JP6825095B2 - Anti-glare anti-reflective film, manufacturing method of anti-glare anti-reflective film, polarizing plate, image display device, and self-luminous display device - Google Patents

Description

The present invention relates to an antiglare antireflection film, a method for producing an antiglare antireflection film, a polarizing plate, an image display device, and a self-luminous display device.

Prevents contrast degradation and image reflection due to reflection of external light in image display devices such as cathode ray tube display devices (CRT), plasma displays (PDP), electroluminescence displays (ELD), and liquid crystal display devices (LCD). Therefore, an antiglare antireflection film may be placed on the outermost surface of the display.

For example, in Patent Documents 1 and 2, an antiglare layer having an uneven shape is provided on a transparent film support, and a low refractive index layer containing hollow silica particles is further provided on the antiglare layer to prevent antiglare reflection. The film is listed. Such an antiglare antireflection film is provided with a low refractive index layer which is a thin film layer having a layer thickness of 200 nm or less on at least the outermost surface, and antireflection is performed by optical interference of the low refractive index layer.

Further, as a technique capable of imparting high antireflection performance, an antireflection film having a fine uneven shape having a period equal to or less than the wavelength of visible light on the surface of the base material, that is, an antireflection film having a so-called moth eye structure is known. There is. The moth-eye structure can create a refractive index gradient layer in which the refractive index continuously changes from air toward the bulk material inside the base material in a pseudo manner, and can prevent light reflection.

As an antiglare antireflection film having a moth-eye structure, Patent Document 3 describes an antiglare layer forming composition containing fine particles and a binder resin forming compound as a base film and an antiglare layer having an uneven shape. Described is an antiglare antireflection film in which a moth-eye structure is formed by applying it on an antiglare layer of a glare film and allowing a binder resin forming compound to permeate into the antiglare layer. Further, Patent Document 4 describes an antiglare antireflection film by a so-called nanoimprint method, in which a curable resin is molded into a mold to form a moth-eye structure.

Japanese Unexamined Patent Publication No. 2006-146027 Japanese Unexamined Patent Publication No. 2006-145736 Japanese Unexamined Patent Publication No. 2016-53601 Japanese Patent No. 6089402

However, the antiglare antireflection film described in Patent Documents 1 and 2 is required to have further antireflection performance.
In the technique of Patent Document 3, when the antireflection layer forming composition is applied on the antiglare layer of the antiglare film having the base film and the antiglare layer to form the antireflection layer, the coating liquid (antireflection layer formation) is formed. It was found that the anti-glare anti-reflection film with low reflectance may not be produced because the leveling of the composition) causes unevenness in the coating amount between the convex and concave portions of the anti-glare layer and causes the number of fine particles to become sparse and dense. It was.
The moth-eye structure produced by the nanoimprint method of Patent Document 4 has a problem of being inferior in scratch resistance.

That is, an object of the present invention is to provide an antiglare antireflection film having sufficient antireflection performance. Another object of the present invention is to provide a method for producing the antiglare antireflection film, a polarizing plate having the antiglare antireflection film, an image display device, and a self-luminous display device.

The present inventors have diligently studied in order to solve the above problems, and by forming an antireflection layer on the antireflection layer of the antiglare film having the base film and the antiglare layer by transfer, the recess of the antiglare layer is formed. It has been found that an antireflection layer having a uniform thickness can be formed at the convex portion, and an antiglare antireflection film having a low reflectance can be produced.

That is, the above problem is solved by the following configuration.
[1]
An anti-glare anti-reflection film having a base film, an anti-glare layer, and an anti-reflection layer in this order.
The integrated reflectance of the antiglare antireflection film is 1.0% or less.
The specular reflectance of the antiglare antireflection film is 0.4% or less.
The uneven shape of the surface of the antiglare antireflection film has an arithmetic average roughness Ra of 0.03 μm ≦ Ra ≦ 0.4 μm and an average spacing Sm of the unevenness of 20 μm ≦ Sm ≦ 700 μm.
The ratio of the average thickness of the antireflection layer in the convex portion of the antiglare antireflection film to the average thickness of the antireflection layer in the concave portion is 1.0 to 0.7.
An antiglare antireflection film having an adhesive layer between the antiglare layer and the antireflection layer.
[2]
The antireflection layer contains particles having an average primary particle diameter of 100 nm or more and 250 nm or less and a binder resin, and has a moth-eye structure due to the particles on the surface opposite to the interface with the antiglare layer, according to [1]. Anti-glare anti-reflective film.
[3]
An anti-glare anti-reflection film having a base film, an anti-glare layer, and an anti-reflection layer in this order.
The integrated reflectance of the antiglare antireflection film is 1.0% or less.
The specular reflectance of the antiglare antireflection film is 0.4% or less.
The uneven shape of the surface of the antiglare antireflection film has an arithmetic average roughness Ra of 0.03 μm ≦ Ra ≦ 0.4 μm and an average spacing Sm of the unevenness of 20 μm ≦ Sm ≦ 700 μm.
The ratio of the average thickness of the antireflection layer in the convex portion of the antiglare antireflection film to the average thickness of the antireflection layer in the concave portion is 1.0 to 0.7.
The antireflection layer contains particles having an average primary particle diameter of 100 nm or more and 250 nm or less and a binder resin, and has a moth-eye structure due to the particles on the surface opposite to the interface with the antiglare layer. the film.
[4]
The antiglare antireflection film according to [2] or [3], wherein the binder resin has a Si—O bond and the average silicon content Si / C of the binder resin is 0.01 or more.
[5]
The antiglare reflection according to any one of [1] to [4], wherein the uneven shape on the surface of the antiglare antireflection film has an arithmetic average roughness Ra of 0.1 μm ≦ Ra ≦ 0.4 μm. Prevention film.
[6]
Item 2. The protection according to any one of [1] to [5], wherein the antiglare layer contains a component having a functional group other than the (meth) acryloyl group capable of forming a covalent bond with the antireflection layer. Dazzling anti-reflective film.
[7]
A method for producing an antiglare antireflection film having a base film, an antiglare layer, and an antireflection layer in this order.
A composition for forming an antiglare layer containing a compound for forming a binder resin for an antiglare layer and particles for an antiglare layer is applied onto the base film, and the composition for forming the antiglare layer is formed by ionizing radiation irradiation or heating. And the process of forming an anti-glare layer by curing
A step of applying an antireflection layer forming composition on a temporary support and semi-hardening it by ionizing radiation irradiation or heating at a surface hardening rate of 10 to 70% to form an antireflection layer.
The step of transferring the antireflection layer from the temporary support onto the antiglare layer, and
A method for manufacturing an antiglare antireflection film having.
[8]
The antiglare according to [7], which comprises a step of providing an adhesive layer on the antiglare layer or on the antireflection layer before transferring the antireflection layer from the temporary support onto the antiglare layer. A method for manufacturing an antireflection film.
[9]
The method for producing an anti-glare anti-reflection film according to [7] or [8], which comprises a step of heating the anti-reflection layer and the anti-glare layer in a bonded state.
[10]
On the temporary support, particles (a2) having an average primary particle diameter of 100 nm or more and 250 nm or less and a curable compound (a1) are placed in a layer (a) containing the curable compound (a1). Step (1), which is provided with a thickness that allows the particles to be buried
Step (2) of obtaining a layer (ca) by curing a part of the layer (a).
Step (3) of laminating the layer (b) of the adhesive film having the support and the layer (b) containing the adhesive on the support with the layer (ca).
The layer (ca) is buried in the combined layer of the layer (ca) and the layer (b), and the particles (a2) protrude from the interface of the layer (ca) on the support side. ), The step (4) of bringing the position of the interface on the support side closer to the temporary support side.
Step (5) of peeling off the temporary support,
Step (6) of laminating the antiglare layer of the antiglare film having the base film and the antiglare layer and the layer (ca) of the laminate containing the layer (ca) obtained in the step (5). ,
The step (7) of curing the layer (ca) in a state where the particles (a2) are buried in a layer in which the layer (ca) and the layer (b) are combined, and
Step (8) of peeling the adhesive film,
The method for producing an antiglare antireflection film according to any one of [7] to [9], wherein
[11]
A polarizing plate having the antiglare antireflection film according to any one of [1] to [6] as a polarizing plate protective film.
[12]
An image display device having the antiglare antireflection film according to any one of [1] to [6] or the polarizing plate according to [11].
[13]
A self-luminous display device provided with the antiglare antireflection film according to any one of [1] to [6] on the surface.
Although the present invention relates to the above [1] to [13], other matters are also described in the present specification for reference.

<1>
An anti-glare anti-reflection film having a base film, an anti-glare layer, and an anti-reflection layer in this order.
The integrated reflectance of the antiglare antireflection film is 1.0% or less.
The specular reflectance of the antiglare antireflection film is 0.4% or less.
The uneven shape of the surface of the antiglare antireflection film has an arithmetic average roughness Ra of 0.03 μm ≦ Ra ≦ 0.4 μm and an average spacing Sm of the unevenness of 20 μm ≦ Sm ≦ 700 μm.
An antiglare antireflection film in which the ratio of the average thickness of the antireflection layer in the convex portion to the average thickness of the antireflection layer in the concave portion of the antiglare antireflection film is 1.0 to 0.7.
<2>
The antiglare antireflection film according to <1>, wherein the uneven shape on the surface of the antiglare antireflection film has an arithmetic average roughness Ra of 0.1 μm ≦ Ra ≦ 0.4 μm.
<3>
The antiglare antireflection film according to <1> or <2>, which has an adhesive layer between the antiglare layer and the antireflection layer.
<4>
The antiglare layer according to any one of <1> to <3>, wherein the antiglare layer contains a component having a functional group other than the (meth) acryloyl group capable of forming a covalent bond with the antireflection layer. Dazzling anti-reflective film.
<5>
The antireflection layer contains particles having an average primary particle diameter of 100 nm or more and 250 nm or less and a binder resin, and has a moth-eye structure due to the particles on the surface opposite to the interface with the antiglare layer, <1> to < The antiglare antireflection film according to any one of 4>.
<6>
The antiglare antireflection film according to <5>, wherein the binder resin has a Si—O bond and the average silicon content Si / C of the binder resin is 0.01 or more.
<7>
A method for producing an antiglare antireflection film having a base film, an antiglare layer, and an antireflection layer in this order.
A composition for forming an antiglare layer containing a compound for forming a binder resin for an antiglare layer and particles for an antiglare layer is applied onto the base film, and the composition for forming the antiglare layer is formed by ionizing radiation irradiation or heating. And the process of forming an anti-glare layer by curing
A step of applying an antireflection layer forming composition on a temporary support and semi-hardening it by ionizing radiation irradiation or heating at a surface hardening rate of 10 to 70% to form an antireflection layer.
The step of transferring the antireflection layer from the temporary support onto the antiglare layer, and
A method for manufacturing an antiglare antireflection film having.
<8>
The antiglare layer according to <7>, which comprises a step of providing an adhesive layer on the antiglare layer or on the antireflection layer before transferring the antireflection layer from the temporary support to the antiglare layer. A method for manufacturing an antireflection film.
<9>
The method for producing an anti-glare anti-reflection film according to <7> or <8>, which comprises a step of heating the anti-reflection layer and the anti-glare layer in a bonded state.
<10>
On the temporary support, particles (a2) having an average primary particle diameter of 100 nm or more and 250 nm or less and a curable compound (a1) are placed in a layer (a) containing the curable compound (a1). Step (1), which is provided with a thickness that allows the particles to be buried
Step (2) of obtaining a layer (ca) by curing a part of the layer (a).
Step (3) of laminating the layer (b) of the adhesive film having the support and the layer (b) containing the adhesive on the support with the layer (ca).
The layer (ca) is buried in the combined layer of the layer (ca) and the layer (b), and the particles (a2) protrude from the interface of the layer (ca) on the support side. ), The step (4) of bringing the position of the interface on the support side closer to the temporary support side.
Step (5) of peeling off the temporary support,
Step (6) of laminating the antiglare layer of the antiglare film having the base film and the antiglare layer and the layer (ca) of the laminate containing the layer (ca) obtained in the step (5). ,
The step (7) of curing the layer (ca) with the particles (a2) buried in the combined layer of the layer (ca) and the layer (b), and peeling off the adhesive film. Step (8),
The method for producing an antiglare antireflection film according to any one of <7> to <9>, which has the above in this order.
<11>
A polarizing plate having the antiglare antireflection film according to any one of <1> to <6> as a polarizing plate protective film.
<12>
An image display device having the antiglare / antireflection film according to any one of <1> to <6> or the polarizing plate according to <11>.
<13>
A self-luminous display device provided with the antiglare antireflection film according to any one of <1> to <6> on its surface.

According to the present invention, it is possible to provide an antiglare antireflection film having sufficient antireflection performance. Further, according to the present invention, it is possible to provide a method for producing the antiglare antireflection film, a polarizing plate having the antiglare antireflection film, an image display device, and a self-luminous display device.

FIG. 1A is an example of a surface scanning electron microscope (SEM) image of an antiglare antireflection film when an antireflection layer is formed by coating, and FIG. 1B is an example of FIG. 1A. It is a larger version. FIG. 2A is an example of a surface SEM image of the antiglare antireflection film when the antireflection layer is formed by transfer, and FIG. 2B is a magnified view of FIG. 2A. .. It is a schematic diagram which shows an example of the manufacturing method of the antiglare antireflection film of this invention. It is a schematic diagram which shows an example of the manufacturing method of the antiglare antireflection film of this invention. It is a schematic diagram which shows an example of the antiglare antireflection film of this invention. It is a schematic diagram which shows an example of the antiglare antireflection film of this invention. It is a schematic diagram which shows an example of the antiglare antireflection film of this invention.

Hereinafter, the present invention will be described in detail.
In the present specification, "(meth) acrylate", "(meth) acrylic acid", and "(meth) acryloyl" are "acrylate or methacrylate", "acrylic acid or methacrylic acid", and "acryloyl or methacrylic acid", respectively. Represents.
The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.

Further, in the present specification, a film in which an antiglare layer is formed on a base film is referred to as an antiglare film.

<Anti-glare anti-reflective film>
The antiglare antireflection film of the present invention is an antiglare antireflection film having a base film, an antiglare layer, and an antireflection layer in this order.
The integrated reflectance of the antiglare antireflection film is 1.0% or less.
The specular reflectance of the antiglare antireflection film is 0.4% or less.
The uneven shape of the surface of the antiglare antireflection film has an arithmetic average roughness Ra of 0.03 μm ≦ Ra ≦ 0.4 μm and an average spacing Sm of the unevenness of 20 μm ≦ Sm ≦ 700 μm.
This is an anti-glare anti-reflection film in which the ratio of the average thickness of the anti-reflection layer in the convex portion to the average thickness of the anti-reflection layer in the concave portion of the anti-glare anti-reflection film is 1.0 to 0.7.

FIG. 5 is a schematic view showing an example of the antiglare antireflection film of the present invention. The antiglare antireflection film 20 of FIG. 5 has a base film 11, an antiglare layer 12, and an antireflection layer 10. The antiglare layer 12 contains particles 13 for the antiglare layer. The antireflection layer 10 is a moth-eye layer.
FIG. 6 is a schematic view showing another example of the antiglare antireflection film of the present invention. The antiglare antireflection film 20 of FIG. 6 further has an adhesive layer 15 between the antiglare layer 12 and the antireflection layer 10 in FIG.
FIG. 7 is a schematic view showing another example of the antiglare antireflection film of the present invention. In FIG. 5, the antiglare antireflection film 20 of FIG. 7 has an antireflection layer 16 having a low refractive index layer Ln and a high refractive index layer Hn instead of the antireflection layer 10 which is a moth-eye layer.
It should be noted that FIGS. 3 to 7 are schematic views, and the size of each particle, the base material, the thickness of each layer, and the like may not be drawn in the ratio of actual dimensions.

[Anti-glare layer]
The antiglare layer of the antiglare antireflection film of the present invention will be described.
The antiglare layer preferably has an uneven shape on the surface, which can impart antiglare properties to the film due to surface scattering. Further, it is preferable that the film can be provided with a hard coat property for improving the scratch resistance of the film.

As a method for imparting antiglare property, a method of laminating a mat-like polymer having fine irregularities on the surface as described in JP-A-6-16851, and JP-A-2000-206317. As described in JP-A-2000-338310, a method of forming by curing shrinkage of an ionized radiation curable resin due to a difference in the amount of ionized radiation irradiation, the mass ratio of a good solvent to a translucent resin decreases by drying as described in JP-A-2000-338310. As a result, a method of forming irregularities on the surface of the coating film by solidifying the translucent fine particles and the translucent resin while gelling them, and imparting surface irregularities by external pressure as described in JP-A-2000-275404. A method, a method of forming surface irregularities by utilizing phase separation in the process of solvent evaporation from a mixed solution of a plurality of polymers as described in JP-A-2005-195819, and the like are known. Method can be used.

The antiglare layer preferably contains particles for the antiglare layer. As the particles for the antiglare layer, translucent particles or metal oxide fine particles are preferable.
The antiglare layer more preferably contains a binder resin for an antiglare layer capable of imparting hard coat properties, and translucent particles for imparting antiglare properties, and is a protrusion or a plurality of protrusions of the translucent particles themselves. It is preferable that the layer has irregularities formed on the surface by protrusions formed by aggregates of particles.
Further, the antiglare layer is preferably formed by using a composition for forming an antiglare layer containing a binder resin forming compound, translucent particles and a solvent.
The antiglare layer formed by using the antiglare layer forming composition contains a binder resin for the antiglare layer and translucent particles dispersed in the binder resin for the antiglare layer, and has antiglare and hard coat. It is preferable to combine sex.

(Translucent particle 1)
In the present invention, it is preferable that at least one kind of translucent particles is contained in the antiglare layer in order to impart antiglare properties. As one of the preferred embodiments, for example, the translucent particles 1 having an average particle size of the translucent particles larger than the average film thickness of the antiglare layer are used, and the average particle size of the translucent particles 1 is set to the antiglare layer. By making it 0.01 to 4.0 μm larger than the average film thickness of, good antiglare can be imparted. In this case, in order to achieve both the antiglare property and the uniform lamination of the antireflection layer by increasing the ratio of the flat portion on the film surface, the average particle diameter of the translucent particle 1 is the antiglare layer. It is more preferably 0.1 to 3.0 μm larger than the average film thickness, and most preferably 0.5 to 2.5 μm larger. When the average particle size of the translucent particles 1 is 4 μm or less, the average particle size of the translucent particles 1 is preferably 0.1 to 2.5 μm larger than the average film thickness of the antiglare layer, and is 0. Most preferably, it is 1 to 2.0 μm larger.
The average film thickness of the antiglare layer is calculated from an average value obtained by observing the cross section of the antiglare antireflection film with an electron microscope and randomly measuring the film thickness at 30 points.

It is preferable that one convex portion of the antiglare layer is formed by substantially five or less translucent particles 1, and the convex portion is formed by substantially one translucent particle. More preferred. Here, "substantially" means that 90% or more of the convex portions satisfy the preferred embodiment.
When one convex portion of the antiglare layer is formed by substantially one translucent particle 1, it is preferable to select particles having good dispersibility.

Specific examples of the translucent particles 1 include, for example, crosslinked polymethylmethacrylate particles, crosslinked methylmethacrylate-styrene copolymer particles, crosslinked polystyrene particles, crosslinked methylmethacrylate-methylacrylate copolymer particles, and crosslinked alkylacrylate-styrene. Examples thereof include resin particles such as copolymer particles, crosslinked alkyl methacrylate-styrene copolymer particles, melamine / formaldehyde resin particles, and benzoguanamine / formaldehyde resin particles. Of these, crosslinked styrene particles, crosslinked polymethylmethacrylate particles, crosslinked methylmethacrylate-styrene copolymer particles and the like are preferable. Furthermore, surface-modified particles in which compounds containing fluorine atoms, silicon atoms, carboxyl groups, hydroxyl groups, amino groups, sulfonic acid groups, phosphoric acid groups, etc. are chemically bonded to the surface of these resin particles, and nano-sized particles such as silica or zirconia. Examples include particles in which inorganic fine particles are bonded to the surface.
Among them, cross-linked methyl methacrylate-styrene copolymer particles, cross-linked alkyl acrylate-styrene copolymer particles, and cross-linked alkyl methacrylate-in order to adjust the absolute value of the difference in refractive index from the binder component in the antiglare layer. Styrene copolymer particles are preferred.

When the translucent particles 1 are used, visible light scattering such as silica does not occur in order to stabilize the dispersion of the particles in the antiglare layer binder resin or in the antiglare layer forming composition and prevent sedimentation. Dispersants such as sized inorganic fillers and organic compounds (which may be monomers or polymers) may be added.

When the inorganic filler is added, it is effective to prevent the translucent particles from settling as the amount of the inorganic filler added increases, but it is preferable to use the inorganic filler within a range that does not adversely affect the transparency of the coating film. Therefore, it is preferable to contain about 0.1 part by mass of an inorganic filler having a particle size of 0.5 μm or less with respect to 100 parts by mass of the binder resin for the antiglare layer so as not to impair the transparency of the coating film. The dispersant such as an organic compound is preferably added in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the translucent particles. It is more preferably 0.1 to 15 parts by mass, and particularly preferably 0.5 to 10 parts by mass. If it is 0.1 part by mass or more, an additive effect on the dispersion stability appears, and if it is 20 parts by mass or less, the number of components that do not contribute to the dispersion stability increases and problems such as bleed-out do not occur, which is preferable.

As described above, the surface of the translucent particles may be surface-treated for dispersion stability and sedimentation prevention in the binder resin for the antiglare layer or the composition for forming the antiglare layer. The type of surface treatment agent is appropriately selected depending on the binder resin for the antiglare layer and the solvent used. The amount of the surface treatment agent is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the translucent particles. It is more preferably 1 to 25 parts by mass, and particularly preferably 3 to 20 parts by mass. If it is 0.1 part by mass or more, the surface treatment amount for dispersion stability is not insufficient, and if it is 30 parts by mass or less, the components that do not contribute to the surface treatment increase and problems such as bleed-out may occur. It is preferable because it does not exist.

The particle size distribution of the translucent particles is preferably monodisperse particles, that is, particles having a uniform particle size, from the viewpoints of controlling the haze value and diffusivity and homogeneity of the coated surface. The CV value representing the uniformity of the particle size is preferably 0 to 10%, more preferably 0 to 8%, and further preferably 0 to 5%. Further, when particles having a particle size 20% or more larger than the average particle size are defined as coarse particles, the ratio of the coarse particles is preferably 1% or less, more preferably 0.1% or less of the total number of particles. Yes, more preferably 0.01% or less. Translucent particles having such a particle size distribution are also a powerful means for classifying after preparation or synthesis reaction, and particles with a desirable distribution can be obtained by increasing the number of classifications or increasing the degree of classification. be able to. For classification, it is preferable to use a method such as a wind power classification method, a centrifugal classification method, a sedimentation classification method, a filtration classification method, or an electrostatic classification method. The average particle size of the translucent particles is calculated by observing the translucent particles with an optical microscope and calculating the average value of the observed 100 particle diameters.

The addition amount of the translucent particles 1 having an average particle size larger than the average film thickness of the antiglare layer is 0.01 to 1.2% by mass with respect to the total solid content of the antiglare layer. It is preferable in that the ratio of the flat portion on the film surface is increased by making the density of the unevenness sparse, and the antireflection layer is uniformly laminated. The amount of the translucent particles 1 added is more preferably 0.1 to 1.0% by mass, and preferably 0.1 to 0.7% by mass, based on the total solid content of the antiglare layer. More preferred.
It is preferable that the translucent particles project at least 0.01 to 4.0 μm from the binder resin film of the antiglare layer to exhibit antiglare properties.

(Translucent particles 2)
Further, as one of another preferable aspects of the antiglare layer, for example, in order to obtain the required antiglare property, another translucent particle 2 having an average particle diameter different from that of the translucent particle 1 is used alone. Alternatively, they may be used in combination, and further, the translucent particles 1 and the translucent particles 2 may be used in combination to achieve both antiglare and further optical properties.

When the translucent particles 2 are used in the present invention, the translucent particles 2 preferably have an average particle diameter smaller than the average film thickness of the antiglare layer. Specifically, the average particle size of the translucent particles 2 is preferably 10% to 90%, more preferably 20% to 80% of the average film thickness of the antiglare layer.
The translucent particles 2 preferably have good dispersibility. As the particles having good dispersibility, translucent organic resin particles such as polymethylmethacrylate particles and copolymer particles of polymethylmethacrylate and polystyrene are preferable. The polymethylmethacrylate ratio in the copolymer particles is preferably 40% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, and further preferably 75% by mass to 100% by mass from the viewpoint of dispersibility. Most preferably, it is 100% by mass.

The translucent particles 2 are core-shell type particles, the core of which has a refractive index difference from that of the antiglare layer binder and exhibits light scattering properties, and the shell has an affinity with the antiglare layer binder. Particles made of a material having high dispersibility and excellent dispersibility can also be preferably used.
Examples of the material that exhibits light scattering properties include polymethylmethacrylate, crosslinked poly (acrylic-styrene) copolymer, melamine resin, polycarbonate, polystyrene, crosslinked polystyrene, polyvinyl chloride, benzoguanamine-melamine formaldehyde, and the like.
Examples of the material having excellent dispersibility include polymethylmethacrylate and the like.

The translucent particles 2 are preferably 0.1% by mass to 30% by mass with respect to the total solid content of the antiglare layer, preferably from the viewpoint of imparting antiglare property and internal scattering property, and 1 to 15% by mass. It is more preferable to do so.
When a plurality of types of translucent particles 2 are used in combination, it is preferable to use particles having different particle diameters without changing the components constituting the particles from the viewpoint of ease of antiglare control.

In addition, layered inorganic compounds such as organically treated hectorite, bentonite, smectite, and vermiculite can also be used for the purpose of adjusting antiglare and other optical properties. These layered inorganic compounds segregate between the translucent particles 2 to prevent the translucent particles 2 from aggregating more than necessary in the antiglare layer, and to appropriately collect the translucent particles with each other. Dazzle control becomes possible.

(Metal oxide fine particles)
As yet another aspect of the present invention, the antiglare layer contains at least one kind of fine particles, and the fine particles are cohesive metal oxide fine particles.
The cohesive metal oxide fine particles are used for the purposes of [1] imparting surface irregularities to the antiglare layer, [2] adjusting the refractive index, [3] improving hardness, [4] improving brittleness and curling, and the like. Aggregating silica particles and aggregating alumina particles are preferable as the metal oxide fine particles from the viewpoint of transparency and low cost for imparting surface unevenness of the antiglare layer in the present invention, and among them, primary Aggregate silica particles in which particles having a particle diameter of several tens of nm form aggregates are preferable because they can stably impart appropriate surface irregularities. The cohesive silica particles can be obtained by, for example, a so-called wet method of synthesizing by a neutralization reaction of sodium silicate and sulfuric acid, but the present invention is not limited thereto. The wet method is further roughly classified into a sedimentation method and a gelation method, and the present invention may be either method. The secondary particle size of the cohesive silica particles is preferably in the range of 0.1 to 10.0 μm, but is selected in combination with the layer thickness of the antiglare layer containing the particles. The secondary particle size is adjusted by the degree of particle dispersion (controlled by mechanical dispersion using a sand mill or the like, or chemical dispersion using a dispersant or the like). In particular, the value obtained by dividing the secondary particle diameter of the cohesive silica particles by the layer thickness of the antiglare layer containing the cohesive silica particles is preferably 0.1 to 1.5, preferably 0.3 to 1.0. Is more preferable.

The secondary particle diameter of the aggregated silica particles and the like preferably used as the metal oxide fine particles is measured by the Coulter counter method.
The amount of the metal oxide fine particles added is preferably 0.01% by mass to 5% by mass, more preferably 0.1% by mass to 5% by mass, and 0.1 to 3% of the total solid content of the antiglare layer. Mass% is more preferable, and 0.1% by mass to 2% by mass is most preferable.

In addition to the cohesive metal oxide fine particles, preferably the cohesive silica particles, it is also preferable to use a translucent resin fine particles in combination for the purpose of imparting internal scattering property. As the translucent resin fine particles, the above-mentioned (translucent particles 2) can be preferably used.

(Binder resin for antiglare layer)
The binder resin for the antiglare layer is preferably formed from a compound for forming the binder resin for the antiglare layer. The compound for forming a binder resin for an antiglare layer contains one or both of a thermosetting compound and an ionizing radiation curable compound, and it is preferable to cure the compound to form a binder resin for an antiglare layer.

The binder resin for the antiglare layer is preferably formed by a cross-linking reaction or a polymerization reaction of an ionizing radiation curable compound. That is, a composition for forming an antiglare layer containing an ionizing radiation curable polyfunctional monomer and a polyfunctional oligomer as a compound for forming a binder resin for an antiglare layer is applied onto a base film, and the polyfunctional monomer and the polyfunctional oligomer are applied. , It is preferable to form an antiglare layer by a cross-linking reaction or a polymerization reaction. As the functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer, light (ultraviolet rays), electron beam, or radiation-polymerizable group is preferable, and photopolymerizable functional group is particularly preferable. Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as (meth) acryloyl group, vinyl group, styryl group and allyl group, and among them, (meth) acryloyl group is preferable.
As a specific example of the compound for forming the binder resin for the antiglare layer, a compound having a polymerizable unsaturated bond can be preferably used.

(Compound with polymerizable unsaturated bond)
Examples of the compound having a polymerizable unsaturated bond include compounds having a polymerizable functional group such as a (meth) acryloyl group, a vinyl group, a styryl group and an allyl group, and among them, a compound having a (meth) acryloyl group is used. preferable. Particularly preferably, a compound containing two or more (meth) acryloyl groups in one molecule below can be used.

Specific examples of the compound having a polymerizable unsaturated bond include (meth) acrylic acid of alkylene glycol such as neopentyl glycol diacrylate, 1,6-hexanediol di (meth) acrylate, and propylene glycol di (meth) acrylate. Diesters; (meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. (Meta) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate; 2,2-bis {4- (acryloxy diethoxy) phenyl} propane, 2-2-bis {4- (acrylic acid) Polypropoxy) phenyl} propane and other ethylene oxides or (meth) acrylic acid diesters of propylene oxide adducts; etc. can be mentioned.

Further, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

Among them, esters of a polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having three or more (meth) acryloyl groups in one molecule is preferable. For example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO (ethylene oxide) modified trimethylolpropane tri (meth) acrylate, PO (propylene oxide) modified trimethylol Propanetri (meth) acrylate, EO-modified tri (meth) phosphate, trimethylolethanetri (meth) acrylate, trimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate ) Acrylate, dipentaerythritol hex (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-clohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate, caprolactone-modified trimethylolpropane (acryloxyethyl) isocyanurate, etc. Can be mentioned.

Specific compounds of polyfunctional acrylate compounds having a (meth) acryloyl group include KAYARADDPHA, DPHA-2C, PET-30, TMPTA, TPA-320, and TPA-330 manufactured by Nippon Kayaku Co., Ltd. , RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303, V # 3PA, V # manufactured by Osaka Organic Chemical Industry Co., Ltd. Examples thereof include esterified compounds of polyols such as 400, V # 36095D, V # 1000, V # 1080 and (meth) acrylic acid. In addition, purple light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B. , UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310B, UV-3500BA. , UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2750B (manufactured by Nippon Synthetic Chemical Co., Ltd.), UL-503LN (manufactured by Kyoeisha Chemical Co., Ltd.), Unidic 17-806, 17-813, V-4030, V-4000BA (manufactured by Dainippon Ink and Chemicals Co., Ltd.), EB-1290K, EB- 220, EB-5129, EB-1830, EB-4858 (manufactured by Daicel UCB Co., Ltd.), Hicorp AU-2010, AU-2020 (manufactured by Tokushiki Co., Ltd.), Aronix M-1960 (manufactured by Toa Synthetic Co., Ltd.) ), Art resin UN-3320HA, UN-3320HC, UN-3320HS, UN-904, HDP-4T and other trifunctional or higher functional urethane acrylate compounds, Aronix M-8100, M-8030, M-9050 (Toa Synthetic Co., Ltd.) ), KRM-8307 (manufactured by Daicel Cytec Co., Ltd.) and other trifunctional or higher functional polyester compounds can also be preferably used.

Furthermore, resins having three or more (meth) acryloyl groups, such as relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, and polythiol polyene resins. , Oligomers such as polyfunctional compounds such as polyhydric alcohols, prepolymers and the like.

Further, examples of the bifunctional (meth) acrylate compound include, but are not limited to, a compound represented by the following formula.

Further, for example, a dendrimer described in JP-A-2005-76005 and JP-A-2005-36105, or a norbornene ring-containing monomer as described in JP-A-2005-60425 can also be used. Further, a fluorine-containing polyfunctional (meth) acrylate represented by the chemical formula (2) described in JP-A-2002-105141 can also be used.

Two or more kinds of polyfunctional monomers may be used in combination.
The polymerization of these monomers having an ethylenically unsaturated group can be carried out by irradiation or heating with ionizing radiation in the presence of a photoradical initiator or a thermal radical initiator. It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.
When the support 5 described later is a polyethylene terephthalate (PET) film, a polymerization initiator (for example, Irgacure 819 manufactured by BASF Japan Ltd.) that absorbs light having a transmission wavelength of 320 nm or more of the PET film should be used. Is preferable.

Further, the compound for forming a binder resin for an antiglare layer includes a high refractive index monomer or inorganic particles such as ZrO ₂ , TiO ₂ , and SiO ₂ that do not cause visible light scattering for the purpose of controlling the refractive index of the antiglare layer. That is, inorganic particles having an average particle diameter of 100 nm or less, or both of them, can be added. Inorganic particles have the effect of suppressing curing shrinkage due to the cross-linking reaction, in addition to the effect of controlling the refractive index. In the present invention, after the antiglare layer is formed, a polymer produced by polymerizing a compound having a polymerizable unsaturated bond such as a polyfunctional monomer and / or a high refractive index monomer, and an inorganic substance dispersed in the polymer. Including particles, it is called a binder.

The content of the binder resin for the antiglare layer in the antiglare layer is 50 to 99 parts by mass with respect to 100 parts by mass of the total solid content of the antiglare layer, in combination with translucent particles for imparting internal scattering properties. Even in the case of this, it is preferable to maintain the ratio of the flat portion on the film surface, and more preferably 70 to 99 parts by mass.
The strength of the antiglare layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in the pencil hardness test.

(Leveling agent)
The composition for forming an antiglare layer for forming an antiglare layer in the present invention is either a fluorine-based or a silicone-based composition in order to ensure surface uniformity such as coating unevenness, drying unevenness, and point defects. It is preferable to contain a so-called leveling agent containing the above-mentioned surfactant or both. In particular, a fluorine-based surfactant can be preferably used because it has an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects with a smaller addition amount. Productivity can be improved by providing high-speed coating suitability while improving surface uniformity.

Preferred examples of the fluorine-based surfactant include a fluoroaliphatic group-containing copolymer (hereinafter, may be abbreviated as “fluorine-based polymer”), and the above-mentioned fluorine-based polymer is described in (i) below. Acrylic resin, methacrylic resin, and copolymerizable with the repeating unit corresponding to the monomer, or containing the repeating unit corresponding to the monomer of (i) and the repeating unit corresponding to the monomer of (ii) below. A copolymer with a vinyl-based monomer is useful.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula a General formula a

In the general formula a, R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or −N (R ¹² ) −, m is an integer of 1 or more and 6 or less, and n is an integer of 2 to 4. Represent. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, and is preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.
E ₁₁ represents a hydrogen atom or a fluorine atom, and preferably represents a hydrogen atom.

(Ii) Monomer represented by the following general formula (b) copolymerizable with (i) above (b)

In the general formula (b), R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or −N (R ¹⁵ ) −, and R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically. It represents a methyl group, an ethyl group, a propyl group, or a butyl group, and is preferably a hydrogen atom or a methyl group. Y is preferably an oxygen atom, −N (H) −, and −N (CH ₃ ) −.
R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent of the alkyl group of R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkylether group, an arylether group, a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom, a nitro group and a cyano group. , Amino group, etc., but this is not the case. The linear, branched or cyclic alkyl group having 4 to 20 carbon atoms includes a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and an undecyl group which may be linear and branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., monocyclic cycloalkyl group such as cyclohexyl group, cycloheptyl group, bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, etc. Polycyclic cycloalkyl groups such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, and a tetracyclodecyl group are preferably used.

The amount of the fluoroaliphatic group-containing monomer represented by these general formulas A used in the fluoropolymer used in the present invention is 10 mol% or more, preferably 10 mol% or more, based on each monomer of the fluoropolymer. It is in the range of 15 to 70 mol%, more preferably 20 to 60 mol%.

The preferred weight average molecular weight of the fluoropolymer used in the present invention is preferably 3,000 to 100,000, more preferably 5,000 to 80,000. Further, the preferable amount of the fluorinated polymer used in the present invention is in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the coating liquid (composition for forming an antiglare layer), and more preferably 0. The range is 005 to 3 parts by mass, and more preferably 0.01 to 1 part by mass. If the amount of the fluorinated polymer added is 0.001 part by mass or more, the effect of adding the fluorinated polymer can be sufficiently obtained, and if it is 5 parts by mass or less, the coating film cannot be sufficiently dried or coated. There is no problem that the performance as a film (for example, reflectance, scratch resistance) is adversely affected.

The average film thickness of the antiglare layer is preferably 2 to 20 μm from the viewpoint of achieving both hardness and curl suppression, more preferably 2 to 15 μm, and even more preferably 3 to 12 μm.
Therefore, when the translucent particles 1 are used as the translucent particles, the average particle size of the translucent particles 1 is preferably 2.01 to 24 μm, more preferably 2.01 to 19 μm. It is more preferably 3.01 to 16 μm, and most preferably 3.01 to 12 μm.
When the translucent particles 2 are used as the translucent particles, the average particle size of the translucent particles 2 is preferably 2.01 to 16 μm, more preferably 2.01 to 10 μm.
The refractive index of the antiglare layer at a wavelength of 550 nm is preferably 1.48 to 1.70, and more preferably 1.48 to 1.60. In the present invention, all the values of the refractive index specifically shown thereafter indicate values having a wavelength of 550 nm.

(A component having a functional group other than the (meth) acryloyl group capable of forming a chemical bond with the antireflection layer)
The antiglare layer forming composition of the present invention contains a (meth) acryloyl group capable of forming a chemical bond with the antireflection layer (component contained in the antireflection layer) in order to ensure adhesion to the antireflection layer. It is preferable to contain a component having a functional group other than. By containing the above component in the antiglare layer forming composition, a chemical bond is formed between the formed antiglare layer and the antireflection layer, and it works effectively to secure the adhesion between the layers.
In particular, when the antireflection layer is applied by the transfer method, the scratch resistance can be improved by improving the adhesion between the antiglare layer and the antireflection layer.
Further, since the above-mentioned component has a functional group other than the (meth) acryloyl group, when used in combination with a compound having a (meth) acryloyl group, it has a stronger interlayer adhesion than when the (meth) acryloyl group is used alone. Can be expressed. The chemical bond between the antireflection layer and the antiglare layer is not particularly limited, but for example, an ionic bond between boric acid and a hydroxyl group, a reaction between an epoxy group and an acid, a base, or a hydroxyl group, a urethanization reaction of an isocyanate group, etc. Can be mentioned.
As the component contained in the antireflection layer, a binder resin forming compound described later is preferably mentioned.

The functional group other than the (meth) acryloyl group capable of forming a covalent bond with the component contained in the antireflection layer is not particularly limited, but is not particularly limited, but is an unsaturated hydrocarbon group, a boronic acid group, an alkoxysilyl group, an isocyanate group, and an epoxy. Examples thereof include a group, a hydroxyl group, an amino group, a thiol group and a carboxyl group.
Since the above component acts at the interface between the antiglare layer and the antireflection layer, it is preferable to use a component having a high uneven distribution to the interface.

Specific examples of the components when the above components have a boronic acid group will be described below.
(Boronic acid monomer)
In the present invention, a boronic acid monomer can be preferably used. The boronic acid monomer is a compound having a boronic acid group and a polymerizable group represented by the formula 1.

In formula (1), R ¹ and R ² independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, respectively. ..
Examples of the aliphatic hydrocarbon group include a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, an iso-propyl group, etc.) and an aliphatic hydrocarbon group having 3 to 20 carbon atoms. Examples thereof include a substituted or unsubstituted cyclic alkyl group (for example, a cyclohexyl group) and an alkenyl group having 2 to 20 carbon atoms (for example, a vinyl group).
Examples of the aryl group include a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms (for example, a phenyl group, a tolyl group, etc.), a substituted or unsubstituted naphthyl group having 10 to 20 carbon atoms, and the like.
The heterocyclic group is, for example, a substituted or unsubstituted 5- or 6-membered ring group containing at least one hetero atom (for example, nitrogen atom, oxygen atom, sulfur atom, etc.), for example, a pyridyl group. Examples thereof include an imidazolyl group, a frill group, a piperidyl group, and a morpholino group.
R ¹ and R ² may be linked to each other to form a ring, for example, the isopropyl groups of R ¹ and R ² may be linked to 4,4,5,5-tetramethyl-1,3,2-. A dioxaborolane ring may be formed.
In the formula (1), R ¹ and R ² are preferably used in the case where a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, and R ¹ and R ² are linked to form a ring. It is preferably a hydrogen atom.
In formula (1), * indicates the binding position to the boronic acid monomer residue.
The number of boronic acid groups represented by the formula (1) is not particularly limited, and may be one or a plurality (two or more).

In addition, one or more hydrocarbon groups contained in these aliphatic hydrocarbon groups, aryl groups, and heterocyclic groups may be substituted with arbitrary substituents. Examples of the type of the substituent include the substituents described in paragraph [0046] of JP2013-054201.

The type of the polymerizable group is not particularly limited, and examples thereof include a radical polymerizable group and a cationically polymerizable group. Examples of the radically polymerizable group include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, a styryl group, an allyl group and the like. Examples of the cationically polymerizable group include a vinyl ether group, an oxylanyl group, and an oxetanyl group. Among them, a (meth) acryloyl group, a styryl group, a vinyl group, an oxylanyl group or an oxetanyl group is preferable, a (meth) acryloyl group or a styryl group is more preferable, and a (meth) acryloyl group is particularly preferable.
The (meth) acryloyl group is a concept including both an acryloyl group and a meta-acrylamide group, and the (meth) acrylamide group is a concept including both an acrylamide group and a metaacrylamide group.
The number of polymerizable groups is not particularly limited, and may be one or a plurality (two or more).

The molecular weight of the boronic acid monomer is not particularly limited, but 120 to 1200 is preferable, and 180 to 800 is preferable because it is excellent in compatibility with the binder resin forming compound for the antiglare layer used in the composition for forming the antiglare layer. More preferred.

A preferred embodiment of the boronic acid monomer is a boronic acid monomer represented by the formula 2 in that the adhesion between the antiglare layer and the antireflection layer is more excellent.

The definitions of R ¹ and R ^{2 in} the formula (2) are as described above.
Z represents a polymerizable group. The definition of the polymerizable group is as described above.
X ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include -O-, -CO-, -NH-, -CO-NH-, -COO-, -O-COO-, an alkylene group, an arylene group, and a divalent heterocyclic group. (Heteroarylene group) and a divalent linking group selected from a combination thereof can be mentioned.
Examples of the combination include -allylene group-COO-allylen group-O-alkylene group-, -allylen group-COO-alkylene group-and the like.

Specific examples of the boronic acid monomer will be shown below, but the present invention is not limited thereto.

(Copolymer with a boronic acid group introduced)
In the present invention, a copolymer having a boronic acid group introduced therein can be preferably used. A copolymer having a boronic acid group introduced therein (hereinafter, also formally abbreviated as “polymer compound of the present invention” in the present specification) is a repeating unit represented by the following formula (I) (hereinafter, “I” It is also abbreviated as "part") and a repeating unit represented by the following formula (II) (hereinafter, also abbreviated as "II part").
Further, the polymer compound of the present invention preferably has a repeating unit represented by the following formula (III) (hereinafter, also abbreviated as “III part”).
Further, the polymer compound of the present invention preferably has a repeating unit represented by the following formula (V) (hereinafter, also abbreviated as “V part”).

<I part>
The I part of the polymer compound of the present invention is a repeating unit represented by the following formula (I).

In the above formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and among them, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable. Alkyl groups are more preferred, and hydrogen atoms or methyl groups are even more preferred.

Further, in the above formula (I), X ¹ is a single bond, or -O-, -S-, -COO-, -OCO-, -CONR ^2- , -NR ² COO-, -CR ² N-. , A substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted divalent aromatic group, and a divalent linking group selected from the group consisting of a combination thereof, where R ² is hydrogen. It represents an atom, an alkyl group having 1 to 20 carbon atoms, or -X ^1- P ¹ . When R ² is −X ^{1 −} P ¹ , P ¹ represents a polymerizable group as in P ¹ in the above formula (I). P ¹ will be described later.
In the above description of X ¹ , -COO- means that carbon bonded to R ¹ and C = O are bonded, and P ¹ and O are bonded, and -OCO- is carbon bonded to R ^1. And O are bonded and P ¹ and C = O are bonded, and −CONR ² − indicates that the carbon to which R ¹ is bonded and C = O are bonded and P ¹ and NR ² are bonded. , -NR ² COO- indicates that the carbon to which R ¹ is bonded and NR ² are bonded, and P ¹ and O are bonded, and -CR ² N- indicates that the carbon to which R ¹ is bonded and CR ² are bonded. It means that P ¹ and N are combined.

Here, as the substituted or unsubstituted divalent aliphatic group indicated by X ¹ , for example, it may have an alkylene group having 1 to 20 carbon atoms or a substituent which may have a substituent. Examples thereof include a good cycloalkylene group having 3 to 20 carbon atoms (for example, a cyclohexylene group), and among them, an alkylene group having 1 to 15 carbon atoms is preferable, an alkylene group having 1 to 8 carbon atoms is more preferable, and a methylene group. , Ethylene group, propylene group and butylene group are more preferable.
Further, the substituted or unsubstituted divalent aromatic group indicated by X ¹ may have a divalent aromatic hydrocarbon group which may have a substituent or a divalent group which may have a substituent. Aromatic heterocyclic group of. As the divalent aromatic hydrocarbon group, for example, a hydrogen atom is selected from two carbon atoms constituting the ring structure of the aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, an anthracene ring, a triphenylene ring, and a fluorene ring. Examples thereof include groups obtained by removing one each, and among them, a phenylene group or a naphthylene group obtained by removing one hydrogen atom from each of the two carbon atoms constituting the ring structure of the benzene ring or the naphthalene ring is preferable. .. On the other hand, examples of the divalent aromatic heterocyclic group include aromatic heterocycles such as furan ring, pyrrole ring, thiophene ring, pyridine ring, thiazole ring, benzothiazole ring, oxadiazole ring, thiazolothiazole ring and phenanthrolin ring. Examples thereof include a group obtained by removing one hydrogen atom from each of the two carbon atoms constituting the ring structure of.

Examples of the substituent that the divalent aliphatic group or the divalent aromatic group may have include a halogen atom, a hydroxyl group, an amino group, an acryloyloxy group, a methacryloyloxy group, and an alkyl having 1 to 20 carbon atoms. Group, carboxyl group, cyano group, -X ^1- P ¹ , or these and -O-, -S-, -COO-, -OCO-, -CONR ^2- , -NR ² COO-, -HC = Examples thereof include a group in which any one or more of CH- and -CR ² N- are combined. R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or represent a ^-X 1 -P ^1. When R ² is −X ^{1 −} P ¹ , P ¹ represents a polymerizable group as in P ¹ in the above formula (I).

The alkyl group having 1 to 20 carbon atoms shown by R ² described above is preferably an alkyl group having 1 to 6 carbon atoms, and specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or n-butyl. Examples thereof include a group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.

Further, in the above formula (I), P ¹ represents a polymerizable group.
In the present invention, the polymerizable group represented by P ¹ in the above formula (I) is selected from the group consisting of the groups represented by the following formulas (P-1) to (P-7). It is preferable that it is a polymerizable group of, and more preferably any of the polymerizable groups selected from the group consisting of the groups represented by the following formulas (P-1) to (P-3). , The polymerizable group represented by the following formula (P-1) or (P-2) is more preferable.

In the above formulas (P-1) to (P-7), * represents the bonding position with X ¹ . R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the two R ^3s may be the same or different, and may be linked to each other to form a ring structure.
Specific examples of the alkyl group having 1 to 5 carbon atoms shown by R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and the like.

In the present invention, from the viewpoint of ease of production, economic efficiency and radical polymerization, the repeating unit represented by the above formula (I) is such that R ¹ in the above formula (I) is a hydrogen atom or a methyl group. Yes, X ¹ in the above formula (I) is -O-, -COO-, -OCO-, and a substituted or unsubstituted divalent aliphatic group (preferably an alkylene group having 2 to 8 carbon atoms). A repeating unit that is a divalent linking group consisting of any one or a combination of any two or more selected from the group consisting of) is preferable.

Specific examples of the repeating unit represented by the above formula (I) include a repeating unit represented by the following formula.

In the present invention, the content of the repeating unit represented by the above formula (I) is preferably 5 to 80% by mass, more preferably 7 to 70% by mass, based on all the repeating units. It is more preferably 10 to 50% by mass.

<II part>
The II part of the polymer compound of the present invention is a repeating unit represented by the following formula (II).

In the above formula (II), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and among them, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable. Alkyl groups are more preferred, and hydrogen atoms or methyl groups are even more preferred.

Further, in the above formula ^{(II), X 10} is a single bond, or, -O -, - S -, - COO -, - OCO -, - CONR 13 -, - NR 13 COO -, - CR 13 N- , A substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted divalent aromatic group, and a divalent linking group selected from the group consisting of a combination thereof. R ¹³ is a hydrogen atom. Alternatively, it represents an alkyl group having 1 to 20 carbon atoms.
In the above description of X ¹⁰ , -COO- indicates that the carbon to which R ¹⁰ is bonded and C = O are bonded, and B and O are bonded, and -OCO- is the carbon bonded to R ^10. O binds, indicates that B and C = O are attached, -CONR ¹³ - ^represents the carbon and C = O ^{in which R 10} is bonded is bonded, B and ^{NR 13} is bond, -NR ¹³ COO- indicates that the carbon to which R ¹⁰ is bonded and NR ¹³ are bonded, and B and O are bonded, and -CR ¹³ N- indicates that the carbon to which R ¹⁰ is bonded and CR ¹³ are bonded to B. Indicates that N is combined.
Here, examples of the divalent aliphatic group and the divalent aromatic group represented by X ¹⁰ include those similar to those described in X ¹ in the above formula (I), and R. Examples of the alkyl group having 1 to 20 carbon atoms shown by No. ¹³ include those similar to R ² described in relation to the above formula (I).

Further, in the above formula (II), R ¹¹ and R ¹² are independently hydrogen atom, substituted or unsubstituted aliphatic hydrocarbon group, substituted or unsubstituted aryl group, or substituted or unsubstituted hetero. Representing an aryl group, R ¹¹ and R ¹² may be linked to each other to form a ring, and R ¹¹ and R ¹² form a linking group consisting of an alkylene linking group, an arylene linking group, or a combination thereof. You may.

Substituted or unsubstituted aliphatic hydrocarbon groups indicated by R ¹¹ and R ¹² include alkyl groups, alkenyl groups or alkynyl groups which may have a substituent.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group and a tridecyl group. , Hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl Examples thereof include linear, branched or cyclic alkyl groups such as a group, a 1-adamantyl group and a 2-norbornyl group.
Specific examples of the alkenyl group include linear chains such as a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-methyl-1-propenyl group, a 1-cyclopentenyl group, and a 1-cyclohexenyl group. , Branched or cyclic alkenyl groups.
Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-octynyl group and the like.

Examples of the substituted or unsubstituted aryl group indicated by R ¹¹ and R ¹² include one in which one to four benzene rings form a fused ring, and a benzene ring and an unsaturated five-membered ring forming a fused ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, a fluorenyl group, a pyrenyl group and the like.

As the substituted or unsubstituted heteroaryl group indicated by R ¹¹ and R ¹² , for example, a hydrogen atom on a heteroaromatic ring containing at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom is used. Examples thereof include a heteroaryl group obtained by removing one.
Specific examples of the heteroaromatic ring containing one or more heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom include pyrol, furan, thiophene, pyrazole, imidazole, triazole, oxazole and isoxazole. , Oxazole, thiazole, thiazazole, indol, carbazole, benzofuran, dibenzofuran, thianaften, dibenzothiophene, indazole benzimidazole, anthranil, benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, Examples thereof include quinoline, acrydin, isoquinolin, phthalazine, quinazoline, quinoxalin, naphthylidine, phenanthrolin, and pteridine.

Examples of the substituents that R ¹¹ and R ¹² may have include monovalent non-metal atomic groups excluding hydrogen, and are selected from the following substituent group Y, for example.
(Substituent group Y)
Halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group , N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-ally Lucarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N -Alkylacylacylamino group, N-arylacylamino group, carbonyl group, N'-alkylureido group, N', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureide group, N-alkylureid group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N', N ′ -Dialkyl-N-alkyl carboxylic group, N', N'-dialkyl-N-aryl walide group, N'-aryl-N-alkyl carboxylic group, N'-aryl-N-aryl aldehyde group, N', N '-Diaryl-N-alkyl aldehyde group, N', N'-diaryl-N-aryl ureido group, N'-alkyl-N'-aryl-N-alkyl hydride group, N'-alkyl-N'-aryl- N-arylureid group, alkoxycarbonylamino group, allyloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group , N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugate base group, alkoxycarbonyl group, allyloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkyl Carbonyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfoni Group, a sulfo group (-SO 3 _H) and its conjugated base group, alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N- dialkyl sulfinamoyl group, N- aryl Sulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N- Aryl sulfamoyl group, N, N-diaryl sulfamoyl group, N-alkyl-N-aryl sulfamoyl group, N-acyl sulfamoyl group and its conjugate base group, N-alkylsulfonyl sulfamoyl group ( -SO ₂ NHSO ₂ (alkyl) and its conjugate base group, N-arylsulfonylsulfamoyl group (-SO ₂ NHSO ₂ (aryl)) and its conjugate base group, N-alkylsulfonylcarbamoyl group (-CONHSO ₂ (-CONHSO ₂ )) Alkyl)) and its conjugate base group, N-arylsulfonylcarbamoyl group (-CONHSO ₂ (aryl)) and its conjugate base group, alkoxysilyl group (-Si (Oalkyl) ₃ ), aryloxysilyl group (-Si (Oaryl)) ₃ ), hydroxysilyl group (-Si (OH) ₃ ) and its conjugate base group, phosphono group (-PO ₃ H ₂ ) and its conjugate base group, dialkylphosphono group (-PO ₃ (alkyl) ₂ ), Diarylphosphono groups (-PO ₃ (aryl) ₂ ), alkylarylphosphono groups (-PO ₃ (alkyl) (aryl)), monoalkylphosphono groups (-PO ₃ H (alkyl)) and their conjugate base groups. , Monoarylphosphono group (-PO ₃ H (aryl)) and its conjugate base group, phosphonooxy group (-OPO ₃ H ₂ ) and its conjugate base group, dialkylphosphonooxy group (-OPO ₃ (alkyl) ₂ ) , Diarylphosphonooxy groups (-OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy groups (-OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy groups (-OPO ₃ H (alkyl)) and a conjugated base group thereof, monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugated base group, a cyano group, a nitro group, an aryl group, an alkenyl group and alkynyl group also, these substituents May form a ring by bonding substituents to each other or to a hydrocarbon group which is substituted, if possible.

It is preferable that R ¹¹ and R ¹² in the above formula (II) are hydrogen atoms or are bonded to each other to form an alkylene linking group.

Specific examples of the monomer forming the repeating unit represented by the above formula (II) include the monomers represented by the following formulas II-1 to II-12.

In the present invention, the content of the repeating unit represented by the above formula (II) is preferably 3 to 80% by mass, more preferably 4 to 70% by mass, based on all the repeating units. It is more preferably 5 to 50% by mass.

<Part III>
The polymer compound of the present invention has a repeating unit (III part) represented by the following formula (III) for the reason that the formed antiglare layer has better adhesion to the antireflection layer. Is preferable.
Here, the reason why the adhesiveness is better is that the copolymer is unevenly distributed on the air interface side (adhesive surface side with the antireflection layer) of the antiglare layer formed by having the III part. It is considered that this makes it easier for the III part of the copolymer to interact with the surface component of the antireflection layer.

In the above formula (III), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and among them, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable. Alkyl groups are more preferred, and hydrogen atoms or methyl groups are even more preferred.

Further, in the above formula (III), L ²⁰ is a divalent linking group selected from the group consisting of -O-, -COO-, -OCO-, a divalent aliphatic group, and a combination thereof. Represent. In addition, -COO- indicates that carbon bonded to R ²⁰ and C = O are bonded, and R ²¹ and O are bonded, and -OCO- represents carbon bonded to R ²⁰ and O bonded to R. It represents that ²¹ and C = O are combined.
Examples of the divalent aliphatic group indicated by L ²⁰ include a divalent aliphatic chain group or an aliphatic cyclic group. As the divalent aliphatic chain group, an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable. As the divalent aliphatic cyclic group, a cycloalkylene group having 3 to 20 carbon atoms is preferable, and a cycloalkylene group having 3 to 15 carbon atoms is more preferable.
Among ^{these, L 20,} -COO-, or, -OCO- are preferred, -COO- is more preferable.

Further, in the above formula (III), R ²¹ is an alkyl group having 4 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is replaced with a fluorine atom (hereinafter, “fluoroalkyl group”). (Also also referred to as), or a monovalent organic group containing −Si (R ^a3 ) (R ^a4 ) O−, and R ^a3 and R ^a4 independently contain an alkyl group, a haloalkyl group or an aryl group, respectively. Represent.

In the present invention, R ²¹ in the above formula (III) is a fluoroalkyl group having 1 to 20 carbon atoms for the reason that the adhesion of the formed antiglare layer to the antireflection layer is further improved. , More preferably a fluoroalkyl group having 1 to 18 carbon atoms, and even more preferably a fluoroalkyl group having 2 to 15 carbon atoms.
The number of fluorine atoms is preferably 1 to 25, more preferably 3 to 21, and most preferably 5 to 21.

In the present invention, the repeating unit represented by the above formula (III) is represented by the following formula (IV) from the viewpoint of the adhesion of the formed antiglare layer to the antireflection layer and the radical polymerization property. It is preferably a repeating unit.

In the formula ^{(IV), R 20} is same as ^{R 20} in the formula (III), represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, a preferred embodiment also the same.
Further, in the above formula (IV), ma and na each independently represent an integer of 0 to 19. Among them, ma is preferably an integer of 1 to 8, and more preferably an integer of 1 to 5, from the viewpoint of improving adhesion and obtaining raw materials. Further, na is preferably an integer of 1 to 15, more preferably an integer of 1 to 12, further preferably an integer of 2 to 10, and most preferably an integer of 5 to 7. .. However, ma and na represent integers from 0 to 19 in total.
Further, in the above formula (IV), X ²¹ represents a hydrogen atom or a fluorine atom, and is preferably fluorine.

Specific examples of the monomer forming the repeating unit represented by the above formula (III) or (IV) include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3. , 3,3-Pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) Acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (Perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodeca Fluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H-1- (trifolomethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) ) Acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 3- (Perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-Hydroxypropyl (meth) acrylate and the like can be mentioned.

On the other hand, the monovalent organic group containing −Si ( ^Ra3 ) ( ^Ra4 ) O− represented by R ²¹ in the above formula (III) is an organic group derived from a siloxane bond, and is an organic group derived from a siloxane bond, and is represented by the following formula (VII). It is more preferable that the structure is obtained by polymerizing the compound represented by).

In the formula ^{(VII), R a1} represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ^{also, R a5} represents an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 4 carbon atoms Is more preferable.

In the above formula (VII), ^Ra3 and ^Ra4 independently represent an alkyl group, a haloalkyl group or an aryl group, respectively.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group and a hexyl group.
As the haloalkyl group, a fluorinated alkyl group having 1 to 10 carbon atoms is preferable, and examples thereof include a trifluoromethyl group and a pentafluoroethyl group.
The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
Of these, R ^a3 and R ^a4 are preferably a methyl group, a trifluoromethyl group or a phenyl group, and a methyl group is particularly preferable.

In the above formula (VII), m represents an integer of 10 to 1000, preferably an integer of 20 to 500, and more preferably an integer of 30 to 200.

Examples of the compound represented by the above formula (VII) include one-terminal (meth) acryloyl group-containing polysiloxane macromer (for example, Cyraplane 0721, 0725 (trade name, manufactured by JNC Co., Ltd.), AK-5, etc. AK-30, AK-32 (trade name, manufactured by Toa Synthetic Co., Ltd.), KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X- 22-164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (above, trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like. be able to.

In the present invention, when the repeating unit represented by the above formula (III) is contained, the content is preferably 2 to 80% by mass and 5 to 70% by mass with respect to all the repeating units. More preferably, it is 10 to 60% by mass.

Further, in the present invention, for the reason that the adhesion between the antiglare layer and the antireflection layer to be formed becomes better, when the repeating unit represented by the above formula (III) is provided, the above formula (I) The content of the repeating unit represented by) is 10 to 50% by mass with respect to all the repeating units, and the content of the repeating unit represented by the above formula (II) is 5 to 50% by mass with respect to all the repeating units. The content of the repeating unit represented by the above formula (III) is preferably 10 to 60% by mass with respect to all the repeating units.

<V part>
The polymer compound of the present invention may have a repeating unit (V part) represented by the following formula (V) from the viewpoint of improving adhesion when an epoxy-based adhesive layer is provided. preferable.

In the above formula (V), R ³⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and among them, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable. Alkyl groups are more preferred, and hydrogen atoms or methyl groups are even more preferred.

Specific examples of the monomer forming the repeating unit represented by the above formula (V) include acrylic acid and methacrylic acid.

In the present invention, when the repeating unit represented by the above formula (V) is contained, the content is preferably 1 to 60% by mass and 2 to 40% by mass with respect to all the repeating units. More preferably, it is 4 to 20% by mass.

<Other parts>
The polymer compound of the present invention may have a repeating unit other than the repeating units represented by the above formulas (I), (II), (III) and (V), if necessary.

Examples of the monomer forming another repeating unit include PolymerHandbook 2nd ed. , J. The ones described in Brandrup, Wiley literscience (1975) Chapter 2 Page 1-483 can be used.
For example, a compound having one addition-polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like can be mentioned.
Specifically, the following monomers can be mentioned.

(Acrylic esters)
Specific examples of the acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, chlorethyl acrylate, 2-hydroxyethyl acrylate, trimethyl propane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, and phenoxy. Examples thereof include ethyl acrylate, furfuryl acrylate and tetrahydrofurrill acrylate.

(Methacrylic acid esters)
Specific examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, chlorethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, and phenoxy. Ethyl methacrylate, flufuryl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol monoacetate monomethacrylate and the like can be mentioned.

(Acrylamides)
Specific examples of the acrylamides include acrylamide, N-alkylacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl group, ethyl group, and propyl group), and N, N-dialkylacrylamide (alkyl). Examples of the group include those having 1 to 6 carbon atoms), N-hydroxyethyl-N-methylacrylamide, N-2-acetamide ethyl-N-acetylacrylamide and the like.

(Methacrylamides)
Specific examples of methacrylamides include methacrylamide, N-alkylmethacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl group, ethyl group, and propyl group), N, N-dialkyl. Examples thereof include methacrylamide (alkyl groups having 1 to 6 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamide ethyl-N-acetylmethacrylamide and the like.

(Allyl compound)
Specific examples of the allyl compound include allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate). Etc.), allyloxyethanol and the like.

(Vinyl ethers)
Specific examples of vinyl ethers include alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl). Examples thereof include vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether and tetrahydrofurfuryl vinyl ether.

(Vinyl esters)
Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chlor acetate, and vinyl dichloro acetate. Examples thereof include vinyl methoxy acetate, vinyl butoxy acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate and the like.

(Dialkyl itaconic acid)
Examples of the dialkyl itaconic acid include dimethyl itaconic acid, diethyl itaconic acid, and dibutyl itaconic acid.

(Other)
In addition, dialkyl esters or ruquil esters of fumaric acid; dibutyl fumarate; crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleironitrile, styrene, styrene macromer (AS-6S manufactured by Toa Synthetic Co., Ltd.), methyl methacrylate macromer (AA-6 manufactured by Toa Synthetic Co., Ltd.) and the like.

In the present invention, the content when having other repeating units is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and 1 to 20% by mass with respect to all the repeating units. It is more preferably%.

The weight average molecular weight (Mw) of the polymer compound of the present invention is preferably 1000 to 200,000, more preferably 1500 to 100,000, and even more preferably 3000 to 60,000.
The number average molecular weight (Mn) of the polymer compound of the present invention is preferably 500 to 40,000, more preferably 600 to 35,000, and even more preferably 600 to 30,000.
The dispersity (Mw / Mn) of the polymer compound of the present invention is preferably 1.00 to 12.00, more preferably 1.00 to 11.00, and even more preferably 1.00 to 10.00.
The weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography (GPC) under the following conditions.
<Measurement conditions>
[Eluent] N-methyl-2-pyrrolidone (NMP)
[Device name] EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)
[Column] TSKgel SuperAWM-H (manufactured by Tosoh Corporation))
[Column temperature] 40 ° C
[Flow velocity] 0.50 ml / min

Specific examples of the polymer compound of the present invention having each of the above-mentioned repeating units include compounds represented by the following formulas (A-1) to (A-22). The compounds represented by the following formulas (A-1) to (A-22) are, for example, compounds having a hydroxyl group in the antireflection layer (hydroxyl group appearing after ring opening of the compound having an epoxy group, silane coupling site). It is possible to form a covalent bond with a hydroxyl group (such as a hydroxyl group that appears after hydrolysis of a compound having). The formation of covalent bonds is confirmed by diagonally cutting the antiglare antireflection film, measuring the microscopic Raman spectrum near the interface between the antiglare layer and the antireflection layer, and analyzing the Raman band of covalent boric acid. be able to.

The content of the polymer compound of the present invention is 0.0001 to 40% by mass when the total solid content (all components excluding the solvent) of the antiglare layer forming composition of the present invention is 100% by mass. It is preferably 0.001 to 20% by mass, more preferably 0.1 to 5% by mass.

(Other polymer compounds)
The antiglare layer of the present invention may contain other polymer compounds. By adding the polymer compound, the curing shrinkage can be reduced and the viscosity of the coating liquid (composition for forming an antiglare layer) can be adjusted.

The polymer compound has already formed a polymer when it is added to the coating liquid, and examples of the polymer compound include cellulose esters (for example, cellulose triacetate, cellulose diacetate, cellulose propionate, and cellulose acetate pro. Pionate, cellulose acetate butyrate, cellulose nitrate, etc.), urethane acrylates, polyester acrylates, (meth) acrylic acid esters (eg, methyl methacrylate / (meth) methyl acrylate copolymer, methyl methacrylate / (Meta) ethyl acrylate copolymer, methyl methacrylate / (meth) butyl acrylate copolymer, methyl methacrylate / styrene copolymer, methyl methacrylate / (meth) acrylate copolymer, polymethyl methacrylate Etc.), resins such as polystyrene are preferably used.

From the viewpoint of the effect on curing shrinkage and the effect of increasing the viscosity of the coating liquid, the polymer compound is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, based on the total binder contained in the layer containing the polymer compound. It is preferably contained in the range of mass%. The molecular weight of the polymer compound is preferably 30,000 to 400,000, more preferably 5,000 to 300,000, and even more preferably 5,000 to 200,000 on average by mass.

[Anti-reflective layer]
The antireflection layer included in the antiglare antireflection film of the present invention will be described. The antiglare antireflection film of the present invention has an integrated reflectance of 1.0% or less, a mirror reflectance of 0.4% or less, and an average thickness of the antireflection layer in the convex portion of the antiglare antireflection film. / The average thickness of the antireflection layer in the concave portion (the ratio of the average thickness of the antireflection layer in the convex portion to the average thickness of the antireflection layer in the concave portion) is 1.0 to 0.7. The antireflection layer is not particularly limited as long as it satisfies the above conditions. Further, in the present invention, when the antireflection layer is multi-layered, the above relationship is established for each layer.

How to obtain the average thickness of the antireflection layer in the convex portion of the antiglare antireflection film and the average thickness of the antireflection layer in the concave portion of the antiglare antireflection film will be described.
In the present invention, when the antireflection layer is a moth-eye layer and when the antireflection layer is not a moth-eye layer, the average thickness of the antireflection layer at the convex portion of the antiglare antireflection film is calculated as follows. , The antireflection layer in the recess of the antiglare antireflection film is obtained.

<When the antireflection layer is a moth-eye layer>
When the antireflection layer is a moth-eye layer, it may be difficult to obtain it by the same method as <when the antireflection layer is not a moth-eye layer> described later, so observe the surface of the antiglare antireflection film. By counting the number of particles in the antireflection layer in a region of a certain size, the average thickness of the antireflection layer in the convex portion and the antireflection layer in the concave portion are obtained. This method is based on the idea that the number of particles correlates with the film thickness of the antireflection layer.
For example, when an antireflection layer forming composition containing particles is applied onto an antiglare layer to form an antireflection layer, the convex portion and the concave portion of the antiglare layer are formed by leveling the coating liquid (antireflection layer forming composition). The coating amount becomes uneven, and the number of particles becomes sparse (that is, the number of particles decreases in the convex portion (becomes a sparse portion), and the number of particles increases in the concave portion (becomes a dense portion)). Therefore, in this case, the portion where the particles are sparse can be considered as a convex portion, and the portion where the particles are dense can be considered as a concave portion, and (the number of particles in the sparse portion / the number of particles in the dense portion) can be considered as (reflection of the convex portion). It can be considered as the film thickness of the prevention layer / the film thickness of the antireflection layer of the recess).
Further, when the antireflection layer is formed on the antiglare layer by transfer, sparse and dense particles are unlikely to occur in the antireflection layer. Therefore, in this case, the randomly selected portion can be regarded as a convex portion and a concave portion, and the number of particles of each can be counted and considered as (the film thickness of the antireflection layer of the convex portion / the film thickness of the antireflection layer of the concave portion). ..
Specifically, the measured values calculated from the following methods can be used as the average thickness of the antireflection layer in the convex portion and the average thickness of the antireflection layer in the concave portion of the antiglare antireflection film. That is, the dense part and the sparse part of the particles are determined by surface SEM observation at a low magnification, the sparse part is a convex part, the dense part is a concave part, and the number of particles existing in a 10 μm × 10 μm square is enlarged. Count. When the dense part and the sparse part do not exist by the above method (the dense part and the sparse part cannot be distinguished and are uniform as a whole), the randomly selected visual field is the same as the convex part and the concave part. Will be measured. The average thickness of the antireflection layer at the convex portion / the average thickness of the antireflection layer at the concave portion of the antiglare antireflection film can be obtained by averaging the measured values of 10 times each and taking a ratio.
Determining the dense and sparse parts of the particles by surface SEM observation at low magnification will be described in more detail with reference to the figures.
FIG. 1A is an example of a surface SEM image of the antiglare antireflection film when the antireflection layer is formed by coating. In this case, as shown in FIG. 1A, the dense part and the sparse part of the particles are apparent at first glance. The number of particles existing in the region of 10 μm × 10 μm square is counted for the dense portion and the sparse portion of the particles determined in this way. FIG. 1 (b) is a magnified view of FIG. 1 (a). When the size of the sparse portion is smaller than 10 μm × 10 μm square, a region smaller than the size of the sparse portion can be specified and the number of particles in that region can be counted.
FIG. 2A is an example of a surface SEM image of the antiglare antireflection film when the antireflection layer is formed by transfer, and FIG. 2B is a magnified view of FIG. 2A. .. In this case, it is indistinguishable between the dense part and the sparse part of the particles, and it is uniform throughout. Therefore, the number of particles of each of the randomly selected portions is counted as the convex portion and the concave portion in the same manner as described above.

<When the antireflection layer is not the moth-eye layer>
When the antireflection layer is not a moth-eye layer, the average thickness of the antireflection layer in the convex portion and the average thickness of the antireflection layer in the concave portion of the antiglare antireflection film can be calculated by the following method. That is, the convex portion of the antiglare layer is marked with a marking pen or the like by observing with an optical microscope or the like, and the cross section cut so as to include the marked portion (marking portion) is an optical microscope or a scanning electron microscope (SEM). ) Etc. to calculate the thickness of the antireflection layer. Here, the convex portion is the film thickness of the portion where the thickness of the antireflection layer is the thinnest in the vicinity of the marking portion, and the concave portion is the portion where the thickness of the antireflection layer is the thickest in the cross section, and the average thickness is 10 times. The average value of the measurements.

The average thickness of the antireflection layer in the convex portion of the antiglare antireflection film / the average thickness of the antireflection layer in the concave portion is preferably 1.0 to 0.7, and is preferably 1.0 to 0.9. It is preferable, and 1.0 is most preferable. The closer the ratio is to 1.0, the more an antiglare antireflection film having good reflectance and haze characteristics can be obtained.

(Moss eye layer)
As a specific example of the preferable antireflection layer of the present invention, it contains particles having an average primary particle size of 100 nm or more and 250 nm or less and a binder resin, and has a moth-eye structure composed of the particles on the surface opposite to the interface with the antiglare layer. An antireflection layer (moss eye layer) can be mentioned.
Here, the moth-eye structure refers to a structure that is a processed surface of a substance (material) for suppressing light reflection and has a periodic fine structure pattern. In particular, for the purpose of suppressing the reflection of visible light, it refers to a structure having a microstructure pattern with a period of less than 780 nm. When the period of the fine structure pattern is less than 380 nm, the tint of the reflected light is lost, which is preferable. Further, when the period is 100 nm or more, light having a wavelength of 380 nm can recognize the fine structure pattern and is excellent in antireflection property, which is preferable. The presence or absence of the moth-eye structure can be confirmed by observing the surface shape with a scanning electron microscope (SEM), an atomic force microscope (AFM), or the like and examining whether or not the fine structure pattern is formed.
The materials and manufacturing conditions used for the moth-eye layer will be described later in the manufacturing method section in relation to the process.

(Other anti-reflection layers)
The antireflection layer of the antiglare antireflection film of the present invention may be an antireflection layer (also referred to as “other antireflection layer”) other than the moth-eye layer.
Examples of the other antireflection layer include an antireflection layer including a low refractive index layer. The low refractive index layer is a layer having a lower refractive index (refractive index at a wavelength of 500 nm) than that of the base film.

For the low refractive index layer, a fluorine-containing compound that is cured by heat or ionizing radiation is preferably used. As the curable fluoropolymer compound, a perfluoroalkyl group-containing silane compound (for example, (Heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane) and the like, as well as a fluorine-containing monomer and a crosslinkable group are added. Examples thereof include a fluorine-containing copolymer having a monomer as a constituent unit.
Specific examples of the fluorine-containing monomer unit include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxol and the like. ), Partial or fully fluorinated alkyl ester derivatives of (meth) acrylic acid (for example, Biscort 6FM (manufactured by Osaka Organic Chemistry Co., Ltd.), M-2020 (manufactured by Daikin Co., Ltd.), etc.), Fully or partially fluorinated vinyl ether Among these, hexafluoropropylene is particularly preferable from the viewpoint of low refractive index and ease of handling of the monomer.
As the monomer for imparting a crosslinkable group, in addition to a (meth) acrylate monomer having a crosslinkable functional group in the molecule in advance such as glycidyl methacrylate, it has a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group and the like (meth). ) Acrylic monomers (eg, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.) can be mentioned.

Further, not only the polymer having the above-mentioned fluorine-containing monomer as a constituent unit, but also a copolymer with a monomer not containing a fluorine atom may be used. The monomer unit that can be used in combination is not particularly limited, and for example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylate esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2). -Ethylhexyl), methacrylate esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ethers, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylicamides, acrylonitril derivatives, etc. Yes, it is disclosed in JP-A No. 10-25388 and JP-A-10-147739.

The antireflection layer preferably has a high refractive index layer in addition to the low refractive index layer. The low refractive index layer is a layer having a higher refractive index (refractive index at a wavelength of 500 nm) than that of the base film. The high refractive index layer is formed by coating a coating composition containing high refractive index inorganic microparticles, heat or ionizing radiation curable monomers, initiator and solvent, drying the solvent, and curing by heat and / or ionizing radiation. To. As the inorganic fine particles, those composed of at least one metal oxide selected from the oxides of Ti, Zr, In, Zn, Sn and Sb are preferable. The high refractive index layer thus formed is excellent in scratch resistance and adhesion as compared with a layer obtained by applying a polymer solution having a high refractive index and drying it. Containing a polyfunctional (meth) acrylate monomer and an anionic group as described in Japanese Patent Application Laid-Open No. 11-157033 and Patent No. US6210858 B1 in order to secure dispersion stability, film strength after curing, etc. It is preferable that the (meth) acrylate dispersant is contained in the coating composition.

The average particle size of the inorganic fine particles is preferably 1 to 100 nm as measured by the Coulter counter method. The haze of the high refractive index layer is preferably 3% or less, more preferably 1% or less, and further preferably 0.5% or less.

Further, the antireflection layer may further have a medium refractive index layer in addition to the low refractive index layer and the high refractive index layer.
When the antiglare antireflection film has a medium refractive index layer, a high refractive index layer, and a low refractive index layer in this order, the medium refractive index layer has the following formula (I) with respect to the design wavelength λ (= 500 nm). It is preferable that the high refractive index layer satisfies the lower formula (II) and the low refractive index layer satisfies the lower formula (III).
Further, when the anti-glare anti-reflection film has a high refractive index layer and a low refractive index layer in this order, the high refractive index layer has the lower formula (II) with respect to the design wavelength λ (= 500 nm). It is preferable that the refractive index layer satisfies the following equation (III).
lλ / 4 × 0.80 <n1d1 <lλ / 4 × 1.00 (I)
mλ / 4 × 0.75 <n2d2 <mλ / 4 × 0.95 (II)
nλ / 4 × 0.95 <n3d3 <nλ / 4 × 1.05 (III)
However, in the formula, l is 1, n1 is the refractive index of the medium refractive index layer, d1 is the layer thickness (nm) of the medium refractive index layer, m is 2, and n2 is high refractive index. The index of refraction of the rate layer, and d2 is the layer thickness (nm) of the high index layer, n is 1, n3 is the index of refraction of the low index layer, and d3 is the index of refraction The layer thickness (nm) of the layer.
When the antiglare antireflection film has a medium refractive index layer, a high refractive index layer, and a low refractive index layer in this order, n1 is set with respect to the base film having a refractive index of 1.45 to 1.55. It is preferable that 1.60 to 1.65, n2 has a refractive index of 1.85 to 1.95, and n3 has a refractive index of 1.35 to 1.45.
When the antiglare antireflection film has a high refractive index layer and a low refractive index layer in this order, n2 is 1.85 to 1 with respect to the base film having a refractive index of 1.45 to 1.55. It is preferable that 95 and n3 have a refractive index of 1.35 to 1.45.

[Base film]
Although various base films can be used in the antiglare antireflection film of the present invention, a plastic base film is preferable, and for example, a cellulose resin; cellulose acylate (triacetate cellulose, diacetyl cellulose, acetate). Polyester resin such as butyrate cellulose); base material containing (meth) acrylic resin, polyurethane resin, polycarbonate, polystyrene, olefin resin and the like such as polyethylene terephthalate, and cellulose acylate, polyethylene terephthalate, or ( A base material containing a meta) acrylic resin is preferable, and a base material containing cellulose acylate is more preferable. As the cellulose acylate, the substrate or the like described in JP2012-093723 can be preferably used.
The thickness of the base film is usually about 10 μm to 1000 μm, but 20 μm to 200 μm is preferable, and 25 μm to 100 μm is more preferable from the viewpoint of good handleability, high transparency, and sufficient strength. preferable. The transparency of the base film is preferably 90% or more.

[Adhesive layer]
The antiglare antireflection film of the present invention preferably has an adhesive layer between the antiglare layer and the antireflection layer.
In particular, it was found that when the antireflection layer is applied by the transfer method, the scratch resistance can be improved by providing an adhesive layer between the antiglare layer and the antireflection layer.
The adhesive for forming the adhesive layer is not particularly limited, but an epoxy-based active energy ray-curable adhesive, an acrylate-based ultraviolet curable adhesive, or the like can be used in addition to the polyvinyl alcohol-based adhesive. For example, an adhesive containing an epoxy compound containing no aromatic ring in the molecule and cured by heating or irradiation with active energy rays, as shown in JP-A-2004-245925, is described in JP-A-2008-174667. In 100 parts by mass of the total amount of the (meth) acrylic compound, (a) a (meth) acrylic compound having two or more (meth) acryloyl groups in the molecule and (b) having a hydroxyl group in the molecule and polymerizing. Examples thereof include an active energy ray-curable adhesive containing a (meth) acrylic compound having only one sex double bond and (c) a phenolethylene oxide-modified acrylate or a nonylphenolethylene oxide-modified acrylate. When the antireflection layer is the moth-eye layer, it is preferable to use a (meth) acrylate-based ultraviolet curable adhesive from the viewpoint of adhesion between the antiglare layer and the moth-eye layer, and further, polyfunctional (meth) acrylate is used. The contained acrylate-based ultraviolet rays can be preferably used.

The thickness of the adhesive layer is preferably 0.01 to 3.0 μm, more preferably 0.01 to 1.0 μm, and even more preferably 0.01 to 0.6 μm. The thinner the adhesive layer is, the more preferable it is because an antiglare antireflection film having excellent antiglare property can be obtained without impairing the antiglare property of the antiglare film.

(Surface shape of anti-glare anti-reflection film)
The antiglare antireflection film of the present invention has a concavo-convex shape on the surface on the antireflection layer side, and the concavo-convex shape has an arithmetic mean roughness (Ra) of 0.03 μm ≦ Ra ≦ 0.4 μm. The average spacing (Sm) of the unevenness is 20 μm ≦ Sm ≦ 700 μm.
Here, the arithmetic mean roughness (Ra) and the average spacing (Sm) of the unevenness are measured based on JIS B-0601 (1994).
The arithmetic mean roughness (Ra) and average interval (Sm) of the surface unevenness are measured using a measuring instrument according to JIS B-0601 (1994), for example, a surf coder MODEL SE-3F manufactured by Kosaka Research Institute Co., Ltd. can do.
The uneven shapes Ra and Sm measured by the above measurement are uneven shapes caused by the antiglare layer. Even when the anti-glare antireflection film has a moth-eye layer on the anti-glare layer, the fine uneven shape of the moth-eye layer does not affect the above measurement.

The arithmetic mean roughness (Ra) is 0.03 μm ≦ Ra ≦ 0.4 μm, preferably 0.1 μm ≦ Ra ≦ 0.4 μm.

When the Ra value is 0.03 μm or more, it is easy to obtain a sufficient surface uneven structure that can obtain good antiglare properties, and when it is 0.4 μm or less, it is easy to obtain an uneven structure in which the haze value is in an appropriate range. Therefore, it is preferable. When it is 0.1 μm or more, it is preferable because an antiglare antireflection film having high antiglare property can be obtained. Further, when it is 0.1 μm or more, the reflectance when the antireflection layer is formed by coating tends to increase, and the merit of the method of forming the antireflection layer by the transfer of the present invention can be greatly obtained, which is preferable. Further, when the value of Sm is 20 μm or more, it is preferable that the antireflection layer easily follows the unevenness of the antiglare layer when the antireflection layer is transferred, and it is preferably 700 μm or less from the viewpoint of ensuring the antiglare performance.

[Manufacturing method of anti-glare anti-reflection film]
The method for producing an antiglare antireflection film of the present invention is
A method for producing an antiglare antireflection film having a base film, an antiglare layer, and an antireflection layer in this order.
A composition for forming an antiglare layer containing a binder resin forming compound for an antiglare layer and particles for an antiglare layer is applied onto the base film, and the composition for forming the antiglare layer is obtained by irradiation with ionizing radiation or heating. The step of curing to form an antiglare layer (step I) and
A step of applying an antireflection forming composition on the temporary support and semi-hardening it by ionizing radiation irradiation or heating at a surface hardening rate of 10 to 70% to form an antireflection layer (step II).
A step (step III) of transferring the antireflection layer from the temporary support onto a surface of the antiglare layer opposite to the side having the base film.
It is a method of manufacturing an antiglare antireflection film having.

<Step I>
In the method for producing an antiglare antireflection film of the present invention, an antiglare layer forming composition containing a binder resin forming compound for an antiglare layer and particles for an antiglare layer is applied onto a base film, and ionizing radiation is applied. The present invention comprises a step of curing the antiglare layer forming composition by irradiation or heating to form an antiglare layer, that is, a step of forming the base film and the antiglare film having the antiglare layer.

The base film is as described above.

(Composition for forming an antiglare layer)
The antiglare layer forming composition contains a binder resin forming compound for the antiglare layer and particles for the antiglare layer. The binder resin forming compound for the antiglare layer and the particles for the antiglare layer are as described above.
The composition for forming an antiglare layer preferably further contains a solvent. The solvent varies depending on the components constituting the base film, but in the case of a cellulose acylate base material, for example, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), dimethyl carbonate, methyl acetate, acetone, methylene chloride and the like are preferable. It can be used, with methyl ethyl ketone (MEK), dimethyl carbonate, and methyl acetate being more preferred.
In the case of an acrylic base material, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, acetone, methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone methyl acetate, ethyl acetate and the like are preferable.
The solvent used in these antiglare layer forming compositions may be used alone or in combination of two or more.

-Polymerization initiator-
The composition for forming an antiglare layer may contain a polymerization initiator.
When the binder resin forming compound for the antiglare layer contained in the composition for forming the antiglare layer is a photopolymerizable compound, it is preferable to contain a photopolymerization initiator.
Photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, etc. Fluoroamine compounds, aromatic sulfoniums, loffin dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like can be mentioned. Specific examples of the photopolymerization initiator, preferred embodiments, commercially available products, and the like are described in paragraphs <0133> to <0151> of JP-A-2009-098658, and can be preferably used in the present invention as well. it can.

"Latest UV Curing Technology" {Technical Information Association, Inc.} (1991), p. 159 and "Ultraviolet Curing System" by Kiyomi Kato (published by General Technology Center in 1989), p. Various examples are also described in 65 to 148, which are useful for the present invention.

The content of the photopolymerization initiator in the antiglare layer forming composition is sufficiently large to polymerize the binder resin forming compound for the antiglare layer contained in the antiglare layer forming composition, and the starting points are excessively increased. It is preferably 0.5 to 8% by mass, more preferably 1 to 5% by mass, based on the total solid content in the antiglare layer forming composition, because the amount is set to a sufficiently small amount so as not to occur.

The method for applying the antiglare layer forming composition is not particularly limited, and a known method can be used. For example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method and the like can be mentioned.

In step I, the antiglare layer forming composition applied on the base film is cured by ionizing radiation irradiation or heating to form an antiglare layer. The solvent is preferably dried in the formation of the antiglare layer.

The type of ionizing radiation in forming the antiglare layer of the present invention is not particularly limited, and depending on the type of the binder resin forming compound for the antiglare layer, ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, etc. Although it can be appropriately selected from X-rays and the like, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferable because they are easy to handle and high energy can be easily obtained.

As the light source of ultraviolet rays for photopolymerizing the ultraviolet curable compound, any light source that generates ultraviolet rays can be used. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Further, ArF excimer laser, KrF excimer laser, excimer lamp, synchrotron radiation and the like can also be used. Of these, ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs, and metal halide lamps can be preferably used.

The irradiation conditions differ depending on each lamp, but the irradiation light amount is preferably 1 mJ / cm ² or more, and more preferably 1 to 2000 mJ / cm ² .
In addition, the surface hardening rate of the antiglare layer before the antireflection layer is laminated can be adjusted by changing the oxygen concentration together with the ultraviolet irradiation conditions, preferably 10% or less, more preferably 5% or less, most preferably. Is cured by irradiating ionizing radiation in an oxygen concentration atmosphere of 2% or less.

The heating may be combined with the heating during solvent drying in the above-mentioned composition for forming an antiglare layer, or may be heated separately from the heating during solvent drying. Appropriate heating conditions vary depending on the type of base film used, but the heating conditions are preferably 60 ° C. or higher, more preferably 60 to 150 ° C., and particularly preferably 60 to 130 ° C. The heating time is preferably 10 seconds to 3 minutes from the viewpoint of ease of production. By appropriately combining the oxygen concentration together with the ionizing radiation irradiation conditions, the hardness of the antiglare layer can be ensured and the surface hardening rate can be adjusted.

The surface hardening rate of the antiglare layer before the step of forming the antireflection layer (the surface hardening rate of the surface of the antiglare layer opposite to the side having the base film) is preferably 80% or less. It is more preferably 10% to 70%, and even more preferably 20% to 60%.
When the surface hardening rate of the antireflection layer before laminating the antireflection layer is 60% or less, the adhesion between the antireflection layer and the antiglare layer is good, and when it is 20% or more, the pressure on the antiglare layer is increased. It is preferable because it can prevent deformation and layer destruction when it is applied.
It is preferable that the antiglare layer is completely cured after the antireflection layer described later is transferred to enhance physical performance such as scratch resistance.

For the surface curing rate, the peak (1660-1800 cm ^-1 ) area of the carbonyl group and the peak height (808 cm ^-1 ) of the double bond were measured for the uncured product and the cured product by IR measurement, respectively, and the double of the cured product was measured. It can be calculated by dividing the normalized peak height of the bond by the normalized peak height of the double bond of the uncured product.

After forming the antiglare layer and before forming the antireflection layer, the surface of the antiglare layer may be surface-treated, and then the antireflection layer may be formed.
Examples of the surface treatment in this case include a method of modifying the film surface by corona discharge treatment, glow discharge treatment, ultraviolet irradiation treatment, flame treatment, ozone treatment, acid treatment, alkali treatment and the like. The glow discharge treatment referred to here may be low-temperature plasma generated under a low-pressure gas of ^{10-3 to} 20 Torr, and plasma treatment under atmospheric pressure is also preferable. A plasma-excited gas is a gas that is plasma-excited under the above conditions, and includes fluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, and tetrafluoromethane, and mixtures thereof. Be done. Details of these are described in detail on pages 30 to 32 of Publication No. 2001-1745 of the Institute of Invention and Innovation (issued on March 15, 2001, Institute of Invention and Innovation), and are preferably used in the present invention. be able to.
Of these treatments, plasma treatment and corona treatment are preferable.

[Plasma processing]
Examples of the plasma treatment include vacuum glow discharge, atmospheric pressure glow discharge, and the like, and other methods include frame plasma treatment and the like. For these, for example, the methods described in JP-A-6-123062, JP-A-11-293011, JP-A-11-5857 and the like can be used.

[Corona discharge processing]
The corona discharge treatment can be performed by any conventionally known method, for example, Japanese Patent Application Laid-Open No. 48-5043, 47-51905, 47-28067, 49-83767, 51-41770. , 51-131576, Japanese Patent Application Laid-Open No. 2001-272503, and the like.

<Step II>
In the method for producing an anti-glare anti-reflection film of the present invention, an anti-reflection forming composition is applied on a temporary support, and the anti-reflection layer is semi-hardened at a surface hardening rate of 10 to 70% by ionizing radiation irradiation or heating. Has a step of forming.

The temporary support will be described later in the method for forming the moth-eye layer.

(Composition for forming an antireflection layer)
The antireflection layer forming composition contains a binder resin forming compound and a solvent.
As the binder resin forming compound, a compound having a polymerizable functional group (preferably an ionizing radiation curable compound) is preferable. As the compound having a polymerizable functional group, various monomers, oligomers or polymers can be used, and as the polymerizable functional group (polymerizable group), light, electron beam and radiopolymerizable ones are preferable, and among them, photopolymerization Sexual functional groups are preferred.
Examples of the photopolymerizable functional group include polymerizable unsaturated groups (carbon-carbon unsaturated double-bonding groups) such as (meth) acryloyl group, vinyl group, styryl group and allyl group, and among them, (meth). ) Acryloyl groups are preferred. Specific examples are the same as those described for the moth-eye layer described later.
Examples of the solvent contained in the antireflection layer forming composition include methyl ethyl ketone (MEK), dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, acetone, cyclopentanone, cyclohexanone methyl acetate, ethyl acetate, butyl acetate, ethanol, and methanol. Isopropyl alcohol is preferable, and each solvent may be used alone or in combination of two or more.
The antireflection layer forming composition may contain a polymerization initiator, and specific examples and preferable examples of the polymerization initiator are the same as those of the above-mentioned polymerization initiator of the antiglare layer forming composition.

The solid content concentration of the antireflection layer forming composition is preferably 1% by mass or more and 90% by mass or less.

In the antireflection layer forming composition, the content of the binder resin forming compound is preferably 10% by mass or more and 97% by mass or less with respect to the mass of the total solid content of the antireflection layer forming composition.
The antireflection layer forming composition may contain a polymerization initiator.
When the compound for forming the binder resin is a photopolymerizable compound, it preferably contains a photopolymerization initiator. The photopolymerization initiator is the same as that described in the moth-eye layer described later.

The method of applying the antireflection layer forming composition is the same as the above-mentioned method of applying the antiglare layer forming composition.

The preferred conditions for ionizing radiation irradiation or heating are preferably an ionizing radiation irradiation amount of 1 mJ / cm ² or more, more preferably ² to 2000 mJ / cm ² , and the oxygen concentration during ionizing radiation irradiation is preferably 0.1% or less. , More preferably 0.01% or less, and most preferably 0.005% or less.
The heating conditions are preferably 60 ° C. or higher, more preferably 60 to 150 ° C., particularly preferably 80 to 130 ° C., and the heating time is preferably 10 seconds to 10 minutes, more preferably 30 seconds to 5 minutes. ..

The surface hardening rate of the antireflection layer before transfer to the antiglare layer (the surface hardening rate of the surface of the antireflection layer opposite to the side having the temporary support) is 10 to 70%, and 20 to 60%. Is more preferable. When the surface hardening rate is 10% or more, it is possible to prevent a part of the antireflection layer from being deformed during transfer and the antireflection ability from being lowered, and the surface hardening rate is 70% or less. As a result, the adhesion between the antiglare layer and the antireflection layer can be kept good. When the surface hardening rate is 20 to 60%, the adhesion between the antiglare layer and the antireflection layer can be further maintained, and the effect of improving the scratch resistance is great.

The surface hardening rate can be calculated by the same measuring method as the surface hardening rate of the antiglare layer. If the film thickness of the antireflection layer is thin and it is difficult to obtain measurement data of only the antireflection layer, prepare an antireflection layer with an increased film thickness for measuring the surface hardening rate and perform the same measurement. , The calculated surface hardening rate can be used as the surface hardening rate for convenience.

<Step III>
The method for producing an antiglare antireflection film of the present invention includes a step of transferring the antireflection layer from the temporary support onto a surface of the antiglare layer opposite to the side having the base film.

The antireflection layer and the surface of the antiglare layer opposite to the side having the base film are bonded to each other with a nip roller or the like, and then the temporary support is removed through a process of bringing the two into close contact with each other to prevent reflection. The layer is transferred to the surface of the anti-glare layer opposite to the side having the base film. As a method of bringing the antireflection layer into close contact with the surface of the antiglare layer on the side opposite to the side having the base film, a compound having a polymerizable functional group contained in both of them may be used as a light, an electron beam, or It is preferably polymerized by radiation or heat, and most preferably photopolymerization.

<Other processes>
In the method for producing an antiglare antireflection film of the present invention, a step of providing an adhesive layer on the antiglare layer or on the antireflection layer before transferring the antireflection layer from the temporary support to the antiglare layer is performed. It is also preferable to have. The adhesive layer is as described above. Dose when curing the adhesive layer by the ionizing radiation dose is preferably from 50 mJ / cm ² or more, more preferably from 100 to 2000 mJ / cm ^2, oxygen concentration during irradiation with ionizing radiation is preferably 0. It is 1% or less, more preferably 0.01% or less, and most preferably 0.005% or less. The heating conditions at the time of adhesion can be appropriately adjusted according to the adhesiveness and permeability of the antireflection layer and the antiglare layer.

As another aspect, in the method for producing an anti-glare anti-reflection film of the present invention, it is preferable to have a step of heating the anti-reflection layer and the anti-glare layer in a bonded state. By providing such a step, the adhesion between the antireflection layer and the antiglare layer can be improved. The heating temperature and time can be appropriately adjusted according to the antireflection layer and the antiglare layer.

(Manufacturing method of anti-glare anti-reflection film in which the anti-reflection layer is a moth-eye layer)
A moth-eye layer can be mentioned as a preferable antireflection layer of the present invention.
The method for producing an antiglare antireflection film in which the antireflection layer of the present invention is a moth-eye layer is
Particles (a2) having an average primary particle size of 100 nm or more and 250 nm or less and a curable compound (a1) are placed on a temporary support, and the particles (a2) are placed in a layer (a) containing the curable compound (a1). Step (1), which is provided with a thickness that allows the particles to be buried
Step (2) of obtaining a layer (ca) by curing a part of the layer (a).
Step (3) of laminating the layer (b) of the adhesive film having the support and the layer (b) containing the adhesive on the support with the layer (ca).
The layer (ca) is buried in the combined layer of the layer (ca) and the layer (b), and the particles (a2) protrude from the interface of the layer (ca) on the support side. ), The step (4) of bringing the position of the interface on the support side closer to the temporary support side.
Step (5) of peeling off the temporary support,
Step (6) of laminating the antiglare layer of the antiglare film having the base film and the antiglare layer and the layer (ca) of the laminate containing the layer (ca) obtained in the step (5). ,
A step (7) of curing the layer (ca) in a state where the particles (a2) are buried in a layer in which the layer (ca) and the layer (b) are combined.
Step (8) of peeling the adhesive film,
Is a method for producing an antiglare antireflection film having the above in this order.

Between the step (4) and the step (5), the particles (a2) of the layer (ca) are buried in a layer in which the layer (ca) and the layer (b) are combined. It is preferable to have a step (4-2) of curing a part.

In the method for producing an antiglare antireflection film of the present invention, after the step (8), the particles (a2) are further formed from the interface of the layer (ca) opposite to the interface of the base film side. Step (9) of curing the layer (ca) in a protruding state,
Step of cleaning with solvent (10)
Is more preferable to have in this order.

In the present invention, the "thickness in which the particles (a2) are buried in the layer (a)" means that the thickness of the layer (a) is 0.8 times or more the average primary particle size of the particles (a2). It shall represent.
Further, in the present invention, "the particles (a2) are buried in the layer in which the layer (ca) and the layer (b) are combined" means that the thickness of the layer in which the layer (ca) and the layer (b) are combined is used. Indicates that is 0.8 times or more the average primary particle size of the particles (a2).

In the present invention, in the step (1), the layer (a) is formed with a thickness in which the particles (a2) are buried. Therefore, in the step (4) and thereafter, the surface protruding from the layer (ca) of the particles (a2) is layered. A thin layer of (ca) may cover. The particles (a2) coated with the thin layer are also referred to as particles (a2) for convenience.

A schematic diagram of an example of the steps (1) to (5) is shown in FIG.
FIG. 4 shows a schematic diagram of an example of steps (6) to (10).

[Step (1)]
In the step (1), the curable compound (a1) and the particles (a2) having an average primary particle size of 100 nm or more and 250 nm or less are placed on the temporary support in the layer (a) containing the curable compound (a1). This is a step of providing the particles (a2) with a thickness at which they are buried.
As described above, in the present invention, the "thickness in which the particles (a2) are buried in the layer (a)" means a thickness of 0.8 times or more the average primary particle size of the particles (a2). ..

In the step (1), the method of providing the layer (a) on the temporary support is not particularly limited, but it is preferably provided by applying the layer (a) on the temporary support. In this case, the layer (a) is a layer formed by applying a layer (a) forming composition containing a curable compound (a1) and particles (a2) having an average primary particle size of 100 nm or more and 250 nm or less. .. That is, the layer (a) forming composition corresponds to the above-mentioned antireflection layer forming composition. The coating method is not particularly limited, and a known method can be used. For example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method and the like can be mentioned.

In the layer (a) provided on the temporary support in the step (1), it is preferable that a plurality of particles (a2) do not exist in the direction orthogonal to the surface of the layer (a). Here, the fact that a plurality of particles (a2) do not exist in the direction orthogonal to the surface of the layer (a) means that 10 μm × 10 μm in the plane of the layer (a) was observed in three fields with a scanning electron microscope (SEM). At that time, the ratio of the number of particles (a2) in a state in which a plurality of particles (a2) are not present in a direction orthogonal to the surface is 80% or more, and is preferably 95% or more.

(Temporary support)
The temporary support is not particularly limited as long as it has a smooth surface. The temporary support preferably has a surface roughness of about 30 nm or less and does not interfere with the application of the composition for forming the layer (a), and is a temporary support made of various materials. Although it can be used, for example, a polyethylene terephthalate (PET) film or a cycloolefin resin film is preferably used.
In the present invention, the surface roughness of the temporary support is measured using SPA-400 (manufactured by Hitachi High-Technologies Science) under the measurement conditions of a measurement range of 5 μm × 5 μm, a measurement mode: DFM, and a measurement frequency: 2 Hz.

(Layer (a))
The layer (a) is a layer containing the curable compound (a1) and particles (a2) having an average primary particle size of 100 nm or more and 250 nm or less.
The curable compound (a1) contained in the layer (a) can become a resin (binder resin) in the antireflection layer by being cured. That is, the curable compound (a1) is a kind of binder compound. Further, the curable compound (a1) corresponds to the above-mentioned binder resin forming compound.
The particles (a2) having an average primary particle size of 100 nm or more and 250 nm or less contained in the layer (a) protrude from the surface of the film (layer (ca)) made of the binder resin in the finished antiglare antireflection film, and the particles. These are particles that form a fine uneven shape (moth-eye structure) according to (a2).
The film thickness of the layer (a) in the step (1) is preferably 0.8 times or more and 2.0 times or less, and 0.8 times or more and 1.5 times or less the average primary particle size of the particles (a2). Is more preferable, and 0.9 times or more and 1.2 times or less is further preferable.

<Curable compound (a1)>
As the curable compound (a1), a compound having a polymerizable functional group (preferably an ionizing radiation curable compound) is preferable. As the compound having a polymerizable functional group, various monomers, oligomers or polymers can be used, and as the polymerizable functional group (polymerizable group), light, electron beam and radiopolymerizable ones are preferable, and among them, photopolymerization Sexual functional groups are preferred.
Examples of the photopolymerizable functional group include polymerizable unsaturated groups (carbon-carbon unsaturated double-bonding groups) such as (meth) acryloyl group, vinyl group, styryl group and allyl group, and among them, (meth). ) Acryloyl groups are preferred.

Specific examples of the compound having a polymerizable unsaturated group include (meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, and propylene glycol di (meth) acrylate;
(Meta) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
(Meta) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
Ethylene oxides such as 2,2-bis {4- (acryloxydiethoxy) phenyl} propane, 2-2-bis {4- (acryloxypolypropoxy) phenyl} propane, or (meth) acrylic acid diesters with propylene oxide adducts Kind; etc.

Further, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as compounds having a photopolymerizable functional group.

Among them, esters of a polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, one molecule contains at least one polyfunctional monomer having three or more (meth) acryloyl groups.
For example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO (ethylene oxide) modified trimethylolpropane tri (meth) acrylate, PO (propylene oxide) modified trimethylol Propanetri (meth) acrylate, EO-modified tri (meth) phosphate, trimethylolethanetri (meth) acrylate, trimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate ) Acrylate, dipentaerythritol hex (meth) acrylate, pentaerythritol hex (meth) acrylate, 1,2,3-clohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate, caprolactone-modified trics (acryloxyethyl) isocyanurate, etc. Can be mentioned.

Specific compounds of polyfunctional acrylate compounds having a (meth) acryloyl group include KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, and TPA-manufactured by Nippon Kayaku Co., Ltd. 330, RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303, V # 3PA, V manufactured by Osaka Organic Chemical Industry Co., Ltd. Examples thereof include esterified compounds of polyols such as # 400, V # 36095D, V # 1000, V # 1080 and (meth) acrylic acid. In addition, purple light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B. , UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310B, UV-3500BA. , UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2750B (manufactured by Nippon Synthetic Chemical Co., Ltd.), UA-306H, UA-306I, UA-306T, UL-503LN (manufactured by Kyoeisha Chemical Co., Ltd.), Unidic 17-806, 17-813, V-4030, V-4000BA (Dainippon Ink and Chemicals) EB-1290K, EB-220, EB-5129, EB-1830, EB-4858 (manufactured by Daicel UCB Co., Ltd.), U-4HA, U-6HA, U-10HA, U-15HA (manufactured by Daicel UCB Co., Ltd.) Shin-Nakamura Chemical Industry Co., Ltd.), Hicorp AU-2010, AU-2020 (Tokushiki Co., Ltd.), Aronix M-1960 (Toa Synthetic Co., Ltd.), Art Resin UN-3320HA, UN-3320HC, Trifunctional or higher urethane acrylate compounds such as UN-3320HS, UN-904, HDP-4T, Aronix M-8100, M-8030, M-9050 (manufactured by Toa Synthetic Co., Ltd., KRM-8307) (Dicel Cytec Co., Ltd.) A trifunctional or higher functional polyester compound such as (manufactured by) can also be preferably used.

Further, a resin having three or more polymerizable functional groups, for example, a polyester resin having a relatively low molecular weight, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiol polyene resin, Also mentioned are oligomers such as polyfunctional compounds such as polyhydric alcohols or prepolymers.

Further, the compounds described in JP-A-2005-76005 and JP-A-2005-36105, dendrimers such as SIRIUS-501 and SUBARU-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), JP-A-2005-60425. Norbornene ring-containing monomers as described in Japanese Patent Publication No. can also be used.

Further, from the viewpoint of imparting light resistance, it is also preferable to use an oligomer or prepolymer having a Si—O bond as a main skeleton and having a polymerizable functional group as the curable compound (a1), and the general formula R ¹ _x It is preferably an oligomer composed of a compound represented by −Si (OR ² ) _4-x, which has one or more Si atoms and one or more C atoms in the molecule and has a polymerizable group. A compound having a Si—O bond as a main skeleton absorbs less visible light to UV light, and is particularly excellent in blue light resistance. Specific examples thereof include a cage-like silsesquioxane compound containing a polymerizable group described in JP-A-2011-84672, JP-A-2017-8148, and Japanese Patent No. 6219250. Examples thereof include polyorganosylsesquioxane compounds containing an epoxy group.

Further, when a compound having a polymerizable functional group is used as the curable compound (a1), the curable compound (a1) is used in order to bond the particles (a2) and the curable compound (a1) to form a strong film. As a silane coupling agent having a polymerizable functional group, a silane coupling agent may be used.
Specific examples of the silane coupling agent having a polymerizable functional group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxipropyl. Dimethylmethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxiethyltri Examples thereof include ethoxysilane, 4- (meth) acryloxybutyltrimethoxysilane, 4- (meth) acryloxybutyltriethoxysilane, and the like. Specifically, KBM-503, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), silane coupling agents X-12-1048, X-12-1049, X-12 described in JP-A-2014-123091. -1050 (manufactured by Shin-Etsu Chemical Co., Ltd.), compound C3 represented by the following structural formula, and the like can be mentioned.

Further, as a compound that acts to suppress the aggregation of the particles (a2), a silane coupling agent having a polymerizable functional group other than a radical reactive group may be used. Specific examples of the silane coupling agent having a polymerizable functional group other than the radical reactive group include KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, and KBM-4803 (Shin-Etsu Chemical Co., Ltd.). (Made by Kogyo Co., Ltd.).

Further, as described above, when the antireflection layer has a moth-eye structure and imparts excellent light resistance, it is possible to use the silane coupling agent having the above-mentioned polymerizable functional group as a binder component ratio having a Si—O bond. It is also preferable in that

Two or more kinds of compounds having a polymerizable functional group may be used in combination. The polymerization of these compounds having a polymerizable functional group can be carried out by irradiation or heating with ionizing radiation in the presence of a photoradical initiator or a thermal radical initiator.

The layer (a) can further contain a binder compound other than the curable compound (a1) as the binder compound. Examples of the binder compound other than the curable compound (a1) include compounds having no polymerizable functional group.
In the present invention, as the curable compound (a1), a compound having two or less polymerizable functional groups in one molecule may be used, but in particular, it has three or more polymerizable functional groups in one molecule. It is preferable to use the compound in combination with a compound having two or less polymerizable functional groups in one molecule, or a compound having no polymerizable functional group as a compound other than the curable compound (a1).
As the compound having two or less polymerizable functional groups in one molecule or the compound having no polymerizable functional group, the weight average molecular weight Mwa is preferably 40 <Mwa <500. Since the above compound has two or less polymerizable functional groups or does not contain a polymerizable functional group, shrinkage during curing is small and stress concentration on the temporary support can be avoided.
The compound having two or less polymerizable functional groups in one molecule is preferably a compound having one polymerizable functional group in one molecule.

Further, the compound having two or less polymerizable functional groups in one molecule or the compound having no polymerizable functional group preferably has a viscosity at 25 ° C. of 100 mPas or less, more preferably 1 to 50 mPas. A compound in such a viscosity range is preferable because it easily penetrates into the layer containing the pressure-sensitive adhesive, acts to suppress the aggregation of the particles (a2), and can suppress haze and cloudiness.

The compound having two or less polymerizable functional groups in one molecule preferably has a (meth) acryloyl group, an epoxy group, an alkoxy group, a vinyl group, a styryl group, an allyl group or the like as the polymerizable functional group.

As the compound having no polymerizable functional group, an ester compound, an amine compound, an ether compound, an aliphatic alcohol compound, a hydrocarbon compound and the like can be preferably used, and an ester compound is particularly preferable. More specifically, dimethyl succinate (viscosity 2.6 mPas), diethyl succinate (viscosity 2.6 mPas), dimethyl adipate (viscosity 2.8 mPas), dibutyl succinate (viscosity 3.9 mPas), bis adipate (viscosity 3.9 mPas). 2-Butoxyethyl) (viscosity 10.8 mPas), dimethyl sverate (viscosity 3.7 mPas), diethyl phthalate (viscosity 9.8 mPas), dibutyl phthalate (viscosity 13.7 mPas), triethyl citrate (viscosity 22.6 mPas) ), Acetyltriethyl citrate (viscosity 29.7 mPas), diphenyl ether (viscosity 3.8 mPas) and the like.

The weight average molecular weight and the number average molecular weight in the present invention are values measured by gel permeation chromatography (GPC) under the following conditions.
[Solvent] Tetrahydrofuran [Device name] TOSOH HLC-8220GPC
[Column] TOSOH TSKgel Super HZM-H
Use by connecting 3 (4.6 mm x 15 cm).
[Column temperature] 25 ° C
[Sample concentration] 0.1% by mass
[Flow velocity] 0.35 ml / min
[Calibration curve] TOSOH TSK standard polystyrene Mw = 2800000-1050 7 samples calibration curve is used.

The coating amount of the curable compound in the layer (a) (a1) is ^preferably from ^{100mg / m 2 ~800mg / m 2} , more preferably ^{100mg / m 2 ~600mg / m 2} , 100mg / m 2 ~400mg / M ² is most preferred.
When the curable compound (a1) and the compound having no polymerizable functional group are used in combination, the total coating amount of these is preferably in the above range.

<Particles with an average primary particle size of 100 nm or more and 250 nm or less (a2)>
Particles (a2) having an average primary particle size of 100 nm or more and 250 nm or less are also referred to as “particles (a2)”.
Examples of the particles (a2) include metal oxide particles, resin particles, and organic-inorganic hybrid particles having a core of metal oxide particles and a resin shell, and metal oxide particles are preferable from the viewpoint of excellent film strength.
Examples of the metal oxide particles include silica particles, titania particles, zirconia particles, and antimony pentoxide particles. However, since the refractive index is close to that of many binders, haze is unlikely to occur and a moth-eye structure is easily formed. Silica particles are preferred.
Examples of the resin particles include polymethyl methacrylate particles, polystyrene particles, melamine particles and the like.

The average primary particle size of the particles (a2) is 100 nm or more and 250 nm or less, more preferably 140 nm or more and 200 nm or less, and further preferably 150 nm or more and 180 nm or less from the viewpoint that the particles can be arranged to form a moth-eye structure. ..
As the particles (a2), only one type of particles may be used, or two or more types of particles having different average primary particle sizes may be used.

The average primary particle size of the particles (a2) refers to a cumulative 50% particle size of the volume average particle size. A scanning electron microscope (SEM) can be used to measure the particle size. Observe the powder particles (in the case of a dispersion, dried and volatilized the solvent) at an appropriate magnification (about 5000 times) by SEM observation, measure the diameter of each of the 100 primary particles, and measure the volume thereof. Can be calculated and the cumulative 50% particle size can be used as the average primary particle size. If the particle is not spherical, the average of the major and minor diameters is considered to be the diameter of the primary particle. When measuring the particles contained in the antiglare antireflection film, it is calculated by observing the antiglare antireflection film from the surface side by SEM in the same manner as described above. At this time, the sample may be appropriately subjected to carbon vapor deposition, etching treatment, or the like for easy observation.

The shape of the particles (a2) is most preferably spherical, but there is no problem even if the particles (a2) are not spherical such as indeterminate.
The particles (a2) may be solid particles or hollow particles, but are preferably solid particles.
Further, the silica particles may be either crystalline or amorphous.

As the particles (a2), it is preferable to use surface-treated inorganic fine particles for improving dispersibility in the coating liquid, improving film strength, and preventing aggregation. Specific examples of the surface treatment method and preferable examples thereof are the same as those described in <0119> to <0147> of JP-A-2007-298974.
In particular, from the viewpoint of imparting binding property to the curable compound (a1) which is a binder component and improving the film strength, a compound having an unsaturated double bond on the particle surface and a functional group having reactivity with the particle surface. It is preferable to modify the surface with (1) to impart an unsaturated double bond to the particle surface. As the compound used for surface modification, the above-mentioned silane coupling agent having a polymerizable functional group as the curable compound (a1) can be preferably used.

Specific examples of particles having an average primary particle size of 100 nm or more and 250 nm or less include Seahoster KE-P10 (average primary particle size 100 nm, amorphous silica manufactured by Nippon Catalyst Co., Ltd.) and Epostal S (average primary particle size 200 nm, Japan Catalyst melamine-formaldehyde condensate), Epostal MA-MX100W (average primary particle size 175 nm, polymethylmethacrylate (PMMA) cross-linked product manufactured by Nippon Catalyst Co., Ltd.), Staphyroid (Aika Kogyo Co., Ltd.) Multilayered organic fine particles), Ganzpearl (polymethylmethacrylate, polystyrene particles manufactured by Aika Industries, Ltd.) and the like can be preferably used.

As the particles (a2), calcined silica particles are particularly preferable because the amount of hydroxyl groups on the surface is moderately large and the particles are hard particles.
The calcined silica particles are produced by a known technique of calcining silica particles after hydrolyzing and condensing a hydrolyzable silicon compound in an organic solvent containing water and a catalyst. For example, JP-A-2003-176121 and JP-A-2008-137854 can be referred to.
The silicon compound as a raw material for producing calcined silica particles is not particularly limited, but chlorosilanes such as tetrachlorosilane, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylvinyldichlorosilane, trimethylchlorosilane, and methyldiphenylchlorosilane. Compounds; tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, 3-glycidoxypropyltrimethoxysilane, 3-chloro Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 3-glycid Alkoxysilanes such as xypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethoxydiethoxysilane, trimethylmethoxysilane, and trimethylethoxysilane. Compounds; Asyloxysilane compounds such as tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane, and trimethylacetoxysilane; silanol compounds such as dimethylsilanediol, diphenylsilanediol, and trimethylsilanol. ; Etc. can be mentioned. Among the above-exemplified silane compounds, the alkoxysilane compound is particularly preferable because it is more easily available and the obtained calcined silica particles do not contain halogen atoms as impurities. As a preferable form of the calcined silica particles according to the present invention, it is preferable that the content of halogen atoms is substantially 0% and no halogen atoms are detected.
The firing temperature is not particularly limited, but is preferably 800 ° C. to 1300 ° C., more preferably 1000 ° C. to 1200 ° C.

The coating amount of the particles (a2) is ^preferably from ^{50mg / m 2 ~200mg / m 2} , more preferably ^{100mg / m 2 ~180mg / m 2} , 130mg / m 2 ~170mg / m 2 is most preferred. Above the lower limit, many convex portions of the moth-eye structure can be formed, so that the antireflection property is more likely to be improved, and when it is below the upper limit, agglutination in the liquid is less likely to occur, and a good moth-eye structure is easily formed.

Containing only one type of monodisperse silica fine particles having an average primary particle size of 100 nm or more and 250 nm or less and a particle size dispersion (CV value) of less than 5% makes the height of unevenness of the moth-eye structure uniform. This is preferable because the reflectance is further lowered. The CV value is usually measured using a laser diffraction type particle size measuring device, but other particle size measuring methods may be used, and image analysis is performed from the surface SEM image of the antireflection layer of the antiglare antireflection film of the present invention. It is also possible to obtain and calculate the particle size distribution by. More preferably, the CV value is less than 4%.

The layer (a) may contain components other than the curable compound (a1) and the particles (a2). For example, the above-mentioned compound having no polymerizable functional group, a solvent, a polymerization initiator, and particles ( It may contain the dispersant, leveling agent, antifouling agent and the like of a2).

<Solvent>
As the solvent, it is preferable to select a solvent having a polarity close to that of the particles (a2) from the viewpoint of improving dispersibility. Specifically, for example, when the particles (a2) are metal oxide particles, an alcohol-based solvent is preferable, and methanol, ethanol, 2-propanol, 1-propanol, butanol, and the like can be mentioned. Further, for example, when the particle (a2) is a metal resin particle having a hydrophobic surface modification, a solvent such as a ketone type, an ester type, a carbonate type, an alkane, or an aromatic type is preferable, and methyl ethyl ketone (MEK) or dimethyl carbonate is used. , Methyl acetate, acetone, methylene chloride, cyclohexanone and the like. A plurality of these solvents may be mixed and used as long as the dispersibility is not significantly deteriorated.

<Dispersant for particles (a2)>
The dispersant of the particles (a2) can facilitate uniform arrangement of the particles (a2) by reducing the cohesive force between the particles. The dispersant is not particularly limited, but anionic compounds such as sulfates and phosphates, cationic compounds such as aliphatic amine salts and quaternary ammonium salts, nonionic compounds and polymer compounds are preferable, and adsorption groups. A polymer compound is more preferable because the degree of freedom in selecting each of the steric repulsive groups is high. A commercially available product can also be used as the dispersant. For example, BYK Japan made of (stock) DISPERBYK160, DISPERBYK161, DISPERBYK162, DISPERBYK163, DISPERBYK164, DISPERBYK166, DISPERBYK167, DISPERBYK171, DISPERBYK180, DISPERBYK182, DISPERBYK2000, DISPERBYK2001, DISPERBYK2164, Bykumen, BYK-2009, BYK-P104, BYK-P104S, BYK-220S, Anti-Terra203, Anti-Terra204, Anti-Terra205 (hereinafter referred to as trade names) and the like can be mentioned.

<Leveling agent>
By lowering the surface tension of the composition for forming the layer (a), the leveling agent can stabilize the liquid after coating and facilitate uniform arrangement of the curable compound (a1) and the particles (a2). For example, the compounds described in JP-A-2004-331812 and JP-A-2004-163610 can be used.

The leveling agent is preferably contained in an amount of 0.01 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, in the total solid content of the composition for forming the layer (a). It is preferably contained in an amount of 0.01 to 2.0% by mass, most preferably 0.01 to 2.0% by mass.

<Anti-fouling agent>
The antifouling agent can suppress the adhesion of stains or fingerprints by imparting water and oil repellency to the moth-eye structure. For example, the compounds described in JP2012-88699A can be used.

The antifouling agent is preferably contained in an amount of 0.01 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, based on the total solid content in the layer (a), and is 0. Most preferably, it is contained in an amount of 0.01 to 2.0% by mass.

<Polymerization initiator>
The layer (a) may contain a polymerization initiator.
When the curable compound (a1) is a photopolymerizable compound, it preferably contains a photopolymerization initiator.
Photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, etc. Fluoroamine compounds, aromatic sulfoniums, loffin dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like can be mentioned. Specific examples of the photopolymerization initiator, preferred embodiments, commercially available products, and the like are described in paragraphs <0133> to <0151> of JP-A-2009-098658, and can be preferably used in the present invention as well. it can.

"Latest UV Curing Technology" {Technical Information Association, Inc.} (1991), p. 159 and "Ultraviolet Curing System" by Kiyomi Kato (published by General Technology Center in 1989), p. Various examples are also described in 65 to 148, which are useful for the present invention.

The content of the polymerization initiator in the layer (a) is sufficient for polymerizing the polymerizable compound contained in the layer (a), and the starting point is set so as not to increase too much. , 0.1 to 8% by mass, more preferably 0.5 to 5% by mass, based on the total solid content in the layer (a).

In the layer (a), a compound that generates an acid or a base by light or heat in order to react the above-mentioned silane coupling agent having a polymerizable functional group (hereinafter, a photoacid generator, a photobase generator, a thermoacid). It may be referred to as a generator or a thermobase generator).

<Photoacid generator>
Examples of the photoacid generator include onium salts such as diazonium salt, ammonium salt, phosphonium salt, iodonium salt, sulfonium salt, selenium salt, and arsonium salt, organic halogen compounds, organic metals / organic halides, and o-nitrobenzyl type. Examples thereof include photoacid generators having a protective group, compounds that photodecompose to generate sulfonic acid, such as iminosulfonet, disulfone compounds, diazoketosulfone, and diazodisulfone compounds. In addition, triazines (for example, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc.), quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, oximes. Sulfonate compounds can also be mentioned.
Further, a group in which an acid is generated by light or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used.
In addition, V. N. R. Pilrai, Synthesis, (1), 1 (1980), A.I. Abad et al. , Tetrahedron Lett. , (47) 4555 (1971), D.I. H. R. Barton et al. , J. Chem. Soc. , (C), 329 (1970), US Pat. No. 3,779,778, European Patent No. 126,712, etc., which generate acid by light can also be used.

<Thermal acid generator>
Examples of the thermoacid generator include salts composed of acids and organic bases.
Examples of the above-mentioned acids include organic acids such as sulfonic acid, phosphonic acid and carboxylic acid, and inorganic acids such as sulfuric acid and phosphoric acid. From the viewpoint of compatibility with the curable compound (a1), an organic acid is more preferable, a sulfonic acid and a phosphonic acid are further preferable, and a sulfonic acid is most preferable. Preferred sulfonic acids include p-toluene sulfonic acid (PTS), benzene sulfonic acid (BS), p-dodecylbenzene sulfonic acid (DBS), p-chlorobenzene sulfonic acid (CBS), 1,4-naphthalenedi sulfonic acid (NDS). ), Methanesulfonic acid (MsOH), nonafluorobutane-1-sulfonic acid (NFBS) and the like.

As a specific example of the acid generator, those described in JP-A-2016-803 can be preferably used.

<Photobase generator>
Examples of the photobase generator include substances that generate a base by the action of active energy rays. More specifically, (1) salts of organic acids and bases that are decarbonated and decomposed by irradiation with ultraviolet rays, visible light, or infrared rays, and (2) amines that are decomposed by intramolecular nucleophilic substitution reaction or rearrangement reaction. A compound that emits a kind, or (3) a compound that causes some chemical reaction by irradiation with ultraviolet rays, visible light, or infrared rays to release a base can be used.
The photobase generator used in the present invention is not particularly limited as long as it is a substance that generates a base by the action of active energy rays such as ultraviolet rays, electron beams, X-rays, infrared rays and visible rays.
Specifically, those described in JP-A-2010-243773 can be preferably used.

The content of the compound that generates an acid or a base by light or heat in the layer (a) is an amount sufficient to polymerize the polymerizable compound contained in the layer (a), and the starting point is increased. 0.1 to 8% by mass is preferable, and 0.1 to 5% by mass is more preferable, based on the total solid content in the layer (a), because the setting is not too much.

[Step (2)]
The step (2) is a step of curing a part of the layer (a) of the step (1) to obtain the layer (ca), and specifically, the curability in the layer (a) of the step (1). This is a step of curing a part of the compound (a1) to obtain a layer (ca) containing the cured compound (a1c).
By curing a part of the curable compound (a1) in the step (2), the particles (a2) can be made difficult to move and the particles (a2) can be prevented from aggregating.
Curing a part of the curable compound (a1) means curing only a part of the curable compound (a1), not all of it. Only a part of the curable compound (a1) is cured in the step (2), and a part of the uncured curable compound (a1) is permeated into the temporary support in the step (4) (the temporary support forms a functional layer). The thickness of the layer (ca) is reduced by a method of permeating the functional layer (if it is possessed) or a method of permeating the layer (b), and the particles (a2) are placed on the support side of the layer (ca). It is possible to form a good uneven shape (moth-eye structure) by projecting from the interface of the above.

Curing can be performed by irradiating with ionizing radiation. The type of ionizing radiation is not particularly limited, and examples thereof include X-rays, electron beams, ultraviolet rays, visible light, and infrared rays. The curable compound (a1) is a photocurable compound, and the step (2) It is preferable to cure a part of the curable compound (a1) by irradiating with light (preferably ultraviolet rays).
The condition for curing a part of the curable compound (a1) in the step (2) is that the composition obtained by removing the particles (a2) from the composition for forming the layer (a) is applied onto the temporary support to a thickness of 2 μm. When cured, it is preferable that the curing rate is 2 to 20%, more preferably the curing rate is 3 to 15%, and the curing rate is 5 to 12%. It is more preferable that the conditions are met.

Curing rate is
(1-Number of residual polymerizable functional groups after curing / Number of polymerizable functional groups before curing) × 100%, which is measured by the following method.
The polymerizable functional group is a group having a polymerizable carbon-carbon unsaturated double bond.
More specifically, Thermo electron NICOLET6700 FT-IR curable compound itself before curing using (Fourier transform infrared spectrophotometer) was measured KBr-IR of corporation, carbonyl group peak (1660-1800Cm ^{- 1} ) Obtain the peak height (808 cm ^-1 ) of the area and polymerizable carbon-carbon unsaturated double bond, and similarly, from the IR (infrared spectroscopy) measurement of the single reflection after curing, the polymerizable property with respect to the carbonyl group peak area. The peak of the carbon-carbon unsaturated double bond was determined, and the curing rate was calculated by comparing before and after irradiation with ultraviolet rays. When calculating hardening rate here is normalized measurement depth at 808cm ^-1 821nm, a depth of 1660-1800Cm ^-1 as 384 nm.

In step (2), it is preferable to irradiate the irradiation amount of ultraviolet 1~90mJ / cm ^2, it is more preferable to irradiate the irradiation amount of 1.2~40mJ / cm ^2, 1.5~10mJ / cm It is more preferable to irradiate with an irradiation amount of ² . Since the optimum value of the irradiation amount differs depending on the composition of the layer (a) forming composition, it can be appropriately adjusted.

In the step (2), it is preferable in terms of manufacturing suitability that a part of the curable compound (a1) is cured by irradiating ultraviolet rays from the side of the layer (a) opposite to the temporary support side.

It is preferable to carry out the step (2) in an environment of an oxygen concentration of 0.1 to 5.0% by volume, and more preferably to carry out the step (2) in an environment of an oxygen concentration of 0.5 to 1.0% by volume. .. By setting the oxygen concentration in the above range, it is possible to cure the region of the layer (a) on the temporary support side in particular.

The compound (a1c) is a cured product of the curable compound (a1).
The molecular weight of compound (a1c) is not particularly limited. Further, the compound (a1c) may have an unreacted polymerizable functional group.
The layer (ca) obtained in the step (2) is a layer containing the curable compound (a1) and the compound (a1c) in the layer.
In the present invention, the layer (ca) can be further cured in the steps (4-2), (7), and (9) after the step (2), and before the curing in each step. Although the components contained in each layer after curing and the composition thereof (composition ratio of the curable compound (a1) and the cured product (a1c), etc.) are different, in the present invention, the layers (for convenience at any stage) It shall be called ca).

[Step (3)]
The step (3) is a step of laminating the layer (b) of the adhesive film having the support and the layer (b) containing the adhesive on the support with the layer (ca).
The method of bonding the layer (ca) and the layer (b) of the adhesive film is not particularly limited, and a known method can be used, and examples thereof include a laminating method.
It is preferable to attach the adhesive film so that the layer (ca) and the layer (b) are in contact with each other.
Prior to step (3), there may be a step of drying the layer (ca). When the step of drying the layer (ca) is provided, the drying temperature of the layer (ca) is preferably 20 to 60 ° C, more preferably 20 to 40 ° C. The drying time is preferably 0.1 to 120 seconds, more preferably 1 to 30 seconds.

In the present invention, the layer (b) and the layer (ca) of the adhesive film are bonded together in the step (3), and the particles (a2) are combined with each other in the step (4) described later, and the layer (ca) and the layer (b) are combined. By burying it in the layer and projecting it from the interface of the layer (ca) on the support side, and more preferably, in the step (4-2), the particles (a2) are formed in the layer (ca) and the layer (b). By further curing a part of the layer (ca) while being buried in the combined layer, the particles (a2) are not exposed to the air interface before the layer (ca) is cured, and aggregation is suppressed. , A good uneven shape formed by the particles (a2) can be produced.

(Adhesive film)
The pressure-sensitive adhesive film has a support and a layer (b) containing a pressure-sensitive adhesive.

<Layer (b)>
The layer (b) is a layer containing a pressure-sensitive adhesive, and the pressure-sensitive adhesive is preferably a pressure-sensitive adhesive having a gel fraction of 95.0% or more.
When the gel content of the adhesive is 95.0% or more, in the production of the antiglare antireflection film of the present invention, when the adhesive film is peeled off, the adhesive component is applied to the surface of the antiglare antireflection film. It is less likely to remain, and it is highly effective in suppressing the increase in reflectance caused by the adhesive component filling the gaps between the irregularities of the particles.
The gel fraction of the pressure-sensitive adhesive is preferably 95.0% or more and 99.9% or less, more preferably 97.0% or more and 99.9% or less, and 98.0% or more and 99.9%. The following is more preferable.
The gel fraction of the pressure-sensitive adhesive is the ratio of the insoluble content after immersing the pressure-sensitive adhesive in tetrahydrofuran (THF) at 25 ° C. for 12 hours, and is calculated from the following formula.
Gel fraction = (mass of adhesive insoluble in THF) / (total mass of adhesive) x 100 (%)

The weight average molecular weight of the sol component in the pressure-sensitive adhesive is preferably 10,000 or less, more preferably 7,000 or less, and most preferably 5,000 or less. By setting the weight average molecular weight of the sol component in the above range, in the production of the antiglare antireflection film of the present invention, when the adhesive film is peeled off, the adhesive component is less likely to remain on the surface of the antiglare antireflection film. be able to.
The sol component of the pressure-sensitive adhesive represents the dissolved content in THF after the pressure-sensitive adhesive is immersed in tetrahydrofuran (THF) for 12 hours at 25 ° C. The weight average molecular weight can be analyzed by gel permeation chromatography (GPC).

It is also preferable that the storage elastic modulus (G') of the pressure-sensitive adhesive at 30 ° C. and 1 Hz is 1.3 GPa or less, and the weight average molecular weight of the sol component in the pressure-sensitive adhesive is 10,000 or less.
30 ° C. of the adhesive, and the storage modulus (G ') 1.3 × ¹⁰ 5 Pa or less at 1 Hz, and it is also preferable weight average molecular weight of sol component in the adhesive is less than or equal to 10000.
30 ° C. of the adhesive, the storage elastic modulus at 1 Hz (G ') is more preferably 0.1 × ¹⁰ 5 Pa or more 1.3 × ¹⁰ 5 Pa or less, 0.1 × ¹⁰ 5 Pa or more 1.2 × 10 ⁵ Pa or less is more preferable. When the storage elastic modulus is 0.1 × 10 5 ^Pa or more, hardly causes cohesive failure of the pressure-sensitive adhesive, it is easy to handle. When the storage elastic modulus is 1.3 × 10 ⁵ Pa or less, the adhesive easily enters the gaps between the particles, so that the effect of suppressing the aggregation of the particles can be easily obtained, and at 1.2 × 10 ⁵ Pa or less. If present, an antiglare antireflection film having a particularly good reflectance can be obtained.
Further, the preferable range of the weight average molecular weight of the sol component in the pressure-sensitive adhesive in this case is also the same as that described above.

The film thickness of the layer (b) is preferably 0.1 μm or more and 50 μm or less, more preferably 1 μm or more and 30 μm or less, and further preferably 1 μm or more and 20 μm or less.

The pressure-sensitive adhesive preferably contains a polymer, and more preferably contains a (meth) acrylic polymer. In particular, a polymer of at least one type of (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 18 carbon atoms (a copolymer in the case of two or more types of monomers) is preferable. The weight average molecular weight of the (meth) acrylic polymer is preferably 200,000 to 2,000,000.

Examples of the (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 18 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. , Pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate , Decyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isomyristyl (meth) acrylate, isosetyl (meth) acrylate, isostearyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate , Stearyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate and other alkyl (meth) acrylate monomers. The alkyl group of the alkyl (meth) acrylate monomer may be linear, branched or cyclic. Two or more kinds of the above-mentioned monomers may be used in combination.

Preferable examples of the (meth) acrylate monomer having an aliphatic ring include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, isobornyl (meth) acrylate and the like. Of these, cyclohexyl (meth) acrylate is particularly preferable.

The (meth) acrylic polymer is a copolymer composed of at least one (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 18 carbon atoms and at least one other copolymerizable monomer. You may. In this case, as the other copolymerizable monomer, a copolymerizable vinyl monomer containing at least one group selected from a hydroxyl group, a carboxyl group, and an amino group, a copolymerizable vinyl monomer having a vinyl group, and an aromatic type Examples include monomers.

Examples of the copolymerizable vinyl monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-. Hydroxyl-containing (meth) acrylic acid esters such as hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate, and N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl. Examples thereof include hydroxyl group-containing (meth) acrylamides such as (meth) acrylamide, and at least one selected from these compound groups is preferable.

It is preferable that 0.1 to 15 parts by mass of a copolymerizable vinyl monomer containing a hydroxyl group is contained with respect to 100 parts by mass of the (meth) acrylic polymer.

Examples of the copolymerizable vinyl monomer containing a carboxyl group include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. It is preferably at least one selected from these compound groups.

It is preferable that 0.1 to 2 parts by mass of a copolymerizable vinyl monomer containing a carboxyl group is contained with respect to 100 parts by mass of the (meth) acrylic copolymer.

Examples of the copolymerizable vinyl monomer containing an amino group include monoalkyls such as monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, and monoethylaminopropyl (meth) acrylate. Aminoalkyl (meth) acrylate and the like can be mentioned.

Examples of the aromatic monomer include aromatic group-containing (meth) acrylic acid esters such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, as well as styrene and the like.

Examples of copolymerizable vinyl monomers other than the above include various vinyl monomers such as acrylamide, acrylonitrile, methyl vinyl ether, ethyl vinyl ether, vinyl acetate, and vinyl chloride.

The pressure-sensitive adhesive may contain a cured product of a composition for forming the pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive composition).
The pressure-sensitive adhesive composition preferably contains the above polymer and a cross-linking agent, and may be cross-linked using heat, ultraviolet rays (UV), or the like. As the cross-linking agent, one or more cross-linking agents selected from the compound group consisting of a bifunctional or higher functional isocyanate-based cross-linking agent, a bifunctional or higher functional epoxy-based cross-linking agent, and an aluminum chelate-based cross-linking agent are preferable. When a cross-linking agent is used, 100 parts by mass of the polymer is used in the production of the antiglare antireflection film of the present invention from the viewpoint of making it difficult for the adhesive component to remain on the surface of the antireflection film when the adhesive film is peeled off. On the other hand, it is preferably contained in an amount of 0.1 to 15 parts by mass, more preferably 3.5 to 15 parts by mass, more preferably more than 3.5 parts by mass and less than 15 parts by mass, and further preferably 5.1 to 10 parts. It is particularly preferable to contain by mass.

The bifunctional or higher functional isocyanate compound may be a polyisocyanate compound having at least two or more isocyanate (NCO) groups in one molecule, and may be hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, or xylylene. Bullet-modified products of diisocyanates (compounds having two NCO groups in one molecule) such as isocyanates, and trivalent or higher polyols such as isocyanurate-modified products, trimethylolpropane or glycerin (at least three in one molecule). Examples thereof include an adduct form (polypolymodified form) with the above compound having an OH group.
Further, the trifunctional or higher functional isocyanate compound is a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule, particularly an isocyanurate form of a hexamethylene diisocyanate compound and an isocyanurate form of an isophorone diisocyanate compound. It is preferably at least one selected from the compound group consisting of an adduct of a hexamethylene diisocyanate compound, an adduct of an isophorone diisocyanate compound, a bullet body of a hexamethylene diisocyanate compound, and a bullet body of an isophorone diisocyanate compound.
The bifunctional or higher functional isocyanate-based cross-linking agent is preferably contained in an amount of 0.01 to 5.0 parts by mass, more preferably 0.02 to 3.0 parts by mass with respect to 100 parts by mass of the polymer.

The pressure-sensitive adhesive composition may contain an antistatic agent in order to impart antistatic performance. The antistatic agent is preferably an ionic compound, more preferably a quaternary onium salt.

Examples of the antistatic agent which is a quaternary onium salt include an alkyldimethylbenzylammonium salt having an alkyl group having 8 to 18 carbon atoms, a dialkylmethylbenzylammonium salt having an alkyl group having 8 to 18 carbon atoms, and an alkyl methylbenzylammonium salt having 8 to 18 carbon atoms. A trialkylbenzylammonium salt having 18 alkyl groups, a tetraalkylammonium salt having an alkyl group having 8 to 18 carbon atoms, an alkyldimethylbenzylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, an alkyl having 8 to 18 carbon atoms. A dialkylmethylbenzylphosphonium salt having a group, a trialkylbenzylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, a tetraalkylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, and an alkyl group having 14 to 20 carbon atoms. Alkyltrimethylammonium salts, alkyldimethylethylammonium salts having an alkyl group having 14 to 20 carbon atoms, and the like can be used. These alkyl groups may be alkenyl groups having an unsaturated bond.

Other antistatic agents include nonionic, cationic, anionic, and amphoteric surfactants, ionic liquids, alkali metal salts, metal oxides, metal fine particles, conductive polymers, carbon, carbon nanotubes, and the like. be able to.

Examples of the alkali metal salt include a metal salt composed of lithium, sodium, and potassium, and a compound containing a polyoxyalkylene structure may be added to stabilize the ionic substance.

The antistatic agent is preferably contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer.

The pressure-sensitive adhesive composition may further contain a polyether-modified siloxane compound having an HLB of 7 to 15 as an antistatic auxiliary agent.
HLB is a hydrophilic lipophilic balance (hydrophilic lipophilic ratio) defined by, for example, JIS (Japanese Industrial Standards) K3211 (surfactant term).

The pressure-sensitive adhesive composition may further contain a cross-linking accelerator. The cross-linking accelerator may be a substance that functions as a catalyst for the reaction (cross-linking reaction) between the polymer and the cross-linking agent when the polyisocyanate compound is used as the cross-linking agent, and is an amine compound such as a tertiary amine. , Organic metal compounds such as metal chelate compounds, organic tin compounds, organic lead compounds, and organozinc compounds. In the present invention, a metal chelate compound or an organic tin compound is preferable as the cross-linking accelerator.

The cross-linking accelerator is preferably contained in an amount of 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the copolymer.

After the step (3) is completed, the laminate has three or more cross-linking groups in one molecule on the surface of the layer (b) on the layer (ca) side, has a cross-linking group equivalent of 450 or less, and is made of fluorine or silicone. It is preferable that a slip agent having a low friction portion (hereinafter, also referred to as “slip agent a”) is present.
The presence of the slip agent a on the surface of the layer (b) on the layer (ca) side causes the layer (b) to be peeled off in the step (8) in the production of the antiglare antireflection film of the present invention. b) It is possible to effectively prevent the adhesive inside from remaining (transferred) on the surface of the antiglare antireflection film.

<Support>
The support in the adhesive film will be described.
As the support, a plastic film made of a transparent and flexible resin is preferably used. Suitable plastic films for the support include polyester films such as polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, and polybutylene terephthalate, (meth) acrylic resin, polycarbonate resin, polystyrene resin, and polyolefin resin. Examples thereof include a film made of a resin, a cyclic polyolefin resin, a polyethylene resin such as cellulose acylate, and the like. However, the (meth) acrylic resin includes a polymer having a lactone ring structure, a polymer having a glutaric anhydride ring structure, and a polymer having a glutarimide ring structure.
In addition, other plastic films can be used as long as they have the required strength and optical suitability. The support may be a non-stretched film, uniaxially or biaxially stretched, or may be a plastic film in which the stretching ratio or the angle of the axial method formed by the crystallization of stretching is controlled.

As the support, one having ultraviolet transparency is preferable. Having ultraviolet transparency enables ultraviolet irradiation from the support side when the layer (ca) is cured in steps (4-2) and (7), which is preferable in terms of production suitability.
Specifically, the maximum transmittance of the support at a wavelength of 250 nm to 300 nm is preferably 20% or more, more preferably 40% or more, and most preferably 60% or more. When the maximum transmittance at a wavelength of 250 nm to 300 nm is 20% or more, it is preferable that the layer (ca) is easily cured by irradiating ultraviolet rays from the support side.
Further, the maximum transmittance of the pressure-sensitive adhesive film having the layer (b) formed on the support at a wavelength of 250 nm to 300 nm is preferably 20% or more, more preferably 40% or more, and more preferably 60% or more. Is the most preferable.

The film thickness of the support is not particularly limited, but is preferably 10 μm or more and 100 μm or less, more preferably 10 μm or more and 50 μm or less, and further preferably 10 μm or more and 40 μm or less.

As the adhesive film having the layer (b) formed on the support, a commercially available protective film can be preferably used. Specifically, AS3-304, AS3-305, AS3-306, AS3-307, AS3-310, AS3-0421, AS3-0520, AS3-0620, LBO-307, NBO- manufactured by Fujimori Kogyo Co., Ltd. 0424, ZBO-0421, S-362, TFB-4T3-367AS and the like can be mentioned.

In steps (4-2) and (7), the particles (a2) are hardened while maintaining the state of being buried in the combined layer of the layer (ca) and the layer (b). In the step before 4-2) (that is, after the completion of step (4)), it is preferable that the particles (a2) protrude from the interface on the support side of the layer (ca). By doing so, after the layer (ca) is cured in the step (7), when the layer (b) is peeled off in the step (8), the surface of the layer (ca) (the antiglare layer after the completion of the step (8)) It is possible to obtain an antiglare antireflection film having a moth-eye structure formed by projecting particles (a2) from the surface opposite to the interface of the above.
In order to ensure that the particles (a2) protrude from the interface on the support side of the layer (ca) in the step before the step (4-2), the curable compound (a1) is prepared in the step (4). It is preferable to allow a part of the layer (b) to penetrate.

[Step (4)]
In step (4), the layer (ca) is such that the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b) and protrude from the interface on the support side of the layer (ca). ) Is a step of bringing the position of the interface (the interface between the layer (ca) and the layer (b)) on the support side closer to the temporary support side.
In other words, "the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b) and protrude from the interface on the support side of the layer (ca)". , "The particles (a2) are not exposed from the combined layer of the layer (ca) and the layer (b), and are present across both the layers (ca) and the layer (b) ( The particles (a2) exist across the interface between the layer (ca) and the layer (b)) ".
The step (4) is preferably carried out by infiltrating a part of the curable compound (a1) into the layer (b).
When a part of the curable compound (a1) is permeated into the layer (b) in the step (4), it is preferable to keep the laminated body at less than 60 ° C. after the completion of the step (3), and keep the temperature below 40 ° C. It is more preferable to keep. By keeping the temperature below 40 ° C., the viscosities of the curable compound (a1), the compound (a1c), and the pressure-sensitive adhesive can be kept high, and the thermal motion of the particles (a2) can be suppressed. It is highly effective in preventing a decrease in antireflection ability and an increase in haze or cloudiness due to aggregation of particles (a2). The lower limit of the temperature at which the laminate is maintained is not particularly limited, and may be room temperature (25 ° C.) or a temperature lower than room temperature.

[Step (4-2)]
The step (4-2) is a step of curing a part of the layer (ca) in a state where the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b), specifically. , A step of curing a part of a compound selected from the group consisting of the curable compound (a1) and the compound (a1c) in the layer (ca).
Curing a part of the layer (ca) means curing only a part of the curable compound (a1) and the compound (a1c) in the layer (ca), not all of them. This makes it possible to form a binder resin in the antireflection layer of the antiglare antireflection film. Further, by leaving the uncured curable compound (a1) in the layer (ca) after the completion of the step (4-2), the layer (ca) and the base film are formed in the step (6) described later. An antiglare film having an antiglare layer can be bonded or adhered to the antiglare layer.
By maintaining the state in which the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b) in the step (4-2), the aggregation of the particles (a2) is suppressed and the moth-eye structure is formed. can do.
After the layer (b) is provided, the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b) due to volatilization of the layer (b) or the components of the layer (ca). If it is considered that the layer (b) cannot be maintained, an operation such as thickening the layer (b) in advance can be performed.
The mechanism by which particle agglomeration is suppressed by maintaining the state in which the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b) is that the particles (a2) are cured before the layer (ca) is cured. ) Is exposed to the air interface, it is known that a large attractive force derived from surface tension called lateral capillary force acts, and the particles (a2) are buried in the combined layer (ca) and layer (b). It is presumed that the above-mentioned attractive force can be reduced by keeping it.

Curing in step (4-2) can be performed by irradiating ionizing radiation. The type of ionizing radiation is not particularly limited, and examples thereof include X-rays, electron beams, ultraviolet rays, visible light, and infrared rays, but ultraviolet rays are widely used. For example, if the coating film is UV curable, curing the part 10mJ ^/ cm 2 ~1000mJ ^/ layers by irradiating the irradiation amount of ultraviolet cm ² (ca) curable compound in the (a1) by UV lamp Is preferable. When the irradiation amount of ultraviolet rays is 10 mJ / cm ² or more, the adhesion between the layer (b) and the portion including the particles (a2) and the layer (ca) becomes moderately strong, and the step of peeling off the temporary support (5). ), The particles (a2) and the layer (ca) are unlikely to remain on the temporary support, and defects (regions in which the reflectance does not decrease) are unlikely to occur in the obtained antiglare antireflection film. Further, when the irradiation amount of ultraviolet rays is 1000 mJ / cm ² or less, the residual amount of the curable compound (a1) in the layer (ca) after the completion of the step (4-2) does not decrease too much, and the step (6) ), An appropriate adhesive force between the layer (ca) and the antiglare layer in the antiglare film can be obtained. The irradiation amount in the step (4-2) is not particularly limited, and the adhesion between the layer (b) to be used and the portion containing the particles (a2) and the layer (ca), and the layer (ca) and the antiglare layer It can be adjusted as appropriate in consideration of the adhesion. At the time of irradiation, the above energy may be applied all at once, or may be divided and irradiated. As the ultraviolet lamp type, a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used.

The oxygen concentration at the time of curing in the step (4-2) is preferably 0 to 1.0% by volume, more preferably 0 to 0.1% by volume, and 0 to 0.05% by volume. Is the most preferable. By making the oxygen concentration at the time of curing smaller than 1.0% by volume, the film is less susceptible to the inhibition of curing by oxygen, and a strong film is formed.

In step (4-2), when a part of the compound selected from the group consisting of the curable compound (a1) and the compound (a1c) in the layer (ca) is cured, it is combined with the layer (ca) side of the support. May be irradiated with ultraviolet rays from the opposite side, or may be irradiated with ultraviolet rays from the temporary support side.

[Step (5)]
The step (5) is a step of peeling the temporary support from the laminated body after the completion of the step (4) or (4-2).
In order for the temporary support to be peeled off from the laminated body after the completion of the step (4) or (4-2), an appropriate adhesive force is provided between the layer (ca) and the temporary support. , It is preferable that the portion containing the layer (ca) and the particles (a2) can be transferred to the adhesive film. For example, in the bending or transport tension of the laminate during the manufacturing process, the portion containing the layer (ca) and the particles (a2) does not separate from the temporary support, but when it is brought into contact with the layer (b) or the layer (b). ), And the portion containing the layer (ca) and the particles (a2) is preferably in a desorbed state when irradiated with ultraviolet rays.

In steps (2), (3), (4), (4-2), and (5), it is preferable that a plurality of particles (a2) do not exist in the direction orthogonal to the surface of the layer (ca).
Here, the fact that a plurality of particles (a2) do not exist in the direction orthogonal to the surface of the layer (ca) means that 10 μm × 10 μm in the plane of the layer (ca) was observed in three fields with a scanning electron microscope (SEM). At that time, the ratio of the number of particles (a2) in a state in which a plurality of particles (a2) are not present in a direction orthogonal to the surface is 80% or more, and is preferably 95% or more.

In steps (4), (4-2), and (5), the total film thickness of the film thickness of the layer (ca) and the film thickness of the layer (b) is larger than the average primary particle size of the particles (a2). Is preferable.
When the total film thickness of the film thickness of the layer (ca) and the film thickness of the layer (b) is larger than the average primary particle size of the particles (a2), the particles (a2) form the layer (ca) and the layer (b). It is preferable because it can be buried in the combined layers.

Further, in steps (4), (4-2) and (5), the film thickness of the layer (ca) is preferably 5 to 70% of the average primary particle size of the particles (a2), and is preferably 20 to 40%. More preferably. When the film thickness of the layer (ca) is 5% or more of the average primary particle size of the particles (a2), the adhesive film is peeled off in the step (8) described later to include the layer (ca) and the particles (a2). It is preferable because the particles (a2) are less likely to fall off from the antiglare antireflection film obtained after the portion is transferred to the antiglare layer of the antiglare film, and the scratch resistance is improved. Further, when the film thickness of the layer (ca) is 70% or less of the average primary particle size of the particles (a2), the inclination of the refractive index becomes sufficient, and sufficient antireflection performance can be obtained. It is preferable that the film thickness of the layer (ca) is 20 to 40% of the average primary particle size of the particles (a2) because sufficient scratch resistance and antireflection ability can be achieved at the same time. The same applies to the steps (6) to (10) described later.
The film thickness of the layer (ca) after the completion of the step (5) is obtained by observing the film cross section of the layer (ca) with a scanning electron microscope (SEM) and arbitrarily measuring the film thickness at 100 points and averaging the film thickness. When the value is determined, it is preferable to adjust the value to 10 nm to 100 nm (more preferably 20 nm to 90 nm, further preferably 30 nm to 70 nm).

It is preferable that the particles (a2) do not protrude from the surface of the layer (ca) obtained by completing the step (5) on the side opposite to the layer (b) side.
The surface roughness of the surface of the layer (ca) on the side opposite to the layer (b) side in the laminate obtained by completing the step (5) is preferably 30 nm or less, more preferably 10 nm or less.
When the surface roughness of the surface of the layer (ca) opposite to the layer (b) side is 30 nm or less, the particles (a2) protrude from the surface of the layer (ca) opposite to the layer (b) side. It is not transferred when the adhesive film is peeled off in the step (8) described later and the portion (antireflection layer) containing the layer (ca) and the particles (a2) is transferred to the antiglare layer in the antiglare film. It is easy, and defects are less likely to occur in the antireflection layer after transfer. Further, if the surface roughness of the surface of the layer (ca) opposite to the layer (b) side is 10 nm or less, it is good when the layer (ca) and the antiglare layer are bonded together in the step (6). Adhesion can be ensured, and the generation of voids between the transfer layer (the portion containing the particles (a2) and the layer (ca)) -the antiglare layer that causes an increase in haze of the antiglare antireflection film can be suppressed. Therefore, it is preferable.
In the present invention, the surface roughness was measured using SPA-400 (manufactured by Hitachi High-TechnoScience) under the measurement conditions of a measurement range of 5 μm × 5 μm, a measurement mode: DFM, and a measurement frequency: 2 Hz.

The portion of the laminate obtained by completing the step (5) containing the particles (a2) and the layer (ca) can be peeled off from the layer (b) of the adhesive film.
The part containing the particles (a2) and the layer (ca) can be peeled off from the layer (b) of the adhesive film between the part containing the particles (a2) and the layer (ca) and the layer (b) of the adhesive film. By imparting an appropriate adhesive force, the portion containing the particles (a2) and the layer (ca) is separated from the surface of the layer (b) in the transfer step (step (8)) described later, and the antiglare film is formed. It indicates that the film can be transferred to the surface of the antiglare layer. The portion (antireflection layer) containing the particles (a2) and the layer (ca) can be transferred to the surface of the antiglare layer, that is, the transferability is defined as the transfer surface (antireflection layer) of the antiglare antireflection film after transfer. When a black polyethylene terephthalate sheet with adhesive (manufactured by Tomagawa Paper Co., Ltd .; "Clearly Mieru") is attached to the side opposite to the surface with the antireflection layer and visually observed, the reflectance is higher than that before the antireflection layer is transferred. It means that the ratio of the area of the region where is lowered is 80% or more with respect to the area to be transferred. The adhesive strength between the portion containing the particles (a2) and the layer (ca) and the layer (b) is not particularly limited, but for example, the particles of a transfer member having a width of 25 mm (a laminate obtained by completing step (5)). The portion containing the particles (a2) and the layer (ca) is fixed to a glass substrate having a thickness of 1.1 mm using an adhesive, and the portion containing the particles (a2) and the layer (ca) and the layer (b) are oriented in the 90 ° direction. It can be measured by the peeling force when peeling at a speed of 1000 mm / min. The peeling force measured by the above method is preferably 0.2 N / 25 mm to 4.0 N / 25 mm, and more preferably 0.6 N / 25 mm to 4.0 N / 25 mm. If the peeling force is 0.6 N / 25 mm or more, part of the particles (a2) and the layer (ca) is unlikely to remain on the temporary support when the temporary support is peeled in the step (5). , The reflectance and haze of the finally obtained antiglare antireflection film are reduced. When the peeling force is 4.0 N / 25 mm or less, in the step (8), when the adhesive film is peeled off, a part of the particles (a2) is unlikely to remain in the layer (b), so that the finally obtained prevention The reflectance and haze of the dazzling antireflection film are reduced.

The laminate obtained by completing the step (5) is a value obtained by subtracting the haze of the portion obtained by removing the portion containing the particles (a2) and the layer (ca) from the laminate (Δ haze) from the total haze of the laminate. ) Is preferably 1.00% or less.
The haze can be measured by measuring a film sample of 40 mm × 80 mm at 25 ° C. and a relative humidity of 60% with a haze meter NDH4000 manufactured by Nippon Denshoku Kogyo Co., Ltd. according to JIS-K7136 (2000).
The Δ haze may be a negative value. The Δ haze is preferably 1.00% or less, more preferably 0.80% or less, and further preferably 0.40% or less. By setting the Δ haze to 1.00% or less, the haze of the antiglare antireflection film obtained by using the laminate obtained by completing the step (5) is lowered, and good antireflection performance is obtained. Is possible. Black polyethylene with adhesive on the side opposite to the transfer surface of the antiglare antireflection film obtained by using the laminate obtained by completing step (5), especially when the Δhaze is 0.40% or less. Even when it is attached to a terephthalate sheet (manufactured by Tomagawa Paper Co., Ltd .; "Clearly Mieru") and visually observed, there is no cloudiness due to haze, and an excellent antiglare antireflection film can be obtained.

The surface hardening rate of the layer (ca) in the laminate obtained by completing the step (5) is 10 to 70%. When the surface hardening rate is 10% or more, a part of the antireflection layer (that is, the portion containing the layer (ca) and the particles (a2)) is deformed during transfer, and the antireflection ability is lowered. It is possible to prevent it, and when the surface hardening rate is 70% or less, the adhesion between the antiglare layer and the antireflection layer can be kept good.

[Step (6)]
The step (6) is a step of laminating the layer (ca) in the laminated body obtained by completing the step (5) and the antiglare layer of the antiglare film.
The method of bonding the layer (ca) and the antiglare layer is not particularly limited, and a known method can be used, and examples thereof include a roll laminating method.
It is preferable to attach the antiglare film so that the layer (ca) and the antiglare layer are in contact with each other.

In the present invention, it is also preferable that the step (6) includes a step of providing an adhesive layer between the layer (ca) in the laminate obtained by completing the step (5) and the antiglare layer of the antiglare film. .. The adhesive layer is as described above.

Further, in the present invention, in the step (6), it is also preferable to provide a heating step after laminating the layer (ca) in the laminate obtained by completing the step (5) and the antiglare layer of the antiglare film. .. By performing the heating step, the adhesion between the antiglare layer and the antireflection layer can be improved, and the scratch resistance of the antiglare antireflection film can be improved.

[Step (7)]
The step (7) is a step of curing the layer (ca) in a state where the particles (a2) are buried in the combined layer of the layer (b) and the layer (ca), and specifically, the layer (ca). ) Is a step of curing a part or all of the compound selected from the group consisting of the curable compound (a1) and the compound (a1c). It should be noted that curing all of the compounds selected from the group consisting of the curable compound (a1) and the compound (a1c) in the layer (ca) could not be completely cured when cured by a usual method. It also includes the case where the compound remains. The curing rate in the step (7) is not particularly limited, but from the viewpoint of film strength, the curing rate is preferably 60% or more, and more preferably 80% or more.
By the step (7), the antiglare layer and the layer (ca) in the antiglare film bonded in the above step (6) can be adhered.

The curing in the step (7) is preferably performed under the same conditions as those described in the above step (4-2).

[Step (8)]
The step (8) is a step of peeling the adhesive film from the laminate obtained in the step (7).
In order to peel off the adhesive film in the step (8), an index of the adhesive force between the portion containing the particles (a2) and the layer (ca) and the layer (b) in the laminate obtained by completing the step (5). The peeling force measured by the above measuring method is preferably 0.2 N / 25 mm or more and 4.0 N / 25 mm or less.

After the step (8) is completed, an antiglare antireflection film having a moth-eye structure having an uneven shape formed by particles (a2) on the surface of the layer (ca) is obtained, and after that, a further step (9) is obtained. ) And (10) may be performed.

[Step (9)]
The step (9) is a step of curing the layer (ca) in a state where the particles (a2) protrude from the interface on the side opposite to the interface on the base film side of the layer (ca). , A step of curing all the curable compound (a1) and the compound (a1c) in the layer (ca). When all the curable compound (a1) and the compound (a1c) in the layer (ca) are cured in the above-mentioned step (7), the step (9) does not have to be performed.

The curing in the step (9) is preferably performed under the same conditions as those described in the above step (4-2).
In step (9), it is necessary to irradiate ultraviolet rays from the side of the layer (ca) opposite to the base film side to cure the curable compound (a1) and the compound (a1c) in the layer (ca) for manufacturing suitability. preferable.

The layer (ca) after the completion of the step (9) is a layer containing the compound (a1c) in the layer. However, as described above, when the compound is cured by a usual method, the compound that has not been completely cured may remain.

[Step (10)]
The step (10) is a step of cleaning the laminate after the completion of the step (9) with a solvent.
In the production of the antiglare antireflection film of the present invention, the adhesive does not easily remain on the layer (ca) side even when the support and the layer (b) are peeled off, but the base film can be obtained by the step (10). The antiglare layer and the layer (ca) may not be dissolved and may be washed with a solvent (methyl isobutyl ketone, methyl ethyl ketone, acetone, etc.) that dissolves the adhesive.

[Polarizing plate protective film]
The antiglare antireflection film of the present invention can be used as a surface protective film (polarizing plate protective film) for a polarizing film.

The antiglare antireflection film of the present invention can also be saponified prior to bonding with the polarizer. The saponification treatment is a treatment in which an antiglare antireflection film is immersed in a heated alkaline aqueous solution for a certain period of time, washed with water, and then washed with an acid for neutralization. Any treatment condition may be used as long as the surface of the antiglare antireflection film of the present invention on the side to be bonded to the polarizing film of the base film is hydrophilic. Therefore, the concentration of the treatment agent, the temperature of the treatment agent liquid, and the treatment Although the time is appropriately determined, the processing conditions are usually determined so that the processing can be performed within 3 minutes from the necessity of ensuring productivity. As a general condition, the alkali concentration is 3% by mass to 25% by mass, the treatment temperature is 30 ° C. to 70 ° C., and the treatment time is 15 seconds to 5 minutes. Sodium hydroxide and potassium hydroxide are suitable as the alkaline species used for the alkali treatment, sulfuric acid is suitable as the acid used for acid washing, and ion-exchanged water or pure water is preferable as the water used for washing with water.
The surface of the base film on the opposite side of the antireflection layer is saponified and bonded to the polarizer using an aqueous polyvinyl alcohol solution.

Further, an ultraviolet curable adhesive can also be used for bonding the antiglare antireflection film of the present invention and the polarizer. It is preferable to provide an ultraviolet curable adhesive layer on the surface of the base film opposite to the antireflection layer of the present invention, and a specific ultraviolet curable resin is used particularly for the purpose of improving productivity by short-time drying. It is preferable to use it and attach it to a polarizer. For example, Japanese Patent Application Laid-Open No. 2012-144690 states that the Tg of each homopolymer is 60 ° C. or higher, the SP (Solubility Parameter) value is 29 to 32, 20 to 60% by mass, and the SP value is 18 to 18 to 60% by mass. Adhesiveness by adhering to a polarizer via an adhesive layer containing 3 types of 21 radically polymerizable compounds 10 to 30% by mass and 20 to 60% by mass of radically polymerizable compounds having an SP value of 21 to 23. , Durability and water resistance are improved. When this adhesive layer is used, the antiglare / antireflection film of the present invention may or may not be saponified before being bonded to the polarizer.

[Polarizer]
The polarizing plate of the present invention is a polarizing plate having a polarizing element and at least one protective film that protects the polarizing element, and at least one of the protective films is the antiglare antireflection film of the present invention. The polarizer may be sandwiched between a protective film (the antiglare antireflection film of the present invention) and a film other than the antiglare antireflection film of the present invention, or may be a combination of the protective film and the polarizer.
The film other than the antiglare antireflection film of the present invention is preferably an optical compensation film having an optical compensation layer including an optically heterogeneous layer. The optical compensation film (phase difference film) can improve the viewing angle characteristics of the liquid crystal display screen. As the optical compensation film, a known one can be used, but the optical compensation film described in JP-A-2001-100042 is preferable in terms of widening the viewing angle.

The polarizer includes an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, and a polyene-based polarizing film. The iodine-based polarizing film and the dye-based polarizing film can generally be produced by using a polyvinyl alcohol-based film.

[Image display device]
The image display device of the present invention has the antiglare antireflection film or polarizing plate of the present invention.
The antiglare antireflection film and polarizing plate of the present invention are suitable for an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). It can be used, and a liquid crystal display device is particularly preferable.
Generally, a liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides of the liquid crystal cell, and the liquid crystal cell supports a liquid crystal between two electrode substrates. Further, one optically anisotropic layer may be arranged between the liquid crystal cell and one polarizing plate, or two layers may be arranged between the liquid crystal cell and both polarizing plates. The liquid crystal cell is a TN mode, a VA (Vertical Birefringence) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane Switching) mode, or an ECB (Electrically Controlled Birefringence) mode.

The antiglare antireflection film and polarizing plate of the present invention are next-generation image display devices, high-contrast self-luminous displays, specifically, organic electroluminescence (OLED) displays, LED array displays, and fields. It can also be used for emission displays and the like. By using the antiglare antireflection film of the present invention or the polarizing plate having the antiglare antireflection film of the present invention on the surface of the self-luminous display, the reflection of external light can be suppressed, and particularly bright. Helps improve contrast in the room.

However, when used on the surface of a self-luminous display, the distance to the light emitting element is shorter than that of the liquid crystal display device, and the number of optical films existing up to the outermost surface tends to be smaller. Durability is essential. In particular, it is required to have high durability against high-energy blue light. Among the anti-glare anti-reflection films of the present invention, in the anti-glare anti-reflection film having a moth-eye structure using silica particles, in order to further improve the durability against blue light, the binder resin forming the anti-reflection layer is used. The average silicon content = Si / C is preferably 0.01 or more, more preferably 0.05 or more, and further preferably 0.08 or more. The content rate Si / C represents the molar ratio of silicon and carbon in the binder resin. For example, by measuring the silicon content rate (Si) and the carbon atom content rate (C) using an XPS surface analyzer. Can be sought.

In order to explain the present invention in detail, examples will be given below, but the present invention is not limited to these examples. Unless otherwise specified, "parts" and "%" are based on mass.

<Preparation of coating liquid for forming antiglare layer>
Each component is added according to the composition described below, the obtained composition is put into a mixing tank, stirred, filtered through a polypropylene filter having a pore size of 30 μm, and coated liquids for forming an antiglare layer BO-1 to BO-. It was set to 8.

(Coating liquid BO-1 for forming an antiglare layer)
PET-30 57.0 parts by mass M-321 34.0 parts by mass Irgacure 127 3.0 parts by mass SSX-108 4.5 parts by mass CAB 1.4 parts by mass SP-13 0.1 parts by mass Methyl ethyl ketone (MEK) 30 .0 parts by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Coating liquid BO-2 for forming an antiglare layer)
PET-30 49.0 parts by mass M-321 29.5 parts by mass Irgacure 127 3.0 parts by mass SSX-108 17.0 parts by mass CAB 1.4 parts by mass SP-13 0.1 parts by mass Methyl ethyl ketone (MEK) 30 .0 parts by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Coating liquid BO-3 for forming an antiglare layer)
PET-30 49.0 parts by mass M-321 29.5 parts by mass Irgacure 819 3.0 parts by mass SSX-108 17.0 parts by mass CAB 1.4 parts by mass SP-13 0.1 parts by mass Methyl ethyl ketone (MEK) 30 .0 parts by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Coating liquid BO-4 for forming an antiglare layer)
PET-30 49.0 parts by mass M-321 29.5 parts by mass Irgacure 127 3.0 parts by mass SSX-108 17.0 parts by mass CAB 1.4 parts by mass Copolymer (A-16) 0.1 parts by mass Methyl ethyl ketone (MEK) 30.0 parts by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Coating liquid BO-5 for forming an antiglare layer)
PET-30 49.0 parts by mass M-321 29.5 parts by mass Irgacure 127 3.0 parts by mass SSX-108 17.0 parts by mass CAB 1.4 parts by mass Copolymer (A-7) 0.02 parts by mass Copolymer (A-16) 0.08 parts by mass Methyl ethyl ketone (MEK) 30.0 parts by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Coating liquid BO-6 for forming an antiglare layer)
PET-30 57.0 parts by mass M-321 34.0 parts by mass Irgacure 127 3.0 parts by mass SSX-108 0.1 parts by mass CAB 1.4 parts by mass SP-13 0.1 parts by mass Methyl ethyl ketone (MEK) 30 .0 parts by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Coating liquid BO-7 for forming an antiglare layer)
PET-30 57.0 parts by mass M-321 34.0 parts by mass Irgacure 127 3.0 parts by mass SSX-108 40.0 parts by mass CAB 1.4 parts by mass SP-13 0.1 parts by mass Methyl ethyl ketone (MEK) 30 .0 parts by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Coating liquid BO-8 for forming an antiglare layer)
PET-30 57.0 parts by mass M-321 34.0 parts by mass Irgacure 127 3.0 parts by mass SSX-108 0.01 parts by mass CAB 1.4 parts by mass SP-13 0.1 parts by mass Methyl ethyl ketone (MEK) 30 .0 parts by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

The compounds used for each are shown below.
-PET-30: Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate [manufactured by Nippon Kayaku Co., Ltd.]
M-321: Trimethylolpropane PO-modified (n≈2) triacrylate [manufactured by Toagosei Corporation]
-Irgacure 127: Polymerization initiator [manufactured by BASF Japan Ltd.]
-Irgacure 819: Polymerization initiator [manufactured by BASF Japan Ltd.]
-SSX-108: PMMA particles with an average particle size of 8 μm [manufactured by Sekisui Plastics Co., Ltd.]
-CAB: Cellulose acetate butyrate, CAB531-1 [manufactured by Eastman Chemical Company]
-SP-13: Fluorine-based surface modifier having the following structure (the content ratio of the repeating unit is the molar ratio)

<Synthesis example of copolymer (A-7)>
6.7 g of cyclohexanone and 1.7 g of isopropanol were charged in a 300 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, and the temperature was raised to 73 ° C.
Then, 12.3 g (29.3 mmol) of 2- (perfluorohexyl) ethyl acrylate, 5.6 g (14.7 mmol) of 4- (4-acryloyloxybutoxy) benzoyloxyphenylboronic acid, 2.1 g of acrylic acid. A mixed solution consisting of (29.3 mmol), 26.4 g of cyclohexanone, 6.6 g of isopropanol, and 0.51 g of an azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise in 150 minutes. Dropped at a constant velocity to complete. After the dropping was completed, the temperature was raised to 90 ° C., and stirring was continued for another 4 hours.
Then, 4.2 g (29.3 mmol) of glycidyl methacrylate, 1.5 g (4.7 mmol) of tetrabutylammonium bromide, 0.4 g of p-methoxyphenol, 16.2 g of cyclohexanone, and 4.1 g of isopropanol were charged, and 80 The temperature was raised to ° C., stirring was continued for 8 hours, and a cyclohexanone / isopropanol solution of a copolymer represented by the following formula (A-7) (hereinafter, abbreviated as “copolymer (A-7)”) 88. 6 g was obtained.
The weight average molecular weight (Mw) of this copolymer (A-7) was 60,300 (gel permeation chromatography (EcoSECHLC-8320GPC (manufactured by Tosoh Corporation)), eluent NMP, flow velocity 0.50 ml / min. Calculated in polystyrene conversion under measurement conditions at a temperature of 40 ° C., and the column used was TSKgel SuperAWM-H x 3 (manufactured by Tosoh Corporation). The acid value of the obtained copolymer (A-7) was 7.3 mgKOH / g, and the residual ratio of carboxylic acid was 5 mol%. The content ratio of the repeating unit in the following formula is the molar ratio.

<Synthesis example of copolymer (A-16)>
A copolymer (A-16) having the following structure was synthesized in the same manner as the copolymer (A-7) except that the 2- (perfluorohexyl) ethyl acrylate was changed. The weight average molecular weight (Mw) of this copolymer (A-16) was 60,300. The acid value of the obtained copolymer (A-16) was 7.3 mgKOH / g, and the residual ratio of carboxylic acid was 5 mol%. The content ratio of the repeating unit in the following formula is the molar ratio.

<Making anti-glare film>
(Production of antiglare film AG-1)
A cellulose triacetate film (TDP60UL, manufactured by FUJIFILM Corporation) was unwound in a roll form, and a coating liquid BO-1 for forming an antiglare layer was applied using a coater having a slot die. Apply at a transport speed of 20 m / min, dry at 40 ° C for 15 seconds, 90 ° C for 30 seconds, and then purge with nitrogen to create an atmosphere with an oxygen concentration of 1.4%, and use an air-cooled metal halide lamp of 240 W / cm. Using (manufactured by Eye Graphics Co., Ltd.), the coating layer was cured by irradiating with ultraviolet rays having an irradiation amount of 10 mJ / cm ² , 1 mW / cm ² , and an antiglare layer having an average thickness of 12.0 μm was formed. AG-1 was prepared.

(Preparation of antiglare film AG-2)
In the production of AG-1, AG-2 was produced in the same manner as AG-1 except that the antiglare layer forming coating liquid BO-2 was applied instead of the antiglare layer forming coating liquid BO-1. ..

(Production of anti-glare film AG-3)
In the production of AG-2, the ultraviolet irradiation conditions are changed to an oxygen concentration of less than 0.1%, an irradiation amount of 600 mJ / cm ² , and 150 mW / cm ² , and the antiglare layer after ultraviolet irradiation is subjected to the following corona treatment. AG-3 was produced in the same manner as AG-2 except for the above. Specifically, AG-2 was subjected to corona discharge treatment at 20 m / min using a solid-state corona processing machine 6KVA model (manufactured by Pillar) under the trade name. At this time, from the readings of the current and voltage, the processing conditions were 0.375 KV · A · min / m ² , the processing discharge frequency was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

(Production of anti-glare film AG-4)
In the production of AG-1, AG-4 was produced in the same manner as AG-1 except that the antiglare layer forming coating liquid BO-3 was applied instead of the antiglare layer forming coating liquid BO-1. ..

(Preparation of antiglare film AG-5)
In the production of AG-4, AG-5 was produced in the same manner as AG-4, except that the ultraviolet irradiation conditions were changed to an irradiation amount of 5 mJ / cm ² and 1 mW / cm ² .

(Preparation of antiglare film AG-6)
In the production of AG-4, AG-6 was produced in the same manner as AG-4, except that the ultraviolet irradiation conditions were changed to an irradiation amount of 2.5 mJ / cm ² , 1 mW / cm ² .

(Production of antiglare film AG-7)
In the production of AG-1, AG-7 was produced in the same manner as AG-1 except that the antiglare layer forming coating liquid BO-4 was applied instead of the antiglare layer forming coating liquid BO-1. ..

(Preparation of antiglare film AG-8)
In the production of AG-1, AG-8 was produced in the same manner as AG-1 except that the antiglare layer forming coating liquid BO-5 was applied instead of the antiglare layer forming coating liquid BO-1. ..

(Preparation of antiglare film AG-9)
In the production of AG-1, AG-9 was produced in the same manner as AG-1 except that the antiglare layer forming coating liquid BO-6 was applied instead of the antiglare layer forming coating liquid BO-1. ..

(Preparation of antiglare film AG-10)
In the production of AG-1, AG-10 was produced in the same manner as AG-1 except that the antiglare layer forming coating liquid BO-7 was applied instead of the antiglare layer forming coating liquid BO-1. ..

(Preparation of antiglare film AG-11)
In the production of AG-1, AG-11 was produced in the same manner as AG-1 except that the antiglare layer forming coating liquid BO-8 was applied instead of the antiglare layer forming coating liquid BO-1. ..

(Preparation of antireflection layer)
[Synthesis of silica particles P1]
67.54 kg of methyl alcohol and 26.33 kg of 28% by mass aqueous ammonia (water and catalyst) were charged into a 200 L reactor equipped with a stirrer, a dropping device and a thermometer, and the liquid temperature was adjusted to 33 ° C. while stirring. Adjusted to. On the other hand, a solution prepared by dissolving 12.70 kg of tetramethoxysilane in 5.59 kg of methyl alcohol was charged into the dropping device. While maintaining the liquid temperature in the reactor at 33 ° C., the above solution was added dropwise from the dropping device over 44 minutes, and after the completion of the dropping, stirring was performed while maintaining the liquid temperature at the above temperature for another 44 minutes. Hydrolysis and condensation of methoxysilane were carried out to obtain a dispersion containing a silica particle precursor. Silica is obtained by air-drying this dispersion using an instantaneous vacuum evaporator ((Cracks system CVX-8B type manufactured by Hosokawa Micron Co., Ltd.) at a heating tube temperature of 175 ° C. and a reduced pressure of 200 torr (27 kPa). Particle P1 was obtained.
The average primary particle size of the silica particles P1 was 170 nm, the particle size dispersion (CV value) was 3.3%, and the indentation hardness was 340 MPa.

[Preparation of calcined silica particles P2]
5 kg of silica particles P1 were placed in a crucible and calcined at 900 ° C. for 2 hours using an electric furnace, cooled, and then pulverized using a crusher to obtain preclassified calcined silica particles. Further, the calcined silica particles P2 were obtained by crushing and classifying the calcined silica particles before classification using a jet pulverization classifier (IDS-2 type manufactured by Nippon Pneumatic Co., Ltd.).

[Preparation of Silane Coupling Agent-treated Silane Particles P3]
5 kg of calcined silica particles P2 were charged into a 20 L Henschel mixer (FM20J type manufactured by Mitsui Mining Co., Ltd.) equipped with a heating jacket. While stirring the calcined silica particles P2, 45 g of 3-acryloxypropyltrimethoxysilane (KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise by dissolving a solution in 90 g of methyl alcohol and mixed. Then, the temperature was raised to 150 ° C. over about 1 hour while mixing and stirring, and the temperature was maintained at 150 ° C. for 12 hours for heat treatment. In the heat treatment, the scraping device was constantly rotated in the direction opposite to that of the stirring blade to scrape off the deposits on the wall surface. In addition, a spatula was used to scrape off the wall deposits as appropriate. After heating, it was cooled and crushed and classified using a jet pulverization classifier to obtain silane coupling agent-treated silica particles P3.
The average primary particle size of the silane coupling agent-treated silica particles P3 was 171 nm, the particle size dispersion (CV value) was 3.3%, and the indentation hardness was 470 MPa.

[Preparation of silica particle dispersion PA-1]
50 g of silane coupling agent-treated silica particles P3, 200 g of MEK, and 600 g of zirconia beads with a diameter of 0.05 mm are placed in a 1 L bottle container with a diameter of 12 cm, set in a ball mill V-2M (Irie Shokai), and dispersed at 250 rpm for 10 hours. did. In this way, the silica particle dispersion liquid PA-1 (solid content concentration 20% by mass) was prepared.
The average primary particle size, CV value, and indentation hardness of the silica particles contained in the silica particle dispersion liquid PA-1 are the same as those in the silane coupling agent-treated silica particles P3.

[Preparation of silica particle dispersion PA-2]
50 g of calcined silica particles P2, 200 g of ethanol, and 600 g of zirconia beads having a diameter of 0.05 mm were placed in a 1 L bottle container having a diameter of 12 cm, set in a ball mill V-2M (Irie Shokai), and dispersed at 250 rpm for 10 hours. In this way, a silica particle dispersion liquid PA-2 (solid content concentration 20% by mass) was prepared.

[Synthesis of compound C3]
19.3 g of 3-isocyanatepropyltrimethoxysilane, 3.9 g of glycerin 1,3-bisacrylate, 6.8 g of 2-hydroxyethyl acrylate, 0.1 g of dibutyltin dilaurate in a flask equipped with a reflux condenser and a thermometer. , 70.0 g of toluene was added, and the mixture was stirred at room temperature for 12 hours. After stirring, 500 ppm of methyl hydroquinone was added and distilled off under reduced pressure to obtain compound C3.

[Preparation of composition for forming layer (a)]
Each component was put into a mixing tank so as to have the following composition, stirred for 60 minutes, and dispersed by an ultrasonic disperser for 30 minutes to prepare a coating liquid.

Composition (A-1)
U-15HA 1.4 parts by mass Compound C3 1.5 parts by mass A-TMPT 1.7 parts by mass KBM-4803 4.1 parts by mass Irgacure 127 0.2 parts by mass Compound P 0.1 parts by mass FP-2 0. 1 part by mass Silica particle dispersion PA-1 32.3 parts by mass Ethanol 12.7 parts by mass Methyl ethyl ketone 33.2 parts by mass Acetone 12.7 parts by mass

U-15HA, compound C3, A-TMPT, and KBM-4803 are curable compounds (a1).

Composition (A-2)
SIRIUS-501 2.8 parts by mass X-12-1049 1.5 parts by mass A-TMPT 1.7 parts by mass Acetyltriethyl citrate 4.1 parts by mass Irgacure 127 0.2 parts by mass Compound P 0.1 parts by mass FP -2 0.1 parts by mass Silica particle dispersion PA-1 32.3 parts by mass Ethanol 12.7 parts by mass Methyl ethyl ketone 31.8 parts by mass Acetone 12.7 parts by mass

SIRIUS-501, X-12-1049, and A-TMPT are curable compounds (a1).

Composition (B-1)
Compound I-30 1.4 parts by mass X-12-1049 1.5 parts by mass KR-513 1.7 parts by mass Acetyltriethyl citrate 4.1 parts by mass Irgacure 127 0.2 parts by mass Compound P 0.1 parts by mass FP-2 0.1 part by mass Silica particle dispersion PA-1 32.3 part by mass Ethanol 12.7 part by mass Methyl ethyl ketone 33.2 part by mass Acetone 12.7 part by mass

Compounds I-30, X-12-1049, and KR-513 are curable compounds (a1).

Composition (B-2)
Curable resin C 1.4 parts by mass KR-516 1.5 parts by mass KBM-4803 1.7 parts by mass Acetyltriethyl citrate 4.1 parts by mass Irgacure 127 0.2 parts by mass Compound P 0.1 parts by mass FP- 2 0.1 part by mass Silica particle dispersion PA-2 32.3 part by mass Methyl ethyl ketone 45.9 part by mass Acetone 12.7 part by mass

The curable resin C, KR-516, and KBM-4803 are curable compounds (a1).

The compounds used for each are shown below.
U-15HA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.): Urethane acrylate SIRIUS-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd.): Dendrimer acrylate Compound I-30: Compound I- described in JP-A-2011-84672 30 (Cage-type polysilsesquioxane having a polymerizable group and a non-polymerizable group)
Curable resin C: Curable resin C (epoxy group-containing polyorganosylsesquioxane) described in JP-A-2017-8148.
A-TMPT: Polyfunctional acrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
X-12-1049: Silane coupling agent having multiple acryloyl groups (manufactured by Shin-Etsu Chemical Co., Ltd.)
KR-513: Silane coupling agent oligomer having an acryloyl group / methyl group (manufactured by Shin-Etsu Chemical Co., Ltd.)
KR-516: Silane coupling agent oligomer having an epoxy group / methyl group (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-4803: Silane coupling agent having a reactive group (epoxy group) other than radical reactive group (manufactured by Shin-Etsu Chemical Co., Ltd.)
Acetyltriethyl citrate: manufactured by Tokyo Chemical Industry Co., Ltd. Irgacure 127: Photopolymerization initiator (manufactured by BASF Japan Ltd.)
Compound P: Photoacid generator represented by the following structural formula (manufactured by Wako Pure Chemical Industries, Ltd.)

FP-2: Fluorine-containing compound represented by the following formula

<Preparation of anti-glare anti-reflection film 1>
(Process (1) Coating of layer (a))
The composition (A-1) was applied to a polyethylene terephthalate film (FD100M, manufactured by FUJIFILM Corporation) of 100 μm as a temporary support at 2.8 ml / m ² using a die coater, and dried at 30 ° C. for 90 seconds. It was. The layer (a) was coated in this way.

(Step (2) Pre-exposure of layer (a))
A layer (a) using a high-pressure mercury lamp (Dr. honle AG model: 33351N part number: LAMP-HOZ 200 D24 U 450 E) while purging nitrogen so that the oxygen concentration becomes an atmosphere of 1.4% by volume. ) Side was irradiated with light at an irradiation volume of 5.0 mJ / cm ² and an illuminance of 0.60 mW, and a part of the curable compound (a1) was cured to obtain a layer (ca). The irradiation amount was measured by attaching a HEAD SENSER PD-365 to the UV METER UVPF-A1 eye ultraviolet integrated illuminance meter manufactured by Eye Graphic Co., Ltd. and measuring in a measurement range of 0.00.

(Step (3) Adhesive film bonding)
Next, on the layer (ca), the pressure-sensitive adhesive film obtained by peeling the release film from the protective film (Musstack TFB AS3-304) manufactured by Fujimori Kogyo Co., Ltd. It was pasted so that it was on the ca) side. For bonding, a commercial laminator Bio330 (manufactured by DAE-EL Co.) was used, and the bonding was performed at a speed of 1.
The protective film here refers to a laminate composed of a support / adhesive layer / release film, and a laminate composed of a support / adhesive layer obtained by peeling the release film from the protective film. It is an adhesive film.

The protective film used is shown below.
-Musstack TFB AS3-304 (Optical protective film with antistatic function manufactured by Fujimori Kogyo Co., Ltd.) (hereinafter also referred to as "AS3-304")
Support: Polyester film (thickness 38 μm)
Adhesive layer thickness: 20 μm
Maximum transmittance at wavelengths of 250 nm to 300 nm with the release film peeled off: less than 0.1%

The transmittance was measured using an ultraviolet-visible near-infrared spectrophotometer UV3150 manufactured by Shimadzu Corporation.

(Step (4) Permeation of curable compound (a1) into layer (b))
After the adhesive film was attached, it was allowed to stand in an environment of 25 ° C. for 5 minutes to allow the curable compound (a1) to penetrate into the layer (b).

(Partial curing of step (4-2) layer (ca))
Subsequently, a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used while purging nitrogen so that the oxygen concentration became 0.01% by volume or less, and the layer (ca) side of the support was used. A part of the layer (ca) was cured by irradiating ultraviolet rays having an illuminance of 150 mW / cm ² and an irradiation volume of 600 mJ / cm ² from the opposite side.

(Step (5) Peeling of temporary support Preparation of laminated body)
From the above laminated body, FD100M, which is a temporary support, was peeled off at a speed of 30 m / min in a direction in which the peeling angle became 180 °.

(Step (6) Lamination of antiglare film and laminate)
The antiglare layer side of the antiglare film AG-1 and the layer (ca) side of the laminate 1 from which the temporary support was removed in the step (5) were bonded together. For bonding, a commercial laminator Bio330 (manufactured by DAE-EL Co.) was used, and the bonding was performed at a speed of 1. Then, the bonded laminate was heated at 140 ° C. for 2 minutes.

(Step (7) Partial curing of layer (ca))
Subsequently, a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used while purging nitrogen so that the oxygen concentration became 0.01% by volume or less, and the layer (ca) side of the support was used. A part of the layer (ca) was cured by irradiating ultraviolet rays having an illuminance of 150 mW / cm ² and an irradiation volume of 600 mJ / cm ² from the opposite side.

(Step (8) Peeling of adhesive film)
The adhesive film (the release film was peeled off from Massac TFB AS3-304) was peeled off from the above-mentioned laminated body.

(Step (9) Curing of layer (ca))
Subsequently, a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used while purging nitrogen so that the oxygen concentration became 0.01% by volume or less, and the base film of the layer (ca) was used. The layer (ca) was cured by irradiating ultraviolet rays having an illuminance of 150 mW / cm ² and an irradiation volume of 600 mJ / cm ² from the opposite side.

(Step (10) Cleaning)
Subsequently, methyl isobutyl ketone was poured over the surface to which the adhesive film was bonded to wash away the residue of the adhesive layer. Then, it was dried at 25 degreeC for 10 minutes to obtain an antiglare antireflection film 1.

<Making anti-glare anti-reflection films 2 to 10>
In the production of the antiglare antireflection film 1, the antiglare film to be bonded in step (6) was changed as shown in Table 1 below, and the heating conditions after bonding in step (6) were changed as shown in Table 1 below. Then, antiglare and antireflection films 2 to 10 were produced.

<Preparation of anti-glare anti-reflection film 11>
In the production of the antiglare antireflection film 1, the antiglare film was changed to AG-2, and in the step (6), the antiglare layer side and the layer of the laminated body 1 from which the temporary support was removed in the step (5). Except for injecting UV1 of the ultraviolet curable adhesive UV1 on the (ca) side, bonding at a speed of 1 of the commercial laminator Bio330 (manufactured by DAE-EL Co.), and shifting to step (7) without heating. An antiglare antireflection film 11 was produced in the same manner as the antiglare antireflection film 1. The anti-glare anti-reflection film 11 has an adhesive layer between the anti-glare layer and the anti-reflection layer.

The ultraviolet curable adhesive UV1 was prepared by adding each component with the composition described below, putting the obtained composition into a mixing tank, and stirring the mixture.
UV curable adhesive UV1
PET-30 20.0 parts by mass 4-Hydroxybutyl acrylate 78.0 parts by mass Irgacure 907 1.5 parts by mass DETX-S 0.5 parts by mass

The compounds used for each are shown below.
4-Hydroxybutyl acrylate (manufactured by Nihon Kasei Co., Ltd.): Monofunctional acrylate Irgacure 907: Photopolymerization initiator (manufactured by BASF Japan Ltd.)
DETX-S: 2,4-diethylthioxanthone, photopolymerization accelerator (manufactured by Nippon Kayaku Co., Ltd.)

<Preparation of anti-glare anti-reflection film 12>
In the production of the antiglare antireflection film 11, the antiglare antireflection film 12 was produced in the same manner except that the ultraviolet curable adhesive was changed to UV2. The anti-glare anti-reflection film 12 has an adhesive layer between the anti-glare layer and the anti-reflection layer.

The ultraviolet curable adhesive UV2 was prepared by adding each component with the composition described below, putting the obtained composition into a mixing tank, and stirring the mixture.
UV curable adhesive UV2
Aronix M-220 20.0 parts by mass 4-Hydroxybutyl acrylate 78.0 parts by mass Irgacure 907 1.5 parts by mass DETX-S 0.5 parts by mass

The compounds used are shown below.
Aronix M220: Tripropylene glycol (n≈3) diacrylate (manufactured by Toagosei Corporation)

<Preparation of anti-glare anti-reflection film 13>
The composition (A-1) was applied to the antiglare film AG-1 by 2.8 ml / m ² using a die coater, dried at 30 ° C. for 90 seconds, and then the oxygen concentration was 1.4% by volume. Irradiation amount 5.0 mJ from the layer (a) side using a high-pressure mercury lamp (Dr. honle AG model: 33351N part number: LAMP-HOZ 200 D24 U 450 E) while purging nitrogen so as to create the atmosphere of Light was irradiated at / cm ² and an illuminance of 0.60 mW to cure a part of the curable compound (a1) to obtain a layer (ca). The irradiation amount was measured by attaching a HEAD SENSER PD-365 to the UV METER UVPF-A1 eye ultraviolet integrated illuminance meter manufactured by Eye Graphic Co., Ltd. and measuring in a measurement range of 0.00.
Next, on the layer (ca), the pressure-sensitive adhesive film obtained by peeling the release film from the protective film (Musstack TFB AS3-304) manufactured by Fujimori Kogyo Co., Ltd. It was pasted so that it was on the ca) side. For bonding, a commercial laminator Bio330 (manufactured by DAE-EL Co.) was used, and the bonding was performed at a speed of 1.
After the adhesive film was attached, it was allowed to stand in an environment of 25 ° C. for 5 minutes to allow the curable compound (a1) to penetrate into the layer (b).
Subsequently, a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used while purging nitrogen so that the oxygen concentration became 0.01% by volume or less, and the layer (ca) side of the support was used. A part of the layer (ca) was cured by irradiating ultraviolet rays having an illuminance of 150 mW / cm ² and an irradiation volume of 600 mJ / cm ² from the opposite side.
The adhesive film (the release film was peeled off from the massac TFB AS3-304) was peeled off from the above-mentioned laminated body, and then 160 W / while purging nitrogen so that the oxygen concentration became 0.01% by volume or less. Using a cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), the layer is irradiated with ultraviolet rays having an illuminance of 150 mW / cm ² and an irradiation amount of 600 mJ / cm ² from the side opposite to the base film of the layer (ca). (Ca) was cured. Finally, methyl isobutyl ketone was poured over the surface to which the adhesive film was bonded to wash away the residue of the adhesive layer, and the film was dried at 25 ° C. for 10 minutes to obtain an antiglare antireflection film 13.

<Preparation of anti-glare anti-reflection film 14>
In the production of the antiglare antireflection film 13, the antiglare antireflection film 14 was produced in the same manner except that the antiglare film was changed to AG-2.

<Preparation of anti-glare anti-reflection film 15-21>
In the production of the antiglare antireflection film 1, the ultraviolet irradiation amount in the step (4-2) was changed as shown in Table 1 below, and the antiglare film to be bonded in the step (6) was changed as shown in Table 1 below. Then, antiglare and antireflection films 15 to 21 were produced.

<Preparation of anti-glare anti-reflection film 22>
(Preparation of coating liquid for high refractive index layer)
54 parts by mass of cyclohexanone and 18 parts by mass of methyl ethyl ketone, 0.13 parts by mass of photopolymerization initiator (Irgacure 907, manufactured by BASF Japan Ltd.) and photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0. 04 parts by mass was dissolved. Further, 26.4 parts by mass of the titanium dioxide dispersion and 1.6 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) were added, and the mixture was stirred at room temperature for 30 minutes. Then, it was filtered through a polypropylene filter (PPE-03) having a pore size of 3 μm to prepare a coating liquid HN1 for a high refractive index layer.

(Preparation of coating liquid for low refractive index layer)
A methyl ethyl ketone solution (JN-7228, manufactured by JSR Co., Ltd.) having a refractive index of 1.42 and 6% by mass of a heat-crosslinkable fluoropolymer was substituted with a solvent to obtain 85% by mass of methyl isobutyl ketone and 15% by mass of 2-butanol. A polymer solution containing 10% by mass of solid content in a mixed solvent consisting of% was obtained. 70 parts by mass of this polymer solution, 10 parts by mass of MEK-ST (methyl ethyl ketone dispersion of SiO ₂ sol having an average particle size of 10 to 20 nm and a solid content concentration of 30% by mass, manufactured by Nissan Chemical Co., Ltd.), and 42 parts by mass of methyl isobutyl ketone. A portion and 28 parts by mass of cyclohexanone were added, and after stirring, filtration was performed with a polypropylene filter (PPE-03) having a pore size of 3 μm to prepare a coating liquid LN1 for a low refractive index layer.

In the steps (1) to (5) for producing the antiglare antireflection film 1, the coating liquid HN1 for a high refractive index layer was used instead of the composition (A-1), and the coating amount was 1.8 ml / m. ^A high-refractive index transfer laminate 1 was obtained by performing the same method except for the case of ² .
In the steps (1) to (5) for producing the antiglare antireflection film 1, the coating liquid LN1 for a low refractive index layer was used instead of the composition (A-1), and the coating amount was 0.8 ml / m. ^A low refractive index transfer laminate 1 was obtained by performing the same method except for the case of ² .
By performing the same method in the steps (6) to (10) for producing the antiglare antireflection film 1 except that the laminate 1 for high refractive index transfer is used instead of the laminate 1, the antiglare film is covered. An antiglare film A with a high refractive index layer was prepared by transferring a high refractive index layer to the surface.
In the steps (6) to (10) for producing the antiglare antireflection film 1, an antiglare film A with a high refractive index layer is used instead of the antiglare film AG-1, and a low refractive index is used instead of the laminated body 1. An antiglare antireflection film 22 in which a high refractive index layer and a low refractive index layer were formed by transfer on the antiglare film was produced by performing the same method except that the transfer laminate 1 was used.

<Preparation of anti-glare anti-reflection film 23>
1.8 ml / m ^{2 of the} coating liquid HN1 for a high refractive index layer was applied onto the antiglare film AG-1 using a die coater, dried at 30 ° C. for 90 seconds, and then the oxygen concentration was 1.0 volume. While purging nitrogen so as to create an atmosphere of%, the irradiation amount is 90 mJ / cm ² from the coated side using a high-pressure mercury lamp (Dr. honle AG model: 33351N part number: LAMP-HOZ 200 D24 U 450 E). An antiglare film B with a high refractive index layer was produced by irradiating light with an illuminance of 20 mW and applying a high refractive index layer on the antiglare film.
On the antiglare film B with a high refractive index layer, 0.8 ml / m ^{2 of the} coating liquid LN1 for a low refractive index layer was applied using a die coater, dried at 30 ° C. for 90 seconds, and then the oxygen concentration was 0. Irradiation amount from the coated side using a high-pressure mercury lamp (Dr. honle AG model: 33351N part number: LAMP-HOZ 200 D24 U 450 E) while purging nitrogen so as to create an atmosphere of 0.01% by volume or less. An anti-glare anti-reflection film 23 was produced by irradiating light at 300 mJ / cm ² and an illuminance of 60 mW to form a high refractive index layer and a low refractive index layer on the anti-glare film.

(Thickness of adhesive layer)
Anti-glare and anti-reflection films 11 and 12 provided with an adhesive layer are bonded by preparing a film-cut cross section with a microtome and observing the cross section using a scanning electron microscope S-3400N (manufactured by Hitachi High-Technologies Corporation). When the thickness of the layer was determined, the thickness of the adhesive layer was 0.4 μm.

(Surface hardening rate of antireflection layer)
In the step (6), the surface hardening rate of the moth-eye layer before being attached to the antiglare layer of the antiglare film was measured by the following measuring method.
That is, in the method for producing the antireflection layer described in the production of the antiglare antireflection film 1, the composition (A-1) is not changed except that the composition (A-1) is applied on the temporary support so as to have a film thickness of 3 μm. A sample that had been subjected to step (5) was prepared, and the surface IR measurement was performed before transferring to the antiglare layer of the antiglare film. From the surface IR measurement, the peak area of the carbonyl group (1660-1800 cm ^-1 ) and the peak height of the double bond (808 cm ^-1 ) were obtained, and the peak height of the double bond was divided by the peak area of the carbonyl group (value). (Hereinafter referred to as P101) was obtained. The same IR measurement was performed on the same sample prepared under the condition of not irradiating with ultraviolet rays, and the value obtained by dividing the peak height of the double bond by the peak area of the carbonyl group (expressed as Q101) was obtained, and the following formula 1 was calculated from these values. The surface cure rate was calculated using.

Formula 1 Surface hardening rate = (1- (P101 / Q101)) x 100 (%)
The surface hardening rate of the antireflection layer before transfer to the antiglare layer is shown in Table 1 below.

<Evaluation of anti-glare anti-reflection film>
Various characteristics of the antiglare antireflection film were evaluated by the following methods.

(Surface shape of anti-glare anti-reflection film Ra, Sm evaluation)
Based on JIS B-0601 (1994), the surface shape of the produced anti-glare anti-reflection film is the arithmetic average roughness (Ra) and average interval (Sm) of the surface unevenness, and the surf coder MODEL manufactured by Kosaka Laboratory Co., Ltd. It was evaluated by SE-3F. For Sm, the measurement length was 8 mm and the cutoff value was 0.8 mm.
The uneven shapes Ra and Sm measured by the above measurement are uneven shapes caused by the antiglare layer, and even when the antiglare antireflection film has the moth eye layer on the antiglare layer, the moth eye layer The fine uneven shape does not affect the above measurement.

(Average thickness unevenness of antireflection layer)
The surface of the obtained antiglare antireflection film was observed using a scanning electron microscope S-3400N (manufactured by Hitachi High-Technologies Corporation).
For anti-glare anti-reflection films 1 to 21 in which the anti-reflection layer is a moth-eye layer, the dense and sparse parts of the particles are determined from low-magnification observation, and the number of particles of 10 μm × 10 μm square is counted by enlarging. did. When sparseness was not observed at low magnification, the same observation was performed by randomly selecting a visual field. (Number of particles in the sparse part / Number of particles in the dense part) is calculated, and the average ratio of the measured values of 10 times is taken for each, and the average thickness unevenness of the antireflection layer (the average thickness of the antireflection layer in the convex portion). / Average thickness of antireflection layer in recess).
For the anti-glare anti-reflection films 22 and 23 whose anti-reflection layer is not a moth-eye layer, the average thickness of the anti-reflection layer in the convex portion and the average thickness of the anti-reflection layer in the concave portion of the anti-glare anti-reflection film are calculated by the following method. did. That is, the convex portion of the antiglare layer is marked with a marking pen by observing with an optical microscope or the like, and the cross section cut so as to include the marked portion (marking portion) is an optical microscope or a scanning electron microscope (SEM). The thickness of the antireflection layer is calculated by observing with. Here, the convex portion is the film thickness of the portion where the thickness of the antireflection layer is the thinnest in the vicinity of the marking portion, and the concave portion is the portion where the thickness of the antireflection layer is the thickest in the cross section, and the average thickness is 10 times. The average value of the measurements was used.

(Integral reflectance)
Anti-glare anti-reflection film (the surface opposite to the interface on the anti-glare layer side of the base film) is roughened with sandpaper and then treated with black ink to eliminate back reflection. An adapter ARV-474 is attached to V-550 (manufactured by JASCO Corporation), the integrated reflectance at an incident angle of 5 ° is measured in the wavelength region of 380 to 780 nm, and the average reflectance is calculated to calculate the integrated reflectance. It was a rate.

(Specular reflectance)
Using the film (sample), device, and adapter used for the above integrated reflectance measurement, the specular reflectance was measured at a light receiving angle of 5 ° with respect to an incident angle of 5 ° in the wavelength range of 380 nm to 780 nm, and the average reflectance was measured. The rate was calculated and used as the specular reflectance.

(All haze)
The surface uniformity was evaluated by the haze value. The total haze value (%) of the obtained antiglare antireflection film was measured according to JIS-K7136 (2000). A haze meter NDH4000 manufactured by Nippon Denshoku Kogyo Co., Ltd. was used as the apparatus.

(Anti-glare)
A black polyethylene terephthalate sheet with adhesive (manufactured by Tomoegawa Paper Co., Ltd .; "Clear Mieru") is laminated on the surface opposite to the side of the anti-glare anti-reflection film base material where the anti-reflection layer is provided, and the light on the back surface. A 30 cm × 30 cm sample with anti-reflection was prepared. A bare fluorescent lamp (8000 cd / m ² ) without a louver was projected on the sample from an angle of 45 degrees, and the degree of blurring of the reflected image when observed from a direction of −45 degrees was evaluated according to the following criteria.
A: I don't know the outline of the fluorescent lamp at all B: I can see the outline of the fluorescent lamp slightly C: The outline of the fluorescent lamp is blurred, but the outline can be identified D: The outline of the fluorescent lamp is almost not blurred

(Scratch resistance: integrated reflectance after scratch resistance test)
Steel wool (manufactured by Nippon Steel Wool Co., Ltd., grade No. 0000) is wrapped around the rubbing tip (1 cm x 1 cm) that comes into contact with the sample of the rubbing tester to prepare in advance, and then the surface of the prepared sample (antireflection layer). The surface of the tester was brought into contact with the rubbing portion of the tester, and the tester was rubbed 10 times back and forth under the conditions of a load of 200 g, a rubbing speed of 10 cm / sec, and a moving distance (one way) of 10 cm, and a scratch resistance test was performed. For the obtained sample, the integrated reflectance was measured by the same method as the above-mentioned integrated reflectance measurement, and the integrated reflectance after the scratch resistance test was calculated. The reflectance difference before and after the scratch resistance test was evaluated according to the following criteria.
A: Reflectance difference is 0.5% or less before and after the scratch resistance test B: Reflectance difference is more than 0.5% and 0.7% or less before and after the scratch resistance test C: Reflectance difference is 0 before and after the scratch resistance test . More than 7% and 1.0% or less D: Reflectance difference before and after the scratch resistance test is more than 1.0% and 1.5% or less E: Reflectance difference before and after the scratch resistance test is more than 1.5% Practical characteristics Above, it is preferably A to D, more preferably A to C, and even more preferably A to B.

The results obtained are summarized in Table 2.

The antiglare antireflection films 1 to 12, 15 to 20 and 22 of Examples 1 to 19 have a uniform structure in which the average thickness of the antireflection layer of the concave and convex portions of the antiglare antireflection film is not uneven. The integrated reflectance was 1.0% or less, and the specular reflectance was 0.4% or less, which were good results. On the other hand, in the antiglare antireflection films 13 and 14 of Comparative Examples 1 and 2, the average thickness unevenness of the antireflection layer of the concave portion and the convex portion in the antiglare antireflection film is large, and the integrated reflectance is 1. It exceeded 0% and the specular reflectance exceeded 0.4%.
The antiglare antireflection film 21 of Comparative Example 3 did not have sufficient antiglare property because the uneven shape of the antiglare layer was not in the desired range.
Further, in the antiglare antireflection film 23 of Comparative Example 4, the average thickness unevenness of the antireflection layer of the concave portion and the convex portion in the antiglare antireflection film is large, the integrated reflectance exceeds 1.0%, and specular reflection occurs. The rate exceeded 0.4%.
It has been shown that the method for producing an antiglare antireflection film of the present invention is an effective technique for imparting antireflection ability to a base material having an uneven shape such as an antiglare layer.

When preparing the antiglare antireflection film of Example 10, the compositions (A-2), (B-1), and (B-2) were used instead of the composition (A-1), respectively. Except for the above, antiglare and antireflection films of Examples 24, 25, and 26 were produced in the same manner.

(Measurement of silicon content (Si / C) of antireflection layer)
The number of silicon atoms and carbon atoms in the antireflection layer binder of each of the produced antireflection films was measured at a measurement angle of 0 ° under the above conditions using ESCALAB-200R manufactured by VG Scientifix Co., Ltd. as an XPS surface analyzer. (Measurement depth 6 nm), the silicon content (Si) and the carbon atom content (C) were measured, and Si / C was calculated from the results.

Assuming that it will be used on the outermost surface of a self-luminous display, a durability test against blue light was conducted.

(Blue durability)
Place the anti-glare anti-reflection film side by side on a commercially available blue light source (OPSM-H150X142B manufactured by OPTEX-FA) in a room maintained at a temperature of 25 ° C. and a relative humidity of 60%, and emit blue light to the anti-reflection film. Irradiation was performed continuously for 200 hours. The measurement was carried out by the same method as the above-mentioned integrated reflectance measurement, and the integrated reflectance after the blue durability test was calculated. The reflectance difference before and after the durability test was evaluated according to the following criteria.
A: Reflectance difference is 0.2% or less before and after the durability test B: Reflectance difference is more than 0.2% and 0.5% or less before and after the durability test C: Reflectance difference is 0 before and after the durability test If it exceeds 5.5%, it is 1.0% or less. D: The reflectance difference before and after the durability test is more than 1.0%. From the practical characteristics, it is preferably A to C, and more preferably A to B.

From the results in Table 3, in the antiglare antireflection film of the present application, if the Si / C ratio of the binder resin is 0.05 or more, the binder is not damaged even if it is irradiated with blue light for a long time, and the binder is prevented. It was found that the dazzling antireflection film has improved durability and can maintain low reflectance.
Regarding Examples 24 to 26, the surface shapes (Ra and Sm) of the antiglare antireflection film and the average thickness unevenness of the antireflection layer were the same as the results of Example 10.

1 Temporary support 2 Layer (a), Layer (ca)
3 particles (a2)
4 layers (b)
5 Support 6 Adhesive film 7 Laminate 10 Moss eye layer (anti-reflection layer)
11 Base film 12 Anti-glare layer 13 Anti-glare layer particles 14 Anti-glare film 15 Adhesive layer 16 Anti-reflection layer 20 Anti-glare anti-reflection film Ln Low refractive index layer Hn High refractive index layer UV UV

Claims (13)

An anti-glare anti-reflection film having a base film, an anti-glare layer, and an anti-reflection layer in this order.
The integrated reflectance of the antiglare antireflection film is 1.0% or less.
The specular reflectance of the antiglare antireflection film is 0.4% or less.
The uneven shape of the surface of the antiglare antireflection film has an arithmetic average roughness Ra of 0.03 μm ≦ Ra ≦ 0.4 μm and an average spacing Sm of the unevenness of 20 μm ≦ Sm ≦ 700 μm.
Wherein Ri average ratio of thickness 1.0 to 0.7 der antireflection layer in the average thickness / the recess of the anti-reflection layer at the convex portion of the anti-glare and anti-reflection film,
An antiglare antireflection film having an adhesive layer between the antiglare layer and the antireflection layer . The antireflection layer comprises the following particles having an average primary particle diameter of 100nm or more 250nm and a binder resin, and wherein the interface between the antiglare layer having a moth-eye structure by the particles on the surface of the opposite side, according to claim 1 Anti-glare anti-reflective film. An anti-glare anti-reflection film having a base film, an anti-glare layer, and an anti-reflection layer in this order.
The integrated reflectance of the antiglare antireflection film is 1.0% or less.
The specular reflectance of the antiglare antireflection film is 0.4% or less.
The uneven shape of the surface of the antiglare antireflection film has an arithmetic average roughness Ra of 0.03 μm ≦ Ra ≦ 0.4 μm and an average spacing Sm of the unevenness of 20 μm ≦ Sm ≦ 700 μm.
The ratio of the average thickness of the antireflection layer in the convex portion of the antiglare antireflection film to the average thickness of the antireflection layer in the concave portion is 1.0 to 0.7.
The antireflection layer contains particles having an average primary particle diameter of 100 nm or more and 250 nm or less and a binder resin, and has a moth-eye structure due to the particles on the surface opposite to the interface with the antiglare layer. the film. The antiglare antireflection film according to claim 2 or 3 , wherein the binder resin has a Si—O bond and the average silicon content Si / C of the binder resin is 0.01 or more. The antiglare antireflection film according to any one of claims 1 to 4, wherein the uneven shape of the surface of the antiglare antireflection film has an arithmetic mean roughness Ra of 0.1 μm ≦ Ra ≦ 0.4 μm. .. The antiglare property according to any one of claims 1 to 5 , wherein the antiglare layer contains a component having a functional group other than the (meth) acryloyl group capable of forming a covalent bond with the antireflection layer. Anti-reflection film. A method for producing an antiglare antireflection film having a base film, an antiglare layer, and an antireflection layer in this order.
A composition for forming an antiglare layer containing a compound for forming a binder resin for an antiglare layer and particles for an antiglare layer is applied onto the base film, and the composition for forming the antiglare layer is formed by ionizing radiation irradiation or heating. And the process of forming an anti-glare layer by curing
A step of applying an antireflection layer forming composition on a temporary support and semi-hardening it by ionizing radiation irradiation or heating at a surface hardening rate of 10 to 70% to form an antireflection layer.
A step of transferring the antireflection layer from the temporary support onto the antiglare layer,
A method for manufacturing an antiglare antireflection film having. The antiglare according to claim 7, further comprising a step of providing an adhesive layer on the antiglare layer or on the antireflection layer before transferring the antireflection layer from the temporary support onto the antiglare layer. A method for manufacturing an antireflection film. The method for producing an antiglare antireflection film according to claim 7, further comprising a step of heating the antireflection layer and the antiglare layer in a bonded state. On the temporary support, particles (a2) having an average primary particle diameter of 100 nm or more and 250 nm or less and a curable compound (a1) are placed in a layer (a) containing the curable compound (a1). Step (1), which is provided with a thickness that allows the particles to be buried
Step (2) of obtaining a layer (ca) by curing a part of the layer (a).
Step (3) of laminating the layer (b) of the support and the pressure-sensitive adhesive film having the layer (b) containing the pressure-sensitive adhesive on the support with the layer (ca).
The layer (ca) is buried in a layer in which the layer (ca) and the layer (b) are combined, and the particles (a2) protrude from the interface of the layer (ca) on the support side. ), The step (4) of bringing the position of the interface on the support side closer to the temporary support side.
Step (5) of peeling off the temporary support,
Step (6) of laminating the antiglare layer of the antiglare film having the base film and the antiglare layer and the layer (ca) of the laminate containing the layer (ca) obtained in the step (5). ,
The step (7) of curing the layer (ca) in a state where the particles (a2) are buried in a layer in which the layer (ca) and the layer (b) are combined, and the adhesive film is peeled off. Step (8),
The method for producing an antiglare antireflection film according to any one of claims 7 to 9, wherein the antiglare antireflection film is prepared in this order. A polarizing plate having the antiglare antireflection film according to any one of claims 1 to 6 as a polarizing plate protective film. An image display device having the antiglare antireflection film according to any one of claims 1 to 6 or the polarizing plate according to claim 11. A self-luminous display device provided with the antiglare antireflection film according to any one of claims 1 to 6 on the surface thereof.