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

Abstract

To provide an active energy ray-curable resin composition that, when cured, exhibits high hardness, excellent appearance, scratch resistance, flexibility, curl resistance, long-term stability, and adhesion, and further exhibits excellent recoatability, and to provide a cured coating film, and a laminated film.SOLUTION: An active energy ray-curable resin composition of the present invention comprises the following components (A) to (D), wherein the ratio of the component (A) is 30 mass% or more in the total solid content, and the ratio of the component (B) is 1 to 20 mass% in the total solid content. It is preferable to contain a photopolymerization initiator as the component (E). Component (A): a polyfunctional urethane (meth)acrylate having three or more functional groups; Component (B): a (meth)acrylate having two or more functionalities, in which the Tg of a homopolymer is 10°C or lower, modified with an alkylene oxide; (C): an antistatic agent; and Component (D): a solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable resin composition, a coating film obtained by curing the composition, and a laminate film including the coating film. [Background technology]

[0002] In recent years, displays that can be deformed, such as by bending or rolling, have been developed for use in smartphones and other devices. However, glass, which is generally used to prevent scratches on the display surface, is hard and will break when bent, making it unsuitable for foldable displays. Therefore, plastic films with a scratch-resistant hard coat layer are being considered as surface protection layers for foldable displays instead of glass.

[0003] In order to impart scratch resistance to the hard coat, which is a cured product of a photocurable composition, in the above-mentioned plastic film, it is generally necessary to increase the crosslink density in the hard coat, and multifunctional acrylate-based materials are often used. However, it is widely known that increasing the crosslink density in the hard coat deteriorates the flexibility and elongation of the film. As such, there is a trade-off between the scratch resistance and flexibility of the hard coat, and the challenge is to achieve both properties at the same time.

[0004] To solve the above problems, for example, in the following Patent Document 1, a perfluoropolyether containing a poly(oxyperfluoroalkylene) group and silica particles whose surfaces are modified with a silane coupling agent having a nitrogen-containing proton-donating functional group are blended with an oxyethylene-modified or lactone-modified active energy ray-curable polyfunctional monomer. In Patent Document 1, a certain degree of flexibility is imparted by a specific polyfunctional monomer, and by blending silica and a fluorine-based additive, the slipperiness of the coating surface is increased, and scratch resistance is imparted without reducing flexibility. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2020 / 162323 [Patent Document 2] Japanese Patent Application Publication No. 2023-70690 [Patent Document 3] Patent Publication No. 2021-56512 [Patent Document 4] Japanese Patent Application Publication No. 2017-171794 [Patent Document 5] Japanese Patent Application Laid-Open No. 2014-122987 Summary of the Invention [Problem to be solved by the invention]

[0006] Furthermore, in recent hard coat films used in foldable displays, a functional layer such as an anti-reflection layer may be laminated on the hard coat layer as a top coat. In the case of such laminated coating films, the hard coat layer is important not only for its adhesion to the undercoat, which is the substrate, but also for its adhesion to the top coat, i.e., its recoatability.

[0007] The inventors have studied the above prior art documents in light of the recoatability described above and have found that Patent Document 1 in particular uses a fluorine-based additive to increase the surface slipperiness, which significantly reduces the surface wettability, potentially resulting in problems with recoatability. They have also found that the use of silica raises concerns about poor compatibility with antistatic agents such as quaternary ammonium salts and reduced stability over time of the coating material.

[0008] The problem to be solved by the present invention is to provide an active energy ray-curable resin composition, a cured coating film, and a laminate film which, when formed into a cured product layer, have high hardness and good appearance, are excellent in abrasion resistance, flexibility, curl resistance, stability over time, and adhesion, and further have excellent recoatability. [Means for solving the problem]

[0009] As a result of intensive research to solve the above problems, the inventors discovered that scratch resistance can be achieved by using a hard multifunctional urethane acrylate as the main component, while flexibility can be imparted without sacrificing scratch resistance by adding a small amount of a specific acrylate with a long EO chain and low Tg. They also discovered that the use of an antistatic agent such as a quaternary ammonium salt in combination with the compound can impart high antistatic properties while maintaining appearance such as transparency, making it possible to use the compound in recoating applications.

[0010] The mechanism of the present invention is presumed to be as follows. The hard multifunctional urethane acrylate and the low Tg acrylate containing EO chains undergo phase separation within the film, forming an island-sea structure that improves flexibility without sacrificing scratch resistance. The low Tg soft component does not copolymerize with the hard urethane acrylate in the coating film, but exists in a state close to a homopolymer, which relieves stress during bending and tensile tests and suppresses the occurrence of cracks. Furthermore, there is no need to use components that affect the surface slipperiness, such as fluorine-based additives, making it easy to recoat.

[0011] That is, the present invention provides the following inventions. [1] An active energy ray-curable resin composition comprising the following components (A) to (D), wherein the ratio of component (A) is 30 mass % or more of the total solid content, and the ratio of component (B) is 1 to 20 mass % of the total solid content: (A) Component: Trifunctional or higher polyfunctional urethane (meth)acrylate Component (B): an alkylene oxide-modified di- or higher functional (meth)acrylate having a homopolymer Tg of 10°C or less Component (C): Antistatic agent (D) Component: Solvent [2] The active energy ray-curable resin composition according to [1], which contains a photopolymerization initiator as component (E). [3] A coating film which is a cured reaction product of the active energy ray-curable resin composition according to [1] or [2]. [4] A laminated film comprising the coating film described in [3] and a substrate. [Effects of the Invention]

[0012] The active energy ray-curable resin composition of the present invention can form a cured coating film that has good appearance, high hardness, and excellent scratch resistance, flexibility, curl resistance, stability over time, adhesion, and recoatability. Therefore, it can be suitably used as a protective coating agent for various substrate surfaces. Furthermore, a laminate film having the cured coating film has excellent scratch resistance, curl resistance, and adhesion, as well as high flexibility and resistance to cracking when bent or wound up. Furthermore, it has impact resistance that makes it difficult to crack even when an object falls on the film. DETAILED DESCRIPTION OF THE INVENTION

[0013] In this specification, "acrylate" and "methacrylate" are collectively referred to as "(meth)acrylate", and "(meth)acryloyl" and "acryloyl" are collectively referred to as "(meth)acryloyl". In addition, an active energy ray-curable resin composition may be simply referred to as "composition".

[0014] [Active energy ray curable resin composition] The composition of the present invention comprises the following components (A) to (D), with the proportion of component (A) being 30% by mass or more of the total solid content, and the proportion of component (B) being 1 to 20% by mass of the total solid content. (A) Component: Trifunctional or higher polyfunctional urethane (meth)acrylate Component (B): an alkylene oxide-modified di- or higher functional (meth)acrylate having a homopolymer Tg of 10°C or less Component (C): Antistatic agent (D) Component: Solvent The composition of the present invention may contain components other than the above components (A) to (D), each of which will be described in detail below.

[0015] [Component (A)] The tri- or higher functional polyfunctional urethane (meth)acrylate of component (A) is a resin having a urethane bond and three or more acrylic groups, and preferably has an aliphatic structure for superior flexibility. Examples of the aliphatic structure include an alkyl group having 4 to 20 carbon atoms, which may have a linear or branched chain, and an alicyclic structure having 6 to 12 carbon atoms, such as cyclohexane. Component (A) can be used alone or in combination of two or more types.

[0016] The number of acrylate functional groups in component (A) is three or more, preferably 4 to 15, and more preferably 5 to 12. By making it three or more functional groups, the crosslink density can be increased when a cured coating film is formed, and high hardness can be achieved.

[0017] Component (A) can be obtained, for example, by reacting polyisocyanate (a1) with compound (a2) having a hydroxyl group and a (meth)acryloyl group. A compound (a3) having a hydroxyl group other than compound (a2) may also be used as a reaction raw material.

[0018] The polyisocyanate (a1) is not particularly limited as long as it can form the component (A) used in the present invention having a specific content of (meth)acryloyl groups, and can be appropriately selected depending on the purpose. Examples of the diisocyanate include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; and isocyanurate-modified compounds, biuret-modified compounds, and allophanate-modified compounds of these compounds.

[0019] Furthermore, if the polyisocyanate (a1) is particularly isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, or an isocyanurate-modified hexamethylene diisocyanate, it is more preferable in terms of forming a cured product that has a soft feel and is excellent in tear strength and resilience.

[0020] The compound (a2) having a hydroxyl group and a (meth)acryloyl group is not particularly limited as long as it can form the component (A), and can be appropriately selected depending on the purpose. For example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and the like can be mentioned. In addition, (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various compounds having a hydroxyl group and a (meth)acryloyl group, and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various compounds having a hydroxyl group and a (meth)acryloyl group, etc. can also be used.

[0021] Furthermore, when the compound (a2) having a hydroxyl group and a (meth)acryloyl group is particularly hydroxyethyl (meth)acrylate or a lactone-modified product thereof, it is more preferable in terms of forming a cured product that has a soft feel and excellent tear strength and recovery force.

[0022] The compound (a3) having a hydroxyl group is not particularly limited as long as it is a compound having a hydroxyl group but not having a (meth)acryloyl group in the molecule, and can be appropriately selected according to the purpose. For example, polyhydric alcohols having a linear alkyl structure such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc.; polyhydric alcohols having a branched alkyl structure such as 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, etc.; polycarbonate polyols synthesized by transesterification of these polyhydric alcohols and carbonate esters; polyester polyols synthesized by dehydration condensation of the above polyhydric alcohols and dibasic acids; polytetramethylene ether glycol, polyethylene glycol, polypropylene glycol, copolymers of polyethylene glycol and polypropylene glycol, etc. can be used.

[0023] Furthermore, it is more preferable that the compound (a3) having a hydroxyl group is polypropylene glycol or polytetramethylene ether glycol, since this gives a curable resin composition that can form a cured product that has a soft feel and is excellent in tear strength and resilience. Furthermore, the number average molecular weight of the polypropylene glycol and polytetramethylene ether glycol is preferably in the range of 200 to 5000, more preferably in the range of 400 to 3500, and particularly preferably in the range of 500 to 3000. By setting the number average molecular weight within these ranges, a curable resin composition can be obtained that is capable of forming a cured product that has a soft feel and is excellent in tear strength and recovery force.

[0024] The production method is not particularly limited, and any method may be used. For example, the polyisocyanate (a1) and the compound (a2) having a hydroxyl group and a (meth)acryloyl group may be reacted together as reaction raw materials, or the reaction raw materials may be reacted in portions one by one. The compound (a3) having a hydroxyl group may or may not be used as a reaction raw material.

[0025] In the production, for example, dibutyltin laurate, dibutyltin acetate, etc. can be used as a catalyst, and the production can be carried out under the conditions of a commonly used urethane reaction. If necessary, a solvent such as ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, etc., or a radical polymerizable monomer that does not contain a site reactive with isocyanate and does not contain a hydroxyl group or an amino group can also be used as a solvent.

[0026] The component (A) may be obtained by synthesis from polyisocyanate (a1) and compound (a2) having a hydroxyl group and a (meth)acryloyl group as described above, but a commercially available product may also be used as is. Commercial products include Miramer PU-320, Miramer PU-330, Miramer PU-340, Miramer PU-370, Miramer PU-3000, Miramer PU-3200, Miramer PU-3210, Miramer PU-3410, Miramer PU-3420, Miramer PU-3450, Miramer PU-460, Miramer PU-5000, Miramer PU-610, Miramer PU-620, Miramer PU-6510, Miramer PU-640, Miramer MU-9500, Miramer MU-9800, Miramer SC-2152 (all manufactured by MIWON), UA-306H, UA-306T, UA-306I, UA-510H (all manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL 4220, EBECRYL 4513, EBECRYL 4738, EBECRYL 4740, EBECRYL 4820, EBECRYL 8311, KRM 8667, KRM 8296, EBECRYL 4265, EBECRYL 4587, EBECRYL 8465, EBECRYL 9260, EBECRYL 8701, EBECRYL 4666, EBECRYL 4680, EBECRYL 8210, EBECRYL 8405, EBECRYL 8606, KRM 8528, EBECRYL 1290, EBECRYL 5129, EBECRYL 8301R, KRM 8200, KRM 8200AE, KRM 8530, KRM 8904, KRM 8531BA, KRM 8452, EBECRYL 220 (manufactured by Daicel Allnex Corporation), ART RESIN UN-3320HA, ART RESIN UN-3320HC, ART RESIN UN-3320HS, ART RESIN UN-904, ART RESIN UN-901T, ART RESIN UN-952, ART RESIN UN-954, ART RESIN UN-905 (manufactured by Negami Kogyo Co., Ltd.), LUXYDIR V-4260, LUXYDIRExamples of suitable acrylic acid esters include V-4263, LUXYDIR 17-806, LUXYDIR 17-806, LUXYDIR 17-813, LUXYDIR EPS-1306, LUXYDIR ENS-836, and LUXYDIR ESS-620 (all manufactured by DIC Corporation).

[0027] The weight average molecular weight (Mw) of component (A) is preferably in the range of 1,000 to 150,000, more preferably 1,200 to 120,000, and particularly preferably 1,500 to 100,000.The (meth)acryloyl group equivalent is preferably in the range of 200 to 1,500 g / equivalent, more preferably 250 to 1,200 g / equivalent, and preferably 280 to 1,000 g / equivalent.

[0028] The content of component (A) in the composition of the present invention is 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more of the total solid content. By adjusting the content within these ranges, a composition can be obtained that can form a cured coating film that has high hardness and excellent scratch resistance, flexibility, and curl resistance. In this specification, the term "solid content" refers to the entire solid content contained in the composition.

[0029] [(B) Component] The bifunctional or higher functional (meth)acrylate of component (B) has a homopolymer Tg (glass transition temperature) of 10°C or lower, preferably 0°C or lower, and more preferably -10°C or lower. A Tg within this range results in softness, and the coating film is not copolymerized with the hard urethane acrylate, remaining in a state close to a homopolymer, thereby relieving stress and suppressing cracking. Tg can be measured using a TG / DTA (thermogravimetric analyzer) or a DSC (differential scanning calorimetry) analyzer. Component (B) can be used alone or in combination of two or more types. Compounds that fall under component (A) are not considered to be included in component (B).

[0030] Examples of bifunctional (meth)acrylates include bisphenol A EO-modified di(meth)acrylate, bisphenol A PO-modified di(meth)acrylate, bisphenol F EO-modified di(meth)acrylate, bisphenol F PO-modified di(meth)acrylate, hexanediol EO-modified di(meth)acrylate, triethylene glycol EO-modified di(meth)acrylate, polyethylene glycol EO-modified di(meth)acrylate, polypropylene glycol EO-modified di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and neopentyl glycol EO-modified di(meth)acrylate.

[0031] Examples of trifunctional (meth)acrylates include trimethylolpropane EO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, glycerin EO-modified tri(meth)acrylate, glycerin PO-modified tri(meth)acrylate, pentaerythritol EO-modified tri(meth)acrylate, and pentaerythritol PO-modified tri(meth)acrylate.

[0032] Examples of tetrafunctional (meth)acrylates include ditrimethylolpropane tetra(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Examples of pentafunctional (meth)acrylates include dipentaerythritol hydroxypenta(meth)acrylate and alkyl-modified dipentaerythritol penta(meth)acrylate.

[0033] As the component (B), a commercially available product may be used as is. Commercially available products include, for example, Miramer M286, Miramer M284, Miramer M280, Miramer M202, Miramer M2040, Miramer M2070, Miramer M2100, Miramer M2200, Miramer M2300, Miramer M3150, Miramer M3160, Miramer M3190, Miramer M2301, Miramer M251, and Miramer M281 (all manufactured by MIWON), NK Ester A-PTMG65, NK Ester A-400, NK Ester A-600, NK Ester A-1000, NK Ester APG-200, NK Ester APG-400, NK Ester APG-700, NK Ester A-BPE-10, NK Ester A-BPE-20, NK Ester A-BPE-30, and NK Ester A-PTMG65. Examples of suitable acrylates include A-TMPT-9EO, NK ester A-TMPT-6PO, NK ester A-GLY-9E, NK ester A-GLY-20E, NK ester A-GLY-9P, NK ester ATM-8EL, NK ester ATM-35E, NK ester A-DPH-24E, and NK ester A-DPH-48E (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate 9EG-A, Light Acrylate 14EG-A, and Light Acrylate PTMGA-250 (all manufactured by Kyoeisha Chemical Co., Ltd.).

[0034] The weight average molecular weight (Mw) of component (B) is preferably in the range of 200 to 4,000, more preferably 250 to 3,000, and particularly preferably 300 to 2,000. The (meth)acryloyl group equivalent is preferably in the range of 100 to 2,000 g / equivalent, more preferably 125 to 1,500 g / equivalent, and preferably 150 to 1,000 g / equivalent.

[0035] The content of component (B) in the composition of the present invention is 1 to 20 mass %, preferably 3 to 18 mass %, and more preferably 5 to 15 mass %, of the total solid content. By setting it within these ranges, excellent flexibility, curl resistance, crack resistance, and stability over time can be achieved.

[0036] [(C) component] Examples of the antistatic agent for component (C) include anionic antistatic agents, cationic antistatic agents, nonionic antistatic agents, amphoteric antistatic agents, metal oxide fine particles, conductive polymers, etc. Component (C) can be used alone or in combination of two or more types.

[0037] Examples of anionic antistatic agents include fatty acid salts, higher alcohol sulfate salts, liquid fatty oil sulfate salts, sulfate salts of fatty amines and fatty amides, fatty alcohol phosphate salts, sulfonates of dibasic fatty acid esters, fatty amide sulfonates, alkyl aryl sulfonates, and formalin condensation naphthalene sulfonates. Examples of cationic antistatic agents include fatty amine salts, quaternary ammonium salts, and alkylpyridinium salts. Examples of nonionic antistatic agents include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and polyoxyethylene sorbitan alkyl esters. Examples of amphoteric antistatic agents include imidazoline derivatives, betaine-type higher alkylamino derivatives, sulfate derivatives, and phosphate derivatives. Examples of metal oxide fine particles include titanium oxide, zirconium oxide, cerium oxide, tin oxide, antimony tin oxide, indium tin oxide, phosphorus tin oxide, antimony oxide, aluminum zinc oxide, and gallium zinc oxide. Examples of conductive polymers include substituted or unsubstituted conductive polyaniline, polyparaphenylene, polyparaphenylene vinylene, polythiophene, polyfuran, polypyrrole, polyselenophene, polyisothianaphthene, polyphenylene sulfide, polyacetylene, polypyridyl vinylene, polyazine, and derivatives thereof.

[0038] In the present invention, quaternary ammonium salts, which are cationic antistatic agents, are particularly preferred. Commercially available quaternary ammonium salts include 1SX-1090 and 1SX-1055F (both manufactured by Taisei Fine Chemical Co., Ltd.).

[0039] The content of the antistatic agent is preferably 1 to 15 mass % of the total solid content, and more preferably 2 to 12 mass %.

[0040] [(D) component] Examples of the solvent for component (D) include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, ethanol, isopropanol, butanol, and propylene glycol monomethyl ether; and glycol ether solvents such as alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ether acetates. These solvents can be used alone or in combination. These organic solvents are mainly used to adjust the viscosity of the active energy ray-curable composition, and it is usually preferable to adjust the nonvolatile content to a range of 10 to 80% by mass.

[0041] [Photopolymerization initiator] The composition of the present invention preferably contains a photopolymerization initiator. 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(t-butylperoxycarbonyl)benzophenone; xanthones and thioxanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone; various acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; α-diketones such as benzil and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; and 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-diphenylethan-1-one, 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-Hydroxy-2-methyl-1-phenylpropan-1-one, 2,4 ,6-Trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethyl sulfide, 2,2'-diethoxyacetophenone, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, bis(4-dimethylaminophenyl)ketone, p-dimethylaminoacetophenone, α,α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl Examples of photopolymerization initiators include dimers, 2,4-bis-trichloromethyl-6-[di-(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-triazineanthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, and β-chloroanthraquinone. These photopolymerization initiators can be used alone or in combination of two or more.

[0042] Furthermore, among photopolymerization initiators, it is preferable to use one or a mixture of two or more selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, because these initiators are active over a wider range of wavelengths and can improve the curing properties of the cured coating film of the composition.

[0043] Commercially available photopolymerization initiators include, for example, "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-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", and "Omnirad-1000". Examples of suitable anti-inflammatory agents include "IGM (Irradiation Group)", "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA", and "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Baicure-10", "Baicure-55" (manufactured by Stauffer Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo), "Sandray 1000" (manufactured by Sandoz), "Deep" (manufactured by Upjohn), "Quantacure-PDO", "Quantacure-ITX", and "Quantacure-EPD" (manufactured by Ward-Blenkinsop), and "Runtecure-1104" (manufactured by Runtec).

[0044] The amount of the photopolymerization initiator added is preferably an amount that can fully exhibit its function as a photopolymerization initiator and is within a range that does not cause crystal precipitation or deterioration of the physical properties of the coating film. Specifically, the amount 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, per 100 parts by mass of the total solid content.

[0045] [Other ingredients] The composition of the present invention may contain, in addition to the components (A) and (B), a photocurable compound other than the component (A), a photosensitizer, an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, a silane coupling agent, a phosphate ester compound, organic beads, inorganic fine particles, an inorganic filler, a rheology control agent, a defoaming agent, an antifogging agent, a colorant, and the like.

[0046] Other photocurable compounds include, for example, monofunctional (meth)acrylate compounds, polyfunctional (meth)acrylate compounds, difunctional or lower urethane (meth)acrylates, polyester (meth)acrylates, epoxy (meth)acrylates, and acrylic (meth)acrylates.

[0047] Examples of the monofunctional (meth)acrylate compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, glycidyl (meth)acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, and isopropyl acrylate. Sodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phosphate (meth)acrylate, ethylene oxide-modified phosphate (meth)acrylate, phenoxy (meth)acrylate, ethylene oxide-modified phenoxy (meth)acrylate, propylene oxide-modified phenoxy (meth)acrylate, nonylphenol (meth)acrylate, ethylene oxide modified nonylphenol (meth)acrylate, propylene oxide modified nonylphenol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxy Ethyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hexahydrohydrogen phthalate, 2-(meth)acryloyloxypropyl tetrahydrohydrogen phthalate, dimethylaminoethyl (meth)acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropropyl (meth)acrylate, octafluoropropyl (meth)acrylate,Examples include mono(meth)acrylates such as adamantyl mono(meth)acrylate.

[0048] Examples of polyfunctional (meth)acrylate compounds include glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate dipentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0049] Examples of photosensitizers 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-benzylisothiuronium-p-toluenesulfonate.

[0050] Examples of ultraviolet absorbers 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'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbers can be used alone or in combination of two or more.

[0051] Examples of antioxidants include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, phosphate ester-based antioxidants, etc. These antioxidants can be used alone or in combination of two or more.

[0052] Examples of silicon-based additives include polyorganosiloxanes having alkyl or phenyl groups, such as dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, and amino-modified dimethylpolysiloxane copolymer, polydimethylsiloxanes having polyether-modified acrylic groups, and polydimethylsiloxanes having polyester-modified acrylic groups. These silicon-based additives can be used alone or in combination of two or more.

[0053] Examples of fluorine-based additives include the "Megaface" series manufactured by DIC Corp. These fluorine-based additives can be used alone or in combination of two or more.

[0054] Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. Acryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl) (Benzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special aminosilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane Vinyl-based silane coupling agents such as vinylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(2-methoxyethoxy)silane; epoxy-based silane coupling agents such as diethoxy(glycidyloxypropyl)methylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styrene-based silane coupling agents such as p-styryltrimethoxysilane;(Meth)acryloxy-based silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-triethoxysilyl-N-(1,3-dimethyl- Examples of suitable silane coupling agents include amino-based silane coupling agents such as N-butylidenepropylamine and N-phenyl-3-aminopropyltrimethoxysilane; ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane; chloropropyl-based silane coupling agents such as 3-chloropropyltrimethoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.

[0055] Examples of phosphate ester compounds include those having a (meth)acryloyl group in their molecular structure. Commercially available products include, for example, "Kayamar PM-2" and "Kayamar 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, "Viscoat #3PA" and "Viscoat #3PMA" manufactured by Osaka Organic Chemical Industry Ltd., and "New Frontier S-23A" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.; and "SIPOMER PAM 5000" manufactured by SOLVAY, which is a phosphate ester compound having an allyl ether group in its molecular structure.

[0056] 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, polyethylene fluoride resin beads, and polyethylene resin beads. These organic beads can be used alone or in combination of two or more. The average particle size of these organic beads is preferably in the range of 1 to 10 μm.

[0057] Examples of inorganic fine particles include fine particles of silica, alumina, zirconia, titania, barium titanate, antimony trioxide, etc. These inorganic fine particles can be used alone or in combination of two or more. The average particle size of these inorganic fine particles is preferably in the range of 10 to 300 nm, and more preferably in the range of 30 to 150 nm.

[0058] When inorganic fine particles are contained, a dispersing aid can be used. Examples of the dispersing aid include phosphate ester compounds such as isopropyl acid phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphate dimethacrylate. These dispersing aids can be used alone or in combination of two or more. Commercially available dispersing aids include "Kayamar PM-21" and "Kayamar PM-2" manufactured by Nippon Kayaku Co., Ltd., and "Light Ester P-2M" manufactured by Kyoeisha Chemical Co., Ltd.

[0059] [Cured coating film] The cured coating film of the present invention is obtained by curing the composition of the present invention. Examples of methods for curing the composition include heating and irradiating with active energy rays such as ultraviolet rays.

[0060] The curing method involves heating for 0.5 to 60 minutes in a temperature range of 60 to 200° C. As a method for irradiating active energy rays, for example, in the case of ultraviolet rays, curing can be achieved by using an ultraviolet lamp such as 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, or an LED as an ultraviolet light source.

[0061] As the active energy ray, in addition to ultraviolet rays, for example, ionizing radiation such as electron beams, α rays, β rays, and γ rays can be used. The irradiation dose of the active energy ray is 0.05 to 5 J / cm. 2 The range is preferably 0.1 to 3 J / cm 2 More preferably, it is in the range of 0.1 to 1 J / cm 2 It is particularly preferable that the range is as follows: The above-mentioned ultraviolet irradiation amount is based on a value measured in the wavelength range of 300 to 390 nm using a UV checker UVR-N1 (manufactured by Japan Storage Battery Co., Ltd.).

[0062] [Laminated film] The laminated film of the present invention has the above-mentioned cured coating film on a substrate. Examples of a method for producing the laminated film of the present invention include a method in which the above-mentioned curable resin composition is applied to at least one surface of a substrate, and then the substrate is irradiated with active energy rays.

[0063] Examples of the substrate include metal substrates, plastic substrates, glass substrates, paper substrates, wood substrates, fibrous substrates, etc. Among these substrates, plastic substrates are preferred because they have excellent adhesion to the curable resin composition.

[0064] Examples of materials for plastic substrates include polyethylene terephthalate, polyester, acrylic resins (such as polymethyl methacrylate), polycarbonate, acrylonitrile-butadiene-styrene copolymers (ABS resins), composite resins of ABS resin and polycarbonate, polystyrene, polyurethane, epoxy resins, polyvinyl chloride, polyamides, polyolefins (such as polyethylene, polypropylene, and polycycloolefins (COP)), triacetyl cellulose (TAC), and polyimides. Examples of plastic substrates include plastic molded products such as mobile phones, home appliances, automotive interior and exterior materials, and office automation equipment. Film substrates made of plastic can also be used.

[0065] Examples of methods for applying the composition include coating methods using a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, flow coater, spin coater, dipping, screen printing, spraying, brush coating, applicator, bar coater, etc.

[0066] The thickness of the coating film can be adjusted appropriately depending on the application, but is usually preferably in the range of 0.01 to 50 μm.

[0067] The laminated film of the present invention may have, in addition to the substrate and the layer made of the cured product, a functional film layer such as an anti-reflection film, a diffusion film, or a polarizing film.

[0068] The laminated film of the present invention has a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance, and can therefore be used as a coating layer to protect the surface of a substrate, for example, as a front panel for a liquid crystal display or an organic EL display.

[0069] Examples of articles having the laminated film of the present invention include plastic molded articles such as mobile phones, housings for home appliances, automobile bumpers, and office automation equipment. [Example]

[0070] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the compositions of the following examples, "%" means "% by mass" and "parts" means "parts by mass."

[0071] [Example 1] 92 parts of Miramer PU-610 (manufactured by MIWON) as component (A), 8 parts of Miramer M286 (manufactured by MIWON) as component (B), 5 parts of Runtecure® 1104 (manufactured by Runtec Chemicals) as a photopolymerization initiator, 6 parts of Acrylit 1SX-1055U4 (manufactured by Taisei Fine Chemicals) as an antistatic agent, and a 3 / 1 solution of methyl ethyl ketone (MEK) / methyl isobutyl ketone (MIBK) as a solvent were mixed to obtain an active energy ray curable composition. The obtained curable resin composition was then applied to a 50 μm thick polyethylene terephthalate film (PET film) using a bar coater and dried at 60° C. for 1 minute. Next, under a nitrogen atmosphere, ultraviolet light was applied at 150 mJ / cm using a 120 W high-pressure mercury lamp. 2 After irradiation, a laminated film having a cured coating film with a thickness of 5 μm on the PET film was obtained.

[0072] [Examples 2 to 10, Comparative Examples 1 to 9] Curable resin compositions and laminated films were obtained in the same manner as in Example 1, except that the coating materials were changed as shown in Tables 1 and 2 below.

[0073] [Table 1]

[0074] [Table 2]

[0075] The abbreviations in Tables 1 and 2 represent the following compounds: Miramer PU-610: Aliphatic urethane acrylate (MIWON) Miramer PU-9500: Aliphatic urethane acrylate (manufactured by MIWON) LUXYDIR (registered trademark) 17-806: urethane acrylate (manufactured by DIC Corporation) Aronix M-450: Multifunctional acrylate (manufactured by Toagosei Co., Ltd.) EBECRYL8402: Difunctional urethane acrylate (manufactured by Daicel Allnex Co., Ltd.) Miramer M286: Polyethylene glycol diacrylate (MIWON) Miramer M284: Polyethylene glycol diacrylate (MIWON) Miramer M3150: Trimethylolpropane EO-modified triacrylate (manufactured by MIWON) Miramer M2040: Polypropylene glycol diacrylate (MIWON) Miramer M2100: EO-modified bisphenol A diacrylate (manufactured by MIWON) NK Ester A-PTMG65: Polytetramethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Miramer M282: Polyethylene glycol diacrylate (MIWON) Miramer M170: Ethoxydiethylene glycol acrylate (manufactured by MIWON) Runtecure® 1104: Photopolymerization initiator (manufactured by Runtec Chemicals) Acrylit 1SX-1055U4: Antistatic agent (manufactured by Taisei Fine Chemical Co., Ltd.)

[0076] The laminated films obtained in the above Examples and Comparative Examples were subjected to the following evaluations.

[0077] [Painting material and coating appearance] The laminated film was visually inspected for any defects in appearance such as cloudiness or cracks.

[0078] [Surface resistance value (Ω / □)] The surface resistance of the laminated film was measured at a temperature of 23°C and humidity of 50% in accordance with JIS test method K6911-1995 using a high resistivity meter ("Hiresta-UPMCP-HT450" manufactured by Mitsubishi Chemical Analytech Co., Ltd.) at an applied voltage of 500 V for a measurement time of 10 seconds. 9 The following is an A (pass), 5.0 x 10 9 Less than 5.0 x 10 10 The following is a B (pass), 5.0 x 10 10 Less than 5.0 x 10 11 The following are graded as C (fail), 5.0 x 10 11 Less than 5.0 x 10 12 The following will be considered a D (fail).

[0079] [SW test: Scratch resistance] A disc-shaped indenter with a diameter of 2.4 cm was wrapped in 0.5 g of steel wool ("Bonstar #0000" manufactured by Nippon Steel Wool Co., Ltd.), and a load of 500 g was applied to the indenter, which was then moved back and forth 10 times over the surface of the laminated film obtained in the Examples and Comparative Examples to perform an abrasion test. After the test, the surface was visually inspected for scratches.

[0080] [Mandrel test: flexibility] Using a mandrel testing machine (TP Giken Co., Ltd.'s "Flexibility Tester"), the laminated films obtained in the Examples and Comparative Examples were wrapped around a test rod, and a test was conducted to visually check whether cracks occurred. The smallest diameter of the test rod that did not cause cracks was used as the evaluation result. Test rods with diameters ranging from 2 mm to 12 mm in 1 mm increments were used. A diameter of 2 mm or less was considered a pass, and a diameter of 3 mm or more was considered a fail.

[0081] [Elongation: Tensile test] The laminated film was evaluated for breaking elongation under the following conditions in accordance with JIS K6251:2010. The breaking elongation is the value obtained by subtracting the initial chuck distance from the chuck distance at tensile break, expressed as a percentage. A breaking elongation of 10% or more was rated A (pass), less than 10% and 6% or more was rated B (pass), less than 6% and 3% or more was rated C (fail), and less than 3% was rated D (fail). Measuring equipment: Tensilon universal material testing machine (manufactured by Orientec Co., Ltd.) Sample shape: Strip (10mm x 150mm) Initial chuck distance: 100 mm Pulling speed: 10 mm / min Measurement atmosphere: Temperature 23°C, humidity 50%

[0082] As can be seen from Tables 1 and 2, Examples 1 to 10, which use a combination of component (A), a polyfunctional urethane (meth)acrylate with tetrafunctionality or higher, and component (B), an alkylene oxide-modified bifunctional or trifunctional (meth)acrylate whose homopolymer Tg is 10°C or less, have good appearance, low surface resistance, and excellent scratch resistance, flexibility, and curl resistance.

Claims

1. An active energy ray-curable resin composition comprising the following components (A) to (D), wherein the ratio of component (A) is 30 mass% or more of the total solid content, and the ratio of component (B) is 1 to 20 mass% of the total solid content: Component (A): Tri- or higher functional urethane (meth)acrylate Component (B): an alkylene oxide-modified di- or higher functional (meth)acrylate having a homopolymer Tg of 10° C. or less Component (C): Antistatic agent Component (D): Solvent

2. 2. The active energy ray-curable resin composition according to claim 1, further comprising a photopolymerization initiator as component (E).

3. A coating film which is a cured reaction product of the active energy ray-curable resin composition according to claim 1 or 2.

4. A laminated film comprising the coating film according to claim 3 and a substrate.

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