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 having a resin layer which is a cured layer of a curable composition that exhibits curability by active energy rays, and a transparent electrode film. [Background technology]

[0002] As an electrode material for display devices such as touch panels, a transparent electrode film is used, in which a transparent conductive layer having a desired pattern, such as ITO (indium tin oxide), is laminated on a light-transmitting substrate layer such as polyethylene terephthalate (PET) film. An optical clear adhesive (OCA) film is attached to the transparent electrode film and incorporated into the touch panel module.

[0003] Patent Document 1 proposes a light-transmitting conductive film in which an ITO layer is formed on a PET film, and the wetting tension of the PET film surface is adjusted to 34 dyn / cm or more by plasma treatment. This solves the problems of air bubbles and voids occurring during the baking process of a light-transmitting transparent conductive film to which an OCA film is attached, and the problem of the OCA film partially peeling off and causing misalignment at the adhesive surface with the light-transmitting conductive film when the film is roll-conveyed after the OCA is attached, causing it to protrude from the edges of the light-transmitting conductive film.

[0004] Patent Document 2 proposes a curable composition containing an active energy ray curable compound and silica particles, which can impart high antiblocking properties to the film surface and form a hard coat layer with high transparency and high adhesive adhesion to OCA, etc., and in which the wettability of the surface of the cured coating film is 35 to 60 mN / m. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2016-155366 [Patent Document 2] International Publication No. 2018 / 100929 [Overview of the project] [Problems that the invention aims to solve]

[0006] Laminates suitable for use as electrode materials in display devices such as touch panels are highly sought after in the market. These laminates not only possess excellent optical properties and scratch resistance, but also have a high yield even when manufactured using the roll-to-roll method, and exhibit excellent adhesion to OCA film regardless of whether an annealing process is used. While the above describes the challenges of laminates used in transparent electrode films, similar challenges may arise in all applications where the above characteristics are required.

[0007] This invention was made in view of the above background, and aims to provide laminates and transparent electrode films that have excellent optical properties and scratch resistance, and furthermore, have a high yield even when manufactured by the roll-to-roll method, and have excellent OCA adhesion regardless of whether or not annealing treatment is performed. [Means for solving the problem]

[0008] After diligent research by the inventors, we discovered that the problems of the present invention can be solved in the following embodiment, and thus completed the present invention. [1]: A laminated structure having a resin layer (B) 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) that exhibits curability by active energy rays (excluding particles (R)). The particle (R) is 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, when measured from the surface layer side of the resin layer (B), the haze value is 2.0% or less, The main surface (F) of the resin layer (B) opposite to the light-transmissive base material 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 after annealing treatment at 150°C for 3 hours and peeling off the heat-resistant protective polyethylene terephthalate film, the wetting 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 N , N , N , , , , , ) having at least one of a tertiary amino group and a quaternary ammonium base, and (ii) contains a hydrophilic agent (T) (excluding particles (R)) that does not show curability by active energy rays, The hydrophilic agent (T) contains a hydrophilic agent (T N ) having at least one of a tertiary amino group and a quaternary ammonium base, A laminate satisfying at least any one of the above. [2]: The curable compound (Q[[ID=2​​​​​​​​​​​ 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 described in [5], wherein an optically transparent adhesive film is further laminated on the main surface of the resin layer (B) opposite to the light-transmitting substrate layer (A). [Effects of the Invention]

[0009] According to the present invention, it is possible to provide laminates and transparent electrode films that have excellent optical properties and scratch resistance, and furthermore, have a high yield even when manufactured by the roll-to-roll method, and have excellent OCA adhesion regardless of whether or not annealing treatment is performed, thus achieving excellent effects. [Brief explanation of the drawing]

[0010] [Figure 1] A schematic cross-sectional view showing an example of a transparent electrode film according to this embodiment. [Modes for carrying out the invention]

[0011] The present invention will now be described in detail. It goes without saying that other embodiments are also included in the scope of the present invention, as long as they are consistent with the spirit of the invention. In this specification, numerical ranges specified using "~" include the numerical values ​​before and after "~". In this specification, "film" and "sheet" are not distinguished by thickness. Furthermore, unless otherwise noted, the various components mentioned in this specification may be used individually or in combination of two or more.

[0012] [[Laminate]] The laminate according to this embodiment has a laminated structure in which a light-transmitting substrate layer (A) and a resin layer (B) formed directly on at least one surface of the light-transmitting substrate layer (A) or via one or more other layers are laminated. The resin layer (B) is a layer obtained by curing a curable composition (S) containing particles (R) and a curable compound (Q) that exhibits curability by active energy rays (excluding particles (R)). Here, particles (R) are either inorganic particles or resin beads. Particles (R) may be crystalline or amorphous. Inorganic particles are particles (fillers) made of substances other than organic compounds, and examples include particles made of metals, hydrides of nonmetallic elements, borides, nitrides, carbides, oxides, halides, chalcogenides and compounds thereof. 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, which are the sample to be measured, heating and extracting them in a Soxhlet extractor with 100 mL of methyl ethyl ketone (MEK), weighing the extracted soluble matter, and using the following formula (1). Equation (1): Gel fraction (%) relative to MEK = {(1 - mass of soluble matter (g)) / 1} × 100 The gel fraction mentioned above is more preferably 90% by mass or more.

[0013] The main surface (F) of the resin layer (B), opposite to the light-transmitting substrate layer (A), has an initial wetting tension (hereinafter also referred to as "initial wetting tension") of 38-60 mN / m before annealing treatment. A heat-resistant protective polyethylene terephthalate film (hereinafter also referred to as "heat-resistant protective PET film") is then applied to the main surface (F) of the resin layer (B), and annealing treatment is performed at 150°C for 3 hours. After peeling off the heat-resistant protective PET film, the wetting tension of the main surface (F) of the resin layer (B) (hereinafter also referred to as "wetting tension after annealing treatment") is 30-54 mN / m. Furthermore, the resin layer (B) used is a laminated structure consisting of a 1 μm thick resin layer (B) and a 50 μm thick polyethylene terephthalate layer, and when measured from the surface side of the resin layer (B), a haze value of 2.0% or less is used. 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 base N ) contains. (ii) Contains a hydrophilic agent (T) that does not exhibit curability by active energy rays, and the hydrophilic agent (T) has at least one of a tertiary amino group and a quaternary ammonium base. N ) contains. The initial wetting tension, wetting tension after annealing, and haze values ​​disclosed herein refer to the values ​​obtained by the methods described in the examples below.

[0014] Here, "curable compound (Q) exhibiting curability upon activation of active energy rays" refers to a compound that hardens by polymerization and / or crosslinking upon irradiation with active energy rays, excluding cases where it corresponds 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 rays, visible light, infrared rays, electron beams (EB), and radiation. Furthermore, "hardened layer" refers to a layer that has been hardened to such an extent that the hardening reaction does not substantially proceed even when irradiated with active energy rays. In this embodiment, a state in which a portion of the curable compound (Q) has undergone a hardening reaction when forming the layer of the curable composition (S) is not included in the definition of a hardened layer.

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

[0016] When manufacturing laminates using the roll-to-roll method, as mentioned above, a decrease in yield due to film adhesion is a problem. According to the laminate according to this embodiment, by using a cured layer of a curable composition (S) containing a curable compound (Q) and particles (R) as the resin layer (B), and by using the laminate in which the initial wetting tension and the wetting tension after annealing are within the specified range, excellent antiblocking properties and scratch resistance are achieved. Furthermore, even when manufactured using the roll-to-roll method, blocking between films can be effectively suppressed. As a result, the yield can be significantly increased. Moreover, in addition to excellent transparency and scratch resistance, a laminate with excellent OCA adhesion can be provided regardless of whether or not annealing treatment is performed. Each layer will be described in detail below.

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

[0018] The material of the light-transmitting substrate layer (A) is not particularly limited as long as it has excellent transparency. Preferred examples include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cyclic polyolefin resins such as cycloolefin resins (COP), polyethylene, polypropylene, chain polyolefin resins such as 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 is highly versatile, and cycloolefin resins, which have excellent 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 arbitrarily selected as long as it has a thickness sufficient to function as a support for the resin layer (B). Typically, it can be around 25 to 188 μm. From the viewpoint of transparency, a thickness of 25 to 125 μm is preferable, and a range of 25 to 100 μm is more preferable.

[0020] [Resin layer (B)] The resin layer (B) is a layer cured by irradiating the curable composition (S) with active energy rays, and is suitable for the manufacture of laminates by the roll-to-roll method because it has excellent scratch resistance and antiblocking properties. For example, a laminate can be manufactured by unwinding a light-transmitting substrate layer (A) wound in a roll, coating it with a curable composition (S), irradiating it with active energy rays to obtain a cured resin layer (B), and then winding it back onto a roll. Alternatively, the light-transmitting substrate layer (A) wound in a roll and the resin layer (B) wound in a roll may be bonded together, and then wound back onto a roll. This method significantly improves productivity compared to laminating a resin layer (B) onto a single 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 providing excellent antiblocking properties, it is preferably 1 to 10 μm, more preferably 1 to 5 μm, and even more preferably 1 to 3 μm.

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

[0023] The initial wetting tension of the main surface (F) of the resin layer (B) is 38-60 mN / m, a more preferable range is 40-60 mN / m, and a particularly preferable range is 42-60 mN / m. Furthermore, the wetting tension after annealing is 30-54 mN / m, a more preferable range is 32-54 mN / m, and a particularly preferable range is 36-54 mN / m.

[0024] The method of setting the surface layer of the resin layer (B) to have an initial wetting tension of 38 to 60 mN / m and a wetting tension after annealing (150 °C × 3 hours) of 30 to 54 mN / m can be adjusted according to the composition of the curable composition (S). Further, in combination with the above adjustment method, surface treatment may be performed to adjust the initial wetting tension and the wetting tension after annealing of the surface layer of the resin layer (B) to be as described above. The adjustment according to the composition of the curable composition (S) is (1) As the curable compound (Q), a method of containing a curable compound (Q N ) having at least one of a tertiary amino group and a quaternary ammonium base, (2) A method of further containing a hydrophilic agent (T) that does not exhibit active energy ray curability in the curable composition (S), and as the hydrophilic agent (T), a hydrophilic agent (T N ) having at least one of a tertiary amino group and a quaternary ammonium base, and (3) There is a method of using any one of the methods of using (1) and (2) in combination.

[0025] As a method of adjusting the wetting tension by surface treatment, an example is a method of subjecting the surface layer 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, excellent transparency can be obtained by using a layer having a haze value of 2.0% or less as measured from the surface layer 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] A method of adjusting the resin layer (B) to satisfy the above haze value is a method of adjusting according to the composition of the curable composition (S). For example, as described later, a hydroxyl group-containing curable compound (Q OBy using this in combination with particles (R) and tertiary amino groups and / or quaternary ammonium bases, the haze value can be reduced. This method has the advantage of eliminating the need for corona treatment and ozone treatment processes.

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

[0029] <Curable compound (Q)> The curable compound (Q) can be any compound that undergoes polymerization and / or crosslinking reactions upon irradiation with active energy rays, and can be selected regardless of molecular weight, including low molecular weight compounds and high molecular weight compounds. However, compounds corresponding to particles (R) are excluded. The curable compound (Q) can be used alone or in combination of two or more types.

[0030] Examples of the curable groups in the curable compound (Q) include radical polymerizable groups such as vinyl groups, (meth)acryloyl groups, and allyl groups. Among these, curable compound (Q) having a (meth)acryloyl group is preferred. 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% or more by mass of trifunctional or more (meth)acrylate per 100% by mass of the curable compound (Q), more preferably 50 to 100% or more by mass, and even more preferably 80 to 100% or more by mass.

[0032] Examples of (meth)acrylates with four or more functions include dimethylpropanetetra(meth)acrylate, ethylene oxide-modified dimethylpropanetetra(meth)acrylate, prolene oxide-modified dimethylpropanetetra(meth)acrylate, tetramethylene oxide-modified dimethylpropanetetra(meth)acrylate, ditrimethylpropanetetra(meth)acrylate, pentaerythritoltetra(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 difunctional (meth)acrylates include 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, tricyclodecanedimethanol di(meth)acrylate, and other di(meth)acrylates; 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) Alkylene oxy 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, ethylene oxide-modified di(meth)acrylate isocyanurate, propylene oxide-modified di(meth)acrylate isocyanurate, butyl oxide-modified di(meth)acrylate isocyanurate, and butyl oxide-modified di(meth)acrylate isocyanurate; Examples of polyol ester-based di(meth)acrylates include 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 alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, n-hexyl acrylate, lauryl acrylate, and stearyl acrylate; Perfluoroalkyl esters of (meth)acrylate 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 (meth)acrylate (methoxycarbonyl)methyl, (meth)acrylate 2-(ethoxycarbonyloxy)hexyl, (meth)acrylate 2-(propoxycarbonyloxy)ethyl, and (meth)acrylate 2-(octyloxycarbonyloxy)butyl; 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-tert-butyl-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 glycidyl laurate (meth)acrylate; Cyclohexanedimethanol mono(meth)acrylate, cyclohexanediethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, 2-a(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid, and other cyclic (meth)acrylic acid esters; (Meth)acrylic acid esters having hydroxyl groups at the molecular termini, synthesized by ring-opening addition of ε-caprolactone to mono(meth)acrylates containing hydroxyl groups; Alkylene oxide-added (meth)acrylic acid esters are obtained by repeatedly adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to a mono(meth)acrylate having a hydroxyl group; Examples of monofunctional (meth)acrylamides include N,N-dimethyl(meth)acrylamide, (meth)acrylmorpholin, 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, oligomers and polymers are polymers in which a finite number of monomers are bonded together. An oligomer is a compound with a weight-average molecular weight of 10,000 or less, and a polymer is a compound with a weight-average molecular weight greater 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. In this specification, the weight-average molecular weight is the value measured using polystyrene with a known weight-average molecular weight as a standard substance by gel permeation chromatography (GPC).

[0037] Polyurethane-based (meth)acrylate oligomers are compounds having urethane bonds and radically polymerizable functional groups. Polyurethane-based (meth)acrylate oligomers can be obtained, for example, by reacting a compound having two or more isocyanate groups with a compound having a hydroxyl group, or by reacting a compound having an isocyanate group at the terminal with a (meth)acryloyl group having a hydroxyl group. Alternatively, they can be synthesized by reacting a compound having a hydroxyl group with a compound having both an isocyanate group and a (meth)acrylate group. Examples of polyurethane-based (meth)acrylate oligomers (A1) include those having a polyether skeleton and those having a polyester skeleton. Compounds having two or more isocyanate groups include, for example, aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 1,4-phenylenebismethylene diisocyanate; and aliphatic isocyanates such as 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate and hexamethylene diisocyanate. Examples of polyurethane-based (meth)acrylate oligomer products include aromatic polyurethane oligomers such as EBECRYL210, EBECRYL220 (both manufactured by Daicel Ornex Corporation), CN9782, CN9783 (both manufactured by SARTOMER Corporation); and aliphatic polyurethane oligomers such as Shiko UV3000B, Shiko UV3300B (both manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL8402, EBECRYL8701 (all manufactured by Daicel Ornex Corporation).

[0038] Polyester-based (meth)acrylate oligomers are compounds having ester bonds and radical polymerizable functional groups. For example, they can be synthesized by esterification reactions of hydroxyl groups found in polyesters synthesized by polycondensation of polybasic acids and polyhydric alcohols with carboxyl groups in (meth)acrylates (e.g., (meth)acrylic acid). Examples of polybasic acids include aliphatic polybasic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, suberic acid, maleic acid, fumaric acid, itaconic acid, succinic anhydride, and maleic anhydride; alicyclic polybasic acids such as dimer acids and cyclohexanedicarboxylic acid; and aromatic polybasic acids such as isophthalic acid, terephthalic acid, and biphenyldicarboxylic acid. Examples of polyhydric alcohols include polyethylene glycol, propylene glycol, and other polyols with a number-average molecular weight (Mn) of 50 to 500, as well as polyols with a number-average molecular weight (Mn) of 500 to 30,000, and trimethylolpropane, glycerin, pentaerythritol, and the like. Examples of polyester-based (meth)acrylate oligomer products 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] Epoxy (meth)acrylate oligomers are compounds with radically polymerizable functional groups, formed by reacting the epoxy group of an epoxy group-containing compound with a carboxyl group or hydroxyl group-containing compound. It is acceptable for a small amount of epoxy group to remain in epoxy (meth)acrylate oligomers. Examples of epoxy (meth)acrylate oligomer products include aromatic epoxy oligomers such as CN104, CN110 (both manufactured by SARTOMER), EBECRYL600, and EBECRYL3701 (both manufactured by Daicel Ornex), and aliphatic epoxy oligomers such as CN111, CN113 (both manufactured by SARTOMER), and EBECRYL860 (manufactured by Daicel Ornex).

[0040] As specific examples of (meth)acrylate polymers, compounds obtained by substituting polymers for the specific examples of oligomers mentioned above can be cited.

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

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

[0043] A curable compound having a tertiary amino group (Q N As the ) a (meth)acrylate having a tertiary amino group is preferred. Examples of preferred meth)acrylates include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate, as well as N,N-dialkylaminoalkyl (meth)acrylates, N-[2-methacryloyloxyethyl]piperidine, N-[2-methacryloyloxyethyl]pyrrolidine, N-[2-methacryloyloxyethyl]morpholine, and 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate. Furthermore, other examples include methacrates having a ring-opened epoxy group and a hydroxyl group, obtained by reacting glycidyl (meth)acrylate with a secondary amino compound such as dimethylamine, diethylamine, and dipropylamine, or a compound having a tertiary amino group and a secondary amino group such as dimethylaminopropylmethylamine; and (meth)acrylates having urethane bonds or urea bonds, obtained by reacting an isocyanate group-containing (meth)acrylate 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)acrylate is more preferred.

[0044] A curable compound having a quaternary ammonium base (Q NAs the quaternary ammonium base, (meth)acrylates having a quaternary ammonium base are preferred. As a preferred example, (meth)acrylates obtained by reacting a (meth)acrylate having a tertiary amino group with a quaternizing agent can be cited. 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; sulfonic acid esters such as methyl methanesulfonate, methyl p-toluenesulfonate, and methyl trifluoromethanesulfonate; and sulfuric acid esters such as dimethyl sulfate and diethyl sulfate. A quaternary ammonium salt can be obtained by reacting the quaternary ammonium base with a tertiary amino group. Furthermore, when an organic halide is used as the quaternizing agent, the nitrogen atom is a cation and the counterion halogen is an anion to form a quaternary ammonium salt, but monomers obtained by exchanging that anion with another anion may also be used. As the compound having the anion, conventionally known compounds can be used, for example, inorganic salt compounds such as sodium tetrafluoroborate, sodium trifluoromethyl sulfate, sodium perchlorate, sodium hexafluorophosphate, and sodium bis(trifluoromethanesulfonyl)imide. Examples of commercially available products include Acrylit 8WX-018 (manufactured by Taisei Fine Chemical Co., Ltd.) and Aminoion RE3000MF (manufactured by Nippon Emulsifier Co., Ltd., an acrylic group-containing reactive ion).

[0045] A curable compound having a tertiary amino group and / or a quaternary ammonium base (Q N The total content of (Q) can be designed as appropriate and is not particularly limited, but it is preferably 3 to 40% by mass, more preferably 3 to 30% by mass, and even more preferably 3 to 20% by mass, out of 100% by mass of curable compound (Q). By setting it in the range of 3 to 40% by mass, it is possible to have both excellent antiblocking properties and excellent adhesion to OCA. Note that the curable compound (Q N) may contain both a tertiary amino group and a quaternary ammonium base, and in this case, it goes without saying that the content is calculated as a single compound when calculating the total content.

[0046] As the curable compound (Q), a curable compound (Q) having at least one of a tertiary amino group and a quaternary ammonium base. N By using this method, 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 for the binder resin and particles (R) other than the hydrophilic groups. Therefore, the tertiary amino group and / or quaternary ammonium base are more easily exposed on the surface side of the resin layer (B). Furthermore, since these groups are immobilized 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 included. Hydroxyl group-containing curable compound (Q O By including this compound, the compatibility and dispersibility between the particles (R) and the tertiary amino group and / or quaternary ammonium base are improved, resulting in excellent coating stability. Furthermore, the haze value of the coating film of the resin layer (B) can be reduced. In addition, the initial wetting tension is improved and the decrease in wetting tension after annealing treatment is suppressed, allowing for a more effective balance of OCA adhesion. As a result, the dispersibility of particles (R) in the resin layer (B) can be more effectively improved, and transparency can be significantly enhanced. Hydroxyl group-containing curable compound (Q O The content of ) is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 5 to 20% by mass, based on 100% by mass of the curable compound (Q).

[0048] Hydroxyl group-containing curable compound (Q OPreferred examples of these include the hydroxyl group-containing (meth)acrylates mentioned above. Among these, 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 may contain a hydrophilizing agent (T) as an optional component. Here, the hydrophilizing agent (T) is a compound that does not exhibit curability by active energy rays and, when added, can reduce the water contact angle of the surface layer (the surface layer opposite to 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). Compounds that reduce the water contact angle to 60° or less are preferred, and 55° or less are more preferred. However, compounds corresponding to particles (R) are excluded.

[0050] A preferred example of the hydrophilizing agent (T) is a hydrophilizing agent (T) having at least one of a tertiary amino group and a quaternary ammonium base. N Examples include ionic hydrophilic agents having a quaternary ammonium base and nonionic hydrophilic agents having a tertiary amino group. From the viewpoint of easily adjusting the wetting tension, it is preferable that the amine value is 140 to 370 mg KOH / g. When the hydrophilic agent (T) is a polymer, it is preferable that 100 to 50% by mass of the monomer-derived constituent units used in the polymerization of the polymer are monomer-derived constituent units having a tertiary amino group and / or a quaternary ammonium salt.

[0051] Examples of trade names for ionic hydrophilizing agents containing quaternary ammonium bases include Acrit 8WX-030 (manufactured by Taisei Fine Chemical Co., Ltd.) and Aminoion RE3000MF (manufactured by Nippon Emulsifier Co., Ltd.). Suitable examples of nonionic hydrophilic agents having tertiary amino groups include vinyl resins having tertiary amino groups and (meth)acrylic resins having tertiary amino groups. Among these, (meth)acrylic resins containing dialkylamino groups are preferred.

[0052] Furthermore, preferred examples of the above-mentioned ionic hydrophilic agents and nonionic hydrophilic agents include curable compounds (Q N Examples include polymers obtained by homopolymerizing monomers or oligomers of ) or copolymers containing some or all of the monomer components. Also, the aforementioned curable compound (Q N Examples include compounds obtained by crosslinking monomers or oligomers of ). These may be single compounds or mixtures.

[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 antiblocking properties, it is preferably 3 to 40% by mass. The aforementioned content is 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 may be either a low-molecular-weight compound or a high-molecular-weight compound. However, from the viewpoint of effectively suppressing bleed-out in high-temperature and high-humidity environments, it is preferable that it be a high-molecular-weight compound with 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] A curable compound having a tertiary amino group and / or a quaternary ammonium base (Q N ), as well as hydrophilizing agents having a tertiary amino group or / and a quaternary ammonium base (T N Total content of (curable compound (Q) N ) and hydrophilizing agent (T N The nonvolatile component of the curable composition (S) is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass, based on 100% by mass of the nonvolatile component. By setting the amount in the range of 3 to 50% by mass, the wettability of the main surface (F) of the resin layer (B) can be set to a desired range, regardless of whether or not annealing treatment is performed, and excellent adhesion to OCA can be achieved.

[0056] <Particle(R)> This composition contains particles (R). As mentioned above, particles (R) are at least one selected from resin beads and inorganic particles. Particles (R) primarily play a role in providing antiblocking properties. Particles (R) can be used alone or in combination of two or more types. Particles (R) may be surface-treated, such as hydrophilic or hydrophobic treatment, or they may be left untreated.

[0057] Examples of resin beads include acrylic resin, urethane resin, urethane-acrylic resin, urea resin, polyvinyl chloride, polystyrene, polyacrylonitrile, polyamide, polyimide, and polycarbonate. Among these, acrylic resin and urethane-acrylic resin, whose hardness can be adjusted by crosslinking, are preferred from the viewpoint of scratch resistance. The resin beads may also be reactive resin beads. Reactive resin beads have groups that react upon heating or irradiation with active energy rays, and from the viewpoint of productivity, resin beads that react upon irradiation with active energy rays are preferred. The reactive group may be a functional group that chemically bonds with the curable compound (Q). Examples of reactive functional groups include polymerizable vinyl groups and ethylenically unsaturated groups such as (meth)acryloyl groups. The refractive index of the resin beads can be adjusted as appropriate, but from the viewpoint of improving transparency, 1.3 to 1.8 is preferred, and 1.4 to 1.6 is more preferred. Examples of commercially available acrylic resin beads include Chemisnow (registered trademark, manufactured by Soken Chemical 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 Kogyo Co., Ltd.), and Gantz 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. From the viewpoint of antiblocking properties, silica particles and alumina are particularly preferred as inorganic particles.

[0059] The antiblocking properties can be enhanced by adding particles (R). 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 diameter of particle (R) is preferably 10 to 100 nm, more preferably 10 to 50 nm. The average particle diameter (median diameter) is 1000 nm or less, more preferably 500 nm or less, and even more preferably 100 nm or less.

[0061] The average particle size mentioned above can be measured using a particle size distribution analyzer, particularly one using a dynamic light scattering method (such as the "NANOTRAC WAVE II UZ152" manufactured by Microtrac-Bell). In this invention, methyl ethyl ketone was used as the solvent, and the average value of three 60-second measurements were taken at a concentration in the range of 1.0 ± 0.2.

[0062] The particle content (R) should be adjusted appropriately according to the particle size of the particles (R) and the thickness of the resin layer (B) so that, in a laminated structure of a 1 μm thick resin layer (B) and a 50 μm thick polyethylene terephthalate layer, the haze value measured from the surface side of the resin layer (B) is 2.0% or less. From the viewpoint of achieving both high transparency and antiblocking properties, it is preferable to have a particle content of 0.01 to 40% by mass relative to 100% by mass of the nonvolatile components of the curable composition (S). From the viewpoint of achieving even better antiblocking properties, it is more preferable to have a particle content of 3 to 40% by mass, even more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. Furthermore, when using particles with a large average particle diameter relative to the thickness of the resin layer (B), the haze value can be easily adjusted by reducing the particle content (for example, 0.01 to 0.5% by mass). Here, nonvolatile components refer to components that make up the composition other than the solvent.

[0063] The surface of the inorganic particles may be surface-treated, including with organic compounds. Reactive inorganic particles may also be used. Reactive inorganic particles are inorganic particles that react upon heating or irradiation with active energy rays. Examples include particles having reactive groups on their surface, such as polymerizable vinyl groups, ethylenically unsaturated groups like (meth)acryloyl groups, or epoxy groups. Reactive groups are obtained by surface modification with compounds containing reactive groups. For example, silane coupling agents having ethylenically unsaturated groups can be used. As surface treatment agents for inorganic particles, known treatment agents such as silane coupling agents such as 3-(meth)acryloxypropyltrimethoxysilane, β-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, hexamethyldisilazane, and dimethyldichlorosilane, or silicone oil can be used.

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

[0065] A curable compound having a tertiary amino group and / or a quaternary ammonium base (Q N ) or / and hydrophilizing agent (T N By using ) and surface-treated particles (R) in combination, a curable compound (Q N ) or / and hydrophilizing agent (T N ) and particle (R) can be prevented more effectively. In addition to excellent antiblocking properties, the dispersion of particle (R) in the resin layer (B) is significantly improved, and from the viewpoint of achieving excellent coating stability and a good haze value, the above combination can be further improved by adding a hydroxyl group-containing curable compound (Q O It is preferable to include ) in the formulation. In particular, when silica is used as particles (R), a curable 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 By combining it with (Q), a curable compound (Q N ) or / and hydrophilizing agent (T N ) and silica aggregation can be prevented more effectively. In addition to excellent antiblocking properties, the dispersion of silica particles in the resin layer (B) is significantly improved, and from the viewpoint of achieving excellent coating stability and a good haze value, the above combination can be further enhanced with a hydroxyl group-containing curable compound (Q O It is preferable to include ) in the formulation.

[0066] <Photopolymerization initiators and photosensitizers> The curable composition (S) may optionally contain a photopolymerization initiator. It is preferable to add a photopolymerization initiator when the active energy ray is ultraviolet light. The photopolymerization initiator can be any agent that has the function of initiating polymerization and / or crosslinking of a curable compound (Q) by photoexcitation, and is not particularly limited. Preferred examples include monocarbonyl compounds, dicarbonyl compounds, acetophenone compounds, benzoin ether compounds, acylphosphine oxide compounds, aminocarbonyl compounds, and the like.

[0067] The aforementioned monocarbonyl compounds include benzophenone, 4-methyl-benzophenone, 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)metaammonium oxalate, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy-N,N,N-trimethyl-1-propanamine hydrochloride, and benzoylmethylene-3-methylnaphtho(1,2-d)thiazoline. Examples of the dicarbonyl compounds include 1,2,2-trimethyl-bicyclo[2.1.1]heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, methyl-α-oxobenzene acetate, and 4-phenylbenzyl. The acetophenone compounds 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-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymer, diethoxyacetophenone, and dibutoxyacetophenone. Examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-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, and 3,6-bis(2-methyl-2-morpholino-propanonyl)-9-butylcarbazole. Examples of the benzoin ether compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin n-butyl ether. Examples of the aforementioned acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di(2,6-dichlorobenzoyl)phosphine oxide. Examples of the aforementioned aminocarbonyl compounds include methyl-4-(dimethoxyamino)benzoate, ethyl-4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate, isoamyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethylbenzoate, 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 from IGM-Resins BV, as well as Lucilin TPO from IGM-Resins BV and Esacure One from DKSH Japan. In particular, Omnirad 184 and EsaCureOne are preferred in terms of resistance to yellowing after active energy ray curing.

[0069] The photopolymerization initiator is not limited to the above-mentioned compounds; any substance capable of initiating polymerization is acceptable. The photopolymerization initiator may be used alone or in a mixture of two or more types. There are no particular restrictions on the amount of photopolymerization initiator used, but it is preferable to use it in the range of 1 to 20% by mass relative to 100% by mass of the curable compound (Q).

[0070] Examples of sensitizers include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyradinoporphyrazine derivatives. Examples of sensitizers include conductors, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal arene complexes, organoruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone, etc. Sensitizers are used individually or in combination of two or more.

[0071] <Other ingredients> The curable composition (S) of this embodiment may contain a solvent as needed. If a solvent is added, it is preferable to perform the curing treatment with active energy rays after the solvent has evaporated. The solvent is not particularly limited, and various known organic solvents can be used. Specifically, 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, methylpyrrolidone, etc. Two or more of these organic solvents may be used in combination. Furthermore, other components not listed above may be included, as long as they do not impair the purpose or effects of the present invention. Examples include surfactants, colorants, stabilizers, resins, surface treatment agents, viscosity modifiers, adhesion promoters, antioxidants, anti-aging agents, crosslinking accelerators, UV absorbers, plasticizers, preservatives, dispersants, defoamers, silane coupling agents, and inorganic fillers.

[0072] [Method for producing a curable composition (S)] The curable composition (S) can be obtained by known methods and is not particularly limited. For example, a method may be used in which a curable compound (Q) and particles (R) are mixed and dispersed, and a solvent, a photopolymerization initiator, and various other components are added and adjusted as needed.

[0073] [Method for manufacturing laminates] A method for manufacturing the laminate of this embodiment will now be described. The laminate of this embodiment is formed by laminating a resin layer (B) on at least one side 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 by active energy rays and particles (R).

[0074] Known methods can be used to coat a curable composition (S) onto a light-transmitting substrate layer (A). For example, various coating methods such as using a rod, wire bar, microgravure, gravure, die, curtain, lip, slot, or spin can be used. After forming a coating film of the curable composition (S), it is allowed to dry naturally or by forced drying. Then, a resin layer (B) is obtained by curing it by irradiation with active energy rays. As a light source of ultraviolet light and visible light with a wavelength of 400-500 nm, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, gallium lamps, xenon lamps, carbon arc lamps, etc. can be used. As an electron source, a thermionic radiation gun, electrolytic radiation gun, etc. can be used. The amount of active energy irradiated should be sufficient to obtain adequate curing, for example, 50-2000 mJ / cm². 2 It can be considered to be of a certain degree.

[0075] [Transparent electrode film] The transparent electrode film of this embodiment comprises at least the laminate and a transparent conductive layer. Figure 1 shows an example of the transparent electrode film of this embodiment. As shown in the figure, the transparent electrode film 1 is laminated in the following order: laminate 2, index matching layer (hereinafter also referred to as IM layer) 3, and transparent conductive layer 4. 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 transparent conductive layer 4 may be laminated directly on the light-transmitting substrate layer (A) of the laminate 2 without providing the IM layer 3. Each layer may be a single layer or multiple layers, independently of each other.

[0076] The IM layer 3 is a high refractive index layer laminated to make the shape of the patterned transparent conductive layer 4 difficult to see. For example, it can be formed by a cured layer of a composition containing high refractive index metal oxide particles and an active energy ray curable component. Preferably, the refractive index of the IM layer 3 is 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. For example, examples of high refractive index metal oxide particles include titanium oxide (nD=2.72), zirconium oxide (nD=2.22), and aluminum oxide (nD=1.77). An example of an active energy ray curable component is the curable compound (Q) contained in the aforementioned resin layer (B). The thickness of the IM layer 3 is, for example, about 0.03 μm to 30 μm. A low refractive index layer and a high refractive index layer may be laminated as the IM layer.

[0077] The transparent conductive layer 4 is a transparent layer with conductivity and can be formed from indium tin oxide (ITO), tin oxide, zinc oxide, silver, or copper nanowires, etc. The transparent conductive layer 4 can be deposited by methods such as vacuum deposition (physical or chemical deposition), sputtering, or ion plating. After the transparent conductive layer 4 is provided on the IM layer 3, circuits and electrode patterns can be formed by methods such as etching. The thickness of the transparent conductive layer 4 can be, for example, 1 nm to several tens of micrometers, from the viewpoint of improving conductivity and adhesion with the IM layer 3.

[0078] An anchor layer (not shown) may be placed between the IM layer 3 and the transparent conductive layer 4. The anchor layer can be formed, for example, by a vacuum deposition method, similar to that used for the transparent conductive layer 4. Silicon oxide is preferred as the metal oxide used to form the anchor layer because it can provide strong adhesion.

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

[0080] <<Examples>> The present invention will be described in more detail below, but the following examples do not limit the scope of the present invention in any way. In the examples, "parts" and "%" represent "parts by mass" and "% by mass," respectively. 5、6、9、10、 13, 23、 Reference examples 24 and 25 are provided for the purpose of aligning with the scope of claim 1. 5、6、9、10、 13, 23、 These should be interpreted as 24 and 25. Mw stands for weight-average molecular weight, and it is the polystyrene-equivalent molecular weight when using a TSKgel column (Tosoh Corporation) and a GPC (Tosoh Corporation, HLC-8320GPC) equipped with an RI detector, with DMF as the developing solvent. Furthermore, the amine value of the tertiary amino group-containing curable compound is the total amine value (mgKOH / g) measured according to the method of ASTM D 2074, converted to solid content. In this specification, non-volatile content refers to the value calculated from the mass of the sample after heating / the mass of the sample before heating when 1 g of the sample is heated at 180°C for 20 minutes.

[0081] The abbreviations for each component of the curable composition (S) used in this embodiment 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., contains quaternary ammonium base. • q-6 (amino ion RE3000MF): Cationic polymer, manufactured by Nippon Emulsifier Co., Ltd., contains a quaternary ammonium base. • q-7: A curable vinyl resin containing tertiary amino groups. Furthermore, the above q-1 and q-4 are hydroxyl group-containing curable compounds (Q O This corresponds to ). [Particle (R)] • r-1 (Aeroxide AluC dispersion): D50: 62nm, alumina. • r-2 (Techpolymer NH): Manufactured by Sekisui Chemical Co., Ltd., D50: 80nm, 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, contains quaternary ammonium base.

[0082] <Example of production of a tertiary amino group-containing curable compound (q-7)> In a reaction vessel equipped with a gas inlet tube, condenser, stirring blade, and thermometer, 50.6 parts by mass of ethyl acetate, 180 parts by mass of N,N-diethylaminoethyl methacrylate, and 20 parts by mass of 2-hydroxyethyl methacrylate were charged. The mixture was heated to 50°C while purging with nitrogen, then 2.3 parts of 1-thioglycerol were added, and the temperature was raised to 70°C. In a dropping vessel, 16.8 parts by mass of ethyl acetate and 0.6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) were charged and stirred until homogeneous. These were then added dropwise to the reaction vessel over 7 hours, and the reaction was continued at the same temperature for 1 hour. Solid content measurement confirmed that more than 95% of the mixture had reacted. Next, the flask was purged with air, and 32.8 parts by mass of 2-acryloyloxyethyl isocyanate (AOI) and 0.1 parts by mass of hydroquinone were charged, and the reaction was carried out at 70°C for 4 hours. After confirming the disappearance of the 2270 cm⁻¹ peak based on the isocyanate group by FT-IR, the reaction solution was cooled to obtain a vinyl resin solution containing a tertiary amino group and an acryloyl group. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Ethyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 45% by weight to obtain a curable compound (q-7) solution, which is a vinyl resin containing 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.

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

[0084] <Example of production of tertiary amino group-containing hydrophilizing agent (t-1)> In a reaction vessel equipped with a gas inlet tube, condenser, stirring blade, and thermometer, 50.6 parts of isopropyl alcohol and 200 parts of N,N-dimethylaminoethyl methacrylate were charged. The mixture was heated to 50°C while purging with nitrogen, then 2.3 parts of 1-thioglycerol were added, and the temperature was raised to 70°C. In a dropping vessel, 16.8 parts of isopropyl alcohol and 0.6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were charged and stirred until homogeneous. These were then added dropwise to the reaction vessel over 7 hours, and the reaction was continued at the same temperature for 1 hour to obtain a vinyl resin solution containing tertiary amino groups. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Isopropyl alcohol was added to the previously synthesized resin solution to obtain a hydrophilic agent (t-1) solution, which is a vinyl resin having a tertiary amino group with an amine value of 357 mgKOH / g per solid content and a number average molecular weight of 21,000.

[0085] <Example of production of tertiary amino group-containing hydrophilizing agent (t-2)> In a reaction vessel equipped with a gas inlet pipe, condenser, stirring blade, and thermometer, 50.6 parts of isopropyl alcohol and 200 parts of N,N-diethylaminoethyl methacrylate were charged. The mixture was heated to 50°C while purging with nitrogen, then 2.3 parts of 1-thioglycerol were added, and the temperature was raised to 70°C. In a dropping tank, 16.8 parts of isopropyl alcohol and 0.6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were charged. After stirring until homogeneous, the mixture was added dropwise to the reaction vessel over 7 hours, and the reaction was continued at the same temperature for 1 hour to obtain a solution of vinyl resin having a tertiary amino group. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Isopropyl alcohol was then added to the previously synthesized resin solution to reduce the non-volatile content to 45% to obtain a hydrophilic agent (t-2) solution, which is a vinyl resin having tertiary amino groups with an amine value of 301 mg KOH / g per solid content and a number average molecular weight of 20,000.

[0086] <Example of production of tertiary amino group-containing hydrophilizing agent (t-3)> In a reaction vessel equipped with a gas inlet pipe, condenser, stirring blade, and thermometer, 50.6 parts of isopropyl alcohol, 100 parts of N,N-diethylaminoethyl methacrylate, and 100 parts of methyl methacrylate were charged. The temperature was raised to 50°C while purging with nitrogen, then 2.3 parts of 1-thioglycerol were added, and the temperature was raised to 70°C. In a dropping tank, 16.8 parts of isopropyl alcohol and 0.6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were charged and stirred until homogeneous. These were then added dropwise to the reaction vessel over 7 hours, and the reaction was continued at the same temperature for 1 hour to obtain a solution of vinyl resin having a tertiary amino group. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Isopropyl alcohol was then added to the previously synthesized resin solution to reduce the non-volatile content to 45% to obtain a hydrophilic agent (t-3) solution, which is a vinyl resin having tertiary amino groups with an amine value of 151 mg KOH / g per solid content and a number average molecular weight of 21,000.

[0087] <Example of manufacturing a curable composition (S)> (Example 1) 94.5 parts of pentaerythritol triacrylate (KAYARAD PET30, manufactured by Nippon Kayaku Co., Ltd., containing a portion of pentaerythritol tetraacrylate), 5.5 parts of Acrit 8WX-030 (manufactured by Taisei Fine Chemical Co., Ltd.), 5.0 parts of Omnirad 184 (manufactured by IGM-Resins BV), and 50 parts of methylpropylene glycol were uniformly mixed. Next, an aeroxide AluC dispersion was added to this mixture so that the alumina content was 5.5% by mass of the non-volatile components, and methylpropylene glycol was added so that the non-volatile components amounted to 50% by mass, and the mixture was uniformly mixed to obtain a curable composition (S).

[0088] (Examples 2-25, Comparative Examples 1-6) Curable compositions (S) for each example and comparative example were obtained by the same method as in Example 1, except that the formulation amounts were changed as shown in Tables 1 to 3.

[0089] [Table 1]

[0090]

Table 2

[0091]

Table 3

[0092] <Production Example of Laminated Body> (Example 1) A 50-μm-thick easily adherable 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 laminated body according to Example 1 was obtained. (Examples 2 to 25, Comparative Examples 1 to 6) Laminated bodies 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 adherable 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 obtained by mixing Toyo Chem's "Olivine BPS5896" and "Olivine BXX5627" in a solid content ratio of 100 / 0.5. This adhesive was then coated onto a 100 μm thick easy-adhesion treated polyethylene terephthalate film (Toray's "Lumirror U403") using a bar coater. The film was then dried in a 100°C hot air oven for 2 minutes to remove the organic solvent, resulting in an OCA film with a 5 μm adhesive layer.

[0095] <Measurement of initial wetting tension> The initial wetting tension of the main surface (F) (see Figure 1) of the resin layer (B) of each example and comparative example laminate before annealing was measured by the following procedure. Specifically, the wetting tension of the main surface (F) of the resin layer (B) was determined using a wettability check Dynepen (a test pen for evaluating surface energy values) manufactured by Arcotest, under conditions of 23°C and 50% relative humidity. In particular, the laminate (test piece) of each example and comparative example was placed on a glass plate, and a liquid film of approximately 1 cm × 5 cm was formed on the main surface (F) of the resin layer (B) of the test piece using the Dynepen. The judgment was made by observing the liquid film of the Dynepen in a bright place and evaluating the state of the liquid film after 5 seconds. If the short side of the liquid film was maintained at 95% or more, it was judged to be wet. If the wetting was maintained at 95% or more, the evaluation proceeded to the next Dynepen with a higher surface tension; conversely, if it was not maintained at 95% or more, the evaluation proceeded to the next mixed liquid with a lower surface tension. Another known method for measuring wetting tension is JIS K6768. According to this method, a failure is judged if the liquid film breaks within 2 seconds or less after application of the dye pen / ink, making this test method a more accurate evaluation method. Compared to JIS K6768, the wetting tension obtained by this test method tends to be a smaller value.

[0096] <Measurement of wetting tension after annealing> The resin layer (B) of the laminates in each example and comparative example, and the heat-resistant protective PET film obtained in the manufacturing example were left to stand for 30 minutes in an environment of 23°C and 50% relative humidity. Then, the main surface (F) of the resin layer (B) and the adhesive layer of the heat-resistant protective PET film were bonded together using a 2kg roller. Next, after annealing treatment at 150°C for 3 hours, the heat-resistant protective PET film was peeled off, and the wetting tension of the exposed main surface (F) of the resin layer (B) was measured in the same manner as the initial wetting tension.

[0097] <Haze value measurement> A 50 μm thick polyethylene terephthalate (Lumirror U403, manufactured by Toray Industries, Inc., haze value 1.1%, total light transmittance 91%) was coated with the curable composition (S) shown in Table 1 using a bar coater and dried at 100°C for 1 minute. The active energy rays and irradiation dose need to be appropriately changed depending on the type of curable composition (S), but in this example and comparative example, a high-pressure mercury lamp was used as the light source with a light intensity of 400 mJ / cm² in the UVA ultraviolet region. 2 A measurement sample having a resin layer (B) consisting of a cured film with a thickness of 1 μm was obtained by irradiating it with ultraviolet light. Then, the haze value of the measurement sample (50 μm polyethylene terephthalate / resin layer (B)) for each example and comparative example was determined 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 antiblocking 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 testing machine (trade name: "CO-201 Permanent Distortion Testing Machine (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 anti-blocking property (hereinafter abbreviated as "AB property") was evaluated according to the following criteria based on the ratio of the area where the overlapping surfaces of the test pieces were stuck together (a watermark-like appearance was formed). 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 testing machine so that the resin layer became the test surface, and the surface of the resin layer was rubbed back and forth 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%. Then, 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 testing machine, and the peel strength was measured. The adhesion was evaluated according to the following criteria based on the obtained peel strength value. A: The peel strength is 25 N or more. B: Peel strength of 10N or more and 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 of less than 30 mN / m after annealing treatment exhibited poor OCA adhesion, as shown in Comparative Examples 1 and 2. Furthermore, laminates with an initial wetting tension exceeding 60 mN / m and a surface tension exceeding 54 mN / m after annealing treatment exhibited poor scratch resistance and antiblocking properties, as shown in Comparative Example 3. Additionally, as shown in Comparative Example 4, while a higher particle (R) content improved antiblocking properties, it also resulted in a decrease in haze value. On the other hand, this embodiment confirmed that the laminate exhibited excellent optical properties and scratch resistance, high yield even when manufactured using the roll-to-roll method, and excellent OCA adhesion regardless of whether annealing treatment was performed. [Industrial applicability]

[0103] The laminate of the present invention is suitable as an optical film because it provides a laminate with excellent adhesion to OCA film, excellent antiblocking properties, scratch resistance, and transparency. For example, a transparent electrode film formed by laminating a transparent conductive layer onto the laminate is suitable as a touch panel component for smartphones, tablets, PCs, televisions, car navigation systems, and other commercial facilities such as information boards and ticket vending machines. Furthermore, since the resin layer (B) of the laminate of the present invention has excellent surface hardness, it is also suitable as a scratch-preventing film for the surface of flat panel displays (FPDs) such as liquid crystal displays (LCDs), organic light-emitting diodes (OLEDs), and plasma displays (PDPs).

Claims

1. The laminated structure has a light-transmitting substrate layer (A) on at least one surface to which a resin layer (B) is laminated directly or via one or more other layers. The resin layer (B) is a layer obtained by curing a curable composition (S) containing particles (R) and a curable compound (Q) that exhibits curability by active energy rays (excluding particles (R)). The particle (R) is at least one selected from inorganic particles (but not silica particles) and resin beads having a gel fraction of 80% by mass or more relative to methyl ethyl ketone, the primary particle diameter of the particle (R) is 10 to 100 nm, and the average particle diameter (median diameter) is 100 nm or less. The curable compound (Q) contains a curable compound having a hydroxyl group, In a laminated structure consisting 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 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. Furthermore, a heat-resistant protective polyethylene terephthalate film is attached to the main surface (F) of the resin layer (B), and an annealing treatment is performed at 150°C for 3 hours. After peeling off the heat-resistant protective polyethylene terephthalate film, the wettability 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 base Ｎ ) containing, and (ii) Contains a hydrophilic agent (T) (excluding particles (R)) that does not exhibit curing properties when exposed to active energy rays, The hydrophilic agent (T) is a hydrophilic agent (T) having at least one of a tertiary amino group and a quaternary ammonium base. Ｎ ) contains Satisfying at least one of the following conditions, When the curable composition (S) contains at least one of a curable compound (QN) having a quaternary ammonium base and a hydrophilizing agent (TN) having a quaternary ammonium base, the total content of the curable compound (QN) having a quaternary ammonium base and the hydrophilizing agent (TN) having a quaternary ammonium base is 3 to 20% by mass with respect to 100% by mass of the non-volatile components. A laminate in which the particle (R) content is 5 to 30% by mass relative to 100% by mass of the nonvolatile components of the curable composition (S).

2. A curable compound having at least one of a tertiary amino group and a quaternary ammonium base (Q Ｎ The laminate according to claim 1, wherein the laminate has (meth)acryloyl groups.

3. A curable compound having at least one of a tertiary amino group and a quaternary ammonium base (Q Ｎ ), and hydrophilizing agents having at least one of a tertiary amino group and a quaternary ammonium base (T Ｎ The laminate according to claim 1 or 2, wherein the total content of ) is 3 to 40% by mass with respect to 100% by mass of the nonvolatile components of the curable composition (S).

4. The laminate according to any one of claims 1 to 3, wherein the particle (R) is at least one selected from inorganic particles (excluding silica particles, zirconium oxide, and titanium oxide) and resin beads having a gel fraction of 80% by mass or more relative to methyl ethyl ketone.

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

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

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