Active energy ray curable composition, cured product, 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 surface protection and decoration of resin molded materials such as automotive interior and exterior parts, electronic devices, general merchandise, and building material components, methods such as hard coating or film adhesion are known. Decoration methods include insert molding, thermal lamination, and transfer methods. Generally, hard coat layers are known to be curable compositions containing a compound with radical polymerization groups and a photopolymerization initiator, cured by radical polymerization. However, while using a hard coat layer to protect the surface improves abrasion resistance and scratch resistance, it can worsen the elongation during molding, making it unsuitable for decorative applications. Furthermore, ensuring proper adhesion between the substrate and the hard coat layer to prevent peeling during processing is also a challenge.

[0003] Patent Document 1 describes an insert film for in-mold labels, Reference Document 2 describes a hard coat agent for decorative molding, Reference Document 3 describes a decorative sheet for automotive interiors, and Reference Document 4 describes a decorative hard coat film 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 Publication No. 2005-288720 [Patent Document 2] Japanese Patent Publication No. 2016-180082 [Patent Document 3] Japanese Patent Publication No. 2019-189043 [Patent Document 4] Japanese Patent Publication No. 2011-110903 [Overview of the project] [Problems that the invention aims to solve]

[0005] The hard coat layer described in Patent Document 1 has excellent abrasion resistance, but does not necessarily satisfy the elongation requirements during molding, and does not easily conform to the surface shape of the molding material, which may cause the hard coat layer to peel off or crack. Similarly, the hard coat agent described in Patent Document 2 has excellent abrasion resistance, but does not necessarily satisfy the elongation requirements and adhesion to the substrate. The sheet described in Patent Document 3 does not sufficiently satisfy the abrasion resistance of the surface protective layer, and it is difficult to ensure elongation with the hard coat film described in Patent Document 4. The present invention aims to provide an active energy ray curable composition capable of forming a hard coat layer that is excellent in wear resistance, has excellent elongation during molding (suppresses crack formation), and has excellent adhesion to the 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. In other words, the above objectives of the present invention can be achieved by the following means [1] to

[10] . [1] An active energy ray curable composition comprising a resin having a radical polymerizable double bond equivalent of 100 to 10000 g / mol and a hydroxyl value of 5 to 500 mg KOH / g. [2] The active energy ray curable composition of [1], comprising an active energy ray curable compound other than the resin. [3] An active energy ray curable composition of [2] in which the active energy ray curable compound other than the resin is (meth)acrylate. [4] The active energy ray curable composition according to [3], wherein the (meth)acrylate is a trifunctional or more (meth)acrylate. [5] An active energy ray curable composition according to any one of [1] to [4], containing a leveling agent. [6] An active energy ray curable composition according to any one of [1] to [5], containing an ultraviolet absorber. A cured product of an active energy ray curable composition described in any one of the items [7][1] to [6]. [8] A cured product of [7] having an elongation of 5% or more in a tensile test at 140°C. [9] A laminate in which the cured material described in [7] or [8] is laminated on a substrate.

[10] A laminate of [9] having a transmittance of 80% or less at a wavelength of 360 nm. [Modes for carrying out 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 A group is 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, "difunctional" 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 10000 g / mol and a hydroxyl value of 5 to 500 mgKOH / g.

[0009] The radical polymerizable double bond equivalent in resins 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 resins within this range makes it possible to achieve both abrasion resistance when a cured film (hard coat layer) is formed and elongation during molding. The radical polymerizable double bond equivalent can also be measured, for example, by reacting the resin composition with a mixed solution of sodium bromide and potassium bromate, mixing it with a potassium iodide solution, and then defining the mixture with a sodium thiosulfate solution using a starch solution as an indicator.

[0010] Furthermore, the hydroxyl value of the resin is typically in the range of 5 to 500 mg KOH / g, preferably 10 to 300 mg KOH / g, more preferably 15 to 250 mg KOH / g, even more preferably 25 to 220 mg KOH / g, particularly preferably 40 to 170 mg KOH / g, and most preferably 60 to 150 mg KOH / g. Using a resin within this range ensures good adhesion to the substrate. The hydroxyl value can also 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 facilitate the formation of a hard coat layer with appropriate properties.

[0012] Methods for introducing a radically polymerizable double bond into (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). Furthermore, these methods may be used in combination. In the following, monomers having a radically polymerizable double bond may be referred to as vinyl monomers.

[0013] In Method 1 described above, examples of vinyl monomers having epoxy groups used to obtain an acrylic resin having epoxy groups include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. Among these, glycidyl (meth)acrylate is particularly preferred, and glycidyl methacrylate is especially preferred, considering its good reactivity and ease of use. These may be used individually or in combination of two or more.

[0014] In addition, examples of the compound having a double bond and a carboxyl group in the above Method 1 include, for example, (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, an adduct of pentaerythritol tri(meth)acrylate and phthalic anhydride, and the like. Among these, an adduct of (meth)acrylic acid, pentaerythritol tri(meth)acrylate and succinic anhydride is preferable, (meth)acrylic acid is more preferable, and acrylic acid is even more preferable. Note that only one kind of the compound having a double bond and a carboxyl group may be used, or two or more kinds may be combined.

[0015] In the above Method 2, examples of the vinyl monomer having a carboxyl group used for obtaining the acrylic resin having a carboxyl group include, for example, (meth)acrylic acid, carboxyethyl (meth)acrylate, polybasic acid-modified (meth)acrylate, and the like. Among these, (meth)acrylic acid is preferable, and acrylic acid is more preferable. These may be used alone or in combination of two or more kinds.

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

[0017] In the above Method 3, examples of the vinyl monomer having a hydroxyl group used for obtaining the acrylic resin having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, and the like. These may be used alone or in combination of two or more kinds.

[0018] Furthermore, in Method 3, the compound having a double bond and a carboxyl group can be the same as the compound in Method 1.

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

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

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

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

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

[0024] Furthermore, in method 6 described above, examples of compounds having a double bond and an isocyanate group include isocyanate ethyl (meth)acrylate. These may be used individually or in combination of two or more.

[0025] Of the above methods, Method 1 or Method 2 is preferred because it allows for the simultaneous introduction of hydroxyl groups. Furthermore, Method 1 is more preferred because the reaction is easier to control. In Method 1, the double bond is introduced by a ring-opening and addition reaction between the epoxy group of the acrylic resin having the epoxy group and the carboxyl group of the compound having the double bond and carboxyl group.

[0026] In Method 1 described above, the monomers having epoxy groups in the acrylic resin having epoxy groups are preferably in the range of 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, of the total amount of monomers constituting the acrylic resin having epoxy groups. There is no particular upper limit, but it is preferably in the range of 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 within this range, it is possible to achieve not only improved adhesion, scratch resistance, and hardness of the cured film to the substrate, but also stretchability that prevents cracking due to stress during decorative molding.

[0027] Furthermore, in Method 1, the compound having a double bond and a carboxyl 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 the amount that allows the reaction to proceed without excess or deficiency. By using this range, radical polymerizable double bonds can be effectively introduced.

[0028] It is also possible to introduce hydroxyl groups by methods other than Method 1 or Method 2 described above. For example, one method is to copolymerize a compound having hydroxyl groups as a monomer during the production of (meth)acrylic resin.

[0029] Examples of monomers having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, and other hydroxyalkyl (meth)acrylates. Among these, hydroxyethyl (meth)acrylate is preferred from the viewpoint of ease of introduction and efficient adjustment of the hydroxyl value.

[0030] Furthermore, (meth)acrylic resins, such as the (meth)acrylic resin having the epoxy group described above, may be copolymers of (meth)acrylates or other vinyl monomers other than those described above. The polymerization reaction of these raw materials is typically 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, and octoxy (poly)propylene glycol (meth)acrylate. Examples include (meth)acrylates such as acrylate, 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 monomers such as styrene, p-chlorostyrene, and p-bromostyrene. These may be used individually or in combination of two or more.

[0032] (Meth)acrylic resin can be produced by a radical polymerization reaction using the above-mentioned vinyl monomer raw materials. The radical polymerization reaction 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 individually 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 individually or in combination of two or more. It is preferable to use the radical polymerization initiator in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the total vinyl monomer raw materials.

[0035] Furthermore, during radical polymerization, chain transfer agents can be used to control the weight-average molecular weight of the (meth)acrylic resin. Examples of chain transfer agents include butanethiol, octanthiol, 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, and 2,2-(ethylenedi Examples of thiol compounds include oxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, 2-mercaptoethyl octanoate, 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, mercaptosuccal acid, and 2-mercaptoethanesulfonic acid. These may be used individually or in combination of two or more.

[0036] The amount of 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 amount of vinyl monomer raw materials.

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

[0038] To react (meth)acrylic resin with compounds having double bonds and carboxyl groups, the compounds having double bonds and carboxyl groups are added to the (meth)acrylic resin obtained as described above, and the reaction is carried out at a temperature of usually 90 to 140°C, preferably 100 to 120°C, for usually 3 to 9 hours in the presence of one or more catalysts such as triphenylphosphine, tetrabutylammonium bromide, tetramethylammonium chloride, and triethylamine. Here, it is preferable to use the catalyst in a ratio of about 0.5 to 3 parts by weight per 100 parts by weight of the total of the raw material (meth)acrylic acid ester polymer and the compounds having double bonds and carboxyl groups. This reaction may be carried out immediately after producing the (meth)acrylic resin by polymerization, or the (meth)acrylic resin may be separated from the reaction system first, and then the compounds having double bonds and carboxyl groups may be added.

[0039] The weight-average molecular weight of the resin should be appropriately selected depending on the application of the curable composition, but 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. Using a resin within this range improves abrasion resistance, adhesion to the substrate, and elongation during molding. It also makes it easier to set the viscosity of the composition within an appropriate range, resulting in excellent coating properties. The weight-average molecular weight (Mw) of the resin can be determined using gel permeation chromatography (GPC) as a converted value based on the polystyrene standard. Specific measurement conditions are shown in the examples below.

[0040] The content of the above-mentioned resin in the active energy ray curable composition varies depending on the application and the required characteristics of the cured film, so it cannot be stated definitively, but it is preferably in the range of 5 to 100% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 85% by mass, particularly preferably 30 to 80% by mass, and most preferably 40 to 75% by mass, relative to the non-volatile content. By using within this range, it is possible to ensure wear resistance while also achieving good elongation during molding and adhesion to the substrate. Furthermore, for applications where elongation is particularly important, the mass is preferably in the range of 50 to 100% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 90% by mass. Non-volatile content refers to the total mass of components other than the solvent, such as organic solvents. The non-volatile content of an active energy ray curable composition can be measured by conventionally known methods. For example, it can be measured by the change in weight when 1 g of the composition is spread out and heated at 100°C for 1 hour to evaporate 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 resin mentioned above as the active energy ray-curable composition in order to improve or adjust the wear resistance and hardness of the cured film.

[0042] As active energy ray curable compounds other than resins, conventionally known materials can be used, but (meth)acrylate is a preferred material, for example. The (meth)acrylate is not particularly limited and may be monofunctional (meth)acrylate, difunctional (meth)acrylate, or polyfunctional (meth)acrylate with three or more functions. (Meth)acrylate that is commercially available as a curable resin material can also be used. The (meth)acrylate may contain other components as long as it does not impair the purpose of the present invention. Among these, difunctional or polyfunctional (meth)acrylate with three or more functions is preferred because it has excellent abrasion resistance, and trifunctional (meth)acrylate with three or more functions is particularly preferred. Furthermore, epoxy (meth)acrylate, urethane (meth)acrylate, silicone (meth)acrylate, etc. can also be used as the (meth)acrylate.

[0043] The aforementioned monofunctional (meth)acrylates 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, and dimethylaminoethyl (meth)acrylate. Examples include mono(meth)acrylates such as tulaminoethyl (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, as well as mono(meth)acrylate compounds such as adducts of phthalic anhydride and 2-hydroxyethyl (meth)acrylate.

[0044] Examples of difunctional and polyfunctional (meth)acrylates include alkane diol 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 polyfunctional (meth)acrylates with three or more functions 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, and ethylene oxide-modified penta(meth)acrylate. Examples include ethylene oxide-modified (meth)acrylates such as lithritol tetra(meth)acrylate, isocyanuric acid-modified tri(meth)acrylates such as ethylene oxide-modified isocyanurate, isocyanuric acid-modified tri(meth)acrylates such as ε-caprolactone-modified tris(acrooxyethyl)isocyanurate, 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, (meth)acrylates with four or more functions are preferred due to their excellent wear resistance, and (meth)acrylates with six or more functions are even more preferred. Furthermore, considering compatibility with elongation during molding, polyfunctional (meth)acrylates with extended alkyl chains are preferred, particularly (meth)acrylates with four or more functions with extended alkyl chains, and (meth)acrylates with six or more functions with extended alkyl chains are even more preferred. For example, caprolactone-modified dipentaerythritol hexa(meth)acrylate is an optimal material. In particular, if there are two or more caprolactone modifications per molecule of (meth)acrylate, it is preferable for elongation, and for applications where elongation is particularly important, it is even preferable to have six or more modifications.

[0046] The content of active energy ray-curable compounds other than the resins mentioned above in the active energy ray-curable composition varies depending on the application and the required characteristics of the cured film, so it is difficult to generalize, but it is preferably in the range of 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, relative to the non-volatile content. By using within this range, it is possible to improve wear resistance while ensuring elongation during molding. Furthermore, in applications where elongation is particularly important, the amount is preferably 50% by mass or less, more preferably 3 to 30% by mass, and even more preferably 5 to 20% by mass.

[0047] <Leveling agent> To improve the appearance of the cured product, a leveling agent can be added to 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 preferable from the viewpoint of improving wear resistance, which is one of the issues addressed in this invention. Furthermore, since it is also important to prevent the leveling agent from bleeding out after the formation of the hard coat layer, such as during molding, silicone leveling agents having radical polymerizable functional groups are particularly preferred. Silicone leveling agents impart slip properties to the cured product, achieving high wear resistance. Silicone leveling agents having radical polymerizable functional groups are incorporated into the cured product by reacting with the active energy ray curable composition, and are very useful because they can achieve slip properties, wear resistance, and chemical resistance over a long period of time.

[0048] The leveling agent content 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, relative to the non-volatile content. Using this range not only improves the appearance of the cured film but also improves its abrasion resistance.

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

[0050] Triazine-based UV absorbers are not limited to the following, but for example, 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(registered trademark) 400 (Manufactured by BASF), 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol), reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester (Tinuvin® 405, manufactured by BASF), 2,4-bis"2-hydroxy-4- Examples include butoxyphenyl-6-(2,4-dibutoxyphenyl)-1,3-5-triazine (Tinuvin® 460, manufactured by BASF), 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol (Tinuvin® 1577, manufactured by BASF), 2-(4,6-diphenyl-1,3,5-triazine-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® 479, manufactured by BASF).

[0051] Benzotriazole-based UV absorbers are not limited to those listed below, but include, for example, 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, and 2-[2'-hydroxy-5'-tert-butyl- Examples include 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, and 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole.

[0052] Examples of cyclic iminoester UV 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-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-Benzoxazine-4-one, 2-p-(or m-)phthalimidophenyl-3,1-benzoxazine-4-one, N-phenyl-4-(3,1-benzoxazine-4-on-2-yl)phthalimido, N-benzoyl-4-(3,1-benzoxazine-4-on-2-yl)aniline, N-benzoyl-N-methyl-4-(3,1-benzoxazine-4-on-2-yl)aniline, 2-(p-(N-methylcarbonyl)phenyl)-3,1-benzoxazine-4-one, 2,2'-bis(3,1-benzoxazine-4-one), 2,2'-ethylenebis(3,1-benzoxazine-4-one), 2,2'-tetramethylenebis(3,1-benzoxazine-4-one), 2,2'-decamethylenebis(3,1-benzoxazine-4-one) , 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-m-phenylenebis(3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2,6-or 1,5-naphthylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(1,4-cyclohexylene)bis(3,1-Benzoxazine-4-one), 1,3,5-tri(3,1-benzoxazine-4-one-2-yl)benzene, 1,3,5-tri(3,1-benzoxazine-4-one-2-yl)naphthalene, 2,4,6-tri(3,1-benzoxazine-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-benzoxazine-4-one), 6,6'-bis(2-ethyl-4H,3,1-benzoxazine -4-one), 6,6'-bis(2-phenyl-4H,3,1-benzoxazine-4-one), 6,6'-methylenebis(2-methyl-4H,3,1-benzoxazine-4-one), 6,6'-methylenebis(2-phenyl-4H,3,1-benzoxazine-4-one), 6,6'-ethylenebis(2-methyl-4H,3,1-benzoxazine-4-one), 6,6'-ethylenebis(2-phenyl-4H,3,1- 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), (Tyl-4H,3,1-benzoxazine-4-one), 6,6'-sulfonylbis(2-phenyl-4H,3,1-benzoxazine-4-one), 6,6'-carbonylbis(2-methyl-4H,3,1-benzoxazine-4-one), 6,6'-carbonylbis(2-phenyl-4H,3,1-benzoxazine-4-one), 7,7'-methylenebis(2-methyl-4H,3,1-benzoxazine-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'-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) Examples include 6,7'-methylenebis(2-methyl-4H,3,1-benzoxazine-4-one) and 6,7'-methylenebis(2-phenyl-4H,3,1-benzoxazine-4-one).

[0053] Examples of benzophenone-based UV absorbers (benzophenone compounds) and oxybenzophenone-based UV absorbers (oxybenzophenone 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 Chemicals Co., Ltd.), 2,2',4,4'-tetrahydroxybenzophenone (trade name "SEESORB106", manufactured by Cipro Chemicals Co., Ltd.), and 2,2'-dihydroxy-4,4-dimethoxybenzophenone.

[0054] Examples of salicylic acid ester-based UV absorbers (salicylic acid ester 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® 120, manufactured by BASF).

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

[0056] The amount of 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, relative to the non-volatile content. Using this range allows for effective formation of a cured film and improves the weather resistance of the cured film.

[0057] When used in applications requiring weather resistance, good UV absorption is preferable. The transmittance of the laminate after curing 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 for applications requiring strong weather resistance, a lower limit is preferable, so it is 0%. By using within this range, excellent weather resistance can be achieved.

[0058] <Light stabilizer> To further improve the weather resistance of the cured product, a light stabilizer can be added to the active energy ray curable composition. The light stabilizer is not particularly limited as long as it is a hindered amine type light stabilizer. Specific examples of 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- Decaniloxy-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-methoxybenzylidene) 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 tetracarboxylate, condensates of 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])undecane)diethanol, 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 amino ether group-containing compounds include the condensate with undecane diethanol, the 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 (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). Among these, amino ether 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. Furthermore, these compounds may be used individually 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, relative to the non-volatile content. Using this range allows for effective formation of a cured film and improves the weather resistance of the cured film.

[0060] <Photopolymerization initiator> A photopolymerization initiator may be added to accelerate 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, benzyl dimethyl ketal, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, and 1-hydroxy Examples include cyclohexylphenyl ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, tribromophenylsulfone, and tribromomethylphenylsulfone. These photopolymerization initiators may be used individually or in combination of two or more.

[0061] The content of 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, relative to the non-volatile content. Using this range effectively promotes the formation of a cured film.

[0062] The active energy ray curable composition may further contain various additives as needed, such as organic solvents, antioxidants, anti-yellowing agents, bluing agents, pigments, dyes, defoamers, thickeners, anti-settling agents, antistatic agents, and anti-fogging agents.

[0063] Furthermore, when forming a cured film, organic solvents may be used as needed to improve the workability when applying the active energy ray curable composition onto the substrate. Examples of organic solvents 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 phenethole; 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 halogen solvents such as dichloromethane and chloroform. These organic solvents may be used individually 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 easily improve workability during application.

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

[0065] If the active energy ray curable composition contains an organic solvent, it is preferable to pre-heat and dry it before irradiating it with active energy rays. Pre-heating and drying effectively removes the organic solvent from the coating film. 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 curing properties and prevention of resin degradation, with ultraviolet rays being more preferred. Furthermore, the irradiation dose of active energy rays can be appropriately selected according to the active energy rays being irradiated.

[0067] For example, when using ultraviolet light, the integrated light intensity of the irradiation is 20 to 5000 mJ / cm². 2 Preferably, 100-3000 mJ / cm² 2 More preferably, 200-2000 mJ / cm² 2 This is even more preferable. Furthermore, the illuminance should be 50-600 mW / cm². 2 Preferably, 75-450 mW / cm² 2 More preferably, 100-300 mW / cm² 2 This is even more preferable. As a 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 or curtain-type electron beam accelerating path, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or a low-pressure mercury lamp can be used.

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

[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 easier to achieve the desired properties such as wear resistance. The thickness of the hardened material can be determined by cross-sectional observation using an electron microscope or similar device.

[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 in the 140°C tensile test described later. When used in applications where elongation is particularly important, it is preferably in the range of 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 it within this range, defects such as cracks during molding can be suppressed.

[0071] Regarding the wear resistance of the hardened material, the change in haze in the wear test described later 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 a lower limit of 0.0%. By keeping it within this range, it is possible to prevent damage during the processing steps and damage after molding.

[0072] In the chemical resistance tests described later, 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 a lower limit of 0.0%. By keeping it within this range, excellent chemical resistance is achieved after molding.

[0073] <Laminate> The laminate of the present invention (hereinafter also referred to as "this laminate") comprises a base layer and a layer consisting of a cured product (cured film, hard coat layer) of an active energy ray curable composition. This laminate may further have one or more layers selected from the group consisting of a primer layer provided between the base layer and the cured product, and a back surface functional layer provided on the surface of the base layer opposite to the cured product side. Furthermore, a surface functional layer may be provided on the surface of the cured product opposite to the base layer side, provided that it does not impair the effects of the present invention.

[0074] (base material layer) As the base layer, known materials can be used, such as resin base materials, metal base materials, and paper base materials. Among these, resin base materials are preferred from the viewpoint of processability. The resin substrate may be a single layer or a multilayer structure of two or more layers, and is not particularly limited. It is preferable to have a multilayer structure of two or more layers in the resin substrate, giving each layer its own characteristics to achieve multifunctionality.

[0075] Various resin films (sheets) can be used as the resin substrate, including, for example, polyester film, poly(meth)acrylate film, polyurethane film, polyolefin film, polycarbonate film, polyimide film, triacetylcellulose film, polystyrene film, polyvinyl chloride film, polyvinyl alcohol film, nylon film, etc.

[0076] When this laminate is used for surface protection and decoration of resin molded materials such as automotive interior and exterior layer parts and electronic equipment, polyester film, poly(meth)acrylate film, polyurethane film, and polyolefin film are preferred. Furthermore, considering moldability, polyester film, poly(meth)acrylate film, and polyurethane film are preferred, with polyester film and poly(meth)acrylate film being particularly preferred.

[0077] The polyester film may be an unstretched film or a stretched film, with the stretched film being preferred. Among these, a uniaxially stretched film or a biaxially stretched film is preferred, and the biaxially stretched film is more preferred from the viewpoint of superior balance of mechanical properties and flatness. Furthermore, an easy-to-form type with improved moldability is preferred, for example, a polyester in which a copolymer such as an isophthalic acid structure is incorporated into the polyethylene terephthalate structure.

[0078] The base layer may contain particles to provide slipperiness, prevent scratching during each process, and improve blocking resistance, and it may also contain UV absorbers to improve weather resistance. In addition, additives other than the aforementioned particles and UV absorbers may be included as needed. Known additives such as antioxidants, antistatic agents, heat stabilizers, lubricants, plasticizers, dyes, and pigments can be used.

[0079] The thickness of the substrate layer is not particularly limited, but for example, 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] Furthermore, the substrate layer may be subjected to corona treatment or plasma treatment to improve adhesion with the cured product of the active energy ray curable composition.

[0081] (Primer layer) A primer layer is provided between the substrate layer and the cured product of the active energy ray curable composition to impart various functions. Examples include an adhesion-enhancing layer and an antistatic layer.

[0082] In a preferred embodiment, the primer layer is an adhesion-enhancing 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-enhancing 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 resin, acrylic resin, urethane resin, and polyvinyl resin (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.).

[0083] <Application> The cured products obtained from the active energy ray curable composition of the present invention exhibit excellent abrasion resistance, substrate adhesion, and stretchability, making them suitable for use as curable compositions for decorative films. For example, they can be effectively applied to various components such as interior and exterior building materials, automobiles, home appliances, and information and electronic materials. [Examples]

[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 unless it exceeds the gist of the invention. The various manufacturing conditions and evaluation result values ​​in the following examples are intended to represent preferred upper or lower limits in embodiments of the present invention, and the preferred range may be defined by a combination of the aforementioned upper or lower limits and the values ​​of the following examples or the values ​​of the examples themselves. The measurement and evaluation methods used in this invention are as follows.

[0085] The evaluation method for cured products produced using the active energy ray curable compositions prepared in the following examples and comparative examples is as follows.

[0086] (1) Weight average molecular weight The weight-average molecular weight of the copolymer was measured using GPC under the following conditions. Equipment: Waters "e2695", Column: "TSKgel Super H3000+H4000+H6000" manufactured by Tosoh Corporation. 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 For laminates formed with cured active energy ray curable compositions, the haze values ​​before and after treatment were evaluated on the cured surface using a JSPS-type friction tester (RT-200, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) under an atmosphere of 23°C and 50% RH, by applying a 300g weight and performing 1000 reciprocations of Kanakin No. 3 with an R contact arm. Furthermore, haze was measured using a haze meter (manufactured by Murakami Color Technology Research Institute Co., Ltd.) in accordance with JIS K-7136 (2000). The change in haze 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 testing For laminates formed with cured active energy ray curable compositions, the haze values ​​were evaluated before and after treatment using a JSPS-type friction tester (RT-200, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) at 23°C and 50% RH, by applying 1 mL of methyl ethyl ketone to a nonwoven fabric (Bencot® M-3II, manufactured by Asahi Kasei Corporation) and performing 50 back-and-forth passes with the R contact arm. Furthermore, haze was measured using a haze meter (manufactured by Murakami Color Technology Research Institute Co., Ltd.) in accordance with JIS K-7136 (2000). The change in haze 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) Laminates formed from cured active energy ray curable compositions were cut into 10 mm wide strips. These strips were then stretched using a Tensilon tensile testing machine ("MX2-500N" manufactured by Imada Corporation) under the conditions of a temperature of 140°C, a tensile speed of 40 mm / min, and a chuck distance of 40 mm. The elongation at break (the elongation until a crack was observed visually) was measured, and the elongation rate was evaluated. The elongation rate was calculated by dividing the length of the crack in the hardened material by the length before the tensile test.

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

[0091] (6) Method for evaluating adhesion A laminate formed with a cured product of an active energy ray curable composition was subjected to a 18mm wide tape (Nichiban Co., Ltd.'s Cellotape® CT-18) applied to the cured side under conditions of 23°C and 50%RH. The tape was then rapidly peeled off at a 180-degree angle, and the peeled surface was observed. A was defined as having no peeling, and B as having peeling. The absence of peeling indicates good adhesion to the substrate.

[0092] The compounds used in the examples and comparative examples are as follows: (Meth)acrylic resin (A-1) (Meth)acrylic resin manufactured by the method shown below. In a flask equipped with a thermometer, stirrer, and reflux condenser, 178 parts by mass of propylene glycol monomethyl ether, 20 parts by mass of glycidyl methacrylate, 79 parts by mass of methyl methacrylate, 1.0 part by mass of ethyl acrylate, and 0.6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) were added and reacted at 65°C for 3 hours. Then, 0.3 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added and reacted for another 3 hours, after which 48 parts by mass of propylene glycol monomethyl ether and 0.5 parts by mass of p-methoxyphenol were added and heated to 100°C. Next, acrylic acid (10 parts by mass) and triphenylphosphine (1.6 parts by mass) were added and the mixture was 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 introduced acryloyl groups)) of 615 g / mol. The weight-average molecular weight was 48800. The hydroxyl value was 91 mgKOH / g. • (Meth)acrylic resin (A-2) (Meth)acrylic resin manufactured by the method shown below. In a flask equipped with a thermometer, stirrer, and reflux condenser, 178 parts by mass of propylene glycol monomethyl ether, 40 parts by mass of glycidyl methacrylate, 59 parts by mass of methyl methacrylate, 1.0 part by mass of ethyl acrylate, and 0.6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) were added and reacted at 65°C for 3 hours. Then, 0.3 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added and reacted for another 3 hours, after which 48 parts by mass of propylene glycol monomethyl ether and 0.5 parts by mass of p-methoxyphenol were added and heated to 100°C. Next, acrylic acid (21 parts by mass) and triphenylphosphine (1.6 parts by mass) were added and the mixture was reacted at 110°C for 6 hours to obtain (meth)acrylic polymer (A-1) with a double bond amount (acryloyl group concentration (amount of introduced acryloyl groups)) 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) A methyl methacrylate polymer (weight-average molecular weight 8000) that does not have radically polymerizable double bonds or hydroxyl groups. • (Meth)acrylate: B-1 Dipentaerythritol hexaacrylate (hexafunctional) modified with 12 caprolactone molecules per molecule (Kayarad® DPCA-120, manufactured by Nippon Kayaku Co., Ltd.) • (Meth)acrylate: B-2 Dipentaerythritol hexaacrylate (hexafunctional) modified with 2 caprolactone molecules per molecule (Kayarad® DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) • (Meth)acrylate: B-3 Dipentaerythritol hexaacrylate (hexafunctional) (manufactured by Nippon Kayaku Co., Ltd., Kayarad® DPHA) • Leveling agent: C Silicone-based leveling agent with radically polymerizable functional groups (BYK-UV 3500, manufactured by BYK Corporation) • UV absorber: D 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (Tinuvin 479, manufactured by BASF) • Light stabilizer: E Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1,dimethylethyl)-4-hydroxyphenyl]methyl](Tinuvin 144, manufactured by BASF) • Photopolymerization initiator: F 1-Hydroxycyclohexylphenyl 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 onto the corona-treated surface of a readily formable polyester film (thickness: 100 μm) that had been corona-treated, using a bar coater so that the dried coating film thickness would be 5 μm, and then heat-dried at 80°C for 2 minutes. Thereafter, ultraviolet rays were irradiated in an air atmosphere using a high-pressure mercury lamp with an integrated light amount of 300 mJ / cm 2 and an illuminance of 200 mW / cm 2 (using the UV conveyor of a high-output UV device (model: US5-X1802-X1202) manufactured by Eye Graphics Co., Ltd.) to form a cured product (cured film) and obtain a laminate.

[0095] The obtained 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] In Example 1, it was manufactured in the same manner as in Example, except that the coating agent composition was changed to the coating agent composition shown in Table 1, to obtain a laminate having a cured film. The properties of the obtained laminate are shown in Table 2 below.

[0097] [Example 6] In Example 1, the base material was changed to a polymethacrylate film (Acrypren HBS006H (thickness 53 μm) manufactured by Mitsubishi Chemical Corporation), and it was manufactured in the same manner as in Example 1, except that the coating agent composition was changed to the coating agent composition shown in Table 1, to obtain a laminate having a cured film. 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 rays to electron beams (using an electron beam irradiation device (CB175, manufactured by Eye Graphics Co., Ltd.), irradiating the dried coating film with electron beams under the conditions of an acceleration voltage of 165 kV and an irradiation dose of 5 Mrad, and then aging at 23°C for 1 day), and it was manufactured in the same manner as in Example 1, except that the coating agent composition was changed to the coating agent composition shown in Table 1, to obtain a laminate having a cured film. The properties of the obtained laminate are shown in Table 2 below.

[0099] [Comparative Examples 1 to 5] In Example 1, the same procedure as in Example 1 was followed, except that the coating composition was changed to the one shown in Table 1, to obtain a laminate with a cured film. The properties of the obtained laminate are shown in Table 2 below, and the results were poor in terms of properties such as abrasion resistance and adhesion. Furthermore, in the chemical resistance evaluation of Comparative Examples 1 to 3, the adhesion was so weak that the coating film peeled off the substrate, making it impossible to accurately evaluate the amount of haze change.

[0100] [Table 1] The coatings in Table 1 were prepared by adjusting the coating solution with methyl ethyl ketone so that the non-volatile component content was 25%. All values ​​in the table are expressed in parts by mass.

[0101] [Table 2]

Claims

1. The present invention comprises a resin having a radical polymerizable double bond equivalent of 150 to 2500 g / mol, a hydroxyl value of 60 to 150 mgKOH / g, and a weight-average molecular weight of 5000 to 200000, and an active energy ray curable compound other than the aforementioned resin and an ultraviolet absorber. The resin includes a resin in which a compound having a double bond and a carboxyl group is bonded to an acrylic resin having an epoxy group, a resin in which a compound having a double bond and an epoxy group is bonded to an acrylic resin having a carboxyl group, a resin in which a compound having a double bond and a carboxyl group is bonded to an acrylic resin having a hydroxyl group, or a resin in which a compound having a double bond and a hydroxyl group is bonded to an acrylic resin having a carboxyl group. The active energy ray curable compound is a trifunctional or more (meth)acrylate, and each molecule of the trifunctional or more (meth)acrylate is modified by two or more caprolactone molecules. An active energy ray curable composition in which the content of the active energy ray curable compound is 5 to 20% by mass.

2. The active energy ray curable composition according to claim 1, wherein the ultraviolet absorber is one or more selected from triazine-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers.

3. The active energy ray curable composition according to claim 1 or 2, further comprising a light stabilizer.

4. The active energy ray curable composition according to any one of claims 1 to 3, wherein the radical polymerizable double bond equivalent of the resin is 150 to 1500 g / mol, the hydroxyl value is 60 to 150 mg KOH / g, and the weight-average molecular weight is 10,000 to 60,000.

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

6. A cured product of an active energy ray curable composition according to any one of claims 1 to 5.

7. The cured product according to claim 6, wherein the elongation rate in a tensile test at 140°C is 5% or more.

8. A laminate in which a cured product according to claim 6 or 7 is laminated on a substrate.

9. The laminate according to claim 8, wherein the transmittance at a wavelength of 360 nm is 80% or less.

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