TW201840431A - Antireflection laminate, and polarizing plate and image display device including same - Google Patents

Abstract

The present invention provides an antireflection laminate which can sufficiently suppress reflection of a keyboard due to a load, and which has excellent scratch resistance, and a polarizing plate and an image display device that include the same. This antireflection laminate is a laminate formed by laminating at least a resin film, a hard coat layer, and an inorganic oxide layer in this order, wherein the pencil hardness of the laminate is 4H or more, the stiffness thereof is 8.0 N.mm or more, and the Knoop hardness thereof is 150 to 300 mN/mm2.

Description

 Anti-reflection laminate, polarizing plate and image display device therewith  

The present invention relates to an antireflection laminate and a polarizing plate and an image display device having the antireflection laminate.

In order to prevent external light such as sunlight and fluorescent lamps from being reflected on the display screen, an anti-reflection film is provided on the front surface of an optical display device such as an LCD (Liquid Crystal Display), a CRT (Cathode Ray Tube Display), or a plasma display.

As an antireflection film having an antireflection layer, for example, Patent Document 1 discloses an antireflection film which is laminated on at least one surface of a polyethylene terephthalate film as a transparent base film. Made of coating and anti-reflection layer. In the antireflection film, the antireflection film has a haze of 0.4% or less, a total light transmittance of 92% or more, and a visual reflectance of 0.9% or less, and the base film, the hard coat layer, and the antireflection layer film have A specific range of film thickness. Further, Patent Document 2 discloses a laminate which is an antireflection laminate having an antireflection layer on a substrate, wherein the thickness of the antireflection layer is 100 nm or more, and the indentation hardness of the antireflection laminate is relative to the pressure. The intrusion test at a depth of 100 nm was 11 GPa or more and 15 GPa or less. Patent Document 3 describes an antireflection film in which a hard coat layer and an antireflection layer are sequentially formed on at least one surface of a transparent substrate. The antireflection film is formed with two or more hard coat layers, and the elastic modulus σ _m of the hard coat layer formed closest to the transparent substrate is higher than the elastic modulus σ _S of the hard coat layer of the surface layer.

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-92003

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-271958

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2000-214791

A representative example of a device including an optical display device is a notebook personal computer (notebook PC). In recent years, the thinning of the notebook PC has progressed, and as the thickness is reduced, a larger load is easily applied to the surface of the display in the state of folding the notebook PC.

It has been found that in a notebook PC having an anti-reflection film, a trace of a keyboard being transferred onto the surface of the display due to the above-described load is generated, or a foreign matter is caught between the display and the keyboard to cause a depression on the surface of the display, or scratches or the like ( The so-called "keyboard transfer" problem). Further, the problem of the keyboard transfer occurs in a smart phone or the like, for example, as a phenomenon in which the casing is transferred to the display.

As a result of intensive studies, the inventors have found that by increasing the pencil hardness of the surface film in the antireflection film, it is possible to suppress the keyboard transfer caused by the load. On the other hand, however, it has been found that when the surface hardness is increased, there is a new problem that the abrasion resistance of the antireflection film is deteriorated.

The present invention has been made in view of the above problems, and an object of the present invention is to provide an antireflection laminate which is excellent in abrasion resistance and which is excellent in abrasion resistance, and a polarizing plate having the antireflection laminate. Image display device.

The present inventors have conducted intensive studies to solve the above problems, and as a result, it has been found that the pencil hardness of the surface of the antireflection film and the rigidity of the entire antireflection film are increased to a specific value or more, and further, the antireflection film is further provided. The hardness is set to a specific range, which can effectively suppress keyboard transfer on the surface of the display, and can also impart sufficient rub resistance to the surface of the display.

The present invention has been completed in view of the above findings.

That is, the above problems are solved by the following means.

(1)

An anti-reflection laminate comprising at least a resin film, a one-side hard coat layer disposed on the resin film, and an inorganic oxide layer disposed on the hard coat layer, wherein the anti-reflection laminate body

The laminated body has a pencil hardness of 4H or more, a rigidity of 8.0 N‧ mm or more, and a Knoop hardness of 150 to 300 mN/mm ² .

(2)

The antireflection laminate according to the above aspect, wherein the polymerizable hardened body of the hard coat layer composition contains a polymerizable compound 1 having a radical polymerizable group, and is different from the polymerizable compound 1. The polymerizable compound 2 having a cationically polymerizable group and a radical polymerizable group in the same molecule and/or the polymerizable compound 3 having an alkoxy group and a radical polymerizable group in the same molecule.

(3)

The antireflection layered product according to the above aspect, wherein the content of the polymerizable compound 2 in all the polymerizable compounds contained in the composition is 30% by mass or more.

(4)

The antireflection laminate according to the above aspect, wherein the content of the polymerizable compound 3 in all the polymerizable compounds contained in the composition is 30% by mass or more.

(5)

The antireflection laminate according to any one of (2), wherein the cationically polymerizable group is an epoxy group.

(6)

The antireflection laminate according to (5), wherein the epoxy group is an alicyclic epoxy group.

(7)

The antireflection laminate according to any one of (2) to (6) wherein the alkoxy group is an ethoxy group.

(8)

The antireflection laminate according to any one of (1), wherein the hard coat layer has a thickness of 15 μm to 40 μm.

(9)

The antireflection laminate according to any one of (1) to (8) wherein the resin film has a thickness of from 80 μm to 250 μm.

(10)

A polarizing plate comprising the antireflection layered body according to any one of (1) to (9) and a polarizer.

(11)

An image display device comprising the antireflection laminate according to any one of (1) to (9).

In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

In the present specification, "(meth) acrylate" is used in the meaning of one or both of acrylate and methacrylate. Further, the "(meth)acrylonitrile group" is used in the sense of one or both of an acryloyl group and a methacryl group. "(Meth)acrylic acid" is used in the meaning of one or both of acrylic acid and methacrylic acid.

Each component described in the present specification may be composed of only one type, or two or more types of structures may be used in combination. In addition, when two or more types of structures are used in combination, the content of each component means the total content of these.

In the present specification, the weight average molecular weight (Mw) can be measured by GPC as a polystyrene-converted molecular weight unless otherwise specified. At this time, the GPC apparatus used HLC-8220 (manufactured by TOSOH CORPORATION), the column was G3000HXL+G2000HXL, and the RI was used at 23 ° C at a flow rate of 1 mL/min. As the eluent, it can be selected from THF (tetrahydrofuran), chloroform, NMP (N-methyl-2-pyrrolidone), m-cresol/chloroform (manufactured by Shonan Wako Pure Chemical Industries, Ltd.), if dissolved Use THF.

In the present specification, the thickness, modulus of elasticity, pencil hardness, specular reflectance, and Knoop hardness of each layer are measured by the methods described in the examples.

The antireflection laminate of the present invention can be suitably used as an antireflection film.

According to the present invention, the antireflection laminate of the present invention can sufficiently suppress the keyboard transfer accompanying the load, and is excellent in abrasion resistance. Further, the polarizing plate and the image display device of the present invention have the antireflection layered body of the present invention, and it is possible to sufficiently suppress the keyboard transfer accompanying the load and to exhibit excellent scratch resistance.

1A‧‧‧ resin film

2A‧‧‧hard coating (HC layer)

3A‧‧‧Inorganic oxide layer (AR layer)

4A, 4B‧‧‧ anti-reflection laminate

5A‧‧‧Bonded layer

1‧‧‧Electric film for touch panel

2‧‧‧ touch panel

3‧‧‧Bonded layer

4C‧‧‧Anti-reflective laminate

5‧‧‧Transparent insulating substrate

6A, 6B‧‧‧ conductive members

7A, 7B‧‧‧ protective layer

8‧‧‧1st conductive layer

9‧‧‧2nd conductive layer

11A‧‧‧1st dummy electrode

11‧‧‧1st electrode

12‧‧‧1st perimeter wiring

13‧‧‧1st external connection terminal

14‧‧‧1st connection

15‧‧‧1st metal thin line

21‧‧‧2nd electrode

22‧‧‧2nd perimeter wiring

23‧‧‧2nd external connection terminal

24‧‧‧2nd connection

25‧‧‧2nd metal wire

C1‧‧‧Unit 1

C2‧‧‧Unit 2

D1‧‧‧1st direction

D2‧‧‧2nd direction

M1‧‧‧1st grid pattern

M2‧‧‧2nd grid pattern

S1‧‧‧Active area

Surrounding area of S2‧‧

Fig. 1 is a longitudinal sectional view showing the configuration of an antireflection laminate of the present invention.

Fig. 2 is a longitudinal cross-sectional view showing an embodiment of a structure of an antireflection laminate of the present invention having a bonded layer.

Fig. 3 is a schematic cross-sectional view showing an embodiment of a capacitive touch panel.

4 is a schematic view of a conductive film for a touch panel.

Fig. 5 is a schematic view showing an intersection of the first electrode 11 and the second electrode 21 in Fig. 4 .

Fig. 6 is a schematic view showing an embodiment of the first dummy electrode 11A which the first conductive layer 8 in the active region S1 in Fig. 4 can have.

A preferred embodiment of the antireflection laminate of the present invention will be described.

[anti-reflection laminate]

A preferred embodiment of the antireflection laminate of the present invention is shown in Fig. 1. The antireflection laminate 4A shown in Fig. 1 has at least a resin film 1A, a hard coat layer (hereinafter also referred to as "HC layer") 2A disposed on the resin film 1A, and a layer disposed on the HC layer. An anti-reflection laminate of 3A on the inorganic oxide layer (hereinafter also referred to as "AR layer"). In the antireflection laminate of the present invention, the rigidity of the laminate is 8.0 N ‧ mm or more, the pencil hardness of the laminate is 4H or more, and the Knoop hardness of the laminate is 150 to 300 mN/mm ² .

According to the anti-reflection laminate of the present invention, it is possible to sufficiently suppress the keyboard transfer (the transfer of the keyboard trace, the occurrence of the depression, and the occurrence of scratches) accompanying the load, and it is possible to achieve excellent rub resistance. By setting the pencil hardness and rigidity of the laminated body to a specific value or more, it is possible to suppress keyboard transfer. On the other hand, if the hardness of the laminated body is high, sufficient abrasion resistance cannot be obtained. In the present invention, it is estimated that the frictional stress is relaxed by setting the Knoop hardness of the laminated body within a specific range, and the stress concentrated on the interface between the AR layer and the HC layer is dispersed, thereby suppressing the peeling of the AR layer. Improves rub resistance.

Further, the antireflection laminate of the present invention has an antireflection function. Specifically, the specular reflectance at 380 nm to 780 nm is preferably 1% or less.

(rigidity of anti-reflection laminate)

From the viewpoint of suppressing the transfer of the keyboard accompanying the load, particularly the transfer of the keyboard marks and the generation of the depression, the rigidity of the anti-reflection laminate is 8.0 N ‧ mm or more, preferably 9.0 N ‧ or more, 10 N ‧ More than mm is better. The upper limit is not particularly limited, but it is preferably 70 N ‧ or less, and more preferably 20 N ‧ or less.

(pencil hardness of the laminated body)

From the viewpoint of suppressing the occurrence of scratches accompanying the load, the pencil hardness of the laminate is 4H or more, and 5H or more is preferable.

(Knoop hardness of anti-reflection laminate)

The anti-reflection laminate has a Knoop hardness of 150 to 300 mN/mm ² , preferably 160 to 290 mN/mm ^{2 , and more} preferably 170 to 280 mN/mm ² from the viewpoint of rubbing resistance.

The Knoop hardness of the antireflection laminate can be adjusted by adjusting the Knoop hardness of the HC layer. The Knoop hardness of the HC layer can be adjusted by, for example, the type of the polymerizable mixture in the curable composition for forming an HC layer, the blending ratio, etc., and from the viewpoint of rubbing resistance, 150 to 300 mN/mm ² is preferable. 170~280mN/mm ² is better.

(thickness)

The thickness of the resin film and the HC layer constituting the antireflection laminate of the present invention can be appropriately adjusted according to the present invention.

Here, the rigidity of the anti-reflection laminate can be adjusted by the elastic modulus and thickness of each layer, and the pencil hardness of the laminate can be adjusted by the elastic modulus and thickness of the HC layer. However, from the viewpoint of adjusting the Knoop hardness of the antireflection laminate to an appropriate range, the thickness of the thickened layer is preferable.

Specifically, the thickness of the resin film is preferably 80 μm or more, and the thickness of the HC layer is preferably 10 μm or more. In addition, from the viewpoint of the toughness, the resin film is preferably 250 μm or less, and from the viewpoint of suppressing occurrence of curl and toughness, the HC layer is preferably 40 μm or less.

In summary, the thickness of the resin film is preferably from 80 to 250 μm, more preferably from 90 to 200 μm, and further preferably from 100 to 180 μm. Further, the thickness of the HC layer is preferably 10 to 40 μm, more preferably 15 to 40 μm, and further preferably 20 to 35 μm.

The thickness of the antireflection laminate of the present invention is preferably 90 μm or more, more preferably 100 μm or more, and still more preferably 110 μm or more. The upper limit is 300 μm or less.

(elastic modulus)

From the viewpoint of rigidity, the elastic modulus of the HC layer is preferably high, and from the viewpoint of adjusting the Knoop hardness to an appropriate range, 3 to 20 GPa is preferable, and 5 to 15 GPa is further preferable.

From the viewpoint of toughness, the elastic modulus of the resin film is preferably from 3 to 15 GPa, and further preferably from 3 to 10 GPa.

In the antireflection laminate of the present invention, the resin film, the HC layer, the AR layer, and the like may be a single layer or a plurality of layers.

Further, in the antireflection laminate of the present invention, the resin film may be isotropic or anisotropic.

Hereinafter, the components and preparation of the film and layer constituting the antireflection laminate of the present invention will be described in detail.

(1) Resin film

(Material of resin film)

The material of the resin film used in the present invention is not particularly limited.

Examples of the resin film include a cellulose resin film such as an acrylic resin film, a polycarbonate (PC) resin film, and a triacetyl cellulose (TAC) resin film, and polyethylene terephthalate (PET). a resin film, a polyolefin resin film, a polyester resin film, and an acrylonitrile-butadiene-styrene copolymer film selected from the group consisting of an acrylic resin film, a cellulose ester resin film, and polyethylene terephthalate The film of the diester resin film and the polycarbonate resin film is preferable, and the cellulose ester resin film is more preferable from the viewpoint of moisture permeability.

In addition, the acrylic resin film refers to a resin film of a polymer or copolymer selected from one or more compounds selected from the group consisting of acrylates and methacrylates. An example of the acrylic resin film is a polymethyl methacrylate resin (PMMA) film.

The weight average molecular weight of the resin is preferably from 10,000 to 1,000,000, more preferably from 100,000 to 1000,000.

(Composition of resin film)

Further, the configuration of the resin film is not limited, and may be a single layer or a laminated film including two or more layers, but a laminated film of two or more layers is preferable. The number of laminated layers of the laminated film is preferably 2 to 10 layers, more preferably 2 to 5 layers, and further preferably 2 or 3 layers. In the case of three or more layers, a layer other than the outer layer and the outer layer (core layer or the like) is preferably a film having a different composition. Further, a film having the same outer layer and the same composition is preferable.

Specifically, a film and a polycarbonate having a laminate structure of TAC-a/TAC-b/TAC-a, acrylic-a/PC/acrylic-a, and PET-a/PET-b/PET-a may be mentioned. A film of a single layer of resin. Here, a film (for example, Tac-a) denoted by the same symbol (a or b) means a film of the same composition.

(additive)

The resin film may contain an additive in addition to the above resin. Examples of the additive include inorganic particles, matting particles, an ultraviolet absorber, a fluorine-containing compound, a surface conditioner, and a leveling agent described in the hard coat layer to be described later.

In the melt film forming method to be described later, the resin melt obtained by mixing and melting the above additive and resin can be used for the formation of a resin film. In the solution film forming method to be described later, a thick slurry obtained by mixing a solvent (which can be described in the hard coat layer described later), a resin, and the above-mentioned additives can be used for the formation of the resin film.

(thickness of resin film monomer)

The thickness of the resin film hardly changes before and after the production of the antireflection laminate of the present invention.

(easy adhesion layer)

Further, the resin film used in the present invention may have an easy-adhesion layer on the surface opposite to the surface having the HC layer.

The content of the method for producing the polarizer-side easy-adhesion layer and the polarizer-side easy-adhesion layer described in paragraphs 0098 to 0133 of JP-A-2015-224267 can be incorporated into the present invention. In the manual.

In this case, the easy-adhesion layer is a layer constituting the resin film in the anti-reflection laminate of the present invention.

(Method of film formation of resin film)

The resin film can be formed by any method, and examples thereof include a melt film forming method and a solution film forming method.

<Fused film forming method, smoothing>

When the film formation of the resin film is carried out by the melt film formation method, it is preferable to include a melting process of melting the resin by an extruder, a process of extruding the molten resin from a die into a sheet form, and a process of forming into a film shape. Depending on the material of the resin, a filtration process of the molten resin can be provided after the melting process, and cooling can be performed when extruded into a sheet form.

Hereinafter, a specific solution film forming method will be described, but the present invention is not limited thereto.

[Method of Forming Resin Film]

The method for producing a resin film includes: a melting process of melting a resin by an extruder; a filtration process of filtering the molten resin through a filter device provided with a filter; and extruding the filtered resin from a die into a sheet, borrowing A film forming process for forming an unstretched resin film by cooling and solidifying it on a cooling drum, and a stretching process of uniaxially or biaxially stretching the unstretched resin film.

According to this configuration, a resin film can be produced. When the pore diameter of the filter used in the filtration process of the molten resin is 1 μm or less, foreign matter can be sufficiently removed. As a result, the surface roughness of the obtained resin film in the film width direction can be controlled.

Specifically, the method of forming the resin film includes the following process.

<Melting process>

The method for producing the above resin film includes a melting process of melting a resin with an extruder.

After the resin or the mixture of the resin and the additive is dried to a water content of 200 ppm or less, it is preferably introduced into a monoaxial or biaxial extruder to be melted. At this time, in order to suppress decomposition of the resin, it is preferred to carry out the melting in nitrogen or in a vacuum. The detailed conditions can be referred to in Japanese Patent No. 4,962,266, <0051> to <0052> (<0085> to <0086> of US2013/0100378), and the contents described in the publications are incorporated herein. In the manual.

The extruder is preferably a uniaxial kneading extruder.

Further, in order to improve the delivery accuracy of the molten resin (melt), it is also preferable to use a gear pump.

<Filter Process>

The method for producing a resin film includes a filtration process in which a molten resin is filtered by a filter device provided with a filter, and a filter having a pore size of 1 μm or less is preferably used.

The filter device having the filter of such a pore size range may be provided in only one set or two or more sets in the filtration process.

<Film forming process>

The method for producing a resin film includes a film forming process in which a filtered resin is extruded from a die into a sheet shape, and is cooled and solidified by being adhered to a cooling drum to form an unstretched film. Resin film.

When melting (and kneading) is carried out and the filtered resin (melt containing the resin) is extruded into a sheet form from a mold, it may be extruded in a single layer or in a plurality of layers. When extruded in a plurality of layers, for example, a layer containing an ultraviolet absorber and a layer containing no ultraviolet absorber may be laminated, and more preferably, the ultraviolet absorber may be used as a three-layer structure of the inner layer to suppress deterioration of the polarizer caused by ultraviolet rays. On the basis of this, it is preferable to suppress the bleeding of the ultraviolet absorber.

When the resin film is produced by multilayer extrusion, the thickness of the preferred inner layer of the obtained resin film is preferably 50% or more and 99% or less with respect to the thickness of all the layers, more preferably 60% or more and 98%. Hereinafter, it is more preferably 70% or more and 97% or less. Such a laminate can be implemented by using a feed block die or a multi-manifold die.

According to <0059> of JP-A-2009-269301, a resin (a melt containing a resin) extruded from a die is extruded on a cooling drum (casting drum), and cooled and solidified to obtain an A stretched resin film (rolled film) is preferred.

In the method for producing a resin film, the temperature of the resin extruded from the mold is preferably 280 ° C or more and 320 ° C or less, and more preferably 285 ° C or more and 310 ° C or less. When the temperature of the resin extruded from the die in the melting process is 280 ° C or more, it is preferable to reduce the melt residue of the raw material resin and suppress the generation of foreign matter. When the temperature of the resin extruded from the die in the melting process is 320 ° C or less, the decomposition of the resin can be reduced to suppress the generation of foreign matter, which is preferable.

Regarding the temperature of the resin extruded from the mold, the surface of the resin can be measured in a non-contact manner using a radiation thermometer (manufactured by Hayashi Denko Co., Ltd., model: RT61-2, used at an emissivity of 0.95).

In the method for producing a resin film, it is preferred to use an electrostatic application electrode when the resin is adhered to the cooling drum in the film forming process. Thereby, the resin can be strongly adhered to the cooling drum to prevent the film from being roughened.

In the method for producing a resin film, the temperature of the resin when the resin is adhered to the cooling drum (the point at which the molten resin extruded from the mold first comes into contact with the cooling drum) is preferably 280 ° C or higher. Thereby, the conductivity of the resin is improved, and it is possible to strongly adhere to the cooling drum by electrostatic application, and it is possible to suppress surface roughness of the film.

Regarding the temperature of the resin when it is intimately attached to the cooling drum, the surface of the resin can be measured in a non-contact manner by using a radiation thermometer (manufactured by Hayas Hi Denko Co., Ltd., model: RT61-2, at an emissivity of 0.95). .

<Stretching Process>

The method for producing the above resin film includes a stretching process of uniaxially or biaxially stretching the unstretched resin film.

In the longitudinal stretching process (the process of stretching in the same direction as the film conveying direction), after the resin film is preheated, the resin film is heated, and the peripheral speed difference is used (that is, the conveying speed is different) The roller set is stretched in the conveying direction.

The preheating temperature in the longitudinal stretching process is preferably Tg-40 ° C or more and Tg + 60 ° C or less with respect to the glass transition temperature (Tg) of the resin film, and Tg-20 ° C or more and Tg + 40 ° C or less. More preferably, Tg or more and Tg + 30 ° C or less are further preferable. Further, the stretching temperature in the longitudinal stretching process is preferably Tg or more and Tg + 60 ° C or less, more preferably Tg + 2 ° C or more and Tg + 40 ° C or less, and Tg + 5 ° C or more and Tg + 30 ° C or less. It is further preferred. The stretching ratio in the longitudinal direction is preferably 1.0 times or more and 2.5 times or less, and more preferably 1.1 times or more and 2 times or less.

The transverse stretching process is performed in the width direction by a longitudinal stretching process and a transverse stretching process (a process of stretching in a direction perpendicular to the conveying direction of the film) or by a transverse stretching process instead of the longitudinal stretching process. In the transverse stretching process, for example, a tenter can be suitably used, and both ends of the resin film in the width direction are gripped by a clip and stretched in the lateral direction.

The transverse stretching is preferably carried out using a tenter. The preferred stretching temperature is relative to the glass transition temperature (Tg) of the resin film, preferably Tg or more and Tg + 60 ° C or less, more preferably Tg. +2 ° C or more and Tg + 40 ° C or less, more preferably Tg + 4 ° C or more and Tg + 30 ° C or less. The stretching ratio is preferably 1.0 times or more and 5.0 times or less, and more preferably 1.1 times or more and 4.0 times or less. It is also preferred to perform relaxation in either or both of the longitudinal direction and the transverse direction after the transverse stretching.

Further, the variation in the thickness in the width direction and the longitudinal direction is 10% or less, preferably 8% or less, more preferably 6% or less, further preferably 4% or less, and most preferably 2% or less. good.

Here, the variation in thickness can be obtained as follows.

The stretched resin film was sampled by 10 m (meter), and both end portions in the film width direction were removed by 20%, and 50 points were sampled at equal intervals in the width direction and the longitudinal direction from the film center portion, and the thickness was measured.

Find the thickness average value Th _TD-av , the maximum value Th _TD-max , the minimum value Th _TD-min , (Th _TD-max -Th _TD-min ) ÷Th _TD-av ×100[%] in the width direction

The variation in thickness in the width direction.

Further, the thickness average value Th _MD-av , the maximum value Th _MD-max , the minimum value Th _MD-min , (Th _MD-max -Th _MD-min ) ÷Th _MD-av ×100 [%] in the longitudinal direction are obtained.

The change in thickness in the longitudinal direction.

The thickness precision of the resin film can be improved by the above stretching process.

The stretched resin film can be wound into a roll shape during the winding process. At this time, it is preferable that the winding tension of the resin film is 0.02 kg/mm ² or less.

In the case of the melt-forming film, the content described in <0134>-<0148> of JP-A-2015-224267 is incorporated into the present specification by the present invention, and the Japanese patent is opened for the drawing process. The contents described in 2007-137028 are incorporated herein by reference.

<solution film forming method, smoothing>

When the resin film is formed by the solution film forming method, it is preferable to include a process of casting a thick slurry on a casting tape to form a cast film, a process of drying a cast film, and a process of stretching a cast film. Specifically, it is preferred to form a film by the method described in Japanese Patent No. 4889335.

In the present invention, the following method is preferred.

For example, the method described in Japanese Laid-Open Patent Publication No. H11-123732, the drying rate of the cast film is 300% by mass/min based on the dry amount of the solvent (= 5 mass%/s) ) Slowly dry below. Further, a method described in Japanese Laid-Open Patent Publication No. 2003-276037 is proposed in which a co-casting method of a cast film having a multilayer structure having a surface layer (outer layer) on both surfaces of a core layer of an intermediate layer is improved. The viscosity of the thick slurry of the core layer is formed to ensure the strength of the cast film and to lower the viscosity of the thick paste forming the outer layer. Further, a method of rapidly drying the cast film, forming a film on the surface of the cast film, smoothing the surface by the leveling effect of the formed film, and a method of stretching the cast film may be preferably used.

(2) Hard coating (HC layer)

The antireflection laminate of the present invention has a hard coat layer (HC layer) on one side of the resin film. The type and the like of the curable composition used for the formation of the HC layer are appropriately selected or the elastic modulus and thickness of the HC layer are adjusted so that the pencil hardness and the Knoop hardness of the laminate are set to predetermined values.

The HC layer used in the present invention can be obtained by curing an active energy ray by irradiating a curable composition for forming a HC layer. In addition, in the present invention and the present specification, "active energy ray" means ionizing radiation, and includes X-rays, ultraviolet rays, visible light, infrared rays, electron beams, alpha rays, beta rays, gamma rays, and the like.

The curable composition for forming an HC layer used for the formation of the HC layer contains at least one component (hereinafter also referred to as "active energy ray-curable component") having a property of being cured by irradiation with an active energy ray. The active energy ray-curable component is preferably at least one polymerizable compound selected from the group consisting of a radical polymerizable compound and a cationically polymerizable compound. In the present invention and the present specification, the "polymerizable compound" is a compound containing one or more polymerizable groups in one molecule. The polymerizable group is a group which can participate in the polymerization reaction, and as a specific example, a group included in various polymerizable compounds to be described later can be exemplified. Further, examples of the polymerization reaction include various polymerization reactions such as radical polymerization, cationic polymerization, and anionic polymerization.

The HC layer used in the present invention may have a single layer structure or a laminated structure of two or more layers. However, the HC layer including a one-layer structure or a two-layer or more laminated structure as described in detail below is preferable.

1) 1-layer structure

In a preferred aspect of the curable composition for forming a HC layer having a one-layer structure, the first aspect includes at least one polymerizable group having two or more ethylenically unsaturated groups in one molecule. A curable composition for forming a HC layer of a compound. The ethylenically unsaturated group means a functional group containing an ethylenically unsaturated double bond. Further, the second aspect of the invention is a curable composition for forming an HC layer comprising at least one radical polymerizable compound and at least one cationically polymerizable compound.

Hereinafter, the curable composition for forming a HC layer of the first aspect will be described.

The polymerizable compound having two or more ethylenically unsaturated groups in one molecule contained in the curable composition for forming a layer for forming a HC layer according to the first aspect may, for example, be a polyol or a (meth)acrylic acid. Ester (for example, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, 1,4-cyclohexanediacrylate, neopentyl Tetraol tetra (meth) acrylate, neopentyl alcohol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, two Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol hexa(meth)acrylate, 1,2,3-cyclohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate], ethylene oxide modified body of the above ester, polyethylene oxide modified body or caprolactone Modified body, vinyl benzen and its derivatives [Example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-propenylethyl ester, 1,4-divinylcyclohexanone 〕, vinyl hydrazine (example) Divinyl sulfone), acrylamide (for example, methylene bis acrylamide) and methyl acrylamide.

The polymerization of the polymerizable compound having an ethylenically unsaturated group can be carried out by irradiation with an active energy ray in the presence of a radical photopolymerization initiator. As the radical photopolymerization initiator, a radical photopolymerization initiator described later can be preferably used. In addition, the content ratio of the radical photopolymerization initiator to the polymerizable compound having an ethylenically unsaturated group in the curable composition for forming a layer of HC can be preferably applied to the radical photopolymerization initiator described later. The content ratio of the radically polymerizable compound is described.

Next, a curable composition for forming a second layer of HC layer will be described.

The curable composition for forming a HC layer of the second aspect contains at least one radical polymerizable compound and at least one cationically polymerizable compound. As a preferred aspect, the curable composition for forming an HC layer comprising: two or more members selected from the group consisting of a propylene group and a methacryl group in one molecule a radical polymerizable compound of a base polymerizable group; and a cationically polymerizable compound.

The curable composition for forming a HC layer described above preferably contains a radical photopolymerization initiator and a cationic photopolymerization initiator. A preferred embodiment of the second aspect is a curable composition for forming an HC layer, comprising: two or more selected from the group consisting of an acrylonitrile group and a methacryl fluorenyl group in one molecule. a radically polymerizable compound of a radical polymerizable group in the group; a cationically polymerizable compound; a radical photopolymerization initiator; and a cationic photopolymerization initiator.

Hereinafter, this aspect will be described as the second aspect (1).

In the second aspect (1), the radical polymerizable compound contains two or more radical polymerizable groups in one molecule, and one or more urethane bonds are contained in one molecule. Preferably.

In another preferred aspect of the second aspect, the curable composition for forming an HC layer comprising: a) an alicyclic epoxy group and an ethylenically unsaturated group, and one molecule The number of the alicyclic epoxy groups contained in the one is one, and the number of the ethylenically unsaturated groups contained in one molecule is one, and the cationically polymerizable compound having a molecular weight of 300 or less; b) in one a radically polymerizable compound containing three or more ethylenically unsaturated groups in the molecule; c) a radical polymerization initiator; and d) a cationic polymerization initiator.

Hereinafter, this aspect will be described as the second aspect (2). The HC layer obtained by curing the curable composition for forming the HC layer of the second aspect (2) preferably has a structure derived from the above a) when the total solid content of the HC layer is 100% by mass. 15 to 70% by mass, 25 to 80% by mass of the structure derived from the above b), 0.1 to 10% by mass of the above c), and 0.1 to 10% by mass of the above d). In addition, in the first aspect, the curable composition for forming an HC layer of the second aspect (2) includes the above a) when the total solid content of the curable composition for forming a HC layer is 100% by mass. 15 to 70% by mass is preferred. Further, the "alicyclic epoxy group" means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.

Hereinafter, various components which can be contained in the curable composition for forming a HC layer of the second aspect, preferably the second aspect (1) or the second aspect (2) will be described in further detail.

- Radical polymerizable compound -

The curable composition for forming a second layer of HC layer contains at least one radically polymerizable compound and at least one cationically polymerizable compound. The radically polymerizable compound in the second aspect (1) contains, in one molecule, two or more radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryl group. The radically polymerizable compound may include, in one molecule, preferably, for example, 2 to 10 radical polymerizable groups selected from the group consisting of a acrylonitrile group and a methacryl fluorenyl group, and more preferably 2 ~6.

As the radically polymerizable compound, a radically polymerizable compound having a molecular weight of 200 or more and less than 1,000 is preferred. Further, in the present invention and the present specification, "molecular weight" means a weight average molecular weight measured by gel permeation chromatography (GPC) in terms of polystyrene for a polymer. Examples of specific measurement conditions of the weight average molecular weight include the following measurement conditions.

GPC device: HLC-8120 (manufactured by TOSOH CORPORATION)

Column: TSK gel Multipore HXL-M (manufactured by TOSOH CORPORATION, inner diameter 7.8mm × column length 30.0cm)

Eluent: tetrahydrofuran

As described above, the radical polymerizable compound preferably contains one or more urethane bonds in one molecule. The number of the urethane bonds contained in one molecule of the radical polymerizable compound is preferably one or more, more preferably two or more, still more preferably two to five, and for example, two. Further, among the radically polymerizable compounds containing two urethane bonds in one molecule, the radical polymerizable group selected from the group consisting of an acryloyl group and a methacryl group may be directly or via The linker is only bonded to a urethane bond, and may also be bonded to the two urethane bonds, either directly or via a linker. In one aspect, one or more radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryl fluorenyl group are bonded to each of two urethane bonds bonded via a linking group. It is better.

More specifically, in the above radical polymerizable compound, the urethane bond may be directly bonded to a radical polymerizable group selected from the group consisting of an acryloyl group and a methacryl fluorenyl group, or may be directly bonded. A linking group is present between the urethane bond and a radical polymerizable group selected from the group consisting of an acryloyl group and a methacryl group. The linking group is not particularly limited, and examples thereof include a linear or branched saturated or unsaturated hydrocarbon group, a cyclic group, and a group containing two or more of these. The carbon number of the hydrocarbon group is, for example, about 2 to 20, but is not particularly limited. In addition, examples of the cyclic structure contained in the cyclic group include an aliphatic ring (such as a cyclohexane ring) and an aromatic ring (such as a benzene ring or a naphthalene ring). The above group may be unsubstituted or may have a substituent. Further, in the present invention and the present specification, the groups described may have a substituent or may be unsubstituted, unless otherwise specified. When a certain group has a substituent, examples of the substituent include an alkyl group (for example, an alkyl group having 1 to 6 carbon atoms), a hydroxyl group, an alkoxy group (for example, an alkoxy group having 1 to 6 carbon atoms), and a halogen. An atom (for example, a fluorine atom, a chlorine atom or a bromine atom), a cyano group, an amine group, a nitro group, a fluorenyl group, a carboxyl group or the like.

The radically polymerizable compound described above can be synthesized by a known method. Moreover, it can also be obtained as a commercial item. For example, as an example of the synthesis method, a method of reacting a hydroxyl group-containing compound such as an alcohol, a polyol, and/or a hydroxyl group-containing (meth)acrylic acid with an isocyanate or, if necessary, using (meth)acrylic acid, may be mentioned. The urethane compound obtained by the above reaction is esterified. Further, "(meth)acrylic acid" means one or both of acrylic acid and methacrylic acid.

The commercially available product of the radically polymerizable compound containing one or more urethane bonds in one molecule is not limited to the following, and may be, for example, KYOEISHA CHEMICAL Co., Ltd. UA-306H, UA-306I, UA-306T, UA-510H, UF-8001G, UA-101I, UA-101T, AT-600, AH-600, AI-600, BPZA-66, BPZA-100, Shin- U-4HA, U-6HA, U-6LPA, UA-32P, U-15HA, UA-1100H, Nippon Synthetic Chemical Industry Co., Ltd. manufactured by Nakamura Chemical Co., Ltd., UV-1400B, violet UV-1700B, violet UV-6300B, violet UV-7550B, violet UV-7600B, violet UV-7605B, violet UV-7610B, violet UV-7620EA, violet UV-7630B, violet UV-7640B, violet UV-6630B, violet UV-7000B, violet UV-7510B, violet UV-7461TE, violet UV-3000B, violet UV-3200B, violet UV-3210EA, violet UV-3310EA, violet UV-3310B, violet UV-3500BA, violet UV-3520TL, violet UV-3700B, violet UV-6100B, violet UV-6640B, violet UV-2000B, violet UV-2010B, violet UV-2250EA. Further, violent UV-2750B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., UL-503LN manufactured by KYOEISHA CHEMICAL Co., Ltd., UNIDIC 17-806 manufactured by Dainippon Ink and Chemicals, Inc., UNIDIC can also be cited. 17-813, UNIDIC V-4030, UNIDIC V-4000BA, EB-1290K manufactured by Daicel UCB Co., Ltd., HI-COAP AU-2010, HI-COAP AU-2020 manufactured by TOKUSHIKI CO., Ltd., and the like.

In the following, as a specific example of the radically polymerizable compound containing one or more urethane bonds in one molecule, the exemplified compounds A-1 to A-8 are shown, but the present invention is not limited to the following. Specific examples are described.

[Chemical Formula 1]

[Chemical Formula 2]

In the above, a radically polymerizable compound containing one or more urethane bonds in one molecule has been described. However, two or more molecules including at least one selected from the group consisting of acrylonitrile and methacrylic acid are included in one molecule. The radically polymerizable compound of the radical polymerizable group in the group of the group may also be a group having no urethane bond. Further, the curable composition for forming an HC layer of the second aspect (1) includes two or more radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryl fluorenyl group in one molecule. In addition to the radically polymerizable compound, one or more kinds of radical polymerizable compounds other than the radical polymerizable compound may be contained.

In the following, two or more radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryl fluorenyl group are contained in one molecule, and one or more urethanes are contained in one molecule. The radically polymerizable compound of the bond is described as a "first radical polymerizable compound", and whether or not a radical polymerization of two or more groups selected from the group consisting of an acryloyl group and a methacryl group is included in one molecule The radically polymerizable compound which does not belong to the first radical polymerizable compound is described as a "second radical polymerizable compound". The second radical polymerizable compound may have one or more urethane bonds in one molecule or may not have a urethane bond. When the first radical polymerizable compound and the second radical polymerizable compound are used in combination, the mass ratio is the first radical polymerizable compound/second radical polymerizable compound = 3/1 to 1/30. Preferably, 2/1 to 1/20 is better, and 1/1 to 1/10 is further preferred.

The free form of the curable composition for forming an HC layer of the second aspect (1) includes two or more radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryl group. The content of the base polymerizable compound (with or without a urethane bond) is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more based on 100% by mass of the total amount of the composition. . Further, in the curable composition for forming an HC layer of the second aspect (1), two or more radical polymerizable groups selected from the group consisting of a propylene group and a methacryl group are contained in one molecule. The content of the radically polymerizable compound (with or without a urethane bond) is preferably 100% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass based on 100% by mass of the total amount of the composition. %the following.

In addition, the content of the first radical polymerizable compound of the curable composition for forming an HC layer of the second aspect (1) is preferably 100% by mass or more, more preferably 30% by mass or more, more preferably 50% by mass based on the total amount of the composition. The mass% or more is more preferably 70% by mass or more. On the other hand, the content of the first radically polymerizable compound is preferably 100% by mass or less based on the total amount of the composition, 98% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less.

In one aspect, the second radical polymerizable compound is preferably a radically polymerizable compound containing two or more radical polymerizable groups in one molecule and having no urethane bond. The radical polymerizable group contained in the second radical polymerizable compound is preferably an ethylenically unsaturated group, and a vinyl group is preferred in one aspect. In other aspects, the ethylenically unsaturated group is preferably a radical polymerizable group selected from the group consisting of an acryloyl group and a methacryl group. In other words, the second radical polymerizable compound has one or more radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryl fluorenyl group in one molecule and does not have a urethane bond. It is also better. In addition, the second radical polymerizable compound may contain one or more radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryl group in one molecule as a radically polymerizable compound. One or more of the radical polymerizable groups other than the above.

The number of the radical polymerizable groups contained in one molecule of the second radical polymerizable compound is preferably at least 2, more preferably 3 or more, still more preferably 4 or more. Further, in one aspect, the number of the radical polymerizable groups contained in one molecule of the second radical polymerizable compound is, for example, 10 or less, but may be more than 10. Further, as the second radical polymerizable compound, a radically polymerizable compound having a molecular weight of 200 or more and less than 1,000 is preferable.

As the second radical polymerizable compound, for example, the following can be exemplified. However, the present invention is not limited to the following exemplified compounds.

For example, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 300 di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, polyethylene glycol 600 two (Meth) acrylate, triethylene glycol di(meth) acrylate, epichlorohydrin modified ethylene glycol di(meth) acrylate (commercially available, for example, manufactured by NAGASE & CO., LTD.) De nacol DA-811, etc.), polypropylene glycol 200 di(meth)acrylate, polypropylene glycol 400 di(meth)acrylate, polypropylene glycol 700 di(meth)acrylate, ethylene oxide (EO; Ethylene Oxide) ‧ propylene oxide (PO; Propylene Oxide) block polyether di(meth) acrylate (as a commercial product, such as the BLEMMER PET series manufactured by Nippon Oil & Eats Co., Ltd.), dipropylene glycol II ( Methyl acrylate, bisphenol A EO, and bis (meth) acrylate (as a commercial product, for example, M-210 manufactured by TOAGOSEI CO., LTD., NK Ester manufactured by Shin-Nakamura Chemical Co., Ltd.) A-BPE-20, etc., hydrogenated bisphenol AEO addition di(meth)acrylate (NK Ester A-HPE-4, manufactured by Shin-Nakamura Chemical Co., Ltd.), bisphenol A PO addition molding II Methyl) propyl An enoate (a commercially available product such as LIGHT ACRYLATE BP-4PA manufactured by KYOEISHA CHEMICAL Co., LTD.), bisphenol A epichlorohydrin plus a di(meth) acrylate (as a commercial product such as Daicel) Ebecryl 150 manufactured by UCB Co., Ltd., etc.), bisphenol A EO‧PO addition bis(meth) acrylate (as a commercial product, for example, BP-023-PE manufactured by Toho Chemical Industry Co., Ltd.) Etc.), bisphenol F EO plus di(meth) acrylate (as a commercial product such as ARONIX M-208 manufactured by TOAGOSEI CO., LTD.), 1,6-hexanediol di(methyl) Acrylate and its epichlorohydrin modification, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate and its caprolactone modification, 1,4 - Butanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, tricyclodecane dimethanol di(methyl) ) acrylate, pentaerythritol di(meth) acrylate monostearate, trimethylolpropane acrylate benzoate, isocyanuric acid EO modified di(meth) acrylate (as city For sale, such as ARONI manufactured by TOAGOSEI CO., LTD. A bifunctional (meth) acrylate compound such as X M-215 or the like.

Further, trimethylolpropane tri(meth)acrylate and EO, PO, epichlorohydrin modified product, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate may be mentioned. And EO, PO, epichlorohydrin modified product, isocyanuric acid EO modified tri(meth) acrylate (as a commercial product, such as ARONIX M-315 manufactured by TOAGOSEI CO., LTD., etc.), three (Meth) propylene methoxyethyl phosphate, hydrogen (2-(2,2,2-tri-(methyl) propylene methoxymethyl) ethyl phthalate, glycerol tri(meth) acrylate And its EO, PO, epichlorohydrin modified products and other trifunctional (meth) acrylate compounds; neopentyl alcohol tetra (meth) acrylate and its EO, PO, epichlorohydrin modification, ditrihydroxy a tetrafunctional (meth) acrylate compound such as methyl propane tetra(meth) acrylate; dipentaerythritol penta (meth) acrylate and its EO, PO, epichlorohydrin, fatty acid, alkyl modified product Equivalent 5-functional (meth) acrylate compound; dipentaerythritol hexa(meth) acrylate and its EO, PO, epichlorohydrin, fatty acid, alkyl modification, sorbitol hexa(meth) acrylate Ester and its EO, PO, epichlorohydrin, fatty acid, alkane Modified products such as 6-functional (meth) acrylate.

Two or more kinds of second radical polymerizable compounds may also be used in combination. In this case, a mixture "DPHA" (manufactured by Nippon Kayaku Co., Ltd.) or the like of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate can be preferably used.

Further, as the second radical polymerizable compound, a polyester (meth) acrylate or an epoxy (meth) acrylate having a weight average molecular weight of 200 or more and less than 1,000 is also preferable. Among the commercially available products, as the polyester (meth) acrylate, a product name of Beam set 700 manufactured by Arakawa Chemical Industries, Ltd., for example, Beam set 700 (6-functional), Beam set 710 (4-functional) can be mentioned. , Beam set 720 (3 functional) and so on. Further, examples of the epoxy (meth) acrylate include a product name SP series manufactured by Showa Polymer Co., Ltd., for example, SP-1506, 500, SP-1507, 480, VR series, for example, VR-77, Trade names manufactured by Shin-Nakamura Chemical Co., Ltd. are EA-1010/ECA, EA-11020, EA-1025, EA-6310/ECA, and the like.

Further, specific examples of the second radical polymerizable compound include the following exemplified compounds A-9 to A-11.

The second aspect of the second aspect (2) of the second layer (2) has a curable composition for forming an HC layer comprising b) a radical containing three or more ethylenically unsaturated groups in one molecule. Polymeric compound. Hereinafter, b) a compound containing three or more ethylenically unsaturated groups in one molecule is also referred to as a "b) component.

Examples of the component b) include esters of polyhydric alcohols and (meth)acrylic acid, vinylbenzene and derivatives thereof, vinyl anthracene, (meth)acrylamide, and the like. Among them, a radically polymerizable compound containing three or more radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryl fluorenyl group in one molecule is preferable. Specific examples thereof include a compound having three or more ethylenically unsaturated groups in one molecule as an ester of a polyhydric alcohol and (meth)acrylic acid. More specifically, for example, (di) pentaerythritol tetra(meth)acrylate, (b) pentaerythritol tri(meth)acrylate, trimethylolpropane tri(methyl) may be mentioned. Acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, EO modified tris(meth)acrylate, trishydroxyl Ethylene tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, (b)pentaerythritol penta(methyl) Acrylate, dipentaerythritol hexa(meth) acrylate, neopentyl alcohol hexa(meth) acrylate, 1,2,3-cyclohexane tetramethacrylate, polyurethane polyacrylate, polyester Polyacrylate, caprolactone modified tris(propenyloxyethyl)isocyanurate, trinepentaerythritol triacrylate, trinepentaerythritol hexatriacrylate, 1,2,4-ring Hexane tetra(meth)acrylate, pentaglycerin triacrylate, and the like. Further, the above "(di) pentaerythritol" is used in the sense of one or both of pentaerythritol and dipentaerythritol.

Further, a resin containing three or more radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryl fluorenyl group in one molecule is also preferable.

The resin containing three or more radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryl fluorenyl group in one molecule may, for example, be a polyester resin or a polyether resin. Acrylic resin, epoxy resin, urethane resin, alkyd resin, acetal resin, polybutadiene resin, polythiol polyene resin, polyfunctional compound such as polyol, etc. Polymers, etc.

Specific examples of the radical polymerizable compound containing three or more radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryl fluorenyl group in one molecule include JP-A-2007- An exemplary compound shown in paragraph 0096 of 256844.

In addition, a specific example of a radically polymerizable compound containing three or more radical polymerizable groups selected from the group consisting of an acryloyl group and a methacryl fluorenyl group in one molecule can be exemplified by Nippon Kayaku Co. KAYARAD DPHA, KAYARAD DPHA-2C, KAYARAD PET-30, KAYARAD TMPTA, KAYARAD TPA-320, KAYARAD TPA-330, KAYARAD RP-1040, KAYARAD T-1420, KAYARAD D-310, KAYARAD DPCA-20 manufactured by Ltd. , KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD GPO-303, an organic ester of (meth)acrylic acid such as V #400, V# 36095D manufactured by Osaka Organic Chemical Industry Ltd. Also, it is also suitable to use violet UV-1400B, violet UV-1700B, violet UV-6300B, violet UV-7550B, violet UV-7600B, violet UV-7605B, violet UV-7610B, violet UV-7620EA, violet UV-7630B , violet UV-7640B, violet UV-6630B, violet UV-7000B, violet UV-7510B, violet UV-7461TE, violet UV-3000B, violet UV-3200B, violet UV-3210EA, violet UV-3310EA, violet UV-3310B , violet UV-3500BA, violet UV-3520TL, violet UV-3700B, violet UV-6100B, violet UV-6640B, violet UV-2000B, violet UV-2010B, violet UV-2250EA, violet UV-2750B (Nippon Synthetic Chemical Industry Manufactured by Co., Ltd., UL-503LN (manufactured by KYOEISHA CHEMICAL Co., LTD.), UNIDIC 17-806, UNIDIC 17-813, UNIDIC V-4030, UNIDIC V-4000BA (manufactured by Dainippon Ink and Chemicals, Inc.) ), EB-1290K, EB-220, EB-5129, EB-1830, EB-4358 (manufactured by Daicel UCB Co., Ltd.), HI-COAP AU-2010, HI-COAP AU-2020 (TOKUSHIKI CO., (manufactured by Ltd.), ARONIX M-1960 (manufactured by TOAGOSEI CO., LTD.), Art resin UN-3320HA, UN-3320HC, UN-3320HS, UN-904, HDP-4T and other trifunctional or higher urethanes Acrylate Was co-, ARONIX M-8100, M-8030, M-9050 (TOAGOSEI CO., LTD., Ltd.), trifunctional or more KBM-8307 (DAICEL-ALLNEX LTD., Ltd.) of a polyester compound.

Further, as the component b), only one type may be used, or two or more types different in structure may be used in combination.

As described above, the HC layer obtained by curing the curable composition for forming the HC layer of the second aspect (2) preferably has a total solid content of the HC layer of 100% by mass. The structure of a) is 15 to 70% by mass, the structure derived from the above b) is 25 to 80% by mass, the above c) is 0.1 to 10% by mass, and the above d) is 0.1 to 10% by mass. When the total solid content of the HC layer is 100% by mass, it is preferable to contain 40 to 75% by mass of the structure derived from b), and more preferably 60 to 75% by mass. In addition, when the total solid content of the curable composition for forming a layer of HC is 100% by mass, the curable composition for forming an HC layer of the second aspect (2) contains b) a component of 40 to 75% by mass. Preferably, it is more preferably 60 to 75% by mass.

- Cationic polymerizable compound -

The curable composition for forming an HC layer of the second aspect preferably contains at least one radically polymerizable compound and at least one cationically polymerizable compound. The cationically polymerizable compound can be used without any limitation as long as it has a polymerizable group (cationic polymerizable group) capable of cationic polymerization. Further, the number of cationically polymerizable groups contained in one molecule is at least one. The cationically polymerizable compound may be a monofunctional compound containing one cationically polymerizable group in one molecule, or may be a polyfunctional compound containing two or more cationically polymerizable groups. The number of the cationically polymerizable groups contained in the polyfunctional compound is not particularly limited, and is, for example, 2 to 6 in one molecule. Further, the polyfunctional compound may have two or more cationically polymerizable groups in one molecule, or may be two or more different in structure.

Further, in one aspect, the cationically polymerizable compound has a cationically polymerizable group, and one or more radical polymerizable groups in one molecule are also preferable. The above description of the radically polymerizable compound can be referred to as the radical polymerizable group of the cationically polymerizable compound. The ethylenically unsaturated group is preferred, and the ethylenically unsaturated group is more preferably a vinyl group, and a radical polymerizable group selected from the group consisting of an acryloyl group and a methacryl group. The number of radical polymerizable groups in one molecule of the cationically polymerizable compound having a radical polymerizable group is at least one, preferably from 1 to 3, more preferably one.

The cationically polymerizable group is preferably an oxygen-containing heterocyclic group or a vinyl ether group. Further, the cationically polymerizable compound may contain one or more oxygen-containing heterocyclic groups and one or more vinyl ether groups in one molecule.

As the oxygen-containing hetero ring, it may be a single ring or a fused ring. Further, those having a double ring skeleton are also preferred. The oxygen-containing heterocyclic ring may be a non-aromatic ring or an aromatic ring, and a non-aromatic ring is preferred. Specific examples of the single ring include an epoxy ring, a tetrahydrofuran ring, and an oxetane ring. Further, as the double-ring skeleton, an oxabicyclic ring can be mentioned. Further, the cationically polymerizable group containing an oxygen-containing hetero ring is contained in the cationically polymerizable compound as a monovalent substituent or as a divalent or higher polyvalent substituent. Further, the fused ring may be obtained by condensing two or more oxygen-containing heterocyclic rings, or one or more of the oxygen-containing heterocyclic rings and one or more of the ring structures other than the oxygen-containing heterocyclic ring may be obtained. The ring structure other than the oxygen-containing hetero ring is not limited thereto, and examples thereof include a cycloalkane ring such as a cyclohexane ring.

Specific examples of the oxygen-containing hetero ring are shown below. However, the present invention is not limited to the specific examples described below.

[Chemical Formula 4]

The cationically polymerizable compound may contain a partial structure other than the cationically polymerizable group. The partial structure is not particularly limited, and may be a linear structure, a branched structure, or a cyclic structure. These partial structures may contain one or more hetero atoms such as an oxygen atom or a nitrogen atom.

In a preferred embodiment of the cationically polymerizable compound, a compound having a cyclic structure (a compound having a cyclic structure) may be mentioned as a cationic polymerizable group or a partial structure other than the cationic polymerizable group. The cyclic structure contained in the compound having a cyclic structure may be, for example, one or two or more in one molecule. The number of the cyclic structures contained in the compound having a cyclic structure is, for example, 1 to 5 in one molecule, but is not particularly limited. The compound containing two or more cyclic structures in one molecule may contain the same cyclic structure, or may contain two or more cyclic structures having different structures.

An example of the cyclic structure contained in the compound having a cyclic structure is an oxygen-containing hetero ring. The details are as described above.

The cationically polymerizable group obtained by dividing the molecular weight (hereinafter referred to as "B") by the number of cationically polymerizable groups contained in one molecule of the cationically polymerizable compound (hereinafter referred to as "C") The equivalent (=B/C) is, for example, 300 or less, and from the viewpoint of improving the adhesion between the HC layer obtained by curing the curable composition for forming a HC layer and the resin film, it is preferably less than 1 50. On the other hand, from the viewpoint of the hygroscopicity of the HC layer obtained by curing the curable composition for forming a HC layer, the cationically polymerizable group equivalent system is preferably 50 or more. Moreover, in one aspect, the cationically polymerizable group contained in the cationically polymerizable compound having a cationically polymerizable group equivalent may be an epoxy group (epoxy ring). That is, in one aspect, the cationically polymerizable compound is a compound containing an epoxy ring. The epoxy ring-containing compound removes the molecular weight by the number of epoxy rings contained in one molecule from the viewpoint of improving the adhesion between the HC layer obtained by curing the curable composition for forming a HC layer and the resin film. It is preferred to find an epoxy group equivalent of less than 150. Further, the epoxy group equivalent of the compound containing an epoxy ring is, for example, 50 or more.

Further, the molecular weight of the cationically polymerizable compound is preferably 500 or less, and more preferably 300 or less. It is presumed that the cationically polymerizable compound having a molecular weight in the above range tends to easily penetrate into the resin film, and it is possible to contribute to the improvement of the adhesion between the HC layer obtained by hardening the curable composition for forming a HC layer and the resin film.

The curable composition for forming an HC layer of the second aspect (2) contains a cationically polymerizable compound containing a) an alicyclic epoxy group and an ethylenically unsaturated group, and is contained in one molecule. The number of the alicyclic epoxy groups is one, and the number of the ethylenically unsaturated groups contained in one molecule is one, and the molecular weight is 300 or less. Hereinafter, the above a) is described as "a) component".

Examples of the ethylenically unsaturated group include a radical polymerizable group including an acrylonitrile group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group, and an acryloyl group, a methacryloyl group, and the like. C(O)OCH=CH ₂ is preferred, and propylene fluorenyl and methacryl fluorenyl groups are more preferred. The number of the alicyclic epoxy group and the ethylenically unsaturated group in one molecule is preferably one.

The molecular weight of the component a) is 300 or less, preferably 210 or less, more preferably 200 or less.

A preferred embodiment of the component a) is a compound represented by the following formula (1).

In the formula (1), R represents a monocyclic hydrocarbon or a crosslinked hydrocarbon, L represents a single bond or a divalent linking group, and Q represents an ethylenically unsaturated group.

When R in the formula (1) is a monocyclic hydrocarbon, a monocyclic hydrocarbon-based alicyclic hydrocarbon is preferred, and an alicyclic group having 4 to 10 carbon atoms is more preferred, and the carbon number is 5 to 7 The alicyclic group is further preferably, and the alicyclic group having 6 carbon atoms is particularly preferable. As a preferable specific example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclohexyl group are more preferable.

When R in the formula (1) is a crosslinked hydrocarbon, a crosslinked hydrocarbon-based 2-ring-based crosslinked hydrocarbon (bicyclic ring) or a 3-ring-based crosslinked hydrocarbon (tricyclic ring) is preferred. Specific examples thereof include a crosslinked hydrocarbon having 5 to 20 carbon atoms, and examples thereof include a thiol group, a fluorenyl group, an isodecyl group, a tricyclodecyl group, a dicyclopentenyl group, and a dicyclopentanyl group. Tricyclopentenyl, tricyclopentanyl, adamantyl, lower (e.g., C 1 to 6) alkyl substituted adamantyl, and the like.

When L represents a divalent linking group, a divalent linking group is preferably a divalent aliphatic hydrocarbon group. The carbon number of the divalent aliphatic hydrocarbon group is preferably in the range of 1 to 6, more preferably in the range of 1 to 3, and further preferably 1 is preferable. As the divalent aliphatic hydrocarbon group, a linear, branched or cyclic alkyl group is preferred, and a linear or branched alkyl group is more preferred, and a linear alkyl group is further preferred. .

Examples of Q include ethylenically unsaturated groups including an acryl fluorenyl group, a methacryl fluorenyl group, a vinyl group, a styryl group, and an allyl group, among which an acryl fluorenyl group, a methacryl fluorenyl group, and a C(O) group. OCH=CH ₂ is preferred, and propylene fluorenyl and methacryl fluorenyl groups are more preferred.

Specific examples of the component a) include various compounds exemplified in paragraph 0015 of JP-A-10-17614, compounds represented by the following formula (1A) or (1B), and 1,2-rings. Oxy-4-vinylcyclohexane and the like. Among them, a compound represented by the following formula (1A) or (1B) is more preferable. Further, an isomer of the compound represented by the following formula (1A) is also preferred.

In the general formulae (1A) and (1B), R ₁ represents a hydrogen atom or a methyl group, and L ₂ represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.

The carbon number of the divalent aliphatic hydrocarbon group represented by L ₂ in the general formulae (1A) and (1B) is in the range of 1 to 6, more preferably in the range of 1 to 3, and still more preferably 1 carbon. As the divalent aliphatic hydrocarbon group, a linear, branched or cyclic alkyl group is preferred, and a linear or branched alkyl group is more preferred, and a linear alkyl group is further preferred. .

The HC layer obtained by curing the curable composition for forming the HC layer of the second aspect (2) is preferably a structure 15 derived from the above a) when the total solid content of the HC layer is 100% by mass. It is preferably from 70% by mass, more preferably from 18 to 50% by mass, even more preferably from 22 to 40% by mass. In addition, when the total solid content of the curable composition for forming an HC layer is 100% by mass, the curable composition for forming an HC layer of the second aspect (2) contains 15 to 70% by mass of the component a). Preferably, it is more preferably 18 to 50% by mass, and further preferably 22 to 40% by mass.

Another example of the cyclic structure contained in the compound having a cyclic structure may be a nitrogen-containing hetero ring. From the viewpoint of improving the adhesion between the HC layer and the resin film obtained by curing the curable composition for forming a HC layer, a compound containing a nitrogen-containing hetero ring is preferably a cationically polymerizable compound. The compound containing a nitrogen-containing heterocyclic ring has one or more selected from the group consisting of an isocyanurate ring (a nitrogen-containing hetero ring contained in the exemplified compounds B-1 to B-3 described later) and a glycoluril ring. The nitrogen-containing heterocyclic compound in the group of the nitrogen-containing heterocyclic ring (exemplified in the exemplified compound B-10 described later) is preferred. In the viewpoint of improving the adhesion between the HC layer obtained by curing the curable composition for forming a HC layer and the resin film, a compound containing an isocyanurate ring (a compound containing an isocyanurate ring) A more preferred cationically polymerizable compound. The inventors presume that this is because the isocyanurate ring is excellent in affinity with the resin constituting the resin film. In this regard, the surface of the surface-based acrylic resin film which is in contact with the HC layer obtained by curing the curable composition for forming a HC layer is more preferable, and the resin film including the acrylic resin film is more preferable.

Moreover, as another example of the cyclic structure included in the compound containing a cyclic structure, an alicyclic structure is mentioned. Examples of the alicyclic structure include a monocyclic ring, a bicyclic ring, and a tricyclic ring structure. Specific examples thereof include a dicyclopentanyl ring and a cyclohexane ring.

The cationically polymerizable compound described above can be synthesized by a known method. Moreover, it can also be obtained as a commercial item.

Specific examples of the cationically polymerizable compound containing an oxygen-containing heterocyclic ring as a cationically polymerizable group include, for example, 3,4-epoxycyclohexylmethyl methacrylate (a commercially available product such as CYCLOMER M100 manufactured by Daicel Corporation). 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (for example, UVR6105 manufactured by Union Carbide Corporation, UV R6110, and CELLOXIDE 2021 manufactured by Daicel Chemical Industries, Ltd.) , bis (3,4-epoxycyclohexylmethyl) adipate (for example, UVR6128 manufactured by Union Carbide Corporation), vinyl cyclohexene monooxide (for example, manufactured by Daicel Chemical Industries, Ltd.) CELLOXIDE 2000), ε-caprolactone modified 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (for example, CELLOXIDE 2081 manufactured by Daicel Chemical Industries, Ltd.), 1- Methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4.1.0]heptane (for example, CELLOXIDE 3000 manufactured by Daicel Chemical Industries, Ltd.), 7,7'-dioxane Hetero-3,3'-bis[bicyclo[4.1.0]heptane] (for example, CELLOXIDE 8000 manufactured by Daicel Chemical Industries, Ltd.), 3-ethyl-3- Hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(phenoxy) Methyl)oxetane, 3-ethyl-3-(2-ethylcyclohexylmethyl)oxetane and bis[1-ethyl(3-oxetanyl)]methyl ether Wait.

Moreover, specific examples of the cationically polymerizable compound containing a vinyl ether group as a cationically polymerizable group include 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, and bismuth. Alcohol divinyl ether, cyclohexanediol divinyl ether, cyclohexane dimethanol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, neopentyl alcohol tetravinyl Ether and the like. As the cationically polymerizable compound containing a vinyl ether group, those having an alicyclic structure are also preferred.

In addition, as a cationically polymerizable compound, JP-A-H08-143806, JP-A-H08-283320, JP-A-2000-186079, JP-A-2000-327672, JP-A-2000-327672 A compound exemplified in JP-A-2005-29632, and the like.

Hereinafter, the exemplified compounds B-1 to B-14 are shown as specific examples of the cationically polymerizable compound, but the present invention is not limited to the following specific examples.

[Chemical Formula 9]

In addition, from the viewpoint of improving the adhesion between the HC layer and the resin film obtained by curing the curable composition for forming a HC layer, a preferred aspect of the curable composition for forming a HC layer is as follows. Describe the situation. It is more preferable to satisfy one or more of the following aspects, more preferably two or more, more preferably three or more, and even more preferably. Further, it is also preferred that one cationically polymerizable compound satisfies a plurality of aspects. For example, a cationic polymerizable group equivalent of a compound containing a nitrogen-containing hetero ring may be exemplified as a preferred aspect.

(1) The cationically polymerizable compound contains a compound containing a nitrogen-containing hetero ring. Preferably, the nitrogen-containing heterocycle having a nitrogen-containing heterocyclic ring is selected from the group consisting of an isocyanurate ring and a glycoluril ring. The compound containing a nitrogen-containing hetero ring is more preferably a compound containing an isocyanurate ring. The compound containing an isocyanurate ring is more preferably an epoxy ring-containing compound containing one or more epoxy rings in one molecule.

(2) The cationically polymerizable compound contains a cationically polymerizable compound having a cationic polymerizable group equivalent of less than 150. It is preferred to contain an epoxy group-containing compound having an epoxy group equivalent of less than 150.

(3) The cationically polymerizable compound contains an ethylenically unsaturated group.

(4) The cationically polymerizable compound contains a compound containing an oxetane ring and one or more cationically polymerizable compounds containing one or more oxetane rings in one molecule. The compound containing an oxetane ring is preferably a compound which does not contain a nitrogen-containing hetero ring.

The content of the cationically polymerizable compound in the curable composition for forming a layer of HC is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more, based on 100 parts by mass of the total of the radical polymerizable compound and the cationically polymerizable compound. Further, it is more preferably 20 parts by mass or more. In addition, the content of the cationically polymerizable compound of the curable composition for forming a layer of HC is preferably 50 parts by mass or less based on 100 parts by mass of the total content of the radical polymerizable compound and the cationically polymerizable compound.

In addition, the content of the cationically polymerizable compound in the curable composition for forming a layer of HC is preferably 0.05 parts by mass or more based on 100 parts by mass of the total content of the first radical polymerizable compound and the cationically polymerizable compound. It is preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more. On the other hand, the content of the cationically polymerizable compound is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, based on 100 parts by mass of the total content of the first radical polymerizable compound and the cationically polymerizable compound.

In addition, in the present invention and the present specification, the compound having both the cationically polymerizable group and the radical polymerizable group is classified into a cationically polymerizable compound, and is a content which defines a curable composition for forming an HC layer.

- Polymerization initiator -

The curable composition for forming a layer of HC is preferably a polymerization initiator, and more preferably a photopolymerization initiator. The curable composition for forming a HC layer containing a radical polymerizable compound preferably contains a radical photopolymerization initiator, and the curable composition for forming an HC layer containing a cationically polymerizable compound contains a cationic photopolymerization initiator. good. Further, the radical photopolymerization initiator may be used singly or in combination of two or more kinds of structures. This is also true for the cationic photopolymerization initiator.

Hereinafter, each photopolymerization initiator will be described in order.

(i) Free radical photopolymerization initiator

As the radical photopolymerization initiator, a radical which is an active species can be generated by light irradiation, and a known radical photopolymerization initiator can be used without any limitation. Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 4-(2-hydroxyethyl). Oxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholinyl (4-thiomethylphenyl)propane-1 -ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylethylene Phenyl]acetone oligomer, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propane Acetones such as 1-ketones; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzamide)], ethyl ketone, 1-[9- Anthracene esters such as ethyl-6-(2-methylbenzhydryl)-9H-carbazol-3-yl]-1-(O-acetamidine); benzoin, benzoin methyl ether, Benzoin such as benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzolobenzoate, 4-phenylbenzophenone, 4- Benzamethylene-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 2,4,6-three Methyl benzophenone, 4-benzylidene-N,N-dimethyl-N-[2-(1-oxo-2-propanyl) Benzo)ethyl benzomethanaminium bromide, benzophenone such as (4-benzylidenebenzyl)trimethylammonium chloride; 2-isopropylthioxanthene Ketone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3- Thiophenones such as dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one methyl chloride; 2,4,6-trimethylbenzhydryl -diphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4,6-trimethylbenzene Mercapto-based phosphine oxides such as phenylphosphine oxide. Further, as an auxiliary agent for the radical photopolymerization initiator, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (michlerone), 4, 4' may be used in combination. -diethylaminobenzophenone, 2-dimethylaminoethyl benzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy Ethyl ester, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-di Isopropyl thioxanthone and the like.

The above radical photopolymerization initiator and auxiliary agent can be synthesized by a known method, and can also be obtained as a commercially available product. As a commercially available radical photopolymerization initiator, as a preferred example, IRGACURE (127, 651, 184, 819, 907, 1870 (CGI-403/Irg 184 = 7/3 mixed initiator) manufactured by BASF can be cited. 500, 369, 1173, 2959, 4265, 4263, etc.), OXE01), etc., KAYACURE manufactured by Nippon Kayaku Co., Ltd. (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX) , EPD, ITX, QTX, BTC, MCA, etc.), Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT) manufactured by Sartomer Company, Inc., and the like.

The content of the radical photopolymerization initiator of the curable composition for forming the HC layer is not particularly limited as long as it is appropriately adjusted in the range of the polymerization reaction (radical polymerization) of the radically polymerizable compound. 100 parts by mass of the radically polymerizable compound contained in the curable composition for forming a layer of HC, for example, in the range of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 10 parts by mass. The range of parts by mass.

(ii) cationic photopolymerization initiator

As the cationic photopolymerization initiator, a cationic ion polymerization initiator which can be used as an active species can be produced by light irradiation, and a known cationic photopolymerization initiator can be used without any limitation. Specific examples thereof include a known onium salt, an ammonium salt, a phosphonium salt (for example, a diarylsulfonium salt), a triarylsulfonium salt, a diazonium salt, and an imide salt. More specifically, for example, a cationic photopolymerization initiator represented by the formulas (25) to (28) shown in paragraphs 0050 to 0053 of JP-A-8-143806, and JP-A No. 8-283320 In the paragraph 0020 of the publication, it is exemplified as a cationic polymerization catalyst. Further, the cationic photopolymerization initiator can be synthesized by a known method, and can also be obtained as a commercially available product. As a commercial item, for example, CI-1370, CI-2064, CI-2397, CI-2624, CI-2639, CI-2734, CI-2758, CI-2823, CI manufactured by Nippon Soda Co., Ltd. can be used. -2855 and CI-5102, etc., PHOTOINITIATOR 2047 manufactured by Rhodia, UVI-6974 manufactured by Union Carbide Corporation, UVI-6990, and CPI-10P manufactured by San-Apro Ltd.

As the cationic photopolymerization initiator, a diazonium salt, a phosphonium salt, a phosphonium salt, and an imide salt are preferred from the viewpoints of sensitivity to light of a photopolymerization initiator, stability of a compound, and the like. Further, from the viewpoint of weather resistance, barium salts are preferred.

Specific examples of the commercial product of the sulfonium-based cationic photopolymerization initiator include B2380 manufactured by Tokyo Chemical Industry Co., Ltd., BBI-102 manufactured by Midori Kagaku Co., Ltd., and Wako Pure Chemical Industries. WPI-113 manufactured by Ltd., WPI-124 manufactured by Wako Pure Chemical Industries, Ltd., WPI-169 manufactured by Wako Pure Chemical Industries, Ltd., WPI-170 manufactured by Wako Pure Chemical Industries, Ltd., Toyo Gosei kagaku DTBPI-PFBS manufactured by Co., Ltd.

Moreover, as a specific example of the onium salt compound which can be used as a cationic photopolymerization initiator, the following compounds PAG-1 and PAG-2 are also mentioned.

[Chemical Formula 12]

The content of the cationic photopolymerization initiator of the curable composition for forming the HC layer is not particularly limited as long as it is appropriately adjusted in the range of the polymerization reaction (cation polymerization) of the cationically polymerizable compound. The amount of the cationically polymerizable compound is, for example, 0.1 to 200 parts by mass, preferably 1 to 150 parts by mass, more preferably 2 to 100 parts by mass, per 100 parts by mass of the cationically polymerizable compound.

The photopolymerization initiator described in paragraphs 0052 to 0055 of JP-A-2009-204725 is incorporated herein by reference.

The number of functional groups of the polymerizable compound is preferably from 3 to 5 in terms of the average functional group number in the film defined by the following formula from the viewpoint of setting the Knoop hardness to the above range. Here, the "the average number of functional groups in the film" means the average number of functional groups in the curable composition for forming an HC layer used in forming the HC layer. The curable composition for forming a HC layer may contain two or more kinds of polymerizable compounds.

f _k : the number of functional groups of each polymerizable compound contained in the curable composition for forming an HC layer

Here, the number of functional groups means the total number of reactive groups such as the number of radical polymerizable groups and the number of cationically polymerizable groups.

a _k : weight ratio of the total weight of each polymerizable compound to the polymerizable compound contained in the curable composition for forming an HC layer

n: the number of types of polymerizable compounds

The curable composition for forming an HC layer preferably contains two or more kinds of polymerizable compounds, and contains a polymerizable compound 1 having a radical polymerizable group and has the same molecule in the same molecule. The polymerizable compound 2 having a cationically polymerizable group and a radical polymerizable group and/or the polymerizable compound 3 having an alkoxy group and a radical polymerizable group in the same molecule are more preferable. However, the polymerizable compound 1, the polymerizable compound 2, and the polymerizable compound 3 are different polymerizable compounds, and when it is a plurality of polymerizable compounds among the polymerizable compounds 1 to 3, the polymerizable compound 3 and the polymerizable compound 2 are used. The order of the polymerizable compound 1 is preferentially classified.

The "alkyleneoxy group" of the polymerizable compound 3 means a poly(alkyleneoxy group) having a repeating amount of 2 or more, such as a poly(ethyleneoxy) group and a poly(propoxyl) group, and an ethylidene group and a propyl group. The dioxy isocyanyl group has two or more alkyl (oxyalkyl) groups of the oxy group (-O-). Similarly, "extended ethoxy group" means both a repeating amount of two or more poly-extension ethoxy groups and two or more ethoxy groups.

Among all the polymerizable compounds contained in the curable composition for forming a layer of HC, the content of the polymerizable compound 2 having a cationically polymerizable group and a radical polymerizable group in the same molecule is preferably 10 to 90% by mass. 30~70% is better.

Among all the polymerizable compounds contained in the curable composition for forming a layer of HC, the content of the polymerizable compound 3 having an alkoxy group and a radical polymerizable group in the same molecule is preferably 10 to 90%, and preferably 30. ~70% is better.

As the polymerizable compound 1, the description of the above-mentioned radical polymerizable compound can be preferably applied, and as the polymerizable compound 2, the description of the component a) of the above cationically polymerizable compound can be preferably applied.

Specific examples of the polymerizable compound 3 having an alkoxy group and a radical polymerizable group in the same molecule include butoxydiethylene glycol methacrylate and methoxy polyethylene glycol methacrylic acid. Ester, methoxy polyethylene glycol methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol #200 two Methacrylate, polyethylene glycol #400 dimethacrylate, polyethylene glycol #600 dimethacrylate, polyethylene glycol #1000 dimethacrylate, polyethylene glycol #200 diacrylate , polyethylene glycol #400 diacrylate, polyethylene glycol #600 diacrylate, polyethylene glycol #1000 diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol #400 diacrylate , polypropylene glycol (#700) diacrylate, polytetramethylene glycol #650 diacrylate, ethoxylated polypropylene glycol #700 dimethacrylate, polypropylene glycol #400 dimethacrylate, ethoxy A neopentyl alcohol tetraacrylate or glycerin dimethacrylate. Further, the number described later in # indicates the molecular weight of the ethoxy group.

Further, in addition to the above, it is also possible to have a monomer having an alkoxy group and a reactive group A (for example, a hydroxyl group) and a radical polymerizable group and a reactive group B (for example, a hydroxyl group or an amine group). The monomer is reacted and synthesized. In this case, it is possible to carry out the synthesis by forming a bond between the reactive group A and the reactive group B, or to further form a reactive group C capable of forming a bond with the reactive groups A and B (for example, The monomer of the isocyanate group is reacted to carry out the synthesis. Specifically, a urethane acrylate polymer (a reaction product of 2-hydroxyethyl acrylate, polytetramethylene glycol diol, and isophorone diisocyanate) can be given.

From the viewpoint of suppressing the generation of the hardness and the curl, the alkoxy group-extended ethoxy group of the polymerizable compound 3 is preferred.

- a component which can be optionally contained in the curable composition for forming a layer of HC -

The curable composition for forming a HC layer contains at least one component having a property of being cured by irradiation with an active energy ray, and at least one polymerization initiator can be optionally contained, and is preferably contained. The details of these are as described above.

Next, various components which can be arbitrarily contained in the curable composition for forming an HC layer will be described.

(i) inorganic particles

The curable composition for forming a HC layer can contain inorganic particles having an average primary particle diameter of less than 2 μm. From the viewpoint of improving the hardness of the front panel of the HC layer obtained by curing the curable composition for forming a HC layer (and further improving the hardness of the liquid crystal panel having the front panel), the curable composition for forming an HC layer and It is preferred that the HC layer obtained by curing the composition contains inorganic particles having an average primary particle diameter of less than 2 μm. The average primary particle diameter of the inorganic particles is preferably in the range of 10 nm to 1 μm, more preferably in the range of 10 nm to 100 nm, and further preferably in the range of 10 nm to 50 nm.

The average primary particle diameter of the inorganic particles and the matting particles to be described later can be observed by a transmission electron microscope (magnification: 500,000 to 2,000,000 times), and 100 randomly selected particles (primary particles) can be observed. The average value of the diameters is taken as the average primary particle diameter.

Examples of the inorganic particles include cerium oxide particles, titanium oxide particles, zirconium oxide particles, and alumina particles. Among them, cerium oxide particles are preferred.

In order to improve the affinity with the organic component contained in the curable composition for forming an HC layer, it is preferred to treat the surface of the inorganic particles with a surface modifying agent containing an organic segment. As the surface modifier, those having a bond with an inorganic particle or a functional group capable of adsorbing to the inorganic particle and a functional group having a high affinity with the organic component are preferable in the same molecule. As a surface modifier having a functional group capable of bonding or adsorbing to inorganic particles, a decane-based surface modifier, a metal alkoxide surface modifier such as aluminum, titanium, or zirconium, or a phosphate group, a sulfate group, or a sulfonic acid group A surface modifying agent such as an anionic group such as a carboxylic acid group is preferred. Examples of the functional group having high affinity with an organic component include a functional group having the same hydrophilicity and hydrophobicity as the organic component, and a functional group capable of chemically bonding to the organic component. Among them, a functional group or the like which can be chemically bonded to an organic component is preferable, and an ethylenically unsaturated group or a ring-opening polymerizable group is more preferable.

A preferred inorganic particle surface modifier is a metal alkoxide surface modifier or a polymerizable compound having an anionic group and an ethylenically unsaturated group or a ring-opening polymerizable group in the same molecule. By chemically bonding the inorganic particles and the organic component by the surface modifying agent, the crosslinking density of the HC layer can be increased, and as a result, the hardness of the front panel (and further the hardness of the liquid crystal panel including the front panel) can be improved.

Specific examples of the surface modifying agent include the following exemplified compounds S-1 to S-8.

S-1 H ₂ C=C(X)COOC ₃ H ₆ Si(OCH ₃ ) ₃

S-2 H ₂ C=C(X)COOC ₂ H ₄ OTi(OC ₂ H ₅ ) ₃

S-3 H ₂ C=C(X)COOC ₂ H ₄ OCOC ₅ H ₁₀ OPO(OH) ₂

S-4 (H ₂ C=C(X)COOC ₂ H ₄ OCOC ₅ H ₁₀ O) ₂ POOH

S-5 H ₂ C=C(X)COOC ₂ H ₄ OSO ₃ H

S-6 H ₂ C=C(X)COO(C ₅ H ₁₀ COO) ₂ H

S-7 H ₂ C=C(X)COOC ₅ H ₁₀ COOH

S-8 CH ₂ CH(O)CH ₂ OC ₃ H ₆ Si(OCH ₃ ) ₃

(X represents a hydrogen atom or a methyl group)

The surface modification of the inorganic particles based on the surface modifier is preferably carried out in a solution. When the inorganic particles are mechanically dispersed, the surface modifying agent may be present at the same time, or the surface modifying agent may be added after mechanically dispersing the inorganic particles for stirring, or the surface modification may be performed before mechanically dispersing the inorganic particles (heating, if necessary, After drying, heating or power of hydrogen is changed, followed by dispersion. As the solvent for dissolving the surface modifying agent, an organic solvent having a large polarity is preferred. Specifically, a known solvent such as an alcohol, a ketone or an ester can be mentioned.

When the total solid content of the curable composition for forming a layer of HC is 100% by mass, the content of the inorganic particles is preferably 5 to 40% by mass, more preferably 10 to 30% by mass. The shape of the primary particles of the inorganic particles is spherical or non-spherical, and the primary particles of the inorganic particles are preferably spherical, and in the HC layer obtained by curing the curable composition for forming a HC layer, from the viewpoint of further improving the hardness. It is more preferable that the non-spherical secondary particles or more in the form of high-order particles of two or more spherical inorganic particles (primary particles) are connected.

Specific examples of the inorganic particles include ELCOM V-8802 (spherical cerium oxide particles having an average primary particle diameter of 15 nm manufactured by JGC Catal ysts and Chemicals Ltd.) or ELCOM V-8803 (manufactured by JGC Catalysts and Chemicals Ltd.) Alien cerium oxide particles), MiBK-SD (spherical cerium oxide particles having an average primary particle diameter of 10 to 20 nm manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.), and MEK-AC-2140Z (average times manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.) Spherical cerium oxide particles having a particle diameter of 10 to 20 nm, MEK-AC-4130 (spherical cerium oxide particles having an average primary particle diameter of 45 nm manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.), and MiBK-SD-L (NISSAN CHEMICAL INDUSTRIES, LTD. manufactured spherical cerium oxide particles having an average primary particle diameter of 40 to 50 nm, MEK-AC-5140Z (spherical cerium oxide particles having an average primary particle diameter of 85 nm manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.), and the like. Among them, ELCOM V-8802 manufactured by JGC Catalysts and Chemicals Ltd. is preferable from the viewpoint of further improving the hardness.

(ii) matting particles

The curable composition for forming a HC layer can also contain matting particles. The matte particles are particles having an average primary particle diameter of 2 μm or more, and may be inorganic particles, organic particles, or particles of inorganic or organic composite materials. The shape of the matte particles is either spherical or non-spherical. The average primary particle diameter of the matte particles is preferably in the range of 2 to 20 μm, more preferably in the range of 4 to 14 μm, and further preferably in the range of 6 to 10 μm.

Specific examples of the matting particles include inorganic particles such as cerium oxide particles and TiO ₂ particles, crosslinked acrylic particles, crosslinked acrylic acid-styrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine. Organic particles such as resin particles. Among them, the matting particles are preferably organic particles, and the crosslinked acrylic particles, the crosslinked acrylic-styrene particles, and the crosslinked styrene particles are more preferable.

The content of the matte particles per unit volume in the HC layer obtained by curing the curable composition for forming a HC layer is preferably 0.10 g/cm ³ or more, and 0.10 g/cm ³ to 0.40 g/cm ^{3 .} More preferably, 0.10 g/cm ³ to 0.30 g/cm ³ is more preferable.

(iii) UV absorber

It is also preferred that the curable composition for forming a HC layer contains an ultraviolet absorber. Examples of the ultraviolet absorber include a benzotriazole compound and a triazine compound. Here, the benzotriazole compound is a compound having a benzotriazole ring, and specific examples thereof include various benzotriazole-based ultraviolet absorbers described in paragraph 0033 of JP-A-2013-111835. . The triazine compound is a compound having a triazine ring, and specific examples thereof include various triazine-based ultraviolet absorbers described in paragraph 0033 of JP-A-2013-111835. The content of the ultraviolet absorber in the resin film is, for example, about 0.1 to 10 parts by mass based on 100 parts by mass of the resin contained in the film, and is not particularly limited. Further, the ultraviolet absorber can also be referred to paragraph 0032 of JP-A-2013-111835. Further, the ultraviolet light in the present invention and the present specification means light having an emission center wavelength in a wavelength band of 200 to 380 nm.

(iv) fluorochemicals

It is also preferred that the curable composition for forming a HC layer contains a fluorine-containing compound such as a leveling agent or an antifouling agent.

As the leveling agent, a fluoropolymer can be preferably used. For example, a fluoroaliphatic group-containing polymer described in Japanese Patent No. 5,175,831 can be mentioned. In addition, the content of the fluoroaliphatic group-containing monomer represented by the formula (1) constituting the fluoroaliphatic group-containing polymer can be 50% by mass or less of all the polymerization units and the fluoroaliphatic group-containing polymerization. Used as a leveling agent.

If the HC layer contains an antifouling agent, the adhesion of fingerprints or contaminants is reduced, and the attached contaminants can be easily wiped off. Moreover, the rubbing resistance can be further improved by improving the lubricity of the surface.

The antifouling agent preferably contains a fluorine-containing compound. The fluorine-containing compound preferably has a perfluoropolyether group and a polymerizable group (preferably a radical polymerizable group), and has a perfluoropolyether group and a polymerizable group and has a plurality of polymerizable groups in one molecule. Preferably. By adopting such a configuration, the effect of improving the rubbing resistance can be more effectively exhibited.

In the present specification, even when the antifouling agent has a polymerizable group, it is treated as a non-polymerizable compound 1 to 3 and the above other polymerizable compound.

The fluorine-containing compound may be any of a monomer, an oligomer and a polymer, but an oligomer (fluorine-containing oligomer) is preferred.

Further, in addition to the above, the leveling agent and the antifouling agent described in (vi) other components described later may be contained.

In addition to the above, the materials described in paragraphs 0012 to 0101 of JP-A-2012-088699 can be used in the present specification.

As the antifouling agent described above, those synthesized by a known method can be used, and a commercially available product can also be used. As a commercial item, RS-90, RS-78, etc. by DIC Corporation can be used preferably.

When the curable composition for forming a HC layer contains an antifouling agent, the content of the solid component of the curable composition for forming an HC layer is preferably 0.01 to 7% by mass, more preferably 0.05 to 5% by mass, and more preferably 0.1 to 2% by mass. % is further preferred.

The curable composition for forming a layer of HC may contain only one type of antifouling agent, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably in the above range.

Moreover, the curable composition for forming an HC layer can also be configured to contain substantially no antifouling agent.

(v) solvent

It is also preferred that the curable composition for forming a HC layer contains a solvent. The organic solvent is preferably used as the solvent, and one type of the organic solvent or two or more types may be used in combination at any ratio. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol, and isobutanol; and ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone. ; cellosolve such as ethyl cellosolve; aromatics such as toluene and xylene; glycol ethers such as propylene glycol monomethyl ether; acetates such as methyl acetate, ethyl acetate and butyl acetate; diacetone alcohol Wait. Among these, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and methyl acetate are preferred, and cyclohexanone, methyl ethyl ketone, and methyl isobutyl are mixed in an arbitrary ratio. Ketone and methyl acetate are more preferred. By adopting such a configuration, an antireflection laminate which is more excellent in abrasion resistance, punchability, and adhesion can be obtained.

The amount of the solvent in the curable composition for forming a HC layer can be appropriately adjusted in a range in which the coating suitability of the above composition can be ensured. For example, the solvent can be used in an amount of 50 to 500 parts by mass, and preferably 80 to 200 parts by mass, based on 100 parts by mass of the total amount of the polymerizable compound and the photopolymerization initiator.

Further, the solid content of the curable composition for forming HC is preferably 10 to 90% by mass, more preferably 50 to 80% by mass, and particularly preferably 65 to 75% by mass.

(vi) other ingredients

In addition to the above components, the curable composition for forming a layer of HC may contain one or more kinds of known additives in an arbitrary amount. As an additive, a surface conditioner, a leveling agent, a polymerization inhibitor, a polyrotaxane, etc. are mentioned. For the details of the above, for example, paragraphs 0032 to 0034 of JP-A-2012-229412 can be referred to. Further, it is also possible to include a commercially available antifouling agent or an antifouling agent which can be prepared by a known method. However, the additive is not limited to these, and various additives which can be generally added to the curable composition for forming an HC layer can be used.

The curable composition for forming a HC layer can be prepared by sequentially mixing the various components described above at the same time or in an arbitrary order. The preparation method is not particularly limited, and a known mixer or the like can be used in the preparation.

2) Two or more layers of laminated structure

In the anti-reflection layering system of the present invention, it is preferable that the HC layer 2A in Fig. 1 has at least the first HC layer and the second HC layer in this order from the resin film 1A side.

The first HC layer may be placed on the surface of the resin film 1A, or another layer may be provided therebetween. Similarly, the second HC layer may be placed on the surface of the first HC layer, or another layer may be provided between the first HC layers. From the viewpoint of improving the adhesion between the first HC layer and the second HC layer, it is preferable that the second HC layer is provided on the surface of the first HC layer, that is, the two layers are in contact with at least a part of the film surface.

Further, the first HC layer and the second HC layer may be one layer or two or more layers, but one layer is preferable.

In addition, as described later in detail, when the antireflection layered body of the present invention is used for a touch panel, it is preferable to dispose the antireflection layered body such that the second HC layer is on the front surface side of the image display element. The surface of the anti-reflection laminate is excellent in abrasion resistance and punchability, and the second HC layer is preferably disposed on the surface side, particularly the outermost surface of the anti-reflection laminate.

<The first HC layer and the first HC layer-forming curable composition>

The first HC layer used in the present invention is formed of a curable composition for forming a first HC layer.

The curable composition for forming a first HC layer contains a polymerizable compound 1 having a radical polymerizable group, and a polymerizable compound 2 having a cationically polymerizable group and a radical polymerizable group in the same molecule and different from the polymerizable compound 1 . In the polymerizable compound contained in the curable composition for forming a first HC layer, the content of the polymerizable compound 2 is 51% by mass or more.

(polymerizable compound)

As the polymerizable compound 1, the description of the above-mentioned radical polymerizable compound can be preferably applied, and as the polymerizable compound 2, the description of the component a) of the above cationically polymerizable compound can be preferably applied.

In addition, the curable composition for forming the first HC layer may have another polymerizable compound different from the polymerizable compound 1 and the polymerizable compound 2.

The above other polymerizable compound is preferably a polymerizable compound having a cationically polymerizable group. The cationically polymerizable group has the same meaning as the cationically polymerizable group described in the polymerizable compound 2, and the preferred range is also the same. In particular, in the present invention, as the other polymerizable compound, a compound containing a nitrogen-containing hetero ring containing a cationically polymerizable group is preferred. By using such a compound, the adhesion between the resin film and the first HC layer can be more effectively improved. The nitrogen-containing heterocyclic ring may be selected from the group consisting of an isocyanurate ring (a nitrogen-containing hetero ring included in the exemplified compounds B-1 to B-3 described later) and a glycoluril ring (exemplified compound B-10 described later). The nitrogen-containing heterocyclic ring and the isocyanurate ring in the group containing the nitrogen-containing heterocyclic ring are more preferable. The number of the cationic groups of the other polymerizable compound is preferably from 1 to 10, more preferably from 2 to 5. In addition, when a polymerizable compound having a cationically polymerizable group and a nitrogen-containing heterocyclic ring structure is used as the other polymerizable compound, the resin film is preferably a resin film including an acrylic resin film. With such a configuration, the adhesion between the resin film and the first HC layer tends to be further improved.

Specific examples of the other polymerizable compound include the above-exemplified compounds B-1 to B-14, but the present invention is not limited to the above specific examples.

(other)

Further, the description of the polymerization initiator, inorganic particles, matting particles, ultraviolet absorber, fluorine-containing compound, solvent, and other components can be preferably applied.

In particular, the curable composition for forming the first HC layer preferably contains a solvent, and the curable composition for forming the second HC layer preferably contains an antifouling agent.

(thickness of HC layer)

The thickness of the HC layer is preferably 10 to 40 μm, more preferably 15 to 40 μm, and further preferably 20 to 35 μm.

-Formation of HC layer -

The HC layer can be formed by applying a curable composition for forming an HC layer directly or via another layer such as an easy-adhesion layer to a resin film and irradiating an active energy ray. The coating can be carried out by a known coating method such as a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a die coating method, a wire bar coating method, or a gravure method. Further, the HC layer can also be formed into a HC layer having a laminated structure of two or more layers (for example, two to five layers) by simultaneously or sequentially applying a composition of two or more different compositions.

The HC layer can be formed by subjecting the applied curable composition for forming a HC layer to active energy ray irradiation. For example, when the curable composition for forming an HC layer contains a radical polymerizable compound, a cationically polymerizable compound, a radical photopolymerization initiator, and a cationic photopolymerization initiator, each of the radical photopolymerization initiators can be used. The polymerization reaction of the radically polymerizable compound and the cationically polymerizable compound is initiated by the action of a cationic photopolymerization initiator. The wavelength of the irradiation light may be determined depending on the type of the polymerizable compound and the polymerization initiator to be used. Examples of the light source for light irradiation include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, and an LED (Light) that emit light in a wavelength band of 150 to 450 nm. Emitting Diode: Light Emitting Diode). Further, the amount of light irradiation is usually in the range of 30 to 3,000 mJ/cm ² , preferably in the range of 100 to 1,500 mJ/cm ² . One or both of before and after the light irradiation may be subjected to a drying treatment as needed. The drying treatment can be carried out by blowing of warm air, disposition in a heating furnace, transportation in a heating furnace, or the like. When the curable composition for forming the HC layer contains a solvent, the heating temperature is set to a temperature at which the solvent can be removed by drying, and is not particularly limited. Here, the heating temperature means the temperature of the warm air or the ambient temperature in the heating furnace.

(3) Inorganic oxide layer (AR layer)

The AR layer in the antireflection laminate of the present invention has a function as an antireflection layer, and can be, for example, a sputtering method, a reactive sputtering method, a vapor deposition method, an ion plating method, or a chemical vapor deposition (CVD). A dry coating method such as a method is formed. It is preferable to use a sputtering method in which a film having a high uniformity in film thickness and a small number of defects such as pinholes can form a film having excellent visibility and excellent mechanical properties such as compactness and scratch resistance. Among them, since high productivity can be achieved with higher film formation speed and higher discharge stability, a double magnetron sputtering (DMS) method in which film formation is performed by voltage application in an intermediate frequency region is preferable.

Further, when the sputtering method is employed, the pressure at the time of laminating the AR layer is preferably 0.1 to 0.6 Pa. The reason for this is that a sufficient sputtering rate and film density can be obtained.

The AR layer may be any one of a high refractive index layer and a low refractive index layer, and may be a single layer or a plurality of layers.

When the AR layer is a plurality of layers, the AR layer is preferably formed by alternately laminating a high refractive index layer and a low refractive index layer, and the outermost layer of the AR layer (that is, the layer disposed on the opposite side with respect to the HC layer) A low refractive index layer is preferred. Wherein, the AR layer is a laminate of four or more layers obtained by alternately laminating a high refractive index layer and a low refractive index layer, and the outermost layer of the AR layer is preferably a low refractive index layer, and the innermost layer of the AR layer (ie, It is more preferable that the high refractive index layer is a layer disposed on the nearest side with respect to the HC layer.

Examples of the material constituting the high refractive index layer include metals such as indium, tin, titanium, zinc, zirconium, hafnium, magnesium, lanthanum, cerium, lanthanum, aluminum, lanthanum, potassium, lanthanum, cerium, lanthanum, cerium, and lanthanum. And two or more alloys containing the metals, and oxides, fluorides, sulfides, nitrides, and the like. Specific examples thereof include titanium oxide, cerium oxide, zirconium oxide, cerium oxide, zinc oxide, indium oxide, and antimony oxide. However, the present invention is not limited thereto. Further, when a plurality of layers are laminated, it is not necessary to select the same material, and it may be appropriately selected according to the purpose. Among them, when a sputtering method is used, cerium oxide is suitable from the viewpoint of a small number of pinholes of the produced film.

Examples of the material constituting the low refractive index layer include materials such as cerium oxide, magnesium fluoride, barium fluoride, calcium fluoride, barium fluoride, and barium fluoride, but are not limited thereto. Further, when a plurality of layers are laminated, it is not always necessary to select the same material, and it may be appropriately selected according to the purpose. In particular, yttrium oxide is the best material in terms of optical properties, mechanical strength, cost, and film formability. Further, cerium oxide (SiO _x ) as used herein mainly means cerium oxide (SiO ₂ ). However, the _x of SiO _x varies from 1.8 to 2.2 due to the lack and/or increase of oxygen.

The total thickness of the AR layer is preferably from 100 to 300 nm. From the viewpoint of obtaining sufficient reflection performance, the above lower limit value is preferably at least the above, and from the viewpoint of productivity, the above upper limit value is preferably at most.

(4) Other layers

In addition to the resin film, the HC layer, and the AR layer, the antireflection laminate of the present invention may be provided with other layers such as an antifouling layer and a binder layer as needed.

In this case, the rigidity and Knoop hardness of the antireflection layered body mean the rigidity and Knoop hardness of the layered body composed of the resin film, the HC layer, and the AR layer.

(anti-fouling layer)

The antireflection laminate of the present invention may be provided with an antifouling layer on the outermost layer of the AR layer. The antifouling layer is preferably a layer containing a fluorine compound formed by a vacuum deposition method, and a layer comprising a fluorine-containing ruthenium compound having two or more ruthenium atoms bonded to a reactive functional group is further used. good. Here, the reactive functional group means a group which can be bonded to the outermost layer of the AR layer to be bonded. Further, it is also preferred to use a fluorine-containing ruthenium compound having a reactive functional group to form an antifouling layer by reacting the reactive functional groups with each other.

By providing the antifouling layer, it is difficult to adhere to the surface on the surface, and the wiping performance when the contaminant is adhered can be improved. Here, the film formation method of the antifouling layer is not particularly limited, but a film formation method by a vacuum deposition method is preferable. According to this method, even in the case of continuous film formation, film formation can be performed with good uniformity of film thickness.

At this time, in order to have sufficient antifouling performance, it is preferred that at least the water droplet contact angle is 100 or more. Thereby, the wiping property of the contaminants on the surface can be improved. Further, since the friction coefficient is also lowered, the scratch resistance can be further improved. Further, from the viewpoint of the scratch resistance, the antifouling layer is rubbed and rubbed for 10 times at a load of 1.5 kg/cm ^{2 in} an environment of a temperature of 25 ° C and a relative humidity of 55% using steel wool # 0000, and scratching is not caused. good.

(bonded layer)

Further, the resin film used in the present invention may have a bonding layer on the surface opposite to the surface having the HC layer. As an aspect of the optical film having a bonding layer, as shown in FIG. 2, an optical film 4B of the present invention having a structure in which a bonding layer 5A, a resin film 1A, an HC layer 2A, and an AR layer 3A are laminated in this order is exemplified.

The material of the above-mentioned adhesive layer is not particularly limited, and may be a binder or an adhesive, and examples thereof include an acrylic adhesive, an urethane-based adhesive, a synthetic rubber-based adhesive, and a natural rubber-based adhesive. The agent and the lanthanum binder, and the acrylic binder are preferred. Among them, from the viewpoint of productivity, it is preferred to contain an ionizing radiation hardening group and to have ionizing radiation hardenability.

The thickness of the adhesive layer is preferably 100 μm or less, more preferably 50 μm or less, and further preferably 15 μm or less.

Hereinafter, a bonding layer containing an acrylic binder will be described as a specific aspect, but the present invention is not limited to the following specific aspects.

(specific aspect of the bonding layer)

Examples of the acrylic binder include at least a (meth) acrylate polymer A having a weight average molecular weight of 500,000 to 3,000,000, or a (meth) acrylate polymer A and a weight average molecular weight of An acrylic binder having a composition obtained by crosslinking 8,000 to 300,000 (meth) acrylate polymer B. In the (meth) acrylate polymer A and the (meth) acrylate polymer B, the binder layer can be increased by increasing the proportion of the (meth) acrylate polymer B having a smaller weight average molecular weight. The stress relaxation rate can reduce the stress relaxation rate of the bonding layer by reducing the ratio. In the above component, when the (meth) acrylate polymer A is 100 parts by mass, the proportion of the (meth) acrylate polymer B is preferably in the range of 5 to 50 parts by mass, preferably 10 to 10 parts by weight. The range of 30 parts by mass is more preferable.

The details of the (meth) acrylate polymer A and the (meth) acrylate polymer B contained in the above-mentioned components can be referred to in paragraphs 0020 to 0046 of JP-A-2012-214545. In addition, the details of the cross-linking agent can be referred to paragraphs 0049 to 0,058 of JP-A-2012-214545.

The acrylic binder may contain a decane coupling agent, and is preferably contained. For the details of the decane coupling agent, reference can be made to paragraphs 0059 to 0061 of JP-A-2012-214545. Further, the details of the method for preparing the acrylic binder and the additives or solvents which can be arbitrarily included can be referred to paragraphs 0062 to 0071 of JP-A-2012-214545.

In one aspect, the acrylic adhesive is applied to a release-treated surface of a release sheet subjected to release treatment and dried to form a pressure-sensitive adhesive layer, whereby a pressure-sensitive adhesive sheet including a pressure-sensitive adhesive layer can be formed. By bonding the adhesive layer of the adhesive sheet to the resin film, an antireflection laminate having a bonding layer can be formed.

(5) Articles having an anti-reflection laminate

As an article including the anti-reflection laminate of the present invention, it is required to have an anti-reflection function and a load suppression in various industries including the home appliance industry, the electric and electronic industry, the automobile industry, and the residential industry. Keyboard transfer and various items that improve rub resistance. As a specific example, an image display device such as a notebook PC, a touch sensor, a touch panel, or a liquid crystal display device, a window glass of an automobile, a window glass of a house, or the like can be given. By providing the antireflection laminate of the present invention as an antireflection film for the articles, it is possible to provide an article having an antireflection function, sufficiently suppressing the transfer of the keyboard accompanying the load, and exhibiting excellent rub resistance. The antireflection laminate of the present invention is preferably used as an antireflection laminate used in a front panel for an image display device, and more preferably used as a front panel and a touch panel of an image display element of a notebook PC. The antireflection laminate used in the front panel of the image display element is further preferably used as an antireflection laminate used in the front panel of the image display element of the notebook PC.

The notebook PC capable of using the antireflection laminate of the present invention is not particularly limited, and can be appropriately selected depending on the purpose.

The touch panel to which the anti-reflection laminate of the present invention can be used is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include a surface-type capacitive touch panel, a projection type capacitive touch panel, and a resistive touch panel. The details will be described later.

In addition, the touch panel includes a so-called touch sensor. The layer structure of the touch panel sensor electrode portion in the touch panel may be a bonding method in which two transparent electrodes are bonded, a transparent electrode on both sides of one substrate, a single-sided jumper or a through hole ( Any of a through hole method or a single area layer method.

<<Image display device>>

An image display device including the antireflection laminate of the present invention includes an image display device having a front panel and an image display element of the antireflection laminate of the present invention.

The image display device can be used for an image display device such as a liquid crystal display (LCD), a plasma display panel, an electroluminescence display, a cathode tube display device, and a touch panel.

Examples of the liquid crystal display device include a TN (Twisted Nematic) type, an STN (Super-Twisted Nematic) type, and a TSTN (Triple Super Twisted Nematic) type. Multi-domain type, VA (Vertical Alignment) type, IPS (In Plane Switching) type, OCB (Optically Compensated Bend) type.

The image display device is improved in brittleness, excellent in workability, and which does not impair the smoothness of the surface or damage the display quality by wrinkles, and can reduce light leakage during the damp heat test.

In other words, in the image display device having the antireflection laminate of the present invention, the image display element is preferably a liquid crystal display device. Examples of the image display device having a liquid crystal display device include Xperia P manufactured by Sony Ericsson Co., Ltd., and the like.

In the image display device having the antireflection laminate of the present invention, an image display device is preferably an organic electroluminescence (EL) display device.

The organic electroluminescent display element can be applied to known techniques without any limitation. Examples of the image display device having an organic electroluminescence display element include GALAXY SII manufactured by SAMSUNG Co., Ltd., and the like.

In the image display device having the antireflection laminate of the present invention, an image display element is also preferably an In-Cell touch panel display element. The in-line type touch panel display element refers to a person who built the touch panel function into the image display element unit.

The intrinsic touch panel display element can be applied, for example, to a known technique such as Japanese Laid-Open Patent Publication No. 2011-76602, and Japanese Laid-Open Patent Publication No. 2011-222009. Examples of the image display device having an in-cell type touch panel display element include Xperia P manufactured by Sony Ericsson Co., Ltd., and the like.

Further, in the image display device having the antireflection laminate of the present invention, the image display device is also preferably an on-cell touch panel display device. The external touch panel display element refers to a person who arranges the touch panel function outside the image display element unit.

For example, a known technique such as Japanese Laid-Open Patent Publication No. 2012-88683 can be applied without any limitation. As an image display device having an external touch panel display element, GALAXY SII manufactured by SAMSUNG Co., Ltd., or the like can be given.

<<Touch panel>>

A touch panel having the antireflection laminate of the present invention is a touch panel including a touch sensor, in which a touch sensor film is bonded to the antireflection laminate of the present invention. Since the antireflection laminate of the present invention has the HC layer, it is preferable to bond the touch sensor film to the resin film surface on the opposite side to the surface on which the HC layer is disposed.

The touch sensor film is not particularly limited, but a conductive film in which a conductive layer is formed is preferable.

The conductive film is preferably a conductive film in which a conductive layer is formed on any of the supports.

The material of the conductive layer is not particularly limited, and examples thereof include indium tin oxide (ITO), tin oxide, tin oxide, antimony tin oxide (ATO), copper, silver, and Aluminum, nickel, chromium or these alloys.

A conductive layer electrode pattern is preferred. Further, a transparent electrode pattern is also preferable. The electrode pattern may be obtained by patterning a transparent conductive material layer, or may be obtained by patterning a layer of an opaque conductive material.

As the transparent conductive material, an oxide such as ITO or ATO, a silver nanowire, a carbon nanotube, or a conductive polymer can be used.

As a layer of an opaque conductive material, a metal layer is mentioned, for example. As the metal layer, any metal having conductivity can be used, and silver, copper, gold, aluminum, or the like is suitably used. The metal layer may be a single metal or alloy, or may be obtained by bonding metal particles with a bonding material. Further, blackening treatment or rust prevention treatment is applied to the metal surface as needed. When metal is used, the substantially transparent sensor portion and the peripheral wiring portion can be formed at one time.

It is preferred that the conductive layer comprises a plurality of metal thin wires.

The fine metal wires are preferably formed of silver or an alloy containing silver. The conductive layer formed of silver or an alloy containing silver as the metal thin wire is not particularly limited, and a known conductive layer can be used. For example, a conductive layer described in paragraphs 0040 to 0041 of JP-A-2014-168886 is preferably used, and the contents of the publication are incorporated herein by reference.

It is also preferred that the metal thin wires are formed of copper or an alloy containing copper. The above alloy is not particularly limited, and a known conductive layer can be used. For example, it is preferable to use a conductive layer described in paragraphs 0038 to 0059 of JP-A-2015-49852, the contents of which are incorporated herein by reference.

It is also preferred that the conductive layer be formed of an oxide. When the conductive layer is formed of an oxide, the oxide is more preferably formed of indium oxide containing tin oxide or tin oxide containing antimony. The conductive layer formed of the oxide as the conductive layer is not particularly limited, and a known conductive layer can be used. For example, a conductive layer described in paragraphs 0017 to 0037 of JP-A-2010-27293 is preferably used, and the contents of this publication are incorporated herein by reference.

In the conductive layers of the above configuration, the conductive layer includes a plurality of metal thin wires, and the metal thin wires are preferably arranged in a mesh shape or a random shape, and the metal thin wires are preferably arranged in a mesh shape. Among them, the fine metal wires are arranged in a mesh shape and the fine metal wires are formed of silver or an alloy containing silver.

It is also preferred that the touch sensor film has a conductive layer on both sides.

A preferred aspect of the touch sensor film is described in paragraphs 0016 to 0044 of JP-A-2012-206307, the contents of which are incorporated herein by reference.

<<Resistive film type touch panel>>

A resistive film type touch panel having the antireflection laminate of the present invention includes a resistive touch panel having a front panel of the antireflection laminate of the present invention.

The resistive touch panel includes a basic structure in which conductive films having a pair of substrates on the conductive film are disposed opposite to each other via a spacer. Further, the configuration of the resistive touch panel is known, and the known technique can be applied without any limitation in the present invention.

<<Electrostatic capacitive touch panel>>

The capacitive touch panel having the antireflection laminate of the present invention includes a capacitive touch panel having a front panel of the antireflection laminate of the present invention.

Examples of the form of the capacitive touch panel include a surface type electrostatic capacitance type, a projection type electrostatic capacitance type, and the like. The projection type capacitive touch panel includes a basic configuration in which an X-axis electrode and a Y-axis electrode orthogonal to the X electrode are disposed via an insulator. As a specific aspect, a different surface of the X electrode and the Y electrode formed on one substrate may be used; and an X electrode, an insulator layer, and a Y electrode are formed on the one substrate in the above-described order; The X electrode is formed on the substrate, and the Y electrode is formed on the other substrate (in this aspect, the two substrates are bonded together to form the above-described basic configuration). Further, the configuration of the capacitive touch panel is well known, and the known technique can be applied without any limitation in the present invention.

FIG. 3 shows an example of a configuration of an embodiment of a capacitive touch panel. The touch panel 2 is used in combination with a display device. The display device is disposed on the side of the protective layer 7B of FIG. 3, that is, on the display device side. In Fig. 3, the side of the anti-reflection laminate 4C of the present invention is the visual recognition side (i.e., the operator of the touch panel visually recognizes one side of the image of the display device). The anti-reflection laminate 4C of the present invention is used by being bonded to the conductive film 1 for a touch panel. The conductive film 1 for a touch panel has a conductive member 6A (first conductive layer 8) and a conductive member 6B (second conductive layer 9) on both surfaces of the flexible transparent insulating substrate 5. Each of the conductive member 6A and the conductive member 6B constitutes an electrode serving as a touch panel, a peripheral wiring, an external connection terminal, and a connection portion, which will be described later.

Further, as shown in Fig. 3, a transparent protective layer 7A and a protective layer 7B may be disposed to cover the conductive member 6A and the conductive member 6B for the purpose of planarizing or protecting the conductive members 6A and 6B.

In the anti-reflection laminate 4C, a decorative layer that shields the peripheral region S2 to be described later is formed.

As a material of the transparent insulating substrate 5, for example, glass, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), COP (cycloolefin polymer), COC (cycloolefin copolymer) can be used. ), PC (polycarbonate), and the like. Further, the thickness of the transparent insulating substrate 5 is preferably 20 to 200 μm.

An adhesive layer 3 may be provided between the anti-reflection laminate 4C and the conductive film 1 for a touch panel, and as the adhesive layer 3, an optically clear adhesive or an optically clear adhesive resin (Optical Clear Resin) may be used. The thickness of the adhesive layer 3 is preferably 10 to 100 μm. As the optically transparent adhesive sheet, generally, for example, the 8146 series manufactured by 3M Company can be preferably used. The relative dielectric constant of the adhesive layer is preferably from 4.0 to 6.0, more preferably from 5.0 to 6.0.

As the protective layer 7A and the protective layer 7B, for example, an organic film such as gelatin, an acrylic resin, or a urethane resin, or an inorganic film such as cerium oxide can be used. The thickness is preferably 10 nm or more and 100 nm or less. A relative dielectric constant of 2.5 to 4.5 is preferred.

The concentration of the halogen impurities in the protective layer 7A and the protective layer 7B is preferably 50 ppm or less, and more preferably no halogen impurities. In this manner, corrosion of the conductive member 6A and the conductive member 6B can be suppressed.

As shown in FIG. 4, the conductive film 1 for a touch panel is partitioned with a transparent active area S1, and a peripheral area S2 is formed outside the active area S1.

In the active region S1, the first conductive layer 8 formed on the surface (first surface) of the transparent insulating substrate 5 and the back surface (second surface) formed on the transparent insulating substrate 5 are disposed so as to overlap each other. The second conductive layer 9. Further, the first conductive layer 8 and the second conductive layer 9 are disposed in a state of being insulated from each other via the transparent insulating substrate 5.

A plurality of first electrodes 11 extending along the first direction D1 and arranged in parallel in the second direction D2 orthogonal to the first direction D1 are formed by the first conductive layer 8 on the surface of the transparent insulating substrate 5, A plurality of second electrodes 21 extending in the second direction D2 and arranged in parallel along the first direction D1 are formed by the second conductive layer 9 on the back surface of the transparent insulating substrate 5.

The plurality of first electrodes 11 and the plurality of second electrodes 21 constitute the detecting electrodes of the touch panel 2. The electrode width of the first electrode 11 and the second electrode 21 is preferably 1 to 5 mm, and the pitch between the electrodes is preferably 3 to 6 mm.

On the other hand, a plurality of first peripheral wirings 12 connected to the plurality of first electrodes 11 are formed on the surface of the transparent insulating substrate 5 in the peripheral region S2, and a plurality of the first insulating wirings 5 are arranged at the edge of the transparent insulating substrate 5. The external connection terminal 13 is externally connected, and the first connection portion 14 is formed at both ends of each of the first electrodes 11. One end portion of the corresponding first peripheral wiring 12 is connected to the first connection portion 14, and the other end portion of the first peripheral wiring 12 is connected to the corresponding first external connection terminal 13.

In the same manner, a plurality of second peripheral wirings 22 connected to the plurality of second electrodes 21 are formed on the back surface of the transparent insulating substrate 5 in the peripheral region S2, and a plurality of second portions are formed in the edge portion of the transparent insulating substrate 5. The terminal 23 is externally connected, and the second connection portion 24 is formed at both ends of each of the second electrodes 21. One end portion of the corresponding second peripheral wiring 22 is connected to the second connection portion 24, and the other end portion of the second peripheral wiring 22 is connected to the corresponding second external connection terminal 23.

The conductive film 1 for a touch panel has a conductive member 6A including the first electrode 11 , the first peripheral wiring 12 , the first external connection terminal 13 , and the first connection portion 14 on the surface of the transparent insulating substrate 5 , and is on the transparent insulating substrate 5 . The back surface includes a conductive member 6B including the second electrode 21, the second peripheral wiring 22, the second external connection terminal 23, and the second connection portion 24.

In FIG. 4, the first electrode 11 and the first peripheral wiring 12 are connected via the first connecting portion 14, but the first electrode 11 and the first peripheral wiring 12 may be directly connected without providing the first connecting portion 14. In the same manner, the second electrode 21 and the second peripheral wiring 22 may be directly connected without providing the second connecting portion 24.

By providing the first connection portion 14 and the second connection portion 24, it is possible to improve the electrical conduction of the connection portion between the electrode and the peripheral wiring. In particular, when the materials of the electrodes and the peripheral wiring are different, it is preferable to provide the first connecting portion 14 and the second connecting portion 24. The widths of the first connecting portion 14 and the second connecting portion 24 are preferably 1/3 or more of the width of the connected electrode and the width of the electrode is preferably equal to or less than the width of the electrode. The shape of the first connecting portion 14 and the second connecting portion 24 may be a solid film shape, or may be a frame shape or a mesh shape as shown in WO 2013/089085.

The wiring width of the first peripheral wiring 12 and the second peripheral wiring 22 is 10 μm or more and 200 μm or less, and the minimum wiring interval (minimum wiring distance) is preferably 20 μm or more and 100 μm or less.

Each of the peripheral wirings may be covered with a protective insulating film containing a urethane resin, an acrylic resin, an epoxy resin or the like. By providing the protective insulating film, it is possible to prevent migration, rust, and the like of the peripheral wiring. Further, since it is likely to cause corrosion of the peripheral wiring, it is preferable that the insulating film does not contain halogen impurities. The thickness of the protective insulating film is preferably 1 to 20 μm.

When the conductive film 1 for a touch panel is used as a touch panel, the first external connection terminal 13 and the second external connection terminal 23 are electrically connected to a flexible printed circuit (Audio Conductive Film) via an anisotropic conductive film. The flexible wiring substrate is connected to a touch panel control substrate having a driving function and a position detecting function.

The first external connection terminal 13 and the second external connection terminal 23 are formed to have a terminal width larger than the wiring width of the first peripheral wiring 12 and the second peripheral wiring 22 for the purpose of improving the electrical connection with the flexible wiring board. Specifically, the terminal width of the first external connection terminal 13 and the second external connection terminal 23 is preferably 0.1 mm or more and 0.6 mm or less, and the terminal length is preferably 0.5 mm or more and 2.0 mm or less.

Further, the transparent insulating substrate 5 corresponds to a substrate having a first surface and a second surface facing the first surface, and the first conductive layer 8 is disposed on the first surface (surface), and is on the second surface (back surface). The second conductive layer 9 is disposed. In addition, in FIG. 3, the transparent insulating substrate 5 and the first conductive layer 8 and the second conductive layer 9 are directly in contact with each other, but the transparent insulating substrate 5 and the first conductive layer 8 and the second conductive layer 9 are It is also possible to form more than one functional layer such as an adhesion-strengthening layer, an undercoat layer, a hard coat layer, and an optical adjustment layer.

The intersection of the first electrode 11 and the second electrode 21 is shown in FIG. The first electrode 11 disposed on the surface of the transparent insulating substrate 5 is formed of a mesh pattern M1 including the first metal thin wires 15, and the second electrode 21 disposed on the back surface of the transparent insulating substrate 5 also includes the second metal thin wires 25. The mesh pattern M2 is formed. In addition, when the intersection of the first electrode 11 and the second electrode 21 is viewed from the visual recognition side, the first metal thin wires 15 and the second metal thin wires 25 are arranged to intersect each other. In addition, in FIG. 5, in order to make it easy to distinguish the 1st metal thin wire 15 and the 2nd metal thin wire 25, the 2nd metal thin wire 25 is shown by the dotted line, However, It is actually formed by the line connected similarly to the 1st metal thin wire 15.

As the shape of the mesh pattern, a pattern in which the same mesh (shaped unit) is repeatedly arranged as shown in FIG. 5 is preferable, and the shape of the mesh is particularly good as a diamond, but may be a quadrilateral such as a parallelogram, a square, or a rectangle. It can also be a regular hexagon or other polygon. In the case of a rhombic shape, the narrow angle of the rhombic shape is preferably 20° or more and 70° or less from the viewpoint of reducing interference fringes with pixels of the display device. From the viewpoint of visibility, the center-to-center distance (mesh pitch) of the mesh is preferably 100 to 600 μm. It is preferable that the mesh pattern M1 including the first metal thin wires 15 and the mesh pattern M2 including the second metal thin wires 25 have the same shape. Further, from the viewpoint of visibility, as shown in FIG. 5, it is preferable to dispose the mesh pattern M1 including the first metal thin wires 15 and the mesh pattern M2 including the second metal thin wires 25 with the mesh. The grids are arranged at a distance of half the distance and are arranged to form a grid pattern having a grid pitch of half when viewed from the visual recognition side. In another aspect, the shape of the mesh may be a random pattern or a randomness of about 10% of the pitch of the shaped unit of the rhombus as shown in Japanese Laid-Open Patent Publication No. 2013-214545, and the shaped cell shape is given a certain amount. The semi-random shape of randomness.

Further, each of the adjacent first electrodes 11 and the adjacent second electrodes 21 may have a dummy mesh pattern insulated from the electrodes formed by the first metal thin wires 15 and the second metal thin wires 25. The dummy mesh pattern is preferably formed by the same mesh shape as the grid pattern forming the electrodes.

The method of bonding the touch panel 2 and the display device is a method of directly bonding using a transparent adhesive (direct boding method) or a method of bonding only the touch panel 2 and the periphery of the display device using double-sided tape (gas) Air gap), but it can be any way. When the touch panel 2 and the display device are attached, a protective film may be additionally provided on the conductive member 6B or the protective layer 7B. The protective film is, for example, a PET film (thickness: 20 to 150 μm) with a hard coat layer, and can be attached to the conductive member 6B or the protective layer 7B by using an optically clear adhesive sheet (Optical Clear Adhesive).

As with the transparent adhesive layer, the transparent adhesive used in the direct bonding method can use Optical Clear Adhesive or Optical Clear Resin, and preferably has a thickness of 10 μm or more and 100 μm or less. . As the optically transparent adhesive sheet, for example, the 8146 series manufactured by 3M Company can also be preferably used. From the viewpoint of improving the detection sensitivity of the touch panel 2, it is preferable that the relative dielectric constant of the transparent adhesive used in the direct bonding method is smaller than the relative dielectric constant of the transparent adhesive layer. The relative dielectric constant of the transparent adhesive used in the direct bonding method is preferably 2.0 to 3.0.

Moreover, it is preferable that the visible light reflectance of the surface of the first metal thin wire 15 on the visual recognition side and the surface of the second metal thin wire 25 on the visual recognition side is 5% or less, from the viewpoint of the more excellent effect of the present invention. In addition, less than 1% is more preferable. By setting the visible light reflectance within the present range, it is possible to effectively reduce the visibility of the mesh or reduce the haze.

As a method of measuring the visible light reflectance, the measurement was carried out as follows. First, a reflection spectrum was measured using an ultraviolet-visible spectrophotometer V660 (primary reflection measuring unit SLM-721) manufactured by JASCO Corporation at a measurement wavelength of 350 nm to 800 nm and an incident angle of 5 degrees. In addition, the regular reflection light of the aluminum vapor deposition mirror is set as a baseline. The Y value (isochromatic function JIS Z9701-1999) at the XYZ color system, the D65 light source, and the 2 degree field of view was calculated from the obtained reflection spectrum using a color calculation program manufactured by JASCO Corporation as the visible light reflectance.

As the material constituting the first metal thin wire 15 and the second metal thin wire 25, a metal such as silver, aluminum, copper, gold, molybdenum or chromium or the like can be used, and these can be used as a single layer or a laminate. . The line width of the first metal thin wires 15 and the second metal thin wires 25 is preferably 0.5 μm or more and 5 μm or less from the viewpoint of reducing the mesh visibility of the fine metal wires and the interference fringes. The first metal thin wires 15 and the second metal thin wires 25 may have a straight line, a polygonal line, a curved line, or a wavy line shape. In addition, the thickness of the first metal thin wires 15 and the second metal thin wires 25 is 0.1 μm or more from the viewpoint of the electric resistance value, and is preferably 3 μm or less from the viewpoint of visibility from the oblique direction. From the viewpoint of the visibility from the oblique direction and the patterning workability, a more preferable thickness is preferably 1/2 or less with respect to the line width of the fine metal wires. In addition, in order to reduce the visible light reflectance of the first metal thin wires 15 and the second metal thin wires 25, a blackening layer may be provided on the visual recognition side of the first metal thin wires 15 and the second metal thin wires 25.

The conductive member 6A including the first electrode 11 , the first peripheral wiring 12 , the first external connection terminal 13 , and the first connection portion 14 can be formed of a material constituting the first metal thin wire 15 . Thereby, all of the conductive members 6A including the first electrode 11, the first peripheral wiring 12, the first external connection terminal 13, and the first connection portion 14 are formed of the same metal in the same thickness, and can be simultaneously formed.

The same applies to the conductive member 6B including the second electrode 21, the second peripheral wiring 22, the second external connection terminal 23, and the second connection portion 24.

The sheet resistance of the first electrode 11 and the second electrode 21 is preferably 0.1 Ω/□ or more and 200 Ω/□ or less. In particular, when used in a projection type capacitive touch panel, 10 Ω/□ or more and 100 Ω/□ or less are used. Preferably.

Further, as shown in FIG. 6, the first conductive layer 8 disposed on the surface of the transparent insulating substrate 5 in the active region S1 may have a plurality of first dummy electrodes 11A disposed between the plurality of first electrodes 11 . The first dummy electrode 11A is insulated from the plurality of first electrodes 11 and has a first mesh pattern M1 composed of a plurality of first cells C1 similarly to the first electrode 11 .

In addition, the first electrode 11 and the adjacent first dummy electrode 11A are electrically insulated by providing a wire having a width of 5 μm or more and 30 μm or less on a thin metal wire arranged along the continuous first mesh pattern M1. 6 is a shape in which the boundary between the first electrode 11 and the adjacent first dummy electrode 11A is broken, but it may be on the side or partially of the first cell C1 in the first dummy electrode 11A. A broken line is formed.

Further, although not shown, the second conductive layer 9 disposed on the back surface of the transparent insulating substrate 5 in the active region S1 may have a plurality of second dummy electrodes disposed between the plurality of second electrodes 21. The second dummy electrodes are insulated from the plurality of second electrodes 21, and have the second mesh pattern M2 composed of the plurality of second cells C2 similarly to the second electrodes 21.

In addition, the second electrode 21 and the adjacent second dummy electrode are electrically insulated by providing a wire having a width of 5 μm or more and 30 μm or less on a thin metal wire disposed along the continuous second mesh pattern M2. The shape may be such that the boundary between the second electrode 21 and the adjacent first dummy electrode is broken. However, the disconnection may be formed on all sides or portions of the second cell C2 in the second dummy electrode. .

As described above, the conductive film 1 for a touch panel is formed with the conductive member 6A including the first electrode 11, the first peripheral wiring 12, the first external connection terminal 13, and the first connection portion 14 on the surface of the transparent insulating substrate 5. The conductive member 6B including the second electrode 21, the second peripheral wiring 22, the second external connection terminal 23, and the second connection portion 24 is formed on the back surface of the transparent insulating substrate 5 to be manufactured.

At this time, the first electrode 11 is formed of the first conductive layer 8 in which the first metal thin wires 15 are arranged along the first mesh pattern M1, and the second electrode 21 is provided with the second metal thin wires along the second mesh pattern M2. The second conductive layer 9 of 25 is formed, and the first conductive layer 8 and the second conductive layer 9 are disposed so as to overlap each other in the active region S1 via the transparent insulating substrate 5 as shown in FIG.

The method of forming the conductive member 6A and the conductive member 6B is not particularly limited. For example, <0067> to <0083> of JP-A-2012-185813, <0115> to <0126> of JP-A-2014-209332, or <0215> of JP-A-2015-5495 According to <0216>, the conductive members 6A and 6B can be formed by exposing a photosensitive material having an emulsion layer containing a photosensitive silver halide salt and performing development processing.

Further, it is also possible to form a metal thin film on the front surface and the back surface of the transparent insulating substrate 5, to print a resist on each metal thin film in a pattern, or to expose and develop a fully applied resist. The metal of the opening portion is patterned and etched to form the conductive members. Further, in addition to the above, a method of printing a paste containing fine particles of a material constituting the conductive member on the front and back surfaces of the transparent insulating substrate 5 and performing metal plating on the paste can be used; In the inkjet method, an ink containing fine particles constituting a material of the conductive member is used; a method of forming an ink containing fine particles of a material constituting the conductive member by screen printing; and forming a groove in the transparent insulating substrate 5 A method of applying a conductive ink; a micro contact printing patterning method or the like.

In addition, in the above, the conductive member 6A including the first electrode 11, the first peripheral wiring 12, the first external connection terminal 13, and the first connection portion 14 is disposed on the surface of the transparent insulating substrate 5, and is on the transparent insulating substrate 5. The conductive member 6B including the second electrode 21, the second peripheral wiring 22, the second external connection terminal 23, and the second connection portion 24 is disposed on the back surface, but is not limited thereto.

For example, the conductive member 6A and the conductive member 6B may be disposed on the one surface side of the transparent insulating substrate 5 via the interlayer insulating film.

Further, it is also possible to adopt a configuration in which two substrates are provided. In other words, the conductive member 6A can be disposed on the surface of the first transparent insulating substrate, the conductive member 6B can be disposed on the surface of the second transparent insulating substrate, and the first transparent portion can be formed by using an optically clear adhesive sheet (Optical Clear Adhesive). The insulating substrate and the second transparent insulating substrate are bonded together and used.

In addition, the conductive member 6A and the conductive member 6B may be disposed on the surface of the anti-reflection laminate 4C shown in FIG. 3 without using the transparent insulating substrate 5 via the interlayer insulating film.

As the shape of the electrode pattern of the capacitive touch panel, in addition to the so-called bar and stripe electrode pattern shape shown in FIG. 4, it is of course also applicable to, for example, FIG. 16 of International Publication WO2010/012179. The shape of the electrode pattern disclosed in FIG. 7 or FIG. 20 of the publication WO 2013/094728 can also be applied to the electrode pattern of a capacitive touch panel of another shape.

Further, it is also applicable to a touch panel having a configuration of a detecting electrode on only one side of the substrate, as disclosed in US 2012/0262414, and the like.

In addition, the touch panel can also be used in combination with other functional films. A functional film for improving image quality that prevents rainbow unevenness using a substrate having a high retardation value as disclosed in Japanese Laid-Open Patent Publication No. 2014-13264, and the same as disclosed in Japanese Laid-Open Patent Publication No. H2014-142462 A circular polarizing plate that improves the visibility of the electrodes of the touch panel is combined or the like.

<<Polarizer>>

Moreover, as an article containing the antireflection laminated body of this invention, a polarizing plate is mentioned.

The polarizing plate of the present invention has the antireflection laminate of the present invention and a polarizer. In the antireflection laminate of the present invention, a polarizer is provided on a surface of the resin film opposite to one side having one side of the HC layer and the AR layer.

More specifically, the antireflection laminate of the present invention can be used as one or both of the protective films including the polarizer and the polarizing plate disposed on both sides of the protective film. By using the antireflection laminate of the present invention, it is possible to provide a polarizing plate which has an antireflection function, can sufficiently suppress keyboard transfer accompanying a load, and exhibits excellent rub resistance.

As one of the protective films, the antireflection laminate of the present invention can be used, and the other protective film uses a usual cellulose acetate film. In this case, the other protective film is preferably a cellulose acetate film obtained by a film forming method and stretched in the width direction of the film form at a stretching ratio of 10 to 100%.

Further, in the two protective films of the polarizer, the optical compensation film having the optical compensation layer including the optically anisotropic layer of the film other than the antireflection laminate of the present invention is also preferable. The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen. As the optical compensation film, a known one can be used. However, from the viewpoint of widening the viewing angle, the optical compensation film described in JP-A-2001-100042 is preferable.

The polarizer includes an iodine-based polarizer, a dye-based polarizer using a dichroic dye, or a polyolefin-based polarizer. An iodine-based polarizer and a dye-based polarizer are generally produced using a polyvinyl alcohol-based film.

Further, as the polarizer, a known polarizer or a polarizer cut out from a long polarizer whose absorption axis of the polarizer is neither parallel nor perpendicular to the longitudinal direction can be used. A long polarizer whose absorption axis of the polarizer is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.

In other words, the both ends of the polymer film such as a polyvinyl alcohol-based film which is continuously supplied by the holding means are stretched and stretched, and are stretched at least 1.1 to 20.0 times in the film width direction. Then, it can be manufactured by the following stretching method, that is, the traveling speed difference in the longitudinal direction of the holding device at both ends of the film is within 3%, and at the exit of the process for maintaining the both ends of the film, the film conveying direction and the film are The film is oriented in such a manner that the angle of the film is inclined by 20 to 70°, and the film conveying direction is bent while maintaining the both ends of the film. In particular, from the viewpoint of productivity, it is preferred to use a stretching method in which the film transport direction is inclined at an angle of 45 to the angle formed by the substantial stretching direction of the film at the exit of the process for maintaining the both ends of the film.

The method of stretching the polymer film can be applied to the description of paragraphs 0020 to 0030 of JP-A-2002-86554.

 [Examples]  

Hereinafter, the present invention will be described in further detail based on examples. In addition, the invention is not limited thereto. In the following examples, the "parts" and "%" indicating the composition are the mass basis unless otherwise specified.

<Example>

<1-1. Production of resin film (TAC film with a thickness of 100 μm) >

A laminated film of three layers of the cellulose halide of the outer layer/core layer/outer layer was produced by the following method.

(1) Preparation of core layer cellulose halide thick slurry

The following composition was put into a mixing tank and kneaded to prepare a core layer cellulose halide thick slurry solution.

----------------------------------

Core layer cellulose sulphate concentrate

----------------------------------

‧Acetyl cellulose with a degree of substitution of 2.88 and a weight average molecular weight of 260,000 100 parts by mass

‧ 10 parts by mass of phthalate oligomer A with the following structure

‧ compound (A-1) represented by the following formula I, 4 parts by mass

‧ The ultraviolet absorber (manufactured by BASF Corporation) represented by the following formula II: 2.7 parts by mass

‧Light stabilizer (manufactured by BASF, trade name: TINUVIN123) 0.18 parts by mass

‧ N-alkenyl propylene diamine triacetic acid (manufactured by Nagase Chemtex Corporation, trade name: Techrun DO) 0.02 parts by mass

‧ dichloromethane (first solvent) 430 parts by mass

‧Methanol (second solvent) 64 parts by mass

----------------------------------

The compounds used are shown below.

Phthalate oligomer A (weight average molecular weight: 750)

Compound (A-1) represented by the following formula I

Formula I:

Ultraviolet absorber represented by formula II

Formula II: [Chemical Formula 15]

(2) Preparation of outer layer cellulose sulphate thick slurry

To 90 parts by mass of the above-mentioned core layer cellulose sulphate concentrate, 10 parts by mass of the following inorganic particle-containing composition was added to prepare an outer layer cellulose sulphate thick slurry.

-------------------------------

Composition containing inorganic particles

-------------------------------

Cerium oxide particles having an average primary particle diameter of 20 nm (manufactured by NIPPON AEROSIL Corporation, trade name: AEROSIL R972) 2 parts by mass

Dichloromethane (1st solvent) 76 parts by mass

Methanol (second solvent) 11 parts by mass

Core layer cellulose sulphate concentrated slurry 1 part by mass

-------------------------------

(3) Production of resin film

The outer layer cellulose sulphate concentrated slurry is disposed on both sides of the core layer cellulose sulphate concentrated slurry, and the outer layer cellulose sulphate thick slurry, the core layer cellulose sulphate thick slurry and the outer layer cellulose sulphate thick slurry Three kinds of castings were simultaneously cast from the casting opening on a casting belt having a surface temperature of 20 °C.

As the casting tape, a stainless steel endless belt having a width of 2.1 m and a length of 70 m was used. The casting tape was ground to a thickness of 1.5 mm and a surface roughness of 0.05 μm or less. It is made of SUS 316 and uses a casting tape with sufficient corrosion resistance and strength. The thickness of the entire casting tape is not more than 0.5%.

With respect to the obtained cast film, a rapid drying wind having a wind speed of 8 m/s, a gas concentration of 16%, and a temperature of 60 ° C was blown onto the surface of the casting film to form an initial film. Then, a dry air of 140 ° C was sent from the upstream side of the upper portion of the casting belt. Further, dry air of 120 ° C and dry wind of 60 ° C were sent from the downstream side.

After the amount of the residual solvent was about 33% by mass, it was peeled off from the belt. Next, both ends of the obtained film in the width direction were fixed by a tenter jig, and the film having a solvent residual amount of 3 to 15% by mass was dried while being stretched to 1.06 times in the transverse direction. Then, it was further dried by transporting between rolls of the heat treatment apparatus to prepare a TAC film having a thickness of 100 μm (outer layer/core layer/outer layer = 3 μm/94 μm/3 μm). The obtained TAC film is described as TAC in Table 2 below.

<1-2. Production of resin film (TAC film with different thickness)>

The same method as above was used, but the thickness was adjusted to 60 μm (outer layer/core layer/outer layer=3 μm/54 μm/3 μm), 80 μm (outer layer/core layer/outer layer=3 μm/74 μm/3 μm), and 90 μm (outer layer/core layer). / outer layer = 3 μm / 84 μm / 3 μm), 150 μm (outer layer / core layer / outer layer = 3 μm / 144 μm / 3 μm), 200 μm (outer layer / core layer / outer layer = 3 μm / 194 μm / 3 μm), and TAC films having different thicknesses were produced.

<2-1. Preparation of hardenable composition for formation of hard coat layer (HC layer) >

The components were mixed and mixed with a polypropylene filter having a pore size of 10 μm to prepare a curable composition for forming an HC layer A-1 to A-10.

In the above Table 1, the blending ratio is described in parts by mass. Further, "-" means that the component is not contained.

The details of each compound described in Table 1 are shown below.

<Polymerizable Compound 1>

DPHA: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA)

<Polymerizable Compound 2>

CYCLOMER M100: 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Corporation, trade name)

CEL2021P: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name)

<Polymerizable Compound 3>

LIGHT ESTER 2EG: diethylene glycol dimethacrylate (manufactured by KYOEISHA CHEMICAL Co., Ltd., trade name)

BLEMMER GMR: glycerin dimethacrylate (manufactured by Nippon Oil & Fats Co., Ltd., trade name)

A200: Polyethylene glycol #200 diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, molecular weight 308)

UA160TM: a urethane acrylate polymer (reactant of 2-hydroxyethyl acrylate, polytetramethylene glycol diol, and isophorone diisocyanate) (manufactured by Shin-Nakamura Chemical Co., Ltd., Product name)

<Polymerization initiator>

Irg184: 1-hydroxy-cyclohexyl-phenyl-ketone (α-hydroxyalkylphenone-based radical photopolymerization initiator, manufactured by BASF Corporation, trade name: IRGACURE 184)

CPI-100P: Triarylsulfonium salt photocationic polymerization initiator, manufactured by San-Apro Ltd., trade name

[Example 1]

<2-2. Formation of hard coat layer (HC layer) >

The HC layer-forming curable composition A-1 was applied to one surface of a TAC film having a thickness of 100 μm prepared as described above and cured to form a HC layer having a thickness of 25 μm, thereby producing a resin film with an HC layer.

Specifically, the method of coating and hardening is as follows. The curable composition for forming a layer of HC is applied at a conveying speed of 30 m/min by a die coating method using a slit die described in Example 1 of JP-A-2006-122889, and at ambient temperature. It was dried at 60 ° C for 150 seconds. Then, an air-cooled metal halide lamp (manufactured by EYE GRAPHICS Co., Ltd.) of 160 W/cm was used under an oxygen purge at a nitrogen concentration of about 0.1% by volume, and the irradiation illuminance was 20 mW/cm ² and the irradiation amount was 30 mJ/cm ^{2 .} After the ultraviolet ray is applied, the applied HC layer-forming hardenable composition is cured to form an HC layer, and then wound up.

<3. Production of anti-reflection laminate >

An inorganic oxide layer (AR layer) was formed on the HC layer of the resin film with the HC layer prepared above to prepare the antireflection laminate of Example 1. As shown in FIG. 1, the anti-reflection laminated body 4A has a structure in which a resin film 1A, an HC layer 2A, and an AR layer 3A are laminated in this order.

Specifically, the formation of the AR layer is performed by a sputtering method under the conditions of any film formation pressure so that the layer composition becomes Nb ₂ O ₅ /SiO ₂ /Nb ₂ O ₅ /SiO ₂ from the side of the HC layer, and the film thickness of each layer. Film formation was carried out so as to be 15 nm / 2 5 nm / 105 nm / 85 nm, respectively.

[Examples 2 to 6]

The examples 2 to 6 were produced in the same manner as in Example 1 except that the curable composition A-2 to A-6 for forming the HC layer was used instead of the curable composition A-1 for forming the HC layer. Anti-reflection laminate.

[Examples 7 to 11]

The antireflection laminates of Examples 7 to 11 were produced in the same manner as in Example 1 except that the thickness of the TAC film and/or the thickness of the HC layer were changed to the thicknesses described in Table 2 below.

<Comparative example>

[Comparative Examples 1 to 4]

In the same manner as in Example 1, except that the curable composition A-7 to A-10 for forming the HC layer was used instead of the curable composition A-1 for forming the HC layer, Comparative Examples 1 to 4 were produced. Anti-reflection laminate.

[Comparative Examples 5 to 7]

The antireflection laminates of Comparative Examples 5 to 7 were produced in the same manner as in Example 1 except that the thickness of the TAC film and/or the thickness of the HC layer were changed to the thicknesses described in Table 2 below.

[Comparative Example 8]

An antireflection laminate of Comparative Example 8 was produced in the same manner as in Example 1 except that the AR layer was not provided.

<trial>

The following test was carried out on the antireflection laminate produced in the above. A summary of the test results is shown in Table 2 below.

[Test Example 1] Rigidity

The resin film thickness d _S , the resin film elastic modulus σ _S , the HC layer thickness d _H , the HC layer elastic modulus σ _H , the AR layer thickness d _A , and the AR layer elastic modulus σ _{A are} calculated by the following formula The rigidity of the reflective laminate.

Synthetic elastic modulus σ _syn =(σ _S d _S +σ _h d _H +σ _A d _A )/(d _S +d _H +d _A )

Rigidity = σ _syn × (d _S + d _H + d _A ) ³

Further, each of the elastic modulus σ _S , σ _{h ,} and σ _A is calculated by the following method.

(elastic modulus)

Ultra-micro hardness test system: using PICODENTOR (manufactured by Fischer), and using Berkovich type indenter (front end edge 142.3 °) as a triangular pyramid diamond indenter, the indenter is perpendicularly contacted with the sample surface at 25 ° C The load is gradually applied, and after the maximum load is reached, the load is gradually restored to zero. The value P/A at which the maximum load P at this time is divided by the projected area A of the indenter contact portion is calculated as the nanoindentation hardness H. When the slope of the unloading curve was set to S, the nanoindentation elastic modulus σ at 25 ° C was calculated using the following formula. In the following formula, π represents a pi.

σ=(S× π)/(2 A)

The details of the principle are described in Handbook of Micro/NanoTribology (Bharat Bhushan, ed. CRC).

The sample for measuring the elastic modulus described above was produced by the following method.

(sample for measuring elastic modulus)

Method for determining elastic modulus of each layer

Resin film: A resin film was fixed on a glass plate with an adhesive and used as a sample for measurement.

In the HC layer, the curable composition for forming a HC layer was cast on a resin film having a film thickness of 1 mm so that the film thickness after drying became 25 μm, UV-cured, and dried at an ambient temperature of 80 ° C. The HC layer was formed over 10 minutes. The resin film surface side of the resin film with the HC layer was fixed to a glass plate by an adhesive and used as a sample for measurement.

Further, when the thickness of the HC layer is about 25 μm, the elastic modulus measured by this method can be regarded as the elastic modulus of the HC layer.

AR layer: An AR layer was directly formed on a glass plate by a sputtering method in the same manner as the formation of the AR layer in the production of the above-described antireflection laminate, and used as a sample for measurement.

[Test Example 2] Pencil hardness

The pencil hardness was evaluated in accordance with JIS (JIS is Japanese Industrial Standards) K 5400.

The anti-reflection laminate (the layer having the HC layer and the AR layer in this order on the resin film) was conditioned for 2 hours in an environment of a temperature of 25 ° C and a relative humidity of 60%, and then the test of H-9H specified in JIS S 6006 was used. A pencil was used to scratch the five different portions of the surface of the AR layer with a load of 4.9 N. Then, among the hardness of the pencil which was visually confirmed to have 0 to 2 portions of the scratched portion, the pencil hardness having the highest hardness was used as the evaluation result. Regarding the pencil hardness, the higher the numerical value described in the front of "H", the higher the hardness, and the more preferable.

[Test Example 3] Keyboard transfer test (load test)

An antireflection laminate attached to the glass via a bonding agent was placed on the keyboard (manufactured by Apple Inc., trade name: MacBook pro) so that the AR layer was in contact with the keyboard. In addition, the glass and the laminated anti-reflection laminate are the same size (longitudinal × horizontal) as the keyboard. In a state where a load of 1 kg was applied from above the glass, the oscillating machine (manufactured by YAMATO SCIENTIFIC CO., LTD., trade name: KM) was shaken for 3 hours to visually observe the surface of the AR layer of the antireflection laminate. Injuries and depressions were evaluated according to the following criteria.

<Concave: Evaluation Criteria>

A: No depression was observed at all.

B: The dent was slightly observed, but there was no problem in use.

C: A depression was observed in a part, but there was no problem in use.

D: A depression was observed in a part, which was a problematic level of use.

E: A depression was observed on the entire surface, which was a problematic level of use.

<scratch: evaluation criteria>

A: No scratches were observed at all.

B: Scratches were slightly observed, but there was no problem in use.

C: Scratches were observed in one part, but there was no problem in use.

D: Scratches were observed in one part, which was a problematic level of use.

E: Scratches were observed on the entire surface, which was a problematic level of use.

[Test Example 4] Steel wool (SW) friction test

Using a friction tester, the steel wool was wound around the friction front end (1 cm × 1 cm) of the test machine in contact with the AR layer of the anti-reflection laminate at a temperature of 25 ° C and a relative humidity of 60% (NIHON STEEL WOOL CO. , manufactured by No. 0), and band-fixed to prevent movement, and rubbed the surface of the AR layer of the anti-reflection laminate under the following conditions.

Moving distance (one-way): 13 cm, friction speed: 13 cm/sec, load: 500 g, front end contact area: 1 cm × 1 cm.

An oily black ink was applied to the surface of the resin film of the antireflection laminate after the test, and scratches in the portion in contact with the steel wool were visually observed from the AR layer side under reflected light, and evaluated according to the following criteria.

<Evaluation criteria>

A: Even if you look very carefully, you can't completely scratch it.

B: If you look very carefully, you can observe the inconspicuous scratches slightly, but it is not a problem.

C: If you look closely, you can observe inconspicuous scratches, but it is not a problem.

D: A moderate degree of scratching can be observed, which is a significant level of scratching.

E: There is a scratch at a glance, which is a very significant level.

[Test Example 5] Specular reflectance

The "specular reflectance" was measured by the following method.

After the surface of the resin film of the antireflection laminate was roughened with a sandpaper, it was coated with a black ink (supplemented with a black ink) manufactured by Teranishi Chemical Industry Co., Ltd. to prepare a sample for measurement. Using a spectrophotometer: V-550, an option ARV-474 assembly (all manufactured by JASCO Corporation), the surface of the AR layer of the measurement sample was irradiated with light at a wavelength of 380 nm to 780 nm, with respect to an incident angle of 5°. The specular reflectance was measured at a light angle of 5°, and the average reflectance at 380 nm to 780 nm was calculated.

[Test Example 6] Knoop hardness

Based on ISO 14577, the Knoop indenter was used, and the AR layer of the antireflection laminate was pressed under the following conditions, and the arithmetic mean of the measurement 10 times was calculated as the Knoop hardness.

[Measurement device] Micro hardness tester: Fischer scope HM2000 (manufactured by Fischer Instrume nts K.K.)

[loading time] 10 seconds

[pressing load] 50mN

[Test Example 7] Thickness

The "thickness" was measured by a scanning electron microscope (SEM) by the following method.

The cross section of each of the constituent members (resin film, HC layer, and AR layer) or members including the constituent members (for example, a liquid crystal panel or a part thereof) is exposed by a conventional method such as an ion beam or a microtome, and then exposed on the exposed cross section. Cross-sectional observation based on SEM. In the cross-sectional observation, various thicknesses were obtained as arithmetic averages of the thicknesses at three equal points except for both ends when the width direction of the member was divided into four.

In the above Table 2, "-" indicates that the laminate of Comparative Example 8 did not have an AR layer and was not evaluated.

Further, the composition ratio of the polymerizable compound forming the HC layer is a mass ratio.

As described in Table 2, the antireflection laminates of the present invention of Examples 1 to 11 can sufficiently suppress the occurrence of dents and scratches due to load, and also have excellent rub resistance and low specular reflectance. The reflection function is also excellent.

On the other hand, the laminate of Comparative Examples 1 and 2 had a Knoop hardness of more than 300 mN/mm ² . The comparative examples 1 and 2 were inferior in abrasion resistance.

Further, the laminated body of Comparative Example 3 had a pencil hardness of less than 4H, the laminated body of Comparative Example 4 had a pencil hardness of less than 4H, and the laminated body had a Knoop hardness of less than 150 mN/mm ² . The comparative examples 3 and 4 were inferior in suppressing the occurrence of scratches after the keyboard transfer test, and were also inferior in rub resistance.

The laminates of Comparative Examples 5 and 7 each had a rigidity of less than 8.0 N ‧ mm, and the pencil hardness of the laminate was less than 4H. The comparative examples 5 and 7 were inferior in both the generation of the depression and the generation of the scratch after the keyboard transfer test was suppressed. Further, the laminated body of Comparative Example 6 had a pencil hardness of less than 4H. This Comparative Example 6 was inferior in suppressing the occurrence of scratches after the keyboard transfer test.

Further, in Comparative Example 8 which does not have the AR layer, the specular reflectance was 4%, and the antireflection function was insufficient.

When the antireflection laminate of the present invention is used for a polarizing plate and an image display device, it is considered that the polarizing plate or the like can sufficiently suppress the transfer of the keyboard accompanying the load, and the excellent scratch resistance is exhibited.

Claims (11)

An anti-reflection laminate comprising at least a resin film, a one-side hard coat layer disposed on the resin film, and an anti-reflection laminate body of an inorganic oxide layer disposed on the hard coat layer, the laminate body The pencil hardness is 4H or more, the rigidity is 8.0 N ‧ mm or more, and the Knoop hardness is 150 to 300 mN/mm ² .  The antireflection laminate according to claim 1, wherein the hard coat layer is obtained by polymerizing and hardening a composition, and the composition contains a polymerizable compound 1 having a radical polymerizable group, and is different from the polymerizable compound 1 The polymerizable compound 2 having a cationically polymerizable group and a radical polymerizable group in the same molecule and/or the polymerizable compound 3 having an alkoxy group and a radical polymerizable group in the same molecule.    The antireflection laminate of claim 2, wherein the content of the polymerizable compound 2 is 30% by mass or more of all the polymerizable compounds contained in the composition.    The antireflection laminate of claim 2, wherein the content of the polymerizable compound 3 in all the polymerizable compounds contained in the composition is 30% by mass or more.    The antireflection laminate according to any one of claims 2 to 4, wherein the cationically polymerizable group is an epoxy group.    An antireflection laminate according to claim 5, wherein the epoxy group is an alicyclic epoxy group.    The antireflection laminate according to any one of claims 2 to 4, wherein the alkylene oxide is an ethoxy group.    The antireflection laminate according to any one of claims 1 to 4, wherein the hard coat layer has a thickness of from 15 μm to 40 μm.    The antireflection laminate according to any one of claims 1 to 4, wherein the resin film has a thickness of from 80 μm to 250 μm.    A polarizing plate having the antireflection laminate and the polarizer according to any one of claims 1 to 9.    An image display device having the antireflection laminate as claimed in any one of claims 1 to 9.