Transparent electrode film

Abstract

The present invention provides a transparent electrode film having excellent optical properties and scratch resistance, and further having a high yield even when manufactured using a roll-to-roll method, and having excellent OCA adhesion regardless of whether or not an annealing treatment is performed. The laminate of such a transparent electrode film comprises a light-transmitting substrate layer and a resin layer, wherein the resin layer is a hardened layer of a hardening composition containing particles and a hardening compound. In a laminated structure of a 1 μm resin layer and a 50 μm PET, the haze value is set to 2.0% or less when measured from the surface side of the resin layer. The main surface of the resin layer opposite to the light-transmitting substrate layer has an initial wetting tension of 38 mN / m to 60 mN / m before annealing, and the main surface of the resin layer after a heat-resistant protective PET film is attached to the main surface, annealed for 3 hours, and the heat-resistant protective PET film is peeled off has a wetting tension of 30 mN / m to 54 mN / m.

Description

[0001] This application claims priority based on Japanese patent application No. 2021-044727 filed on March 18, 2021, Japanese patent application No. 2021-068628 filed on April 14, 2021, and Japanese patent application No. 2021-201209 filed on December 10, 2021, and all disclosed contents thereof are incorporated into this application. Technical Field

[0002] The present invention relates to a laminate and a transparent electrode film having a resin layer, which is a cured layer of a curable composition that exhibits curability by active energy rays. Background Art

[0003] As electrode materials for display devices such as touch screens, transparent electrode films can be used: a transparent conductive layer made of a material such as indium tin oxide (ITO) with a desired pattern is laminated onto a light-transmitting substrate layer such as polyethylene terephthalate (PET) film. An optically clear adhesive (OCA) film is attached to the transparent electrode film and then incorporated into a touch screen module.

[0004] In Patent Document 1, as a solution to the following problems, namely, the problem of air bubbles and voids generated during the baking process of a translucent transparent conductive film to which an OCA film is attached, and the following problem, namely, the problem that if roller conveying is performed after the OCA is attached, the OCA film is partially peeled off and misaligned with the adhesive surface of the translucent conductive film, thereby being exposed from the end of the translucent conductive film, a translucent conductive film is proposed. An ITO layer is formed on a PET film, and the wetting tension of the surface of the PET film is adjusted to 34 dyn / cm or more by plasma treatment.

[0005] Patent Document 2 proposes a hardening composition containing an active energy ray-hardening compound and silica particles, with the goal of imparting high anti-blocking properties to a film surface and forming a hard coating layer with high transparency and high adhesion to OCA, etc., and wherein the wetting tension of the coating surface after curing is 35 mN / m to 60 mN / m.

[0006] [Prior art literature]

[0007] [Patent Document]

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2016-155366

[0009] Patent Document 2: International Publication No. 2018 / 100929 Summary of the Invention

[0010] [Problems to be solved by the invention]

[0011] Regarding laminates suitable for transparent electrode film applications as electrode materials for display devices such as touch screens, there is a strong market demand for highly versatile laminates that not only exhibit excellent optical properties and scratch resistance, but also achieve high yields when manufactured using a roll-to-roll process and exhibit excellent adhesion to OCA films, regardless of whether an annealing process is used. While the aforementioned content describes issues with laminates used in transparent electrode films, similar issues may arise in all applications requiring these properties.

[0012] The present invention has been made in view of the above background, and its object is to provide a laminate and a transparent electrode film that have excellent optical properties and scratch resistance, high yield even when manufactured by a roll-to-roll method, and excellent OCA adhesion regardless of whether annealing treatment is performed.

[0013] [Technical means to solve the problem]

[0014] The present inventors have diligently studied and, as a result, have found that the problems of the present invention can be solved by the following aspects, thereby completing the present invention.

[0015] [1]: A laminate having a laminate 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 base material layer (A),

[0016] The resin layer (B) is a layer formed by curing a curable composition (S) containing particles (R) and a curable compound (Q) curable by active energy rays (excluding the particles (R)).

[0017] 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,

[0018] 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.

[0019] The initial wetting tension of the main surface (F) of the resin layer (B) opposite to the light-transmitting substrate layer (A) before annealing is 38 mN / m to 60 mN / m,

[0020] A heat-resistant protective polyethylene terephthalate film is attached to the main surface (F) of the resin layer (B), annealed at 150° C. for 3 hours, and then the heat-resistant protective polyethylene terephthalate film is peeled off. The wetting tension of the main surface (F) of the resin layer (B) is 30 mN / m to 54 mN / m.

[0021] The curable composition (S) satisfies at least any one of the following:

[0022] (i) containing a curable compound having at least one of a tertiary amino group and a quaternary ammonium salt group (Q N ) as a hardening compound (Q); and

[0023] (ii) contains a hydrophilizing agent (T) that does not exhibit curing properties due to active energy rays (excluding the particles (R)),

[0024] The hydrophilizing agent (T) contains a hydrophilizing agent (T) having at least one of a tertiary amino group and a quaternary ammonium salt group. N ).

[0025] [2]: The laminate according to [1], wherein the curable compound (Q N ) has a (meth)acryloyl group.

[0026] [3]: The laminate according to [1] or [2], wherein the curable compound (Q N ), and a hydrophilizing agent (T N ) is 3% by mass to 40% by mass relative to 100% by mass of the non-volatile matter of the curable composition (S).

[0027] [4]: The laminate according to any one of [1] to [3], wherein the content of the particles (R) is 0.01% by mass to 40% by mass relative to 100% by mass of the non-volatile component of the curable composition (S).

[0028] [5]: A transparent electrode film comprising a transparent conductive layer and the laminate according to any one of [1] to [4], and

[0029] At least the transparent conductive layer, the light-transmitting base material layer (A) constituting the laminate, and the resin layer (B) constituting the laminate are laminated in this order directly or via one or more layers.

[0030] [6]: The transparent electrode film according to [5], wherein an optically transparent adhesive film is further laminated on the main surface of the resin layer (B) opposite to the light-transmitting base material layer (A) side.

[0031] [Effects of the Invention]

[0032] The present invention provides a laminate and a transparent electrode film having excellent optical properties and scratch resistance, high yield even when produced by a roll-to-roll method, and excellent OCA adhesion regardless of annealing treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is a schematic cross-sectional view showing an example of the transparent electrode film according to this embodiment. DETAILED DESCRIPTION

[0034] Hereinafter, the present invention will be described in detail. Of course, other embodiments are also included in the scope of the present invention as long as they conform to the main purpose of the present invention. In addition, in this specification, the numerical range specified by "to" includes the numerical values ​​recorded before and after "to". In this specification, "film" or "sheet" is not distinguished by thickness. In addition, the various components appearing in this specification can be used independently alone or in combination of two or more unless otherwise noted.

[0035] [[Laminated body]]

[0036] The laminate of the present embodiment has a laminated structure in which a light-transmitting substrate layer (A) is laminated with 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 hardening a curable composition (S), wherein the curable composition (S) contains particles (R) and a curable compound (Q) that exhibits curability by active energy rays (except for particles (R)). Here, the particles (R) are either inorganic particles or resin beads. The particles (R) may be crystalline or non-crystalline. The so-called inorganic particles are particles (fillers) formed from substances other than organic compounds, and examples thereof include particles of hydrides, borides, nitrides, carbides, oxides, halides, chalcogenides and compounds thereof containing metals or non-metallic elements. The so-called resin beads are particles (fillers) made of resin 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 the sample with 100 mL of methyl ethyl ketone (MEK) using a Soxhlet extractor, and weighing the extracted soluble component using the following formula (1).

[0037] Formula (1): Gel fraction relative to MEK (%) = {(1-mass of soluble component (g)) / 1}×100

[0038] The gel fraction is more preferably 90% by mass or more.

[0039] The initial wetting tension (hereinafter referred to as "initial wetting tension") of the main surface (F) of the resin layer (B) opposite the translucent substrate layer (A) before annealing is 38 to 60 mN / m. Furthermore, a heat-resistant protective polyethylene terephthalate film (hereinafter referred to as "heat-resistant protective PET film") is attached to the main surface (F) of the resin layer (B), annealed at 150°C for 3 hours, and the wetting tension (hereinafter referred to as "wetting tension after annealing") of the main surface (F) of the resin layer (B) after peeling off the heat-resistant protective PET film is 30 to 54 mN / m. Furthermore, the resin layer (B) used has a haze value of 2.0% or less when measured from the surface side of the resin layer (B) in a laminated structure of a 1 μm thick resin layer (B) and a 50 μm thick polyethylene terephthalate film. Furthermore, the curable composition (S) satisfies at least any one of the following (i) and (ii).

[0040] (i) containing a curable compound having at least one of a tertiary amino group and a quaternary ammonium salt group (Q N ) as a curable compound (Q).

[0041] (ii) containing a hydrophilizing agent (T) that does not exhibit curing properties due to active energy rays (excluding the particles (R)), wherein the hydrophilizing agent (T) contains a hydrophilizing agent (T) having at least one of a tertiary amino group and a quaternary ammonium salt group. N ).

[0042] In addition, each value of the initial wetting tension, the wetting tension after annealing treatment, and the haze disclosed in this specification refers to the value obtained by the method described in the Examples described later.

[0043] Here, the so-called "hardening compound (Q) that shows hardening properties by active energy rays" refers to a compound that is hardened by polymerization and / or cross-linking of the hardening compound (Q) by irradiation with active energy rays. However, the case of particles (R) is excluded. The so-called active energy rays refer to a broad range of energy rays that can provide the energy required for activation to produce a chemical reaction, including ultraviolet rays, visible rays, infrared rays, electron beams (electron beams, EB) and radiation. In addition, the so-called "hardened layer" refers to a layer that is further hardened to the extent that the hardening reaction does not substantially proceed even when irradiated with active energy rays. When forming the layer of the curable composition (S) of this embodiment, the state in which the curing reaction can be further hardened even if a part of the curing compound (Q) undergoes a hardening reaction is not included in the hardened layer referred to here.

[0044] The light-transmitting substrate layer (A) and the resin layer (B) may be laminated directly or through other layers such as an anchor layer, an adhesion layer, and an adhesive layer. In the laminate of this embodiment, an OCA film may be further laminated on the resin layer (B).

[0045] In the case of utilizing a roll-to-roll method to manufacture a laminate, the yield reduction caused by the adhesion of the films to each other as described above becomes a problem. According to the laminate of the present embodiment, by using a hardened layer of a curable composition (S) containing a curable compound (Q) and particles (R) as a resin layer (B), and making the initial wetting tension and the wetting tension after annealing to be the laminate of the specific range, anti-blocking property and scratch resistance are excellent. In addition, even in the case of utilizing a roll-to-roll method to manufacture, the adhesion of the films to each other can be effectively suppressed. Therefore, the yield can be significantly improved. And then, a laminate having excellent transparency and scratch resistance can be provided regardless of whether or not annealing treatment OCA adhesion is present. Below, each layer is described in detail.

[0046] [Light-transmitting substrate layer (A)]

[0047] The light-transmitting substrate layer (A) functions as a support layer for the resin layer (B). Here, light transparency refers to a transmittance of 80% or greater for light of a desired wavelength, as measured by the thickness of the light-transmitting substrate layer (A) in the laminate. It is more preferably 85% or greater, and even more preferably 90% or greater. When the laminate is used in applications requiring transparency, the desired wavelength corresponds to light in the visible light region (380 nm to 780 nm).

[0048] The material of the light-transmitting substrate layer (A) is not particularly limited as long as it has excellent transmittance. Suitable examples include polyester resins such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), cyclic polyolefin resins such as cycloolefin resins (cycloolefin polymers (COP)), chain 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.

[0049] Among these, polyethylene terephthalate having high versatility and cycloolefin resins having excellent low birefringence, low moisture absorption, high transparency and high heat resistance are suitable.

[0050] The thickness of the light-transmitting substrate layer (A) can be arbitrarily selected as long as it has the function of serving as a support for the resin layer (B). It can generally be set to about 25 μm to 188 μm. From the perspective of transparency, it is preferably in the range of 25 μm to 125 μm, and more preferably in the range of 25 μm to 100 μm.

[0051] [Resin layer (B)]

[0052] The resin layer (B) is formed by curing the curable composition (S) by irradiating it with active energy rays. It has excellent scratch resistance and anti-blocking properties and is therefore suitable for producing a laminate by a roll-to-roll method.

[0053] For example, a roll of light-transmitting substrate layer (A) can be unwound and coated with a curable composition (S), irradiated with active energy rays to obtain a resin layer (B) as a cured film, and then rewound into a roll to produce a laminate. Alternatively, a roll of light-transmitting substrate layer (A) can be laminated to a roll of resin layer (B), and then rewound into a roll. Compared to a method of laminating a resin layer (B) on a single light-transmitting substrate layer (A), productivity can be significantly improved.

[0054] The thickness of the resin layer (B) can be designed according to the application, but is preferably 1 μm to 10 μm, more preferably 1 μm to 5 μm, and even more preferably 1 μm to 3 μm from the viewpoint of imparting excellent anti-blocking properties.

[0055] The present inventors have conducted extensive research and have found that even if the initial wetting tension before annealing is in the range of 38mN / m to 60mN / m, annealing can significantly reduce the wetting tension of the main surface of the resin layer. Furthermore, it has been found that using a resin layer (B) having an initial wetting tension of 38mN / m to 60mN / m and a wetting tension of 30mN / m to 54mN / m after annealing (150°C for 3 hours) results in excellent OCA adhesion, regardless of whether annealing is performed or not.

[0056] The initial wetting tension of the main surface (F) of the resin layer (B) is 38 mN / m to 60 mN / m, preferably 40 mN / m to 60 mN / m, and particularly preferably 42 mN / m to 60 mN / m. Furthermore, the wetting tension after annealing is 30 mN / m to 54 mN / m, preferably 32 mN / m to 54 mN / m, and particularly preferably 36 mN / m to 54 mN / m.

[0057] The method of adjusting the initial wetting tension of the surface layer of the resin layer (B) to 38 mN / m to 60 mN / m and the wetting tension after annealing (150°C x 3 hours) to 30 mN / m to 54 mN / m can be adjusted by adjusting the composition of the curable composition (S). Alternatively, the initial wetting tension and the wetting tension after annealing of the surface layer of the resin layer (B) can be adjusted to the above-mentioned values ​​by performing a surface treatment in combination with the above-mentioned adjustment method.

[0058] The composition of the curable composition (S) can be adjusted by any of the following methods:

[0059] (1) containing a curable compound having at least one of a tertiary amino group and a quaternary ammonium salt group (Q N ) as a curable compound (Q),

[0060] (2) The curable composition (S) further contains a hydrophilizing agent (T) that does not exhibit active energy ray curing properties, and the hydrophilizing agent (T) includes a hydrophilizing agent (T) having at least one of a tertiary amino group and a quaternary ammonium salt group. N ) method and

[0061] (3) A method of using (1) and (2) in combination.

[0062] As a method of adjusting the wetting tension by surface treatment, there can be exemplified 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.

[0063] Excellent transparency can be achieved by using a layer having a haze value of 2.0% or less when measured from the surface of the resin layer (B) in a laminated structure of a 1 μm thick resin layer (B) and a 50 μm thick polyethylene terephthalate layer. 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%.

[0064] The method for adjusting the resin layer (B) to satisfy the above haze value is to adjust the composition of the curable composition (S). For example, as described below, by adding a hydroxyl group-containing curable compound (Q O ) is used in combination with particles (R) and tertiary amino groups or / and quaternary ammonium salt groups to reduce the haze value. The method has the advantage of omitting the steps of corona treatment or ozone treatment.

[0065] [Curable composition (S)]

[0066] The curable composition (S) of this embodiment is a composition that can form a resin layer (B) as 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 exposure to active energy rays and particles (R). Each component is described in detail below.

[0067] Curable compound (Q)

[0068] The curable compound (Q) may be any compound that undergoes a polymerization reaction and / or a crosslinking reaction upon exposure to active energy rays and thus cures, and may be selected from low-molecular-weight compounds and high-molecular-weight compounds, regardless of molecular weight. Compounds that meet the requirements of the particles (R) are excluded. The curable compound (Q) may be used alone or in combination of two or more.

[0069] Examples of the curable group of the curable compound (Q) include free radical polymerizable groups such as vinyl, (meth)acryloyl, and allyl. Of these, a curable compound (Q) having a (meth)acryloyl group is preferred. The curable compound (Q) may be used alone or in combination of two or more. Furthermore, "(meth)acrylate" includes both "acrylate," "methacrylate," and mixtures thereof.

[0070] From the viewpoint of increasing the surface hardness of the resin layer (B), it is preferred to use 30% by mass to 100% by mass or more of a trifunctional or higher-functional (meth)acrylate relative to 100% by mass of the curable compound (Q), more preferably 50% by mass to 100% by mass or more, and even more preferably 80% by mass to 100% by mass or more.

[0071] Examples of tetrafunctional or higher-functional (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, di-trimethylolpropane 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.

[0072] Examples of the trifunctional tri(meth)acrylate 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(acryloyloxyethyl)isocyanurate, caprolactone-modified tris(acryloyloxyethyl)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.

[0073] Examples of the difunctional (meth)acrylate 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.

[0074] Ethylene oxide modified pentylene glycol di(meth)acrylate, propylene oxide modified pentylene glycol di(meth)acrylate, tetramethylene oxide pentylene glycol 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 esters, ethylene oxide-modified heptanediol di(meth)acrylate, propylene oxide-modified heptanediol di(meth)acrylate, tetramethylene oxide-modified heptanediol di(meth)acrylate, ethylene 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, and isocyanuric acid butylene oxide-modified di(meth)acrylate;

[0075] 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.

[0076] Examples of the monofunctional (meth)acrylate include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, n-hexyl acrylate, lauryl acrylate, and stearyl acrylate;

[0077] Perfluoroalkyl (meth)acrylates such as perfluoromethyl (meth)acrylate, 2-perfluoroethyl-ethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate;

[0078] Aliphatic (meth)acrylates 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;

[0079] Aliphatic (meth)acrylates having two carbonyl groups, such as 2-oxobutyrylethyl (meth)acrylate, 3-oxobutyrylpropyl (meth)acrylate, 2,3-di(oxobutyryl)butyl (meth)acrylate, and 2,3-di(oxobutyryl)hexyl (meth)acrylate;

[0080] (Meth)acrylates containing an alkoxy group, 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;

[0081] Alkylene oxide-containing (meth)acrylic acid derivatives such as alkylene oxide adducts of (meth)acrylic acid;

[0082] (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;

[0083] 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;

[0084] (Meth)acrylates such as glycidyl laurate (meth)acrylate and other fatty acid esters;

[0085] Cyclic (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate, cyclohexanediethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalate;

[0086] (Meth)acrylates having a hydroxyl group at the molecular end synthesized by ring-opening addition of ε-caprolactone to a mono(meth)acrylate having a hydroxyl group;

[0087] Alkylene oxide-added (meth)acrylates obtained by repeatedly adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to mono(meth)acrylates having a hydroxyl group;

[0088] Monofunctional (meth)acrylamides such as 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, N-n-butyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N-hydroxymethyl(meth)acrylamide.

[0089] The curable compound (Q) may be an oligomer or a polymer. In addition, in this specification, the so-called oligomers and polymers are polymers formed by bonding a finite number of monomers. An oligomer refers to a compound having a weight average molecular weight of 10,000 or less, and a polymer refers to a compound having a weight average molecular weight of more than 10,000. An oligomer or a polymer may be either a homopolymer or a copolymer. Specific examples of (meth)acrylate oligomers include polyurethane (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and epoxy (meth)acrylate oligomers. The weight average molecular weight in this specification is a value obtained by measuring polystyrene with a known weight average molecular weight as a standard substance using gel permeation chromatography (GPC).

[0090] Polyurethane (meth)acrylate oligomers are compounds having a carbamate bond and a free radical polymerizable functional group. Polyurethane (meth)acrylate oligomers can be obtained by, for example, reacting a compound having two or more isocyanate groups with a compound having a hydroxyl group, or reacting a compound having an isocyanate group at the end with a (meth)acryloyl group having a hydroxyl group. Alternatively, a compound having a hydroxyl group can be reacted with a compound having an isocyanate group and a (meth)acrylate group to synthesize the compound. Examples of polyurethane (meth)acrylate oligomers (A1) include those having a polyether skeleton and those having a polyester skeleton.

[0091] Examples of the compound having two or more isocyanate groups include aromatic isocyanates such as 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, and 1,4-phenylenedimethylene diisocyanate; and aliphatic isocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate and hexamethylene diisocyanate.

[0092] Commercial products of polyurethane (meth)acrylate oligomers include aromatic polyurethane oligomers such as EBECRYL 210 and EBECRYL 220 (both manufactured by DAICEL ALLNEX), CN9782 and CN9783 (both manufactured by SARTOMER); and aliphatic polyurethane oligomers such as Ziguang UV3000B and Ziguang UV3300B (both manufactured by Nippon Gosei Chemical Industry Co., Ltd.), EBECRYL 230, EBECRYL 270, EBECRYL 8402 and EBECRYL 8701 (both manufactured by DAICEL ALLNEX).

[0093] Polyester (meth)acrylate oligomers are compounds having ester bonds and free radical polymerizable functional groups, and can be synthesized, for example, by esterifying hydroxyl groups of polyesters synthesized by polycondensation of polybasic acids and polyols with (meth)acrylates having carboxyl groups (e.g., (meth)acrylic acid).

[0094] Examples of the polybasic acid 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.

[0095] Examples of the polyol include polyols having a number average molecular weight (Mn) of 50 to 500, such as polyethylene glycol and propylene glycol, and polyols having a number average molecular weight (Mn) of 500 to 30,000, as well as trimethylolpropane, glycerin, and pentaerythritol.

[0096] Commercial products of polyester (meth)acrylate oligomers include aromatic polyester oligomers such as CN296, CN2203, CN2259, and CN2261 (all manufactured by Sartomer Co., Ltd.); and aliphatic polyester oligomers such as CN294, CN2270, and CN2271 (all manufactured by Sartomer Co., Ltd.).

[0097] Epoxy (meth)acrylate oligomers are compounds having radical polymerizable functional groups obtained by reacting the epoxy group of a compound having an epoxy group with a compound having a carboxyl group or a hydroxyl group. Epoxy (meth)acrylate oligomers may also have a small amount of residual epoxy groups.

[0098] Commercial products of epoxy (meth)acrylate oligomers include aromatic epoxy oligomers such as CN104 and CN110 (both manufactured by Sartomer), EBECRYL 600, and EBECRYL 3701 (both manufactured by Daicel Allnex), and aliphatic epoxy oligomers such as CN111 and CN113 (both manufactured by Sartomer), and EBECRYL 860 (both manufactured by Daicel Allnex).

[0099] Specific examples of the (meth)acrylate polymer include compounds obtained by replacing the specific examples of the oligomer with polymers.

[0100] As a method for making the initial wetting tension of the main surface (F) of the resin layer (B) on the side opposite to the light-transmitting substrate layer (A) be 38 mN / m to 60 mN / m and the wetting tension after annealing be 30 mN / m to 54 mN / m, there is the method (1) above, i.e., containing a curable compound (Q) having at least one of a tertiary amino group and a quaternary ammonium salt group. N ) as a curable compound (Q). From the perspective of easy adjustment of wetting tension, the amine value is preferably 140 mgKOH / g to 370 mgKOH / g. The amine value is a value obtained by the method of the Examples described below.

[0101] Examples of the tertiary amino group include dialkylamino groups such as dimethylamino, diethylamino, and dibutylamino. Examples of the quaternary ammonium group include trialkylammonium groups such as trimethylammonium, triethylammonium, and tributylammonium. Examples of the counter ion to the nitrogen atom constituting the quaternary ammonium group include chloride ion, bromide ion, hydroxide ion, and the like.

[0102] As a curable compound having a tertiary amino group (Q N ), and (meth)acrylates having a tertiary amino group are suitable. Suitable 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-piperidinyl (meth)acrylate.

[0103] Other examples include methacrylates having hydroxyl groups 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 the like; and (meth)acrylates having a urethane bond or a urea bond obtained by reacting a (meth)acrylate having an isocyanate group such as methacryloyloxyethyl isocyanate with a compound having a hydroxyl group, a primary amino group, a secondary amino group, and a tertiary amino group. Among these, N,N-dialkylaminoalkyl (meth)acrylate is more preferred.

[0104] As a hardening compound having a quaternary ammonium salt group (Q N), preferably a (meth)acrylate having a quaternary ammonium salt group. As a suitable example, a (meth)acrylate 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; sulfonates such as methyl methanesulfonate, methyl p-toluenesulfonate, and methyl trifluoromethanesulfonate; and sulfates such as dimethyl sulfate and diethyl sulfate. A quaternary ammonium salt can be prepared by reacting a quaternizing agent with a tertiary amino group. In addition, when an organic halide is used as the quaternizing agent, the nitrogen atom serves as a cation and the halogen of the counter ion serves as an anion, thereby forming a quaternary ammonium salt. However, a monomer formed by exchanging the anion with another anion can also be used. As the compound having the anion, conventionally known compounds 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.

[0105] Examples of commercially available products include ACRIT 8WX-018 (manufactured by Taisei Fine Chemical Co., Ltd.) and Aminoion RE3000MF (manufactured by Nippon Emulsifier Co., Ltd., a reactive ion containing an acrylic acid group).

[0106] A curable compound having a tertiary amino group and / or a quaternary ammonium salt group (Q N The total content of the curable compound (Q) is not particularly limited as long as it is appropriately designed, but is preferably 3% to 40% by mass, more preferably 3% to 30% by mass, and further preferably 3% to 20% by mass in 100% by mass of the curable compound (Q). By setting it in the range of 3% to 40% by mass, both excellent anti-blocking properties and excellent adhesion to OCA can be achieved. In addition, in the curable compound (Q N ) may have both a tertiary amino group and a quaternary ammonium salt group. In this case, when calculating the total content, the content is of course calculated in the form of one compound.

[0107] By using a curable compound (Q N ) as a curable compound (Q), and at least one of a tertiary amino group and a quaternary ammonium salt group is incorporated into the binder resin in the cured layer. Tertiary amino groups and quaternary ammonium salt groups have high hydrophilicity and low affinity for the binder resin and particles (R) other than hydrophilic groups. Therefore, tertiary amino groups and / or quaternary ammonium salt groups are easily expressed on the surface side of the resin layer (B). Furthermore, these groups are fixed in the form of a resin through the curing reaction, preventing bleed-out and providing excellent stability over time.

[0108] The curable composition (S) may further contain a hydroxyl group-containing curable compound (Q O ). By containing a hydroxyl-containing curable compound (Q O ), thereby improving the compatibility and dispersibility of the particles (R) with tertiary amino groups and / or quaternary ammonium salt groups, thereby achieving excellent coating solution stability. Furthermore, the haze value of the coating film of the resin layer (B) can be reduced. Furthermore, the initial wetting tension can be increased and the decrease in wetting tension after annealing can be suppressed, thereby more effectively improving the balance of OCA adhesion. As a result, the dispersibility of the particles (R) in the resin layer (B) can be more effectively improved, significantly improving transparency.

[0109] The hydroxyl group-containing curable compound (Q) is 100% by mass relative to the curable compound (Q). O ) is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and even more preferably 5% by mass to 20% by mass.

[0110] The hydroxyl-containing curing compound (Q O ) Suitable examples include the (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.

[0111] <Hydrophilicating agent (T)>

[0112] As described above, the curable composition (S) of this embodiment may contain a hydrophilizing agent (T) as an optional component. The hydrophilizing agent (T) herein refers to a compound that does not exhibit curability due to active energy rays and is a compound that, by addition, can reduce the water contact angle of the surface layer (the surface layer on the side opposite to the side on which the light-transmitting substrate layer (A) is laminated) of the cured product of the coating layer of the curable composition (S). Preferably, the compound reduces the water contact angle to 60° or less, and more preferably 55° or less. However, compounds that meet the requirements of particles (R) are excluded.

[0113] Preferred examples of the hydrophilizing agent (T) include hydrophilizing agents (T) having at least one of a tertiary amino group and a quaternary ammonium salt group. N), namely, ionic hydrophilizing agents having a quaternary ammonium salt group, and nonionic hydrophilizing agents having a tertiary amino group. From the perspective of ease of adjusting wetting tension, the amine value is preferably 140 mgKOH / g to 370 mgKOH / g. When the hydrophilizing agent (T) is a polymer, it is preferred that, out of 100% by mass of the structural units derived from the monomers used in the polymerization of the polymer, 100% to 50% by mass comprise structural units derived from monomers having a tertiary amino group and / or a quaternary ammonium salt group.

[0114] Examples of trade names of ionic hydrophilizing agents having a quaternary ammonium salt group include Acrit 8WX-030 (manufactured by Taisei Fine Chemical Co., Ltd.) and Aminoion RE3000MF (manufactured by Nippon Emulsifier Co., Ltd.).

[0115] Preferred 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 preferred.

[0116] In addition, as a suitable example of the ionic hydrophilizing agent and the nonionic hydrophilizing agent, a curable compound (Q N ) monomers or oligomers homopolymerized polymers or copolymers containing part or all of the monomer components. In addition, the curable compound (Q N ) are cross-linked monomers or oligomers of compounds. These may be a single species or a mixture.

[0117] The content of the hydrophilizing agent (T) relative to 100% by mass of the curable composition (S) is not particularly limited, but is preferably 3% to 40% by mass from the viewpoint of achieving excellent anti-blocking properties. The content is more preferably 5% to 30% by mass, and even more preferably 5% to 20% by mass.

[0118] 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 perspective of effectively suppressing bleed-out in a high temperature and high humidity environment, a high molecular weight compound having a weight average molecular weight of 10,000 or greater is preferred. The upper limit of the weight average molecular weight is not particularly limited, but from the perspective of compatibility with the curable composition (S) and the like, it can be, for example, 50,000 or less.

[0119] A curable compound having a tertiary amino group and / or a quaternary ammonium salt group (Q N ) and a hydrophilizing agent (T N) total content (including curable compound (Q N ) and hydrophilizing agent (T N ), 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 non-volatile component of the curable composition (S). By setting the range of 3% to 50% by mass, the wetting tension of the main surface (F) of the resin layer (B) can be adjusted to a desired range regardless of whether or not an annealing treatment is performed, thereby achieving excellent adhesion to the OCA.

[0120] <Particles(R)>

[0121] The present composition contains particles (R). As described above, the particles (R) are at least one selected from resin beads and inorganic particles. The particles (R) primarily impart anti-blocking properties. One type of particle (R) may be used alone or in combination of two or more. The particles (R) may be surface-treated, such as hydrophilic or hydrophobic, or may be untreated.

[0122] Examples of the resin beads include acrylic resins, urethane resins, urethane acrylic resins, urea resins, polyvinyl chloride, polystyrene, polyacrylonitrile, polyamide, polyimide, and polycarbonate. Among these, acrylic resins or urethane acrylic resins whose hardness can be adjusted by cross-linking are suitable from the perspective of scratch resistance. The resin beads may be reactive resin beads. Reactive resin beads have a group that reacts by heating or irradiation with active energy rays. From the perspective of productivity, resin beads that react by irradiation with active energy rays are suitable. The reactive group may be a functional group that reacts with the curable compound (Q) and chemically bonds. Examples of the reactive functional group include polymerizable vinyl groups, (meth)acryloyl groups, and other ethylenically unsaturated groups. The refractive index of the resin beads can be appropriately adjusted, but from the perspective of improving transparency, it is preferably 1.3 to 1.8, and more preferably 1.4 to 1.6. Examples of commercially available acrylic resin beads include Chemisnow (registered trademark, manufactured by Soken Chemical Co., Ltd.), Techpolymer (registered trademark, manufactured by Sekisui Chemicals Co., Ltd.), Eposter (registered trademark, manufactured by Nippon Catalyst Co., Ltd.), Artpearl (manufactured by Negami Industry Co., Ltd.), and Ganzpearl (manufactured by AICA Industry Co., Ltd.).

[0123] Examples of the 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 the inorganic particles are silica particles and alumina, particularly preferred from the perspective of anti-blocking properties.

[0124] The anti-blocking property can be improved by adding particles (R). As particles (R), in addition to untreated particles, hydrophilic particles and hydrophobic particles can also be used. The shape of the particles (R) is not limited, and for example, spherical or crushed particles can be used.

[0125] The primary particle size of the particles (R) is preferably 10 nm to 100 nm, more preferably 10 nm to 50 nm, and the average particle size (median diameter) is 1000 nm or less, more preferably 500 nm or less, and even more preferably 100 nm or less.

[0126] The average particle size can be measured using a particle size distribution analyzer, particularly a dynamic light scattering particle size distribution analyzer (e.g., "NANOTRAC WAVE IIUZ152" manufactured by Microtrac BEL). In the present invention, the average value of three 60-second measurements using methyl ethyl ketone as the solvent at a concentration within the load index range of 1.0±0.2 is used.

[0127] About the content of particles (R), as long as in the laminated structure of 1 μm thick resin layer (B) and 50 μm thick polyethylene terephthalate, when measured from the surface side of the resin layer (B), the haze value becomes 2.0% or less in a manner according to the particle size of the particles (R), the thickness of the resin layer (B) is appropriately adjusted. With regard to the viewpoint of both high transparency and anti-blocking properties, it is preferably set to 0.01% to 40% by mass relative to 100% by mass of the non-volatile component of the curable composition (S). With regard to the viewpoint of making anti-blocking properties more excellent, it is more preferably set to 3% to 40% by mass, and further preferably 5% to 40% by mass, and particularly preferably 5% to 30% by mass. In addition, when using particles with a large average particle size relative to the thickness of the resin layer (B), the haze value can be easily adjusted by reducing the particle content (e.g., 0.01% to 0.5% by mass). Here, the so-called non-volatile component refers to the component constituting the composition other than the solvent.

[0128] The surface of the inorganic particles may contain an organic compound and be surface treated. In addition, reactive inorganic particles may also be used. Reactive inorganic particles are inorganic particles that react by heating or irradiation with active energy rays. For example, particles having reactive groups such as polymerizable vinyl groups, ethylenically unsaturated groups such as (meth)acryloyl groups, and epoxy groups on the particle surface may be exemplified. Reactive groups can be obtained by surface modification using compounds having reactive groups. For example, silane coupling agents having ethylenically unsaturated groups may be exemplified.

[0129] As the surface treatment agent for the inorganic particles, for example, a silane coupling agent such as 3-(meth)acryloxypropyltrimethoxysilane, β-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, hexamethyldisilazane, dimethyldichlorosilane, or a known treatment agent such as silicone oil can be used.

[0130] When using silica particles, suitable ones are hydrophobic silica particles. By using hydrophobic silica particles, it is possible to obtain an effect that is not easy to absorb moisture even under high temperature or high humidity environments. Hydrophobic silica particles are obtained by surface treating silica particles. As commercially available hydrophobic silica particles that have been surface treated, "Megasil 525RCS" manufactured by SIBELCO JAPAN can be exemplified.

[0131] By forming a hardening compound (Q N ) or / and hydrophilizing agent (T N ) and surface treated particles (R) can more effectively prevent the curing compound (Q N ) or / and hydrophilizing agent (T N ) and the aggregation of particles (R). From the viewpoint of significantly improving the dispersibility of the particles (R) in the resin layer (B) on the basis of excellent anti-blocking properties, achieving excellent coating stability and a good haze value, it is preferred to further mix a hydroxyl-containing curable compound (Q O ).

[0132] In particular, when silica is used as the particles (R), a curable compound (Q) having a tertiary amino group or / and a quaternary ammonium salt group may be used. N ) or / and hydrophilizing agent (T N ), and hydrophobic silica (R H ) can be combined to more effectively prevent the curing compound (Q N ) or / and hydrophilizing agent (T N) and silica. From the perspective of significantly improving the dispersibility of silica particles in the resin layer (B) on the basis of excellent anti-blocking properties, achieving excellent coating stability and a good haze value, it is preferred to further formulate a hydroxyl-containing curable compound (Q O ).

[0133] <Photopolymerization initiators and photosensitizers>

[0134] The curable composition (S) may contain a photopolymerization initiator as an optional component. When the active energy ray is ultraviolet light, it is preferable to add a photopolymerization initiator.

[0135] The photopolymerization initiator is not particularly limited as long as it can initiate 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.

[0136] 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-pentaoxytridecyl)benzophenone, and 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone. Benzophenone, 4-benzoyl-N,N,N-trimethyl-1-propaneamine hydrochloride, 4-benzoyl-N,N-dimethyl-N-2-(1-oxo-2-propenyloxyethyl)ammonium metaoxalate, 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-propaneamine hydrochloride, benzoylmethylene-3-methylnaphthalene(1,2-d)thiazoline.

[0137] Examples of the dicarbonyl compound include 1,2,2-trimethyl-bicyclo[2.1.1]heptane-2,3-dione, benzil, 2-ethylanthraquinone, 9,10-phenanthrenequinone, methyl-α-oxophenylacetate, and 4-phenylbenzil.

[0138] Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-di-2-methyl-1-phenylpropane-1-one, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-styrylpropane-1-one polymer, diethoxyacetophenone, dibutoxyacetophenone, 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, 3,6-bis(2-methyl-2-morpholino-propanone)-9-butylcarbazole.

[0139] 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.

[0140] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-bis(2,6-dichlorobenzoyl)phosphine oxide.

[0141] Examples of the aminocarbonyl compound include methyl-4-(dimethoxyamino)benzoate, ethyl-4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate, isopentyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethyl benzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, and 2,5'-bis(4-diethylaminobenzylidene)cyclopentanone.

[0142] Commercially available photopolymerization initiators include Omnirad 184, Omnirad 651, Omnirad 500, Omnirad 907, Omnirad 127, Omnirad 369, Omnirad 784, and Omnirad 2959 manufactured by IGM-Resins BV, Lucirin TPO manufactured by IGM-Resins BV, and Esacure ONE manufactured by DKSH Japan.

[0143] In particular, from the viewpoint of resistance to yellowing after active energy ray curing, Omnirad 184 or Esacure ONE is preferred.

[0144] The photopolymerization initiator is not limited to the above compounds, and may be any substance as long as it has the ability to initiate polymerization. A single photopolymerization initiator may be used, or two or more may be used as a mixture.

[0145] The amount of the photopolymerization initiator used is not particularly limited, but is preferably used in a range of 1% by mass to 20% by mass relative to 100% by mass of the curable compound (Q).

[0146] Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzylideneacetone, 1,2-diketone derivatives represented by benzyl or 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 pigments such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, and the like. Biological, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalinoporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal aromatic complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylates (methyl phenylglyoxylates) Sensitizers may be used alone or in combination of two or more.

[0147] <Other ingredients>

[0148] The curable composition (S) of this embodiment may contain a solvent as needed. When a solvent is added, it is preferable to volatilize the solvent and then perform a curing treatment using active energy rays.

[0149] As solvent, there is no particular limitation, and various known organic solvents can be used. Specifically, for example, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetylacetone, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propyl alcohol, isopropyl alcohol, 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, isopentyl acetate, dimethyl adipate, dimethyl succinate, dimethyl glutarate, tetrahydrofuran, methyl pyrrolidone, etc. These organic solvents can also be used in combination of two or more.

[0150] Furthermore, other components not in accordance with the above may be contained within the scope that does not impair the purpose or effect of the present invention. Examples thereof include surfactants, colorants, stabilizers, resins, surface treatment agents, viscosity modifiers, adhesion-imparting agents, antioxidants, anti-aging agents, crosslinking accelerators, ultraviolet absorbers, plasticizers, preservatives, dispersants, defoaming agents, silane coupling agents, and inorganic fillers.

[0151] [Method for producing curable composition (S)]

[0152] The curable composition (S) can be prepared by a known method without particular limitation. For example, the curable compound (Q) and the particles (R) are mixed and dispersed, and a solvent, a photopolymerization initiator, and other various ingredients are added and adjusted as needed.

[0153] [Method for producing laminate]

[0154] The 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 formed by curing a curable composition (S) containing a curable compound (Q) and particles (R) that exhibit curability by active energy rays.

[0155] The curable composition (S) can be applied to the light-transmitting substrate layer (A) by any known method, for example, a method using a rod or wire bar, or various coating methods such as micro-gravure, gravure, die, curtain, lip, slit, or spin coating.

[0156] After forming the coating of the curable composition (S), it is dried naturally or forcibly dried. Then, the resin layer (B) can be obtained by curing it by irradiating it with active energy rays. As a light source for ultraviolet rays or visible light with a wavelength of 400nm to 500nm, 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 thermal electron radiation gun, an electrolytic radiation gun, etc. can be used. The amount of active energy ray irradiated can be as long as sufficient curability is obtained, for example, it can be set to 50mJ / cm 2 ~2000mJ / cm 2 about.

[0157] [Transparent electrode film]

[0158] The transparent electrode film of this embodiment includes at least the present laminate and a transparent conductive layer. Figure 1 An example of the transparent electrode film of this embodiment is shown. Figure 1 As shown, the transparent electrode film 1 is sequentially stacked with a laminate 2, an index matching layer (hereinafter also referred to as an IM layer) 3, and a transparent conductive layer 4. In the example of this embodiment, the laminate 2 is composed of a resin layer (B) and a translucent substrate layer (A), and the IM layer 3 is stacked on the translucent substrate layer (A). An OCA film may also be stacked on the surface of the resin layer (B). Alternatively, the IM layer 3 may not be provided, and the transparent conductive layer 4 may be stacked directly above the translucent substrate layer (A) of the laminate 2. Each layer may be independently a single layer or a multilayer.

[0159] The IM layer 3 is a layer with a high refractive index that is stacked so that the shape of the patterned transparent conductive layer 4 is not easily discernible. For example, it can be formed by a cured layer of a composition containing metal oxide particles with a high refractive index and an active energy ray-curable component. The refractive index of the IM layer 3 is preferably as close as possible to the refractive index of the transparent conductive layer 4. The metal oxide particles with a high refractive index and the active energy ray-curable component can be obtained using known materials. For example, as metal oxide particles with a high refractive index, titanium oxide (nD = 2.72), zirconium oxide (nD = 2.22), aluminum oxide (nD = 1.77), etc. can be listed. In addition, as an active energy ray-curable component, the curable compound (Q) contained in the resin layer (B) can be exemplified. The thickness of the IM layer 3 is, for example, about 0.03 μm to 30 μm. As the IM layer, a low refractive index layer and a high refractive index layer can also be stacked.

[0160] The transparent conductive layer 4 is a transparent layer with electrical conductivity and can be formed from materials such as indium tin oxide (ITO), tin oxide, zinc oxide, silver, or copper nanowires. The transparent conductive layer 4 can be formed, for example, by vacuum deposition (physical or chemical vapor deposition), sputtering, or ion plating. After the transparent conductive layer 4 is formed on the IM layer 3, a circuit or electrode pattern can be formed by etching or other methods. To improve conductivity and adhesion to the IM layer 3, the thickness of the transparent conductive layer 4 can be, for example, from 1 nm to several tens of μm.

[0161] An anchor layer (not shown) may be provided between the IM layer 3 and the transparent conductive layer 4. The anchor layer can be formed, for example, by a vacuum film formation method similar to the transparent conductive layer 4. Examples of metal oxides used to form the anchor layer include silicon oxide, which is preferred because it imparts strong adhesion.

[0162] 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. This OCA film can then be incorporated into the transparent electrode film of, for example, a touch screen module. The transparent electrode film of this embodiment can be suitably used in electronic devices such as smartphones, tablets, personal computers, televisions, guide plates for car navigation systems, and other commercial facilities, or transportation ticket machines.

[0163] <<Example>>

[0164] The present invention will be described in more detail below. The following examples are not intended to limit the scope of the present invention. In the examples, "parts" and "%" represent "parts by mass" and "% by mass," respectively.

[0165] Mw refers to the weight average molecular weight and is a polystyrene-equivalent molecular weight when a TSKgel column (manufactured by Tosoh Corporation) is used and a gel permeation chromatograph (GPC) (manufactured by Tosoh Corporation, HLC-8320GPC) equipped with a refractive index (RI) detector is used and dimethylformamid (DMF) is used as the developing solvent.

[0166] The amine value of a curable compound containing a tertiary amino group is the total amine value (mgKOH / g) measured according to the American Society for Testing and Materials (ASTM) D 2074 method, converted to solids. In this specification, the non-volatile content is calculated by dividing the weight of a 1g sample heated at 180°C for 20 minutes by the weight of the sample before heating.

[0167] The abbreviations of the components of the curable composition (S) used in the present examples are as follows.

[0168] [Curing compound (Q)]

[0169] q-1 (PET-30): Pentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd.

[0170] q-2 (KAYARAD DPHA): Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.

[0171] q-3 (Miramer PU610): Urethane acrylate, manufactured by MIWON.

[0172] q-4 (4HBA): 4-Hydroxybutyl acrylate, manufactured by Mitsubishi Chemical Corporation.

[0173] q-5 (ACRIT 8WX-030): Cationic polymer, manufactured by Taisei Fine Chemical Co., Ltd., containing a quaternary ammonium salt group.

[0174] q-6 (Aminoion RE3000MF): Cationic polymer, manufactured by Japan Emulsifier Co., Ltd., containing a quaternary ammonium base.

[0175] q-7: a hardening vinyl resin containing a tertiary amino group.

[0176] In addition, the above q-1 and q-4 correspond to the hydroxyl-containing curable compound (Q O ).

[0177] [Particles(R)]

[0178] r-1 (MSD-57): manufactured by Sakai Chemical Co., Ltd., D50: 200 nm, surface treated with 3-methacryloxypropyltriethoxysilane. Silica particles.

[0179] r-2 (MEK-ST-2040): manufactured by Nissan Chemical Co., Ltd., D50: 100 nm, surface treated with a silane coupling agent. Silica particles.

[0180] r-3 (Aerosil 200 dispersion): manufactured by Aerosil Japan, D50: 42.2 nm, no surface treatment. Silica particles.

[0181] r-4 (Aeroxide AluC dispersion): D50: 62 nm, aluminum oxide.

[0182] r-5 (Techpolymer NH): manufactured by Sekisui Chemicals Co., Ltd., D50: 80 nm, resin beads (gel fraction: 80% by mass or more).

[0183] [Hydrophilicating agent (T)]

[0184] ·t-1: hydrophilizing agent containing tertiary amino group, containing tertiary amino group.

[0185] ·t-2: hydrophilizing agent containing tertiary amino group, containing tertiary amino group.

[0186] ·t-3: hydrophilizing agent containing tertiary amino group, containing tertiary amino group.

[0187] t-4 (FC-4400): Ionic liquid, manufactured by 3M, containing a quaternary ammonium salt base.

[0188] <Production Example of a Tertiary Amino Group-Containing Curable Compound (q-7)>

[0189] 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 mass of N,N-diethylaminoethyl methacrylate, and 20 parts by mass of 2-hydroxyethyl methacrylate. The temperature was raised to 50°C while purging with nitrogen. 2.3 parts of 1-thioglycerol was then added, and the temperature was raised to 70°C. A dripping vessel was charged with 16.8 parts by mass of ethyl acetate and 0.6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile). After stirring until homogeneous, the mixture was added dropwise to the reaction vessel over 7 hours. The reaction was then continued at the same temperature for 1 hour, and solids content measurement confirmed that the reaction had progressed to 95% or more. Subsequently, the flask was purged with air, and 32.8 parts by mass of 2-acryloyloxyethyl isocyanurate (AOI) and 0.1 parts by mass of hydroquinone were added. The reaction was then continued at 70°C for 4 hours. The isocyanate group-derived ions at 2270 cm-1 were confirmed by Fourier transform-infrared spectroscopy (FT-IR). -1After the peak disappeared, the reaction solution was cooled to obtain a solution of a vinyl resin having tertiary amino groups and acryloyl groups. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes. The non-volatile content was measured. Ethyl acetate was added to the previously synthesized resin solution to adjust the non-volatile content to 45% by weight. This yielded a solution of a vinyl resin having tertiary amino groups, namely, a curable compound (q-7), having an amine value per solids of 234 mgKOH / g and a number average molecular weight of 22,000.

[0190] <Production Example of Aerosil 200 Dispersion (r-3)>

[0191] 15.0 parts of silica particles ("Aerosil 200" manufactured by AEROSIL Japan Co., Ltd.), 1.5 parts of a dispersant ("DYSPERBYK 142"), and 83.5 parts of a 1 / 1 mixed solvent of methyl ethyl ketone / methoxybutanol were mixed. The mixture was subjected to two stages: preliminary dispersion (using zirconium oxide beads (0.5 mm) as a medium and dispersing for 1 hour using a paint shaker) and main dispersion (using zirconium oxide beads (0.1 mm) as a medium and dispersing using a UAM-015 disperser manufactured by Kotobuki Industry Co., Ltd.) to obtain an Aerosil 200 dispersion.

[0192] <Production Example of Aeroxide AluC Dispersion (r-4)>

[0193] 15.0 parts of aluminum oxide ("Aeroxide AluC" manufactured by AEROSIL Co., Ltd. of Japan), 1.5 parts of a dispersant ("DYSPERBYK 142"), and 83.5 parts of a 1 / 1 mixed solvent of methyl ethyl ketone / methoxybutanol were mixed, and the mixture was dispersed in two stages: preliminary dispersion (using zirconium oxide beads (0.5 mm) as a medium and dispersing for 1 hour using a paint mixer) and main dispersion (using zirconium oxide beads (0.1 mm) as a medium and dispersing using a disperser UAM-015 manufactured by Kotobuki Industry Co., Ltd.) to obtain an Aeroxide AluC dispersion.

[0194] <Production Example of a Tertiary Amino Group-Containing Hydrophilizing Agent (t-1)>

[0195] 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-dimethylaminoethyl methacrylate. The temperature was raised to 50°C while nitrogen was purged. 2.3 parts of 1-thioglycerol was then added, and the temperature was raised to 70°C. A dripping vessel was charged with 16.8 parts of isopropyl alcohol and 0.6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile). After stirring until uniform, the mixture was added dropwise to the reaction vessel over 7 hours. The reaction was then continued at the same temperature for 1 hour to obtain a solution of a vinyl resin having tertiary amino groups. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes. The non-volatile content was then measured. Isopropyl alcohol was added to the previously synthesized resin solution to adjust the nonvolatile content to 45%, thereby obtaining a hydrophilizing agent (t-1) solution of 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.

[0196] <Production Example of a Tertiary Amino Group-Containing Hydrophilizing Agent (t-2)>

[0197] A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 50.6 parts of isopropyl alcohol and 200 parts of N,N-diethylaminoethyl methacrylate. The temperature was raised to 50°C while nitrogen was purged. Then, 2.3 parts of 1-thioglycerol was added and the temperature was raised to 70°C. A dripping vessel was charged with 16.8 parts of isopropyl alcohol and 0.6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile). After stirring until uniform, the mixture was added dropwise to the reaction vessel over 7 hours. The reaction was then continued at the above temperature for 1 hour to obtain a solution of a vinyl resin having a tertiary amino group. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes, and the non-volatile component was measured. Isopropyl alcohol was added to the previously synthesized resin solution to make the non-volatile component 45%, and a vinyl resin with a tertiary amino group having an amine value of 301 mgKOH / g per solid component and a number average molecular weight of 20,000, namely a hydrophilizing agent (t-2) solution was obtained.

[0198] <Production Example of a Tertiary Amino Group-Containing Hydrophilizing Agent (t-3)>

[0199] A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 50.6 parts of isopropyl alcohol, 100 parts of N,N-diethylaminoethyl methacrylate, and 100 parts of methyl methacrylate. The temperature was raised to 50°C while nitrogen was purged. Then, 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). After stirring until uniform, the mixture was added dropwise to the reaction vessel over 7 hours. The reaction was then continued at the above temperature for 1 hour to obtain a solution of a vinyl resin having a tertiary amino group. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes. The non-volatile component was measured, and isopropyl alcohol was added to the previously synthesized resin solution to make the non-volatile component 45%. A vinyl resin having a tertiary amino group with an amine value of 151 mgKOH / g per solid component and a number average molecular weight of 21,000, namely a hydrophilizing agent (t-3) solution, was obtained.

[0200] <Production Example of Curable Composition (S)>

[0201] (Example 1)

[0202] 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. MSD-57 was then added to the mixture to achieve a silica particle content of 5% by mass in the nonvolatile component, and methylpropylene glycol was added to achieve a nonvolatile content of 50% by mass. The mixture was then uniformly mixed to obtain a curable composition (S).

[0203] (Example 2 to Example 25, Comparative Example 1 to Comparative Example 7)

[0204] Except having changed into the compounding quantity shown in Table 1 - Table 3, the curable composition (S) of each Example and Comparative Example was obtained by the same method as Example 1.

[0205]

[0206]

[0207] [Table 3]

[0208] Table 3

[0209]

[0210] (Example 26)

[0211] 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. Subsequently, an Aeroxide AluC dispersion was added to the mixture so that the aluminum oxide content in the non-volatile component was 5.5% by mass, and methylpropylene glycol was added so that the non-volatile component content was 50% by mass. The mixture was then uniformly mixed to obtain a curable composition (S).

[0212] (Examples 27 to 50, Comparative Examples 8 to 13)

[0213] Except having changed into the compounding quantity shown in Table 4 - Table 6, the curable composition (S) of each Example and Comparative Example was obtained by the same method as Example 1.

[0214]

[0215]

[0216] [Table 6]

[0217] Table 6

[0218]

[0219] <Production Example of Laminated Body>

[0220] (Example 1)

[0221] As the light-transmitting substrate layer (A), a 50 μm thick easy-adhesion treated polyethylene terephthalate film ("Lumirror U403" manufactured by Toray Industries, Inc.) was used. The curable composition (S) obtained in the Examples / Comparative Examples was applied to the light-transmitting substrate layer (A) using a bar coater and dried in a hot air oven at 100°C for 1 minute to remove the organic solvent. Subsequently, the film was irradiated with a high-pressure mercury lamp at 400 mJ / cm 2 The resin layer (B) was formed to a thickness of 1 μm by ultraviolet light, thereby obtaining the laminate of Example 1.

[0222] (Example 2 to Example 50, Comparative Example 1 to Comparative Example 13)

[0223] By the same method as in Example 1, laminated bodies of Examples 2 to 50 and Comparative Examples 1 to 13 were obtained.

[0224] Tables 7 and 8 show the results of various evaluations of the Examples and Comparative Examples.

[0225] <Production Example of Heat-Resistant Protective Film>

[0226] An adhesive mixture of "CYABINE SH101" and "CYABINE T-501B" (manufactured by Toyo Chemical) at a solids ratio of 100 / 20 was applied using a bar coater onto a 100 μm thick, easily adhesive-treated polyethylene terephthalate film ("Lumirror U403" manufactured by Toray Industries, Inc.). The film was then dried in a hot air oven at 100°C for 2 minutes to remove the organic solvent, resulting in a heat-resistant protective PET film with a 5 μm thick adhesive layer.

[0227] <Production Example of OCA Film>

[0228] An adhesive mixture of "ORIBAIN BPS5896" and "ORIBAIN BXX5627" manufactured by Toyo Chemical Co., Ltd. at a solids ratio of 100 / 0.5 was applied using a bar coater onto a 100 μm thick, easily adhesive-treated polyethylene terephthalate film ("Lumirror U403" manufactured by Toray Industries, Inc.). The film was then dried in a hot air oven at 100°C for 2 minutes to remove the organic solvent, resulting in an OCA film with a 5 μm thick adhesive layer.

[0229] <Measurement of initial wetting tension>

[0230] The main surface (F) of the resin layer (B) before annealing of the laminated body of each example and comparative example (see Figure 1) is measured. That is, in an environment of 23°C and a relative humidity of 50%, a Dynepen (a test pen for evaluating surface energy values) manufactured by Arcotest is used to determine the wetting tension of the main surface (F) of the resin layer (B). Specifically, the laminate (test piece) of each embodiment and comparative example is placed on a glass plate, and the Dynepen is used to form a Dynepen liquid film of about 1 cm × 5 cm on the main surface (F) of the resin layer (B) of the test piece. The judgment is made by observing the Dynepen liquid film in a bright place and the state of the liquid film after 5 seconds. The liquid film whose short side remains above 95% is judged to be wet. When the wetting is maintained at above 95%, the Dynepen with high surface tension is then introduced. On the contrary, when it is not maintained at above 95%, the next mixed liquid with low surface tension is introduced for evaluation. Another known method for measuring wetting tension is Japanese Industrial Standards (JIS) K6768. According to this method, if the liquid film breaks within 2 seconds after application of the dyne pen / ink, the test is considered a failure (NG). This test method is a more accurate evaluation method. Compared to JIS K6768, the wetting tension obtained using this test method tends to be lower.

[0231] <Measurement of wetting tension after annealing>

[0232] The resin layer (B) of the laminated bodies of each Example and Comparative Example and the heat-resistant protective PET film obtained in the Production Example were allowed to stand for 30 minutes in an environment of 23°C and 50% relative humidity. The main surface (F) of the resin layer (B) was then placed on 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 wetting tension of the exposed main surface (F) of the resin layer (B) was measured using the same method as for the initial wetting tension.

[0233] <Measurement of Haze Value>

[0234] The curable composition (S) shown in Table 1 was applied to a 50 μm thick polyethylene terephthalate film (Lumirror U403, manufactured by Toray Industries, Ltd., haze value 1.1%, total light transmittance 91%) using a bar coater and dried at 100°C for 1 minute. The active energy ray and irradiation dose need to 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 the UVA ultraviolet ray dose was 400 mJ / cm 2The samples were irradiated with ultraviolet light to obtain a 1 μm thick resin layer (B) containing a cured film. The haze values ​​of the samples (50 μm thick polyethylene terephthalate / resin layer (B)) of each Example and Comparative Example were then determined in accordance with JIS K 7136 using a haze meter (manufactured by Nippon Denshoku Industries, trade name "SH7000") at 23°C and 50% RH. The measurements were performed from the resin layer (B) side.

[0235] <Evaluation of Anti-blocking Properties>

[0236] The test sample was prepared as follows. That is, the laminate obtained before annealing and the light-transmitting substrate layer (A) without the resin layer were cut into test pieces of 4 cm × 4 cm in size, and the surface of the resin layer (B) of the laminate was overlapped with the light-transmitting substrate layer (A) in such a way that the surface was in contact with the light-transmitting substrate layer. The test pieces were placed on the test bench of a permanent deformation tester (trade name "CO-201 permanent deformation tester (constant load type)", manufactured by Japan Tester Industry Co., Ltd.), a load of 200 kg was applied, and the test pieces were left to stand in an oven heated to 50°C for 24 hours. Thereafter, immediately after the load was removed, the ratio of the area of ​​the overlapping surfaces of the test pieces to form a watermark (an appearance like water infiltration) was evaluated as anti-blocking property (hereinafter referred to as "AB property").

[0237] A: The pasted area is less than 10%.

[0238] B: The area of ​​the bonded portion is more than 10% and less than 30%.

[0239] C: The pasted area exceeds 30%.

[0240] <Evaluation of scratch resistance>

[0241] The obtained laminate was placed in a Gakushin testing machine with the resin layer serving as the test surface. The surface of the resin layer was rubbed back and forth 10 times with No. 0000 steel wool under a load of 200 g. The number of scratches on the surface of the IM layer after the test was determined and evaluated according to the following criteria.

[0242] A: 0 to 10.

[0243] B: 11 to 20.

[0244] C: 21 or more.

[0245] <OCA Adhesion Evaluation>

[0246] The test sample was prepared as follows. That is, the laminated bodies of each embodiment and comparative example before annealing (initial stage) and after annealing, as well as the OCA film obtained in the manufacturing example, were left to stand for 30 minutes at 23°C and a relative humidity of 50%. Then, the main surface (F) of the resin layer (B) was attached to the adhesive layer of the OCA film and pasted using a 2kg roller. Thereafter, a 180° peel test was performed at a speed of 300mm / min using a tensile testing machine, and the peel strength was measured. The adhesion was evaluated based on the peel strength values ​​obtained and in accordance with the following criteria.

[0247] A: Peel strength is 25 N or more.

[0248] B: The peel strength is 10N or more and less than 25N.

[0249] C: Peel strength is less than 10N.

[0250] [Table 7]

[0251] Table 7

[0252]

[0253] [Table 8]

[0254] Table 8

[0255]

[0256] For a laminate having an initial wetting tension of less than 38 mN / m and a surface tension of less than 30 mN / m after annealing, as shown in Comparative Example 1, poor OCA adhesion was confirmed. Furthermore, for a laminate having an initial wetting tension exceeding 60 mN / m and a surface tension exceeding 54 mN / m after annealing, poor scratch resistance and anti-blocking properties were confirmed as shown in Comparative Example 3. Furthermore, as shown in Comparative Example 4, it was found that if the content of particles (R) was high, anti-blocking properties were improved, while the haze value deteriorated. On the other hand, according to this embodiment, excellent optical properties and scratch resistance were confirmed, and further, a high yield was achieved even when manufactured using a roll-to-roll method, and excellent OCA adhesion was achieved regardless of the presence or absence of annealing.

[0257] [Industrial Applicability]

[0258] About the laminate of the present invention, it is possible to provide a laminate having excellent adhesion to an OCA film, excellent anti-blocking property and excellent scratch resistance and transparency, and therefore it is suitable as an optical film. For example, a transparent electrode film formed by stacking a transparent conductive layer on a laminate is suitable as a touch screen member for a guide plate or a traffic ticket vending machine etc. carried on a smart phone, an input board, a PC, a television, a car navigation or other commercial facilities etc. In addition, due to the excellent surface hardness of the resin layer (B) of the laminate of the present invention, it is also suitable as a film for preventing damage on the surface of a flat panel display (Flat Panel Display, FPD) such as a liquid crystal display (LCD), an organic electroluminescence (EL) display (organic light emitting display (OLED)), a plasma display (Plasma Display Panel, PDP).

Claims

1. A transparent electrode film comprising a transparent conductive layer and a laminate having a laminate 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). At least the transparent conductive layer, the light-transmitting base material layer (A) constituting the laminate, and the resin layer (B) constituting the laminate are laminated in this order directly or via one or more layers. The resin layer (B) is a layer formed by curing a curable composition (S) containing particles (R) and a curable compound (Q) that is curable by active energy rays, wherein the curable compound (Q) does not contain particles (R). 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 layer, the haze value measured from the surface side of the resin layer (B) is 2.0% or less. The initial wetting tension of the main surface (F) of the resin layer (B) opposite to the light-transmitting substrate layer (A) before annealing is 38 mN / m to 60 mN / m, A heat-resistant protective polyethylene terephthalate film is attached to the main surface (F) of the resin layer (B), annealed at 150° C. for 3 hours, and then the heat-resistant protective polyethylene terephthalate film is peeled off. The wetting tension of the main surface (F) of the resin layer (B) is 30 mN / m to 54 mN / m. The curable composition (S) satisfies at least any one of the following: (i) containing a curable compound having at least one of a tertiary amino group and a quaternary ammonium salt group (Q N ) as a hardening compound (Q); and (ii) containing a hydrophilizing agent (T) that does not exhibit curability due to active energy rays, wherein the curable hydrophilizing agent (T) does not contain particles (R), The hydrophilizing agent (T) contains a hydrophilizing agent (T) having at least one of a tertiary amino group and a quaternary ammonium salt group. N ), The gel fraction is calculated by weighing 1.00 g of polymer particles as a measurement sample, extracting them with 100 mL of methyl ethyl ketone using a Soxhlet extractor, and weighing the extracted soluble components using the following formula (1): Formula (1): Gel fraction relative to methyl ethyl ketone (%) = {(1 - mass of soluble component (g)) / 1} × 100, The haze value is determined using a haze meter in an environment of 23°C and a relative humidity of 50% in accordance with JIS K 7136. The wetting tension is determined using a surface energy value evaluation test pen in an environment of 23° C. and a relative humidity of 50%.

2. The transparent electrode film according to claim 1, wherein A curable compound (Q) having at least one of a tertiary amino group and a quaternary ammonium salt group N ) has a (meth)acryloyl group.

3. The transparent electrode film according to claim 1 or 2, wherein: A curable compound (Q) having at least one of a tertiary amino group and a quaternary ammonium salt group N ), and a hydrophilizing agent (T N ) is 3% by mass to 40% by mass relative to 100% by mass of the non-volatile matter of the curable composition (S).

4. The transparent electrode film according to claim 1 or 2, wherein The content of the particles (R) is 0.01% by mass to 40% by mass relative to 100% by mass of the nonvolatile component of the curable composition (S).

5. The transparent electrode film according to claim 1 or 2, wherein An optically transparent adhesive film is further laminated on the main surface of the resin layer (B) opposite to the light-transmitting base material layer (A) side.

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