JP6981565B1 - Laminates and transparent electrode films - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated body and a transparent electrode film having excellent optical properties and scratch resistance, high yield even when manufactured by a roll-to-roll method, and excellent OCA adhesion regardless of the presence or absence of annealing treatment. do. SOLUTION: The laminated body of the present invention is a resin which is a cured layer of a curable composition (S) containing a light-transmitting base material layer (A), a curable compound (Q) and silica particles (R). It has a layer (B). In the laminated structure of the 1 μm resin layer (B) and the 50 μm PET, the haze value is 2.0% or less when measured from the surface layer side of the resin layer (B), and the light transmitting base material layer (A) side. The main surface (F) of the resin layer (B) opposite to the above has an initial wetting tension of 38 to 60 mN / m before the annealing treatment, and a heat-resistant protective PET film is attached to the main surface (F) for 3 hours. The wetting tension of the main surface (F) of the resin layer (B) after the annealing treatment is performed and the heat-resistant protective PET film is peeled off is 30 to 54 mN / m. [Selection diagram] Fig. 1

Description

The present invention relates to a laminate having a resin layer which is a cured layer of a curable composition exhibiting curability by active energy rays, and a transparent electrode film.

As an electrode material for a display device such as a touch panel, a transparent conductive layer having a desired pattern such as ITO (indium tin oxide) is laminated on a light transmissive base material layer such as a polyethylene terephthalate (hereinafter, also referred to as PET) film. The transparent electrode film used is used. An Optical Clear Adhesive (OCA) film is attached on top of the transparent electrode film and incorporated into the touch panel module.

Patent Document 1 describes the problem that bubble voids are generated during the baking process of the light-transmitting transparent conductive film to which the OCA film is attached, and that the OCA film is partially conveyed when the OCA is attached and then rolled. The ITO layer is provided on the PET film as a configuration for solving the problem that the adhesive surface with the light-transmitting conductive film is displaced from the edge of the light-transmitting conductive film due to the peeling. A light-transmitting conductive film has been proposed which is formed and the wet tension is adjusted to 34 dyn / cm or more by plasma treatment on the surface of the PET film.

Patent Document 2 describes an active energy ray-curable compound and silica particles as an object of forming a hard coat layer having high transparency and high adhesive adhesion to OCA and the like, which can impart high anti-blocking property to the film surface. A curable composition containing the above-mentioned material and having a wetting tension on the surface of the cured coating film of 35 to 60 mN / m has been proposed.

Japanese Unexamined Patent Publication No. 2016-155366 International Publication No. 2018/100929

A laminate that can be suitably used for transparent electrode films, which are electrode materials for display devices such as touch panels, is not only excellent in optical properties and scratch resistance, but also when manufactured by the roll-to-roll method. However, a highly versatile laminate having high yield and excellent adhesion to OCA film regardless of the presence or absence of an annealing process is eagerly desired in the market. Although the problems of the laminate used for the transparent electrode film have been described above, the same problems may occur in all the applications where the above characteristics are required.

The present invention has been made in view of the above background, has excellent optical properties and scratch resistance, has a high yield even when manufactured by the roll-to-roll method, and adheres to OCA regardless of the presence or absence of annealing treatment. It is an object of the present invention to provide a laminate having excellent properties and a transparent electrode film.

As a result of diligent studies by the present inventors, they have found that the problems of the present invention can be solved in the following aspects, and have completed the present invention.
[1]: The resin layer (B) has a laminated structure in which the resin layer (B) is laminated directly or via one or more other layers on at least one surface of the light-transmitting base material layer (A).
The resin layer (B) is a layer obtained by curing a curable composition (S) containing a curable compound (Q) exhibiting curability by active energy rays and silica particles (R).
In the laminated structure of the resin layer (B) having a thickness of 1 μm and the polyethylene terephthalate having a thickness of 50 μm, the haze value is 2.0% or less when measured from the surface layer side of the resin layer (B).
The main surface (F) of the resin layer (B) opposite to the light-transmitting base material layer (A) has an initial wetting tension of 38 to 60 mN / m before the annealing treatment is performed.
Further, a heat-resistant protective polyethylene terephthalate film is attached to the main surface (F) of the resin layer (B), an annealing treatment is performed at 150 ° C. for 3 hours, and the heat-resistant protective polyethylene terephthalate film is peeled off from the resin layer (B). A laminated body having a wet tension of 30 to 54 mN / m on the main surface (F).
[2]: The curable composition (S) is
(I) a curable compound as a (Q), a curable compound having at least one tertiary amino group and a quaternary ammonium salt containing (Q _N), and (ii) do not exhibit curability with an active energy ray, Contains a hydrophilizing agent (T),
_{The hydrophilizing agent (T) contains a hydrophilizing agent (TN} ) having at least one of a tertiary amino group and a quaternary ammonium base.
The laminate according to [1], which satisfies at least one of the above.
[3]: tertiary curable compound having at least one amino group and a quaternary ammonium salt (Q _N) is laminate according to [2] having a (meth) acryloyl groups.
[4]: Sum of curable compounds having at least one tertiary amino group and a quaternary ammonium salt (Q _N), as well as tertiary amino group and a quaternary ammonium salt of the hydrophilizing agent having at least one (T _N) The laminate according to [2] or [3], wherein the content is 3 to 40% by mass with respect to 100% by mass of the non-volatile component of the curable composition (S).
[5]: The content according to any one of [1] to [4], wherein the content of the silica particles (R) is 3 to 40% by mass with respect to 100% by mass of the non-volatile component of the curable composition (S). Laminated body.
[6]: The transparent conductive layer and the laminate according to any one of [1] to [5] are provided.
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 either directly or via one or more layers. Transparent electrode film.
[7]: The transparent electrode film according to [6], wherein an optical transparent pressure-sensitive adhesive film is further laminated on a main surface of the resin layer (B) opposite to the light-transmitting base material layer (A) side.

According to the present invention, a laminate and a transparent electrode having excellent optical properties and scratch resistance, high yield even when manufactured by the roll-to-roll method, and excellent OCA adhesion regardless of the presence or absence of annealing treatment. It has the excellent effect of being able to provide film.

The schematic cross-sectional view which shows an example of the transparent electrode film which concerns on this embodiment.

Hereinafter, the present invention will be described in detail. Needless to say, other embodiments are also included in the scope of the present invention as long as they are in line with the gist of the present invention. In addition, the numerical range specified by using "~" in this specification includes the numerical values described before and after "~". In the present specification, "film" and "sheet" are not distinguished by thickness. In addition, various components appearing in the present specification may be used independently or in combination of two or more, unless otherwise specified.

[[Laminate]]
The laminate according to the present embodiment is formed on the light transmitting base material layer (A) and at least one surface of the light transmitting base material layer (A) directly or via one or more other layers. It has a laminated structure in which the resin layer (B) is laminated. The resin layer (B) is a layer obtained by curing a curable composition (S) containing a curable compound (Q) exhibiting curability by active energy rays and silica particles (R). The main surface (F) opposite to the light-transmitting base material layer (A) side of the resin layer (B) has an initial wetting tension (hereinafter, also referred to as “initial wetting tension”) 38 before the annealing treatment is performed. It is ~ 60 mN / m. Then, a heat-resistant protective polyethylene terephthalate film (hereinafter, heat-resistant protective PET film) was attached to the main surface (F) of the resin layer (B), and an annealing treatment was performed at 150 ° C. for 3 hours to peel off the heat-resistant protective PET film. The wetting tension (hereinafter, also referred to as “wetting tension after annealing treatment”) of the main surface (F) of the resin layer (B) after that is 30 to 54 mN / m. Further, the resin layer (B) has a haze value of 2.0% when measured from the surface layer side of the resin layer (B) in a laminated structure of the resin layer (B) having a thickness of 1 μm and polyethylene terephthalate having a thickness of 50 μm. Use the following. The initial wetting tension, the wetting tension after the annealing treatment, and the haze values disclosed in the present specification refer to the values obtained by the method described in Examples described later.

Here, the "curable compound (Q) exhibiting curability by active energy rays" means a compound in which the curable compound (Q) is cured by polymerization and / or crosslinking by irradiation with active energy rays. Further, the active energy ray means an energy ray in a broad sense capable of providing the energy required for activation for causing a chemical reaction, including ultraviolet rays, visible rays, infrared rays, electron beams (EB), and radiation. Further, the “cured layer” refers to a layer that has been cured to such an extent that the curing reaction does not substantially proceed even when irradiated with active energy rays. When forming the layer of the curable composition (S) of the present embodiment, even if a part of the curable compound (Q) undergoes a curing reaction, the state in which it can be further cured is in the cured layer referred to here. Does not include.

In addition to the embodiment in which the light-transmitting base material layer (A) and the resin layer (B) are directly laminated, they can be laminated via other layers such as an anchor layer, an easy-adhesion layer, and an adhesive layer. Further, in the laminated body of the present embodiment, the OCA film may be further laminated on the resin layer (B).

When the laminated body is manufactured by the roll-to-roll method, there is a problem that the yield is lowered due to the sticking of the films to each other as described above. According to the laminate according to the present embodiment, the cured layer of the curable composition (S) containing the curable compound (Q) and the silica particles (R) is used as the resin layer (B), and the initial wetting tension and annealing are used. By using the above-mentioned laminated body in which the subsequent wetting tension is within the above-mentioned specific range, anti-blocking property and scratch resistance are excellent. Further, even when manufactured by the roll-to-roll method, blocking between films can be effectively suppressed. Therefore, the yield can be significantly increased. Further, in addition to excellent transparency and scratch resistance, it is possible to provide a laminate having excellent OCA adhesion regardless of the presence or absence of annealing treatment. Hereinafter, each layer will be described in detail.

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

The material of the light-transmitting base material layer (A) is not particularly limited as long as it has excellent transparency. Suitable examples include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cyclic polyolefin resins of cycloolefin resins (COP), polyethylene, polypropylene, and chained polyolefins of ethylene-α olefin copolymers. Based resin, polyester resin, polyacrylic resin, polymethacrylic resin, polyolefin resin, polyether resin, polycarbonate resin, polystyrene resin, polyimide resin, polyamide resin, polyvinyl chloride resin, polyacetal type Examples thereof include resins, polyvinylidene chloride resins, polyphenylene sulfide resins and acetate resins.
Among these, polyethylene terephthalate having high versatility and cycloolefin resin having excellent low birefringence, low moisture absorption, high transparency and high heat resistance are suitable.

The thickness of the light-transmitting base material layer (A) may be arbitrarily selected as long as it has a thickness that functions as a support for the resin layer (B). Usually, it can be about 25 to 188 μm. From the viewpoint of transparency, it is preferably 25 to 125 μm, and more preferably 25 to 100 μm.

[Resin layer (B)]
The resin layer (B) is a layer obtained by irradiating the curable composition (S) with active energy rays to cure it, and is excellent in scratch resistance and anti-blocking property. Therefore, a laminate is formed by a roll-to-roll method. Is suitable for.
For example, the light-transmitting base material layer (A) wound in a roll shape is unwound, the curable composition (S) is applied, and the resin layer (B) which is a cured film is obtained by irradiating with active energy rays. After that, the laminate can be manufactured through a process of winding it on a roll again. Further, it may be manufactured by laminating the light-transmitting base material layer (A) wound in a roll shape and the resin layer (B) wound in a roll shape, and then winding the resin layer (B) into a roll again. Compared with the method of laminating the resin layer (B) on the light-transmitting base material layer (A) of a single leaf, the productivity can be significantly improved.

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

As a result of diligent studies by the present inventor, even if the initial wetting tension range before the annealing treatment is 38 to 60 mN / m, the main surface (F) of the resin layer (B) is wetted after the annealing treatment. It was found that the tension may decrease significantly. Then, by using the resin layer (B) having an initial wetting tension of 38 to 60 mN / m and a wetting tension of 30 to 54 mN / m after annealing (150 ° C. × 3 hours), the presence or absence of the annealing treatment can be determined. Nevertheless, it was found that the OCA adhesion was excellent.

The initial wetting tension of the main surface (F) of the resin layer (B) is 38 to 60 mN / m, a more preferable range is 40 to 60 mN / m, and a particularly preferable range is 42 to 60 mN / m. After the annealing treatment, the content is 30 to 54 mN / m, a more suitable range is 32 to 54 mN / m, and a particularly suitable range is 36 to 54 mN / m.

The method of setting the initial wetting tension of the surface layer of the resin layer (B) to 38 to 60 mN / m and the wetting tension after annealing (150 ° C. × 3 hours) to 30 to 54 mN / m is the method of the curable composition (S). There are methods of adjusting by composition and / and methods of adjusting by surface treatment.

As a method of adjusting according to the composition of the curable composition (S),
(1) a method of containing a curable compound (Q), a curable compound having at least one tertiary amino group and a quaternary ammonium base (Q _N),
(2) The curable composition (S) further contains a hydrophilic agent (T) that does not exhibit active energy ray curability, and the hydrophilic agent (T) is a tertiary amino group and a quaternary ammonium base. _{Examples thereof include a method of incorporating a hydrophilizing agent (TN} ) having at least one of them, and (3) a method of using the above (1) and (2) in combination.

As a method for adjusting the wetting tension by surface treatment, an example is a method in which the surface layer of the resin layer (B) is subjected to at least one treatment selected from the group consisting of corona discharge treatment, ozone treatment, plasma treatment, and ultraviolet irradiation treatment. can.

In the laminated structure of the resin layer (B) having a thickness of 1 μm and the polyethylene terephthalate having a thickness of 50 μm, 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). can get. The haze value is more preferably 1.0% or less, and further preferably 0.5% or less. The lower limit of the haze value is 0%.

As a method for adjusting the resin layer (B) for satisfying the haze value, there is a method for adjusting the composition of the curable composition (S). Specifically, as described later, a hydroxyl group-containing curable compound (Q _O), by combination with the silica particles (R) and tertiary amino group and / or quaternary ammonium bases, to reduce the haze value Can be done. According to this method, there is an advantage that the steps of corona treatment and ozone treatment can be omitted.

[Curable composition (S)]
The curable composition (S) of the present embodiment refers to a composition capable of forming a resin layer (B) which is a cured layer by advancing a polymerization reaction and / or a crosslinking reaction by irradiation with active energy rays. The curable composition (S) contains at least a curable compound (Q) exhibiting curability by active energy rays and silica particles (R). Hereinafter, each component will be described in detail.

<Curable compound (Q)>
The curable compound (Q) may be any compound as long as it is a compound that is cured by the progress of the polymerization reaction and / or the crosslinking reaction by irradiation with active energy rays, and is selected regardless of the molecular weight such as a low molecular weight compound and a high molecular weight compound. Can be done. The curable compound (Q) is used alone or in combination of two or more.

Examples of the group exhibiting curability of the curable compound (Q) include radically polymerizable groups such as a vinyl group, a (meth) acryloyl group, and an allyl group. Among these, the curable compound (Q) having a (meth) acryloyl group is preferable. The curable compound (Q) can be used alone or in combination of two or more. In addition, "(meth) acrylate" includes both "acrylate", "methacrylate" and a mixture thereof.

From the viewpoint of increasing the surface hardness of the resin layer (B), it is preferable to use 30 to 100% by mass or more of trifunctional or higher (meth) acrylate with respect to 100% by mass of the curable compound (Q), and 50 to 100% by mass. % Or more is more preferable, and 80 to 100% by mass or more is further preferable.

Examples of the tetrafunctional or higher functional (meth) acrylate include dimethylol propanetetra (meth) acrylate, ethylene oxide-modified dimethylol propanetetra (meth) acrylate, prolenoxide-modified dimethylol propanetetra (meth) acrylate, and tetramethylene oxide. Modified Dimethylol Propane Tetra (Meta) Acrylate, Ditrimethylol Propane Tetra (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol Penta (Meta) Acrylate, Alkyl Modified Dipentaerythritol Penta (Meta) Acrylate, Dipentaerythritol Hexa (meth) acrylates, caprolactone-modified dipentaerythritol hexa (meth) acrylates, and polypentaerythritol polyacrylates can be mentioned.

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, and 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 dipenta Examples thereof include erythritol tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, ethylene oxide-modified glycerol triacrylate, propylene oxide-modified glycerol triacrylate, εcaprolactone-modified trimethylolpropane triacrylate, and pentaerythritol triacrylate.

Examples of the bifunctional (meth) acrylate include pentandiol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 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 pentandiol di (meth) acrylate, propylene oxide-modified pentandiol di (meth) acrylate, tetramethylene oxide-modified pentandiol di (meth) acrylate, ethylene oxide-modified 2,2-dimethylpropane-1,3-diol di ( Meta) acrylate, propylene oxide modified 2,2-dimethylpropane-1,3-diol di (meth) acrylate, tetramethylene oxide modified 2,2-dimethylpropane-1,3-diol di (meth) acrylate, ethylene oxide-modified hexanediol Di (meth) acrylate, propylene oxide-modified hexanediol di (meth) acrylate, tetramethylene oxide-modified hexanediol di (meth) acrylate, ethylene oxide-modified heptanediol di (meth) acrylate, propylene oxide-modified heptanediol di (meth) acrylate. , Tetramethylene oxide modified heptanediol di (meth) acrylate, ethylene glycol-propylene glycol di (meth) acrylate, diethylene glycol-propylene glycol di (meth) acrylate, diethylene glycol-dipropylene glycol di (meth) acrylate, poly (ethylene glycol-) Tetramethylene glycol) di (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, isocyanuric acid propylene oxide-modified di (meth) acrylate, isocyanuric acid butyl oxide-modified di (meth) acrylate and isocyanuric acid butyl oxide-modified di (meth) acrylate. Di (meth) acrylate containing alkyleneoxy group such as meta) acrylate;
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, Examples thereof include polyol ester-based di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate.

Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, n-hexyl acrylate, lauryl acrylate, and stearyl (stearyl acrylate). (Meta) Acrylic acid alkyl ester;
(Meta) Acrylic acid perfluoroalkyl esters such as (meth) acrylic acid perfluoromethyl, (meth) acrylic acid 2-perfluoroethyl-ethyl, and (meth) acrylic acid 2-perfluorohexadecylethyl-;
(Meta) Acrylic Acid (methoxycarbonyl) Methyl, (Meta) Acrylic Acid 2- (ethoxycarbonyloxy) Hexyl, (Meta) Acrylic Acid 2- (Propoxycarbonyloxy) Ethyl-, and (Meta) Acrylic Acid 2- (Octyl) Oxycarbonyloxy) An aliphatic (meth) acrylic acid ester having one carbonyl group such as butyl;
2-oxobutanoylethyl (meth) acrylate, 3-oxobutanoylpropyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, 2,3-di (meth) acrylate An aliphatic (meth) acrylic acid ester having two carbonyl groups such as di (oxobutanoyl) hexyl;
2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, Alkoxy group-containing (meth) acrylic acid esters such as (meth) acrylic acid 3-butoxyethyl and (meth) acrylic acid 4-butoxyethyl;
An alkylene oxide-containing (meth) acrylic acid derivative such as an alkylene oxide adduct of (meth) acrylic acid;
Cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexanol (meth) acrylate, 4-tertiary 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) (Meta) acrylate having an alicyclic structure such as acrylate, 2-propyl-2-adamantyl (meth) acrylate;
2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, Monofunctional (meth) such as (meth) acrylic acid 8-hydroxyoctyl, cyclohexanedimethanol mono (meth) acrylic acid ester, (meth) acrylic acid 12-hydroxylauryl, (meth) acrylic acid ethyl-α- (hydroxymethyl). ) Acrylic acid glycerol;
Fatty acid ester-based (meth) acrylic acid ester such as (meth) glycidyl lauric acid ester;
Cyclic of cyclohexanedimethanol mono (meth) acrylate, cyclohexanediethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-a (meth) acryloylxyethyl-2-hydroxyethyl-phthalic acid, etc. (Meta) acrylic acid ester;
A (meth) acrylic acid ester having a hydroxyl group at the end of the molecule synthesized by ring-opening addition of ε-caprolactone to a mono (meth) acrylate having a hydroxyl group;
An alkylene oxide-added (meth) acrylic acid ester obtained by repeatedly adding an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to a mono (meth) acrylate having a hydroxyl group;
N, N-dimethyl (meth) acrylamide, (meth) acryloylmorpholine, hydroxyethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (Meta) acrylamide, N-propyl (meth) acrylamide, Nn-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Monofunctional (meth) acrylamide such as N-methylol (meth) acrylamide can be exemplified.

The curable compound (Q) may be an oligomer or a polymer. In the present specification, the oligomer and the polymer are polymers in which a finite number of monomers are bonded, the oligomer means a compound having a weight average molecular weight of 10,000 or less, and the polymer means a compound having a weight average molecular weight of more than 10,000. Say. The oligomer or polymer may be a homopolymer or a copolymer. Specific examples of the (meth) acrylate oligomer include polyurethane-based (meth) acrylate oligomers, polyester-based (meth) acrylate oligomers, and epoxy-based (meth) acrylate oligomers. The weight average molecular weight in the present specification is a value measured by gel permeation chromatography (GPC) using polystyrene having a known weight average molecular weight as a standard substance.

The polyurethane-based (meth) acrylate oligomer is a compound having a urethane bond and a radically polymerizable functional group. The polyurethane-based (meth) acrylate oligomer is obtained, for example, by reacting a compound having two or more isocyanate groups with a compound having a hydroxyl group, and adding a (meth) acryloyl group having a hydroxyl group to the compound having an isocyanate group at the terminal. It can be obtained by reacting. Alternatively, it can be synthesized by reacting a compound having a hydroxyl group with a compound having an isocyanate group and a (meth) acrylate group. Examples of the polyurethane-based (meth) acrylate oligomer (A1) include those having a polyether skeleton and those having a polyester skeleton.
Compounds having two or more isocyanate groups include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 1,4-phenylene bismethylene diisocyanate; 3-isocyanatemethyl-3. , 5,5-trimethylcyclohexyl isocyanate, hexamethylene diisocyanate and other aliphatic isocyanates.
As commercial products of polyurethane-based (meth) acrylate oligomers, aromatic polyurethane oligomers such as EBECRYL210, EBECRYL220 (above, manufactured by Dycel Ornex), CN9782, CN9783 (above, manufactured by SARTOMER); purple light UV3000B, purple light UV3300B (above, Japan). An aliphatic polyurethane oligomer such as (manufactured by Synthetic Chemical Industry Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL8402, EBECRYL8701 (all manufactured by Daicel Ornex) can be exemplified.

The polyester-based (meth) acrylate oligomer is a compound having an ester bond and a radically polymerizable functional group, and has, for example, a hydroxyl group and a carboxyl group of a polyester synthesized by polycondensing a polybasic acid and a polyhydric alcohol (). A meta) acrylate (eg, (meth) acrylic acid, etc.) can be synthesized by an esterification reaction.
The polybasic acid is an aliphatic polybase such as oxalic acid, malonic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, suberic acid, maleic acid, fumaric acid, itaconic acid, succinic acid anhydride and maleic anhydride. Acids; examples include alicyclic acids such as dimer acid and cyclohexanedicarboxylic acid, and aromatic acids such as isophthalic acid, terephthalic acid and biphenyldicarboxylic acid.
The polyhydric alcohol is, for example, polyethylene glycol, propylene glycol or the like, a polyol having a number average molecular weight (Mn) of 50 to 500, a polyol having a number average molecular weight (Mn) of 500 to 30,000, and trimethylolpropane, glycerin, pentaerythritol. And so on.
As commercial products of polyester-based (meth) acrylate oligomers, aromatic polyester oligomers such as CN296, CN2203, CN2259, and CN2261 (all manufactured by SARTOMER); aliphatic polyester oligomers such as CN294, CN2270, and CN2271 (all manufactured by SARTOMER). Can be exemplified.

The epoxy-based (meth) acrylate oligomer is a compound having a radically polymerizable functional group obtained by reacting an epoxy group of a compound having an epoxy group with a compound having a carboxyl group or a hydroxyl group. In the epoxy-based (meth) acrylate oligomer, a small amount of epoxy group may remain.
As commercial products of epoxy-based (meth) acrylate oligomers, aromatic epoxy oligomers such as CN104, CN110 (above, manufactured by SARTOMER), EBECRYL600, EBECRYL3701 (above, manufactured by Dycel Ornex), CN111, CN113 (above, manufactured by SARTOMER). ), EBECRYL860 (manufactured by Daicel Ornex) and the like, and examples thereof include aliphatic epoxy oligomers.

As a specific example of the (meth) acrylate polymer, a compound obtained by replacing the specific example of the oligomer with a polymer can be exemplified.

The initial wetting tension of the main surface (F) of the resin layer (B) opposite to the light-transmitting base material layer (A) side is 38 to 60 mN / m, and the wetting tension after annealing is 30 to 54 mN / m. as a method of the method of the aforementioned (1), i.e., as the curable compound (Q), there is a method of containing a curable compound having at least one tertiary amino group and a quaternary ammonium salt (Q _N) .. From the viewpoint of easily adjusting the wetting tension, the amine value is preferably 140 to 370 mgKOH / g. The amine value is a value obtained by the method of Examples described later.

Examples of the tertiary amino group include dialkylamino groups such as a dimethylamino group, a diethylamino group and a dibutylamino group. Examples of the quaternary ammonium group include a trialkylammonium group such as a trimethylammonium group, a triethylammonium group and a tributylammonium group. Examples of the counterion for the nitrogen atom constituting the quaternary ammonium group include chloride ion, bromide ion, hydroxide ion and the like.

Curable compound having a tertiary amino group as a (Q _N), it is preferred (meth) acrylates having a tertiary amino group. Suitable examples are N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N, N-diethylaminopropyl (meth) acrylate. N, N-dialkylaminoalkyl (meth) acrylates such as N- [2-methacryloyloxyethyl] piperidine, N- [2-methacryloyloxyethyl] pyrrolidine, N- [2-methacryloyloxyethyl] morpholine, and 1, 2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate can be exemplified.
Further, glycidyl (meth) acrylate and 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. Metacrate having a hydroxy group by opening the ring of an epoxy group; a (meth) acrylate having an isocyanate group such as methacryloyloxyethyl isocyanate, which has a hydroxy group or a primary or secondary amino group. Moreover, a (meth) acrylate having a urethane bond or a urea bond, which is obtained by reacting a compound having a tertiary amino group, and the like can also be mentioned. Of these, N, N-dialkylaminoalkyl (meth) acrylates are more preferred.

Curable compound having a quaternary ammonium base as a (Q _N), it is preferred (meth) acrylate having a quaternary ammonium base. As a preferred example, a (meth) acrylate obtained by reacting a (meth) acrylate having a tertiary amino group with a quaternary agent can be mentioned. Examples of the quaternizing agent include organic halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide, propyl chloride, dodecyl lolide, benzyl chloride, benzyl bromide, methyl iodide, and benzyl iodide; methane sulfonate. Sulfonic acid esters such as methyl acid, methyl p-toluenesulfonate, and methyl trifluoromethanesulfonate; sulfate esters such as dimethylsulfate and diethylsulfate, and the like. The quaternary agent can be reacted with a tertiary amino group to form a quaternary ammonium salt. When an organic halide is used as the quaternary agent, the nitrogen atom is a cation and the counterion halogen is a quaternary ammonium salt as an anion, but the anion can be exchanged with another anion. May be used. As the compound having the anion, a conventionally known compound can be used, for example, sodium tetrafluoroborate, sodium trifluoromethylsulfate, sodium perchlorate, sodium hexafluorophosphate, bis (trifluoromethanesulfonyl) imide sodium. Examples include compounds of inorganic salts such as.
Examples of commercially available products include Acryloyl 8WX-018 (manufactured by Taisei Fine Chemical Co., Ltd.), Amino Ion RE3000MF (manufactured by Nippon Embroidery Co., Ltd., acrylic group-containing reactive ion) and the like.

_{The total content of the curable compound (Q N} ) having a tertiary amino group and / and a quaternary ammonium base is preferably 3 to 40% by mass in 100% by mass of the curable compound (Q), 3 to 3 to. It is more preferably 30% by mass, further preferably 3 to 20% by mass. By setting it in the range of 3 to 40% by mass, it is possible to have both excellent anti-blocking property and excellent adhesion to OCA. Incidentally, the curable compound (Q _N) 3 amino groups and may have both a quaternary ammonium base in, when the calculation of the total content in this case, to calculate the content of the first compound is Needless to say.

As the curable compound (Q), 3 tertiary curable compound having at least one amino group and a quaternary ammonium salt by using (Q _N), 3 amino groups and a quaternary ammonium at least one base is hardened layer It is taken into the binder resin of. The tertiary amino group and the quaternary ammonium base are highly hydrophilic and have a low affinity with the binder resin other than the hydrophilic group and the silica particles (R). Therefore, the tertiary amino group and / or the quaternary ammonium base is easily exposed on the surface layer side of the resin layer (B). Further, since these groups are immobilized as a resin by a curing reaction, they do not bleed out and are excellent in stability over time.

The curable composition (S), further, may contain hydroxyl group-containing curable compound (Q _O). By containing the hydroxyl group-containing curable compound (Q _O), to improve the compatibility and dispersion of the silica particles (R) and tertiary amino group and / or quaternary ammonium bases, excellent coating liquid stability can get. Further, the haze value of the coating film of the resin layer (B) can be lowered. Further, it is possible to improve the initial wetting tension and suppress the decrease in the wetting tension after the annealing treatment, and to more effectively enhance the balance of OCA adhesion. As a result, the dispersibility of the silica particles (R) in the resin layer (B) can be enhanced more effectively, and the transparency can be significantly enhanced.
Content of the hydroxyl group-containing curable compound _{(Q O)} is curable compound (Q) with respect to 100 wt%, preferably from 3 to 40 wt%, more preferably from 5 to 30 mass%, further 5 to 20 wt% preferable.

Preferred examples of the hydroxyl group-containing curable compound (Q _O) is (meth) acrylate having the above hydroxyl group can be exemplified. Among them, particularly preferable examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.

<Hydrophilic agent (T)>
As described above, the curable composition (S) of the present embodiment can further contain a hydrophilic agent (T) as an optional component. Here, the hydrophilic agent (T) is a layered surface layer (light-transmitting base material layer (A)) of the resin layer (B) which is a cured product of the coating layer of the curable composition (S) by being added. A compound that can reduce the water contact angle of the surface layer on the side opposite to the side where it is formed. A compound that reduces the water contact angle to 60 ° or less is preferable, and 55 ° or less is more preferable.

Examples of the hydrophilic agent (T) include an ionic hydrophilic agent having a quaternary ammonium base and a nonionic hydrophilic agent having a tertiary amino group. From the viewpoint of easily adjusting the wetting tension, the amine value is preferably 140 to 370 mgKOH / g. It is preferable that 100 to 50% by mass of the total constituent unit of the hydrophilizing agent (T) is a tertiary amino group and / or a quaternary ammonium salt.

Examples of trade names of ionic hydrophilic agents having a quaternary ammonium base include Acryt 8WX-030 (manufactured by Taisei Fine Chemical Co., Ltd.) and Amino Ion RE3000MF (manufactured by Nippon Embroidery Co., Ltd.).
As a suitable example of the nonionic hydrophilic agent having a tertiary amino group, a vinyl resin having a tertiary amino group and a (meth) acrylic resin having a tertiary amino group can be exemplified. Among these, a (meth) acrylic resin containing a dialkylamino group is preferable.

Further, preferred examples of the ionic hydrophilizing agents and nonionic hydrophilizing agents, curable compound (Q _N) copolymer containing a part or all of the monomer or polymer or monomer component oligomer homopolymerization of Can be exemplified. Further, compounds obtained by crosslinking monomer or oligomer curable compounds described above (Q _N) can be exemplified. These may be single varieties or mixtures.

The content of the hydrophilic agent (T) with respect 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 improving the anti-blocking property. The content is more preferably 5 to 30% by mass, further preferably 5 to 20% by mass.

The molecular weight of the hydrophilizing agent (T) is not limited and may be a low molecular weight compound or a high molecular weight compound, but from the viewpoint of effectively suppressing bleed-out in a high temperature and high humidity environment, the weight average molecular weight is 10,000 or more. It is preferably a polymer compound. The upper limit of the weight average molecular weight is not particularly limited, but may be, for example, 50,000 or less from the viewpoint of compatibility with the curable composition (S) and the like.

Tertiary amino group and / or a curable compound having a quaternary ammonium salt (Q _N), as well as tertiary amino group and / or hydrophilizing agent having a quaternary ammonium base total content (T _N), the curable It is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass in 100% by mass of the non-volatile component of the composition (S). By setting the range to 3 to 50% by mass, the wetting tension of the main surface (F) of the resin layer (B) is within a desired range regardless of the presence or absence of annealing treatment, and excellent adhesion to OCA is excellent. Can be.

<Silica particles (R)>
The silica particles (R) mainly play a role of imparting anti-blocking property. Anti-blocking property can be enhanced by adding silica particles (R). As the silica particles (R), hydrophilic silica particles and hydrophobic silica particles can be used in addition to untreated silica particles. The shape of the silica particles (R) is not limited, but for example, spherical silica, crushed silica, and the like can be used.

The primary particle size of the silica particles (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, still more preferably 100 nm or less.

The average particle size can be measured by a particle size distribution measuring device, particularly a particle size distribution measuring device using a dynamic light scattering method (“NANOTRAC WAVE II UZ152” manufactured by Microtrac Bell, etc.). In the present invention, methyl ethyl ketone was used as a solvent, and the average value obtained by performing the measurement for 60 seconds three times at a concentration in which the loading index was in the range of 1.0 ± 0.2 was used.

The content of the silica particles (R) is preferably 3 to 40% by mass with respect to 100% by mass of the non-volatile component of the curable composition (S). It is more preferably 5 to 40% by mass, still more preferably 5 to 30% by mass. By containing it in the range of 3 to 50% by mass, the resin layer (B) having more excellent anti-blocking property can be obtained. Here, the non-volatile component refers to a component that constitutes a composition other than the solvent.

As the silica particles (R), hydrophobic silica particles are suitable. By using the hydrophobic silica particles, it is possible to obtain the effect of making it difficult to absorb moisture even in a high temperature or high humidity environment. Hydrophobic silica particles are obtained by surface-treating the silica particles.
Examples of the surface treatment agent for silica particles include silanes such as β-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, hexamethyldisilazane, and dimethyldichlorosilane. A coupling agent or a known treatment agent such as silicone oil can be used. The surface-treated hydrophobic silica particles are available as commercial products. For example, "Megasil 525RCS" manufactured by Sibelco Japan Co., Ltd. can be exemplified.

Tertiary amino group and / or a curable compound having a quaternary ammonium salt (Q _N) or / and hydrophilizing agent (T _N), by the combined use with the hydrophobic silica (R _H), the curable compound (Q _N ) Or / and the effect of preventing aggregation of the _{hydrophilic agent (TN) and silica can be obtained.} In addition to the excellent anti-blocking property, from the viewpoint of remarkably enhancing the dispersibility of the silica particles (R) in the resin layer (B) to realize excellent coating stability and a good haze value, a hydroxyl group is further added to the above combination. it is preferable to blend containing curable compound (Q _O).

<Photopolymerization initiator and photosensitizer>
The curable composition (S) can contain a photopolymerization initiator as an optional component. When the active energy ray is ultraviolet rays, it is preferable to add a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it has a function of initiating the polymerization and / or crosslinking of the curable compound (Q) by photoexcitation. Preferable examples include monocarbonyl compounds, dicarbonyl compounds, acetophenone compounds, benzoin ether compounds, acylphosphine oxide compounds, aminocarbonyl compounds and the like.

Examples of the monocarbonyl compound include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl-etanone, and 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-benzoyl-N, N, N-trimethyl-1-propaneamine 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-9H thioxanthone-2-iroxy-N, N, N-trimethyl-1-propaneamine hydrochloride Examples thereof include salts, benzoylmethylene-3-methylnaphtho (1,2-d) thiazolin.
Examples of the dicarbonyl compound include 1,2,2-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxo. Examples thereof include benzene acetate and 4-phenylbenzyl.
Examples of the acetphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 -(4-Isopropylphenyl) -2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexylphenylketone, 2-hydroxy-2-methyl-1-styrylpropane-1- On Polymers, Diethoxyacetophenone, Dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-diethoxy-1,2-diphenylethan-1-one, 2-methyl- 1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 1-phenyl-1,2 Examples thereof include −propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholino-propanol) -9-butylcarbazole.
Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin n-butyl ether.
Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide.
Examples of the aminocarbonyl compound include methyl-4- (dimethoxyamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl-4- (dimethylamino) benzoate, and isoamyl-4- (dimethylamino). Benzoate, 2- (dimethylamino) ethylbenzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, 2,5'-bis (4-diethylaminobenzal) cyclo Pentanone can be exemplified.

Commercially available photopolymerization initiators include IGM-Resins B.I. V. Omnirad 184, 651, 500, 907, 127, 369, 784, 2959, IGM-Resins B. V. Examples include Lucillin TPO manufactured by DKSH Japan and Esacure One manufactured by DKSH Japan.
In particular, Omnirad 184 and Esacure One are preferable from the viewpoint of yellowing resistance after curing with active energy rays.

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

Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, aclysine derivatives, azine derivatives, thiadine derivatives, oxadin derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglycilate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4'- Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-diethylaminobenzophenone. The sensitizer may be used alone or in combination of two or more.

<Other ingredients>
The curable composition (S) of the present embodiment may contain a solvent, if necessary. When a solvent is added, it is preferable to carry out a curing treatment with active energy rays after the solvent is volatilized.
The solvent is not particularly limited, and various known organic solvents can be used. Specifically, for example, cyclohexanone, methylisobutylketone, methylethylketone, 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 monon-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethylene Examples thereof include glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, butyl acetate, isoamyl acetate, dimethyl adipate, dimethyl succinate, dimethyl glutarate, tetrahydrofuran, methylpyrrolidone and the like. Two or more kinds of these organic solvents may be used in combination.
In addition, other components that do not fall under the above can be contained as long as the object and effect of the present invention are not impaired. For example, surfactants, colorants, stabilizers, resins, surface treatment agents, viscosity modifiers, adhesion-imparting agents, antioxidants, anti-aging agents, cross-linking accelerators, UV absorbers, plasticizers, preservatives, etc. Dispersants, defoamers, silane coupling agents, inorganic fillers and the like can be mentioned.

[Method for producing curable composition (S)]
The curable composition (S) can be obtained by a known method and is not particularly limited. For example, there is a method of mixing and dispersing the curable compound (Q) and the silica particles (R), and adding and adjusting a solvent, a photopolymerization initiator and various other compounding components as needed.

[Manufacturing method of laminated body]
The method of manufacturing the laminated body of this embodiment will be described. The laminate of the present embodiment is formed by laminating the resin layer (B) on at least one surface of the light-transmitting base material layer (A). The resin layer (B) is a layer obtained by curing a curable composition (S) containing a curable compound (Q) exhibiting curability by active energy rays and silica particles (R).

As a method of applying the curable composition (S) on the light-transmitting base material layer (A), a known method can be used. For example, a lot, a method using a wire bar, various coating methods such as microgravure, gravure, die, curtain, lip, slot or spin can be used.
After forming the coating film of the curable composition (S), it is naturally or forcibly dried. Then, the resin layer (B) is obtained by irradiating it with active energy rays to cure it. As a light source of ultraviolet rays and visible light having a wavelength of 400 to 500 nm, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used. As the electron beam source, a thermionic radiation gun, an electrolytic radiation gun, or the like can be used. The active energy dose to be irradiated may be, for example, ^{about 50 to 2000 mJ / cm 2 as} long as sufficient curability can be obtained.

[Transparent electrode film]
The transparent electrode film of the present embodiment has at least the present laminated body and the transparent conductive layer. FIG. 1 shows an example of the transparent electrode film of the present embodiment. As shown in the figure, in the transparent electrode film 1, a laminate 2, an index matching layer (hereinafter, also referred to as an IM layer) 3, and a transparent conductive layer 4 are laminated in this order. In the example of the present embodiment, the laminated body 2 is composed of a resin layer (B) and a light-transmitting base material layer (A), and the IM layer 3 is laminated on the light-transmitting base material layer (A). An OCA film may be further laminated on the surface layer of the resin layer (B). Further, the transparent conductive layer 4 may be laminated directly on the light transmissive base material layer (A) of the laminated body 2 without providing the IM layer 3. Each layer may be independently single layer or multiple layers.

The IM layer 3 is a layer having a high refractive index, which is laminated for the purpose of making it difficult to visually recognize the shape of the transparent conductive layer 4 in which a pattern is formed. For example, metal oxide particles having a high refractive index and active energy ray curability. It can be formed by a cured product layer of a composition containing components. The refractive index of the IM layer 3 is preferably as close as possible to the refractive index of the transparent conductive layer 4. Metal oxide particles having a high refractive index and active energy ray-curable components can be obtained by using known materials. For example, examples of the metal oxide particles having a high refractive index include titanium oxide (nD = 2.72), zirconium oxide (nD = 2.22), aluminum oxide (nD = 1.77), and the like. Further, as the active energy ray-curable component, the curable compound (Q) contained in the resin layer (B) described above can be exemplified. 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.

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

An anchor layer (not shown) may be arranged between the IM layer 3 and the transparent conductive layer 4. The anchor layer can be formed, for example, by a film forming method using a vacuum as in the case of the transparent conductive layer 4. Examples of the metal oxide used for forming the anchor layer include silicon oxide, which is preferable because it can impart strong adhesion.

The OCA film can be further laminated on the main surface (F) of the resin layer (B) of the laminated body 2 of the transparent electrode film 1. Then, through this OCA film, it can be incorporated into a transparent electrode film, for example, in a module of a touch panel. The transparent electrode film of the present embodiment can be suitably used by being mounted on, for example, a smartphone, a tablet, a PC, a television, a car navigation system, an information board of other commercial facilities, or an electronic device such as a transportation ticket vending machine.

<< Example >>
The present invention will be described in more detail, but the following examples do not limit the scope of rights of the present invention in any way. In addition, "part" and "%" in an Example represent "part by mass" and "% by mass", respectively.
Mw means weight average molecular weight, which is a polystyrene-equivalent molecular weight when a TSKgel column (manufactured by Tosoh Corporation) is used and a GPC (manufactured by Tosoh Co., Ltd., HLC-8320GPC) equipped with an RI detector and DMF is used as a developing solvent. be.
The amine value of the tertiary amino group-containing curable compound is a value obtained by converting the measured total amine value (mgKOH / g) into a solid content according to the method of ASTM D 2074. In the present specification, the non-volatile content means a 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.

The abbreviations of each component of the curable composition (S) used in this example are as follows.
[Curable compound (Q)]
-Q-1 (PET-30): Pentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd.
-Q-2 (KAYARAD DPHA): Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
-Q-3 (Miramer PU610): Urethane acrylate, manufactured by MIWON.
-Q-4 (4HBA): 4-Hydroxybutyl acrylate, manufactured by Mitsubishi Chemical Corporation.
-Q-5 (Acryt 8WX-030): Cationic polymer, manufactured by Taisei Fine Chemical Co., Ltd., containing quaternary ammonium base.
-Q-6 (amino ion RE3000MF): Cationic polymer, quaternary ammonium base manufactured by Nippon Emulsorium Co., Ltd.
Q-7: Curable vinyl resin containing a tertiary amino group.
Incidentally, the q-1 and q-4 is, corresponds to the hydroxyl group-containing curable compound _{(Q O).}
[Silica particles (R)]
-R-1 (MSD-57): D50: 200 nm, manufactured by Sakai Chemical Co., Ltd., surface treated with 3-methacryloxypropyltriethoxysilane.
-R-2 (MEK-ST-2040): manufactured by Nissan Chemical Industries, Ltd., D50: 100 nm, surface treated with silane coupling agent.
-R-3 (Aerosil 200 dispersion): manufactured by Nippon Aerosil, D50: 42.2 nm, no surface treatment
[Hydrophilic agent (T)]
T-1: Tertiary amino group-containing hydrophilizing agent, manufactured by Toyochem Co., Ltd., containing a tertiary amino group.
T-2: Tertiary amino group-containing hydrophilizing agent, manufactured by Toyochem Co., Ltd., containing a tertiary amino group.
T-3: Tertiary amino group-containing hydrophilizing agent, manufactured by Toyochem Co., Ltd., containing a tertiary amino group.
-T-4 (FC-4400): Ionic liquid, manufactured by 3M Ltd., containing a quaternary ammonium base.

<Production example of tertiary amino group-containing curable compound (q-7)>
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a 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, and nitrogen was charged. After raising the temperature to 50 ° C. while substituting, 2.3 parts of 1-thioglycerol was added and the temperature was raised to 70 ° C. 16.8 parts by mass of ethyl acetate and 0.6 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) were charged in the dropping tank, stirred until uniform, and then dropped into the reaction tank over 7 hours. After that, the reaction was continued at the same temperature for 1 hour, and it was confirmed by solid content measurement that the reaction was 95% or more. Next, the inside of the flask was replaced with air, 32.8 parts by mass of 2-acryloyloxyethyl isocyanate (AOI) and 0.1 part by mass of hydroquinone were charged, and the reaction was carried out at 70 ° C. for 4 hours. After confirming the disappearance of the peak of 2270 cm-1 based on the isocyanate group by FT-IR, the reaction solution was cooled to obtain a solution of a vinyl resin having a tertiary amino group and an acryloyl group. After cooling to room temperature, about 2 g of the resin solution is sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and ethyl acetate is added to the previously synthesized resin solution so that the non-volatile content is 45% by weight. Then, a curable compound (q-7) solution, which is a vinyl resin having a tertiary amino group having an amine value of 234 mgKOH / g and a number average molecular weight of 22,000, was obtained.

<Production Example of Tertiary Amino Group-Containing Hydrophilizing Agent (t-1)>
50.6 parts of isopropyl alcohol and 200 parts of N, N-dimethylaminoethyl methacrylate were charged in a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 50 ° C. while substituting with nitrogen. , 2.3 parts of 1-thioglycerol was added and the temperature was raised to 70 ° C. 16.8 parts of isopropyl alcohol and 0.6 part of 2,2'-azobis (2,4-dimethylvaleronitrile) were charged in the dropping tank, stirred until uniform, and then dropped into the reaction tank over 7 hours. After that, the reaction was continued at the same 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 to measure the non-volatile content. A vinyl-based resin having a tertiary amino group having an amine value of 357 mgKOH / g and a number average molecular weight of 21,000 by adding isopropyl alcohol to the previously synthesized resin solution so that the non-volatile content becomes 45%. A solution of the hydrophilizing agent (t-1) was obtained.

<Production Example of Tertiary Amino Group-Containing Hydrophilizing Agent (t-2)>
50.6 parts of isopropyl alcohol and 200 parts of N, N-diethylaminoethyl methacrylate were charged in a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 50 ° C. while substituting with nitrogen. 2.3 parts of 1-thioglycerol was added and the temperature was raised to 70 ° C. 16.8 parts of isopropyl alcohol and 0.6 part of 2,2'-azobis (2,4-dimethylvaleronitrile) were charged in the dropping tank, stirred until uniform, and then dropped into the reaction tank over 7 hours. After that, the reaction was continued at the same 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 is sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and isopropyl alcohol is added to the previously synthesized resin solution so that the non-volatile content becomes 45%. A solution of a hydrophilic agent (t-2), which is a vinyl resin having a tertiary amino group having an amine value of 301 mgKOH / g and a number average molecular weight of 20,000, was obtained.

<Production Example of Tertiary Amino Group-Containing Hydrophilizing Agent (t-3)>
A reaction vessel equipped with a gas introduction 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, and was charged at 50 ° C. with nitrogen substitution. After raising the temperature to 70 ° C., 2.3 parts of 1-thioglycerol was added and the temperature was raised to 70 ° C. 16.8 parts of isopropyl alcohol and 0.6 part of 2,2'-azobis (2,4-dimethylvaleronitrile) were charged in the dropping tank, stirred until uniform, and then dropped into the reaction tank over 7 hours. After that, the reaction was continued at the same 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 is sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and isopropyl alcohol is added to the previously synthesized resin solution so that the non-volatile content becomes 45%. A solution of a hydrophilic agent (t-3), which is a vinyl resin having a tertiary amino group having an amine value of 151 mgKOH / g and a number average molecular weight of 21,000, was obtained.

<Production example of Aerosil 200 dispersion (r-3)>
15.0 parts of silica particles (“Aerosil 200” manufactured by Nippon Aerosil Co., Ltd.), 1.5 parts of dispersant (“DYSPERBYK142”), and 83.5 parts of methyl ethyl ketone / methoxybutanol = 1/1 mixed solvent are mixed and pre-dispersed. (Uses zirconia beads (0.5 mm) as media and disperses with a paint shaker for 1 hour) and main dispersion (uses zirconia beads (0.1 mm) as media and disperses with UAM-015, a disperser manufactured by Kotobuki Kogyo Co., Ltd.). ) Was carried out in two steps to obtain Aerosil 200 dispersion.

<Production example of curable composition (S)>
(Example 1)
Pentaerythritol triacrylate ("KAYARAD PET30" manufactured by Nippon Kayaku Co., Ltd., partially containing pentaerythritol tetraacrylate) 94.5 parts, Acryt 8WX-030 (manufactured by Taisei Fine Chemical Co., Ltd.) 5.5 parts, Omnirad 184 (IGM-Resins) B.V.) 5.0 parts and 50 parts of methyl propylene glycol were uniformly mixed. Next, MSD-57 was added to the silica particles so that the content of the silica particles was 5% by mass in the non-volatile component, and methylpropylene glycol was added so that the non-volatile component was 50% by mass, and the mixture was uniformly mixed to generate active energy rays. A curable composition (S-1) was obtained.

(Examples 2 to 25, Comparative Examples 1 to 7)
The curable composition (S) according to each Example and Comparative Example was obtained by the same method as in Example 1 except that the blending amounts shown in Tables 1 to 3 were changed.

<Manufacturing example of laminated body>
(Example 1)
An easy-adhesion-treated polyethylene terephthalate film (“Lumilar U403” manufactured by Toray Industries, Inc.) having a thickness of 50 μm was used as the light-transmitting substrate layer (A). The curable composition (S) obtained in Examples and Comparative Examples is coated on the light-transmitting substrate layer (A) using a bar coater, and used in a hot air oven at 100 ° C. for 1 minute. It was dried and the organic solvent was removed. Then, the resin layer (B) of 1 μm was formed by irradiating with ultraviolet rays of ^{400 mJ / cm 2} using a high-pressure mercury lamp to obtain the laminate according to Example 1.
(Examples 2 to 25, Comparative Examples 1 to 7)
The laminates according to Examples 2 to 25 and Comparative Examples 1 to 7 were obtained by the same method as in Example 1.
Table 4 shows the results of various evaluations of each Example and Comparative Example.

<Manufacturing example of heat-resistant protective film>
An adhesive obtained by mixing "Siavine SH101" and "Siavine T-501B" manufactured by Toyo Chem Co., Ltd. in a solid content ratio of 100/20 is mixed with a 100 μm-thick easy-adhesive polyethylene terephthalate film (using a bar coater). It was applied on "Lumirror U403") manufactured by Toray Industries, Inc. Then, it was dried for 2 minutes using a hot air oven at 100 ° C. to remove the organic solvent to obtain a heat-resistant protective PET film provided with an adhesive layer of 5 μm.

<Manufacturing example of OCA film>
A 100 μm-thick easy-adhesive polyethylene terephthalate film (100 μm thick) was prepared by mixing Toyochem's “Olivine BPS5896” and “Olivine BXX5627” with a solid content of 100 / 0.5 and using a bar coater. It was applied on "Lumirror U403") manufactured by Toray Industries, Inc. Then, it was dried for 2 minutes using a hot air oven at 100 ° C. to remove the organic solvent, and an OCA film having an adhesive layer of 5 μm was obtained.

<Measurement of initial wetting tension>
The initial wetting tension of the main surface (F) (see FIG. 1) of the resin layer (B) before annealing of the laminates of each Example and Comparative Example was measured by the following procedure. That is, in an environment of 23 ° C. and a relative humidity of 50%, the wetting tension of the main surface (F) of the resin layer (B) is applied by using a dyne pen for checking the wetting property (test pen for evaluating the surface energy value) manufactured by Arcotest. I asked. Specifically, the laminated bodies (test pieces) of each Example and Comparative Example are placed on a glass plate, and 1 cm × 5 cm is placed on the main surface (F) of the resin layer (B) of the test piece using the Dyne pen. A degree of Dynepen liquid film was formed. Judgment was made by observing the liquid film of Dynepen in a bright place and in the state of the liquid film after 5 seconds. Those in which the short side of the liquid film was maintained at 95% or more were judged to be wet. When the wettability was maintained at 95% or more, the evaluation was made by proceeding to the next high surface tension Dyne pen, and conversely, when the wettability was not maintained at 95% or more, the evaluation was made by proceeding to the next low surface tension mixed solution. JIS K 6768 is known as another method for measuring wet tension. According to this measurement method, if the liquid film breaks within 2 seconds after applying Dyne Pen / Ink, it is judged to be NG, and this test method is a more accurate evaluation method. The wetting tension obtained by this test method tends to be smaller than that of JIS K6768.

<Measurement of wet tension after annealing>
The resin layer (B) of the laminated body of each Example and Comparative Example and the heat-resistant protective PET film obtained in the production example were allowed to stand in an environment of 23 ° C. and a relative humidity of 50% for 30 minutes, and then the resin layer ( The main surface (F) of B) and the adhesive layer of the heat-resistant protective PET film were bonded and attached using a 2 kg roller. Then, after performing an annealing treatment at 150 ° C. for 3 hours, the heat-resistant protective PET film was peeled off, and the wetting tension of the main surface (F) of the exposed resin layer (B) was adjusted by the same method as the initial wetting tension. It was measured.

<Measurement of haze value>
The curable composition (S) shown in Table 1 is coated on a 50 μm thick polyethylene terephthalate (Lumilar U403, manufactured by Toray Industries, Inc., haze value 1.1%, total light transmittance 91%) using a bar coater. , 100 ° C. for 1 minute. The active energy rays and the irradiation amount need to be appropriately changed depending on the type of the curable composition (S), but in this example and the comparative example, a high-pressure mercury lamp is used as a light source and the amount of light in the UVA ultraviolet region is 400 mJ /. A measurement sample having a resin layer (B) made of a cured film having a thickness of 1 μm was obtained by irradiating with ultraviolet rays of cm ^2. Then, the measurement sample (50 μm polyethylene terephthalate / resin layer (B)) according to each Example and Comparative Example was subjected to a haze meter (manufactured by Japanese Industrial Standards Co., Ltd., trade name “” in an environment of 23 ° C. and 50% RH. SH7000 ”) was used to determine the haze value according to JIS K 7136. The measurement was performed from the resin layer (B) side.

<Evaluation of anti-blocking property>
The measurement sample was prepared as follows. That is, a test piece obtained by cutting out the laminated body before the annealing treatment obtained above and the light-transmitting base material layer (A) in which the resin layer is not laminated to a size of 4 cm × 4 cm is prepared, and the resin of the laminated body is prepared. A permanent strain tester (trade name "CO-201 permanent strain tester (constant load type)", Nippon Tester Sangyo Co., Ltd. The product was placed on a test table and allowed to stand for 24 hours in an oven heated to 50 ° C. with a load of 200 kg. After that, immediately after removing the load, the ratio of the area where the overlapped surfaces of the test pieces are stuck together (a watermark (appearance that looks like water has entered) is formed) is set according to the following criteria. It was evaluated as blocking property (hereinafter, abbreviated as "AB property").
A: The area of sticking is 10% or less.
B: The area of sticking is more than 10% and less than 30%.
C: The area of sticking exceeds 30%.

<Evaluation of scratch resistance>
The resin layer of the laminate obtained above was set in a Gakushin tester so as to be a test surface, and the surface of the resin layer was made of steel wool No. It was rubbed 10 times at 0000 under the condition of a load of 200 g. 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 pieces.
B: 11 to 20 pieces.
C: 21 or more.

<Evaluation of OCA adhesion>
The measurement sample was prepared as follows. That is, the OCA films obtained from the laminates of the Examples and Comparative Examples before the annealing (initial stage) and the annealing and the production examples were allowed to stand in an environment of 23 ° C. and a relative humidity of 50% for 30 minutes. .. Next, the main surface (F) of the resin layer (B) and the adhesive layer of the OCA film were bonded together and bonded using a 2 kg roller. Then, a 180 ° peel test was performed at a speed of 300 mm / min with a tensile tester to measure the peel strength. From the obtained peel strength values, the adhesion was evaluated according to the following criteria.
A: Peeling strength is 25N or more.
B: Peeling strength is 10 N or more and less than 25 N.
C: Peeling strength is less than 10N.

In the laminated body having an initial wetting tension of less than 38 mN / m and a surface tension of less than 30 mNm after the annealing treatment, poor OCA adhesion was observed, for example, as shown in Comparative Example 1. Further, as shown in Comparative Example 3, the laminate having an initial wetting tension of more than 60 mN / m and a surface tension of more than 54 mN / m after the annealing treatment was found to have poor scratch resistance and anti-blocking property. rice field. Further, as shown in Comparative Example 4, it can be seen that when the content of the silica particles is large, the anti-blocking property is improved, but the haze value is lowered. On the other hand, according to this embodiment, the results are excellent in optical properties and scratch resistance, high yield even when manufactured by the roll-to-roll method, and excellent OCA adhesion regardless of the presence or absence of annealing treatment. It was confirmed that it could be obtained.

The laminate of the present invention is suitable as an optical film because it can provide a laminate having excellent adhesion to an OCA film and excellent anti-blocking property, scratch resistance and transparency. For example, a transparent electrode film obtained by laminating a transparent conductive layer on a laminated body is suitable as a touch panel member mounted on a guide plate of a smartphone, a tablet, a PC, a television, a car navigation system, a guide plate of other commercial facilities, a transportation ticket vending machine, or the like. Is. Further, since the resin layer (B) of the laminate of the present invention has excellent surface hardness, the surface of a flat panel display (FPD) such as a liquid crystal display (LCD), an organic EL display (OLED), or a plasma display (PDP) is scratched. It is also suitable as a preventive film.

Claims (6)

It has a laminated structure in which the resin layer (B) is laminated directly or via one or more other layers on at least one surface of the light-transmitting base material layer (A).
The resin layer (B) is a layer obtained by curing a curable composition (S) containing a curable compound (Q) exhibiting curability by active energy rays and silica particles (R).
In the laminated structure of the resin layer (B) having a thickness of 1 μm and the polyethylene terephthalate having a thickness of 50 μm, the haze value is 2.0% or less when measured from the surface layer side of the resin layer (B).
The main surface (F) of the resin layer (B) opposite to the light-transmitting base material layer (A) has an initial wetting tension of 38 to 60 mN / m before the annealing treatment is performed.
Further, a heat-resistant protective polyethylene terephthalate film is attached to the main surface (F) of the resin layer (B), an annealing treatment is performed at 150 ° C. for 3 hours, and the heat-resistant protective polyethylene terephthalate film is peeled off from the resin layer (B). Ri wet tension is 30~54mN / m der of the main surface (F),
The curable composition (S) is
(I) a curable compound as a (Q), containing a curable compound having at least one tertiary amino group and a quaternary ammonium salt (Q _N), and
(Ii) Contains a hydrophilizing agent (T) that does not show curability by active energy rays,
_{The hydrophilizing agent (T) contains a hydrophilizing agent (TN} ) having at least one of a tertiary amino group and a quaternary ammonium base.
A laminate that meets at least one of the above. Curable compound having at least one tertiary amino group and a quaternary ammonium salt (Q _N) is laminate according to claim 1 having a (meth) acryloyl groups. Curable compound having at least one tertiary amino group and a quaternary ammonium salt (Q _N), as well as tertiary amino group and a quaternary ammonium hydrophilic agent having at least one of the bases total content of (T _N) is, The laminate according to claim 1 or 2 , which is 3 to 40% by mass with respect to 100% by mass of the non-volatile component of the curable composition (S). The laminate according to any one of claims 1 to 3 , wherein the content of the silica particles (R) is 3 to 40% by mass with respect to 100% by mass of the non-volatile component of the curable composition (S). The transparent conductive layer and the laminate according to any one of claims 1 to 4 are provided.
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 either directly or via one or more layers. Transparent electrode film. The transparent electrode film according to claim 5 , wherein an optical transparent pressure-sensitive adhesive film is further laminated on a main surface of the resin layer (B) opposite to the light-transmitting base material layer (A) side.

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