WO2018212051A1

WO2018212051A1 - Anti-glare anti-reflection film, anti-glare anti-reflection film production method, polarization plate, image display device, and self-luminous display device

Info

Publication number: WO2018212051A1
Application number: PCT/JP2018/018042
Authority: WO
Inventors: 悠太福島; 伊吹　俊太郎
Original assignee: 富士フイルム株式会社
Priority date: 2017-05-19
Filing date: 2018-05-10
Publication date: 2018-11-22
Also published as: JP6825095B2; JPWO2018212051A1

Abstract

Provided are: an anti-glare anti-reflection film having sufficient anti-reflection performance; a production method for such an anti-glare anti-reflection film; a polarization plate having such an anti-glare anti-reflection film; an image display device; and a self-luminous display device. This anti-glare anti-reflection film includes a base film, an anti-glare layer, and an anti-reflection layer in this order, has an integrated reflection of at most 1.0% and a mirror reflectivity of at most 0.4%, satisfies conditions 0.03 μm≤Ra≤0.4 μm and 20 μm≤Sm≤700 μm, and has a ratio of 1.0-0.7 in terms of the average thickness in a convex portion of the anti-reflection layer with respect to the average thickness in a concave portion of the anti-reflection layer.

Description

Antiglare antireflection film, method for producing antiglare antireflection film, polarizing plate, image display device, and self-luminous display device

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.

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

For example, in

Patent Documents

1 and 2, antiglare antireflection, in which 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. A film is described. 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 performs antireflection by optical interference of the low refractive index layer.

In addition, as a technique capable of imparting high antireflection performance, an antireflection film having a fine uneven shape whose period is not more than the wavelength of visible light on the surface of the substrate, that is, an antireflection film having a so-called moth eye structure is known. Yes. With the moth-eye structure, it is possible to create a refractive index gradient layer in which the refractive index continuously changes from air to the bulk material inside the substrate, thereby preventing light reflection.

As an antiglare antireflection film having a moth-eye structure, Patent Document 3 discloses an antireflection layer forming composition containing fine particles and a binder resin forming compound as a base film and an antiglare layer having an uneven shape. An antiglare antireflection film is described in which a moth-eye structure is prepared by coating on an antiglare layer of a glare film and allowing a binder resin-forming compound to penetrate into the antiglare layer. Patent Document 4 describes an antiglare antireflection film by a so-called nanoimprint method in which a moth-eye structure is produced by molding a curable resin into a mold shape.

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

However, the antiglare antireflection film described in

Patent Documents

1 and 2 requires further antireflection performance.
In the technique of Patent Document 3, when an antireflection layer is formed by applying an antireflection layer forming composition on an antiglare layer of an antiglare film having a base film and an antiglare layer, a coating solution (antireflection layer formation) is used. The leveling of the composition) causes unevenness in the coating amount between the convex and concave portions of the antiglare layer, and the density of fine particles occurs, which indicates that an antiglare antireflection film with low reflectance may not be produced. It was.
The moth-eye structure produced by the nanoimprint method of Patent Document 4 has a problem that it is 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 diligently studied to solve the above-mentioned problems, and formed an antireflection layer on the antiglare layer of the antiglare film having the base film and the antiglare layer by transfer, thereby forming a recess in the antiglare layer. It was found that an antireflection layer having a uniform thickness can be formed at the convex portions, 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 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 antiglare antireflection film surface has an arithmetic average roughness Ra of 0.03 μm ≦ Ra ≦ 0.4 μm, and an average interval Sm of unevenness of 20 μm ≦ Sm ≦ 700 μm,
An antiglare antireflection film, wherein the ratio of the average thickness of the antireflection layer at the convex portion of the antiglare antireflection film to the average thickness of the antireflection layer at the concave portion is 1.0 to 0.7.
<2>
The uneven shape on the surface of the antiglare antireflection film is the antiglare antireflection film according to <1>, wherein the arithmetic average roughness Ra is 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 a (meth) acryloyl group capable of forming a covalent bond with the antireflection layer. Dazzling antireflection film.
<5>
The antireflection layer contains particles having an average primary particle diameter of 100 nm to 250 nm and a binder resin, and has a moth-eye structure of the particles on the surface opposite to the interface with the antiglare layer. 4> The anti-glare 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 binder resin has an average silicon content Si / C of 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,
On the base film, a composition for forming an antiglare layer containing a binder resin forming compound for an antiglare layer and particles for the antiglare layer is applied, and the composition for forming an antiglare layer is irradiated with ionizing radiation or heated. A step of curing the antiglare layer,
Applying a composition for forming an antireflection layer on a temporary support, and semi-curing it at a surface curing rate of 10 to 70% by irradiation with ionizing radiation or heating to form an antireflection layer;
Transferring the antireflection layer from the temporary support onto the antiglare layer;
The manufacturing method of the anti-glare antireflection film which has this.
<8>
The antiglare layer according to <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. For producing antireflective film.
<9>
<7> or <8> The method for producing an antiglare antireflection film according to <7>, comprising a step of heating the antireflection layer and the antiglare 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 the curable compound (a1) are contained in the layer (a) containing the curable compound (a1). A step (1) of providing the thickness to be buried
A step (2) of obtaining a layer (ca) by curing a part of the layer (a);
A step (3) of bonding the layer (b) of the pressure-sensitive adhesive film having a support and a layer (b) containing a pressure-sensitive adhesive on the support to the layer (ca);
The layer (ca) is embedded such that the particles (a2) are embedded in the layer including the layer (ca) and the layer (b) and protrude from the interface of the layer (ca) on the support side. Step (4) of bringing the position of the interface on the support side closer to the temporary support side,
A step (5) of peeling the temporary support,
A 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 including the layer (ca) obtained in the step (5). ,
Step (7) of curing the layer (ca) in a state where the particle (a2) is embedded in a layer combining the layer (ca) and the layer (b), and the adhesive film is peeled off. Step (8),
The method for producing an antiglare and 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 comprising 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 comprising the antiglare and antireflection film according to any one of <1> to <6> on a surface thereof.

According to the present invention, an antiglare antireflection film having sufficient antireflection performance can be provided. Moreover, according to this invention, the manufacturing method of the said anti-glare antireflection film, the polarizing plate which has the said anti-glare antireflection film, an image display apparatus, and a self-light-emitting display apparatus can be provided.

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. It is a larger one. 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 an enlargement of FIG. 2A. . It is a schematic diagram which shows an example of the manufacturing method of the anti-glare antireflection film of this invention. It is a schematic diagram which shows an example of the manufacturing method of the anti-glare antireflection film of this invention. It is a schematic diagram which shows an example of the anti-glare antireflection film of this invention. It is a schematic diagram which shows an example of the anti-glare antireflection film of this invention. It is a schematic diagram which shows an example of the anti-glare 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 methacryloyl”, respectively. Represents.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

In the present specification, a film in which an antiglare layer is formed on a base film is expressed as an antiglare film.

<Anti-glare anti-reflection 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 antiglare antireflection film surface has an arithmetic average roughness Ra of 0.03 μm ≦ Ra ≦ 0.4 μm, and an average interval Sm of unevenness of 20 μm ≦ Sm ≦ 700 μm,
The antiglare antireflection film has a ratio of the average thickness of the antireflection layer at the convex portion of the antiglare antireflection film to the average thickness of the antireflection layer at the concave portion of 1.0 to 0.7.

FIG. 5 is a schematic view showing an example of the antiglare antireflection film of the present invention. An antiglare antireflection film 20 in FIG. 5 includes a base film 11, an antiglare layer 12, and an antireflection layer 10. The antiglare layer 12 includes antiglare layer particles 13. 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 in FIG. 6 further includes 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. The antiglare antireflection film 20 in FIG. 7 has an antireflection layer 16 having a low refractive index layer Ln and a high refractive index layer Hn in place of the antireflection layer 10 which is a moth-eye layer in FIG.
3 to 7 are schematic diagrams, and the size of each particle, the thickness of the base material and each layer, and the like may not be drawn in actual dimensional ratios.

[Anti-glare layer]
The antiglare layer of the antiglare antireflection film of the present invention will be described.
The antiglare layer preferably has a concavo-convex shape on the surface, which can impart antiglare properties to the film by surface scattering. Moreover, what can provide the hard-coat property for improving the abrasion resistance of a film preferably is preferable.

As a method of imparting anti-glare properties, a method of laminating and forming a mat-shaped shaping film having fine irregularities on the surface as described in JP-A-6-16851, described in JP-A-2000-206317 A method of forming by curing shrinkage of an ionizing radiation curable resin due to a difference in ionizing radiation dose, as described in JP 2000-338310 A, and a mass ratio of a good solvent to a translucent resin is reduced by drying. A method of forming unevenness on the coating film surface by solidifying the light-transmitting fine particles and the light-transmitting resin by gelation, and providing surface unevenness by external pressure as described in JP-A-2000-275404 Surface unevenness by utilizing phase separation in the process of evaporation of a solvent from a mixed solution of a plurality of polymers as described in JP-A-2005-195819 A method of forming, have been known such as, can use these known methods.

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.
More preferably, the antiglare layer includes a binder resin for an antiglare layer capable of imparting hard coat properties, and translucent particles for imparting antiglare properties. A layer in which irregularities are formed on the surface by projections formed by an aggregate of particles is preferable.
Moreover, it is preferable that an anti-glare layer is formed using the composition for anti-glare layer containing the compound for binder resin formation, translucent particle | grains, and a solvent.
The antiglare layer formed using the composition for forming an antiglare layer includes a binder resin for the antiglare layer and translucent particles dispersed in the binder resin for the antiglare layer, and has an antiglare property and a hard coat. It is preferable to combine the properties.

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

It is preferable that one convex portion of the antiglare layer is substantially formed by 5 or less translucent particles 1, and that the convex portion is substantially formed by one translucent particle. More preferred. Here, “substantially” means that 90% or more of the convex portions satisfy a preferable mode.
When one convex part of the anti-glare layer is formed substantially by one translucent particle 1, it is preferable to select a particle with good dispersibility.

Specific examples of the translucent particles 1 include, for example, crosslinked polymethyl methacrylate particles, crosslinked methyl methacrylate-styrene copolymer particles, crosslinked polystyrene particles, crosslinked methyl methacrylate-methyl acrylate copolymer particles, crosslinked alkyl acrylate-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 polymethyl methacrylate particles, and crosslinked methyl methacrylate-styrene copolymer particles are preferred. Furthermore, surface modified particles obtained by chemically bonding a compound containing fluorine atom, silicon atom, carboxyl group, hydroxyl group, amino group, sulfonic acid group, phosphoric acid group, etc. on the surface of these resin particles, nano-sized such as silica or zirconia Examples of the particles include inorganic fine particles bonded to the surface.
Among them, in order to adjust the absolute value of the refractive index difference with the binder component in the antiglare layer, crosslinked methyl methacrylate-styrene copolymer particles, crosslinked alkyl acrylate-styrene copolymer particles, crosslinked alkyl methacrylate- Styrene copolymer particles are preferred.

When the translucent particles 1 are used, visible light scattering of silica or the like does not occur for the dispersion stability of the particles in the binder resin for the antiglare layer or the antiglare layer forming composition and for preventing sedimentation. You may add dispersing agents, such as a size inorganic filler and an organic compound (a monomer or a polymer may be sufficient).

In addition, when adding an inorganic filler, it is effective for the sedimentation prevention of translucent particle | grains, so that the addition amount increases, However, It is preferable to use in the range which does not have a bad influence on the transparency of a coating film. Therefore, it is preferable to add about 0.1 parts by mass of an inorganic filler having a particle size of 0.5 μm or less to the extent that the transparency of the coating film is not impaired with respect to 100 parts by mass of the binder resin for the antiglare layer. 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. More preferred is 0.1 to 15 parts by mass, and particularly preferred is 0.5 to 10 parts by mass. If it is 0.1 part by mass or more, the effect of addition to the dispersion stability appears, and if it is 20 parts by mass or less, the components that do not contribute to the dispersion stability increase and problems such as bleeding out do not occur.

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

The particle size distribution of the translucent particles is preferably monodisperse particles, that is, particles having a uniform particle diameter, from the viewpoints of control of haze value and diffusibility, and uniformity of the coated surface. The CV value representing the uniformity of the particle diameter is preferably 0 to 10%, more preferably 0 to 8%, still more preferably 0 to 5%. Further, when a particle having a particle size of 20% or more than the average particle size is defined as a coarse particle, the proportion of the coarse particle is preferably 1% or less of the total number of particles, more preferably 0.1% or less. Yes, more preferably 0.01% or less. The translucent particles having such a particle size distribution are also effective means of classification after the preparation or synthesis reaction. By increasing the number of times of classification or increasing the degree thereof, particles having a desired distribution can be obtained. be able to. It is preferable to use a method such as an air classification method, a centrifugal classification method, a sedimentation classification method, a filtration classification method, or an electrostatic classification method for classification. The average particle diameter of the translucent particles is calculated from an average value of 100 observed particle diameters obtained by observing the translucent particles with an optical microscope.

The addition amount of the translucent particles 1 having an average particle diameter 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 density of the unevenness is made sparse so that the ratio of the flat portion on the film surface is increased and the antireflection layer is uniformly laminated. The addition amount of the translucent particles 1 is more preferably 0.1 to 1.0% by mass, and preferably 0.1 to 0.7% by mass with respect to the total solid content of the antiglare layer. Further preferred.
The translucent particles preferably project at least 0.01 to 4.0 μm from the binder resin film of the antiglare layer to exhibit antiglare properties.

(Translucent particle 2)
Further, as another preferred embodiment of the antiglare layer, for example, another translucent particle 2 having an average particle diameter different from that of the translucent particle 1 in order to obtain a necessary antiglare property is used alone. Alternatively, they may be used in combination, and it is also possible to achieve both antiglare properties and further optical properties by using the light transmitting particles 1 and the light transmitting particles 2 in combination.

When using the translucent particle | grains 2 in this invention, it is preferable that the translucent particle | grains 2 have an average particle diameter smaller than the average film thickness of a glare-proof layer. Specifically, the average particle diameter 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 polymethyl methacrylate particles and polymethyl methacrylate / polystyrene copolymer particles are preferable. The polymethyl methacrylate ratio in the copolymer particles is preferably 40% by mass to 100% by mass from the viewpoint of dispersibility, more preferably 50% by mass to 100% by mass, and 75% by mass to Most preferably, it is 100 mass%.

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

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, from the viewpoint of imparting antiglare properties and internal scattering properties, and are 1 to 15% by mass. More preferably.
In the case where a plurality of kinds of translucent particles 2 are used in combination, it is preferable from the viewpoint of easy antiglare control that particles having different particle diameters are used without changing the components constituting the particles.

Also, for the purpose of adjusting the antiglare property and other optical properties, organically treated layered inorganic compounds such as hectorite, bentonite, smectite and vermiculite can be used. These layered inorganic compounds segregate between the translucent particles 2, prevent the translucent particles 2 from aggregating more than necessary in the antiglare layer, and gather the translucent particles appropriately. Dazzle control is possible.

(Metal oxide fine particles)
As still another embodiment of the present invention, at least one kind of fine particles are contained in the antiglare layer, and the fine particles are cohesive metal oxide fine particles.
The agglomerated metal oxide fine particles are used for the purpose of [1] imparting surface irregularities, [2] adjusting the refractive index, [3] improving the hardness, [4] improving the brittleness, and curling of the antiglare layer. In terms of imparting surface irregularities to the antiglare layer in the present invention, the metal oxide fine particles are preferably agglomerated silica particles and agglomerated alumina particles from the viewpoint of transparency and inexpensiveness. Agglomerated silica particles in which particles having a particle size of several tens of nanometers form aggregates are preferable in that they can stably impart appropriate surface irregularities. The cohesive silica particles can be obtained, for example, by a so-called wet method, which is synthesized by a neutralization reaction between sodium silicate and sulfuric acid, but is not limited thereto. The wet method is further roughly classified into a sedimentation method and a gelation method, but the present invention may be any method. The secondary particle diameter 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 adjustment of the secondary particle diameter is performed by the degree of particle dispersion (control 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 thickness of the antiglare layer containing the same is preferably 0.1 to 1.5, and preferably 0.3 to 1.0. Is more preferable.

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

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

(Binder resin for anti-glare layer)
The binder resin for the antiglare layer is preferably formed from a compound for forming the binder resin for the antiglare layer. It is preferable that 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, which are cured to form a binder resin for an antiglare layer.

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

(Compound having a 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. preferable. Particularly preferably, a compound containing two or more (meth) acryloyl groups in one molecule described 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, propylene glycol di (meth) acrylate and the like. 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, polypropylene glycol di (meth) acrylate, etc. ; (Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate; 2,2-bis {4- (acryloxydiethoxy) phenyl} propane, 2-2bis {4 (Meth) acrylic acid diester such (acryloxy-polypropoxy) phenyl} ethylene oxide or propylene oxide adducts such as propane; and the like.

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

Of these, esters of polyhydric alcohol and (meth) acrylic acid are preferred. More preferably, a polyfunctional monomer having 3 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 Propane tri (meth) acrylate, EO-modified phosphate tri (meth) acrylate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-chlorohexa Tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate and caprolactone-modified tris (acryloyloxyethyl) isocyanurate.

Specific examples of the polyfunctional acrylate compounds having a (meth) acryloyl group include KAYARAADDPHA, 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. 400, V # 36095D, V # 1000, V # 1080 and the like, and (meth) acrylic acid esterified products. Purple light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7630B, UV-7640B UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310EA, UV-3310B, UV-3500BA UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2250EA (manufactured by Nippon Synthetic Chemical Co., Ltd.), UL-503LN (manufactured by Kyoeisha Chemical Co., Ltd.), Unidic 17-80 17-813, V-4030, V-4000BA (Dainippon Ink Chemical Co., Ltd.), EB-1290K, EB-220, EB-5129, EB-1830, EB-4858 (Daicel UCB ( Ltd.), High Corp AU-2010, AU-2020 (manufactured by Tokushi Co., Ltd.), Aronix M-1960 (manufactured by Toagosei Co., Ltd.), Art Resin UN-3320HA, UN-3320HC, UN-3320HS, UN -904, HDP-4T and other trifunctional or more urethane acrylate compounds, Aronix M-8100, M-8030, M-9050 (manufactured by Toagosei Co., Ltd.), KRM-8307 (manufactured by Daicel Cytec Co., Ltd.), etc. A trifunctional or higher functional polyester compound can also be suitably 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, polythiol polyene resins And oligomers or prepolymers such as polyfunctional compounds such as polyhydric alcohols.

Furthermore, specific examples of the bifunctional (meth) acrylate compound include compounds represented by the following formula, but are not limited thereto.

Further, for example, dendrimers described in JP-A-2005-76005 and JP-A-2005-36105, or norbornene ring-containing monomers as described in JP-A-2005-60425 can be used. Further, a fluorine-containing polyfunctional (meth) acrylate represented by the chemical formula (2) described in JP-A No. 2002-105141 can also be used.

Two or more polyfunctional monomers may be used in combination.
Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical 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 that absorbs light having a transmission wavelength of 320 nm or longer of the PET film (for example, Irgacure 819 manufactured by BASF Japan Ltd.) is used. Is preferred.

In addition, the compound for forming a binder resin for the antiglare layer includes, for the purpose of controlling the refractive index of the antiglare layer, a high refractive index monomer, or inorganic particles such as ZrO ₂ , TiO ₂ , and SiO ₂ that do not cause visible light scattering. That is, inorganic particles having an average particle diameter of 100 nm or less, or both of them can be added. In addition to the effect of controlling the refractive index, the inorganic particles also have the effect of suppressing cure shrinkage due to the crosslinking reaction. In the present invention, after formation of the antiglare layer, a polymer formed by polymerization of a compound having a polymerizable unsaturated bond, such as a polyfunctional monomer and / or a high refractive index monomer, and an inorganic dispersed in the polymer The particles including the particles are 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. Even in this case, it is preferable for maintaining 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 a pencil hardness test.

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

Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (hereinafter sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following (i): An acrylic resin, a methacrylic resin, or a copolymerizable copolymer containing a repeating unit corresponding to the monomer or a repeating unit corresponding to the monomer (i) and a repeating unit corresponding to the monomer (ii) below. Copolymers with various vinyl monomers are useful.

(I) Fluoroaliphatic group-containing monomer represented by the following 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 represents an integer of 1 to 6, and n represents an integer of 2 to 4. To express. 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, 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 the above (i)

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 ) —, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically Specifically, it represents a methyl group, an ethyl group, a propyl group, or a butyl group, 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 for the alkyl group represented by R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. , Amino groups and the like, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

The amount of the fluoroaliphatic group-containing monomer represented by the general formula (a) used in the fluoropolymer used in the present invention is 10 mol% or more based on each monomer of the fluoropolymer, preferably It is 15 to 70 mol%, more preferably in the range of 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. Furthermore, the preferable addition amount of the fluoropolymer used in the present invention is in the range of 0.001 to 5 parts by mass, more preferably 0.001 to 100 parts by mass with respect to 100 parts by mass of the coating liquid (antiglare layer forming composition). The range is 005 to 3 parts by mass, and more preferably 0.01 to 1 part by mass. If the addition amount of the fluorine-based polymer is 0.001 part by mass or more, the effect of adding the fluorine-based polymer is sufficiently obtained, and if the addition amount is 5 parts by mass or less, the coating film cannot be sufficiently dried or applied. There is no problem of adversely affecting the performance as a film (for example, reflectance, scratch resistance).

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 particle 1 is used as the translucent particle, the average particle diameter of the translucent particle 1 is preferably 2.01 to 24 μm, and more preferably 2.01 to 19 μm. The thickness is preferably 3.01 to 16 μm, more preferably 3.01 to 12 μm.
When the translucent particle 2 is used as the translucent particle, the average particle diameter of the translucent particle 2 is preferably 2.01 to 16 μm, and 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, the refractive index values specifically shown hereinafter all show values at a wavelength of 550 nm.

(A component having a functional group other than a (meth) acryloyl group capable of forming a chemical bond with the antireflection layer)
The antiglare layer-forming composition of the present invention has 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 with the antireflection layer. It is preferable to contain the component which has functional groups other than. By containing the said component in the composition for anti-glare layer formation, it forms a chemical bond between the formed anti-glare layer and an antireflection layer, and acts effectively in order to secure adhesion between layers.
In particular, when the antireflection layer is applied by a transfer method, the scratch resistance can be improved by improving the adhesion between the antiglare layer and the antireflection layer.
In addition, the above component has a functional group other than the (meth) acryloyl group, and 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. For example, ionic bond between boric acid and hydroxyl group, reaction between epoxy group and acid, base, or hydroxyl group, urethanization reaction of isocyanate group, etc. Is mentioned.
The component contained in the antireflection layer is preferably a binder resin forming compound described below.

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 an unsaturated hydrocarbon group, boronic acid group, alkoxysilyl group, isocyanate group, epoxy. Group, hydroxyl group, amino group, thiol group, carboxyl group and the like.
Since the above components act at the interface between the antiglare layer and the antireflection layer, it is preferable to use a component that is highly unevenly distributed at the interface.

Specific examples of the component when the above component has a boronic acid group are 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 represented by Formula 1 and a polymerizable group.

In formula (1), R ¹ and R ² each 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. .
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.), a C 3 to 20 carbon group, and the like. Examples thereof include a substituted or unsubstituted cyclic alkyl group (for example, cyclohexyl group) and an alkenyl group having 2 to 20 carbon atoms (for example, 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 and a tolyl group), 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-membered or 6-membered group containing at least one heteroatom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.), such as a pyridyl group, Examples include imidazolyl group, furyl group, piperidyl group, morpholino group and the like.
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 are linked to

form

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 a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, and a case where R ¹ and R ² are connected to form a ring, Preferably, it is a hydrogen atom.
In the formula (1), * indicates a bonding position to the boronic acid monomer residue.
The number of boronic acid groups represented by formula (1) is not particularly limited, and may be one or plural (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 any substituent. Examples of the substituent include the substituents described in paragraph [0046] of JP2013-05201A.

The type of the polymerizable group is not particularly limited, and examples thereof include a radical polymerizable group and a cationic polymerizable group. Examples of the radical polymerizable group include (meth) acryloyl group, (meth) acrylamide group, vinyl group, styryl group, and allyl group. Examples of the cationic polymerizable group include a vinyl ether group, an oxiranyl group, and an oxetanyl group. Among them, a (meth) acryloyl group, a styryl group, a vinyl group, an oxiranyl 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 methacryloyl group, and the (meth) acrylamide group is a concept including both an acrylamide group and a methacrylamide group.
The number of the polymerizable groups is not particularly limited, and may be one or plural (two or more).

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

A preferred embodiment of the boronic acid monomer is a boronic acid monomer represented by 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 divalent linking groups selected from combinations thereof.
Examples of the combination include -arylene group-COO-arylene group-O-alkylene group-, -arylene group-COO-alkylene group- and the like.

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

(Copolymer introduced with boronic acid group)
In the present invention, a copolymer having a boronic acid group introduced can be preferably used. A copolymer into which a boronic acid group has been introduced (hereinafter also abbreviated as “the polymer compound of the present invention” formally in the present specification) is represented by a repeating unit represented by the following formula (I) (hereinafter referred to as “I And a repeating unit represented by the following formula (II) (hereinafter also abbreviated as “II part”).
The polymer compound of the present invention preferably has a repeating unit represented by the following formula (III) (hereinafter also abbreviated as “III part”).
Furthermore, the polymer compound of the present invention preferably has a repeating unit represented by the following formula (V) (hereinafter also abbreviated as “V part”).

<Part I>
The I part possessed by 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. 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. Are more preferable, and a hydrogen atom or a methyl group is still more preferable.

In the above formula (I), X ¹ represents a single bond, or —O—, —S—, —COO—, —OCO—, —CONR ² —, —NR ² COO—, —CR ² N— Represents a divalent linking group selected from the group consisting of a substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted divalent aromatic group, and combinations thereof, and R ² represents hydrogen. An atom, an alkyl group having 1 to 20 carbon atoms, or —X ¹ —P ¹ is represented. In the case where R ² is —X ¹ —P ¹ , P ¹ represents a polymerizable group in the same manner as P ¹ in the above formula (I). It will be described later P ^1.
In the above description of X ¹ , —COO— represents that carbon bonded to R ¹ is bonded to C═O, and P ¹ and O are bonded. —OCO— represents carbon bonded to R ^1. Represents a bond between P ¹ and C═O, and —CONR ² — represents a bond between R ¹ bonded carbon and C═O, and a bond between P ¹ and NR ^2. , —NR ² COO— represents that R ¹ is bonded to NR ² and P ¹ is bonded to O, —CR ² N— is bonded to R ¹ and carbon ² And P ¹ and N are bonded to each other.

Here, the substituted or unsubstituted divalent aliphatic group represented by X ¹ may be, for example, an alkylene group having 1 to 20 carbon atoms which may have a substituent or a substituent. Preferred examples thereof include cycloalkylene groups having 3 to 20 carbon atoms (eg, cyclohexylene group). Among them, alkylene groups having 1 to 15 carbon atoms are preferable, alkylene groups having 1 to 8 carbon atoms are more preferable, and methylene group More preferred are an ethylene group, a propylene group, and a butylene group.
Also shown is X ^1, a substituted or the divalent aromatic group unsubstituted divalent aromatic which may have a substituent hydrocarbon group or may have a substituent divalent The aromatic heterocyclic group of these is mentioned. Examples of the divalent aromatic hydrocarbon group include a hydrogen atom from two carbon atoms constituting the ring structure of an aromatic hydrocarbon ring such as a benzene ring, naphthalene ring, anthracene ring, triphenylene ring, fluorene ring, etc. A group obtained by removing one by one is mentioned, and among them, a phenylene group or a naphthylene group obtained by removing one hydrogen atom from each of two carbon atoms constituting the ring structure of a benzene ring or naphthalene ring is preferable. . On the other hand, the divalent aromatic heterocyclic group includes an aromatic heterocyclic ring such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, a benzothiazole ring, an oxadiazole ring, a thiazolothiazole ring, and a phenanthroline ring. And a group obtained by removing one hydrogen atom from each of two carbon atoms constituting the ring structure.

Examples of the substituent that the divalent aliphatic group or divalent aromatic group may have include, for example, a halogen atom, a hydroxyl group, an amino group, an acryloyloxy group, a methacryloyloxy group, and an alkyl group 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═ And a group in which 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 —X ¹ —P ¹ . In the case where R ² is —X ¹ —P ¹ , P ¹ represents a polymerizable group in the same manner as P ¹ in the above formula (I).

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

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 any one selected from the group consisting of groups represented by the following formulas (P-1) to (P-7) Among these, a polymerizable group selected from the group consisting of groups represented by the following formulas (P-1) to (P-3) is more preferable. A 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 a bonding position with X ¹ . R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and two R ^{3 s} 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 represented by R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group.

In the present invention, from the viewpoint of ease of production, economy, and radical polymerizability, the repeating unit represented by the formula (I) is such that R ¹ in the formula (I) is a hydrogen atom or a methyl group. X ¹ in the above formula (I) is —O—, —COO—, —OCO—, or a substituted or unsubstituted divalent aliphatic group (preferably an alkylene group having 2 to 8 carbon atoms). The repeating unit which is a divalent linking group formed by combining any one or two or more selected from the group consisting of:

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. More preferably, it is 10 to 50% by mass.

<Part II>
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. 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. Are more preferable, and a hydrogen atom or a methyl group is still more preferable.

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- Represents a divalent linking group selected from the group consisting of a substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted divalent aromatic group, and combinations thereof, and R ¹³ represents a hydrogen atom. Or an alkyl group having 1 to 20 carbon atoms.
Note that in the above description of X ¹⁰ , —COO— represents that carbon bonded to R ¹⁰ is bonded to C═O, and B and O are bonded. —OCO— represents carbon bonded to R ¹⁰ O represents a bond, B represents C═O, and —CONR ¹³ — represents a bond between R ¹⁰ and C═O, B represents a bond with NR ¹³ , and —NR ¹³ COO— represents that R ¹⁰ is bonded to NR ¹³ and B is bonded to O; —CR ¹³ N— is a bond of R ¹⁰ to carbon ¹³ and CR ¹³ ; N represents bonding.
Here, examples of the divalent aliphatic group and divalent aromatic group represented by X ¹⁰ include the same as those described for X ¹ in the above formula (I), and R Examples of the alkyl group having 1 to 20 carbon atoms represented by ¹³ include those similar to R ² described in relation to the above formula (I).

In the above formula (II), R ¹¹ and R ¹² each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero group. Represents an aryl group, and 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. May be.

Examples of the substituted or unsubstituted aliphatic hydrocarbon group represented by R ¹¹ and R ¹² include an alkyl group, an alkenyl group or an alkynyl group which may have a substituent.
Specific examples of the alkyl group include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl. , 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 And linear, branched or cyclic alkyl groups such as 1-adamantyl group and 2-norbornyl group.
Specific examples of the alkenyl group include linear groups such as a vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group, and the like. , Branched, or cyclic alkenyl groups.
Specific examples of the alkynyl group include ethynyl group, 1-propynyl group, 1-butynyl group, 1-octynyl group and the like.

Examples of the substituted or unsubstituted aryl group represented by R ¹¹ and R ¹² include those in which 1 to 4 benzene rings form a condensed ring, and a benzene ring and an unsaturated five-membered ring form a condensed ring. Specific examples 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.

Examples of the substituted or unsubstituted heteroaryl group represented by R ¹¹ and R ¹² include a hydrogen atom on a heteroaromatic ring containing one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. One may be removed to give a heteroaryl group.
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 pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole and isoxazole. , Oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thianaphthene, dibenzothiophene, indazolebenzimidazole, anthranyl, benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, Examples include quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroline, and pteridine.

Examples of the substituent that R ¹¹ and R ¹² may have include a monovalent non-metallic atomic group excluding hydrogen. For example, the substituent is selected from the following substituent group Y.
(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-ary Rucarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N -Alkylacylamino group, N-aryl Silamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido Group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido , Alkoxycarbonylamino group, aryloxycarbonylamino 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, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N- arylcarbamoyl group, N, N- di arylcarbamoyl group, N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group _(-SO 3 H)及Its conjugate base group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfina Moyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfur Famoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N-alkylsulfonylsulfamoyl group (—SO ₂ NHSO ₂ (alkyl)) and its conjugate base group, N- aryl sulfonylsulfamoyl group _(-SO 2 NHS ₂ (aryl)) and its conjugated base group, N- alkylsulfonylcarbamoyl group _(-CONHSO 2 _(alkyl)) and its conjugated base group, N- aryl sulfonyl carbamoyl group _(-CONHSO 2 _(aryl)) and its conjugated base group , Alkoxysilyl groups (—Si (Oalkyl) ₃ ), aryloxysilyl groups (—Si (Oaryl) ₃ ), hydroxysilyl groups (—Si (OH) ₃ ) and their conjugate base groups, phosphono groups (—PO ₃ H) ₂ ) and its conjugate base group, dialkylphosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphono group (—PO ₃ (aryl) ₂ ), alkylarylphosphono group (—PO ₃ (alkyl) (aryl) )), monoalkyl phosphono group _(-PO 3 H _(alkyl)) and its conjugated base group Monoarylphosphono group _(-PO 3 H (aryl)) and its conjugated base group, a phosphonooxy group (-OPO ₃ H ₂₎ and its conjugated base group, a dialkyl phosphono group _{_{(-OPO 3 (alkyl) 2)}} , Diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its Conjugated base groups, monoarylphosphonooxy groups (—OPO ₃ H (aryl)) and their conjugated base groups, cyano groups, nitro groups, aryl groups, alkenyl groups and alkynyl groups, and these substituents are possible. If present, they may be bonded to each other or with a substituted hydrocarbon group to form a ring.

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

Specific examples of the monomer that forms the repeating unit represented by the above formula (II) include 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. More preferably, it is 5 to 50% by mass.

<Part III>
The polymer compound of the present invention has a repeating unit (Part III) represented by the following formula (III) because the adhesion between the antiglare layer to be formed and the antireflection layer becomes better. It is preferable.
Here, the reason why the adhesiveness becomes 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. This is considered to be because the III part of the copolymer easily interacts 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, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Are more preferable, and a hydrogen atom or a methyl group is still more preferable.

In the formula (III), L ²⁰ represents a divalent linking group selected from the group consisting of —O—, —COO—, —OCO—, a divalent aliphatic group, and combinations thereof. To express. In addition, —COO— represents that carbon bonded to R ²⁰ is bonded to C═O, and R ²¹ and O are bonded. —OCO— is bonded to carbon bonded to R ²⁰ and O; ²¹ and C═O are bonded to each other.
Examples of the divalent aliphatic group represented 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.
Of these, L ²⁰ is preferably —COO— or —OCO—, more preferably —COO—.

In the formula (III), R ²¹ represents an alkyl group having 4 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (hereinafter referred to as “fluoroalkyl group”). Or a monovalent organic group containing —Si (R ^a3 ) (R ^a4 ) O—, and each of R ^a3 and R ^a4 independently represents an alkyl group, a haloalkyl group or an aryl group. To express.

In the present invention, R ²¹ in the above formula (III) is a fluoroalkyl group having 1 to 20 carbon atoms because the adhesion of the antiglare layer to be formed to the antireflection layer is further improved. Are preferred, 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 adhesion between the antiglare layer to be formed and the antireflection layer, and radical polymerizability. 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.
In the formula (IV), ma and na each independently represents an integer of 0 to 19. Among these, from the viewpoints of improving adhesion and obtaining raw materials, ma is preferably an integer of 1 to 8, and more preferably an integer of 1 to 5. 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 an integer of 0 to 19 in total.
Further, in the above formula (IV), X ²¹ represents a hydrogen atom or a fluorine atom is preferably a fluorine.

Specific examples of the monomer that forms the repeating unit represented by the above formula (III) or (IV) include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3, and the like. , 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-tetrafluor Propyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H -1- (trifluoromethyl) 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 Ethylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyl-octyl) -2-hydroxypropyl (meth) acrylate.

On the other hand, the monovalent organic group containing —Si (R ^a3 ) (R ^a4 ) O— represented by R ²¹ in the above formula (III) 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 a compound represented by

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

In the formula (VII), R ^a3 and R ^a4 each independently represent an alkyl group, a haloalkyl group, or an aryl group.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, and a hexyl group.
The haloalkyl group is preferably a fluorinated alkyl group having 1 to 10 carbon atoms, 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.
Among these, R ^a3 and R ^a4 are preferably a methyl group, a trifluoromethyl group or a phenyl group, and particularly preferably a methyl group.

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

Examples of the compound represented by the formula (VII) include polysiloxane macromers containing one terminal (meth) acryloyl group (for example, Silaplane 0721, 0725 (above, trade name, manufactured by JNC Corporation), AK-5, AK-30, AK-32 (trade name, manufactured by Toagosei 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 Co., Ltd.) be able to.

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

Moreover, in this invention, when it has the repeating unit represented by the said Formula (III) from the reason which the adhesiveness of the glare-proof layer and antireflection layer to be formed becomes favorable, when the said formula (I) The content of the repeating unit represented by the formula (II) 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 good adhesion when an epoxy 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. 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. Are more preferable, and a hydrogen atom or a methyl group is still more preferable.

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

In the present invention, the content of the repeating unit represented by the formula (V) is preferably 1 to 60% by mass, and preferably 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) as necessary.

As other monomers forming the repeating unit, Polymer Handbook 2nd ed. , J .; Brandrup, Wiley lnterscience (1975) Chapter 2 Page 1-483 can be used.
Examples thereof include compounds 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.
Specifically, the following monomers can be mentioned.

(Acrylic acid esters)
Specific examples of acrylic esters include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, phenoxy Examples include ethyl acrylate, furfuryl acrylate, and tetrahydrofurfuryl acrylate.

(Methacrylic acid esters)
Specific examples of the methacrylic acid esters include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, and phenoxy. Examples include ethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, and ethylene glycol monoacetoacetate monomethacrylate.

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

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

(Allyl compound)
Specific examples of the allyl compound include allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate). And allyloxyethanol.

(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, for example, vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, Examples thereof include vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

(Dialkyl itaconates)
Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(Other)
Other dialkyl esters or alkyl esters of fumaric acid; dibutyl fumarate; crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleilonitrile, styrene, styrene macromer (AS-6S manufactured by Toa Gosei Co., Ltd.), methyl methacrylate macromer (Toa Gosei Co., Ltd. AA-6).

In the present invention, the content in the case of having other repeating units is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, more preferably 1 to 20% by mass with respect to all repeating units. % Is more preferable.

The weight average molecular weight (Mw) of the polymer compound of the present invention is preferably 1,000 to 200,000, more preferably 1500 to 100,000, and still more preferably 3000 to 60,000.
The number average molecular weight (Mn) of the polymer compound of the present invention is preferably 500 to 40000, more preferably 600 to 35000, and still more preferably 600 to 30000.
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.
In addition, a weight average molecular weight and a number average molecular weight are the values measured on condition of the following by gel permeation chromatography (GPC).
<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 rate] 0.50 ml / min

Specific examples of the polymer compound of the present invention having each repeating unit described above include compounds represented by the following formulas (A-1) to (A-22). The compounds represented by the following formulas (A-1) to (A-22) include, for example, a compound having a hydroxyl group in the antireflection layer (a hydroxyl group appearing after ring opening of a compound having an epoxy group, a silane coupling site) And a covalent bond can be formed with a hydroxyl group or the like appearing after hydrolysis of a compound having a hydrogen atom. The formation of covalent bonds is confirmed by obliquely cutting the antiglare antireflection film, measuring the micro Raman spectrum near the interface between the antiglare layer and the antireflection layer, and analyzing the Raman band of the 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 composition for forming an antiglare layer of the present invention is 100% by mass. Preferably, the content is 0.001 to 20% by mass, and 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 a polymer compound, curing shrinkage can be reduced, or the viscosity of the coating liquid (antiglare layer forming composition) can be adjusted.

The polymer compound has already formed a polymer when added to the coating solution. Examples of the polymer compound include cellulose esters (for example, cellulose triacetate, cellulose diacetate, cellulose propionate, cellulose acetate Pionate, cellulose acetate butyrate, cellulose nitrate, etc.), urethane acrylates, polyester acrylates, (meth) acrylic acid esters (for example, methyl methacrylate / (meth) methyl acrylate copolymer, methyl methacrylate / (Meth) ethyl acrylate copolymer, methyl methacrylate / (meth) butyl acrylate copolymer, methyl methacrylate / styrene copolymer, methyl methacrylate / (meth) acrylic acid copolymer, polymethyl methacrylate etc), Resins such as polystyrene are preferably used.

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

[Antireflection layer]
The antireflection layer of the antiglare antireflection film of the present invention will be described. The antiglare antireflection film of the present invention has an integral reflectance of 1.0% or less, a specular reflectance of 0.4% or less, and the average thickness of the antireflection layer at the convex portion of the antiglare antireflection film. The average thickness of the antireflection layer in the recess (ratio of the average thickness of the antireflection layer in the protrusion to the average thickness of the antireflection layer in the recess) is 1.0 to 0.7. The antireflection layer is not particularly limited as long as it satisfies the above conditions. In the present invention, when the antireflection layer is a multilayer, the above relationship is established for each layer.

The method for obtaining the average thickness of the antireflection layer at the convex portion of the antiglare antireflection film and the average thickness of the antireflection layer at 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 as follows. The antireflection layer in the concave portion 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, the surface of the antiglare antireflection film should be observed because it may be difficult to obtain in the same manner as described below in <When the antireflection layer is not a motheye layer>. By counting the number of particles in the antireflection layer in a region having 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 thickness of the antireflection layer.
For example, when an antireflection layer is formed by applying an antireflection layer-forming composition containing particles on the antiglare layer, the convex and concave portions of the antiglare layer are formed by leveling the coating liquid (antireflection layer forming composition). As a result, the coating amount becomes uneven and the number of particles is sparse and dense (that is, the number of particles in the convex portion decreases (becomes a sparse portion) and the number of particles increases in the concave portion (becomes a dense portion)). Therefore, in this case, the sparse part can be considered as a convex part, and the dense part can be considered as a concave part, and (the number of particles in the sparse part / the number of particles in the dense part) is (reflective part of the convex part). The thickness of the anti-reflection layer / the thickness of the anti-reflection layer in the concave portion).
In addition, when the antireflection layer is formed on the antiglare layer by transfer, the density of the particles hardly occurs in the antireflection layer. Therefore, in this case, the randomly selected portions are regarded as convex portions and concave portions, and the number of each particle is counted, and can be considered as (film thickness of the antireflection layer of the convex portion / film thickness of the antireflection layer of the concave portion). .
Specifically, the measurement value calculated from the following method can be used as the average thickness of the antireflection layer at the convex portion of the antiglare antireflection film and the average thickness of the antireflection layer at the concave portion. That is, the surface SEM observation at low magnification determines the dense and sparse parts of the particles, 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 expanded. Count. If there is no dense part and sparse part in the above method (the dense part and the sparse part are indistinguishable and are uniform throughout), the randomly selected field of view is the same as the convex part and concave part. Measurements shall be conducted. The average value of the antireflective layer in the convex part of the antiglare antireflection film / the average thickness of the antireflective layer in the concave part can be obtained by averaging the measured values of 10 times and taking the ratio.
Determining dense and sparse parts of particles by surface SEM observation at low magnification will be described in more detail with reference to the drawings.
Fig.1 (a) is an example of the surface SEM image of the glare-proof antireflection film at the time of forming an antireflection layer by application | coating. In this case, as shown in FIG. 1A, the dense and sparse parts of the particles are apparent at a glance. The number of particles present in a 10 μm × 10 μm square area is counted for the dense and sparse parts of the particles thus determined. FIG. 1B is an enlarged view of FIG. When the size of the sparse part is smaller than 10 μm × 10 μm square, an area smaller than the size of the sparse part can be designated and the number of particles in the area 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 an enlargement of FIG. 2A. . In this case, the dense and sparse parts of the particles cannot be distinguished and are uniform throughout. Accordingly, the number of particles is counted in the same manner as described above, with the randomly selected portions as convex portions and concave portions.

<When the antireflection layer is not a moth-eye layer>
When the antireflection layer is not a moth-eye layer, the average thickness of the antireflection layer at the convex portion and the average thickness of the antireflection layer at the concave portion of the antiglare antireflection film can be calculated by the following methods. That is, by observing with an optical microscope or the like, the convex part of the antiglare layer is marked with a scribing pen or the like, and the cross section cut to include the marked part (marking part) is an optical microscope or a scanning electron microscope (SEM). ) Etc., the film thickness of the antireflection layer is calculated. Here, the convex portion is the thickness of the thinnest portion of the antireflection layer near the marking portion, and the concave portion is the thickest portion of the antireflection layer in the cross section, and the average thickness is 10 times. Use the average value of the measurement.

The average thickness of the antireflection layer at the convex portions of the antiglare antireflection film / the average thickness of the antireflection layer at the concave portions is preferably 1.0 to 0.7, and preferably 1.0 to 0.9. Preferably, 1.0 is most preferable. As the ratio is closer to 1.0, an antiglare antireflection film having better reflectance and haze characteristics can be obtained.

(Moth eye layer)
As a specific example of a preferred 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 of the particles on the surface opposite to the interface with the antiglare layer. An antireflection layer (moth eye layer) may be mentioned.
Here, the moth-eye structure is a processed surface of a substance (material) for suppressing light reflection, and refers to a structure having a periodic fine structure pattern. In particular, for the purpose of suppressing the reflection of visible light, it refers to a structure having a fine structure pattern with a period of less than 780 nm. It is preferable that the period of the fine structure pattern is less than 380 nm because the color of the reflected light is eliminated. A period of 100 nm or more is preferable because light with a wavelength of 380 nm can recognize a fine structure pattern and is excellent in antireflection properties. 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 the fine structure pattern is formed.
The material used for the moth-eye layer and the production conditions will be described later in the manufacturing method section in association with the process.

(Other antireflection 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”) that is not a moth-eye layer.
Examples of the other antireflection layer include an antireflection layer including a low refractive index layer. A low refractive index layer is a layer whose refractive index (refractive index of wavelength 500nm) is lower than a base film.

The low refractive index layer is preferably a fluorine-containing compound that is cured by heat or ionizing radiation. Examples of curable fluorine-containing polymer compounds include perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane) and the like, as well as addition of fluorine-containing monomers and crosslinkable groups. And a fluorine-containing copolymer having a monomer as a constituent unit.
Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc. ), (Meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical Co., Ltd.), M-2020 (manufactured by Daikin)), 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 a 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, etc. ) Acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.).

Further, not only a polymer having the above-mentioned fluorine-containing monomer as a structural unit but also a copolymer with a monomer not containing a fluorine atom may be used. There are no particular limitations on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ethers), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Krilo can be exemplified nitrile derivatives, disclosed by Japanese Patent Laid-Open 10-25388 and JP-10-147739 JP.

The antireflection layer preferably further 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 the base film. The high refractive index layer is formed by applying a coating composition containing inorganic fine particles having a high refractive index, a thermal or ionizing radiation curable monomer, an initiator and a solvent, drying the solvent, curing by heat and / or ionizing radiation. The The inorganic fine particles are preferably made of at least one metal oxide selected from oxides of Ti, Zr, In, Zn, Sn, and Sb. The thus formed high refractive index layer is superior in scratch resistance and adhesion as compared with a layer obtained by applying and drying a polymer solution having a high refractive index. In order to ensure dispersion stability, film strength after curing, etc., it contains a polyfunctional (meth) acrylate monomer and an anionic group as described in JP-A No. 11-153703 and Patent No. US6210858 B1 It is preferable that a (meth) acrylate dispersant is contained in the coating composition.

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

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.
In the case where the antiglare antireflection film has a middle refractive index layer, a high refractive index layer, and a low refractive index layer in this order, the middle 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 following formula (II) and the low refractive index layer satisfies the following formula (III).
In the case where the antiglare antireflection film has a high refractive index layer and a low refractive index layer in this order, the high refractive index layer has the following formula (II) with respect to the design wavelength λ (= 500 nm). It is preferable that the refractive index layer satisfies the following formula (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)
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 highly refractive. The refractive index of the refractive index layer, and d2 is the layer thickness (nm) of the high refractive index layer, n is 1, n3 is the refractive index of the low refractive index layer, and d3 is the low refractive index. The layer thickness (nm) of the layer.
In the case where the antiglare antireflection film has a middle refractive index layer, a high refractive index layer, and a low refractive index layer in this order, n1 is relative to the base film having a refractive index of 1.45 to 1.55. It is preferable that the refractive index is 1.60 to 1.65, n2 is 1.85 to 1.95, and n3 is 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 1.5 with respect to the base film having a refractive index of 1.45 to 1.55. 95 and n3 preferably have a refractive index of 1.35 to 1.45.

[Base film]
The base film in the antiglare antireflection film of the present invention can be variously used, but is preferably a plastic base film, for example, a cellulose resin; cellulose acylate (triacetate cellulose, diacetyl cellulose, acetate (Butyrate cellulose) and the like, polyester resins; polyethylene terephthalate and the like, (meth) acrylic resins, polyurethane resins, polycarbonates, polystyrenes, olefinic resins and the like, and cellulose acylate, polyethylene terephthalate, A base material containing a (meth) acrylic resin is preferred, and a base material containing cellulose acylate is more preferred. As the cellulose acylate, the base material described in JP 2012-093723 A can be preferably used.
The thickness of the base film is usually about 10 μm to 1000 μm, but is preferably 20 μm to 200 μm, more preferably 25 μm to 100 μm from the viewpoint of good handleability, high transparency, and sufficient strength. preferable. As the transparency of the base film, those having a transmittance of 90% or more are preferable.

[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 has been 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.
Although it does not specifically limit as an adhesive agent which forms a contact bonding layer, In addition to a polyvinyl alcohol-type adhesive agent, an epoxy-type active energy ray hardening-type adhesive agent, an acrylate type ultraviolet curing adhesive agent, etc. can be used. For example, an adhesive that contains an epoxy compound that does not contain an aromatic ring in the molecule and is cured by heating or irradiation with active energy rays, as disclosed in JP-A-2004-245925, disclosed in JP-A-2008-174667 In a total amount of 100 parts by weight of the (meth) acrylic compound, (a) a (meth) acrylic compound having two or more (meth) acryloyl groups in the molecule, and (b) a hydroxyl group in the molecule, polymerization And an active energy ray-curable adhesive containing a (meth) acrylic compound having only one ionic double bond and (c) phenolethylene oxide-modified acrylate or nonylphenolethylene oxide-modified acrylate. When the antireflection layer is the moth-eye layer, it is preferable to use a (meth) acrylate-based UV curable adhesive from the viewpoint of adhesion between the antiglare layer and the moth-eye layer, and moreover, a polyfunctional (meth) acrylate is used. The acrylate ultraviolet rays contained 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 still more preferably 0.01 to 0.6 μm. A thinner adhesive layer is preferable because an antiglare antireflection film having excellent antiglare properties can be obtained without impairing the antiglare properties of the antiglare film.

(Surface shape of antiglare antireflection film)
The antiglare antireflection film of the present invention has an uneven shape on the surface on the antireflection layer side, the uneven shape has an arithmetic average roughness (Ra) of 0.03 μm ≦ Ra ≦ 0.4 μm, and The average interval (Sm) of the irregularities is 20 μm ≦ Sm ≦ 700 μm.
Here, the arithmetic average roughness (Ra) and the average interval (Sm) of the unevenness are measured based on JIS B-0601 (1994).
Arithmetic average roughness (Ra) and average interval (Sm) of surface irregularities are measured using a measuring instrument according to JIS B-0601 (1994), for example, a surf coder MODEL SE-3F manufactured by Kosaka Laboratory. can do.
In addition, uneven | corrugated shaped Ra and Sm measured by the said measurement are uneven | corrugated shapes resulting from an anti-glare layer. Even when the antiglare antireflection film has a moth-eye layer on the antiglare layer, the fine uneven shape of the moth-eye layer does not affect the measurement.

The arithmetic average roughness (Ra) is 0.03 μm ≦ Ra ≦ 0.4 μm, and 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 capable of obtaining good antiglare properties, and when it is 0.4 μm or less, an uneven structure having an appropriate haze value is easily obtained. Therefore, it is preferable. When the thickness is 0.1 μm or more, an antiglare antireflection film having high antiglare properties is obtained, which is preferable. Furthermore, when the thickness is 0.1 μm or more, the reflectance when the antireflection layer is formed by coating is likely to increase, so that the merit of the method of forming the antireflection layer by the transfer of the present invention can be greatly obtained. Further, when the value of Sm is 20 μm or more, the antireflection layer easily follows the unevenness of the antiglare layer when the antireflection layer is transferred, and is preferably 700 μm or less from the viewpoint of securing the antiglare performance.

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

<Process I>
The method for producing an antiglare antireflection film of the present invention comprises applying a composition for forming an antiglare layer containing a binder resin forming compound for an antiglare layer and particles for the antiglare layer on a base film, and ionizing radiation. It has the process of hardening the said composition for glare-proof layer formation by irradiation or a heating, and forming the glare-proof layer, ie, the process of forming the glare-proof film which has the said base film and the said glare-proof layer.

The base film is as described above.

(Anti-glare layer forming composition)
The composition for forming an antiglare layer contains a binder resin forming compound for an 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.
It is preferable that the composition for forming an antiglare layer further contains a solvent. The solvent varies depending on the components constituting the substrate film, but in the case of a cellulose acylate substrate, for example, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), dimethyl carbonate, methyl acetate, acetone, methylene chloride and the like are preferable. Methyl ethyl ketone (MEK), dimethyl carbonate, and methyl acetate are more preferable.
In the case of an acrylic substrate, 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 for these anti-glare 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 an antiglare layer contained in the composition for forming an antiglare layer is a photopolymerizable compound, it is preferable to include a photopolymerization initiator.
As photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, Examples include fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, and coumarins. Specific examples, preferred embodiments, commercially available products, and the like of the photopolymerization initiator are described in paragraphs <0133> to <0151> of JP-A-2009-098658, and can be suitably used in the present invention as well. it can.

“Latest UV Curing Technology” {Technical Information Association, Inc.} (1991), p. 159, and “UV Curing System” written by Kiyomi Kato (published by the General Technology Center in 1989), p. Various examples are also described in 65 to 148 and are useful in 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 point is excessively increased. The amount is preferably set to a sufficiently small amount so that it is preferably 0.5 to 8% by mass, more preferably 1 to 5% by mass with respect to the total solid content in the composition for forming an antiglare layer.

The application method of the composition for forming an antiglare layer is not particularly limited, and a known method can be used. Examples include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and die coating.

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

The ionizing radiation species in the formation of the antiglare layer of the present invention are 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, X-rays and the like can be selected as appropriate, but ultraviolet rays and electron beams are preferred, and ultraviolet rays are particularly preferred because they are easy to handle and high energy can be easily obtained.

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

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

The heating may be combined with the heating at the time of solvent drying in the above-described composition for forming an antiglare layer, or may be heated separately from the heating at the time of solvent drying. Although suitable heating conditions vary depending on the type of substrate film to be used, 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 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 further preferably 20% to 60%.
When the surface curing rate of the antiglare layer before lamination of the antireflection layer is 60% or less, the adhesion between the antireflection layer and the antiglare layer becomes good, and when it is 20% or more, pressure is applied to the antiglare layer. This is preferable because deformation and layer breakage when added can be prevented.
In addition, it is suitable for an anti-glare layer to improve physical performances, such as abrasion resistance, by hardening | curing completely after transferring the antireflection layer mentioned later.

The surface cure rate was determined by measuring the peak (1660-1800 cm ⁻¹ ) area of the carbonyl group and the peak height (808 cm ⁻¹ ) of the double bond for each of the uncured product and the cured product by IR measurement. 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 the antiglare layer is formed and before the antireflection layer is formed, the surface of the antiglare layer may be subjected to surface treatment, 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 or the like. The glow discharge treatment here may be low-temperature plasma that occurs under a low pressure gas of 10 ⁻³ to 20 Torr, and plasma treatment under atmospheric pressure is also preferred. A plasma-excitable gas is a gas that is plasma-excited under the above conditions, and includes chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane, and mixtures thereof. It is done. Details of these are described in detail in pages 30 to 32 of the Invention Association Public Technical Bulletin No. 2001-1745 (issued March 15, 2001, Invention Association), and are preferably used in the present invention. be able to.
Of these treatments, plasma treatment and corona treatment are preferred.

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

[Corona discharge treatment]
Corona discharge treatment can be performed by any conventionally known method, for example, Japanese Patent Publication Nos. 48-5043, 47-51905, Japanese Patent Publication Nos. 47-28067, 49-83767, and 51-41770. This can be achieved by the methods disclosed in JP-A-51-131576, JP-A-2001-272503, and the like.

<Step II>
The method for producing an antiglare antireflection film of the present invention comprises applying an antireflection forming composition on a temporary support, and semi-curing it at a surface curing rate of 10 to 70% by irradiation with ionizing radiation or heating. Forming a step.

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

(Antireflection layer forming composition)
The composition for forming an antireflection layer contains a compound for forming a binder resin 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 the polymerizable functional group (polymerizable group) is preferably a light, electron beam, or radiation-polymerizable one, and particularly, photopolymerization. A functional group is preferred.
Examples of the photopolymerizable functional group include polymerizable unsaturated groups (carbon-carbon unsaturated double bond groups) such as (meth) acryloyl group, vinyl group, styryl group, and allyl group. ) An acryloyl group is preferred. Specific examples are the same as those described for the moth-eye layer described later.
As the solvent contained in the composition for forming an antireflection layer, methyl ethyl ketone (MEK), dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, acetone, cyclopentanone, cyclohexanone methyl acetate, ethyl acetate, butyl acetate, ethanol, methanol, Isopropyl alcohol is preferred, and each solvent may be used alone or in combination of two or more.
The composition for forming an antireflection layer may contain a polymerization initiator, and specific examples and preferred examples of the polymerization initiator are the same as those for the composition for forming an antiglare layer.

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

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

The method for applying the composition for forming an antireflection layer is the same as the method for applying the composition for forming an antiglare layer.

The preferable conditions of ionizing radiation irradiation or heating are preferably an ionizing radiation dose 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, it is 0.01% or less, and most preferably 0.005% or less.
The heating condition is 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 transferring to the antiglare layer (surface hardening rate of the surface of the antireflection layer opposite to the side having the temporary support) is 10 to 70%, 20 to 60%. It is more preferable that 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 to prevent the antireflection ability from being lowered, and the surface hardening rate is 70% or less. Thereby, the adhesiveness of an anti-glare layer and an antireflection layer can be kept favorable. When the surface curing rate is 20 to 60%, the adhesion between the antiglare layer and the antireflection layer can be kept better, and the effect of improving the scratch resistance is great.

The surface curing rate can be calculated by the same measurement method as the surface curing 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, an antireflection layer with an increased film thickness for surface hardening rate measurement is prepared and the same measurement is performed. The calculated surface hardening rate can be used as the surface hardening rate for convenience.

<Step III>
The manufacturing method of the anti-glare antireflection film of the present invention includes a step of transferring the anti-reflection layer from the temporary support to the surface opposite to the side having the base film of the anti-glare layer.

After attaching the antireflection layer and the surface of the antiglare layer on the side opposite to the side having the base film with a nip roller, etc., after passing through the process of adhering both together, the temporary support is removed to prevent reflection. The layer is transferred to the surface opposite to the side having the base film of the antiglare layer. As a method for bringing the antireflection layer and the surface of the antiglare layer opposite to the side having the base film into close contact, a compound having a polymerizable functional group contained in both is made of light, an electron beam, or Polymerization with radiation or the like or heat is preferred, and photopolymerization is most preferred.

<Other processes>
In the method for producing an antiglare antireflection film of the present invention, before transferring the antireflection layer from the temporary support onto the antiglare layer, a step of providing an adhesive layer on the antiglare layer or on the antireflection layer. It is also preferable to have it. The adhesive layer is as described above. The irradiation dose when curing the adhesive layer with the ionizing radiation dose is preferably 50 mJ / cm ² or more, more preferably 100 to 2000 mJ / cm ^2. The oxygen concentration at the time of ionizing radiation irradiation is preferably 0.00. 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 adhesion and permeability of the antireflection layer or the antiglare layer.

As another aspect, the method for producing an antiglare and antireflection film of the present invention preferably includes a step of heating in a state where the antireflection layer and the antiglare layer are bonded together. By providing such a process, the adhesion between the antireflection layer and the antiglare layer can be improved. About the temperature and time of a heating, it can adjust suitably according to an antireflection layer or a glare-proof layer.

(Production method of antiglare antireflection film in which the antireflection layer is a moth-eye layer)
A moth-eye layer can be mentioned as a preferred 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,
On the temporary support, particles (a2) having an average primary particle size of 100 nm or more and 250 nm or less and the curable compound (a1) are mixed with the particles (a2) in the layer (a) containing the curable compound (a1). A step (1) of providing the thickness to be buried
A step (2) of obtaining a layer (ca) by curing a part of the layer (a);
A step (3) of bonding the layer (b) of the pressure-sensitive adhesive film having a support and a layer (b) containing a pressure-sensitive adhesive on the support to the layer (ca);
The layer (ca) is embedded such that the particles (a2) are embedded in the layer including the layer (ca) and the layer (b) and protrude from the interface of the layer (ca) on the support side. Step (4) of bringing the position of the interface on the support side closer to the temporary support side,
A step (5) of peeling the temporary support,
A 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 including 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 formed by combining the layer (ca) and the layer (b);
Step (8) of peeling the adhesive film;
In this order.

Between the step (4) and the step (5), the particles (a2) are embedded in a layer combining the layer (ca) and the layer (b). It is preferable to have a step (4-2) of partially curing.

In the method for producing an antiglare and antireflection film of the present invention, after the step (8), the particles (a2) are separated from the interface on the side opposite to the base film side of the layer (ca). A step (9) of curing the layer (ca) in a protruding state;
Cleaning with solvent (10)
Are more preferable in this order.

In the present invention, “the thickness at 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 diameter of the particles (a2). .
In the present invention, “the particle (a2) is buried in the layer including the layer (ca) and the layer (b)” means that the thickness of the layer including the layer (ca) and the layer (b) is combined. Represents 0.8 times or more the average primary particle size of the particles (a2).

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

FIG. 3 shows a schematic diagram of an example of steps (1) to (5).
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 to 250 nm are placed on the temporary support in the layer (a) containing the curable compound (a1). In this step, the particles (a2) are provided in such a thickness that they are buried.
As described above, in the present invention, the “thickness in which the particles (a2) are buried in the layer (a)” represents a thickness that is 0.8 times or more the average primary particle diameter of the particles (a2). .

In step (1), the method for providing the layer (a) on the temporary support is not particularly limited, but it is preferable to provide the layer (a) on the temporary support. In this case, the layer (a) is a layer formed by applying a composition for forming a layer (a) containing the curable compound (a1) and particles (a2) having an average primary particle size of 100 nm to 250 nm. . That is, the composition for forming a layer (a) corresponds to the above-described composition for forming an antireflection layer. A coating method is not particularly limited, and a known method can be used. Examples include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and die coating.

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 a direction perpendicular to the surface of the layer (a). Here, the fact that a plurality of particles (a2) do not exist in the direction perpendicular to the surface of the layer (a) is that 10 μm × 10 μm in the plane of the layer (a) was observed with three fields of view with a scanning electron microscope (SEM). In this case, the ratio of the number of particles (a2) that are not overlapped in the direction orthogonal to the surface is 80% or more, preferably 95% or more.

(Temporary support)
The temporary support is not particularly limited as long as the support has a smooth surface. The temporary support preferably has a surface flatness with a surface roughness of about 30 nm or less, and does not interfere with the application of the composition for forming the layer (a). Temporary supports made of various materials are used. For example, a polyethylene terephthalate (PET) film or a cycloolefin-based 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-Technology) under the measurement conditions of measurement range 5 μm × 5 μm, measurement mode: DFM, measurement frequency: 2 Hz.

(Layer (a))
The layer (a) is a layer containing a curable compound (a1) and particles (a2) having an average primary particle size of 100 nm to 250 nm.
The curable compound (a1) contained in the layer (a) can be a resin (binder resin) in the antireflection layer by being cured. That is, the curable compound (a1) is a kind of binder compound. The curable compound (a1) corresponds to the above-described 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 a binder resin in the finished antiglare antireflection film. It is a particle that forms 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 diameter of the particles (a2). It is more preferable that it is 0.9 times or more and 1.2 times or less.

<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 the polymerizable functional group (polymerizable group) is preferably a light, electron beam, or radiation-polymerizable one, and particularly, photopolymerization. A functional group is preferred.
Examples of the photopolymerizable functional group include polymerizable unsaturated groups (carbon-carbon unsaturated double bond groups) such as (meth) acryloyl group, vinyl group, styryl group, and allyl group. ) An acryloyl group is 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, propylene glycol di (meth) acrylate;
(Meth) 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;
(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxydiethoxy) phenyl} propane, 2-2bis {4- (acryloxypolypropoxy) phenyl} propane And the like.

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

Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, at least one polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferably contained.
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 Propane tri (meth) acrylate, EO-modified phosphate tri (meth) acrylate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-chlorohexa Tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate and caprolactone-modified tris (acryloyloxyethyl) isocyanurate.

Specific examples of the 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 from Osaka Organic Chemical Industry Co., Ltd. Examples include esterified products of polyols such as # 400, V # 36095D, V # 1000, V # 1080, and (meth) acrylic acid. Purple light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7630B, UV-7640B UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310EA, UV-3310B, UV-3500BA UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2250EA (manufactured by Nippon Synthetic Chemical Co., Ltd.), UA-306H, UA-306I, UA-306T, UL-503L (Kyoeisha Chemical Co., Ltd.), Unidic 17-806, 17-813, V-4030, V-4000BA (Dainippon Ink Chemical Co., Ltd.), 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 Shin-Nakamura Chemical Co., Ltd.), Hicorp AU-2010, AU-2020 (manufactured by Tokushi Co., Ltd.), Aronix M-1960 (manufactured by Toa Gosei Co., Ltd.), Art Resin UN-3320HA, UN-3320HC, UN-3320HS, UN-904, HDP-4T, etc. The above urethane acrylate compounds, Aronix M-8100, M-8030, M-9050 (manufactured by Toagosei Co., Ltd., KRM-8307 (Da Such as a cell-Cytec Co., Ltd.) three or more functional groups of the polyester compound, such as may also be suitably used.

Furthermore, resins having three or more polymerizable functional groups, such as relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, Also included are oligomers or prepolymers such as polyfunctional compounds such as polyhydric alcohols.

Further, 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. Gazette can also be used.

From the viewpoint of imparting light resistance, it is also preferable to use, as the curable compound (a1), an oligomer or prepolymer having a Si—O bond as a main skeleton and having a polymerizable functional group. The general formula R ¹ _x An oligomer composed of a compound having one or more Si atoms and one or more C atoms in the molecule and having a polymerizable group, represented by —Si (OR ² ) _4-x . A compound having a Si—O bond as a main skeleton has little absorption of visible light to UV light, and is particularly excellent in blue light resistance. Specific examples include a cage silsesquioxane compound containing a polymerizable group described in JP 2011-84672 A, or JP 2017-8148 A and JP 6219250 A. Examples thereof include polyorganosilsesquioxane 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 to bond the particles (a2) and the curable compound (a1) to form a strong film. A silane coupling agent having a polymerizable functional group may be used.
Specific examples of the silane coupling agent having a polymerizable functional group include, for example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropyl. Dimethylmethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltri Examples include ethoxysilane, 4- (meth) acryloxybutyltrimethoxysilane, 4- (meth) acryloxybutyltriethoxysilane, and the like. Specifically, silane coupling agents X-12-1048, X-12-1049, X-12 described in KBM-503, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), and JP-A-2014-123091. -1050 (manufactured by Shin-Etsu Chemical Co., Ltd.), and compound C3 represented by the following structural formula.

Furthermore, a silane coupling agent having a polymerizable functional group other than a radical reactive group may be used as a compound that functions to suppress aggregation of the particles (a2). 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, KBM-4803 (and above, Shin-Etsu Chemical). Kogyo Co., Ltd.).

In addition, as described above, when the antireflection layer has a moth-eye structure and imparts excellent light resistance, the use of the silane coupling agent having the polymerizable functional group described above may cause a binder component ratio having a Si—O bond. It is also preferable from the point of increasing.

Two or more kinds of compounds having a polymerizable functional group may be used in combination. The polymerization of the compound having a polymerizable functional group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical 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, a compound having 2 or less polymerizable functional groups in one molecule may be used as the curable compound (a1), and in particular, it has 3 or more polymerizable functional groups in one molecule. It is preferable to use a compound and a compound having no polymerizable functional group as a compound other than the compound having two or less polymerizable functional groups in one molecule or the curable compound (a1).
As a compound having 2 or less polymerizable functional groups in one molecule, or a 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, the 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, a compound having 2 or less polymerizable functional groups in one molecule or a 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 having such a viscosity range is preferable because it easily penetrates into the layer containing the pressure-sensitive adhesive, functions to suppress aggregation of the particles (a2), and can suppress haze and cloudiness.

The compound having 2 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, or 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) ( 2-butoxyethyl) (viscosity 10.8 mPas), dimethyl suberate (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 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
Three (4.6 mm x 15 cm) are connected and used.
[Column temperature] 25 ° C
[Sample concentration] 0.1% by mass
[Flow rate] 0.35 ml / min
[Calibration curve] TSK standard polystyrene manufactured by TOSOH Mw = 2800000-1050 calibration curves with 7 samples are used.

The coating amount of the curable compound (a1) contained in the layer (a) is preferably 100 mg / m ² to 800 mg / m ^2, more preferably 100 mg / m ² to 600 mg / m ² , and 100 mg / m ² to 400 mg. / M ² is most preferred.
Moreover, when using together the sclerosing | hardenable compound (a1) and the compound which does not have a polymerizable functional group, it is preferable that these total coating amounts are the said range.

<Particles (a2) having an average primary particle size of 100 nm to 250 nm>
The particles (a2) having an average primary particle size of 100 nm to 250 nm are also referred to as “particles (a2)”.
Examples of the particles (a2) include metal oxide particles, resin particles, organic-inorganic hybrid particles having a metal oxide particle core 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, antimony pentoxide particles, and the like. Silica particles are preferred.
Examples of the resin particles include polymethyl methacrylate particles, polystyrene particles, and melamine particles.

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

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

The shape of the particle (a2) is most preferably spherical, but there is no problem even if it is other than a spherical shape such as an indefinite shape.
The particles (a2) may be solid particles or hollow particles, but are preferably solid particles.
The silica particles may be either crystalline or amorphous.

As the particles (a2), it is preferable to use inorganic fine particles which have been surface-treated for improving dispersibility in the coating liquid, improving film strength, and preventing aggregation. Specific examples of the surface treatment method and preferred 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 properties with the curable compound (a1) as the binder component and improving the film strength, the compound having a functional group having reactivity with the unsaturated double bond and the particle surface on the particle surface It is preferable to modify the surface with, so as to impart an unsaturated double bond to the particle surface. As the compound used for the surface modification, the silane coupling agent having a polymerizable functional group described above as the curable compound (a1) can be suitably 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 Shokubai Co., Ltd.), Eposter S (average primary particle size 200 nm, Japan (Melamine / formaldehyde condensate manufactured by Catalyst Co., Ltd.), Eposta MA-MX100W (average primary particle size 175 nm, polymethyl methacrylate (PMMA) cross-linked product manufactured by Nippon Shokubai Co., Ltd.), Staphyroid (manufactured by Aika Industries Co., Ltd.) Multilayer structured organic fine particles), Ganzpearl (polymethyl methacrylate, polystyrene particles manufactured by Aika Industry Co., Ltd.) and the like can be preferably used.

The particle (a2) is particularly preferably a calcined silica particle because the surface has a moderately large amount of hydroxyl groups and is a hard particle.
The calcined silica particles are manufactured by a known technique in which silica particles are obtained by hydrolyzing and condensing a hydrolyzable silicon compound in an organic solvent containing water and a catalyst, and then the silica particles are calcined. For example, Japanese Patent Application Laid-Open Nos. 2003-176121 and 2008-137854 can be referred to.
Although it does not specifically limit as a raw material silicon compound which manufactures a burning silica particle, Chlorosilanes, such as tetrachlorosilane, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylvinyldichlorosilane, trimethylchlorosilane, methyldiphenylchlorosilane Compound: Tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, 3-glycidoxypropyltrimethoxysilane, 3-chloro Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, Alkoxysilane compounds such as diphenyldimethoxysilane, diphenyldiethoxysilane, dimethoxydiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane; tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane Acyloxysilane compounds such as trimethylacetoxysilane; dimethylsilanediol, diphenylsilanediol, tri Silanol compounds such as chill silanol; and the like. Of the above-exemplified silane compounds, the alkoxysilane compound is particularly preferred because it is more easily available and the resulting fired silica particles do not contain halogen atoms as impurities. As a preferred form of the calcined silica particles according to the present invention, it is preferred that the halogen atom content 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, a large number of convex parts of the moth-eye structure can be formed, so that the antireflection property is more likely to be improved.

It is possible to make the unevenness of the moth-eye structure uniform by containing only one type of monodispersed silica fine particles having an average primary particle diameter of 100 nm or more and 250 nm or less and a degree of dispersion (CV value) of less than 5%. This is preferable because the reflectance is further lowered. The CV value is usually measured using a laser diffraction particle size measuring device, but other particle size measurement 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. Thus, the particle size distribution can be obtained and calculated. 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 compound having no polymerizable functional group, a solvent, a polymerization initiator, particles ( It may contain a dispersing agent, leveling agent, antifouling agent and the like of a2).

<Solvent>
A solvent having a polarity similar to that of the particles (a2) is preferably selected from the viewpoint of improving dispersibility. Specifically, for example, when the particles (a2) are metal oxide particles, an alcohol solvent is preferable, and examples thereof include methanol, ethanol, 2-propanol, 1-propanol, and butanol. For example, when the particles (a2) are metal resin particles having a hydrophobic surface modified, solvents such as ketones, esters, carbonates, alkanes and aromatics are preferred, such as methyl ethyl ketone (MEK) and dimethyl carbonate. , Methyl acetate, acetone, methylene chloride, cyclohexanone and the like. These solvents may be used in a mixture of a plurality of types as long as the dispersibility is not significantly deteriorated.

<Dispersant of particle (a2)>
The dispersant for the particles (a2) can facilitate the uniform arrangement of the particles (a2) by reducing the cohesive force between the particles. The dispersant is not particularly limited, but is preferably an anionic compound such as a sulfate or phosphate, a cationic compound such as an aliphatic amine salt or a quaternary ammonium salt, a nonionic compound or a polymer compound. And a steric repulsion group are more preferred because they have a high degree of freedom in selection. A commercial item can also be used as a dispersing agent. 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-Terra 203, Anti-Terra 204, Anti-Terra 205 (trade name) and the like.

<Leveling agent>
A leveling agent can make the liquid after application | coating stable by making the surface tension of the composition for layer (a) formation fall, and can make it easy to arrange | position a sclerosing | hardenable compound (a1) and particle | grains (a2) uniformly. 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). Preferably, the content is 0.01 to 2.0% by mass.

<Anti-fouling agent>
The antifouling agent can suppress adhesion of dirt or fingerprints by imparting water and oil repellency to the moth-eye structure. For example, compounds described in JP 2012-88699 A 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). The content is most preferably 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.
As photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, Examples include fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, and coumarins. Specific examples, preferred embodiments, commercially available products, and the like of the photopolymerization initiator are described in paragraphs <0133> to <0151> of JP-A-2009-098658, and can be suitably used in the present invention as well. it can.

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

The layer (a) includes a compound that generates an acid or a base by light or heat in order to react with the silane coupling agent having a polymerizable functional group described above (hereinafter, photoacid generator, photobase generator, thermal acid. May be referred to as a generator or a thermal base generator).

<Photo acid generator>
Examples of the photoacid generator include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, onium salts such as arsonium salts, organic halogen compounds, organic metal / organic halides, and o-nitrobenzyl type. Examples thereof include photoacid generators having a protecting group, compounds such as iminosulfonate, which generate photosulfonic acid by photolysis, disulfone compounds, diazoketosulfone, and diazodisulfone compounds. Further, triazines (for example, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds, oximes Mention may also be made of sulfonate compounds.
Further, a group that generates an acid by light, or a compound in which a compound is introduced into the main chain or side chain of a polymer can be used.
Furthermore, V. N. R. Pillai, Synthesis, (1), 1 (1980), A.M. Abad et al. Tetrahedron Lett. , (47) 4555 (1971), D.M. H. R. Barton et al. , J .; Chem. Soc. , (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent No. 126,712, and the like, compounds that generate an acid by light can also be used.

<Heat acid generator>
Examples of the thermal acid generator include salts composed of an acid and an organic base.
Examples of the acid 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), organic acids are more preferable, sulfonic acids and phosphonic acids are more preferable, and sulfonic acids are most preferable. Preferred sulfonic acids include p-toluenesulfonic acid (PTS), benzenesulfonic acid (BS), p-dodecylbenzenesulfonic acid (DBS), p-chlorobenzenesulfonic acid (CBS), 1,4-naphthalenedisulfonic acid (NDS). ), Methanesulfonic acid (MsOH), nonafluorobutane-1-sulfonic acid (NFBS), and the like.

As specific examples 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) a salt of an organic acid and a base that is decomposed by decarboxylation upon irradiation with ultraviolet light, visible light, or infrared light, and (2) an amine that is decomposed by an intramolecular nucleophilic substitution reaction or rearrangement reaction. A compound that releases a base, or (3) a compound that causes a chemical reaction upon 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 2010-243773 A can be suitably used.

The content of the compound that generates acid or base by light or heat in the layer (a) is sufficient to polymerize the polymerizable compound contained in the layer (a), and the starting point increases. For the reason that it is set so that it is not too much, it is preferably 0.1 to 8% by mass, more preferably 0.1 to 5% by mass, based on the total solid content in the layer (a).

[Step (2)]
The step (2) is a step of obtaining a layer (ca) by curing a part of the layer (a) in the step (1). Specifically, the curability in the layer (a) in the step (1). In this step, a part of the compound (a1) is cured to obtain a layer (ca) containing the cured compound (a1c).
By hardening a part of the curable compound (a1) in the step (2), the particles (a2) can be made difficult to move and aggregation of the particles (a2) can be suppressed.
Curing a part of the curable compound (a1) means that only a part of the curable compound (a1) is cured, not the whole. Only a part of the curable compound (a1) is cured in the step (2), and a part of the uncured curable compound (a1) is penetrated into the temporary support in the step (4) (the temporary support has a functional layer). If it has, the layer (ca) may be thinned by the method of allowing it to penetrate into the functional layer) or the method of penetrating into the layer (b), etc., and the particles (a2) are separated from the layer (ca) on the support side. By projecting from the interface, a favorable uneven shape (moth eye structure) can be formed.

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 to apply a composition obtained by removing the particles (a2) from the composition for forming the layer (a) on the temporary support in a thickness of 2 μm. When cured, the curing rate is preferably 2 to 20%, more preferably the curing rate is 3 to 15%, and the curing rate is 5 to 12%. More preferably, the conditions are satisfied.

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

In the step (2), it is preferable to irradiate ultraviolet rays at a dose of 1 to 90 mJ / cm ² , more preferably at a dose of 1.2 to 40 mJ / cm ² , and more preferably 1.5 to 10 mJ / cm 2. It is more preferable to irradiate with a dose of ² . Since the optimum value of the dose varies depending on the composition of the layer (a) forming composition, it can be appropriately adjusted.

In the step (2), it is preferable for manufacturing suitability to irradiate ultraviolet rays from the side opposite to the temporary support side of the layer (a) to cure a part of the curable compound (a1).

The step (2) is preferably performed in an environment with an oxygen concentration of 0.1 to 5.0% by volume, and the step (2) is more preferably performed in an environment with an oxygen concentration of 0.5 to 1.0% by volume. . By making oxygen concentration into the said range, the area | region by the side of the temporary support body of a layer (a) can be hardened especially.

The compound (a1c) is a cured product of the curable compound (a1).
The molecular weight of the compound (a1c) is not particularly limited. Moreover, the compound (a1c) may have an unreacted polymerizable functional group.
The layer (ca) obtained in the step (2) is a layer containing a curable compound (a1) and a 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). The components contained in each layer after curing and the composition thereof (such as the composition ratio of the curable compound (a1) and the cured compound (a1c)) are different, but in the present invention, the layer ( It shall be called ca).

[Step (3)]
Step (3) is a step of bonding a layer (b) of an adhesive film having a support and a layer (b) containing an adhesive on the support to the layer (ca).
A method for bonding the layer (ca) and the layer (b) of the pressure-sensitive adhesive film is not particularly limited, and a known method can be used, for example, a laminating method.
The adhesive film is preferably bonded so that the layer (ca) and the layer (b) are in contact with each other.
You may have the process of drying a layer (ca) before a process (3). In the case of having a step of drying the layer (ca), the drying temperature of the layer (ca) is preferably 20 to 60 ° C, more preferably 20 to 40 ° C. The drying time is preferably from 0.1 to 120 seconds, more preferably from 1 to 30 seconds.

In the present invention, the layer (b) and the layer (ca) of the pressure-sensitive adhesive film are bonded together in the step (3), the particles (a2) are combined in the step (4) described later, and the layers (ca) and (b) are combined. In the step (4-2), the particles (a2) are preferably embedded in the layer (ca) and the layer (b) by being embedded in the layer and protruding from the support side interface of the layer (ca). By further curing a part of the layer (ca) in a state of being embedded in the combined layer, the particles (a2) are prevented from being exposed to the air interface before the layer (ca) is cured, thereby suppressing aggregation. A favorable 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 an adhesive, and the adhesive is preferably an adhesive having a gel fraction of 95.0% or more.
When the pressure-sensitive adhesive has a gel fraction of 95.0% or more, in the production of the antiglare antireflection film of the present invention, the adhesive component is applied to the antiglare antireflection film surface when the adhesive film is peeled off. It is difficult to remain, and the effect of suppressing an increase in reflectance caused by the pressure-sensitive adhesive component filling between the irregularities of the particles is high.
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%. More preferably, it is as follows.
The gel fraction of the pressure-sensitive adhesive is a ratio of insoluble matter after the pressure-sensitive adhesive is immersed in tetrahydrofuran (THF) at 25 ° C. for 12 hours, and is obtained from the following formula.
Gel fraction = (mass of insoluble matter in adhesive in THF) / (total mass of adhesive) × 100 (%)

The weight average molecular weight of the sol component in the pressure-sensitive adhesive is preferably 10,000 or less, more preferably 7000 or less, and most preferably 5000 or less. By making the weight average molecular weight of the sol component within the above range, in the production of the antiglare antireflection film of the present invention, the adhesive component is less likely to remain on the antiglare antireflection film surface when peeling the adhesive film. be able to.
The sol component of the pressure-sensitive adhesive represents the amount dissolved in THF after the pressure-sensitive adhesive is immersed in tetrahydrofuran (THF) at 25 ° C. for 12 hours. The weight average molecular weight can be analyzed by gel permeation chromatography (GPC).

It is also preferable that the storage elastic modulus (G ′) at 30 ° C. and 1 Hz of the pressure-sensitive adhesive 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.
It is also preferable that the storage elastic modulus (G ′) at 30 ° C. and 1 Hz of the pressure-sensitive adhesive is 1.3 × 10 ⁵ Pa 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, 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, cohesive failure of the pressure-sensitive adhesive hardly occurs and handling is easy. When the storage elastic modulus is 1.3 × 10 ⁵ Pa or less, the pressure-sensitive adhesive easily enters the gaps between the particles, so that the effect of suppressing the aggregation of the particles is easily obtained, and is 1.2 × 10 ⁵ Pa or less. When it exists, the anti-glare antireflection film which has a particularly favorable reflectance will be obtained.
In this case, the preferred range of the weight average molecular weight of the sol component in the pressure-sensitive adhesive is the same as described above.

The film thickness of the layer (b) is preferably from 0.1 μm to 50 μm, more preferably from 1 μm to 30 μm, and still more preferably from 1 μm to 20 μm.

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

Examples of (meth) acrylic acid alkyl ester monomers having 1 to 18 carbon atoms in the alkyl group 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, isocetyl (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) Examples include alkyl (meth) acrylate monomers such as acrylate. The alkyl group of the alkyl (meth) acrylate monomer may be linear, branched or cyclic. Two or more of the above 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. May be. In this case, the other copolymerizable monomers include 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 group. And 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, 6- Hydroxyl-containing (meth) acrylic esters such as hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate, and N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl Examples include hydroxyl group-containing (meth) acrylamides such as (meth) acrylamide, and preferably at least one selected from these compound groups.

It is preferable to contain 0.1 to 15 parts by mass of a copolymerizable vinyl monomer containing a hydroxyl group 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, carboxypentyl (meth) acrylate, and the like. Preferably, at least one selected from these compound groups is used.

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

Examples of copolymerizable vinyl monomers containing amino groups include monoalkylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoalkylaminopropyl (meth) acrylate, and other monoalkyl An aminoalkyl (meth) acrylate etc. are mentioned.

Examples of aromatic monomers include styrene in addition to aromatic group-containing (meth) acrylic esters such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.

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 include 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 polymer and a cross-linking agent, and may be cross-linked using heat, ultraviolet light (UV) or the like. As the crosslinking agent, one or more kinds of crosslinking agents selected from the group consisting of a bifunctional or higher functional isocyanate crosslinking agent, a bifunctional or higher epoxy crosslinking agent, and an aluminum chelate crosslinking agent are preferable. When a crosslinking agent is used, in the production of the antiglare antireflection film of the present invention, when peeling the adhesive film, from the viewpoint of making the adhesive component less likely to remain on the antireflection film surface, 100 parts by mass of the polymer. Is preferably contained in an amount of 0.1 to 15 parts by mass, more preferably 3.5 to 15 parts by mass, even more preferably more than 3.5 parts by mass and less than 15 parts by mass. It is particularly preferable to contain part by mass.

The bifunctional or higher isocyanate compound may be a polyisocyanate compound having at least two isocyanate (NCO) groups in one molecule, such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diene. Burette modified products of diisocyanates such as isocyanate (compounds having two NCO groups in one molecule) and trivalent or higher polyols such as isocyanurate modified products, trimethylolpropane or glycerin (at least 3 in one molecule) And adduct bodies (polyol-modified bodies) with the above-mentioned compounds having an OH group.
Further, the trifunctional or higher functional isocyanate compound is a polyisocyanate compound having at least three isocyanate (NCO) groups in one molecule, in particular, an isocyanurate body of a hexamethylene diisocyanate compound, an isocyanurate body of an isophorone diisocyanate compound, At least one selected from the group consisting of adducts of hexamethylene diisocyanate compounds, adducts of isophorone diisocyanate compounds, burettes of hexamethylene diisocyanate compounds, and burettes of isophorone diisocyanate compounds is preferred.
The bifunctional or higher functional isocyanate-based crosslinking 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 that is a quaternary onium salt include alkyldimethylbenzylammonium salts having an alkyl group having 8 to 18 carbon atoms, dialkylmethylbenzylammonium salts having an alkyl group having 8 to 18 carbon atoms, and 8 to 8 carbon atoms. Trialkylbenzylammonium salt having 18 alkyl groups, tetraalkylammonium salt having an alkyl group having 8 to 18 carbon atoms, alkyldimethylbenzylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, alkyl having 8 to 18 carbon atoms Having 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 Alkyl trimethyl Ammonium salts, alkyl dimethyl ethyl ammonium salt having an alkyl group having 14 to 20 carbon atoms 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, fine metal particles, conductive polymers, carbon, carbon nanotubes, etc. be able to.

Examples of the alkali metal salt include metal salts 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 aid.
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 can further contain a crosslinking accelerator. The crosslinking accelerator may be any substance that functions as a catalyst for the reaction between the polymer and the crosslinking agent (crosslinking reaction) when a polyisocyanate compound is used as the crosslinking agent, and is an amine compound such as a tertiary amine. And organic metal compounds such as metal chelate compounds, organic tin compounds, organic lead compounds, and organic zinc compounds. In the present invention, a metal chelate compound or an organic tin compound is preferable as the crosslinking accelerator.

The crosslinking 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.

The layered product after step (3) is completed has 3 or more cross-linking groups in one molecule on the surface of layer (ca) side of layer (b), the cross-linking group equivalent is 450 or less, and fluorine or silicone. It is preferable that a slipping agent having a low friction site (hereinafter also referred to as “slippery a”) is present.
When the adhesive (a) is present on the surface of the layer (b) on the layer (ca) side, in the production of the antiglare antireflection film of the present invention, the layer ( It is possible to effectively prevent the pressure sensitive adhesive in (b) from remaining (transferred) on the surface of the antiglare antireflection film.

<Support>
The support in an adhesive film is demonstrated.
As the support, a plastic film made of a resin having transparency and flexibility is preferably used. The plastic film for the support is preferably a polyester film such as polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, polybutylene terephthalate, (meth) acrylic resin, polycarbonate resin, polystyrene resin, polyolefin resin. Examples thereof include films made of a resin, a cyclic polyolefin resin, a cellulose 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 necessary strength and optical suitability. The support may be an unstretched film, may be uniaxially or biaxially stretched, and may be a plastic film in which the stretching ratio or the angle of the axial method formed with crystallization of stretching is controlled.

As the support, those having ultraviolet transparency are preferable. Having ultraviolet ray permeability is preferable from the viewpoint of production suitability because ultraviolet rays can be irradiated from the support side when the layer (ca) is cured in the steps (4-2) and (7).
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. It is preferable that the maximum transmittance at a wavelength of 250 nm to 300 nm is 20% or more because the layer (ca) is easily cured by irradiating ultraviolet rays from the support side.
Further, the maximum transmittance at a wavelength of 250 nm to 300 nm of the pressure-sensitive adhesive film having the layer (b) formed on the support is preferably 20% or more, more preferably 40% or more, and 60% or more. Is most preferred.

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.

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

In the steps (4-2) and (7), the layer (ca) is cured while maintaining the state in which the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b). In the stage before 4-2) (that is, after completion of step (4)), it is preferable that the particles (a2) protrude from the interface on the support side of the layer (ca). In this way, after the layer (ca) is cured in the step (7), the layer (b) is peeled off in the step (8). Thus, an antiglare antireflection film having a moth-eye structure formed by projecting the particles (a2) from the surface opposite to the interface) can be obtained.
In order to make the particles (a2) protrude from the interface on the support side of the layer (ca) in the step before the step (4-2), in the step (4), the curable compound (a1) It is preferred to partially penetrate the layer (b).

[Step (4)]
In the step (4), the layer (ca) is formed so that the particles (a2) are buried in the layer including 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 on the support side (interface between the layer (ca) and the layer (b)) closer to the temporary support side.
In other words, “the particles (a2) are buried in the combined layer (ca) and layer (b) and project from the interface on the support side of the layer (ca)”. "The particles (a2) are not exposed from the combined layer (ca) and layer (b), and are present across both layers (ca) and (b) ( It can also be said that the particles (a2) exist across the interface between the layer (ca) and the layer (b)).
The step (4) is preferably performed by allowing a part of the curable compound (a1) to penetrate into the layer (b).
In the step (4), when a part of the curable compound (a1) is allowed to penetrate into the layer (b), it is preferable to keep the laminate after the completion of the step (3) at less than 60 ° C. It is more preferable to keep. By keeping the temperature at 40 ° C. or lower, the viscosity 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. The effect of preventing a decrease in antireflection ability due to aggregation of the particles (a2) and an increase in haze or cloudiness is great. The lower limit of the temperature at which the laminate is maintained is not particularly limited, and may be room temperature (25 ° C.) or 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). In this step, 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.
Curing a part of the layer (ca) represents curing only a part of the curable compound (a1) and the compound (a1c) in the layer (ca). Thereby, the binder resin in the antireflection layer of the antiglare antireflection film can be formed. Further, by leaving the uncured curable compound (a1) in the layer (ca) after completion of the step (4-2), in the step (6) described later, the layer (ca), the base film, The antiglare film having the antiglare layer can be bonded or adhered to the antiglare layer.
By maintaining the state in which the particles (a2) are buried in the layer (ca) and the layer (b) in the step (4-2), the aggregation of the particles (a2) is suppressed and a moth-eye structure is formed. can do.
In addition, after providing the layer (b), the state in which the particles (a2) are buried in the combined layer (ca) and the layer (b) by volatilization of the components of the layer (b) or the layer (ca). If it cannot be maintained, an operation such as thickening the layer (b) in advance can be performed.
As a mechanism in which particle aggregation is suppressed by maintaining the state in which the particle (a2) is embedded in the layer (ca) and the layer (b), the particle (a2) is 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 works, and the particles (a2) are buried in the layer combining the layers (ca) and (b). It is presumed that the attractive force can be reduced by letting it be kept.

Curing in the step (4-2) can be performed by irradiating with ionizing radiation. There is no restriction | limiting in particular about the kind of ionizing radiation, Although an X-ray, an electron beam, an ultraviolet-ray, visible light, infrared rays etc. are mentioned, an ultraviolet-ray is used widely. For example, if the coating film is UV curable, to cure a portion of an irradiation dose of ^{10mJ / cm 2 ~ 1000mJ / cm} 2 by an ultraviolet lamps layer (ca) curable compound in (a1) Is preferred. When the irradiation amount of ultraviolet rays is 10 mJ / cm ² or more, the adhesion between the layer (b) and the part containing the particles (a2) and the layer (ca) is moderately strengthened, and the temporary support is removed (5 ), The particles (a2) and the layer (ca) hardly remain on the temporary support, and defects (regions in which the reflectance does not decrease) hardly occur in the resulting antiglare antireflection film. In addition, 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 excessively, and the step (6 ), An appropriate adhesive force between the layer (ca) and the antiglare layer in the antiglare film can be obtained. The amount of irradiation in the step (4-2) is not particularly limited, and the adhesion between the layer (b) to be used and the part containing the particles (a2) and the layer (ca), and the layer (ca) and the antiglare layer It can adjust suitably in consideration of adhesive force. At the time of irradiation, the above-mentioned energy may be applied at once, or irradiation may be performed in divided portions. As the ultraviolet lamp type, a metal halide lamp or a high-pressure mercury lamp is preferably used.

The oxygen concentration at the time of curing in 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 most preferred. By making the oxygen concentration at the time of curing smaller than 1.0% by volume, it becomes difficult to be affected by the inhibition of curing by oxygen and becomes a strong film.

In the 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, the layer (ca) side of the support and May be irradiated with ultraviolet rays from the opposite side, or may be irradiated with ultraviolet rays from the temporary support side.

[Step (5)]
Step (5) is a step of peeling the temporary support from the laminate after completion of step (4) or (4-2).
In order to be able to peel the temporary support from the laminate after completion of the step (4) or (4-2), an appropriate adhesive force is applied between the layer (ca) and the temporary support. It is preferable that the portion including the layer (ca) and the particles (a2) can be transferred to the adhesive film. For example, the layer containing the layer (ca) and the particles (a2) is not detached from the temporary support by bending or conveying tension of the laminate during the manufacturing process, but when contacting the layer (b) or the layer (b It is preferable that the portion including the layer (ca) and the particles (a2) is detached when being irradiated with ultraviolet rays.

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

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

Further, in the steps (4), (4-2), and (5), the thickness of the layer (ca) is preferably 5 to 70% of the average primary particle diameter of the particles (a2), and 20 to 40 % Is more preferable. When the film thickness of the layer (ca) is 5% or more of the average primary particle diameter of the particles (a2), the pressure-sensitive adhesive film is peeled off in the step (8) described later, and the layer (ca) and the particles (a2) are included. The particles (a2) are less likely to fall off from the antiglare antireflection film obtained after the portion is transferred to the antiglare layer in the antiglare film, which is preferable. Moreover, when the film thickness of the layer (ca) is 70% or less of the average primary particle diameter of the particles (a2), the refractive index is sufficiently inclined, and sufficient antireflection performance is obtained. It is preferable that the film thickness of the layer (ca) is 20 to 40% of the average primary particle diameter of the particles (a2) since sufficient scratch resistance and antireflection ability can be achieved at the same time. The same applies to steps (6) to (10) described later.
The film thickness of the layer (ca) after completion of the step (5) is obtained by observing the film cross section of the layer (ca) with a scanning electron microscope (SEM), arbitrarily measuring the film thickness at 100 locations, and averaging When the value is obtained, it is preferably adjusted to be 10 nm to 100 nm (more preferably 20 nm to 90 nm, still more preferably 30 nm to 70 nm).

It is preferable that the particles (a2) do not protrude from the surface opposite to the layer (b) side of the layer (ca) in the laminate obtained by completing the step (5).
30 nm or less is preferable and, as for the surface roughness of the surface on the opposite side to the layer (b) side of the layer (ca) in the laminated body obtained by completing a process (5), 10 nm or less is more preferable.
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. However, it is transferred when the adhesive film is peeled off in the step (8) to be 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 to cause defects in the antireflection layer after transfer. Moreover, when the surface roughness of the surface of the layer (ca) opposite to the layer (b) side is 10 nm or less, it is favorable 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 (part containing particles (a2) and layer (ca)) and 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-Technology) under the measurement conditions of measurement range 5 μm × 5 μm, measurement mode: DFM, measurement frequency: 2 Hz.

The part containing the particles (a2) and the layer (ca) in the laminate obtained by completing the step (5) can be peeled from the layer (b) of the adhesive film.
That the part containing the particles (a2) and the layer (ca) can be separated from the layer (b) of the adhesive film means that the part containing the particles (a2) and the layer (ca) and the layer (b) of the adhesive film In the anti-glare film, the portion including the particles (a2) and the layer (ca) is detached from the surface of the layer (b) in the transfer step (step (8)) to be described later by applying an appropriate adhesive force. It shows that it can be transferred to the surface of the antiglare layer. The portion including the particles (a2) and the layer (ca) (antireflection layer) can be transferred to the surface of the antiglare layer, that is, has transferability, the transfer surface (antireflection layer) of the antiglare antireflection film after transfer. When the black polyethylene terephthalate sheet with adhesive (manufactured by Yodogawa Paper; “Kikkiri Mieru”) is attached to the opposite side to the opposite side, the reflectance is higher than before the antireflection layer is transferred. It represents that the area ratio of the region where is lowered is 80% or more with respect to the area to be transferred. The adhesive force between the layer (b) and the part including the particle (a2) and the layer (ca) is not particularly limited. For example, particles of a transfer member having a width of 25 mm (a laminate obtained by completing the step (5)) The part including (a2) and the layer (ca) is fixed to a glass substrate having a thickness of 1.1 mm using an adhesive, and the part including the particle (a2) and the layer (ca) and the layer (b) are oriented in a 90 ° direction. Can be measured by the peeling force when peeled at a speed of 1000 mm / min. The peel force measured by the above method is preferably 0.2 N / 25 mm to 4.0 N / 25 mm, more preferably 0.6 N / 25 mm to 4.0 N / 25 mm. When the peeling force is 0.6 N / 25 mm or more, part of the particles (a2) and the layer (ca) hardly remain on the temporary support when the temporary support is peeled off in the step (5). The reflectance and haze of the antiglare antireflection film finally obtained are lowered. 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) hardly remains in the layer (b). The reflectance and haze of the antiglare antireflection film are reduced.

The layered product obtained by completing step (5) is a value obtained by subtracting the haze of the part obtained by removing the part containing particles (a2) and layer (ca) from the layered product from the total haze of the layered product (Δ haze). ) Is preferably 1.00% or less.
The haze can be measured according to JIS-K7136 (2000) with a haze meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd. at 25 ° C. and 60% relative humidity at a film sample of 40 mm × 80 mm.
Δhaze 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 Δhaze to 1.00% or less, the haze of the antiglare antireflection film obtained using the laminate obtained by completing the step (5) is lowered, and good antireflection performance is obtained. Is possible. Especially when Δhaze is 0.40% or less, black polyethylene with pressure-sensitive adhesive is provided on the side opposite to the transfer surface of the antiglare antireflection film obtained by using the laminate obtained by completing step (5). Even when bonded to a terephthalate sheet (manufactured by Yodogawa Paper Mill; “Kikkiri 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 curing rate is 10% or more, a part of the antireflection layer (that is, the portion including the layer (ca) and the particles (a2)) is deformed at the time of transfer, and the antireflection ability is reduced. It is possible to prevent this, and when the surface curing rate is 70% or less, the adhesion between the antiglare layer and the antireflection layer can be kept good.

[Step (6)]
Step (6) is a step of bonding the layer (ca) in the laminate obtained by completing step (5) and the antiglare layer of the antiglare film.
The method for laminating the layer (ca) and the antiglare layer is not particularly limited, and a known method can be used, for example, a roll laminating method.
The antiglare film is preferably bonded so that the layer (ca) and the antiglare layer are in contact with each other.

In the present invention, the step (6) preferably 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.

In the present invention, in step (6), it is also preferable to provide a heating step after laminating the layer (ca) in the laminate obtained by completing 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 and 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). Specifically, the step (7) ) In which a part or all of the compound selected from the group consisting of the curable compound (a1) and the compound (a1c) is cured. It should be noted that the curing of 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 cured when cured by a normal method. This includes the case where the compound remains. Although it does not specifically limit about the hardening rate in a process (7), From a viewpoint of film | membrane strength, it is preferable that a hardening rate is 60% or more, and it is more preferable that it is 80% or more.
By the step (7), the antiglare layer and the layer (ca) in the antiglare film bonded in the step (6) can be adhered.

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

[Step (8)]
Step (8) is a step of peeling the adhesive film from the laminate obtained in step (7).
In order to peel off the pressure-sensitive adhesive film in the step (8), an index of the adhesive force between the layer (b) and the part containing the particles (a2) and the layer (ca) in the laminate obtained by completing the step (5). As above, it is preferable that the peeling force measured by the above measurement method is 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 a concavo-convex shape formed by particles (a2) on the surface of the layer (ca) is obtained. ) And (10) may be performed.

[Step (9)]
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 base film side interface of the layer (ca). Specifically, In this step, the curable compound (a1) and the compound (a1c) in the layer (ca) are all cured. In the case where the curable compound (a1) and the compound (a1c) in the layer (ca) are all cured in the step (7), the step (9) may not be performed.

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

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

[Step (10)]
Step (10) is a step of washing the laminate after completion of step (9) with a solvent.
In the production of the antiglare antireflection film of the present invention, the adhesive is unlikely to remain on the layer (ca) side even when the support and the layer (b) are peeled off. You may wash | clean using the solvent (Methyl isobutyl ketone, methyl ethyl ketone, acetone, etc.) which melt | dissolves an adhesive, without melt | dissolving an anti-glare layer and a layer (ca).

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

Prior to bonding with the polarizer, the antiglare antireflection film of the present invention can be saponified. The saponification treatment is a treatment in which an antiglare antireflection film is immersed in a heated alkaline aqueous solution for a certain time, washed with water, and then washed with acid for neutralization. In the antiglare antireflection film of the present invention, any treatment conditions may be used as long as the surface of the substrate film to be bonded to the polarizing film is hydrophilized, so the concentration of the treatment agent, the temperature of the treatment solution, the treatment Although the time is appropriately determined, the processing conditions are determined so that processing can be performed within 3 minutes from the need to ensure normal productivity. As general conditions, 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 preferable as the alkali species used for the alkali treatment, sulfuric acid is preferable as the acid used for the acid cleaning, and ion-exchanged water or pure water is preferable as the water used for the water cleaning.
The surface of the base film opposite to the side on which the antireflection layer is provided is saponified and bonded to a polarizer using a polyvinyl alcohol aqueous solution.

Further, an ultraviolet curable adhesive may 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 preferably used for the purpose of improving productivity by drying for a short time. It is preferable to use and attach to a polarizer. For example, Japanese Patent Application Laid-Open No. 2012-144690 discloses that each homopolymer has a Tg of 60 ° C. or more, a radically polymerizable compound (SP) having a SP (Solubility Parameter) value of 29 to 32, and an SP value of 18 to Adhesive properties are bonded to a polarizer through an adhesive layer containing 10 to 30% by mass of a 21 radical polymerizable compound and 20 to 60% by mass of a radical polymerizable compound having an SP value of 21 to 23. Improves durability and water resistance. 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 polarizer and at least one protective film for protecting the polarizer, and at least one of the protective films is the antiglare antireflection film of the present invention. The polarizer may be sandwiched between films other than the protective film (the antiglare antireflection film of the present invention) and the antiglare antireflection film of the present invention, or may be a combination of a protective film and a polarizer.
The film other than the antiglare antireflection film of the present invention is preferably an optical compensation film having an optical compensation layer comprising an optically anisotropic layer. The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen. As the optical compensation film, known ones can be used, but the optical compensation film described in JP-A-2001-100042 is preferable from the viewpoint of widening the viewing angle.

Polarizers include iodine-based polarizing films, dye-based polarizing films using dichroic dyes, and polyene-based polarizing films. The iodine-based polarizing film and the dye-based polarizing film can be generally produced using a polyvinyl alcohol 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 image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), and cathode ray tube display devices (CRT). A liquid crystal display device is particularly preferable.
In general, a liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates. Furthermore, one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and both polarizing plates. The liquid crystal cell is preferably a TN mode, a VA (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane Switching) mode, or an ECB (Electrically Controlled Birefringence) mode.

The anti-glare antireflection film and polarizing plate of the present invention are high-contrast self-luminous displays, specifically organic electroluminescence (OLED) displays, LED array displays, fields, which are next-generation image display devices. It can also be used for an emission display. 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 a self-luminous display, reflection of external light can be suppressed. 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 the liquid crystal display device, and the number of optical films existing up to the outermost surface tends to be small. Durability is essential. In particular, high durability against high-energy blue light is required. Among the antiglare antireflection films of the present invention, in the antiglare antireflection film having a moth-eye structure using silica particles, in order to further improve the durability against blue light, the binder resin forming the antireflection layer is used. Average silicon content = Si / C is preferably 0.01 or more, more preferably 0.05 or more, and further preferably 0.08 or more. In addition, content rate Si / C represents the molar ratio of the silicon and carbon in binder resin, for example by measuring a silicon content rate (Si) and a carbon atom content rate (C) using an XPS surface analyzer. Can be sought.

In order to describe the present invention in detail, examples will be described below, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

<Preparation of coating solution for forming antiglare layer>
Each component was added with the composition described below, and the resulting composition was put into a mixing tank, stirred, filtered through a polypropylene filter having a pore size of 30 μm, and coating solutions BO-1 to BO— for forming an antiglare layer. It was set to 8.

(Anti-glare layer forming coating solution BO-1)
PET-30 57.0 parts M-321 34.0 parts Irgacure 127 3.0 parts SSX-108 4.5 parts CAB 1.4 parts SP-13 0.1 parts methyl ethyl ketone (MEK) 30 0.0 part by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Anti-glare layer forming coating solution BO-2)
PET-30 49.0 parts by weight M-321 29.5 parts by weight Irgacure 127 3.0 parts by weight SSX-108 17.0 parts by weight CAB 1.4 parts by weight SP-13 0.1 parts by weight Methyl ethyl ketone (MEK) 30 0.0 part by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Anti-glare layer forming coating solution BO-3)
PET-30 49.0 parts by weight M-321 29.5 parts by weight Irgacure 819 3.0 parts by weight SSX-108 17.0 parts by weight CAB 1.4 parts by weight SP-13 0.1 parts by weight Methyl ethyl ketone (MEK) 30 0.0 part by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Anti-glare layer forming coating solution BO-4)
PET-30 49.0 parts M-321 29.5 parts by weight Irgacure 127 3.0 parts by weight SSX-108 17.0 parts by weight CAB 1.4 parts by weight Copolymer (A-16) 0.1 parts by weight Methyl ethyl ketone (MEK) 30.0 parts by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Anti-glare layer coating solution BO-5)
PET-30 49.0 parts by weight M-321 29.5 parts by weight Irgacure 127 3.0 parts by weight SSX-108 17.0 parts by weight CAB 1.4 parts by weight Copolymer (A-7) 0.02 parts by weight 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

(Anti-glare layer forming coating solution BO-6)
PET-30 57.0 parts M-321 34.0 parts Irgacure 127 3.0 parts SSX-108 0.1 parts CAB 1.4 parts SP-13 0.1 parts methyl ethyl ketone (MEK) 30 0.0 part by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Anti-glare layer forming coating solution BO-7)
PET-30 57.0 parts M-321 34.0 parts Irgacure 127 3.0 parts SSX-108 40.0 parts CAB 1.4 parts SP-13 0.1 parts methyl ethyl ketone (MEK) 30 0.0 part by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

(Anti-glare layer forming coating solution BO-8)
PET-30 57.0 parts M-321 34.0 parts Irgacure 127 3.0 parts SSX-108 0.01 parts CAB 1.4 parts SP-13 0.1 parts methyl ethyl ketone (MEK) 30 0.0 part by mass Methyl isobutyl ketone (MiBK) 70.0 parts by mass

The compounds used are shown below.
PET-30: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate [manufactured by Nippon Kayaku Co., Ltd.]
M-321: trimethylolpropane PO-modified (n≈2) triacrylate [manufactured by Toagosei Co., Ltd.]
・ Irgacure 127: Polymerization initiator [manufactured by BASF Japan Ltd.]
・ Irgacure 819: polymerization initiator [manufactured by BASF Japan Ltd.]
SSX-108: Average particle size 8 μm PMMA particles [manufactured by Sekisui Plastics Co., Ltd.]
CAB: cellulose acetate butyrate, CAB531-1 [Eastman Chemical Co., Ltd.]
SP-13: Fluorine-based surface modifier having the following structure (the content ratio of repeating units is a molar ratio)

<Synthesis Example of Copolymer (A-7)>
A 300 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 6.7 g of cyclohexanone and 1.7 g of isopropanol and heated 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, and 2.1 g of acrylic acid (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.) were added dropwise over 150 minutes. It was added dropwise at a constant speed to complete. After completion of the dropwise addition, the temperature was raised to 90 ° C. and stirring was further continued for 4 hours.
Next, 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. The mixture was heated to 0 ° C. and stirred 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 copolymer (A-7) had a weight average molecular weight (Mw) of 60,300 (gel permeation chromatography (EcoSECHLC-8320GPC (manufactured by Tosoh Corp.))), eluent NMP, flow rate 0.50 ml / min. Calculated in terms of polystyrene under the measurement conditions of a temperature of 40 ° C., and the column used was TSKgel SuperAWM-H × 3 (manufactured by Tosoh Corporation). Further, 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 a 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 2- (perfluorohexyl) ethyl acrylate was changed. The copolymer (A-16) had a weight average molecular weight (Mw) of 60,300. Further, 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 a molar ratio.

<Preparation of antiglare film>
(Preparation of antiglare film AG-1)
A cellulose triacetate film (TDP60UL, manufactured by FUJIFILM Corporation) was unwound in a roll form, and coating solution BO-1 for forming an antiglare layer was applied using a coater having a slot die. After coating at a transfer speed of 20 m / min, drying at 40 ° C. for 15 seconds and 90 ° C. for 30 seconds, and then purging with nitrogen to create an atmosphere with an oxygen concentration of 1.4%, 240 W / cm air-cooled metal halide lamp (Made by Eye Graphics Co., Ltd.), the coating layer is cured by irradiating with an irradiation amount of 10 mJ / cm ² and 1 mW / cm ² to form an antiglare layer having an average film thickness of 12.0 μm, AG-1 was produced.

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

(Preparation of antiglare film AG-3)
In the production of AG-2, the ultraviolet irradiation conditions were changed to an oxygen concentration of less than 0.1%, irradiation doses of 600 mJ / cm ² and 150 mW / cm ^2, and the anti-glare layer after ultraviolet irradiation was 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 trade name Solid State Corona Treatment Machine 6KVA model (manufactured by Pillar). At this time, from the current / voltage readings, the processing conditions were 0.375 KV · A · min / m ² , the discharge frequency during processing was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

(Preparation of anti-glare film AG-4)
AG-4 was prepared in the same manner as AG-1, except that the antiglare layer forming coating solution BO-1 was applied instead of the antiglare layer forming coating solution BO-1. .

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

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

(Preparation of antiglare film AG-7)
AG-7 was prepared in the same manner as AG-1, except that the antiglare layer forming coating solution BO-1 was applied instead of the antiglare layer forming coating solution BO-1. .

(Preparation of antiglare film AG-8)
AG-8 was prepared in the same manner as AG-1, except that the antiglare layer forming coating solution BO-1 was applied instead of the antiglare layer forming coating solution BO-1. .

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

(Preparation of antiglare film AG-10)
AG-10 was prepared in the same manner as AG-1, except that the antiglare layer forming coating solution BO-1 was applied instead of the antiglare layer forming coating solution BO-1. .

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

(Preparation of antireflection layer)
[Synthesis of Silica Particle P1]
A 200 L reactor equipped with a stirrer, a dropping device and a thermometer was charged with 67.54 kg of methyl alcohol and 26.33 kg of 28% by mass aqueous ammonia (water and catalyst), and the liquid temperature was kept at 33 ° C. while stirring. Adjusted. Meanwhile, a dropping device was charged with a solution prepared by dissolving 12.70 kg of tetramethoxysilane in 5.59 kg of methyl alcohol. While maintaining the liquid temperature in the reactor at 33 ° C., the above solution was dropped from the dropping device over 44 minutes, and after completion of the dropping, stirring was further performed for 44 minutes while maintaining the liquid temperature at the above temperature. Hydrolysis and condensation of methoxysilane was performed to obtain a dispersion containing a silica particle precursor. This dispersion liquid was air-dried under the conditions of a heating tube temperature of 175 ° C. and a reduced pressure of 200 torr (27 kPa) using an instantaneous vacuum evaporation apparatus (Crax System CVX-8B type manufactured by Hosokawa Micron Corporation), thereby producing silica. Particles P1 were obtained.
Silica particles P1 had an average primary particle size of 170 nm, a particle size dispersity (CV value) of 3.3%, and an indentation hardness of 340 MPa.

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

[Production of Silane Coupling Agent-treated Silica Particles P3]
5 kg of the fired 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 the calcined silica particles P2 were being stirred, a solution prepared by dissolving 45 g of 3-acryloxypropyltrimethoxysilane (KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) in 90 g of methyl alcohol was added dropwise and mixed. Then, it heated up to 150 degreeC over about 1 hour, mixing and stirring, and hold | maintained at 150 degreeC for 12 hours, and heat-processed. In the heat treatment, scrapes on the wall surface were scraped while the scraping device was always rotated in the direction opposite to the stirring blade. Moreover, the wall deposits were also scraped off using a spatula as appropriate. After heating, the mixture was cooled, and pulverization and classification were performed 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]
Silane coupling agent-treated silica particles P3 (50 g), MEK (200 g), 0.05 mm diameter zirconia beads (600 g) 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 for 10 hours at 250 rpm. did. In this way, a silica particle dispersion 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 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 sintered 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 PA-2 (solid content concentration 20% by mass) was produced.

[Synthesis of Compound C3]
In a flask equipped with a reflux condenser and a thermometer, 19.3 g of 3-isocyanatopropyltrimethoxysilane, 3.9 g of glycerol 1,3-bisacrylate, 6.8 g of 2-hydroxyethyl acrylate, 0.1 g of dibutyltin dilaurate 70.0 g of toluene was added and stirred at room temperature for 12 hours. After stirring, 500 ppm of methylhydroquinone 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 with an ultrasonic disperser for 30 minutes to obtain a coating solution.

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

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 weight Silica particle dispersion PA-1 32.3 parts by weight Ethanol 12.7 parts by weight Methyl ethyl ketone 31.8 parts by weight Acetone 12.7 parts by weight

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 parts by weight Silica particle dispersion PA-1 32.3 parts by weight Ethanol 12.7 parts by weight Methyl ethyl ketone 33.2 parts by weight Acetone 12.7 parts by weight

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 parts by mass Silica particle dispersion PA-2 32.3 parts by mass Methyl ethyl ketone 45.9 parts by mass Acetone 12.7 parts by mass

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

The compounds used are shown below.
U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.): urethane acrylate SIRIUS-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd.): dendrimer acrylate Compound I-30: Compound I- described in JP 2011-84672 A 30 (Cage type polysilsesquioxane having a polymerizable group and a non-polymerizable group)
Curable resin C: Curable resin C (epoxy group-containing polyorganosilsesquioxane) described in JP-A-2017-8148
A-TMPT: Multifunctional acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
X-12-1049: Silane coupling agent having a plurality of acroyl groups (manufactured by Shin-Etsu Chemical Co., Ltd.)
KR-513: Silane coupling agent oligomer having acryloyl group / methyl group (manufactured by Shin-Etsu Chemical Co., Ltd.)
KR-516: Epoxy group / methyl group-containing silane coupling agent oligomer (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-4803: Silane coupling agent having reactive groups (epoxy groups) other than radical reactive groups (manufactured by Shin-Etsu Chemical Co., Ltd.)
Acetyltriethyl citrate: manufactured by Tokyo Chemical Industry Co., Ltd. Irgacure 127: photopolymerization initiator (manufactured by BASF Japan)
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 antiglare antireflection film 1>
(Process (1) Coating of layer (a))
On a 100 μm polyethylene terephthalate film (FD100M, FUJIFILM Corporation) as a temporary support, 2.8 ml / m ^{2 of} composition (A-1) was applied using a die coater and dried at 30 ° C. for 90 seconds. It was. Thus, the layer (a) was applied.

(Step (2) Pre-exposure of layer (a))
Using a high pressure mercury lamp (Model: 33351N manufactured by Dr. Honle AG, part number: LAMP-HOZ 200 D24 U 450 E) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.4% by volume (a ) Side was irradiated with light at an irradiation amount of 5.0 mJ / 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 an eye ultraviolet integrated illuminometer UV METER UVPF-A1 manufactured by Eye Graphic Co., Ltd. and measuring range 0.00.

(Process (3) Adhesion of adhesive film)
Next, on the layer (ca), an adhesive film obtained by peeling a release film from a protective film (Mastak TFB AS3-304) manufactured by Fujimori Industry Co., Ltd. is used. It was bonded together so as to be on the ca) side. Lamination was performed using a commercial laminator Bio330 (manufactured by DAE-EL Co.) at a speed of 1.
In addition, the protective film here refers to the laminated body comprised from a support body / adhesive layer / release film, and the laminated body comprised from the support body / adhesive layer which peeled the release film from the protective film. It is an adhesive film.

The protective film used is shown below.
・ Mastak TFB AS3-304 (Fujimori Kogyo Co., Ltd. optical protective film with antistatic function) (hereinafter also referred to as “AS3-304”)
Support: Polyester film (thickness 38 μm)
Adhesive layer thickness: 20 μm
Maximum transmittance at a wavelength of 250 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) penetration of curable compound (a1) into layer (b))
After pasting the adhesive film, it was allowed to stand for 5 minutes in an environment of 25 ° C. to allow the curable compound (a1) to penetrate into the layer (b).

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

(Step (5) Peeling of temporary support Production of laminate)
From the laminate, the temporary support FD100M was peeled off at a speed of 30 m / min in a direction where the peeling angle was 180 °.

(Process (6) Bonding 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 step (5) were bonded together. Lamination was performed using a commercial laminator Bio330 (manufactured by DAE-EL Co.) at a speed of 1. Then, the laminated body bonded together was heated at 140 ° C. for 2 minutes.

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

(Process (8) Peeling of adhesive film)
The pressure-sensitive adhesive film (from which the release film was peeled off from the MASTACK TFB AS3-304) was peeled from the laminate thus produced.

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

(Process (10) Cleaning)
Subsequently, methyl isobutyl ketone was poured over the surface on which the adhesive film had been bonded to wash away the residue of the adhesive layer. Then, it dried for 10 minutes at 25 degreeC, and the anti-glare antireflection film 1 was obtained.

<Preparation of antiglare antireflection films 2 to 10>
In the production of the antiglare antireflection film 1, the antiglare film to be bonded in the step (6) is changed as shown in the following Table 1, and the heating conditions after the step (6) are changed as shown in the following Table 1. Thus, antiglare antireflection films 2 to 10 were produced.

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

The ultraviolet curable adhesive UV1 was prepared by adding each component with the composition described below, and putting the obtained composition into a mixing tank and stirring.
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 are shown below.
4-hydroxybutyl acrylate (manufactured by Nippon 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 antiglare antireflection film 12>
In the production of the antiglare antireflection film 11, an antiglare antireflection film 12 was produced in the same manner except that the ultraviolet curable adhesive was changed to UV2. The antiglare antireflection film 12 has an adhesive layer between the antiglare layer and the antireflection layer.

The ultraviolet curable adhesive UV2 was prepared by adding each component with the composition described below, and putting the obtained composition into a mixing tank and stirring.
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 part by mass

The compounds used are shown below.
Aronix M220: Tripropylene glycol (n≈3) diacrylate (manufactured by Toa Gosei Co., Ltd.)

<Preparation of antiglare antireflection film 13>
On the antiglare film AG-1, the composition (A-1) was applied at 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. While purging with nitrogen so as to obtain an atmosphere, a high pressure mercury lamp (Model: 33351N manufactured by Dr. Honle AG Co., Ltd., part number: LAMP-HOZ 200 D24 U 450 E) was used to emit 5.0 mJ from the layer (a) side. / Cm ² , and irradiation with light at an illuminance of 0.60 mW, 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 an eye ultraviolet integrated illuminometer UV METER UVPF-A1 manufactured by Eye Graphic Co., Ltd. and measuring range 0.00.
Next, on the layer (ca), an adhesive film obtained by peeling a release film from a protective film (Mastak TFB AS3-304) manufactured by Fujimori Industry Co., Ltd. is used. It was bonded together so as to be on the ca) side. Lamination was performed using a commercial laminator Bio330 (manufactured by DAE-EL Co.) at a speed of 1.
After bonding the adhesive film, it was allowed to stand for 5 minutes in an environment of 25 ° C., and the curable compound (a1) was permeated into the layer (b).
Subsequently, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere has an oxygen concentration of 0.01% by volume or less, the support layer (ca) side A part of the layer (ca) was cured by irradiating ultraviolet rays having an illuminance of 150 mW / cm ² and an irradiation amount of 600 mJ / cm ² from the opposite side.
The pressure-sensitive adhesive film (from which the peeling film was peeled off from the MASTACK TFB AS3-304) was peeled off from the produced laminate, and then 160 W / W while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.01% by volume or less. Using an air-cooled metal halide lamp of cm (made by Eye Graphics Co., Ltd.), the layer (ca) was 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 had been bonded to wash away the residue of the adhesive layer, and dried at 25 ° C. for 10 minutes to obtain an antiglare antireflection film 13.

<Preparation of antiglare antireflection film 14>
An antiglare antireflection film 14 was prepared in the same manner as the antiglare antireflection film 13 except that the antiglare film was changed to AG-2.

<Preparation of antiglare antireflection films 15 to 21>
In the production of the antiglare antireflection film 1, the ultraviolet irradiation amount in the step (4-2) is changed as shown in the following Table 1, and the antiglare film bonded in the step (6) is changed as shown in the following Table 1. Thus, antiglare antireflection films 15 to 21 were produced.

<Preparation of antiglare antireflection film 22>
(Preparation of coating solution 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 a photopolymerization initiator (Irgacure 907, manufactured by BASF Japan Ltd.) and photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 04 parts by mass were dissolved. Furthermore, 26.4 parts by mass of 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 stirred at room temperature for 30 minutes. Thereafter, the mixture was filtered through a polypropylene filter (PPE-03) having a pore diameter of 3 μm to prepare a coating solution HN1 for a high refractive index layer.

(Preparation of coating solution for low refractive index layer)
A 6% by mass methyl ethyl ketone solution (JN-7228, manufactured by JSR Corporation) of a heat-crosslinkable fluorine-containing polymer having a refractive index of 1.42 was solvent-substituted, and methyl isobutyl ketone 85% by mass, 2-butanol 15% by mass A polymer solution containing 10% by mass of solid content in a mixed solvent consisting of% was obtained. To 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 concentration of 30% by mass, manufactured by Nissan Chemical Co., Ltd.), and 42 parts by mass of methyl isobutyl ketone And 28 parts by mass of cyclohexanone were added, stirred, and then filtered through a polypropylene filter (PPE-03) having a pore size of 3 μm to prepare a coating solution LN1 for a low refractive index layer.

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

<Preparation of antiglare antireflection film 23>
On the anti-glare film AG-1, 1.8 ml / m ^{2 of the} coating solution HN1 for the high refractive index layer is applied using a die coater and dried at 30 ° C. for 90 seconds, and then the oxygen concentration is 1.0 volume. The amount of irradiation was 90 mJ / cm ² from the coated side using a high-pressure mercury lamp (Model: 33351N manufactured by Dr. Honle AG, Inc., part number: LAMP-HOZ 200 D24 U 450 E) while purging with nitrogen so as to obtain an atmosphere of 50%. The antiglare film B with a high refractive index layer was produced by irradiating light at an illuminance of 20 mW and forming a high refractive index layer on the antiglare film by coating.
On the anti-glare film B with a high refractive index layer, 0.8 ml / m ² of the low refractive index layer coating solution LN1 is applied using a die coater and dried at 30 ° C. for 90 seconds. Irradiation dose from the side coated with a high-pressure mercury lamp (Model: 33351N manufactured by Dr. Honle AG, part number: LAMP-HOZ 200 D24 U 450 E) while purging with nitrogen to an atmosphere of 0.01% by volume or less The antiglare antireflection film 23 was formed 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 antiglare film by coating.

(Adhesive layer thickness)
For anti-glare

antireflection films

11 and 12 provided with an adhesive layer, a cross-section of the film was prepared with a microtome, and the cross-section was observed using a scanning electron microscope S-3400N (manufactured by Hitachi High-Technologies Corporation). When the thickness of the layer was determined, the adhesive layer thickness was 0.4 μm.

(Surface curing rate of antireflection layer)
In the step (6), the surface curing rate of the moth eye layer before being bonded to the antiglare layer of the antiglare film was measured by the following measuring method.
That is, in the preparation method of the antireflection layer described in the preparation of the antiglare antireflection film 1, the composition (A-1) was not changed except that the composition (A-1) was applied on the temporary support so as to have a thickness of 3 μm. The sample which went to the process (5) was produced, and surface IR measurement was performed before transferring to the glare-proof layer of an anti-glare film. From the surface IR measurement, the carbonyl group peak (1660-1800 cm ⁻¹ ) area and double bond peak height (808 cm ⁻¹ ) were determined, and the double bond peak height was divided by the carbonyl group peak area ( (Hereinafter referred to as P101). The same IR measurement was performed on the same sample prepared under the condition not irradiated with ultraviolet rays, and a value (denoted as Q101) obtained by dividing the peak height of the double bond by the carbonyl group peak area was obtained. Used to calculate the surface cure rate.

Formula 1 Surface hardening rate = (1− (P101 / Q101)) × 100 (%)
Table 1 shows the surface hardening rate of the antireflection layer before transferring to the antiglare layer.

<Evaluation of antiglare antireflection film>
Various properties of the antiglare antireflection film were evaluated by the following methods.

(Surface shape Ra, Sm evaluation of antiglare antireflection film)
The surface shape of the produced antiglare antireflection film is based on JIS B-0601 (1994), and the arithmetic average roughness (Ra) and the average interval (Sm) of the surface irregularities are calculated by Surfcorder MODEL manufactured by Kosaka Laboratory. Evaluated by SE-3F. Regarding Sm, the measurement length was 8 mm, and the cut-off value was 0.8 mm.
Note that Ra and Sm of the concavo-convex shape measured by the above measurement are concavo-convex shapes resulting from the antiglare layer, and even when the antiglare antireflection film has a motheye layer on the antiglare layer, The fine uneven shape does not affect the 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 whose 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 10 μm × 10 μm square particles is expanded and counted. did. When the density was not observed at low magnification, the field of view was randomly selected and the same observation was performed. The number of particles in the sparse part / the number of particles in the dense part was calculated, and the average ratio of the 10 measurements was taken for each, and the average thickness unevenness of the antireflection layer (the average thickness of the antireflection layer at the protrusions) / Average thickness of the antireflection layer in the recess).
For the antiglare antireflection films 22 and 23 in which the antireflection layer is not a moth-eye layer, the average thickness of the antireflection layer at the convex portion and the average thickness of the antireflection layer at the concave portion of the antiglare antireflection film are calculated by the following methods. did. That is, when observed with an optical microscope or the like, the convex portion of the antiglare layer is marked with a scribing pen, and the cross section cut to include the marked portion (marking portion) is an optical microscope or a scanning electron microscope (SEM). The film thickness of the antireflection layer is calculated by observing in FIG. Here, the convex portion is the thickness of the thinnest portion of the antireflection layer near the marking portion, and the concave portion is the thickest portion of the antireflection layer in the cross section, and the average thickness is 10 times. The average value of the measurement was used.

(Integral reflectance)
The back side of the anti-glare anti-reflection film (the surface opposite to the anti-glare layer side interface of the base film) is roughened with sandpaper and then treated with black ink to eliminate the back reflection. Attach adapter ARV-474 to V-550 (manufactured by JASCO Corporation), measure the integral reflectance at an incident angle of 5 ° in the wavelength range of 380 to 780 nm, calculate the mean reflectance, and integrate the reflectance Rate.

(Specular reflectance)
Using the film (sample), device, and adapter used in 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 region of 380 nm to 780 nm, and the average reflection was measured. The rate was calculated as the specular reflectance.

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

(Anti-glare)
Laminated with a black polyethylene terephthalate sheet with adhesive ("Mr. Kakiri Mieru") on the opposite side of the base of the anti-glare anti-reflection film to the side where the anti-reflection layer is provided. A sample of 30 cm × 30 cm in which reflection was prevented was produced. An exposed 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 the direction of −45 degrees was evaluated according to the following criteria.
A: The outline of the fluorescent lamp is not understood at all. B: The outline of the fluorescent lamp is slightly understood. C: The fluorescent lamp is blurred, but the outline can be identified. D: The fluorescent lamp is hardly blurred.

(Scratch resistance: integrated reflectivity after scratch resistance test)
After pre-preparing steel wool (grade No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) around the rubbing tip (1 cm × 1 cm) that comes in contact with the rubbing tester surface, the surface of the prepared sample (antireflection layer) The surface was brought into contact with the rubbing part of the tester and rubbed back and forth 10 times 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 conducted. About the obtained sample, the integrated reflectance measurement was performed 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: Reflectivity difference before and after scratch resistance test is more than 1.0% and 1.5% or less E: Reflectance difference before and after scratch resistance test is more than 1.5% In addition, A to D are preferable, A to C are more preferable, and A to B are more preferable.

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 with no unevenness in the average thickness of the concave and convex antireflection layers in the antiglare antireflection film. The integrated reflectance was 1.0% or less and the specular reflectance was 0.4% or less. On the other hand, the

antiglare antireflection films

13 and 14 of Comparative Examples 1 and 2 have large average thickness unevenness of the antireflection layers of the concave and convex portions in the antiglare antireflection film, 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 was not sufficiently antiglare because the uneven shape of the antiglare layer was not in the desired range.
Further, the antiglare antireflection film 23 of Comparative Example 4 has a large average thickness unevenness of the antireflection layer of the concave and convex portions in the antiglare antireflection film, the integrated reflectance exceeds 1.0%, and the specular reflection. 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 performance to a substrate having an uneven shape such as an antiglare layer.

In producing the antiglare antireflection film of Example 10, compositions (A-2), (B-1) and (B-2) were used instead of the composition (A-1), respectively. The antiglare antireflection films of Examples 24, 25, and 26 were prepared in the same manner except for the above.

(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 antireflection films prepared above was measured at an angle of 0 ° under the above-described conditions using an ESCALAB-200R manufactured by VG Scientific as an XPS surface analyzer. (Measurement depth 6 nm), silicon content (Si) and carbon atom content (C) were measured, and Si / C was calculated from the results.

Suppose that it is used for the outermost surface of a self-luminous display, a durability test against blue light was performed.

(Blue durability)
The anti-glare anti-reflection film is placed 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 blue light is applied to the anti-reflection film. Irradiated continuously for 200 hours. Measurement was performed in the same manner as the above-described 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 More than 0.5% and not more than 1.0% D: Reflectance difference is more than 1.0% before and after the durability test. From the practical characteristics, it is preferably A to C, more preferably A to B.

From the results of 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 when irradiated with blue light for a long time. It was found that durability was improved as a dazzling antireflection film, and low reflectance could be maintained.
For Examples 24 to 26, the surface shape (Ra and Sm) of the antiglare antireflection film and the average thickness unevenness of the antireflection layer were the same as those 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 (Antireflection Layer)
DESCRIPTION OF SYMBOLS 11 Base film 12 Anti-glare layer 13 Anti-glare layer particle 14 Anti-glare film 15 Adhesive layer 16 Anti-reflective layer 20 Anti-glare anti-reflective film Ln Low refractive index layer Hn High refractive index layer UV Ultraviolet

Claims

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 antiglare antireflection film surface has an arithmetic average roughness Ra of 0.03 μm ≦ Ra ≦ 0.4 μm, and an average interval Sm of unevenness of 20 μm ≦ Sm ≦ 700 μm,
An antiglare antireflection film, wherein the ratio of the average thickness of the antireflection layer at the convex portion of the antiglare antireflection film to the average thickness of the antireflection layer at the concave portion is 1.0 to 0.7.
2. The antiglare antireflection film according to claim 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.
The antiglare antireflection film according to claim 1 or 2, which has an adhesive layer between the antiglare layer and the antireflection layer.
The antiglare property according to any one of claims 1 to 3, wherein the antiglare layer contains a component having a functional group other than a (meth) acryloyl group capable of forming a covalent bond with the antireflection layer. Antireflection film.
The antireflection layer includes particles having an average primary particle diameter of 100 nm to 250 nm and a binder resin, and has a moth-eye structure of the particles on the surface opposite to the interface with the antiglare layer. The antiglare antireflection film according to any one of the above.
6. The antiglare antireflection film according to claim 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.
A method for producing an antiglare antireflection film having a base film, an antiglare layer, and an antireflection layer in this order,
On the base film, a composition for forming an antiglare layer containing a binder resin forming compound for an antiglare layer and particles for the antiglare layer is applied, and the composition for forming an antiglare layer is irradiated with ionizing radiation or heated. A step of curing the antiglare layer,
Applying a composition for forming an antireflection layer on a temporary support, and semi-curing it at a surface curing rate of 10 to 70% by irradiation with ionizing radiation or heating to form an antireflection layer;
Transferring the antireflection layer from the temporary support onto the antiglare layer;
The manufacturing method of the anti-glare antireflection film which has this.
The antiglare layer 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. For producing antireflective film.
The method for producing an antiglare antireflection film according to claim 7 or 8, comprising a step of heating the antireflection layer and the antiglare layer in a bonded state.
On the temporary support, the particles (a2) having an average primary particle diameter of 100 nm or more and 250 nm or less and the curable compound (a1) are contained in the layer (a) containing the curable compound (a1). A step (1) of providing the thickness to be buried
A step (2) of obtaining a layer (ca) by curing a part of the layer (a);
A step (3) of bonding the layer (b) of the pressure-sensitive adhesive film having a support and a layer (b) containing a pressure-sensitive adhesive on the support to the layer (ca);
The layer (ca) is embedded such that the particles (a2) are buried in the layer including the layer (ca) and the layer (b) and project from the interface of the layer (ca) on the support side. (4) the step of bringing the position of the interface on the support side closer to the temporary support side,
Step (5) of peeling the temporary support,
A 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 including the layer (ca) obtained in the step (5). ,
A step (7) of curing the layer (ca) in a state where the particles (a2) are embedded in a combined layer of the layer (ca) and the layer (b), and the adhesive film is peeled off. Step (8),
The method for producing an antiglare and antireflection film according to any one of claims 7 to 9, wherein
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 apparatus comprising 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 comprising the antiglare antireflection film according to any one of claims 1 to 6 on a surface.