzoxazin-4-one), 6,6'-bis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one) on), 6,6'-methylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-ethylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-ethylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-butylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-butylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-oxybis(2-methyl-4H,3,1-benzoxazin-4-one), 6 ,6'-oxybis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-sulfonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-sulfonylbis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-carbonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-carbonylbis(2-phenyl-4H,3,1-benzoxazin-4-one), 7,7'-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-Methylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 7,7'-bis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-ethylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-oxybis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-sulfonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7 Examples include '-carbonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7'-bis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7'-bis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,7'-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one), and 6,7'-methylenebis(2-phenyl-4H,3,1-benzoxazin-4-one).

[0053] Examples of benzophenone-based ultraviolet absorbers (benzophenone-based compounds) and oxybenzophenone-based ultraviolet absorbers (oxybenzophenone-based compounds) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone (trade name "KEMISORB111", manufactured by Chemipro Chemical Co., Ltd.), 2,2',4,4'-tetrahydroxybenzophenone (trade name "SEESORB106", manufactured by Shipro Chemical Co., Ltd.), and 2,2'-dihydroxy-4,4-dimethoxybenzophenone.

[0054] Examples of salicylate ester-based ultraviolet absorbers (salicylate ester-based compounds) include phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-methylbenzoate, phenyl-2-acryloyloxy-4-methylbenzoate, phenyl-2-acryloyloxy-5-methylbenzoate, phenyl-2-acryloyloxy-3-methoxybenzoate, phenyl-2-hydroxybenzoate, phenyl-2-hydroxy-3-methylbenzoate, phenyl-2-hydroxy-4-methylbenzoate, phenyl-2-hydroxy-5-methylbenzoate, phenyl 2-hydroxy-3-methoxybenzoate, and 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (Tinuvin (registered trademark) 120, manufactured by BASF).

[0055] Examples of cyanoacrylate-based ultraviolet absorbers (cyanoacrylate-based compounds) include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, and alkynyl-2-cyanoacrylate. These compounds may be used alone or in combination of two or more.

[0056] The content of the ultraviolet absorber in the active energy ray-curable composition is preferably 20% by mass or less, more preferably 0.01 to 15% by mass, even more preferably 0.1 to 10% by mass, particularly preferably 0.5 to 8% by mass, and most preferably 1 to 5% by mass, based on the nonvolatile content. By using the ultraviolet absorber in this range, a cured film can be effectively formed and the weather resistance of the cured film can be improved.

[0057] When used in applications requiring weather resistance, it is preferable that the ultraviolet absorption is good, and the transmittance of the laminate after forming a cured product at a wavelength of 360 nm is preferably 80% or less, more preferably 70% or less, even more preferably 60% or less, and particularly preferably 50% or less. The lower limit depends on the application, but in applications where weather resistance is highly required, the lower the better, so it is 0%. By using within this range, it is possible to achieve excellent weather resistance.

[0058] <Light stabilizer> In order to further improve the weather resistance of the cured product, a light stabilizer can be blended into the active energy ray-curable composition. The light stabilizer is not particularly limited as long as it is a hindered amine-based light stabilizer. Specific examples of the light stabilizer 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, bis(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 aminomethyl group-containing compounds such as 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecanediethanol, and 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-pentamethyl-4-piperidinol, and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,Examples of aminoether group-containing compounds include a condensate of 5) undecane and diethanol, a reaction product of a diester compound of decanedicarboxylic acid and 2,2,6,6-tetramethyl-1-octoxy-4-piperidinol with 1,1-dimethylethyl hydroperoxide and octane (manufactured by BASF, trade name Tinuvin 123), and bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1,dimethylethyl)-4-hydroxyphenyl]methyl] (manufactured by BASF, trade name Tinuvin 144). Among these, aminoether group-containing compounds are preferred from the viewpoint of weather resistance of the cured product, and bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1,dimethylethyl)-4-hydroxyphenyl]methyl] is particularly preferred. These compounds may be used alone or in combination of two or more.

[0059] The content of the light stabilizer in the active energy ray-curable composition is preferably 20% by mass or less, more preferably 0.01 to 15% by mass, even more preferably 0.1 to 10% by mass, particularly preferably 0.5 to 8% by mass, and most preferably 1 to 5% by mass, based on the nonvolatile content. By using the light stabilizer in this range, a cured film can be effectively formed and the weather resistance of the cured film can be improved.

[0060] <Photopolymerization initiator> A photopolymerization initiator may be blended to promote the curing of the curable composition. The molecular weight of the photopolymerization initiator is preferably 1000 or less. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl ether, benzil dimethyl ketal, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, 1-hydroxybenzophenone, benzoin methyl ether, benzoin ethyl ... Examples of the photopolymerization initiator include cyclohexyl phenyl ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenyl glyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, tribromophenyl sulfone, tribromomethylphenyl sulfone, etc. These photopolymerization initiators may be used alone or in combination of two or more.

[0061] The content of the photopolymerization initiator in the active energy ray-curable composition is preferably 20% by mass or less, more preferably 0.1 to 15% by mass, even more preferably 0.3 to 10% by mass, particularly preferably 0.5 to 8% by mass, and most preferably 1 to 7% by mass, based on the nonvolatile content. By using it in this range, the formation of a cured film can be effectively promoted.

[0062] The active energy ray-curable composition may further contain various additives, such as an organic solvent, an antioxidant, an anti-yellowing agent, a bluing agent, a pigment, a dye, an antifoaming agent, a thickener, an anti-settling agent, an antistatic agent, and an anti-fogging agent, as needed.

[0063] In addition, when forming a cured film, an organic solvent can be used as needed to improve the workability of applying the active energy ray-curable composition to a substrate. Examples of the organic solvent include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; and halogenated solvents such as dichloromethane and chloroform. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, and ketone-based solvents are preferred because they can easily improve workability during application.

[0064] <Cured product (cured film)> A cured product of the active energy ray-curable composition can be formed by applying the active energy ray-curable composition to a substrate or an article to form a coating film, drying the composition as needed, and then irradiating the coating film with active energy rays. The method for applying the active energy ray-curable composition is not particularly limited. For example, the composition can be applied by a known method such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, or spray coating.

[0065] When the active energy ray-curable composition contains an organic solvent, it is preferable to heat-dry the composition before irradiating it with active energy rays. By heating and drying the composition beforehand, the organic solvent in the coating film can be effectively removed. The drying temperature for heating and drying is preferably 30 to 200°C, more preferably 40 to 150°C, and even more preferably 50 to 120°C. The drying time is preferably 0.01 to 30 minutes, and more preferably 0.1 to 10 minutes.

[0066] Examples of active energy rays include ultraviolet rays, electron beams, visible light, infrared rays, and X-rays. Among these, ultraviolet rays and electron beams are preferred from the viewpoint of curability and prevention of resin deterioration, and ultraviolet rays are more preferred. The irradiation dose of active energy rays can be appropriately selected depending on the active energy rays to be irradiated.

[0067] For example, when ultraviolet light is used, the cumulative light intensity is 20 to 5000 mJ / cm 2 is preferred, and 100 to 3000 mJ / cm 2 More preferably, 200 to 2000 mJ / cm 2 The illuminance is more preferably 50 to 600 mW / cm. 2 is preferred, and 75 to 450 mW / cm 2 More preferably, 100 to 300 mW / cm 2 As the light source, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or an electron beam using a scanning type or curtain type electron beam acceleration path, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a low pressure mercury lamp, etc. can be used.

[0068] When curing is performed by electron beam irradiation, various electron beam irradiation devices can be used. The irradiation dose (Mrad) of the electron beam is usually 0.5 to 20 Mrad, and from the viewpoints of the curability of the active energy ray-curable composition of the present invention, the flexibility of the cured product, and prevention of damage to the substrate, it is preferably 1 to 15 Mrad.

[0069] The thickness of the cured product (cured film) is preferably in the range of 0.1 to 20 μm, more preferably 0.2 to 10 μm, and even more preferably 0.3 to 7 μm. If the thickness of the cured product is within the above range, it is easy to achieve desired properties such as abrasion resistance. The thickness of the cured product can be determined by observing the cross section using an electron microscope or the like.

[0070] The elongation of the cured product is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more, as measured by a tensile test at 140°C, as described below. When used in applications where elongation is particularly important, the range is preferably 40% or more, more preferably 50% or more, and even more preferably 70% or more. There is no particular upper limit, but it is preferably 200%. By keeping the range within this range, defects such as cracks during molding can be suppressed.

[0071] The abrasion resistance of the cured product is measured by the abrasion test described below, and the change in haze is preferably 2.0% or less, more preferably 1.5% or less, even more preferably 1.0% or less, particularly preferably 0.5% or less, and most preferably 0.3% or less, with the lower limit being 0.0%. By keeping the change in haze within this range, it becomes possible to prevent scratches during processing and scratches after molding.

[0072] As for the chemical resistance of the cured product, in the test described below, the change in haze is preferably 2.0% or less, more preferably 1.5% or less, even more preferably 1.0% or less, particularly preferably 0.5% or less, and most preferably 0.3% or less, with the lower limit being 0.0%. By keeping it within this range, the chemical resistance after molding will be excellent.

[0073] <Laminate> The laminate of the present invention (hereinafter also referred to as "the laminate") has a substrate layer and a layer made of a cured product (cured film, hard coat layer) of an active energy ray-curable composition. The laminate may further have one or more layers selected from the group consisting of a primer layer provided between the substrate layer and the cured product, and a back surface functional layer provided on the surface of the substrate layer opposite to the cured product side. Furthermore, the laminate may also have a surface functional layer provided on the surface of the cured product opposite to the substrate layer side, as long as the effects of the present invention are not impaired.

[0074] (base material layer) As the substrate layer, known substrates can be used, such as resin substrates, metal substrates, and paper substrates. Of these, resin substrates are preferred from the viewpoint of processability. The resin substrate may be a single-layer structure or a multi-layer structure of two or more layers, and is not particularly limited. It is preferable that the resin substrate be a multi-layer structure of two or more layers, each of which has its own characteristics, thereby achieving multi-functionality.

[0075] As the resin substrate, various resin films (sheets) can be used, such as polyester film, poly(meth)acrylate film, polyurethane film, polyolefin film, polycarbonate film, polyimide film, triacetyl cellulose film, polystyrene film, polyvinyl chloride film, polyvinyl alcohol film, nylon film, etc.

[0076] When the present laminate is used for surface protection or decoration of resin molding materials for automobile interior and exterior parts, electronic devices, etc., polyester films, poly(meth)acrylate films, polyurethane films, and polyolefin films are preferred, and in consideration of formability, polyester films, poly(meth)acrylate films, and polyurethane films are more preferred, with polyester films and poly(meth)acrylate films being particularly preferred.

[0077] The polyester film may be a non-stretched film or a stretched film, with a stretched film being preferred. Among these, a uniaxially stretched film stretched in one direction or a biaxially stretched film stretched in two directions is preferred, with a biaxially stretched film being more preferred from the viewpoint of excellent balance of mechanical properties and flatness. Furthermore, an easily formable type with improved formability is preferred, such as a polyester in which a copolymer of an isophthalic acid structure or the like is incorporated into a polyethylene terephthalate structure.

[0078] The substrate layer may contain particles for the purposes of imparting easy slip, preventing scratches in each process, and improving blocking resistance, and may also contain an ultraviolet absorber for improving weather resistance. Furthermore, additives other than the above-mentioned particles and ultraviolet absorbers may be included as necessary. Examples of additives that can be used include known additives such as antioxidants, antistatic agents, heat stabilizers, lubricants, plasticizers, dyes, and pigments.

[0079] The thickness of the substrate layer is not particularly limited, but if it is in the form of a film, it is preferably in the range of 2 to 350 μm, more preferably 5 to 250 μm, and even more preferably 10 to 100 μm.

[0080] The substrate layer may be subjected to a corona treatment or a plasma treatment in order to improve adhesion to the cured product of the active energy ray-curable composition.

[0081] (primer layer) The primer layer is provided between the substrate layer and the cured product of the active energy ray-curable composition in order to impart various functions, such as an adhesion improving layer and an antistatic layer.

[0082] In a preferred embodiment, the primer layer is an adhesion-improving layer. If the adhesion between the substrate layer and the cured product is insufficient, the laminate may not be usable depending on the application. By having an adhesion-improving layer, the adhesion between the substrate layer and the cured product is improved, and the laminate can be used for various applications. Examples of components constituting the primer layer include polyester resins, acrylic resins, urethane resins, polyvinyl resins (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymers, etc.), etc.

[0083] <Application> The cured product obtained from the active energy ray-curable composition of the present invention has excellent abrasion resistance, adhesion to substrates, and stretchability, and therefore can be suitably used as a curable composition for decorative films. For example, it can be effectively applied to various components such as interior and exterior building materials, automobiles, home appliances, and information and electronic materials. [Example]

[0084] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. The values ​​of various production conditions and evaluation results in the following examples represent preferred upper or lower limit values ​​in the embodiments of the present invention, and preferred ranges may be defined by a combination of the above-mentioned upper or lower limit values ​​and the values ​​in the following examples or values ​​between the examples. The measurement and evaluation methods used in the present invention are as follows.

[0085] The cured products produced using the active energy ray-curable compositions prepared in the following Examples and Comparative Examples were evaluated as follows.

[0086] (1) Weight average molecular weight The weight average molecular weight of the copolymer was measured by GPC under the following conditions. Equipment: Waters "e2695" Column: Tosoh Corporation "TSKgel Super H3000+H4000+H6000" Detector: Differential refractive index detector (RI detector / built-in), Solvent: tetrahydrofuran, Temperature: 40℃, Flow rate: 0.5mL / min, Injection volume: 10μL, Concentration: 0.2% by mass, Calibration sample: monodisperse polystyrene, Calibration method: Polystyrene equivalent.

[0087] (2) Evaluation method for abrasion resistance test The haze value of the cured surface of the laminate, which had formed a cured product of the active energy ray-curable composition, was evaluated before and after treatment with a Gakushin-type friction tester (RT-200, manufactured by Daiei Scientific Instruments Manufacturing Co., Ltd.) by rubbing Kanakin No. 3 with a 300 g weight and an R contact arm 1,000 times in an atmosphere of 23°C and 50% RH. The haze was measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K-7136 (2000), and the haze change was evaluated by subtracting the haze value before the abrasion test from the haze value after the abrasion test.

[0088] (3) Evaluation method for chemical resistance test The cured surface of the laminate, which had formed a cured product of the active energy ray-curable composition, was subjected to a Gakushin-type friction tester (RT-200 manufactured by Daiei Scientific Instruments Manufacturing Co., Ltd.) in an atmosphere of 23°C and 50% RH, in which the R contact arm was used to reciprocate 50 times with a nonwoven fabric (Bencott (registered trademark) M-3II manufactured by Asahi Kasei Corporation) soaked in 1 mL of methyl ethyl ketone, to evaluate the haze value before and after the treatment. The haze was measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K-7136 (2000), and the haze change was evaluated by subtracting the haze value before the abrasion test from the haze value after the abrasion test.

[0089] (4) Evaluation of elongation (cured product) The laminate having the cured product of the active energy ray-curable composition formed thereon was cut into a width of 10 mm, and stretched using a Tensilon tensile tester (MX2-500N manufactured by Imada Co., Ltd.) under conditions of a temperature of 140°C, a tensile speed of 40 mm / min, and a chuck distance of 40 mm, to measure the breaking elongation (the elongation until cracks were visually observed), and the elongation percentage was evaluated. The elongation was calculated by dividing the length at which a crack appeared in the cured product by the length before the tensile test.

[0090] (5) Measurement of transmittance at 360 nm The laminate having the cured product of the active energy ray-curable composition formed thereon was measured using a spectrophotometer (Ratio Beam Spectrophotometer U-1900 manufactured by Hitachi High-Technologies Corporation) under the conditions of measurement mode: wavelength scan, wavelength: 300 to 600 nm, speed: 400, and cell length: 10 mm, and the transmittance at a wavelength of 360 nm was evaluated.

[0091] (6) Adhesion evaluation method An 18 mm wide tape (Cellotape (registered trademark) CT-18 manufactured by Nichiban Co., Ltd.) was applied to the cured product side of a laminate having a cured product of the active energy ray-curable composition formed thereon in an environment of 23°C and 50% RH, and the tape was rapidly peeled off at a peel angle of 180 degrees, after which the peeled surface was observed, with no peeling being rated A and peeling being rated B. The absence of peeling can be considered to indicate good adhesion to the substrate.

[0092] The compounds used in the examples and comparative examples are as follows. (Meth)acrylic resin (A-1) A (meth)acrylic resin produced by the method shown below. Propylene glycol monomethyl ether (178 parts by mass), glycidyl methacrylate (20 parts by mass), methyl methacrylate (79 parts by mass), ethyl acrylate (1.0 part by mass), and 2,2'-azobis(2,4-dimethylvaleronitrile) (0.6 parts by mass) were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was allowed to react for 3 hours at 65°C. Subsequently, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.3 parts by mass) was added and the mixture was allowed to react for 3 hours, after which propylene glycol monomethyl ether (48 parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and the mixture was heated to 100°C. Next, acrylic acid (10 parts by mass) and triphenylphosphine (1.6 parts by mass) were added and reacted at 110°C for 6 hours to obtain (meth)acrylic resin (A-1) with a radical polymerizable double bond content (acryloyl group concentration (amount of acryloyl group introduced)) of 615 g / mol. The weight-average molecular weight was 48,800. The hydroxyl value was 91 mgKOH / g. (Meth)acrylic resin (A-2) A (meth)acrylic resin produced by the method shown below. Propylene glycol monomethyl ether (178 parts by mass), glycidyl methacrylate (40 parts by mass), methyl methacrylate (59 parts by mass), ethyl acrylate (1.0 part by mass), and 2,2'-azobis(2,4-dimethylvaleronitrile) (0.6 parts by mass) were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was reacted for 3 hours at 65°C. Subsequently, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.3 parts by mass) was added and the mixture was reacted for 3 hours, after which propylene glycol monomethyl ether (48 parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and the mixture was heated to 100°C. Next, acrylic acid (21 parts by mass) and triphenylphosphine (1.6 parts by mass) were added and reacted at 110°C for 6 hours to obtain a (meth)acrylic polymer (A-1) with a double bond content (acryloyl group concentration (amount of acryloyl group introduced)) of 365 g / mol in the side chain. The weight-average molecular weight was 40,000. The hydroxyl value was 154 mgKOH / g. (Meth)acrylic resin (A-3) Methyl methacrylate polymer (weight average molecular weight 8000) that does not have radical polymerizable double bonds or hydroxyl groups. (Meth)acrylate: B-1 Dipentaerythritol hexaacrylate (hexafunctional) modified with 12 caprolactone units per molecule (Kayarad (registered trademark) DPCA-120, manufactured by Nippon Kayaku Co., Ltd.) (Meth)acrylate: B-2 Dipentaerythritol hexaacrylate (hexafunctional) modified with two caprolactone groups per molecule (Kayarad (registered trademark) DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) (Meth)acrylate: B-3 Dipentaerythritol hexaacrylate (hexafunctional) (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) Leveling agent: C Silicone leveling agent with radically polymerizable functional groups (BYK-UV 3500) UV absorber: D 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (BASF Tinuvin 479) Light stabilizer: E Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1,dimethylethyl)-4-hydroxyphenyl]methyl] (BASF Tinuvin 144) Photopolymerization initiator: F 1-Hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resins BV)

[0093] [Example 1]

[0094] The coating solution (active energy ray-curable composition) shown in Table 1 below was applied to the corona-treated surface of a corona-treated, easily moldable polyester film (thickness: 100 μm) as a substrate using a bar coater so that the coating film would have a dry thickness of 5 μm, and then heated and dried at 80° C. for 2 minutes. Thereafter, the coating solution was exposed to a high-pressure mercury lamp in an air atmosphere with an integrated light dose of 300 mJ / cm 2 . 2 , illuminance 200mW / cm 2 The coating was irradiated with ultraviolet light using a UV conveyor (a high-output UV device (model: US5-X1802-X1202) manufactured by Eye Graphics Co., Ltd.) to form a cured product (cured film), thereby obtaining a laminate.

[0095] The resulting laminate had good abrasion resistance, chemical resistance, elongation, and adhesion. The properties of this laminate are shown in Table 2 below.

[0096] [Examples 2 to 5, 7 to 9, and 11 to 16] A laminate having a cured film was obtained in the same manner as in Example 1, except that the coating agent composition in Example 1 was changed to the coating agent composition shown in Table 1. The properties of the obtained laminate are shown in Table 2 below.

[0097] [Example 6] A laminate having a cured film was obtained in the same manner as in Example 1, except that the substrate was changed to a polymethacrylate film (Acryplene HBS006H (thickness 53 μm) manufactured by Mitsubishi Chemical Corporation) and the coating composition was changed to the coating composition shown in Table 1. The properties of the obtained laminate are shown in Table 2 below.

[0098] [Example 10] In Example 1, the curing method was changed from ultraviolet light to electron beams (using an electron beam irradiation device (CB175, manufactured by iGraphics Co., Ltd.), the dried coating film was irradiated with electron beams at an acceleration voltage of 165 kV and an exposure dose of 5 Mrad, and then cured at 23°C for 1 day), and the coating composition was changed to the coating composition shown in Table 1. A laminate having a cured film was obtained in the same manner as in Example 1. The properties of the obtained laminate are shown in Table 2 below.

[0099] [Comparative Examples 1 to 5] A laminate having a cured film was obtained by the same production method as in Example 1, except that the coating composition in Example 1 was changed to the coating composition shown in Table 1. The properties of the obtained laminate were as shown in Table 2 below, and the results showed that properties such as abrasion resistance and adhesion were poor. In addition, in the chemical resistance evaluation of Comparative Examples 1 to 3, the adhesion was so weak that the coating film peeled off from the substrate, making it impossible to accurately evaluate the amount of haze change.

[0100] [Table 1] The coating solution in Table 1 was prepared with methyl ethyl ketone so that the non-volatile content was 25%. The units of each value in the table are parts by mass.

[0101] [Table 2]

Claims

1. An active energy ray-curable composition comprising a resin having a radical polymerizable double bond equivalent of 100 to 10,000 g / mol and a hydroxyl value of 5 to 500 mgKOH / g.

2. The active energy ray-curable composition according to claim 1 , further comprising an active energy ray-curable compound other than the resin.

3. The active energy ray-curable composition according to claim 2 , wherein the active energy ray-curable compound other than the resin is a (meth)acrylate.

4. The active energy ray-curable composition according to claim 3, wherein the (meth)acrylate is a tri- or higher functional (meth)acrylate.

5. The active energy ray-curable composition according to any one of claims 1 to 4, further comprising a leveling agent.

6. The active energy ray-curable composition according to any one of claims 1 to 5, further comprising an ultraviolet absorber.

7. A cured product of the active energy ray-curable composition according to any one of claims 1 to 6.

8. The cured product according to claim 7, which has an elongation of 5% or more in a tensile test at 140°C.

9. A laminate comprising a substrate and the cured product according to claim 7 or 8 laminated thereon.

10. The laminate according to claim 9, which has a transmittance of 80% or less at a wavelength of 360 nm.

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