Laminate

Abstract

To provide a laminate which is excellent in optical characteristics and scratch resistance, has a high yield even when being manufactured by a roll-to-roll method, and is excellent in OCA adhesion regardless of presence / absence of annealing treatment.SOLUTION: A laminate has a light transparent base material layer (A), and a resin layer (B) that is a cured layer of a curable composition (S) containing particles (R) and a curable compound (Q). In a laminated constitution of the resin layer (B) of 1 μm, and PET of 50 μm, a haze value when being measured from the surface layer side of the resin layer (B) is set at 2.0% or less. A main surface (F) of the resin layer (B) opposite to the side of the light transparent base material layer (A) has initial wet tension before annealing treatment of 38-60 mN / m, and wet tension of the main surface (F) of the resin layer (B) after a heat-resistant protective PET film has been stuck to the main surface (F) and has been subjected to annealing treatment for 3 hours, and the heat-resistant protective PET film has been peeled is set at 30-54 mN / m.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminate and a transparent electrode film having a resin layer that is a cured layer of a curable composition that exhibits curability when exposed to active energy rays. [Background technology]

[0002] Transparent electrode films, which are made by laminating a transparent conductive layer having a desired pattern, such as ITO (indium tin oxide), on a light-transmitting substrate layer, such as a polyethylene terephthalate (PET) film, are used as electrode materials for display devices such as touch panels. An optically clear adhesive (OCA) film is attached to the transparent electrode film, and the film is then incorporated into a touch panel module.

[0003] Patent Document 1 proposes a configuration that solves the problems of air bubble voids occurring during the baking process of a light-transmitting transparent conductive film to which an OCA film is attached, and of the problem that when the OCA is attached and then transported by rolls, the OCA film partially peels off, causing a shift in the adhesive surface with the light-transmitting conductive film, causing the film to protrude from the edge of the light-transmitting conductive film. This configuration involves forming an ITO layer on a PET film and adjusting the wetting tension of the PET film surface to 34 dyn / cm or more by plasma treatment.

[0004] Patent Document 2 proposes a curable composition that contains an active energy ray-curable compound and silica particles and that provides a cured coating film with a surface wetting tension of 35 to 60 mN / m, with the objective of forming a hard coating layer that can impart high anti-blocking properties to the film surface and has high transparency and high adhesiveness to OCA and the like. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-155366 [Patent Document 2] International Publication No. 2018 / 100929 Summary of the Invention [Problem to be solved by the invention]

[0006] Laminates suitable for use in transparent electrode films, which are electrode materials for display devices such as touch panels, not only have excellent optical properties and scratch resistance, but also have high yields when manufactured using the roll-to-roll method, and are highly versatile, with excellent adhesion to OCA films, regardless of whether an annealing process is used. While the above describes the challenges facing laminates used in transparent electrode films, similar challenges can arise in all applications requiring the above properties.

[0007] The present invention has been made in view of the above background, and aims to provide a laminate and a transparent electrode film that have excellent optical properties and scratch resistance, have a high yield even when produced by a roll-to-roll method, and have excellent OCA adhesion regardless of whether or not annealing treatment is performed. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have found that the problems of the present invention can be solved by the following aspects, and have thus completed the present invention. [1]: A laminated structure in which a resin layer (B) is laminated directly or via one or more other layers on at least one surface of a light-transmitting substrate layer (A), the resin layer (B) is a layer obtained by curing a curable composition (S) containing particles (R) and a curable compound (Q) (excluding the particles (R)) that exhibits curability when exposed to active energy rays, the particles (R) are at least one selected from inorganic particles and resin beads having a gel fraction of 80% by mass or more relative to methyl ethyl ketone; In a laminated structure of a 1 μm-thick resin layer (B) and a 50 μm-thick polyethylene terephthalate, the haze value is 2.0% or less when measured from the surface layer side of the resin layer (B), the main surface (F) of the resin layer (B) opposite to the light-transmitting base layer (A) side has an initial wetting tension of 38 to 60 mN / m before annealing treatment; and a heat-resistant protective polyethylene terephthalate film is attached to the main surface (F) of the resin layer (B), and the resin layer (B) is annealed at 150°C for 3 hours, and after the heat-resistant protective polyethylene terephthalate film is peeled off, the wet tension of the main surface (F) of the resin layer (B) is 30 to 54 mN / m; The curable composition (S) is (i) As the curable compound (Q), a curable compound (Q) having at least one of a tertiary amino group and a quaternary ammonium salt group is used. N ), and (ii) Contains a hydrophilizing agent (T) (excluding particles (R)) that is not curable by active energy rays, The hydrophilizing agent (T) is a hydrophilizing agent having at least one of a tertiary amino group and a quaternary ammonium base (T N ) containing, A laminate that satisfies at least one of the above. [2]: A curable compound (Q) having at least one of a tertiary amino group and a quaternary ammonium base. N ) has a (meth)acryloyl group. [3]: A curable compound having at least one of a tertiary amino group and a quaternary ammonium base (Q N ), and a hydrophilizing agent having at least one of a tertiary amino group and a quaternary ammonium base (T N ) is 3 to 40 mass % relative to 100 mass % of the nonvolatile components of the curable composition (S). [4]: The laminate according to any one of [1] to [3], wherein the content of the particles (R) is 0.01 to 40 mass % relative to 100 mass % of the nonvolatile components of the curable composition (S). [5]: A transparent conductive layer and the laminate according to any one of [1] to [4], A transparent electrode film in which at least the transparent conductive layer, the light-transmitting substrate layer (A) constituting the laminate, and the resin layer (B) constituting the laminate are laminated in this order, either directly or via one or more layers. [6]: The transparent electrode film according to [5], further comprising an optically transparent pressure-sensitive adhesive film laminated on the main surface of the resin layer (B) opposite to the light-transmitting substrate layer (A). [Effects of the Invention]

[0009] The present invention has the excellent effect of providing a laminate and a transparent electrode film that are excellent in optical properties and scratch resistance, have a high yield even when produced by a roll-to-roll method, and have excellent OCA adhesion regardless of whether annealing treatment is performed or not. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of a transparent electrode film according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. Needless to say, other embodiments are also included within the scope of the present invention as long as they are consistent with the spirit of the present invention. In this specification, a numerical range specified using "to" includes the numerical values ​​written before and after "to." In this specification, "film" and "sheet" are not distinguished by thickness. Furthermore, unless otherwise noted, the various components appearing in this specification may be used independently, either singly or in combination of two or more types.

[0012] [[Laminate]] The laminate according to this embodiment has a laminated structure comprising a light-transmitting substrate layer (A) and a resin layer (B) formed on at least one surface of the light-transmitting substrate layer (A) directly or via one or more other layers. The resin layer (B) is a layer formed by curing a curable composition (S) containing particles (R) and a curable compound (Q) (excluding particles (R)) that exhibits curability when exposed to active energy rays. The particles (R) are either inorganic particles or resin beads. The particles (R) may be crystalline or amorphous. Inorganic particles are particles (fillers) made of substances other than organic compounds, such as metal and nonmetallic hydrides, borides, nitrides, carbides, oxides, halides, and chalcogenides, as well as particles made of these compounds. Resin beads are resin particles (fillers) that are solid at room temperature and pressure and have a gel fraction of 80% by mass or more relative to methyl ethyl ketone. In this specification, the gel fraction is calculated by weighing 1.00 g of polymer particles as a measurement sample, extracting them by heating using 100 mL of methyl ethyl ketone (MEK) in a Soxhlet extractor, weighing the extracted soluble matter, and then calculating it using the following formula (1): Equation (1): Gel fraction (%) relative to MEK = {(1 - mass of soluble matter (g)) / 1} × 100 The gel fraction is more preferably 90% by mass or more.

[0013] The main surface (F) of the resin layer (B) opposite the light-transmitting substrate layer (A) side has an initial wet tension (hereinafter also referred to as "initial wet tension") of 38 to 60 mN / m before annealing. A heat-resistant protective polyethylene terephthalate film (hereinafter also referred to as "heat-resistant protective PET film") is attached to the main surface (F) of the resin layer (B), and annealed at 150°C for 3 hours. After the heat-resistant protective PET film is peeled off, the main surface (F) of the resin layer (B) has a wet tension (hereinafter also referred to as "wet tension after annealing") of 30 to 54 mN / m. The resin layer (B) has a laminated structure of a 1-μm-thick resin layer (B) and a 50-μm-thick polyethylene terephthalate layer, and has a haze value of 2.0% or less when measured from the surface side of the resin layer (B). Furthermore, the curable composition (S) satisfies at least one of the following (i) and (ii). (i) As the curable compound (Q), a curable compound (Q) having at least one of a tertiary amino group and a quaternary ammonium salt group is used. N ) contains. (ii) A composition containing a hydrophilizing agent (T) that does not exhibit curability by active energy rays, the hydrophilizing agent (T) having at least one of a tertiary amino group and a quaternary ammonium salt group (T N ) contains. The initial wetting tension, the wetting tension after annealing treatment, and the haze values ​​disclosed in this specification are values ​​measured by the methods described in the examples below.

[0014] Here, "curable compound (Q) that exhibits curability with active energy rays" refers to a compound in which the curable compound (Q) cures by polymerization and / or crosslinking upon irradiation with active energy rays. However, this does not apply to particles (R). Active energy rays refer to a broad range of energy rays that can provide the energy necessary for activation to cause a chemical reaction, including ultraviolet light, visible light, infrared light, electron beam (EB), and radioactive rays. Furthermore, a "cured layer" refers to a layer that has been cured to the extent that the curing reaction does not substantially proceed even when irradiated with active energy rays. When forming a layer of the curable composition (S) of this embodiment, even if a portion of the curable compound (Q) has undergone a curing reaction, a state in which it can be further cured is not included in the "cured layer" referred to here.

[0015] The light-transmitting substrate layer (A) and the resin layer (B) may be laminated directly or via other layers such as an anchor layer, an easy-adhesion layer, an adhesive layer, etc. The laminate of this embodiment may further include an OCA film laminated on the resin layer (B).

[0016] When producing laminates using the roll-to-roll method, the problem of reduced yield due to film-to-film sticking, as mentioned above, is a major issue. According to the laminate of this embodiment, a cured layer of a curable composition (S) containing a curable compound (Q) and particles (R) is used as the resin layer (B), and the laminate has an initial wet tension and a wet tension after annealing within the above-mentioned specific ranges. This results in excellent anti-blocking and scratch resistance. Furthermore, even when produced using the roll-to-roll method, blocking between films can be effectively suppressed. This significantly increases yield. Furthermore, a laminate can be provided that exhibits excellent transparency and scratch resistance, as well as excellent OCA adhesion, regardless of whether or not annealing is performed. Each layer is described in detail below.

[0017] [Light-transparent base layer (A)] The light-transmitting base layer (A) functions as a support layer for the resin layer (B). Here, light transmittance means that the transmittance of light of a required wavelength is 80% or more when measured through the thickness of the light-transmitting base layer (A) in the laminate. It is more preferably 85% or more, and even more preferably 90% or more. When the laminate is used for applications requiring transparency, the light of a required wavelength corresponds to light in the visible light region (380 to 780 nm).

[0018] The material of the light-transmitting substrate layer (A) is not particularly limited as long as it has excellent light transmittance. Suitable examples include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cyclic polyolefin resins such as cycloolefin resins (COP), linear polyolefin resins such as polyethylene, polypropylene, and ethylene-α-olefin copolymers, polyester resins, polyacrylic resins, polymethacrylic resins, polyolefin resins, polyether resins, polycarbonate resins, polystyrene resins, polyimide resins, polyamide resins, polyvinyl chloride resins, polyacetal resins, polyvinylidene chloride resins, polyphenylene sulfide resins, and acetate resins. Among these, polyethylene terephthalate, which has high versatility, and cycloolefin resins, which have low birefringence, low moisture absorption, high transparency, and high heat resistance, are preferred.

[0019] The thickness of the light-transmitting substrate layer (A) can be selected arbitrarily as long as it functions as a support for the resin layer (B). Usually, it is about 25 to 188 μm. From the viewpoint of transparency, it is preferably 25 to 125 μm, and more preferably in the range of 25 to 100 μm.

[0020] [Resin layer (B)] The resin layer (B) is a layer obtained by curing the curable composition (S) by irradiating it with active energy rays, and has excellent scratch resistance and anti-blocking properties, making it suitable for producing a laminate by a roll-to-roll method. For example, a laminate can be produced by unwinding a roll of light-transmitting substrate layer (A), coating the curable composition (S), irradiating with active energy rays to obtain a cured resin layer (B), and then rewinding the laminate onto a roll. Alternatively, the laminate can be produced by laminating a roll of light-transmitting substrate layer (A) and a roll of resin layer (B) together, and then rewinding the laminate onto a roll. This method can significantly improve productivity compared to a method in which a resin layer (B) is laminated onto a sheet of light-transmitting substrate layer (A).

[0021] The thickness of the resin layer (B) can be designed depending on the application, but from the viewpoint of imparting excellent anti-blocking properties, it is preferably 1 to 10 μm, more preferably 1 to 5 μm, and even more preferably 1 to 3 μm.

[0022] As a result of extensive research, the present inventors have found that even if the initial wet tension before annealing is in the range of 38 to 60 mN / m, annealing can significantly reduce the wet tension of the main surface of the resin layer. They have also found that by using a resin layer (B) with an initial wet tension of 38 to 60 mN / m and a wet tension of 30 to 54 mN / m after annealing (150°C x 3 hours), excellent OCA adhesion can be achieved, regardless of whether annealing is performed or not.

[0023] The initial wet tension of the main surface (F) of the resin layer (B) is 38 to 60 mN / m, more preferably 40 to 60 mN / m, and particularly preferably 42 to 60 mN / m, and the wet tension after annealing is 30 to 54 mN / m, more preferably 32 to 54 mN / m, and particularly preferably 36 to 54 mN / m.

[0024] The method of adjusting the initial wet tension of the surface layer of the resin layer (B) to 38 to 60 mN / m and the wet tension after annealing (150°C x 3 hours) to 30 to 54 mN / m can be adjusted by adjusting the composition of the curable composition (S). In addition to the above adjustment method, surface treatment may be performed to adjust the initial wet tension and wet tension after annealing of the surface layer of the resin layer (B) to the above values. The adjustment by the composition of the curable composition (S) is as follows: (1) As the curable compound (Q), a curable compound (Q) having at least one of a tertiary amino group and a quaternary ammonium salt group is used. N ) containing method, (2) The curable composition (S) further contains a hydrophilizing agent (T) that does not exhibit active energy ray curability, and the hydrophilizing agent (T) is a hydrophilizing agent having at least one of a tertiary amino group and a quaternary ammonium salt group. N ), and (3) There is a method in which the above methods (1) and (2) are used in combination.

[0025] An example of a method for adjusting the wet tension by surface treatment is to subject the surface of the resin layer (B) to at least one treatment selected from the group consisting of corona discharge treatment, ozone treatment, plasma treatment, and ultraviolet irradiation treatment.

[0026] In a laminated structure of a 1 μm-thick resin layer (B) and a 50 μm-thick polyethylene terephthalate layer, excellent transparency can be obtained by using a layer having a haze value of 2.0% or less when measured from the surface of the resin layer (B). The haze value is more preferably 1.0% or less, and even more preferably 0.5% or less. The lower limit of the haze value is 0%.

[0027] The resin layer (B) can be adjusted to satisfy the above haze value by adjusting the composition of the curable composition (S). For example, as described below, the resin layer (B) can be adjusted by adjusting the composition of the curable composition (S). OThe haze value can be reduced by using the compound (R) in combination with particles (R) and a tertiary amino group or / and a quaternary ammonium salt group. This method has the advantage of eliminating the need for corona treatment or ozone treatment.

[0028] [Curable composition (S)] The curable composition (S) of this embodiment refers to a composition that can undergo a polymerization reaction and / or a crosslinking reaction upon irradiation with active energy rays to form a resin layer (B) that is a cured layer. The curable composition (S) contains at least a curable compound (Q) that exhibits curability upon exposure to active energy rays and particles (R). Each component will be described in detail below.

[0029] <Curable compound (Q)> The curable compound (Q) may be any compound that undergoes a polymerization reaction or / and a crosslinking reaction upon irradiation with active energy rays and is cured, and may be selected regardless of molecular weight, such as a low molecular weight compound or a high molecular weight compound, except for compounds that fall under the category of particles (R). The curable compound (Q) may be used alone or in combination of two or more types.

[0030] Examples of the curable group of the curable compound (Q) include radically polymerizable groups such as a vinyl group, a (meth)acryloyl group, and an allyl group. Among these, a curable compound (Q) having a (meth)acryloyl group is preferred. The curable compound (Q) can be used alone or in combination of two or more types. Note that "(meth)acrylate" includes both "acrylate", "methacrylate", and mixtures thereof.

[0031] From the viewpoint of increasing the surface hardness of the resin layer (B), it is preferable to use 30 to 100 mass% or more of a trifunctional or higher (meth)acrylate relative to 100 mass% of the curable compound (Q), more preferably 50 to 100 mass% or more, and even more preferably 80 to 100 mass% or more.

[0032] Examples of tetrafunctional or higher (meth)acrylates include dimethylolpropane tetra(meth)acrylate, ethylene oxide-modified dimethylolpropane tetra(meth)acrylate, propylene oxide-modified dimethylolpropane tetra(meth)acrylate, tetramethylene oxide-modified dimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and polypentaerythritol polyacrylate.

[0033] Examples of trifunctional tri(meth)acrylates include trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tetramethylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, caprolactone-modified tris(acryloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, ethylene oxide-modified glycerol triacrylate, propylene oxide-modified glycerol triacrylate, ε-caprolactone-modified trimethylolpropane triacrylate, and pentaerythritol triacrylate.

[0034] Examples of bifunctional (meth)acrylates include di(meth)acrylates such as pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 2,2-dimethylpropane-1,3-diol di(meth)acrylate, hexanediol di(meth)acrylate, heptanediol di(meth)acrylate, nonanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; Ethylene oxide modified pentanediol di(meth)acrylate, propylene oxide modified pentanediol di(meth)acrylate, tetramethylene oxide modified pentanediol di(meth)acrylate, ethylene oxide modified 2,2-dimethylpropane-1,3-diol di(meth)acrylate, propylene oxide modified 2,2-dimethylpropane-1,3-diol di(meth)acrylate, tetramethylene oxide modified 2,2-dimethylpropane-1,3-diol di(meth)acrylate, ethylene oxide modified hexanediol di(meth)acrylate, propylene oxide modified hexanediol di(meth)acrylate, tetramethylene oxide modified hexanediol di(meth)acrylate, ethylene oxide modified heptanediol di(meth)acrylate alkyleneoxy group-containing di(meth)acrylates such as acrylates, propylene oxide-modified heptanediol di(meth)acrylate, tetramethylene oxide-modified heptanediol di(meth)acrylate, ethylene glycol-propylene glycol di(meth)acrylate, diethylene glycol-propylene glycol di(meth)acrylate, diethylene glycol-dipropylene glycol di(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) di(meth)acrylate, isocyanuric acid ethylene oxide-modified di(meth)acrylate, isocyanuric acid propylene oxide-modified di(meth)acrylate, isocyanuric acid butyloxide-modified di(meth)acrylate, and isocyanuric acid butyloxide-modified di(meth)acrylate; Examples include polyol ester di(meth)acrylates such as neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate.

[0035] Examples of monofunctional (meth)acrylates include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, n-hexyl acrylate, lauryl acrylate, and stearyl acrylate; (meth)acrylic acid perfluoroalkyl esters such as perfluoromethyl (meth)acrylate, 2-perfluoroethyl-ethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate; aliphatic (meth)acrylic acid esters having one carbonyl group, such as (methoxycarbonyl)methyl (meth)acrylate, 2-(ethoxycarbonyloxy)hexyl (meth)acrylate, 2-(propoxycarbonyloxy)ethyl (meth)acrylate, and 2-(octyloxycarbonyloxy)butyl (meth)acrylate; Aliphatic (meth)acrylic acid esters having two carbonyl groups, such as 2-oxobutanoylethyl (meth)acrylate, 3-oxobutanoylpropyl (meth)acrylate, 2,3-di(oxobutanoyl)butyl (meth)acrylate, and 2,3-di(oxobutanoyl)hexyl (meth)acrylate; alkoxy group-containing (meth)acrylic acid esters such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 3-propoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 3-butoxyethyl (meth)acrylate, and 4-butoxyethyl (meth)acrylate; alkylene oxide-containing (meth)acrylic acid derivatives such as alkylene oxide adducts of (meth)acrylic acid; (meth)acrylates having an alicyclic structure, such as cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexanol (meth)acrylate, 4-tertiarybutyl-cyclohexyl (meth)acrylate, 3,3-dicyclopropyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and 2-propyl-2-adamantyl (meth)acrylate; monofunctional glycerol (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 12-hydroxylauryl (meth)acrylate, and ethyl-α-(hydroxymethyl) (meth)acrylate; Fatty acid ester-based (meth)acrylic acid esters such as (meth)acrylic acid glycidyl laurate; cyclic (meth)acrylic acid esters such as cyclohexanedimethanol mono(meth)acrylate, cyclohexanediethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid; (Meth)acrylic acid esters with hydroxyl groups at the molecular terminals, synthesized by ring-opening addition of ε-caprolactone to mono(meth)acrylates with hydroxyl groups; Alkylene oxide-adduct (meth)acrylic acid esters obtained by repeatedly adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to mono(meth)acrylates having a hydroxyl group; Examples of monofunctional (meth)acrylamides include N,N-dimethyl(meth)acrylamide, (meth)acryloylmorpholine, hydroxyethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, Nn-butyl(meth)acrylamide, Nt-butyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N-methylol(meth)acrylamide.

[0036] The curable compound (Q) may be an oligomer or a polymer. In this specification, oligomer and polymer refer to polymers formed by the bonding of a finite number of monomers, with oligomers referring to compounds having a weight-average molecular weight of 10,000 or less, and polymers referring to compounds having a weight-average molecular weight of more than 10,000. Oligomers and polymers may be homopolymers or copolymers. Specific examples of (meth)acrylate oligomers include polyurethane-based (meth)acrylate oligomers, polyester-based (meth)acrylate oligomers, and epoxy-based (meth)acrylate oligomers. The weight-average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) using polystyrene of known weight-average molecular weight as a standard substance.

[0037] The polyurethane (meth)acrylate oligomer is a compound having a urethane bond and a radically polymerizable functional group. For example, the polyurethane (meth)acrylate oligomer can be obtained by reacting a compound having an isocyanate group at a terminal with a (meth)acryloyl group having a hydroxyl group, which is obtained by reacting a compound having two or more isocyanate groups with a compound having a hydroxyl group. Alternatively, the polyurethane (meth)acrylate oligomer can be synthesized by reacting a compound having a hydroxyl group with a compound having an isocyanate group and a (meth)acrylate group. The polyurethane (meth)acrylate oligomer (A1) may have a polyether skeleton or a polyester skeleton. Examples of compounds having two or more isocyanate groups include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 1,4-phenylenebismethylene diisocyanate; and aliphatic isocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate and hexamethylene diisocyanate. Examples of commercial polyurethane (meth)acrylate oligomers include aromatic polyurethane oligomers such as EBECRYL210 and EBECRYL220 (both manufactured by Daicel-Allnex Corporation), CN9782 and CN9783 (both manufactured by SARTOMER), and aliphatic polyurethane oligomers such as Shikou UV3000B and Shikou UV3300B (both manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL8402 and EBECRYL8701 (both manufactured by Daicel-Allnex Corporation).

[0038] A polyester-based (meth)acrylate oligomer is a compound having an ester bond and a radically polymerizable functional group, and can be synthesized, for example, by an esterification reaction between a hydroxyl group possessed by a polyester synthesized by polycondensation of a polybasic acid and a polyhydric alcohol and a (meth)acrylate having a carboxyl group (e.g., (meth)acrylic acid, etc.). Examples of polybasic acids include aliphatic polybasic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, fumaric acid, itaconic acid, succinic anhydride, and maleic anhydride; alicyclic polybasic acids such as dimer acid and cyclohexanedicarboxylic acid; and aromatic polybasic acids such as isophthalic acid, terephthalic acid, and biphenyldicarboxylic acid. Examples of polyhydric alcohols include polyols such as polyethylene glycol and propylene glycol having a number average molecular weight (Mn) of 50 to 500, and polyols having a number average molecular weight (Mn) of 500 to 30,000, as well as trimethylolpropane, glycerin, and pentaerythritol. Examples of commercial polyester (meth)acrylate oligomers include aromatic polyester oligomers such as CN296, CN2203, CN2259, and CN2261 (all manufactured by SARTOMER), and aliphatic polyester oligomers such as CN294, CN2270, and CN2271 (all manufactured by SARTOMER).

[0039] The epoxy (meth)acrylate oligomer is a compound having a radical polymerizable functional group, which is obtained by reacting the epoxy group of a compound having an epoxy group with a compound having a carboxyl group or a hydroxyl group. Note that the epoxy (meth)acrylate oligomer may contain a small amount of residual epoxy group. Examples of commercial epoxy (meth)acrylate oligomers include aromatic epoxy oligomers such as CN104 and CN110 (all manufactured by SARTOMER), EBECRYL600 and EBECRYL3701 (all manufactured by Daicel-Allnex Corporation), and aliphatic epoxy oligomers such as CN111 and CN113 (all manufactured by SARTOMER), and EBECRYL860 (manufactured by Daicel-Allnex Corporation).

[0040] Specific examples of the (meth)acrylate polymer include compounds obtained by replacing the specific examples of the oligomers with polymers.

[0041] As a method for making the initial wetting tension of the main surface (F) of the resin layer (B) opposite to the light-transmitting base layer (A) side 38 to 60 mN / m and the wet tension after annealing 30 to 54 mN / m, the above-mentioned method (1) is used, that is, a curable compound (Q) having at least one of a tertiary amino group and a quaternary ammonium salt group is used as the curable compound (Q N From the viewpoint of easily adjusting the wet tension, the amine value is preferably 140 to 370 mgKOH / g. The amine value is a value obtained by the method in the examples described later.

[0042] Examples of tertiary amino groups include dialkylamino groups such as dimethylamino, diethylamino, and dibutylamino. Examples of quaternary ammonium groups include trialkylammonium groups such as trimethylammonium, triethylammonium, and tributylammonium. Examples of counter ions to the nitrogen atom constituting the quaternary ammonium group include chloride ions, bromide ions, and hydroxide ions.

[0043] Curable compounds with tertiary amino groups (Q N As the alkyl group (meth)acrylate, a (meth)acrylate having a tertiary amino group is preferred. Preferred examples include N,N-dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate, N-[2-methacryloyloxyethyl]piperidine, N-[2-methacryloyloxyethyl]pyrrolidine, N-[2-methacryloyloxyethyl]morpholine, and 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate. Other examples include methacrylates in which an epoxy group is opened to form a hydroxyl group, obtained by reacting glycidyl (meth)acrylate with a secondary amino compound such as dimethylamine, diethylamine, or dipropylamine, or a compound having a tertiary amino group and a secondary amino group, such as dimethylaminopropylmethylamine; and (meth)acrylates having a urethane bond or urea bond, obtained by reacting a (meth)acrylate having an isocyanate group, such as methacryloyloxyethyl isocyanate, with a compound having a hydroxyl group, or a primary or secondary amino group and a tertiary amino group. Among these, N,N-dialkylaminoalkyl (meth)acrylates are more preferred.

[0044] Curable compounds with quaternary ammonium bases (Q NAs the quaternary ammonium salt, a (meth)acrylate having a quaternary ammonium salt group is preferred. A suitable example is a (meth)acrylate obtained by reacting a (meth)acrylate having a tertiary amino group with a quaternizing agent. Examples of quaternizing agents include organic halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide, propyl chloride, dodecyl chloride, benzyl chloride, benzyl bromide, methyl iodide, and benzyl iodide; sulfonate esters such as methyl methanesulfonate, methyl p-toluenesulfonate, and methyl trifluoromethanesulfonate; and sulfate esters such as dimethyl sulfate and diethyl sulfate. A quaternary ammonium salt can be obtained by reacting a quaternary ammonium salt with a tertiary amino group. When an organic halide is used as the quaternizing agent, the nitrogen atom acts as a cation and the counter ion, a halogen atom, acts as an anion to form a quaternary ammonium salt. However, a monomer obtained by exchanging the anion with another anion may also be used. As the compound having such an anion, a conventionally known compound can be used, and examples thereof include inorganic salt compounds such as sodium tetrafluoroborate, sodium trifluoromethylsulfate, sodium perchlorate, sodium hexafluorophosphate, and sodium bis(trifluoromethanesulfonyl)imide. Examples of commercially available products include ACRYT 8WX-018 (manufactured by Taisei Fine Chemical Co., Ltd.) and AMINOION RE3000MF (manufactured by Nippon Nyukazai Co., Ltd., an acrylic group-containing reactive ion).

[0045] Curable compounds having tertiary amino groups and / or quaternary ammonium salt groups (Q N The total content of the curable compound (Q) is not particularly limited and may be appropriately determined, but is preferably 3 to 40 mass %, more preferably 3 to 30 mass %, and even more preferably 3 to 20 mass %, based on 100 mass % of the curable compound (Q). By setting the content in the range of 3 to 40 mass %, it is possible to achieve both excellent anti-blocking properties and excellent adhesion to OCA. N) may have both a tertiary amino group and a quaternary ammonium base, and in this case, when calculating the total content, it goes without saying that the content is calculated as one compound.

[0046] The curable compound (Q) is a curable compound (Q) having at least one of a tertiary amino group and a quaternary ammonium base. N By using the tertiary amino group and / or quaternary ammonium base, at least one of the tertiary amino group and the quaternary ammonium base is incorporated into the binder resin in the cured layer. The tertiary amino group and the quaternary ammonium base are highly hydrophilic and have low affinity with the binder resin and particles (R) other than the hydrophilic group. This makes it easier for the tertiary amino group and / or the quaternary ammonium base to be exposed on the surface of the resin layer (B). Furthermore, because these groups are fixed as resin by the curing reaction, they do not bleed out and have excellent stability over time.

[0047] The curable composition (S) further contains a hydroxyl group-containing curable compound (Q O ) may be contained. O By incorporating ), the compatibility and dispersibility of the particles (R) with tertiary amino groups and / or quaternary ammonium salt groups is improved, resulting in excellent coating stability. It also reduces the haze value of the coating film of the resin layer (B). Furthermore, it improves the initial wetting tension and suppresses the decrease in wetting tension after annealing, more effectively improving the balance of OCA adhesion. As a result, it is possible to more effectively improve the dispersibility of the particles (R) in the resin layer (B), significantly improving transparency. Hydroxyl group-containing curable compound (Q O The content of (Q) is preferably from 3 to 40 mass %, more preferably from 5 to 30 mass %, and even more preferably from 5 to 20 mass %, relative to 100 mass % of the curable compound (Q).

[0048] Hydroxyl group-containing curable compound (Q OSuitable examples of (meth)acrylate include the above-mentioned (meth)acrylates having a hydroxyl group. Among them, particularly preferred examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0049] <Hydrophilic agent (T)> As described above, the curable composition (S) of this embodiment can contain a hydrophilizing agent (T) as an optional component. Here, the hydrophilizing agent (T) refers to a compound that is not curable by active energy rays and that, when added, can reduce the water contact angle of the surface layer (the surface layer opposite the side on which the light-transmitting substrate layer (A) is laminated) of the resin layer (B), which is the cured product of the coating layer of the curable composition (S). A compound that reduces the water contact angle to 60° or less is preferred, and 55° or less is more preferred. However, this does not include compounds that fall under the category of particles (R).

[0050] Suitable examples of the hydrophilizing agent (T) include a hydrophilizing agent (T) having at least one of a tertiary amino group and a quaternary ammonium base. N ), that is, ionic hydrophilizing agents having a quaternary ammonium salt group and nonionic hydrophilizing agents having a tertiary amino group can be exemplified. From the viewpoint of easily adjusting the wetting tension, the amine value is preferably 140 to 370 mgKOH / g. When the hydrophilizing agent (T) is a polymer, it is preferred that 100 to 50 mass% of the structural units derived from monomers used in polymerizing the polymer are structural units derived from monomers having a tertiary amino group and / or a quaternary ammonium salt, out of 100 mass% of the structural units derived from monomers used in polymerizing the polymer.

[0051] Examples of trade names of ionic hydrophilizing agents having a quaternary ammonium base include ACRYT 8WX-030 (manufactured by Taisei Fine Chemical Co., Ltd.) and AMINOION RE3000MF (manufactured by Nippon Nyukazai Co., Ltd.). Suitable examples of nonionic hydrophilizing agents having a tertiary amino group include vinyl resins having a tertiary amino group, (meth)acrylic resins having a tertiary amino group, etc. Among these, (meth)acrylic resins containing a dialkylamino group are suitable.

[0052] Furthermore, preferred examples of the ionic hydrophilizing agent and nonionic hydrophilizing agent include curable compounds (Q N Examples include a polymer obtained by homopolymerizing a monomer or oligomer of the above-mentioned compound (Q) or a copolymer containing the monomer component in part or all of the monomer component. N These may be of a single type or a mixture.

[0053] The content of the hydrophilizing agent (T) relative to 100% by mass of the curable composition (S) is not particularly limited, but from the viewpoint of achieving excellent anti-blocking properties, it is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 5 to 20% by mass.

[0054] The molecular weight of the hydrophilizing agent (T) is not limited, and it may be a low-molecular-weight compound or a high-molecular-weight compound, but from the viewpoint of effectively suppressing bleed-out in a high-temperature, high-humidity environment, it is preferable that the hydrophilizing agent (T) be a high-molecular-weight compound having a weight-average molecular weight of 10,000 or more. The upper limit of the weight-average molecular weight is not particularly limited, but from the viewpoint of compatibility with the curable composition (S), etc., it can be, for example, 50,000 or less.

[0055] Curable compounds having tertiary amino groups and / or quaternary ammonium salt groups (Q N ), and a hydrophilizing agent having a tertiary amino group and / or a quaternary ammonium base (T N ) total content (curable compound (Q N ) and hydrophilizing agent (T N ) or (including either one of the above) is preferably 3 to 50 mass %, more preferably 5 to 40 mass %, and even more preferably 5 to 30 mass %, based on 100 mass % of the nonvolatile components of the curable composition (S). By setting the content in the range of 3 to 50 mass %, the wet tension of the main surface (F) of the resin layer (B) can be set within a desired range, regardless of whether annealing treatment is performed or not, and excellent adhesion to the OCA can be achieved.

[0056] <Particle(R)> This composition contains particles (R). As mentioned above, the particles (R) are at least one type selected from resin beads and inorganic particles. The particles (R) mainly serve to impart anti-blocking properties. The particles (R) are used singly or in combination of two or more types. The particles (R) may be surface-treated, such as hydrophilic or hydrophobic, or may be untreated.

[0057] Examples of resin beads include acrylic resins, urethane resins, urethane acrylic resins, urea resins, polyvinyl chloride, polystyrene, polyacrylonitrile, polyamides, polyimides, and polycarbonates. Among these, acrylic resins and urethane acrylic resins, whose hardness can be adjusted by crosslinking, are preferred from the viewpoint of scratch resistance. The resin beads may be reactive resin beads. Reactive resin beads have a group that reacts upon heating or active energy ray irradiation, and resin beads that react upon active energy ray irradiation are preferred from the viewpoint of productivity. The reactive group may be a functional group that reacts with the curable compound (Q) to chemically bond thereto. Examples of reactive functional groups include ethylenically unsaturated groups such as polymerizable vinyl groups and (meth)acryloyl groups. The refractive index of the resin beads can be adjusted as appropriate, but is preferably 1.3 to 1.8, more preferably 1.4 to 1.6, from the viewpoint of improving transparency. Examples of commercially available acrylic resin beads include Chemisnow (registered trademark, manufactured by Soken Chemical & Engineering Co., Ltd.), Techpolymer (registered trademark, manufactured by Sekisui Chemical Co., Ltd.), Eposter (registered trademark, manufactured by Nippon Shokubai Co., Ltd.), Art Pearl (manufactured by Negami Chemical Industrial Co., Ltd.), and Ganz Pearl (manufactured by Aica Kogyo Co., Ltd.).

[0058] Examples of inorganic particles include silica particles, alumina, aluminum hydroxide, chromium oxide, iron oxide, zirconium oxide, zinc oxide, titanium oxide, barium sulfate, magnesium oxide, glass beads, titanium, carbon black, graphene, graphite, and diamond. Preferred examples of inorganic particles include silica particles and alumina, which are particularly preferred from the viewpoint of antiblocking properties.

[0059] The addition of particles (R) can enhance anti-blocking properties. As particles (R), untreated particles, hydrophilic particles, and hydrophobic particles can be used. The shape of the particles (R) is not limited, but for example, spherical or crushed particles can be used.

[0060] The primary particle size of the particles (R) is preferably 10 to 100 nm, more preferably 10 to 50 nm, and the average particle size (median size) is 1000 nm or less, more preferably 500 nm or less, and even more preferably 100 nm or less.

[0061] The average particle size can be measured using a particle size distribution analyzer, particularly a particle size distribution analyzer using dynamic light scattering (such as the "NANOTRAC WAVE II UZ152" manufactured by Microtrac-Bell). In the present invention, methyl ethyl ketone was used as the solvent, and measurements were performed three times for 60 seconds at a concentration such that the loading index was in the range of 1.0±0.2, and the average value was used.

[0062] The content of particles (R) may be appropriately adjusted depending on the particle size of the particles (R) and the thickness of the resin layer (B) so that the haze value measured from the surface side of the resin layer (B) in a laminate structure of a 1 μm-thick resin layer (B) and a 50 μm-thick polyethylene terephthalate layer is 2.0% or less. From the viewpoint of achieving both high transparency and anti-blocking properties, the content is preferably 0.01 to 40 mass% relative to 100 mass% of the non-volatile components of the curable composition (S). From the viewpoint of achieving better anti-blocking properties, the content is more preferably 3 to 40 mass%, even more preferably 5 to 40 mass%, and particularly preferably 5 to 30 mass%. Furthermore, when particles with a large average particle size relative to the thickness of the resin layer (B) are used, the haze value can be easily adjusted by reducing the particle content (e.g., 0.01 to 0.5 mass%). Here, the non-volatile components refer to the components constituting the composition other than the solvent.

[0063] The surface of the inorganic particles may be subjected to a surface treatment, including an organic compound. Reactive inorganic particles may also be used. Reactive inorganic particles are inorganic particles that react when heated or irradiated with active energy rays, and examples thereof include particles having reactive groups, such as polymerizable vinyl groups, ethylenically unsaturated groups such as (meth)acryloyl groups, and epoxy groups, on the particle surface. The reactive groups can be obtained by surface modification with a compound having a reactive group. For example, a silane coupling agent having an ethylenically unsaturated group can be used. Examples of surface treatment agents that can be used for inorganic particles include silane coupling agents such as 3-(meth)acryloxypropyltrimethoxysilane, β-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, hexamethyldisilazane, and dimethyldichlorosilane, and known treatment agents such as silicone oil.

[0064] When silica particles are used, hydrophobic silica particles are preferred. The use of hydrophobic silica particles provides the effect of reducing moisture absorption even in high temperature or high humidity environments. Hydrophobic silica particles can be obtained by surface-treating silica particles. An example of commercially available surface-treated hydrophobic silica particles is "Megasil 525RCS" manufactured by Sibelco Japan.

[0065] Curable compounds having tertiary amino groups and / or quaternary ammonium salt groups (Q N ) or / and hydrophilizing agent (T N ) and surface-treated particles (R) are used in combination to form a curable compound (Q N ) or / and hydrophilizing agent (T N In addition to the excellent anti-blocking property, the dispersion of the particles (R) in the resin layer (B) is significantly improved, and excellent coating stability and a good haze value are achieved. Therefore, the above combination can further contain a hydroxyl group-containing curing compound (Q O ) is preferably blended. In particular, when silica is used as the particles (R), a curing compound (Q) having a tertiary amino group and / or a quaternary ammonium base is used. N ) or / and hydrophilizing agent (T N ) and hydrophobic silica (R H ) to form a curable compound (Q N ) or / and hydrophilizing agent (T N In addition to the excellent anti-blocking property, the dispersion of silica particles in the resin layer (B) is remarkably improved, and excellent coating stability and a good haze value are realized. Therefore, the above combination is further supplemented with a hydroxyl group-containing curing compound (Q O ) is preferably blended.

[0066] <Photopolymerization initiators and photosensitizers> The curable composition (S) may contain a photopolymerization initiator as an optional component, and when the active energy rays are ultraviolet rays, it is preferable to add a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the function of initiating polymerization and / or crosslinking of the curable compound (Q) by photoexcitation. Suitable examples include monocarbonyl compounds, dicarbonyl compounds, acetophenone compounds, benzoin ether compounds, acylphosphine oxide compounds, and aminocarbonyl compounds.

[0067] Examples of the monocarbonyl compound include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4-(4-methylphenylthio)phenyl-ethanone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(1,3-acryloyl-1,3,3'-dimethyl-4-methoxybenzophenone, 4-(1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl)benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4- Examples include benzoyl-N,N,N-trimethyl-1-propanamine hydrochloride, 4-benzoyl-N,N-dimethyl-N-2-(1-oxo-2-propenyloxyethyl)methammonium oxalate, 2- / 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy-N,N,N-trimethyl-1-propanamine hydrochloride, and benzoylmethylene-3-methylnaphtho(1,2-d)thiazoline. Examples of the dicarbonyl compound include 1,2,2-trimethyl-bicyclo[2.1.1]heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, methyl-α-oxobenzeneacetate, and 4-phenylbenzyl. Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymer, diethoxyacetophenone, and dibutoxyacetophenone. , 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-diethoxy-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, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 3,6-bis(2-methyl-2-morpholino-propanonyl)-9-butylcarbazole can be exemplified. Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin n-butyl ether. Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di(2,6-dichlorobenzoyl)phosphine oxide. Examples of the aminocarbonyl compound include methyl-4-(dimethoxyamino)benzoate, ethyl-4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate, isoamyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethyl benzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, and 2,5'-bis(4-diethylaminobenzal)cyclopentanone.

[0068] Commercially available photopolymerization initiators include Omnirad 184, 651, 500, 907, 127, 369, 784, and 2959 manufactured by IGM-Resins BV, Lucirin TPO manufactured by IGM-Resins BV, and Esacure One manufactured by DKSH Japan. In particular, Omnirad 184 and Esacure One are preferred from the viewpoint of resistance to yellowing after curing with active energy rays.

[0069] The photopolymerization initiator is not limited to the above compounds, and any photopolymerization initiator may be used as long as it has the ability to initiate polymerization. The photopolymerization initiator may be used alone or in combination of two or more types. The amount of the photopolymerization initiator used is not particularly limited, but it is preferably used in the range of 1 to 20% by mass relative to 100% by mass of the curable compound (Q).

[0070] Examples of sensitizers include chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, polymethine dyes such as benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. Examples of the sensitizer include conductors, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3'- or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4'-diethylaminobenzophenone. The sensitizers may be used alone or in combination of two or more.

[0071] <Other ingredients> The curable composition (S) of the present embodiment may contain a solvent, if necessary. When a solvent is added, it is preferable to carry out a curing treatment with active energy rays after volatilizing the solvent. The solvent is not particularly limited, and various known organic solvents can be used. Specific examples include cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetylacetone, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, butyl acetate, isoamyl acetate, dimethyl adipate, dimethyl succinate, dimethyl glutarate, tetrahydrofuran, and methylpyrrolidone. Two or more of these organic solvents may be used in combination. Furthermore, other components not falling under the above may be contained within the scope that does not impair the object and effect of the present invention, such as surfactants, colorants, stabilizers, resins, surface treatment agents, viscosity modifiers, adhesion promoters, antioxidants, antiaging agents, crosslinking accelerators, ultraviolet absorbers, plasticizers, preservatives, dispersants, antifoaming agents, silane coupling agents, inorganic fillers, etc.

[0072] [Method for producing curable composition (S)] The curable composition (S) can be produced by any known method without any particular limitation, for example, by mixing and dispersing the curable compound (Q) and the particles (R), and then adding and adjusting a solvent, a photopolymerization initiator, and other various ingredients as necessary.

[0073] [Method of manufacturing laminate] A method for producing the laminate of this embodiment will be described. The laminate of this embodiment is formed by laminating a resin layer (B) on at least one surface of a light-transmitting substrate layer (A). The resin layer (B) is a layer obtained by curing a curable composition (S) containing a curable compound (Q) that exhibits curability when exposed to active energy rays and particles (R).

[0074] The curable composition (S) can be applied to the light-transmitting substrate layer (A) by any known method, such as a rod or wire bar method, or various coating methods such as microgravure, gravure, die, curtain, lip, slot, or spin coating. After forming a coating film of the curable composition (S), it is dried naturally or forcedly. Then, it is irradiated with active energy rays to cure, thereby obtaining a resin layer (B). As a light source for ultraviolet rays and visible light with a wavelength of 400 to 500 nm, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, etc. can be used. As an electron beam source, a thermionic emission gun, a field emission gun, etc. can be used. The amount of active energy rays to be irradiated may be any amount as long as sufficient curability is obtained, and may be, for example, 50 to 2000 mJ / cm. 2 It can be about.

[0075] [Transparent electrode film] The transparent electrode film of this embodiment includes at least the laminate and a transparent conductive layer. FIG. 1 shows an example of the transparent electrode film of this embodiment. As shown in the figure, the transparent electrode film 1 includes a laminate 2, an index matching layer (hereinafter also referred to as an IM layer) 3, and a transparent conductive layer 4 laminated in this order. In this embodiment, the laminate 2 is composed of a resin layer (B) and a light-transmitting substrate layer (A), with the IM layer 3 laminated on the light-transmitting substrate layer (A). An OCA film may be further laminated on the surface of the resin layer (B). Alternatively, the IM layer 3 may be omitted, and the transparent conductive layer 4 may be laminated directly on the light-transmitting substrate layer (A) of the laminate 2. Each layer may independently be a single layer or multiple layers.

[0076] The IM layer 3 is a high-refractive index layer laminated for the purpose of obscuring the shape of the patterned transparent conductive layer 4. For example, it can be formed from a cured layer of a composition containing high-refractive index metal oxide particles and an active energy ray-curable component. The refractive index of the IM layer 3 is preferably as close as possible to that of the transparent conductive layer 4. The high-refractive index metal oxide particles and the active energy ray-curable component can be obtained using known materials. Examples of high-refractive index metal oxide particles include titanium oxide (n = 2.72), zirconium oxide (n = 2.22), and aluminum oxide (n = 1.77). Examples of the active energy ray-curable component include the curable compound (Q) contained in the resin layer (B). The thickness of the IM layer 3 is, for example, approximately 0.03 μm to 30 μm. The IM layer may be a laminate of a low-refractive index layer and a high-refractive index layer.

[0077] The transparent conductive layer 4 is a transparent layer having electrical conductivity and can be formed from indium tin oxide (ITO), tin oxide, zinc oxide, silver or copper nanowires, or the like. The transparent conductive layer 4 can be formed by, for example, vacuum deposition (physical vapor deposition or chemical vapor deposition), sputtering, ion plating, or the like. After the transparent conductive layer 4 is provided on the IM layer 3, a circuit or electrode pattern can be formed by etching or the like. The thickness of the transparent conductive layer 4 can be, for example, 1 nm to several tens of μm, from the viewpoint of improving electrical conductivity and adhesion to the IM layer 3.

[0078] An anchor layer (not shown) may be disposed between the IM layer 3 and the transparent conductive layer 4. The anchor layer can be formed, for example, by a film formation method utilizing a vacuum, similar to the case of the transparent conductive layer 4. Examples of metal oxides used to form the anchor layer include silicon oxide, which is preferable because it can impart strong adhesion.

[0079] An OCA film can be further laminated on the main surface (F) of the resin layer (B) of the laminate 2 of the transparent electrode film 1. The transparent electrode film can then be incorporated into, for example, a touch panel module via this OCA film. The transparent electrode film of this embodiment can be suitably used by being mounted on, for example, smartphones, tablets, PCs, televisions, car navigation systems, and electronic devices such as guide signs in commercial facilities and transportation ticket vending machines.

[0080] <<Example>> The present invention will be described in more detail below, but the scope of the present invention is not limited by the following examples. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively. Mw means weight average molecular weight, and is the polystyrene equivalent molecular weight when a TSKgel column (manufactured by Tosoh Corporation) is used with a GPC (manufactured by Tosoh Corporation, HLC-8320GPC) equipped with an RI detector and DMF as the developing solvent. The amine value of the tertiary amino group-containing curable compound is the total amine value (mg KOH / g) measured in accordance with the method of ASTM D 2074 and converted into solid content. In this specification, the non-volatile content refers to the value calculated from the sample mass after heating / sample mass before heating when 1 g of sample is heated at 180°C for 20 minutes.

[0081] The abbreviations for the components of the curable composition (S) used in this example are as follows: [Curable compound (Q)] q-1 (PET-30): Pentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd. q-2 (KAYARAD DPHA): Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd. q-3 (Miramer PU610): Urethane acrylate, manufactured by MIWON. · q-4 (4HBA): 4-hydroxybutyl acrylate, manufactured by Mitsubishi Chemical Corporation. q-5 (Acrit 8WX-030): Cationic polymer, manufactured by Taisei Fine Chemical Co., Ltd., containing quaternary ammonium base. q-6 (Aminoion RE3000MF): Cationic polymer, manufactured by Nippon Nyukazai Co., Ltd., containing quaternary ammonium base. ·Q-7: Tertiary amino group-containing curable vinyl resin. The above q-1 and q-4 are hydroxyl group-containing curing compounds (Q O ) applies. [Particle (R)] · r-1 (Aeroxide AluC dispersion): D50: 62nm, alumina. r-2 (Techpolymer NH): Sekisui Chemical Co., Ltd., D50: 80 nm, resin beads (gel fraction: 80% by mass or more). [Hydrophilic agent (T)] ·t-1: Tertiary amino group-containing hydrophilic agent, tertiary amino group-containing. ·t-2: Tertiary amino group-containing hydrophilic agent, tertiary amino group-containing. ·t-3: Tertiary amino group-containing hydrophilic agent, tertiary amino group-containing. · t-4 (FC-4400): Ionic liquid, manufactured by 3M, containing quaternary ammonium base.

[0082] <Production Example of Tertiary Amino Group-Containing Curable Compound (q-7)> A reaction vessel equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 50.6 parts of ethyl acetate, 180 parts by weight of N,N-diethylaminoethyl methacrylate, and 20 parts by weight of 2-hydroxyethyl methacrylate. The mixture was heated to 50°C while purging with nitrogen, followed by the addition of 2.3 parts of 1-thioglycerol and the temperature being raised to 70°C. A dropping vessel was charged with 16.8 parts by weight of ethyl acetate and 0.6 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile), and the mixture was stirred until homogeneous. The mixture was then added dropwise to the reaction vessel over 7 hours. The reaction was continued at the same temperature for 1 hour, and solids content measurements confirmed that the reaction was at least 95% complete. The flask was then purged with air, and 32.8 parts by weight of 2-acryloyloxyethyl isocyanate (AOI) and 0.1 parts by weight of hydroquinone were added. The reaction was carried out at 70°C for 4 hours. After confirming the disappearance of the peak at 2270 cm-1 due to the isocyanate group by FT-IR, the reaction solution was cooled to obtain a solution of a vinyl resin having a tertiary amino group and an acryloyl group. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried by heating at 180 ° C for 20 minutes to measure the nonvolatile content. Ethyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 45 wt%. A solution of curable compound (q-7), a vinyl resin having a tertiary amino group with an amine value of 234 mg KOH / g per solid content and a number average molecular weight of 22,000, was obtained.

[0083] <Production example of Aeroxide AluC dispersion (r-1)> 15.0 parts of alumina ("Aeroxide AluC" manufactured by Nippon Aerosil Co., Ltd.), 1.5 parts of dispersant ("DYSPERBYK142"), and 83.5 parts of a 1 / 1 mixed solvent of methyl ethyl ketone and methoxybutanol were mixed and dispersed in two stages: pre-dispersion (using zirconia beads (0.5 mm) as media and dispersed in a paint shaker for 1 hour) and main dispersion (using zirconia beads (0.1 mm) as media and dispersed in a disperser UAM-015 manufactured by Kotobuki Industries Co., Ltd.), to obtain an Aeroxide AluC dispersion.

[0084] <Production Example of Tertiary Amino Group-Containing Hydrophilizing Agent (t-1)> A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 50.6 parts isopropyl alcohol and 200 parts N,N-dimethylaminoethyl methacrylate. The mixture was heated to 50°C while purging with nitrogen, followed by the addition of 2.3 parts 1-thioglycerol and the subsequent heating to 70°C. A dropping tank was charged with 16.8 parts isopropyl alcohol and 0.6 parts 2,2'-azobis(2,4-dimethylvaleronitrile), and the mixture was stirred until homogeneous. The mixture was then added dropwise to the reactor over 7 hours. The reaction was continued at the same temperature for another hour, yielding a solution of a vinyl resin containing tertiary amino groups. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried at 180°C for 20 minutes, followed by measurement of the nonvolatile content. Isopropyl alcohol was added to the resin solution synthesized previously so that the nonvolatile content was 45%, to obtain a solution of hydrophilizing agent (t-1), which is a vinyl resin with a tertiary amino group and an amine value per solid content of 357 mg KOH / g and a number-average molecular weight of 21,000.

[0085] <Production Example of Tertiary Amino Group-Containing Hydrophilizing Agent (t-2)> A reaction vessel equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 50.6 parts of isopropyl alcohol and 200 parts of N,N-diethylaminoethyl methacrylate, and the temperature was raised to 50°C while purging with nitrogen, after which 2.3 parts of 1-thioglycerol was added and the temperature was raised to 70°C. A dropping vessel was charged with 16.8 parts of isopropyl alcohol and 0.6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and the mixture was stirred until homogeneous. The mixture was then added dropwise to the reaction vessel over 7 hours, and the reaction was continued at the same temperature for 1 hour, yielding a solution of a vinyl resin having a tertiary amino group. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes, and the non-volatile content was measured. Isopropyl alcohol was added to the resin solution synthesized previously so that the non-volatile content was 45%, yielding a solution of hydrophilizing agent (t-2), which is a vinyl resin with a tertiary amino group and an amine value per solid content of 301 mgKOH / g and a number average molecular weight of 20,000.

[0086] <Production Example of Tertiary Amino Group-Containing Hydrophilizing Agent (t-3)> A reaction vessel equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 50.6 parts of isopropyl alcohol, 100 parts of N,N-diethylaminoethyl methacrylate, and 100 parts of methyl methacrylate, and the temperature was raised to 50°C while purging with nitrogen, after which 2.3 parts of 1-thioglycerol was added and the temperature was raised to 70°C. A dropping vessel was charged with 16.8 parts of isopropyl alcohol and 0.6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and the mixture was stirred until homogeneous. The mixture was then added dropwise to the reaction vessel over 7 hours, and the reaction was continued at the same temperature for 1 hour, yielding a solution of a vinyl resin having a tertiary amino group. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes, and the non-volatile content was measured. Isopropyl alcohol was added to the resin solution synthesized previously so that the non-volatile content was 45%, yielding a solution of hydrophilizing agent (t-3), which is a vinyl resin with a tertiary amino group and an amine value per solid content of 151 mgKOH / g and a number average molecular weight of 21,000.

[0087] <Production Example of Curable Composition (S)> Example 1 94.5 parts of pentaerythritol triacrylate ("KAYARAD PET30" manufactured by Nippon Kayaku Co., Ltd., containing some pentaerythritol tetraacrylate), 5.5 parts of Acrit 8WX-030 (manufactured by Taisei Fine Chemical Co., Ltd.), 5.0 parts of Omnirad184 (manufactured by IGM-Resins BV), and 50 parts of methylpropylene glycol were uniformly mixed. Next, Aeroxide AluC dispersion was added thereto so that the alumina content was 5.5% by mass of the nonvolatile components, and methylpropylene glycol was added so that the nonvolatile components were 50% by mass, and the mixture was uniformly mixed to obtain a curable composition (S).

[0088] (Examples 2 to 25, Comparative Examples 1 to 6) Curable compositions (S) according to each of the examples and comparative examples were obtained in the same manner as in Example 1, except that the blending amounts were changed as shown in Tables 1 to 3.

[0089] [Table 1]

[0090]

Table 2

[0091]

Table 3

[0092] <Production Example of Laminate> (Example 1) A 50-μm thick easily-adhesive treated polyethylene terephthalate film (“Lumirror U403” manufactured by Toray Industries, Inc.) was used as the light-transmissive substrate layer (A). On this light-transmissive substrate layer (A), the curable composition (S) obtained in the examples and comparative examples was coated using a bar coater, and dried for 1 minute using a hot air oven at 100°C to remove the organic solvent. Then, ultraviolet rays of 400 mJ / cm 2 were irradiated using a high-pressure mercury lamp to form a 1-μm resin layer (B), and the laminate according to Example 1 was obtained. (Examples 2 to 25, Comparative Examples 1 to 6) Laminates according to Examples 2 to 25 and Comparative Examples 1 to 6 were obtained in the same manner as in Example 1. The results of various evaluations for each example and comparative example are shown in Table 4.

[0093] <Production Example of Heat-Resistant Protection Film> An adhesive obtained by mixing “Cyabine SH101” and “Cyabine T-501B” manufactured by Toyochem Co., Ltd. at a solid content mixing ratio of 100 / 20 was coated onto a 100-μm thick easily-adhesive treated polyethylene terephthalate film (“Lumirror U403” manufactured by Toray Industries, Inc.) using a bar coater. Then, it was dried for 2 minutes using a hot air oven at 100°C to remove the organic solvent, and a heat-resistant protection PET film having an adhesive layer of 5 μm was obtained.

[0094] <Production Example of OCA Film> An adhesive was prepared by mixing Toyochem's "Olivine BPS5896" and "Olivine BXX5627" in a solids ratio of 100 / 0.5, and the resulting adhesive was applied to a 100μm-thick polyethylene terephthalate film (Toray's "Lumirror U403") with an easy-adhesion treatment using a bar coater. The film was then dried in a hot air oven at 100°C for 2 minutes to remove the organic solvent, yielding an OCA film with a 5μm adhesive layer.

[0095] <Measurement of initial wetting tension> The initial wetting tension of the main surface (F) of the resin layer (B) (see Figure 1) of each laminate of Examples and Comparative Examples before annealing was measured using the following procedure. Specifically, the wetting tension of the main surface (F) of the resin layer (B) was determined using a wettability check dyne pen (a test pen for evaluating surface energy values) manufactured by Arcotest under an environment of 23°C and 50% relative humidity. Specifically, the laminate (test piece) of each Example and Comparative Example was placed on a glass plate, and a dyne pen liquid film measuring approximately 1 cm x 5 cm was formed on the main surface (F) of the resin layer (B) of the test piece using the dyne pen. The dyne pen liquid film was observed in a bright place, and the state of the liquid film after 5 seconds was assessed as wet. Wetting was assessed when 95% or more of the short side of the liquid film was maintained. If 95% or more of wetting was maintained, the next dyne pen with a higher surface tension was used. Conversely, if 95% or more of wetting was not maintained, the next mixed liquid with a lower surface tension was used for assessment. JIS K6768 is another known method for measuring wetting tension. According to this method, if the liquid film breaks within 2 seconds of applying the dyne pen / ink, it is judged to be NG, making this test method a more accurate evaluation method. Compared to JIS K6768, the wetting tension determined by this test method tends to be smaller.

[0096] <Measurement of wetting tension after annealing> The resin layer (B) of each laminate of each Example and Comparative Example and the heat-resistant protective PET film obtained in each Production Example were left to stand for 30 minutes in an environment of 23°C and 50% relative humidity, and then the main surface (F) of the resin layer (B) was laminated to the adhesive layer of the heat-resistant protective PET film using a 2 kg roller. After annealing at 150°C for 3 hours, the heat-resistant protective PET film was peeled off, and the wet tension of the exposed main surface (F) of the resin layer (B) was measured using the same method as for the initial wet tension.

[0097] <Haze value measurement> The curable composition (S) shown in Table 1 was applied using a bar coater onto a 50 μm thick polyethylene terephthalate sheet (Lumirror U403, manufactured by Toray Industries, Inc., haze value 1.1%, total light transmittance 91%), and dried at 100° C. for 1 minute. The active energy ray and irradiation dose must be appropriately changed depending on the type of curable composition (S). In this example and comparative example, a high-pressure mercury lamp was used as the light source, and a light dose of 400 mJ / cm in the UVA ultraviolet region was used. 2 The samples were irradiated with ultraviolet light of 1000 W at 1000 W to obtain a measurement sample having a resin layer (B) made of a cured film having a thickness of 1 μm. The measurement samples (50 μm polyethylene terephthalate / resin layer (B)) according to each example and comparative example were then measured for haze value in accordance with JIS K 7136 using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SH7000") in an environment of 23°C and 50% RH. The measurement was performed from the resin layer (B) side.

[0098] <Evaluation of anti-blocking properties> The measurement sample was prepared as follows. That is, a test piece was prepared by cutting out the laminate before annealing obtained above and the light-transmissive base material layer (A) not laminated with the resin layer into a size of 4 cm × 4 cm. The test piece was overlaid so that the surface of the resin layer (B) of the laminate was in contact with the light-transmissive base material layer (A), placed on the test bench of a permanent distortion tester (trade name "CO-201 Permanent Distortion Tester (constant load type)", manufactured by Nippon Tester Sangyo Co., Ltd.), and left standing for 24 hours in an oven heated to 50°C with a load of 200 kg applied. Then, immediately after removing the load, the ratio of the area where the overlapped surfaces of the test pieces were stuck together (a watermark (an appearance as if water had entered) was formed) was evaluated as anti-blocking property (hereinafter abbreviated as "AB property") according to the following criteria. A: The stuck area is 10% or less. B: The stuck area exceeds 10% and is 30% or less. C: The stuck area exceeds 30%.

[0099] <Evaluation of scratch resistance> The laminate obtained above was set on a Kagaku-Shinkou test machine so that the resin layer became the test surface, and the surface of the resin layer was reciprocally rubbed 10 times under the condition of a load of 200 g with No. 0000 of steel wool. The number of scratches on the surface of the IM layer after the test was confirmed and evaluated according to the following evaluation criteria. A: 0 to 10 scratches. B: 11 to 20 scratches. C: 21 scratches or more.

[0100] <Evaluation of OCA adhesion> The measurement sample was prepared as follows. That is, the laminate of each example and comparative example before annealing (initial) and after annealing and the OCA film obtained in the production example were left standing for 30 minutes in an environment of 23°C and a relative humidity of 50%. Next, the main surface (F) of the resin layer (B) was bonded to the adhesive layer of the OCA film and pasted using a 2 kg roller. Then, a 180° peel test was performed at a speed of 300 mm / min using a tensile tester, and the peel strength was measured. The adhesion was evaluated according to the following criteria from the obtained peel strength value. A: The peel strength is 25 N or more. B: Peel strength is 10N or more but less than 25N. C: Peel strength is less than 10N.

[0101] [Table 4]

[0102] Laminates with an initial wetting tension of less than 38 mN / m and a surface tension after annealing of less than 30 mN / m exhibited poor OCA adhesion, as shown in Comparative Examples 1 and 2. Furthermore, laminates with an initial wetting tension of more than 60 mN / m and a surface tension after annealing of more than 54 mN / m exhibited poor scratch resistance and anti-blocking properties, as shown in Comparative Example 3. Furthermore, as shown in Comparative Example 4, a high content of particles (R) improved anti-blocking properties, but also reduced the haze value. On the other hand, this example demonstrated excellent optical properties and scratch resistance, and furthermore, high yields were achieved even when produced using a roll-to-roll process, demonstrating excellent OCA adhesion regardless of whether annealing was performed or not. [Industrial Applicability]

[0103] The laminate of the present invention has excellent adhesion to OCA film and is suitable as an optical film because it can provide a laminate with excellent anti-blocking properties, scratch resistance, and transparency. For example, a transparent electrode film obtained by laminating a transparent conductive layer on the laminate is suitable as a touch panel component installed in smartphones, tablets, PCs, televisions, car navigation systems, and other commercial facilities, such as guide signs and transportation ticket vending machines. Furthermore, the resin layer (B) of the laminate of the present invention has excellent surface hardness, making it suitable as a scratch-preventing film for the surface of flat panel displays (FPDs) such as liquid crystal displays (LCDs), organic light-emitting diode displays (OLEDs), and plasma displays (PDPs).

Claims

1. A laminated structure in which a resin layer (B) is laminated directly or via one or more other layers on at least one surface of a light-transmitting substrate layer (A), The resin layer (B) is a layer obtained by curing a curable composition (S) containing particles (R) and a curable compound (Q) (excluding the particles (R)) that exhibits curability by active energy rays, the particles (R) are at least one type selected from inorganic particles (but excluding silica particles) and resin beads having a gel fraction with respect to methyl ethyl ketone of 80% by mass or more; In a laminated structure of a 1 μm-thick resin layer (B) and a 50 μm-thick polyethylene terephthalate layer, the haze value is 2.0% or less when measured from the surface layer side of the resin layer (B), the main surface (F) of the resin layer (B) opposite to the light-transmitting substrate layer (A) has an initial wetting tension of 38 to 60 mN / m before the annealing treatment; and a heat-resistant protective polyethylene terephthalate film is attached to the main surface (F) of the resin layer (B), and the main surface (F) of the resin layer (B) has a wet tension of 30 to 54 mN / m after the heat-resistant protective polyethylene terephthalate film is peeled off. The curable composition (S) is (i) As the curable compound (Q), a curable compound having at least one of a tertiary amino group and a quaternary ammonium salt group (Q Ｎ ), and (ii) contains a hydrophilizing agent (T) (excluding particles (R)) that does not exhibit curability by active energy rays, The hydrophilizing agent (T) is a hydrophilizing agent having at least one of a tertiary amino group and a quaternary ammonium base (T Ｎ ) At least one of the following is satisfied: A laminate having a particle (R) content of 5 to 30 mass % relative to 100 mass % of the non-volatile components of the curable composition (S).

2. A curable compound having at least one of a tertiary amino group and a quaternary ammonium salt group (Q Ｎ 2. The laminate according to claim 1, wherein said (meth)acryloyl group is contained in said (meth)acryloyl group.

3. A curable compound having at least one of a tertiary amino group and a quaternary ammonium salt group (Q Ｎ ), and a hydrophilizing agent having at least one of a tertiary amino group and a quaternary ammonium salt group (T Ｎ 3. The laminate according to claim 1 or 2, wherein the total content of the non-volatile components (S) is 3 to 40 mass% based on 100 mass% of the non-volatile components of the curable composition (S).

4. A laminate described in any one of claims 1 to 3, wherein the particles (R) are at least one type selected from inorganic particles (excluding silica particles, zirconium oxide and titanium oxide) and resin beads having a gel fraction with respect to methyl ethyl ketone of 80 mass% or more.

5. A laminate described in any one of claims 1 to 4, used for laminating an optically transparent adhesive film to the main surface of the resin layer (B) opposite the light-transmitting substrate layer (A).

6. A laminate according to any one of claims 1 to 4 (excluding a laminate used for the application of forming a transparent conductive layer by adhering a conductive metal compound by a film-forming method utilizing a vacuum to the main surface of the resin layer (B) of the laminate opposite the light-transmitting substrate layer (A) side, and for the application of forming an anchor layer by adhering a metal oxide by a film-forming method utilizing a vacuum).

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