Active energy ray-curable composition, cured coating film, and laminated film

Abstract

The invention provides an active energy ray-curable composition, a cured coating film and a laminated film, wherein the active energy ray-curable composition is low in viscosity and capable of forming a cured coating film which is high in hardness and excellent in adhesion and hemming resistance. The active energy ray-curable composition contains the following component (A) and component (B): 40-89% by mass of component (A), 10-60% by mass of component (B), and 5% by mass or less of an organic solvent. Component (A): a polyfunctional (meth) acrylate having a viscosity at 25 DEG C of 100 mPa.s or less (excluding component (B)); component (B): a bifunctional monomer having a reactive moiety represented by formula (1) and having a viscosity of 10 mPa * s or less at 25 DEG C. [In formula (1), R1, R2, and R3 each independently represent a hydrogen atom or a methyl group, and R4 represents an alkyl chain having 0-3 carbon atoms]. [chemical] # imgabs0 #

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable composition, a cured coating film and a laminated film. Background Art

[0002] On the surface of an optical display such as a liquid crystal display, a hard coating is provided to protect the display from damage, etc. The coating material used in the hard coating layer for such an optical display has a poor appearance of the coating film when it is not coated, and it is necessary to ensure the close adhesion to the substrate. In addition, in order to reduce the viscosity of the coating material and improve the wettability to the substrate, it is generally diluted with an organic solvent. When the solvent-based coating material is coated, a process of drying the solvent after coating is necessary, but from the perspective of carbon neutralization, it is preferably to reduce the drying process that applies a large amount of energy load during the manufacturing process. In addition, from the perspective of reducing volatile organic compounds (VOC) to reduce the load on the environment, it is also required to develop a hard coating material in a solvent-free system.

[0003] When designing a solvent-free hard coating material, it is necessary to ensure low viscosity of the coating material used for coating or close adhesion to the substrate, and hard coating properties are also issues. In order to exhibit hard coating properties, it is necessary to increase the crosslinking density in the coating film, but polyfunctional monomers tend to have high viscosity depending on molecular weight or polarity.

[0004] For example, in Patent Document 1, in order to solve the above problem, a monofunctional (meth)acrylate having a vinyl ether group and / or an allyl ether group and having no hydroxyl group and a trifunctional or higher (meth)acrylate having no hydroxyl group are used. In addition, Patent Document 2, an acrylate mixture containing a specific glycerol triacrylate as a main component, a compound having one or two ethylenically unsaturated groups, and a compound having three or more ethylenically unsaturated groups are used.

[0005] [Prior art literature]

[0006] [Patent Document]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2013-136737

[0008] [Patent Document 2] Japanese Patent Application Publication No. 2019-196461 Summary of the invention

[0009] [Problems to be solved by the invention]

[0010] In Patent Document 1, in order to show hard coating properties, a trifunctional or higher (meth) acrylate is used, so the viscosity of the composition is still high. In addition, in Patent Document 2, the viscosity of the compound with an ethylenically unsaturated group used as a viscosity diluent is about 20 mPa·s, and as a composition, there is a limit to the viscosity reduction method. Therefore, it is difficult to apply according to different coating methods. In addition, if a monofunctional monomer with lower viscosity is used as a diluent as in these prior arts, the viscosity is reduced, but there is a problem of decreased hardness of the coating film and loss of hard coating properties.

[0011] As described above, in order to have excellent coating adaptability regardless of the coating method, it is necessary to reduce the viscosity of the composition as the coating material. If a monofunctional monomer is used as a diluent, the viscosity can be expected to be reduced, but the crosslinking density in the hardened coating film is reduced, so the hard coating property is reduced. When a difunctional monomer is used as a diluent, the viscosity can be reduced to a certain extent while maintaining the hardness, but the effect of reducing the viscosity has a limit.

[0012] Therefore, even a solvent-free type (the content of the solvent is 5% by mass or less) that uses almost no solvent is required to have a sufficiently low viscosity and to form a cured coating film having high hardness, excellent adhesion and curling resistance.

[0013] The problem to be solved by the present invention is to provide an active energy ray-curable composition, a cured coating film, and a laminated film which have low viscosity and can form a cured coating film having high hardness, excellent adhesion and curling resistance even without using almost any solvent.

[0014] [Technical means to solve the problem]

[0015] In order to solve the above-mentioned problems, the present inventors have conducted intensive research and found that by using a low-viscosity polyfunctional (meth)acrylate and a bifunctional monomer having a specific reactive group, even if the content of the organic solvent is 5% by mass or less, the viscosity is sufficiently low (<20 mPa·s), and a hardened coating film with high hardness, excellent adhesion and curling resistance can be formed, thereby completing the present invention.

[0016] That is, the present invention provides the following inventions.

[0017] [1] An active energy ray-curable composition comprising the following components (A) and (B), wherein the component (A) accounts for 40% to 89% by mass, the component (B) accounts for 10% to 60% by mass, and the content of an organic solvent is 5% by mass or less.

[0018] Component (A): a polyfunctional (meth)acrylate having a viscosity of 100 mPa·s or less at 25° C. (excluding component (B))

[0019] Component (B): a bifunctional monomer having a reactive site represented by the following formula (1) and having a viscosity of 10 mPa·s or less at 25° C.

[0020] [Chemistry 1]

[0021]

[0022] [In formula (1), R1, R2, and R3 each independently represent a hydrogen atom or a methyl group, and R4 represents an alkyl chain having 0 to 3 carbon atoms]

[0023] [2] The active energy ray-curable composition according to [1], wherein the component (B) has a vinyl ether group, an allyl ether group, or an isoprene group as the reactive site represented by the formula (1).

[0024] [3] The active energy ray-curable composition according to [1] or [2], further comprising 1% by mass to 25% by mass of the following component (C).

[0025] Component (C): a monofunctional or difunctional monomer having a viscosity of 10 mPa·s or less at 25° C. (excluding component (B))

[0026] [4] The active energy ray-curable composition according to any one of [1] to [3], wherein the viscosity of the component (A) at 25° C. is 70 mPa·s or less.

[0027] [5] The active energy ray-curable composition according to any one of [1] to [4], further comprising a photopolymerization initiator.

[0028] [6] The active energy ray-curable composition according to any one of [1] to [5], further comprising a leveling agent.

[0029] [7] A cured coating film, which is a cured reaction product of the active energy ray-curable composition according to any one of [1] to [6].

[0030] [8] A laminated film comprising the hardened coating film according to [7] and a substrate.

[0031] [Effects of the Invention]

[0032] The active energy ray-curable composition of the present invention has a low viscosity (<20 mPa·s) and therefore has excellent coating adaptability regardless of the coating method, and can form a cured coating film with high hardness, excellent adhesion and curling resistance. Therefore, it can be suitably used as a protective coating agent for various substrate surfaces, a liquid crystal display (LCD), an organic electroluminescence (EL) display (organic light-emitting diode (OLED)), a plasma display panel (PDP) and other flat panel displays (FPD) optical films. DETAILED DESCRIPTION

[0033] In this specification, "acrylate" and "methacrylate" are collectively referred to as "(meth)acrylate", and "(meth)acryl" and "acryl" are collectively referred to as "(meth)acryl". In addition, the active energy ray-curable composition may be simply referred to as "composition".

[0034] [Active energy ray-curable composition]

[0035] The composition of the present invention comprises the following components (A) and (B), wherein the component (A) accounts for 40 to 89% by mass, the component (B) accounts for 10 to 60% by mass, and the content of the organic solvent is 5% by mass or less.

[0036] Component (A): a polyfunctional (meth)acrylate having a viscosity of 100 mPa·s or less at 25° C. (excluding component (B))

[0037] Component (B): a bifunctional monomer having a reactive site represented by the following formula (1) and having a viscosity of 10 mPa·s or less at 25° C.

[0038] [Chemistry 2]

[0039]

[0040] [In formula (1), R1, R2, and R3 each independently represent a hydrogen atom or a methyl group, and R4 represents an alkyl chain having 0 to 3 carbon atoms]

[0041] In addition to the (A) component and the (B) component, an arbitrary component such as the (C) component may be contained.

[0042] ((A) ingredient)

[0043] In the composition of the present invention, by including the component (A) which is a multifunctional (meth)acrylate, the viscosity of the composition can be suppressed and high hardness can be formed when it is hardened. Multifunctional (meth)acrylate refers to all compounds having two or more (meth)acryloyl groups in one molecule (except the component (B)). The viscosity of the component (A) at 25°C is preferably 90 mPa·s or less, more preferably 80 mPa·s or less, and further preferably 70 mPa·s or less.

[0044] Examples of such component (A) include di(meth)acrylate esters such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, poly(1-methylbutylene glycol) di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, and dicyclopentanediol di(meth)acrylate.

[0045] Examples of the component (A) include di(meth)acrylates of caprolactone adducts of hydroxypivalic acid neopentyl glycol, di(meth)acrylates of γ-butyrolactone adducts of hydroxypivalic acid neopentyl glycol, di(meth)acrylates of caprolactone adducts of neopentyl glycol, di(meth)acrylates of caprolactone adducts of butanediol, di(meth)acrylates of caprolactone adducts of cyclohexanedimethanol, di(meth)acrylates of caprolactone adducts of dicyclopentanediol, di(meth)acrylates of caprolactone adducts of bisphenol A, di(meth)acrylates of caprolactone adducts of bisphenol F, dimethyloltricyclodecane di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, di(meth)acrylates of bisphenol A ethylene oxide adducts, and di(meth)acrylates of bisphenol A propylene oxide adducts. esters, di(meth)acrylates such as di(meth)acrylates of bisphenol F ethylene oxide adducts and di(meth)acrylates of bisphenol F propylene oxide adducts; poly(meth)acrylates such as trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide adduct tri(meth)acrylate, trimethylolpropane propylene oxide adduct tri(meth)acrylate, glycerol tri(meth)acrylate, glycerol ethylene oxide adduct tri(meth)acrylate, di-trimethylolpropane ethylene oxide adduct tetra(meth)acrylate, pentaerythritol ethylene oxide adduct tri(meth)acrylate, pentaerythritol ethylene oxide adduct tetra(meth)acrylate, pentaerythritol propylene oxide adduct tri(meth)acrylate, and pentaerythritol propylene oxide adduct tetra(meth)acrylate.

[0046] Examples of the component (A) include tri(meth)acrylates of pentaerythritol caprolactone adducts, tetra(meth)acrylates of pentaerythritol caprolactone adducts, penta(meth)acrylates of dipentaerythritol caprolactone adducts, hexa(meth)acrylates of dipentaerythritol caprolactone adducts, poly(meth)acrylates such as N,N',N"-tri(acryloyloxyethyl)isocyanurate and N,N'-bis(acryloyloxyethyl)-N"-hydroxyethylisocyanurate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, A trimer of an isocyanate compound such as xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, or an adduct polyisocyanate of these diisocyanates with an alkyl polyol (e.g., trimethylolpropane, pentaerythritol, glycerol), or a urethane poly(meth)acrylate in which a hydroxyl-containing (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, or a caprolactone adduct thereof is added to tris(4-isocyanatephenyl)methane.

[0047] Examples of the component (A) include epoxy poly(meth)acrylates obtained by an addition reaction of a polyepoxy compound having a plurality of epoxy groups in a molecule with (meth)acrylic acid, such as bisphenol A glycidyl ether, bisphenol F glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, pentaerythritol polyglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl tri(2-hydroxyethyl)isocyanurate; and polyester poly(meth)acrylates obtained by a condensation reaction of (meth)acrylic acid with two or more kinds of polyols selected from the group consisting of ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol (number of repeating units: 2 to 14), bisphenol A ethylene oxide adducts, trimethylolpropane, and pentaerythritol.

[0048] In addition, examples of the component (A) include epoxy poly(meth)acrylates obtained by an addition reaction of a polyepoxy compound having a plurality of epoxy groups in a molecule with (meth)acrylic acid, such as bisphenol A glycidyl ether, bisphenol F glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, pentaerythritol polyglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl tri(2-hydroxyethyl)isocyanurate; and polyester poly(meth)acrylates obtained by a condensation reaction of (meth)acrylic acid with two or more kinds of polyols selected from the group consisting of ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butanediol, polytetramethylene glycol, bisphenol A ethylene oxide adducts, trimethylolpropane, and pentaerythritol.

[0049] Among them, as component (A), glycidyl triacrylate (GLYTA), ethylene oxide-trimethyl propyl triacrylate (EO-TMPTA), and trimethylpropane triacrylate (TMPTA) are preferred in terms of forming high hardness even with low viscosity. These components (A) may be used alone or in combination of two or more.

[0050] The molecular weight of component (A) is, for example, 190 g / mol or more and 320 g / mol or less, preferably 200 g / mol or more and 300 g / mol or less. By setting it to these ranges, the increase in the viscosity of the composition is further suppressed, and the hardness and curling resistance of the cured coating film are well balanced and improved.

[0051] As the component (A), commercially available products may be used. Examples of such component (A) include Aronix (registered trademark) M-930 (a mixture of glycerol triacrylate containing glycerol diacrylate as the main component, manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-933 (pentaerythritol acrylate, manufactured by Toagosei Co., Ltd.), Miramer M300 (trimethylolpropane triacrylate, manufactured by MIWON Co., Ltd.), Miramer M3130, Miramer M3160, Miramer M3170, Miramer M3161, Miramer M3173, Miramer M3174, Miramer M3175, Miramer M3176, Miramer M3177, Miramer M3178, Miramer M3179, Miramer M3180, Miramer M3190, Miramer M3200, Miramer M3211, Miramer M3213, Miramer M3214, Miramer M3215, Miramer M3216 r) M3190 (trimethylolpropane EO modified triacrylate, manufactured by MIWON), Miramer M360 (trimethylolpropane PO modified triacrylate, manufactured by MIWON), Miramer M320 (glycerol propoxy triacrylate, manufactured by MIWON), Miramer M4004 (pentaerythritol EO modified tetraacrylate, manufactured by MIWON), TMPTA (trimethylolpropane triacrylate, manufactured by Daicel Allnex), EBECRYL 160S (trimethylolpropane ethoxy triacrylate, manufactured by Daicel Allnex), OTA480 (glycerol propoxy triacrylate, manufactured by Daicel Allnex), etc.

[0052] As described above, the ratio of component (A) to the total amount of the composition is 40% to 89% by mass, preferably 45% to 85% by mass, and more preferably 50% to 80% by mass. Since the ratio of component (A) is as described above, the increase in the viscosity of the composition is further suppressed, and the hardness and curling resistance of the cured coating film are well balanced and improved.

[0053] ((B) ingredient)

[0054] The component (B) is a bifunctional monomer having a reactive site represented by the following formula (1) and having a viscosity at 25° C. of 10 mPa·s or less.

[0055] [Chemistry 3]

[0056]

[0057] [In formula (1), R1, R2, and R3 each independently represent a hydrogen atom or a methyl group, and R4 represents an alkyl chain having 0 to 3 carbon atoms]

[0058] The reactive site represented by formula (1) is one of the functional groups in the bifunctional monomer.

[0059] The (B) component preferably has a vinyl ether group, an allyl ether group, or an isoprene group as the reactive site represented by formula (1). In the composition of the present invention, by including the (B) component, the viscosity in the composition can be further reduced, while suppressing the reduction in hardness, and a hardened coating film having excellent adhesion or curling resistance can be prepared. In the (B) component, any one of the vinyl ether group and the allyl ether group can be included, or both can be included. A difunctional monomer refers to all compounds having two reactive groups (for example, reactive vinyl groups such as vinyl ether or allyl ether groups, or (meth) acryloyl groups) in one molecule. The viscosity of the (B) component at 25°C is preferably 8 mPa·s or less, more preferably 6 mPa·s or less, and further preferably 4 mPa·s or less.

[0060] Examples of the compound having a vinyl ether group as component (B) include 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA), 2-(2-vinyloxyethoxy)ethyl methacrylate (VEEM), diethylene glycol divinyl ether (DEGDVE), 1,4-butanediol divinyl ether (BDVE), cyclohexanedimethanol divinyl ether (CHDVE), and triethylene glycol divinyl ether (TEGDVE). Among them, 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA), diethylene glycol divinyl ether (DEGDVE), isoprenyl methacrylate (IPEMA), and diisoprene glycerin ether (DPNG) are preferred.

[0061] Examples of the compound having an allyl ether group as component (B) include allyl ether of α-hydroxymethyl acrylate (RHMA) (AOMA), 1,3-diallyloxy-2-propanol, trimethylolpropane diallyl ether, etc. Among them, allyl ether of α-hydroxymethyl acrylate (RHMA) (AOMA) is preferred.

[0062] Examples of the compound having an isoprene group as the component (B) include isoprene methacrylate (IPEMA) and the like. Among them, isoprene methacrylate (IPEMA) is preferred. These components (B) may be used alone or in combination of two or more.

[0063] The molecular weight of component (B) is, for example, 130 g / mol or more and 220 g / mol or less, preferably 150 g / mol or more and 200 g / mol or less. By setting it to these ranges, the increase in the viscosity of the composition is further suppressed, and the hardness and curling resistance of the cured coating film are well balanced and improved.

[0064] As the component (B), a commercially available item may be used. Examples of such component (B) include 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA (registered trademark), manufactured by Nippon Catalyst Co., Ltd.), cyclopolymerizable monomer (AOMA (registered trademark), manufactured by Nippon Catalyst Co., Ltd.), diethylene glycol divinyl ether (DEGDVE, manufactured by Nippon Carbide Industries, Ltd.), 1,4-butanediol divinyl ether (BDVE, manufactured by Nippon Carbide Industries, Ltd.), cyclohexanedimethanol divinyl ether (CHDVE, manufactured by Nippon Carbide Industries, Ltd.), triethylene glycol divinyl ether (TEGDVE, manufactured by Nippon Carbide Industries, Ltd.), isoprene methacrylate (IPEMA, manufactured by Kuraray Co., Ltd.), NEOALLYL (registered trademark) T-20 (trimethylolpropane diallyl ether, manufactured by Osaka Soda Co., Ltd.), IPEMA (registered trademark) (manufactured by Kuraray Co., Ltd.), and DPNG (registered trademark) (manufactured by Kuraray Co., Ltd.).

[0065] As described above, the (B) component is 10% to 60% by mass, preferably 15% to 50% by mass, and more preferably 20% to 40% by mass relative to the total amount of the composition. Since the proportion of the (B) component is as described above, the increase in the viscosity of the composition is further suppressed, and the hardness and curling resistance when the cured coating film is formed are well balanced and improved.

[0066] ((C) ingredient)

[0067] The component (C) is an optional component and is a monofunctional or difunctional monomer having a viscosity of 10 mPa·s or less at 25°C other than the component (B). The component (C) is a general low-viscosity monofunctional or difunctional monomer other than the component (B) and is a component that can be included within a range that does not impair the effects of the present invention. The viscosity of the component (C) at 25°C is preferably 8 mPa·s or less, more preferably 6 mPa·s or less, and further preferably 4 mPa·s or less.

[0068] Examples of the monofunctional monomer as the component (C) include acryloyl morpholine (ACMO), 4-hydroxybutylacrylate (4-HBA), ethylenedioxyphenol acrylate (Ph(EO)2A), ethylenedioxyethyl acrylate (EOEOEA), isoamyl acrylate (IAA), lauryl acrylate (LA), stearyl acrylate (SA), ethoxy-diethylene glycol acrylate (ECA), methoxytriethylene glycol acrylate (MTGA), 2-ethylhexyl diethylene glycol acrylate (EHDGAT), methoxy-polyethylene glycol acrylate, and methoxy dipropylene glycol acrylate. acrylate, DPMA), phenoxyethyl acrylate, phenoxyethyl acrylate, tetrahydrofurfurylacrylate (Tetrahydrofurfurylacrylate, THFA), isobornyl acrylate (Isobornyl acrylate, IBXA), 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, etc. Among them, acryloyl morpholine (ACMO) and 4-hydroxybutyl acrylate (4-HBA) are preferred.

[0069] Examples of the bifunctional monomer as component (C) include hexanediol diacrylate (HDDA), ethylene glycol EO-modified diacrylate (HD(EO)DA), hydroxypivalic acid neopentyl glycol diacrylate (HPNDA), propylene glycol PO-modified diacrylate (NPG(PO)2DA), triethylene glycol diacrylate (TEGDA), tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), PEG200# diacrylate, polytetramethylene glycol diacrylate (PTMGDA), neopentyl glycol diacrylate (NPG(PO)2DA), and polytetramethylene glycol diacrylate (PTMGDA). diacrylate (NPGDA), 3-methyl-1,5-pentanediol diacrylate, 1,9-nonanediol diacrylate (1,9-Nonanediol Diacrylate, 1,9-NDDA), etc. Among them, hexanediol diacrylate (HDDA), triethylene glycol diacrylate (TEGDA), 1,9-nonanediol diacrylate (1,9-NDDA) are preferred. These (C) components may be used alone or in combination of two or more.

[0070] The molecular weight of component (C) is, for example, 120 g / mol or more and 240 g / mol or less, preferably 120 g / mol or more and 235 g / mol or less. By setting the molecular weight in these ranges, the viscosity of the composition is further suppressed, and the hardness and curling resistance of the cured coating film are well balanced.

[0071] As the component (C), commercially available products may be used. Examples of such component (C) include Miramer M200 (hexanediol diacrylate, manufactured by MIWON), Biscoat #260 (1,9-nonanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Light Acrylate 3EG-A (triethylene glycol diacrylate, manufactured by Kyoeisha Chemical Co., Ltd.), and acryloylmorpholine (manufactured by KJ Chemical Co., Ltd.).

[0072] When the composition of the present invention contains the component (C), the content thereof is, for example, 1 mass % to 25 mass %, or preferably 2 mass % to 20 mass %.

[0073] (Photopolymerization Initiator)

[0074] The composition of the present invention may contain a photopolymerization initiator.

[0075] Examples of the photopolymerization initiator include various benzophenones such as benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, Michler's ketone, and 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone; xanthone and thioxanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone; various acyloin ethers such as benzoin, benzoin methyl ether, benzoin isoethyl ether, and benzoin isopropyl ether; benzyl, dibenzoyl, benzoin-1-yl, benzoin-2-yl, benzoin-3-yl, benzoin-4-yl, benzoin-5-yl, benzoin-6-yl, benzoin-7-yl, benzoin-8-yl, benzoin-9-yl, benzoin-1-yl, benzoin-2 ...3-yl, benzoin-5-yl, benzoin-6-yl, benzoin-7-yl, benzoin-8-yl, benzoin-9-yl, benzoin-1-yl, benzoin-1-yl, benzoin-2-yl, benzoin-3-yl, benzoin-4-yl, benzoin-5-yl, benzoin-6-yl, α-diketones such as acetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate; 3,3'-carbonyl-bis(7-diethylamino)coumarin, 1-hydroxycyclohexylphenyl ketone, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-〔4-(methylthio)phenyl〕-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane- 1-ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-〔4-(2-hydroxyethoxy)phenyl〕-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-benzoyl-4'-methyl dimethyl sulfide, 2,2'-diethoxyacetophenone, benzyl dimethyl ketone, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate Ester, bis(4-dimethylaminophenyl)ketone, p-dimethylaminoacetophenone, α,α-dichloro-4-phenoxyacetophenone, amyl-4-dimethylaminobenzoate, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2,4-bis-trichloromethyl-6-[bis-(ethoxycarbonylmethyl)amino]phenyl-S-triazine, 2,4-bis-trichloromethyl-6-(4-ethoxy)phenyl-S-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-ethoxy)phenyl-S-triazine anthraquinone, 2-tert-butyl anthraquinone, 2-amyl anthraquinone, β-chloroanthraquinone, etc. These photopolymerization initiators may be used alone or in combination of two or more.

[0076] In addition, among the photopolymerization initiators, one or a mixture of two or more selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanol and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one is preferred because it exhibits activity to light having a wider wavelength range and can improve the curability of the cured coating film of the composition.

[0077] The molecular weight of the photopolymerization initiator is not particularly limited, and is, for example, 50 to 500, preferably 50 to 300, and more preferably 50 to 210. From the viewpoint of reducing the viscosity of the composition, it is preferred to use a photopolymerization initiator having a lower molecular weight.

[0078] Examples of commercially available photopolymerization initiators include: "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2 022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM); "KAYACURE-DETX", "KAYACURE-MBP", "KAYACURE-DMBI", "KAYACURE-EPA", "KAYACURE-OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure-10", "Vicure-55" (manufactured by Stoffa Chemical Co., Ltd.); "Trigonal P1" (manufactured by Akzo Chemical); "Sandoray 1000" (manufactured by SANDOZ); "Deap" (manufactured by APJOHN); "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Wardblenkinsop); "Runtecure-1104" (manufactured by Runtec), etc.

[0079] The amount of the photopolymerization initiator added is an amount that can fully exert its function as a photopolymerization initiator, and is preferably within a range that does not cause precipitation of crystals or deterioration of coating properties. Specifically, it is preferably in the range of 0.05 to 20 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass, relative to 100 parts by mass of the resin solid content in the composition.

[0080] (Leveling agent)

[0081] The composition of the present invention may also contain a leveling agent. As the leveling agent, various existing leveling agents can be used. The leveling agent is an additive that has the function of adjusting the fluidity of the composition and making the coating film obtained by coating the composition flatter, and examples thereof include silicone-based, polyacrylate-based, and perfluoroalkyl-based leveling agents.

[0082] As the leveling agent, commercially available products can also be used, and specific examples thereof include DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, and FZ2123 (all of which are manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, and KF6001 (all of which are manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (all of which are manufactured by Momentive Performance Materials Japan Co., Ltd. Japan), fluorinert (registered trademark) FC-72, fluorinert (registered trademark) FC-40, fluorinert (registered trademark) FC-43, fluorinert (registered trademark) FC-3283 (all of the above are manufactured by Sumitomo 3M (Co., Ltd.)), Megafac (registered trademark) R-08, Megafac (registered trademark) R-30, Megafac (registered trademark) R-90, Megafac (registered trademark) F-410, Megafac (registered trademark) F-411, Megafac (registered trademark) F-443, Megafac (registered trademark) Megafac (registered trademark) F-445, Megafac (registered trademark) F-470, Megafac (registered trademark) F-477, Megafac (registered trademark) F-479, Megafac (registered trademark) F-482, Megafac (registered trademark) F-483, Megafac (registered trademark) F-556 (all manufactured by DIC (Co., Ltd.)), Eftop (trade name) EF301, Eftop (trade name) EF303, Eftop (trade name) EF351, Eftop (trade name) EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.),Surflon (registered trademark) S-381, Surflon (registered trademark) S-382, Surflon (registered trademark) S-383, Surflon (registered trademark) S-393, Surflon (registered trademark) SC-101, Surflon (registered trademark) SC-105, Surflon (registered trademark) KH-40, Surflon (registered trademark) SA-100 (all of which are manufactured by AGC Seimi Chemical (AGC Seimi Chemical) Co., Ltd.), trade name E1830, trade name E5844 (Daikin Fine Chemicals Co., Ltd. Chemical) Research Institute (Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-331, BYK-333, BYK-345, BYK-348, BYK-349, BYK-352, BYK-353, BYK-356, BYK-361N, BYK-377, BYK-378, BYK-399 , BYK-3450, BYK-3451, BYK-3455, BYK-UV3500, BYK-UV3505, BYK-UV3510, BYK-UV3530, BYK-UV3535, BYK-UV3570, BYK-UV3575, and BYK-UV3576 (all trade names: manufactured by BYK-Chemie Japan Co., Ltd.). The leveling agent can be used alone or in combination of two or more.

[0083] The content of the leveling agent is preferably in the range of 0.01 to 0.5 parts by mass, more preferably in the range of 0.05 to 0.3 parts by mass, and particularly preferably in the range of 0.08 to 0.2 parts by mass, relative to 100 parts by mass of the resin solid content. If the content of the leveling agent is within the above range, the composition can be smoothly applied to the substrate, and a composition capable of forming a cured coating film having high hardness, excellent adhesion and curling resistance can be obtained.

[0084] (Organic Solvent)

[0085] In the composition of the present invention, the content of the organic solvent is 5% by mass or less, but as long as the viscosity suitable for coating is maintained, the less the content of the organic solvent, the better from the perspective of VOC reduction, preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. There are no particular restrictions on the organic solvent, and examples thereof include: aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and tert-butyl alcohol; esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; glycol ethers such as propylene glycol monomethyl ether. These organic solvents can be used alone or in combination of two or more.

[0086] The composition of the present invention may further contain other additives within the range that does not hinder the solution of the problem of the present invention. Examples of other additives include photosensitizers, ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, silane coupling agents, phosphate compounds, organic beads, inorganic fine particles, inorganic fillers, rheology control agents, defoaming agents, antifogging agents, colorants, and the like.

[0087] Examples of the photosensitizer include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, and sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothiouronium-p-toluenesulfonate.

[0088] Examples of the ultraviolet absorber include triazine derivatives such as 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; 2-(2'-xanthenecarboxyl-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxyl-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbers may be used alone or in combination of two or more.

[0089] Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate-based antioxidants.

[0090] Examples of the silicon-based additive include polyorganosiloxanes having an alkyl group or a phenyl group, such as methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, a fluorine-modified dimethylpolysiloxane copolymer, and an amino-modified dimethylpolysiloxane copolymer.

[0091] As a fluorine-based additive, "Megaface" series manufactured by DIC Corporation etc. are mentioned, for example.

[0092] Examples of the silane coupling agent include vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane, 3-glycidyloxypropyl triethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, Vinyl silane coupling agents such as propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special aminosilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxysilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, and vinyltri(2-methoxyethoxy)silane.

[0093] Examples of the phosphate compound include compounds having a (meth)acryloyl group in the molecular structure, and examples of commercially available products include "Kayamer PM-2" and "Kayamer PM-21" manufactured by Nippon Kayaku Co., Ltd., "Light Ester P-1M", "Light Ester P-2M", and "Light Acrylate P-1A (N)" manufactured by Kyoeisha Chemical Co., Ltd., "SIPOMER PAM 100", "SIPOMER PAM 200", "SIPOMER PAM 300", and "SIPOMER PAM 4000" manufactured by Solvay, "Biscoat #3PA" and "Biscoat #3PMA" manufactured by Osaka Organic Chemical Industry Co., Ltd., and "New Frontier" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. "Frontier S-23A"; "SIPOMER PAM 5000" manufactured by SOLVAY, which is a phosphate ester compound having an allyl ether group in its molecular structure, etc.

[0094] Examples of organic beads include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyvinyl fluoride resin beads, polyethylene resin beads, etc. These organic beads may be used alone or in combination of two or more. In addition, the average particle size of these organic beads is preferably in the range of 1 μm to 10 μm.

[0095] Examples of inorganic particles include particles of silicon dioxide, aluminum oxide, zirconium oxide, titanium dioxide, barium titanate, antimony trioxide, etc. These inorganic particles can be used alone or in combination of two or more. In addition, the average particle size of these inorganic particles is preferably in the range of 10 nm to 300 nm, and more preferably in the range of 50 nm to 150 nm.

[0096] In the case of containing inorganic particles, a dispersing aid can be used. As the dispersing aid, for example, phosphate compounds such as isopropyl acylated phosphate, triisodecyl phosphate, and ethylene oxide modified phosphoric acid dimethacrylate can be listed. In addition, commercial products as dispersing aids, for example, can be listed: "Kayamer PM-21" and "Kayamer PM-2" manufactured by Nippon Kayaku Co., Ltd., "Light Ester P-2M" manufactured by Kyoeisha Chemical Co., Ltd., etc.

[0097] [Hard coating]

[0098] The hardened coating film of the present invention is obtained by hardening the active energy ray-curable composition, and is usually formed by applying the active energy ray-curable composition on a substrate and hardening it as described below. Examples of the hardening method of the active energy ray-curable composition include a heating method and a method of irradiating an active energy ray such as ultraviolet rays.

[0099] As a heating method, the hardening can be achieved by heating in a temperature range of 60°C to 200°C for 0.5 minutes to 60 minutes. In addition, as a method of irradiating active energy rays, for example, in the case of ultraviolet rays, it can be hardened by using a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, an LED or other ultraviolet lamp as a source of ultraviolet rays. As active energy rays, in addition to ultraviolet rays, ionizing radiation such as electron beams, α-rays, β-rays, and γ-rays can also be used. The irradiation amount of active energy rays is preferably 0.05 J / cm 2 ~5J / cm 2 The range is more preferably 0.1 J / cm 2 ~3J / cm 2 The range is particularly preferably 0.1 J / cm 2 ~1J / cm 2 range.

[0100] [Laminated film]

[0101] The laminated film of the present invention has the cured coating film on a substrate. As a method for producing the laminated film of the present invention, for example, there is a method in which an active energy ray-curable resin composition is applied to at least one surface of a substrate and then irradiated with active energy rays.

[0102] As substrate, for example, metal substrate, plastic substrate, glass substrate, paper substrate, wood substrate, fibrous substrate, etc. can be cited. Among these substrates, plastic substrate is preferred in terms of excellent adhesion. As the material of plastic substrate, polyethylene terephthalate, polyester, acrylic resin (polymethyl methacrylate, etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS (Acrylonitrile Butadiene Styrene) resin), composite resin of ABS resin and polycarbonate, polystyrene, polyurethane, epoxy resin, polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (cycloolefin polymer (Cyclo Olefin Polymer, COP)) etc.), triacetyl cellulose (Triacetyl Cellulose, TAC), polyimide, etc. can be cited. As plastic substrate, for example, plastic molded products such as mobile phone, home appliance products, automobile interior and exterior materials, office automation (Office Automation, OA) equipment can be cited. In addition, film substrates with plastic as raw materials can also be used.

[0103] Examples of methods for applying the active energy ray-curable composition include coating methods using a gravure coater, a roll coater, a notch wheel coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a spray coater, a flow coater, a spin coater, dipping, screen printing, spraying, brush coating, an applicator, a rod coater, etc. The film thickness of the coating film formed using the active energy ray-curable composition can be appropriately adjusted depending on the intended use, but is generally preferably in the range of 0.01 μm to 50 μm.

[0104] The laminated film of the present invention may have a functional film layer such as an antireflection film, a diffusion film, or a polarizing film in addition to the substrate and the cured coating film.

[0105] The laminated film of the present invention can be used as a coating layer to protect the surface of a substrate because it has a hardened coating film with high hardness and excellent curling resistance. For example, it can be suitably used as an optical film used in flat panel displays (FPD) such as liquid crystal displays (LCDs), organic EL displays (OLEDs), and plasma displays (PDPs). In addition, articles having the laminated film of the present invention include plastic molded products such as mobile phones, home appliance frames, automobile bumpers, and OA equipment.

[0106] [Example]

[0107] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In addition, "%" in the compositions of the following Examples means "mass %" and "parts" means "mass parts".

[0108] (Example 1: Preparation of active energy ray-curable composition (1))

[0109] An active energy ray-curable composition (1) was prepared by uniformly mixing 80 parts of glyceryl triacrylate ("Aronix M-930" manufactured by Toagosei Co., Ltd., hydroxyl value: 30 mgKOH, viscosity 30 mPa·s), 20 parts of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA (registered trademark), manufactured by Nippon Catalyst Co., Ltd.), 0.1 parts of a leveling agent ("BYK-356" manufactured by BYK-Chemie Japan Co., Ltd.), and 5 parts of a photopolymerization initiator ("Runtecure 1104" manufactured by Runtec Chemical Co., Ltd.).

[0110] (Example 2 to Example 11 and Comparative Example 1 to Comparative Example 9: Preparation of Active Energy Ray-Curable Compositions (2) to (11) and Active Energy Ray-Curable Compositions (R1) to (R9))

[0111] Active energy ray-curable compositions (2) to (11) and active energy ray-curable compositions (R1) to (R9) were obtained by the same method as in Example 1 except that the composition of each component was changed as described in Table 1 or Table 2.

[0112] The following measurements and evaluations were performed using the active energy ray-curable compositions obtained in the examples and comparative examples.

[0113] [Viscosity measurement]

[0114] The viscosity (mPa·s) of the active energy ray-curable composition obtained in each of Examples and Comparative Examples at 25° C. was measured using an E-type viscometer (“TV-25” manufactured by Toki Sangyo Co., Ltd.).

[0115] [Preparation of samples for evaluation]

[0116] The active energy ray-curable composition of each example was applied to a TAC substrate having a thickness of 40 μm ("FTTD40UC" manufactured by Fujifilm Corporation) using a bar coater, and an ultraviolet irradiation device (manufactured by Eyegraphics Co., Ltd., a high-pressure mercury lamp) was used in a nitrogen atmosphere to irradiate the substrate at a light intensity of 150 mJ / cm 2 The irradiation was performed to obtain a TAC substrate having a cured coating film with a thickness of 5 μm to 6 μm, which was used as an evaluation sample.

[0117] [Evaluation of Adhesion]

[0118] A cutter was used to cut slits on the surface of the hardened coating film of the evaluation sample obtained in the above-described process to produce 100 1 mm × 1 mm checkerboards, and a cellophane tape ("Cellotape" (registered trademark) CT-18 manufactured by Nichiban Co., Ltd.) was pasted thereon. The result was then quickly peeled off, and the number of checkerboards remaining without being peeled off was counted. The test was evaluated according to the following criteria, with A being considered acceptable and B to D being considered unacceptable.

[0119] A: The number of remaining squares on the board is 100.

[0120] B: The number of remaining squares is greater than 95 and less than 100.

[0121] C: The number of remaining squares is 10 or more and less than 95.

[0122] D: The number of remaining squares on the board is less than 10.

[0123] [Evaluation of hardness: pencil hardness]

[0124] The hardness of the surface of the cured coating film of the curable resin composition was measured under a load of 500 g in accordance with JIS K5600-5-4 [Scratch hardness (pencil method)]. One hardness was measured five times, and the hardness measured four or more times without damage was regarded as the hardness of the cured coating film.

[0125] In addition, the hardness of pencils is in descending order of hardness: 3H, 2H, H, F, HB, B.

[0126] [Abrasion resistance evaluation: Steel Wool (SW) test]

[0127] The ground contact area of ​​the evaluation sample obtained in the above is 4 cm 2 #0000 steel wool was mounted on a load plate (2 cm×2 cm square), a load of 1000 g was placed, and the test piece was moved back and forth 10 times. Then, the surface was visually inspected for scratches.

[0128] [Evaluation of bending resistance: mandrel test]

[0129] The evaluation sample obtained in the above was wound around a 10 mm φ mandrel test bar with the coated surface facing outward to check whether the hardened coating film had cracks or ruptures. The mandrel diameter was changed to a smaller diameter until the hardened coating film had cracks or ruptures, and the value of the smallest mandrel that did not have cracks or ruptures was evaluated.

[0130] The evaluation results are shown in Tables 1 and 2. The viscosity (mPa·s) of each component is described for reference.

[0131] [Table 1]

[0132]

[0133] [Table 2]

[0134]

[0135] Abbreviations in Tables 1 and 2 other than those described above represent the following compounds.

[0136] Miramer M300: Trimethylolpropane triacrylate (Miramer M300, manufactured by MIWON)

[0137] Aronix M-305: A reaction product of pentaerythritol with pentaerythritol triacrylate / tetraacrylate as the main component and acrylic acid ("Aronix M-305" manufactured by Toagosei Co., Ltd.)

[0138] Luxydir 17-806: Luxydir 17-806 manufactured by DIC

[0139] DEGDVE: "Diethylene glycol divinyl ether" manufactured by Nippon Carbide Industries

[0140] TEGDVE: "Triethylene glycol divinyl ether" manufactured by BASF

[0141] AOMA: Cyclopolymerizable monomer, "AOMA (registered trademark)" manufactured by Nippon Catalyst Co., Ltd.

[0142] IPEMA: Isoprene methacrylate, "IPEMA (registered trademark)" manufactured by Kuraray

[0143] Aronix M-920: Glyceryl diacrylate / triacrylate ("Aronix M-920" manufactured by Toagosei Co., Ltd.)

[0144] Miramer M200: Hexanediol diacrylate (Miramer M200, manufactured by MIWON)

[0145] Biscoat #260: 1,9-nonanediol diacrylate (1,9-NDDA), "Biscoat #260" manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0146] Light Acrylate 3EG-A: Triethylene glycol diacrylate ("Light Acrylate 3EG-A" manufactured by Kyoeisha Chemical Co., Ltd.)

[0147] ACMO: Acryloylmorpholine (ACMO (registered trademark), manufactured by KJ Chemical Co., Ltd.)

[0148] Miramer M221: Dipropylene glycol diacrylate ("Miramer M221" manufactured by MIWON)

[0149] 4-HBA: 4-Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0150] DMAA: N,N-dimethylacrylamide (manufactured by KJ Chemical Co., Ltd., DMAA (registered trademark))

[0151] Runtecure 1104: 1-hydroxy-cyclohexylphenyl-ketone (manufactured by IGM Resins, photopolymerization initiator; Runtecure (registered trademark) 1104)

[0152] BYK-356: Leveling agent (polyacrylate-based surface conditioning agent) ("BYK-356" manufactured by BYK-Chemie Japan)

[0153] According to the evaluation results of the hardened coatings using the compositions of Examples 1 to 17, it is confirmed that the composition of the present invention has low viscosity even without the use of a solvent and can form a hardened coating having excellent adhesion, hardness, and curling resistance. On the other hand, in Comparative Example 1 in which the content of component (B) is less than 10% by mass, the viscosity of the coating material (composition) is high and the curling resistance is reduced. In Comparative Examples 2 to 6 and 8 that do not contain component (B), the viscosity of the composition is increased by the combination of the compounds, or the hardness or scratch resistance of the hardened coating is reduced. In addition, in Comparative Examples 7 and 9 that do not contain component (A), similarly, the viscosity of the composition is increased, or the hardness or scratch resistance of the hardened coating is reduced.

Claims

1. An active energy ray-curable composition comprising the following components (A) and (B), wherein the component (A) accounts for 40% to 89% by mass, the component (B) accounts for 10% to 60% by mass, and the content of the organic solvent is 5% by mass or less, (A) Component: a polyfunctional (meth)acrylate having a viscosity of 100 mPa·s or less at 25° C., wherein: (B) ingredients, Component (B): a bifunctional monomer having a reactive site represented by the following formula (1) and having a viscosity of 10 mPa·s or less at 25° C. In formula (1), R1, R2, and R3 each independently represent a hydrogen atom or a methyl group, and R4 represents an alkyl chain having 0 to 3 carbon atoms.

2. The active energy ray-curable composition according to claim 1, wherein The component (B) has a vinyl ether group, an allyl ether group, or an isoprene group as the reactive site represented by the formula (1).

3. The active energy ray-curable composition according to claim 1 or 2, further comprising 1% by mass to 25% by mass of the following component (C), Component (C): a monofunctional or difunctional monomer having a viscosity of 10 mPa·s or less at 25° C., wherein: (B) Components excluded.

4. The active energy ray-curable composition according to claim 1 or 2, wherein The viscosity of the component (A) at 25° C. is 70 mPa·s or less. The active energy ray-curable composition according to claim 1 or 2, comprising a photopolymerization initiator. 6 . The active energy ray-curable composition according to claim 1 , further comprising a leveling agent.

7. A hardened coating film which is a hardening reaction product of the active energy ray-curable composition according to claim 1 or 2.

8. A laminated film comprising the hardened coating film according to claim 7 and a substrate.

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