Antireflection film, laminate having antireflection film, and method for manufacturing antireflection film

Abstract

Provided is an antireflection film which is a laminate having low surface reflectivity, excellent thermoformability, and, in particular, favorable scratch resistance.　The problem has been solved by an antireflection film comprising: a base material layer containing a thermoplastic resin; and a low-refractive-index layer laminated on at least one surface of the base material layer and having a lower refractive index than the base material layer, wherein the low-refractive-index layer includes an aromatic diisocyanate compound (a1), and a polymer of a resin material containing (meth)acrylate and urethane (meth)acrylate that is derived from at least one (meth)acryloyl compound (a2) having a hydroxyl group and a (meth)acryloyl group in one molecule.

Description

Anti-reflection film, laminate having anti-reflection film, and method for producing anti-reflection film

[0001] The present invention relates to an antireflection film including a substrate layer and a low refractive index layer having a refractive index lower than that of the substrate layer, a laminate including the antireflection film, and the like.

[0002] Conventionally, laminated films having a surface with low reflectance and usable as antireflection films have been known (see Patent Document 1). Laminated films with low surface reflectance are used in applications such as computer screens, television screens, plasma display panels, the surfaces of polarizing plates used in liquid crystal display devices, sunglasses lenses, prescription eyeglass lenses, camera viewfinder lenses, various instrument covers, automobile glass, train glass, in-vehicle display panels, and electronic device housings.

[0003] JP 2014-41244 A

[0004] In the above-mentioned applications, many of the laminated films that have conventionally been used as anti-reflection films do not have sufficient thermoformability and are not necessarily good in abrasion resistance.

[0005] Therefore, an object of the present invention is to provide an anti-reflection film, a laminate having an anti-reflection film, or the like, which has low surface reflectance, excellent thermoformability, and particularly good scratch resistance.

[0006] As a result of extensive research to solve the above-mentioned problems, the present inventors have found that an antireflection film having a substrate layer containing a thermoplastic resin and a low refractive index layer, in which the low refractive index layer contains a polymer of a predetermined resin material, has excellent thermoformability and scratch resistance, and have thus completed the present invention.

[0007] That is, the present invention includes the following: (1) An antireflection film having a substrate layer containing a thermoplastic resin, and a low refractive index layer laminated on at least one surface of the substrate layer and having a refractive index lower than that of the substrate layer, wherein the low refractive index layer contains a polymer of a resin material containing a urethane (meth)acrylate derived from an aromatic diisocyanate compound (a1) and one or more (meth)acryloyl compounds (a2) having a hydroxyl group and a (meth)acryloyl group in one molecule. (2) The antireflection film according to (1) above, wherein the resin material contains a mixture of urethane (meth)acrylates having 2 to 6 (meth)acryloyl groups in one molecule. (3) The antireflection film according to (1), wherein the urethane (meth)acrylate comprises a reaction product of the aromatic diisocyanate compound (a1) and one or more (meth)acryloyl compounds (a2) selected from the group consisting of pentaerythritol tri(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate. (4) The antireflection film according to (1), wherein the (meth)acryloyl compound (a2) comprises a compound (a2-1) having one (meth)acryloyl group per molecule and a compound (a2-2) having three (meth)acryloyl groups per molecule in a molar ratio of (a2-1) / (a2-2) of 80 / 20 to 0 / 100. (5) The antireflection film according to (1), wherein the (meth)acryloyl compound (a2) comprises at least one selected from the group consisting of pentaerythritol tri(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.(6) The antireflection film according to (1) above, wherein the (meth)acrylate is a compound having 4 to 20 carbon atoms, which contains at least one (meth)acryloyl group and at least one vinyl ether group, and which may have a substituent. (7) The antireflection film according to (1) above, wherein the low refractive index layer further contains a low refractive index member. (8) The antireflection film according to (7) above, wherein the low refractive index member contains hollow silica. (9) The antireflection film according to (7) or (8) above, wherein the low refractive index layer contains the resin material and the low refractive index member in a weight ratio of 20:80 to 70:30. (10) The antireflection film according to (1) above, wherein the low refractive index layer further contains at least one of a photoinitiator and a fluorine-based leveling agent. (11) The antireflection film according to (1) above, wherein the resin material contains the urethane acrylate and the (meth)acrylate in a weight ratio of 95:5 to 70:30. (12) The antireflection film according to (1) above, which includes two or more substrate layers. (13) The antireflection film according to (1) above, wherein the thickness of the substrate layer is 50 to 500 μm and the thickness of the low refractive index layer is 10 to 200 nm. (14) The antireflection film according to (1) above, which further includes a hard coat layer laminated between the substrate layer and the low refractive index layer. (15) The antireflection film according to (14) above, wherein the refractive index of the substrate layer is 1.49 to 1.65 and the difference in refractive index between the substrate layer and the hard coat layer is in the range of 0.04 or less. (16) The antireflection film according to (1) above, which further includes a high refractive index layer having a refractive index higher than that of the substrate layer. (17) The antireflection film according to (16) above, wherein the refractive index of the substrate layer is 1.49 to 1.65, the refractive index of the low refractive index layer is 1.31 to 1.40, and the refractive index of the high refractive index layer is 1.68 to 1.75. (18) The antireflection film according to (16) above, wherein the high refractive index layer is laminated between the substrate layer and the low refractive index layer. (19) The antireflection film according to (16) above, further comprising a hard coat layer laminated between the substrate layer and the high refractive index layer.(20) The antireflection film according to (16), further comprising a hard coat layer, wherein the base layer has a thickness of 50 to 500 μm, the hard coat layer has a thickness of 1 to 10 μm, the high refractive index layer has a thickness of 10 to 200 nm, and the low refractive index layer has a thickness of 10 to 200 nm. (21) The antireflection film according to (16), wherein the high refractive index layer contains a polymer of a resin material containing a fluorene-based diol, an isocyanate, and a urethane (meth)acrylate-derived (meth)acrylate and a (meth)acrylate. (22) The antireflection film according to any one of (1) to (21) above, wherein a sample of the antireflection film obtained by cutting into a size of 210 mm x 297 mm x 0.3 mm (thickness) is preheated at 190°C for 40 seconds to have the base layer in contact with the sample, and the sample is placed in a mold including a rectangular protrusion having a deep drawing height of 1 mm or more and dimensions of 30 mm in both length and width, so that the base layer is in contact with the sample, and the sample is subjected to pressure molding using high-pressure air of 1.5 MPa, and the radius R of the region in contact with the rectangular portion of the mold obtained is 3.0 mm or less. (23) An anti-reflection film comprising: a substrate layer containing a thermoplastic resin; and a low refractive index layer laminated on at least one surface of the substrate layer and having a refractive index lower than that of the substrate layer; wherein a sample of the anti-reflection film obtained by cutting to a size of 210 mm × 297 mm × 0.3 mm (thickness) is preheated at 190°C for 40 seconds, the sample is placed in a mold having a deep-drawn height of 1 mm or more and including rectangular protrusions measuring 30 mm in both length and width so that the substrate layer is in contact with the sample, and the sample is subjected to pressure molding using 1.5 MPa high-pressure air; the elongation (%) of the obtained pressure-molded body in the region in contact with the rectangular protrusions of the mold is equal to or greater than 10 times the deep-drawn height (mm) of the mold, and is calculated by the formula: (length between two predetermined points after pressure molding - length between the two points before pressure molding) / length between the two points before pressure molding × 100 (%).(24) An anti-reflection film comprising: a base layer containing a thermoplastic resin; and a low refractive index layer laminated on at least one surface of the base layer and having a refractive index lower than that of the base layer, wherein the reflectance of the surface on the low refractive index layer side measured under the conditions of JIS Z 8722-2009 is 2.0% or less; wherein a sample of the anti-reflection film is cut to 210 mm x 297 mm x 0.3 mm (thickness), the base layer is preheated at 190°C for 40 seconds, the sample is placed in a mold having a deep-draw height of 1 mm or more and including rectangular protrusions measuring 30 mm in both length and width so that the base layer is in contact with the sample, and the sample is pressure-molded using high-pressure air of 1.5 MPa; and the radius R of the region of the pressure-molded body that contacts the rectangular protrusions of the mold is 3.0 mm or less.

[0008] (25) A laminate comprising a transparent resin substrate and the antireflection film according to any one of (1) to (24) above.

[0009] (26) A method for producing an antireflection film, comprising a lamination step of laminating a low refractive index layer having a refractive index lower than that of a base layer containing a thermoplastic resin on at least one surface of the base layer, wherein the low refractive index layer contains a polymer of a resin material containing a urethane (meth)acrylate derived from an aromatic diisocyanate compound (a1) and one or more (meth)acryloyl compounds (a2) having a hydroxyl group and a (meth)acryloyl group in one molecule, and a (meth)acrylate.

[0010] As described above, the antireflection film of the present invention comprises a substrate layer and a low refractive index layer laminated on at least one surface of the substrate layer and having a refractive index lower than that of the substrate layer. The reflectance of the surface of the antireflection film facing the low refractive index layer is sufficiently low, and the antireflection film has excellent thermoformability and particularly excellent scratch resistance.

[0011] Because of these excellent characteristics, the antireflection film of the present invention can be suitably used in applications such as display parts of computers, televisions, plasma displays, etc., surfaces of polarizing plates used in liquid crystal display devices, sunglasses lenses, prescription eyeglass lenses, camera viewfinder lenses, instrument covers, automobile glass, train glass, in-vehicle display panels, and electronic device housings.

[0012] Fig. 1 is a cross-sectional view showing the laminate structure of the anti-reflection film of Example 1. Fig. 2 is a cross-sectional view showing the laminate structure of an anti-reflection film of a specific example different from Example 1. Fig. 3 is a diagram showing elongation after pressure molding in an anti-reflection film having lattice-shaped lines at predetermined intervals printed on the surface.

[0013] The present invention will be described in detail below. Note that the present invention is not limited to the following embodiments, and can be implemented by making any modifications within the scope of the effects of the invention.

[0014] [Anti-reflection film] The anti-reflection film of the present invention has a substrate layer containing a thermoplastic resin and a low refractive index layer laminated on at least one surface of the substrate layer and having a refractive index lower than that of the substrate layer. Hereinafter, each layer member included in the anti-reflection film, which is such a laminate, will be described.

[0015] [Substrate Layer] The substrate layer included in the anti-reflection film contains a thermoplastic resin. The type of thermoplastic resin is not particularly limited, and various resins such as polycarbonate (PC) resin, acrylic resin such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, aromatic polyamide, etc. Of these options, the thermoplastic resin of the substrate layer preferably contains at least a polycarbonate resin.

[0016] The type of polycarbonate resin that can be contained in the substrate layer is not particularly limited as long as it contains an -[O-R-OCO]- unit (where R contains an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear or branched structure) that contains a carbonate bond in the molecular main chain. However, polycarbonates having a bisphenol skeleton are preferred, and polycarbonates having a bisphenol A skeleton or a bisphenol C skeleton are particularly preferred. As the polycarbonate resin, a mixture or copolymer of bisphenol A and bisphenol C may be used. The hardness of the substrate layer can be improved by using a bisphenol C-based polycarbonate resin, for example, a polycarbonate resin containing only bisphenol C, or a polycarbonate resin that is a mixture or copolymer of bisphenol C and bisphenol A. The viscosity average molecular weight of the polycarbonate resin is preferably 15,000 to 40,000, more preferably 20,000 to 35,000, and even more preferably 22,500 to 25,000.

[0017] The acrylic resin that can be contained in the substrate layer is not particularly limited, but examples include homopolymers of various (meth)acrylic acid esters, such as polymethyl methacrylate (PMMA) and methyl methacrylate (MMA), copolymers of PMMA or MMA with one or more other monomers, and mixtures of multiple types of these resins. Among these, (meth)acrylates containing a cyclic alkyl structure, which have low birefringence, low moisture absorption, and excellent heat resistance, are preferred. Examples of such (meth)acrylic resins include, but are not limited to, ACRYPET (manufactured by Mitsubishi Rayon), DELPET (manufactured by Asahi Kasei Chemicals), and PARAPET (manufactured by Kuraray). Using a mixture containing a polycarbonate resin and the above-mentioned acrylic resin is preferred because it can improve the hardness of the substrate layer, particularly the surface layer of the substrate layer in the laminate (the layer on the high refractive index layer side).

[0018] The substrate layer may also contain additives other than the thermoplastic resin, such as at least one additive selected from the group consisting of a heat stabilizer, an antioxidant, a flame retardant, a flame retardant assistant, an ultraviolet absorber, a release agent, and a colorant. Additionally, the substrate layer may also contain additives such as an antistatic agent, a fluorescent brightener, an antifogging agent, a flow improver, a plasticizer, a dispersant, and an antibacterial agent.

[0019] The base layer preferably contains 80% by mass or more of a thermoplastic resin, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of a polycarbonate resin, among the thermoplastic resins of the base layer.

[0020] The substrate layer preferably has a refractive index in the range of 1.49 to 1.65, more preferably 1.49 to 1.60, even more preferably 1.51 to 1.60, and particularly preferably about 1.53 to 1.59.

[0021] The thickness of the substrate layer is not particularly limited, but is, for example, 30 μm to 1000 μm (1 mm), preferably 50 μm to 700 μm, more preferably 50 μm to 500 μm, and particularly preferably 100 μm to 500 μm. In addition, the antireflection film may have two or more substrate layers, and when a plurality of substrate layers are provided, the total thickness of the substrate layers is, for example, 100 μm to 1000 μm, preferably about 200 μm to 500 μm.

[0022] Examples of substrate layers containing the above-mentioned multiple layers, i.e., substrate layers that are multilayer laminates, include the following: a layer of the above-mentioned polycarbonate resin (PC), such as bisphenol A, laminated with an acrylic resin layer such as the above-mentioned acrylic resin, for example, poly(methyl methacrylate resin (PMMA: polymethyl acrylate and / or polymethyl methacrylate), as a surface layer; a layer of a polycarbonate resin (PC) such as bisphenol A, laminated with a polycarbonate resin (PC) such as bisphenol C; etc. In a laminate in which a layer of a polycarbonate resin (PC) containing bisphenol A is laminated with a polycarbonate resin (PC) containing bisphenol C, for example, a polycarbonate resin containing bisphenol C is used as the surface layer. Furthermore, it is preferable to use a surface layer that has high hardness, particularly one that is harder than the other substrate layers.

[0023] The polycarbonate resin, which is the thermoplastic resin used in the substrate layer of the laminate, is preferably the same as the polycarbonate resin forming the single-layer substrate layer, i.e., the above-mentioned resin. For example, a mixture or copolymer of bisphenol A and bisphenol C may be used. By using a bisphenol C-based polycarbonate resin, for example, a polycarbonate resin containing only bisphenol C, or a mixture or copolymer of bisphenol C and bisphenol A, it is possible to improve the hardness of the surface layer (the layer on the low refractive index layer side) of the substrate layer in the laminate. To further improve the hardness, a mixture of a polycarbonate resin, for example, a bisphenol C-based polycarbonate resin, with the above-mentioned acrylic resin may be used.

[0024] [Low Refractive Index Layer (Antireflection Layer)] The antireflection film includes a low refractive index layer. The low refractive index layer is laminated on at least one surface of the substrate layer. The low refractive index layer has a refractive index lower than that of the substrate layer and has an antireflection function. The low refractive index layer is preferably disposed on the outermost side of the antireflection film to suppress reflection from the antireflection film.

[0025] The low refractive index layer contains a polymer of a resin material containing urethane (meth)acrylate and (meth)acrylate, each of which will be described in detail later, and is preferably formed only from a polymer of a resin material containing urethane (meth)acrylate and (meth)acrylate. Each component of the low refractive index layer will be described below.

[0026] <Urethane (meth)acrylate in the resin material of the low refractive index layer> The urethane (meth)acrylate contained in the resin material is derived from an aromatic diisocyanate compound (a1) and one or more (meth)acryloyl compounds (a2) having one hydroxyl group and at least one (meth)acryloyl group in one molecule. More specifically, the urethane (meth)acrylate is preferably formed by a reaction product of the aromatic diisocyanate compound (a1) and the (meth)acryloyl compound (a2).

[0027] (Aromatic diisocyanate compound (a1)) An aromatic diisocyanate compound (a1) is used as a component for forming a urethane (meth)acrylate. A wide variety of aromatic compounds having two isocyanate groups (-NCO groups) are used as the aromatic diisocyanate compound (a1), and for example, compounds having a single or multiple benzene rings, compounds having an aromatic ring, etc. may also be used. For example, an aromatic diisocyanate compound represented by the following formula (1) may be used as the aromatic diisocyanate compound (a1): In formula (1), R is independently a linear or branched alkyl group having 1 to 6 carbon atoms, which may have a substituent or a halogen, or an aromatic ring having 6 to 12 carbon atoms, and n is an integer from 0 to 4. R is preferably an alkyl group having 1 to 3 carbon atoms, which may have a substituent, and examples of the substituent include an alkoxy group. n is preferably an integer from 0 to 2, and more preferably 0 or 1. Alternatively, an aromatic diisocyanate compound in which one or both of the isocyanate groups (-NCO groups) in formula (1) are directly bonded to a benzene ring without an intervening methylene group may be used. For example, an aromatic diisocyanate compound in which the isocyanate groups (-NCO groups) are directly bonded to a benzene ring, such as toluene diisocyanate (2,4-toluene diisocyanate, 2,6-toluene diisocyanate), may be used.

[0028] Specific examples of the aromatic diisocyanate compound (a1) include m- or p-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate (MDI), toluene diisocyanate (2,4-toluene diisocyanate, 2,6-toluene diisocyanate), a trimethylolpropane (TMP) adduct of toluene diisocyanate, an isocyanate of toluene diisocyanate, toluidine diisocyanates such as 4,4'-toluidine diisocyanate, 4,4' 1,5- or 2,6-naphthalene diisocyanates; aromatic diisocyanate compounds such as xylene diisocyanate (XDI; 1,3-bis(isocyanatomethyl)benzene) and TMP adducts of xylene diisocyanate; and aromatic aliphatic diisocyanate compounds such as m- or p-xylylene diisocyanate and tetramethylxylylene diisocyanates such as 1,3- or 1,4-tetramethylxylylene diisocyanate. A preferred specific example of the aromatic diisocyanate compound (a1) is xylene diisocyanate.

[0029] ((Meth)acryloyl Compound (a2)) The (meth)acryloyl compound (a2) used to form the urethane (meth)acrylate has one or more hydroxyl groups and at least one or more (meth)acryloyl groups. The number of hydroxyl groups in the (meth)acryloyl compound (a2) is, for example, 1 to 3, but a (meth)acryloyl compound (a2) having only one hydroxyl group is preferred. The (meth)acryloyl compound (a2) preferably has 1 to 3 (meth)acryloyl groups, and for example, a monofunctional (meth)acryloyl compound (a2-1) having a single (meth)acryloyl group, or a trifunctional (meth)acryloyl compound (a2-2) having three (meth)acryloyl groups, etc. are preferred.

[0030] As the (meth)acryloyl compound (a2), any single type of compound may be used, or a mixture of multiple types of compounds may be used. The (meth)acryloyl compound (a2) includes, for example, a monofunctional compound (a2-1) having one (meth)acryloyl group per molecule, or a trifunctional compound (a2-2) having three (meth)acryloyl groups per molecule. As the (meth)acryloyl compound (a2), either a monofunctional or trifunctional compound may be used alone, or a mixture (mixture) of a monofunctional and a trifunctional compound may be used. Furthermore, as the monofunctional compound (a2-1), a single compound or a mixture of multiple types may be used, and the same applies to the trifunctional compound (a2-2). When a compound (a2-1) having one (meth)acryloyl group per molecule and a trifunctional compound (a2-2) having three (meth)acryloyl groups per molecule are used as the (meth)acryloyl compound (a2), they are preferably used in a molar ratio of (a2-1) / (a2-2)=80 / 20 to 0 / 100, or they may be mixed in a ratio of (a2-1) / (a2-2)=80 / 20 to 20 / 80, or in a ratio of (a2-1) / (a2-2)=70 / 30 to 30 / 70, or (a2-1) / (a2-2)=60 / 40 to 40 / 60, or they may be mixed in equal amounts. Furthermore, instead of the trifunctional compound (a2-2), a bifunctional or tetrafunctional (meth)acryloyl compound may be used in the ratio of the trifunctional compound (a2-2) described above.

[0031] Specific examples of the (meth)acryloyl compound (a2) which is a hydroxyl group-containing acrylate include, but are not limited to, monofunctional or trifunctional (meth)acryloyl compounds such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-acryloyloxyethyl acid phosphate, caprolactone-modified 2-hydroxyethyl acrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, propoxylated pentaerythritol triacrylate, and caprolactone-modified 2-hydroxyethyl acrylate. Further specific examples of the (meth)acryloyl compound (a2) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-(meth)acryloyloxyethyl acid phosphate caprolactone-modified 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, etc. Note that the (meth)acrylate described in this specification can include both acrylate and methacrylate.

[0032] Preferred specific examples of the (meth)acryloyl compound (a2) include pentaerythritol tri(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.

[0033] (Urethane (meth)acrylate) The urethane (meth)acrylate produced as a reaction product of the aromatic diisocyanate compound (a1) and the (meth)acryloyl compound (a2) preferably has 2 to 6 (meth)acryloyl groups. For example, a urethane (meth)acrylate having 2, 4, or 6 (meth)acryloyl groups, obtained by reacting a mixture of a monofunctional (meth)acryloyl compound (a2-1) and a trifunctional (meth)acryloyl compound (a2-2) with the aromatic diisocyanate compound (a1), may be used as the resin material. Furthermore, even in a mixture of urethane (meth)acrylates having 2 to 6 (e.g., 2, 4, or 6) (meth)acryloyl groups, only one specific urethane (meth)acrylate may be used as the resin material.

[0034] The ratio of the aromatic diisocyanate compound (a1) to the total amount of the (meth)acryloyl compound (a2) for forming the urethane (meth)acrylate is preferably 20:80 to 75:25 (weight ratio), more preferably 30:70 to 60:40, and even more preferably 35:65 to 55:45.

[0035] <(Meth)acrylate (Compound) in the Resin Material of the Low Refractive Index Layer> The resin material of the low refractive index layer includes a (meth)acrylate compound in addition to the urethane (meth)acrylate described above. That is, the resin material of the low refractive index layer is preferably obtained as a mixture (liquid mixture) containing the urethane (meth)acrylate and the (meth)acrylate compound described above, and the low refractive index layer is preferably formed as a polymer of the resin material that is such a mixture. The (meth)acrylate compound as one component of the resin material is preferably a compound having 4 to 20 carbon atoms that contains at least one (meth)acryloyl group and at least one vinyl ether group and may have a substituent. The (meth)acrylate preferably has 6 to 18 carbon atoms, more preferably 8 to 16 carbon atoms. Examples of the substituent on the (meth)acrylate include alkyl groups. For example, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate [2-(2-vinyloxyethoxy)ethyl acrylate: VEEA] represented by the following formula is used as the (meth)acrylate. (In the above formula, R is hydrogen or a methyl group.)

[0036] Specific examples of the (meth)acrylate compound contained in the resin material include: alkanediol di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate; alkanepolyol di(meth)acrylates such as glycerin di(meth)acrylate; polyalkylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate; di(meth)acrylates of acid-modified alkanepolyols such as fatty acid-modified pentaerythritol; Examples of the (meth)acrylate compound include bridged cyclic di(meth)acrylates such as tricyclodecane dimethanol di(meth)acrylate, alkane polyol (meth)acrylates such as trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tri(meth)acrylates of C2-4 alkylene oxide adducts of alkane polyols such as trimethylolpropane and glycerin; and tri(meth)acrylates having a triazine ring such as tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate. Further specific examples of the (meth)acrylate compound contained in the resin material include bisphenol A di(meth)acrylate compounds having an ethoxy group.Preferred specific examples of the bisphenol A di(meth)acrylate compound having an ethoxy group include ethoxylated (3 mol) bisphenol A di(meth)acrylate, ethoxylated (4 mol) bisphenol A di(meth)acrylate, ethoxylated (10 mol) bisphenol A di(meth)acrylate, and propoxylated (3 mol) bisphenol A diacrylate, and a more preferred specific example is ethoxylated (4 mol) bisphenol A di(meth)acrylate.

[0037] In the resin material forming the low refractive index layer, the ratio of urethane (meth)acrylate to (meth)acrylate compound ((meth)acrylate) is preferably 95:5 to 70:30 (weight ratio), more preferably 93:7 to 80:20, and even more preferably 90:10 to 85:15. However, in the resin material for the low refractive index layer, the ratio of urethane (meth)acrylate to (meth)acrylate compound may also be 99:1 to 60:40.

[0038] <Low-Refractive Index Member> The low-refractive index layer preferably includes a low-refractive index member. The low-refractive index member is added to reduce the refractive index of the low-refractive index layer. That is, by forming the low-refractive index layer using a low-refractive index member, the difference in refractive index between the low-refractive index layer and the substrate layer can be increased, thereby further reducing the reflectance of the anti-reflection film. Silica, metal fluoride microparticles, etc. are preferred as the low-refractive index member, with silica, particularly hollow silica, being more preferred. When metal fluoride microparticles are used, examples of the metal fluoride contained in the particles include magnesium fluoride, aluminum fluoride, calcium fluoride, and lithium fluoride. The low-refractive index member is preferably a particulate member, and the particle size (diameter: average particle size) of the particulate low-refractive index member is not particularly limited, but is, for example, 10 to 200 nm, preferably 30 to 100 nm, more preferably 35 to 80 nm, and particularly preferably 45 to 65 nm. The (average) particle size of the particulate low refractive index member is measured, for example, by a dynamic light scattering method in accordance with JIS Z 8828:2019 (ISO 22412:2017).

[0039] <Refractive Index of Low Refractive Index Layer> The refractive index of the low refractive index layer is lower than that of the substrate layer. The refractive index of the low refractive index layer is preferably 1.31 to 1.40, more preferably 1.32 to 1.39, and even more preferably about 1.33 to 1.38. The difference between the refractive index of the low refractive index layer and that of the substrate layer is preferably at least 0.09, more preferably at least 0.12, even more preferably at least 0.15, and particularly preferably at least 0.17. In this way, by increasing the difference between the refractive index of the low refractive index layer and that of the substrate layer, the reflectance of the surface of the antireflection film on the low refractive index layer side can be increased.

[0040] <Other Components> The low refractive index layer or the resin material forming the low refractive index layer preferably contains at least one of a photoinitiator (photopolymerization initiator) and a leveling agent, and it is particularly preferable that the low refractive index layer contains a photoinitiator. In addition, the resin material of the low refractive index layer may contain a solvent. Examples of the leveling agent include a fluorine-based leveling agent and a silicone-based leveling agent.

[0041] The low refractive index layer preferably contains the resin material of the low refractive index layer and the low refractive index member in a weight ratio of 20:80 to 70:30, and the ratio of the resin material to the low refractive index member is more preferably 30:70 to 65:35, and even more preferably 35:65 to 60:40.

[0042] The thickness of the low refractive index layer is not particularly limited, but is preferably 10 to 200 nm, more preferably 30 to 160 nm, even more preferably 50 to 120 nm, and particularly preferably 80 to 110 nm.

[0043] [High Refractive Index Layer (Anti-Reflection Layer)] The anti-reflection film may include a high refractive index layer. The high refractive index layer has a refractive index higher than that of the substrate layer, and the high refractive index layer included in the anti-reflection film also has an anti-reflection function similar to the low refractive index layer. Such a high refractive index layer is used as an anti-reflection layer in a laminate. The high refractive index layer is preferably laminated between the low refractive index layer and the substrate layer. The high refractive index layer includes a polymer of a resin material containing a fluorene-based diol, an isocyanate, and a urethane (meth)acrylate derived from a (meth)acrylate, and a (meth)acrylate. That is, the high refractive index layer is preferably a mixture of a urethane (meth)acrylate obtained by a dehydration condensation reaction of at least the three components of a fluorene-based diol, an isocyanate, and a (meth)acrylate.

[0044] <Urethane (meth)acrylate in the resin material of the high refractive index layer> The urethane (meth)acrylate contained in the resin material of the high refractive index layer preferably contains at least a component represented by the following formula (I): (A3)-O(OC)HN-A2-HN(OC)-O-A1-O-(CO)NH-A2-NH-(CO)O-(A3) (I) (In formula (I), A1 represents an alkylene group derived from a fluorene-based diol having a total of 8 to 60 carbon atoms, which may have a substituent; A2 represents each independently an alkylene group derived from an aromatic isocyanate having a total of 6 to 20 carbon atoms, which may have a substituent; and A3 represents each independently an alkyl group having a total of 4 to 30 carbon atoms, which contains at least one (meth)acryloyloxy group, and which may have a substituent, and which is derived from a (meth)acrylate.

[0045] Fluorene-Based Diol (A1) The alkylene group of A1 is a fluorene-based diol that may have a substituent, such as an aryl group such as a phenyl group, and is preferably derived from a fluorene-based diol having a total of 12 to 54 carbon atoms, more preferably from a fluorene-based diol having a total of 16 to 48 carbon atoms, and particularly preferably from a fluorene-based diol having a total of 20 to 40 carbon atoms. Representative specific examples of the fluorene-based diol for forming the structural unit A1, i.e., a compound having a fluorene skeleton, include the following. In this specification, the term "fluorene-based diol" encompasses fluorene compounds containing three or more hydroxyl groups. Examples of fluorene-based diols having two hydroxyl groups include 9,9-bis(hydroxyphenyl)fluorenes, 9,9-bis(hydroxy(poly)alkoxyphenyl)fluorenes, 9,9-bis(hydroxynaphthyl)fluorenes, and 9,9-bis(hydroxy(poly)alkoxynaphthyl)fluorenes. Examples of fluorene-based diols having three or more hydroxyl groups include 9,9-bis(polyhydroxyphenyl)fluorenes, 9,9-bis[poly(hydroxy(poly)alkoxy)phenyl]fluorenes, 9,9-bis(polyhydroxynaphthyl)fluorenes, and 9,9-bis[poly(hydroxy(poly)alkoxy)naphthyl]fluorenes.

[0046] Examples of 9,9-bis(hydroxyphenyl)fluorenes include 9,9-bis(hydroxyphenyl)fluorene [9,9-bis(4-hydroxyphenyl)fluorene (bisphenolfluorene)], 9,9-bis(hydroxyphenyl)fluorene having a substituent {for example, 9,9-bis(alkyl-hydroxyphenyl)fluorene [9,9-bis(4-hydroxy-3-methylphenyl)fluorene (biscresolfluorene), 9,9-bis(4-hydroxy-3-ethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-butylphenyl)fluorene, 9,9-bis(3-hydroxy-2-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, and 9,9-bis(4-hydroxy-2,6-dimethylphenyl)fluorene, 9,9-bis(mono- or di-C1-4 alkyl-hydroxyphenyl)fluorene, etc.], 9,9-bis(cycloalkyl-hydroxyphenyl)fluorene [9,9-bis(mono- or di-C5-8 cycloalkyl-hydroxyphenyl)fluorene such as 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, etc.], 9,9-bis(aryl-hydroxyphenyl)fluorene [for example, 9,9-bis(mono- or di-C6-8 aryl-hydroxyphenyl)fluorene such as 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, etc.], 9,9-bis(aralkyl-hydroxyphenyl)fluorene [for example, 9,9-bis(C6-8 aryl-C1-2 alkyl-hydroxyphenyl)fluorene such as 9,9-bis(4-hydroxy-3-benzylphenyl)fluorene, etc.], and the like.

[0047] Examples of 9,9-bis(hydroxy(poly)alkoxyphenyl)fluorenes include 9,9-bis(hydroxyalkoxyphenyl)fluorene {e.g., 9,9-bis(hydroxyC2-4alkoxyphenyl)fluorenes such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[4-(3-hydroxypropoxy)phenyl]fluorene, and 9,9-bis[4-(4-hydroxybutoxy)phenyl]fluorene).}, 9,9-bis(hydroxyalkoxy-alkylphenyl)fluorene {for example, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene [or 2,2'-dimethyl-4,4'-(9-fluorenylidene)-bisphenoxyethanol], 9,9-bis[2-(2-hydroxyethoxy)-5-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-ethylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-propylphenyl]fluorene, 9,9 -bis[4-(3-hydroxypropoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(4-hydroxybutoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene [or 2,2',6,6'-tetramethyl-4,4'-(9-fluorenylidene)-bisphenoxyethanol], 9,9-bis[4-(2-hydroxyethoxy)-3,5-diethylphenyl]fluorene, 9,9-bis[4-(3-hydroxypropoxy)-3,5-dimethylphenyl]fluorene phenyl]fluorene, 9,9-bis(hydroxyC2-4 alkoxy-mono or diC1-6 alkylphenyl)fluorenes such as 9,9-bis[4-(4-hydroxybutoxy)-3,5-dimethylphenyl]fluorene, etc.}, 9,9-bis(hydroxyalkoxy-cycloalkylphenyl)fluorene {for example, 9,9-bis(hydroxyC2-4 alkoxy-mono or diC5-8 cycloalkylphenyl)fluorenes such as 9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, etc.}, 9,9-bis(hydroxyC2-4 alkoxy-mono or diC5-8 cycloalkylphenyl)fluorenes such as 9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, etc.9-bis(hydroxyalkoxy-arylphenyl)fluorenes {for example, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene [or 2,2'-diphenyl-4,4'-(9-fluorenylidene)-bisphenoxyethanol], 9,9-bis[4-(2-hydroxyethoxy)-3,5-diphenylphenyl]fluorene, and other 9,9-bis(hydroxyC2-4alkoxy-mono- or diC6-8arylphenyl)fluorenes}, 9,9-bis(hydroxyalkoxy-aralkylphenyl)fluorenes {for example, 9,9-bis[4-(2-hydroxyethoxy)-3-benzylphenyl]fluorene, and 9,9-bis[hydroxyC2-4 alkoxy-mono- or di(C6-8 arylC1-4 alkyl)phenyl]fluorenes} such as 9,9-bis[4-(2-hydroxyethoxy)-3,5-dibenzylphenyl]fluorene, and 9,9-bis(hydroxypolyalkoxyphenyl)fluorenes corresponding to these 9,9-bis(hydroxyalkoxyphenyl)fluorenes {for example, 9,9-bis[(hydroxyC2-4 alkoxy)C2-4 alkoxyphenyl]fluorene such as 9,9-bis{4-[2-(2-hydroxyethoxy)ethoxy]phenyl}fluorene, etc.}.

[0048] Examples of 9,9-bis(hydroxynaphthyl)fluorenes include 9,9-bis(hydroxynaphthyl)fluorenes {e.g., 9,9-bis(monohydroxynaphthyl)fluorene which may have a substituent such as 9,9-bis[6-(2-hydroxynaphthyl)]fluorene (or 6,6-(9-fluorenylidene)-di(2-naphthol)), 9,9-bis[1-(6-hydroxynaphthyl)]fluorene (or 5,5-(9-fluorenylidene)-di(2-naphthol)), or 9,9-bis[1-(5-hydroxynaphthyl)]fluorene (or 5,5-(9-fluorenylidene)-di(1-naphthol))}.

[0049] Examples of the 9,9-bis(hydroxy(poly)alkoxynaphthyl)fluorenes include compounds corresponding to the 9,9-bis(hydroxynaphthyl)fluorenes, such as 9,9-bis(hydroxyalkoxynaphthyl)fluorene {e.g., 9,9-bis(hydroxyC2-4alkoxynaphthyl)fluorene which may have a substituent, such as 9,9-bis[6-(2-(2-hydroxyethoxy)naphthyl)]fluorene, 9,9-bis[1-(6-(2-hydroxyethoxy)naphthyl)]fluorene [or 5,5′-(9-fluorenylidene)-bis(2-naphthyloxyethanol)], or 9,9-bis[1-(5-(2-hydroxyethoxy)naphthyl)]fluorene}.

[0050] Examples of 9,9-bis(polyhydroxyphenyl)fluorenes include 9,9-bis(dihydroxyphenyl)fluorenes, 9,9-bis(trihydroxyphenyl)fluorenes, etc. Examples of 9,9-bis(dihydroxyphenyl)fluorenes include 9,9-bis(dihydroxyphenyl)fluorene [9,9-bis(3,4-dihydroxyphenyl)fluorene (biscatecholfluorene), 9,9-bis(3,5-dihydroxyphenyl)fluorene, etc.], substituted 9,9-bis(dihydroxyphenyl)fluorene {for example, 9,9-bis(alkyl-dihydroxyphenyl)fluorene [9,9-bis(3,4-dihydroxy-5-methylphenyl)fluorene, 9,9-bis(3,4-dihydroxy-6-methylphenyl)fluorene, 9,9-bis(2,4-dihydroxy-3,6-dimethylphenyl)fluorene, etc. 9,9-bis(mono- or di-C1-4 alkyl-dihydroxyphenyl)fluorenes such as 9,9-bis(3,4-dihydroxy-5-phenylphenyl)fluorene, etc.], 9,9-bis(aryl-dihydroxyphenyl)fluorenes [for example, 9,9-bis(mono- or di-C6-8 aryl-dihydroxyphenyl)fluorenes such as 9,9-bis(3,4-dihydroxy-5-phenylphenyl)fluorene, etc.], 9,9-bis(alkoxy-dihydroxyphenyl)fluorenes [for example, 9,9-bis(mono- or di-C1-4 alkoxy-dihydroxyphenyl)fluorenes such as 9,9-bis(3,4-dihydroxy-5-methoxyphenyl)fluorene, etc.], etc.

[0051] Examples of 9,9-bis(trihydroxyphenyl)fluorenes include 9,9-bis(trihydroxyphenyl)fluorene [for example, 9,9-bis(2,4,6-trihydroxyphenyl)fluorene, 9,9-bis(2,4,5-trihydroxyphenyl)fluorene, 9,9-bis(3,4,5-trihydroxyphenyl)fluorene, etc.].

[0052] Examples of 9,9-bis[poly(hydroxy(poly)alkoxy)phenyl]fluorenes include 9,9-bis[di(hydroxy(poly)alkoxy)phenyl]fluorenes, 9,9-bis[tri(hydroxy(poly)alkoxy)phenyl]fluorenes, and the like.

[0053] Examples of 9,9-bis[di(hydroxy(poly)alkoxy)phenyl]fluorenes include 9,9-bis[di(hydroxyalkoxy)phenyl]fluorene {for example, 9,9-bis[3,4-di(2-hydroxyethoxy)phenyl]fluorene [or 2,2'-bishydroxyethoxy-4,4'-(9-fluorenylidene)-bisphenoxyethanol], 9,9-bis[3,5-di(2-hydroxyethoxy)phenyl]fluorene [or 3,3'-bishydroxyethoxy-5,5'-(9-fluorenylidene)-bisphenoxyethanol], 9,9-bis[di(hydroxyC2-4alkoxy)phenyl]fluorene such as 9,9-bis[3,4-di(3-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3,5-di(3-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3,4-di(2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3,5-di(2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3,4-di(4-hydroxybutoxy)phenyl]fluorene, and 9,9-bis[3,5-di(4-hydroxybutoxy)phenyl]fluorene 9,9-bis[mono- or di-C1-4 alkyl-di(hydroxyalkoxy)phenyl]fluorene}, 9,9-bis[di(hydroxyalkoxy)phenyl]fluorene having a substituent {for example, 9,9-bis[alkyl-di(hydroxyalkoxy)phenyl]fluorene [for example, 9,9-bis[mono- or di-C1-4 alkyl-di(hydroxyalkoxy)phenyl]fluorene such as 9,9-bis[3,4-di(2-hydroxyethoxy)-5-methylphenyl]fluorene, 9,9-bis[3,4-di(2-hydroxyethoxy)-6-methylphenyl]fluorene, and 9,9-bis[2,4-di(2-hydroxyethoxy)-3,6-dimethylphenyl]fluorene, 9,9-bis[aryl-di(hydroxyalkoxy)phenyl]fluorene, etc.], 9,9-bis[mono- or di-C6-8 aryl-di(hydroxyC2-4 alkoxy)phenyl]fluorene, etc., such as 9,9-bis[3,4-di(2-hydroxyethoxy)-5-arylphenyl]fluorene, etc.], 9,9-bis[alkoxy-di(hydroxyalkoxy)phenyl]fluorene, etc., such as 9,9-bis[3,4-di(2-hydroxyethoxy)-5-methoxyphenyl]fluorene, etc.9,9-bis[di(hydroxyalkoxy)phenyl]fluorenes such as 9,9-bis[mono- or di-C1-4 alkoxy-di(hydroxyC2-4 alkoxy)phenyl]fluorene, etc.}; 9,9-bis[di(hydroxypolyalkoxy)phenyl]fluorenes corresponding to these 9,9-bis[di(hydroxyalkoxy)phenyl]fluorenes {for example, 9,9-bis[di(hydroxyC2-4 alkoxy C2-4 alkoxy]phenyl]fluorenes such as 9,9-bis{3,4-di[2-(2-hydroxyethoxy)ethoxy]phenyl}fluorene and 9,9-bis{3,5-di[2-(2-hydroxyethoxy)ethoxy]phenyl}fluorene, etc.}.

[0054] Examples of the 9,9-bis[tri(hydroxy(poly)alkoxy)phenyl]fluorenes include compounds corresponding to the 9,9-bis[di(hydroxy(poly)alkoxy)phenyl]fluorenes, such as 9,9-bis[tri(hydroxyalkoxy)phenyl]fluorene {for example, 9,9-bis[2,3,4-tri(2-hydroxyethoxy)phenyl]fluorene [or 2,2',6,6'-tetrahydroxyethoxy-5,5'-(9-fluorenylidene)-bisphenoxyethanol], 9,9-bis[2,4,6-tri(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[2,4,5-tri(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[3,4,5-tri(2-hydroxyethoxy)phenyl]fluorene, ]fluorene}, and 9,9-bis[tri(hydroxyC2-4 alkoxy)phenyl]fluorenes}, and 9,9-bis[tri(hydroxypolyalkoxy)phenyl]fluorenes corresponding to these 9,9-bis[tri(hydroxyalkoxy)phenyl]fluorenes {for example, 9,9-bis[tri(hydroxyC2-4 alkoxyC2-4 alkoxy]phenyl]fluorenes (compounds where n = 2) such as 9,9-bis{2,4,6-tri[2-(2-hydroxyethoxy)ethoxy]phenyl}fluorene, 9,9-bis{2,4,5-tri[2-(2-hydroxyethoxy)ethoxy]phenyl}fluorene, and 9,9-bis{3,4,5-tri[2-(2-hydroxyethoxy)ethoxy]phenyl}fluorene}.

[0055] The 9,9-bis(polyhydroxynaphthyl)fluorenes include compounds corresponding to the above-mentioned 9,9-bis(hydroxynaphthyl)fluorenes, such as 9,9-bis(di- or trihydroxynaphthyl)fluorene.

[0056] Furthermore, the 9,9-bis[poly(hydroxy(poly)alkoxy)naphthyl]fluorenes include compounds corresponding to the 9,9-bis(hydroxy(poly)alkoxynaphthyl)fluorenes, for example, 9,9-bis[di- or tri(hydroxy(poly)alkoxy)naphthyl]fluorene and the like.

[0057] A preferred example of the fluorene-based diol is 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene.

[0058] Isocyanate (A2) The alkylene group of A2 is an aromatic isocyanate which may have a substituent, for example, an alkyl group such as a methyl group, and is preferably derived from an aromatic isocyanate having a total of 6 to 16 carbon atoms, more preferably from an aromatic isocyanate having 7 to 14 carbon atoms, and particularly preferably from an aromatic isocyanate having 8 to 12 carbon atoms. The isocyanate used to form the structural unit A2 is preferably an aromatic isocyanate, which can easily achieve a high refractive index, but aliphatic, alicyclic, or other isocyanates can also be used.

[0059] For example, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexa Examples of suitable isocyanates include polyisocyanates such as phenylene diisocyanate, lysine diisocyanate, lysine triisocyanate, and naphthalene diisocyanate, trimer compounds or tetramer compounds of these polyisocyanates, biuret-type polyisocyanates, water-dispersible polyisocyanates (e.g., "AQUANATE 100," "AQUANATE 110," "AQUANATE 200," and "AQUANATE 210," manufactured by Nippon Polyurethane Industry Co., Ltd.), and reaction products of these polyisocyanates with polyols. Among these isocyanates, diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, adducts of toluene diisocyanate with trimethylolpropane (TMP), isocyanurates of toluene diisocyanate, and adducts of xylene diisocyanate with TMP are preferred.

[0060] (Meth)acryloyloxy Group-Containing Alkyl Group (A3) The alkyl group of A3 may have a substituent such as an alkoxy group or an aryloxy group, and is preferably an alkyl group having a total of 6 to 24 carbon atoms, preferably 8 to 20. The number of (meth)acryloyloxy groups in the alkyl group of A3 is preferably 1 to 3.

[0061] A preferred specific example of the component for forming the alkyl group A3 above is a monofunctional (meth)acrylic compound having a hydroxyl group. Examples of the monofunctional (meth)acrylic compound having a hydroxyl group include hydroxyl group-containing mono(meth)acrylates {e.g., hydroxyalkyl(meth)acrylates [e.g., hydroxy C2-20 alkyl-(meth)acrylates such as 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, preferably hydroxy C2-12 alkyl-(meth)acrylate, more preferably hydroxy C2-6 alkyl-(meth)acrylate], polyalkylene glycol mono(meth)acrylates [e.g., poly C2-4 alkylene glycol mono(meth)acrylates such as diethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate], and monofunctional (meth)acrylic compounds having three or more hydroxyl groups. mono(meth)acrylates of polyols having the formula (e.g., alkane polyol mono(meth)acrylates such as glycerin mono(meth)acrylate and trimethylolpropane mono(meth)acrylate, and mono(meth)acrylates of polymers of alkane polyols such as diglycerin mono(meth)acrylate), etc.}, N-hydroxyalkyl(meth)acrylamides (e.g., N-hydroxy C1-4 alkyl(meth)acrylamides such as N-methylol(meth)acrylamide and N-(2-hydroxyethyl)(meth)acrylamide), and adducts in which lactones (e.g., C4-10 lactones such as ε-caprolactone) are added to the hydroxyl groups of these compounds (e.g., hydroxyalkyl(meth)acrylates) (e.g., adducts in which about 1 to 5 moles of lactone are added). These (meth)acrylic compounds may be used alone or in combination of two or more. A preferred example of the compound for forming the alkyl group (A3) containing a (meth)acryloyloxy group is 2-hydroxy-3-phenoxypropyl acrylate.

[0062] Preferred specific examples of the urethane (meth)acrylate contained in the resin material include compounds of the following formulae (II) to (V).

[0063] <Urethane (meth)acrylate as Resin Material for High Refractive Index Layer> The (meth)acrylate contained in the resin material for the high refractive index layer may be the same type of compound as the (meth)acrylate contained in the resin material for the low refractive index layer described above. For example, the (meth)acrylate forming the high refractive index layer may be a compound having 4 to 20 carbon atoms, which contains at least one (meth)acryloyloxy group and at least one vinyl ether group, and may have a substituent. The (meth)acrylate preferably has 6 to 18 carbon atoms, more preferably 8 to 16 carbon atoms. Examples of the substituent for the (meth)acrylate include alkyl groups. For example, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate (VEEA) may be used as the (meth)acrylate.

[0064] <High refractive index member> The high refractive index layer preferably contains a high refractive index member. The high refractive index member is added to increase the refractive index value of the high refractive index layer. That is, by forming the high refractive index layer using a high refractive index member, the difference in refractive index between the high refractive index layer and the substrate layer can be increased, and the reflectance of the anti-reflection film can be further increased. Examples of the high refractive index member include titanium oxide, zirconium oxide (ZrO ２ ), zinc oxide, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, ferric oxide, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, hafnium oxide, niobium oxide, tantalum oxide (Ta ２ O ５ ), barium oxide, indium oxide, europium oxide, lanthanum oxide, zirconium oxide, tin oxide, and lead oxide, as well as their double oxides, such as lithium niobate, potassium niobate, lithium tantalate, and aluminum magnesium oxide (MgAl ２ O４ ) and the like. Furthermore, rare earth oxides can be used as the high refractive index member, such as scandium oxide, yttrium oxide, lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, and lutetium oxide. Of the many options mentioned above, zirconia (zirconium oxide) is preferred as the high refractive index member.

[0065] The high-refractive-index component is preferably a particulate component. The particle size (diameter: average particle size) of the particulate high-refractive-index component is not particularly limited, but is, for example, 1 to 100 nm, preferably 5 to 50 nm, more preferably 7.5 to 30 nm, and particularly preferably 10 to 20 nm. The (average) particle size of the particulate high-refractive-index component is measured, for example, by dynamic light scattering in accordance with JIS Z 8828:2019 (ISO 22412:2017), as described above. Furthermore, for example, the particulate high-refractive-index component preferably includes an organic layer coating as a surface treatment layer covering the outer surface of a metal oxide or the like. The organic layer coating improves the compatibility of the high-refractive-index component with the resin material forming the high-refractive-index layer, thereby firmly bonding the high-refractive-index component to the resin material. The surface treatment layer is preferably an organic layer coating with ultraviolet-reactive (curing) functional groups introduced onto the surface.

[0066] The high refractive index layer preferably contains the above-mentioned resin material and high refractive index member in a weight ratio of 10:90 to 40:60, and the ratio of the resin material to the high refractive index member is more preferably 15:85 to 35:65, and even more preferably 20:80 to 30:70.

[0067] <Refractive Index of High Refractive Index Layer> The refractive index of the high refractive index layer is higher than that of the substrate layer. The refractive index of the high refractive index layer is preferably 1.68 to 1.75, more preferably 1.69 to 1.74, and even more preferably about 1.70 to 1.73. The difference between the refractive index of the high refractive index layer and that of the substrate layer is preferably at least 0.09, more preferably at least 0.12, even more preferably at least 0.15, and particularly preferably at least 0.17. The difference between the refractive index of the high refractive index layer and that of the substrate layer is, for example, in the range of 0.03 to 0.70, preferably 0.10 to 0.50, and even more preferably 0.15 to 0.26. In this way, by increasing the difference between the refractive index of the high refractive index layer and that of the substrate layer, the reflectance of the surface of the antireflection film on the high refractive index layer side can be increased.

[0068] <Other Components> The high refractive index layer or the resin material forming the high refractive index layer preferably contains at least one of a photoinitiator (photopolymerization initiator) and a leveling agent, and particularly preferably contains a photoinitiator. In addition, the resin material may contain a solvent. Examples of the leveling agent include a fluorine-based leveling agent, an acrylic-based leveling agent, and a silicone-based leveling agent.

[0069] <Thickness and Arrangement of High Refractive Index Layer> The thickness of the high refractive index layer is not particularly limited, but is preferably 10 to 300 nm, more preferably 50 to 250 nm, even more preferably 100 to 200 nm, and particularly preferably 130 to 170 nm. The high refractive index layer is preferably laminated between the substrate layer and the low refractive index layer, which will be described in detail later. In an antireflection film having such a laminate structure, the reflectance of the entire film can be reliably reduced.

[0070] [Additional Layer (Layer Other Than Substrate Layer and Antireflection Layer: Other Layer)] In an antireflection film, a layer (additional layer) other than the substrate layer and the antireflection layer (high refractive index layer and low refractive index layer) may be laminated. For example, in an antireflection film, another layer may be provided between the substrate layer and the high refractive index layer, between the substrate layer and the low refractive index layer, or between the high refractive index layer and the low refractive index layer. The thickness of the other layer (additional layer) is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. The antireflection film may further have a hard coat layer as the other layer (additional layer). By providing a hard coat layer, the surface hardness of the antireflection film is improved.

[0071] The hard coat layer is preferably laminated between the substrate layer and the low refractive index layer or between the substrate layer and the high refractive index layer. Furthermore, in an antireflection film having a laminate structure including a low refractive index layer, a high refractive index layer, and a hard coat layer, the hard coat layer is preferably laminated between the substrate layer and the high refractive index layer. That is, in an antireflection film that is a laminate including a low refractive index layer and a hard coat layer in addition to the substrate layer and the high refractive index layer, these layers are preferably laminated in the order of the substrate layer, the hard coat layer, the high refractive index layer, and the low refractive index layer. In an antireflection film having such a laminate structure, a high antireflection effect is achieved, and the surface hardness, i.e., the hardness of the surface opposite to the substrate layer, is improved.

[0072] The hard coat layer is preferably formed by a hard coat treatment applied to the surface of a substrate layer or the like. That is, the hard coat layer is preferably laminated by applying a hard coat material that can be cured by heat or active energy rays and then curing it. Examples of coating materials that can be cured using active energy rays include resin compositions composed of a single or multiple monofunctional or polyfunctional acrylate monomers or oligomers, more preferably resin compositions containing urethane acrylate oligomers. These resin compositions preferably contain a photopolymerization initiator as a curing catalyst. Examples of thermosetting resin coating materials include polyorganosiloxane-based and crosslinked acrylic-based coating materials. Such resin compositions are commercially available as hard coat agents for acrylic resins or polycarbonate resins, and can be selected appropriately taking into account suitability for the coating line. These coating materials may contain, as needed, organic solvents, as well as various stabilizers such as ultraviolet absorbers, light stabilizers, and antioxidants, as well as surfactants such as leveling agents, defoamers, thickeners, antistatic agents, and antifogging agents.

[0073] An example of a hard coat coating that is cured using active energy rays is a photopolymerizable resin composition obtained by mixing 40 to 95% by weight of a hexafunctional urethane acrylate oligomer with 5 to 60% by weight of a (meth)acrylate such as 2-(2-vinyloxyethoxy)ethyl (meth)acrylate [2-(2-vinyloxyethoxy)ethyl acrylate: VEEA] in a ratio of 100 parts by weight to which 1 to 10 parts by weight of a photopolymerization initiator is added.

[0074] The photopolymerization initiator may be any commonly known one, such as benzoin, benzophenone, benzoin ethyl ether, benzoin isopropyl ether, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, azobisisobutyronitrile, or benzoyl peroxide.

[0075] The refractive index of the hard coat layer is preferably similar to that of the substrate layer (a value in the same range). Specifically, the hard coat layer preferably has a refractive index in the range of 1.49 to 1.65. The refractive index of the hard coat layer is more preferably 1.49 to 1.60, even more preferably 1.51 to 1.60, and particularly preferably about 1.53 to 1.59. The difference between the refractive index of the substrate layer and the refractive index of the hard coat layer is preferably 0.04 or less, more preferably 0.03 or less, and even more preferably 0.02 or less.

[0076] The thickness of the hard coat layer is not particularly limited, but is preferably about 1 to 10 μm, more preferably about 2 to 8 μm, and even more preferably about 3 to 7 μm.

[0077] [Properties of anti-reflection film] <Refractive index> The refractive index of light with a wavelength of 589 nm for the resin materials of the following Examples and Comparative Examples was measured using a spectroscopic ellipsometer Auto SE (manufactured by Horiba, Ltd.), which is an automatic thin film measuring device. <Reflectance> The reflectance of the outer surface of the anti-reflection film, i.e., the surface of the low refractive index layer opposite the substrate layer, measured under the conditions of JIS Z 8722 2009, is preferably 2.0% or less, more preferably 1.8% or less, and even more preferably 1.5% or less.

[0078] <Pencil Hardness> The surface of the antireflection film on the antireflection layer side preferably has high hardness. Specifically, for example, the pencil hardness defined in JIS K-5400 on the surface of the low refractive index layer side opposite the substrate layer is preferably 3B or more, more preferably 2B or more, even more preferably F or more, and particularly preferably 2H or more.

[0079] <Abrasion Resistance> The surface of the anti-reflection film on the low refractive index layer side preferably has excellent abrasion resistance. Specifically, for medical nonwoven fabric RP Cross Gauze No. 4 (manufactured by Osaki Medical Co., Ltd.), ２ When the film of each example is reciprocated 10 times on the surface of the low refractive index layer side with a load of 1000 kJ / cm, it is preferable that no visible scratches are produced.

[0080] <Thermoformability (molding processability including deep drawability and right-angle shape forming ability)> In this way, the fact that a pressure-molded body having a sufficiently small value of the radius R is obtained means that the anti-reflection film is easily shaped to fit the right-angle region of the mold, and has excellent deep drawability and right-angle shape forming ability.

[0081] <Film Surface Condition> It is preferable that the surface of the antireflection film, particularly the surface on the low refractive index layer side, is in a good condition. Specifically, even after the process of applying a resin material for forming the low refractive index layer, drying, and curing, it is preferable that cracks, whitening, bubbling, and unevenness (mainly color unevenness) are not observed on the surface of the antireflection film, and the appearance of the obtained antireflection film surface can be said to be good.

[0082] <Elongation> The anti-reflective film also has excellent elongation during molding. Specifically, as in the case of evaluating thermoformability, the polycarbonate resin side of a sample cut to 210 mm x 297 mm x 0.3 mm (thickness) was preheated at 190 ° C. for 40 seconds, and the sample was placed so that the base layer was in contact with a mold having a deep drawing height of 1 mm or more and right-angled protrusions with both vertical and horizontal lengths of 30 mm. When the sample was pressure-molded using 1.5 MPa high-pressure air, it is preferable that the obtained pressure-molded body has a high elongation value calculated as follows in the region in contact with the right-angled protrusions of the mold. Specifically, the elongation value is calculated using the following formula (A) based on the increase in the spacing between the predetermined grid lines after pressure molding compared to before pressure molding, by printing grid lines with a predetermined spacing, such as 1 mm, on the surface of the anti-reflective film sample. (Spacing of grid lines after pressure forming (mm)) - spacing of grid lines before pressure forming (mm) / spacing of grid lines before pressure forming (mm) × 100 (%) Formula (A) The above formula (A) can be said to be equivalent to the formula showing (length between two predetermined points after pressure forming - length between the two points before pressure forming) / (length between the two points before pressure forming) × 100 (%). Using such formula (A), the anti-reflection film before pressure forming is arranged so as to cover a right-angled portion having a deep drawing height of 1 mm or more, and then the elongation (%) of a certain region after pressure forming can be calculated. As exemplified in FIG. 3, grid lines spaced 1 mm apart are printed on the surface of the anti-reflection film before pressure forming, and if the spacing of the grid lines in a predetermined region after pressure forming, for example, the region surrounded by a diamond in FIG. 3, is 2 mm, the elongation is calculated by the above formula (A) as (2 (mm) - 1 (mm)) / 1 (mm) × 100 = 100 (%).

[0083] The anti-reflection film is preferably moldable so that the elongation calculated based on the above formula (A) is sufficiently large. For example, in a sample of the anti-reflection film obtained by cutting into 210 mm × 297 mm × 0.3 mm (thickness), the base layer is preheated at 190 ° C. for 40 seconds, the sample is placed in a mold having a deep-drawing height of 1 mm to 5 mm and a rectangular protrusion with a length and width of 30 mm so that the base layer is in contact with the mold, and the sample is subjected to pressure molding using high-pressure air of 1.5 MPa. The elongation (%) calculated by formula (A) in the region of the obtained pressure-molded body that is in contact with the rectangular portion of the mold is preferably 10 times the deep-drawing height (mm) of the mold or more, more preferably 14 times the deep-drawing height (mm) of the mold or more. More specifically, the anti-reflection film of this example can be placed so as to cover a right-angled portion of a mold having a deep-draw height of 1 mm, and then subjected to pressure forming to achieve an elongation rate of 10% or more, or even 14% or more. Furthermore, when the anti-reflection film of this example is placed so as to cover a right-angled portion (protrusion) of a mold having a deep-draw height of 3 mm and then subjected to pressure forming, an elongation rate of 30% or more, or even 42% or more, can be achieved. Similarly, if the deep-draw height of the right-angled portion of the mold is 7 mm, an elongation rate of at least 70%, or even approximately 100% (98%), can be achieved.

[0084] [Laminate / Laminate Film] The laminate of the present invention, for example, a laminate film, has an anti-reflection film, and preferably has the above-mentioned anti-reflection film and a transparent resin substrate. Examples of the transparent resin substrate include a bisphenol A polycarbonate layer on which a methacrylic resin layer is laminated, and a bisphenol A polycarbonate layer on which a bisphenol C polycarbonate layer is laminated. The thickness of the transparent resin substrate is not particularly limited, but is preferably 30 μm to 1000 μm (1 mm), more preferably 50 μm to 700 μm, and even more preferably 100 μm to 500 μm. The above-mentioned laminate can be used in various applications, as follows. Examples of laminate films include films attached to the surfaces of computers, particularly computer screens, televisions, particularly television screens, plasma display panels, etc.; polarizing plates used in liquid crystal display devices, sunglasses lenses, prescription eyeglass lenses, camera viewfinder lenses, various instrument covers, automobile glass, train glass, in-vehicle display panels, electronic device housings, etc.

[0085] [Method for manufacturing anti-reflection film and laminate film] In manufacturing an anti-reflection film, it is preferable to first form a substrate layer. In manufacturing the substrate layer, a material such as a resin composition is processed into a layer (sheet) by a conventional method. For example, extrusion molding or cast molding is used. An example of extrusion molding is a method in which pellets, flakes, or powder of the resin composition of the present invention are melted and kneaded in an extruder, then extruded from a T-die or the like, and the resulting semi-molten sheet is cooled and solidified while being clamped between rolls to form a sheet.

[0086] The above-mentioned resin material is then applied to the outer surface of one or more substrate layers and cured to form a low refractive index layer. In this way, an anti-reflection layer can be formed by a lamination process in which a low refractive index layer having a lower refractive index than the substrate layer is laminated on at least one surface of the substrate layer containing a thermoplastic resin. A high refractive index layer can also be formed by a process similar to the lamination process for the low refractive index layer using a resin material for the high refractive index layer. Methods such as photocuring and heat curing can be used to cure the resin material.

[0087] Furthermore, a laminate film is produced by laminating a transparent resin substrate onto the antireflection film produced in this manner using a known method, for example.

[0088] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples and can be practiced with any modifications within the scope of the present invention.

[0089] <Substrate Layer> A transparent resin sheet (DF02U manufactured by Mitsubishi Gas Chemical Company, Inc.; total thickness 300 μm) in which a methacrylic resin layer (refractive index 1.491) was laminated onto a polycarbonate resin layer (refractive index 1.584) made of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was used as the substrate layer.

[0090] <Low refractive index paint> As shown below, methyl ethyl ketone was added as a solvent to each of urethane (meth)acrylate resin materials (U-1) to (U-8) as reaction products obtained by reacting each compound, to prepare a mixed liquid (urethane acrylate liquid (resin content 80 mass %: solvent (methyl ethyl ketone)) 20 mass %).

[0091] 1. Urethane acrylate liquids of Examples 1 to 6 (U-1) Polymer of meta-xylene diisocyanate and pentaerythritol triacrylate (refractive index: 1.508) (U-2) Polymer of meta-xylene diisocyanate, pentaerythritol triacrylate, and caprolactone acrylate (U-2-1) Pentaerythritol triacrylate / caprolactone acrylate=50 / 50 molar (refractive index: 1.489) (U-2-2) Pentaerythritol triacrylate / caprolactone acrylate=20 / 80 molar (refractive index: 1.497) (U-2-3) Pentaerythritol triacrylate / caprolactone acrylate=80 / 20 molar (refractive index: 1.503) (U-3) Polymer of meta-xylene diisocyanate, pentaerythritol triacrylate, and 2-hydroxyethyl acrylate (refractive index: 1.508) Pentaerythritol triacrylate / 2-hydroxyethyl acrylate=50 / 50 mol (U-4) Polymer of metaxylene diisocyanate, pentaerythritol triacrylate, and 2-hydroxybutyl acrylate (refractive index: 1.507) Pentaerythritol triacrylate / 2-hydroxybutyl acrylate=50 / 50 mol

[0092] 2. Urethane acrylate liquids of Comparative Examples 1 to 4 (U-5) Polymer of isophorone diisocyanate and pentaerythritol triacrylate (refractive index: 1.495) (U-6) Polymer of isophorone diisocyanate, pentaerythritol triacrylate, and caprolactone acrylate (refractive index: 1.489) Pentaerythritol triacrylate / caprolactone acrylate=50 / 50 mol (U-7) Polymer of isophorone diisocyanate, pentaerythritol triacrylate, and 2-hydroxyethyl acrylate (refractive index: 1.496) Pentaerythritol triacrylate / 2-hydroxyethyl acrylate=50 / 50 mol (U-8) Polymer of isophorone diisocyanate, pentaerythritol triacrylate, and 2-hydroxybutyl acrylate (refractive index: 1.494) Pentaerythritol triacrylate / 2-hydroxybutyl acrylate=50 / 50 mol

[0093] 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA) was added to each of the urethane acrylate solutions (U-1) to (U-8) above, and the mixture was adjusted to a urethane acrylate solution / VEEA ratio of 90 / 10 (wt%). The mixed resin was then mixed with hollow silica (Suluria 4320 manufactured by JGC Catalysts and Chemicals Co., Ltd.: average particle size 50-60 nm) at a ratio of 50 / 50 (wt%). 5 wt% of 1-hydroxycyclohexylphenyl ketone (Omnirad 184 manufactured by IGM Resins B.V.) as a photoinitiator and 1 wt% of leveling agent RS-78 (manufactured by DIC: solids content as a leveling agent is 40 wt% and diluted with MEK solvent) were added and dissolved in the mixed solution, and a solvent (propylene glycol monomethyl ether) was added to adjust the concentration so that the solids content was 1.5 wt%. The obtained material was used as a low refractive index coating material for a low refractive index layer.

[0094] <Hard Coating Paint> (HC-1): Hard coat resin consisting of isophorone diisocyanate (771 parts by weight), 2-acryloylethyl-2-hydroxyethyl-phthalic acid (987 parts by weight), and caprolactone acrylate (1102 parts by weight) (molar ratio of 2-acryloylethyl-2-hydroxyethyl-phthalic acid:caprolactone acrylate:50:50) (HC-2): Hard coat resin consisting of xylene diisocyanate (1175 parts by weight) and 2-hydroxypropyl acrylate (1625 parts by weight) HC-1 and HC-2 were mixed in an 80:20 (weight ratio), and 1-hydroxycyclohexylphenyl ketone (IGM Resins) was used as a photoinitiator. 5% by weight of Omnirad 184 (manufactured by BV) was added, and a solvent (propylene glycol monomethyl ether) was added to adjust the concentration so that the solid content was 30% by weight (HC-3). Note that the values ​​in parts by weight above are the amounts charged.

[0095] <Procedure> A hard coat coating of HC-3 was applied to the methacrylic resin layer of the substrate layer so as to have a dry film thickness of 3 μm, and dried at 100° C. for 1 minute. Then, an integrated light dose of 250 mJ / cm was applied using an ultraviolet curing device. ２ The hard coat layer was then irradiated with ultraviolet light so that the refractive index was 1.51. Next, a low refractive index paint was applied to the hard coat layer so that the dry film thickness was 100 nm, and the coating was dried at 100°C for 1 minute. The coating was then cured in an ultraviolet curing device under nitrogen purging until the integrated light dose reached 250 mJ / cm. ２ The low refractive index layer was formed by irradiating the film with ultraviolet light so that the refractive index became

[0096] Anti-reflection film properties Adhesion: 100 grids were created by cutting 11 cuts in each direction at 1 mm intervals in the cured film with a cutter, and Cellotape (registered trademark) (adhesive tape manufactured by Nichiban Co., Ltd.) was attached to these grids and then peeled off in one go at a 90° angle. The number of grids that remained without peeling of the cured film was counted. A state in which the coating film was present in all grids was rated "good," and a state in which even a small amount of peeling occurred was rated "poor."

[0097] Abrasion resistance: 500 g / cm against medical nonwoven fabric RP Cross Gauze No. 4 (manufactured by Osaki Medical Co., Ltd.)２ The film was reciprocated 1000 times on the surface of the low refractive index layer side of each example film under a load of 1000. The state of scratches was visually evaluated.

[0098] Reflectance (luminous reflectance): Measured in accordance with JIS Z 8722-009 using an SD6000 manufactured by Nippon Denshoku Industries Co., Ltd. In order to prevent reflection from the back surface (substrate layer side) of the film of each example, black vinyl tape was attached to the surface opposite the coated surface.

[0099] The anti-reflection film obtained in each example was cut to a size of 210 mm x 297 mm x 0.3 mm (thickness), and the polycarbonate resin side of the obtained sample was preheated to 190°C for approximately 40 seconds. Immediately afterwards, pressure molding was performed using a mold having right-angled protrusions at a deep draw height using 1.5 MPa high-pressure air. The deep draw height was set in 1 mm increments for the right-angled mold, from 1 mm, 2 mm, to 5 mm or more. The radius R of the region in contact with the right-angled portion of the mold was measured for the pressure-molded body obtained when pressure molding was performed using a mold having right-angled protrusions with a deep draw height of 1 mm or more and dimensions of 30 mm in both length and width, and the value is reported as "right-angled radius R (mm)" in Table 1 below. The smaller this value, the better the moldability. The radius R of the right-angled portion was measured using a contact-type contour measuring instrument CONTOURECORD2700 / 503 (manufactured by Tokyo Seimitsu Co., Ltd.).

[0100] Furthermore, the surface condition (cracks, whitening, foaming, unevenness) of the obtained molded body was observed, and if no cracks, whitening, foaming, or unevenness was observed, the scratch resistance was evaluated as "no scratches." Furthermore, molded bodies with a deep drawing height of 1 mm or more and a radius R of the right-angled portion of 3.0 mm or less that could be molded into a scratch-free state were evaluated as "good" in terms of thermoformability. Furthermore, the deep drawing height of the obtained molded body, i.e., the height of the molded area on the molded convex portion (protrusion) relative to the reference plane of the molded film, was measured and taken as the "deep drawing height (mm)."

[0101] The measurement results of the properties of the films of the above-mentioned Examples and Comparative Examples are as shown in Table 1. The refractive index in the table is the value of the coating material before polymerization for each layer, and the refractive index value after polymerization was generally about 0.02 higher than the value of the coating material before polymerization for each layer.

[0102] From the above, it was confirmed that the anti-reflection films of the examples have high interlayer adhesion, good scratch resistance, and excellent thermoformability despite having high surface hardness, and low surface reflectance.

[0103] Furthermore, unlike Examples 1 to 6, an anti-reflection film 10B having excellent properties can be obtained even when an additional layer (other layer) 18 such as a hard coat layer is formed (see FIG. 2).

[0104] 10A, 10B Anti-reflection film 12 Low refractive index layer 16 High refractive index layer 18 Additional layer (other layer) 20 Methacrylic resin layer (substrate layer) 22 Polycarbonate resin layer (substrate layer)

Claims

1. A base layer containing a thermoplastic resin; a low refractive index layer laminated on at least one surface of the base layer and having a refractive index lower than that of the base layer; The low refractive index layer is A urethane (meth)acrylate derived from an aromatic diisocyanate compound (a1) and one or more (meth)acryloyl compounds (a2) having a hydroxyl group and a (meth)acryloyl group in one molecule, (Meth)acrylate An anti-reflective film comprising a polymer of a resin material comprising:

2. 2. The anti-reflective film of claim 1, wherein the resin material comprises a mixture of urethane (meth)acrylates having 2 to 6 (meth)acryloyl groups in one molecule.

3. The urethane (meth)acrylate is The aromatic diisocyanate compound (a1), and 2. The anti-reflective film according to claim 1, comprising a reaction product of at least one of the (meth)acryloyl compounds (a2) selected from the group consisting of pentaerythritol tri(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.

4. The (meth)acryloyl compound (a2) contains a compound (a2-1) having one (meth)acryloyl group in one molecule and a compound (a2-2) having three (meth)acryloyl groups in one molecule in a molar ratio of (a2-1) / (a2-2)=80 / 20 to 0 / 100. The antireflection film according to claim 1.

5. 2. The anti-reflection film according to claim 1, wherein the (meth)acryloyl compound (a2) comprises at least one selected from pentaerythritol tri(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.

6. The anti-reflection film according to claim 1, wherein the (meth)acrylate is a compound having 4 to 20 carbon atoms, which contains at least one (meth)acryloyl group and at least one vinyl ether group, and which may have a substituent.

7. The anti-reflective film according to claim 1 , wherein the low refractive index layer further comprises a low refractive index member.

8. The anti-reflective film according to claim 7 , wherein the low refractive index member comprises hollow silica.

9. 8. The anti-reflection film according to claim 7, wherein the low refractive index layer contains the resin material and the low refractive index member in a weight ratio of 20:80 to 70:

30.

10. 10. The antireflective film of claim 1, wherein the low refractive index layer further comprises at least one of a photoinitiator and a fluorine-based leveling agent.

11. The anti-reflection film according to claim 1 , wherein the resin material contains the urethane acrylate and the (meth)acrylate in a weight ratio of 95:5 to 70:

30.

12. The anti-reflective film according to claim 1 , comprising two or more of the substrate layers.

13. 2. The anti-reflection film according to claim 1, wherein the thickness of the substrate layer is 50 to 500 μm, and the thickness of the low refractive index layer is 10 to 200 nm.

14. The anti-reflection film according to claim 1 , further comprising a hard coat layer laminated between the substrate layer and the low refractive index layer.

15. The anti-reflection film according to claim 14, wherein the refractive index of the substrate layer is 1.49 to 1.65, and the difference between the refractive index of the substrate layer and the refractive index of the hard coat layer is in the range of 0.04 or less.

16. The anti-reflection film according to claim 1 , further comprising a high refractive index layer having a refractive index higher than that of the base layer.

17. The anti-reflection film according to claim 16, wherein the refractive index of the base layer is 1.49 to 1.65, the refractive index of the low refractive index layer is 1.31 to 1.40, and the refractive index of the high refractive index layer is 1.68 to 1.

75.

18. The anti-reflection film according to claim 16, wherein the high refractive index layer is laminated between the substrate layer and the low refractive index layer.

19. The anti-reflection film according to claim 16, further comprising a hard coat layer laminated between the substrate layer and the high refractive index layer.

20. Further having a hard coat layer, The anti-reflection film according to claim 16, wherein the substrate layer has a thickness of 50 to 500 μm, the hard coat layer has a thickness of 1 to 10 μm, the high refractive index layer has a thickness of 10 to 200 nm, and the low refractive index layer has a thickness of 10 to 200 nm.

21. 17. The anti-reflection film according to claim 16, wherein the high refractive index layer comprises a polymer of a resin material containing a fluorene-based diol, an isocyanate, and a urethane (meth)acrylate derived from a (meth)acrylate, and a (meth)acrylate.

22. 2. The anti-reflection film according to claim 1, wherein when a sample of the anti-reflection film obtained by cutting to 210 mm x 297 mm x 0.3 mm (thickness) is preheated at 190°C for 40 seconds, the sample is placed in a mold including a right-angled protrusion having a deep-drawing height of 1 mm or more and a length and width of 30 mm so that the base material layer is in contact with the sample, and the sample is subjected to pressure molding using high-pressure air of 1.5 MPa, the radius R of the region in contact with the right-angled portion of the mold obtained is within 3.0 mm.

23. A base layer containing a thermoplastic resin; a low refractive index layer laminated on at least one surface of the base layer and having a refractive index lower than that of the base layer; The anti-reflection film sample was cut to 210 mm x 297 mm x 0.3 mm (thickness), and the base layer was preheated at 190° C. for 40 seconds. The sample was placed in a mold including a right-angled protrusion having a deep-drawing height of 1 mm or more and a length and width of 30 mm so that the base layer was in contact with the mold. The sample was then pressure-molded using high-pressure air of 1.5 MPa. In the region of the pressure-molded body that was in contact with the right-angled portion of the mold, The elongation percentage (%) is a value obtained by the formula: (length between two given points after pressure forming-length between the two given points before pressure forming) / length between the two given points before pressure forming×100(%). An anti-reflective film having a value equal to or greater than 10 times the value of the deep drawing height (mm) of the mold.

24. A base layer containing a thermoplastic resin; a low refractive index layer laminated on at least one surface of the base layer and having a refractive index lower than that of the base layer; The antireflection film has a reflectance of 2.0% or less on the surface on the low refractive index layer side measured under the conditions of JIS Z 8722-2009, An anti-reflective film in which the base material layer of a sample of the anti-reflective film obtained by cutting to 210 mm x 297 mm x 0.3 mm (thickness) is preheated at 190°C for 40 seconds, the sample is placed in a mold including a right-angled protrusion having a deep-drawing height of 1 mm or more and a length and width of 30 mm each, so that the base material layer is in contact with the sample, and the sample is subjected to pressure molding using high-pressure air of 1.5 MPa, and the radius R of the area in contact with the right-angled portion of the mold obtained is within 3.0 mm.

25. A laminate comprising a transparent resin substrate and the antireflection film according to any one of claims 1 to 24.

26. On at least one surface of a base layer containing a thermoplastic resin, A method for producing an antireflection film, comprising a lamination step of laminating a low refractive index layer having a refractive index lower than that of the base layer, The low refractive index layer is A urethane (meth)acrylate derived from an aromatic diisocyanate compound (a1) and one or more (meth)acryloyl compounds (a2) having a hydroxyl group and a (meth)acryloyl group in one molecule, (Meth)acrylate A method for producing an anti-reflective film comprising the polymer of a resin material comprising: