JP6868103B2 - Anti-reflective film, polarizing plate, and image display device - Google Patents

Description

The present invention relates to an antireflection film, a polarizing plate, and an image display device.

Display devices using cathode ray tubes (CRT), plasma display panels (PDPs), electroluminescence displays (ELDs), vacuum fluorescent displays (VFDs), field emission displays (FEDs), and liquid crystal displays (LCDs). The device may be provided with an antireflection film in order to prevent a decrease in contrast due to reflection of external light on the display surface and reflection of an image. In addition, an antireflection function may be provided by an antireflection film other than the image display device such as the glass surface of a showroom.

As the antireflection film, an antireflection film having a fine uneven shape having a period equal to or less than the wavelength of visible light on the surface of the base material, that is, an antireflection film having a so-called moth eye structure is known. The moth-eye structure can prevent light reflection by creating a refractive index gradient layer in which the refractive index changes continuously from air toward the bulk material inside the base material in a pseudo manner.
As an antireflection film having a moth-eye structure, Patent Document 1 describes an antireflection film having an antireflection layer having a moth-eye structure having a concavo-convex shape formed by particles on a base film.
Further, it is known that when a composition for forming a hard coat layer is applied by a coating method, a leveling agent made of a fluorine-based compound or the like is added to the composition.

Japanese Patent Application Laid-Open No. 2017-16605

The present inventors apply a composition for forming an antireflection layer containing metal oxide particles and a curable compound which is a compound for forming a binder resin onto a hard coat layer to form a coating film, and then apply the coating film to the coating film. The pressure-sensitive adhesive layer is laminated to diffuse (penetrate) a part of the curable compound into the pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive layer is peeled off to form an uneven shape formed by metal oxide particles. It has been found that an antireflection layer having a moth-eye structure can be formed.
However, according to the study by the present inventors, when a part of the curable compound in the coating film formed from the antireflection layer forming composition is diffused into the pressure-sensitive adhesive layer, the metal oxide in the coating film is used. It has been found that the movement of particles may reduce the regularity of the particles. This decrease in particle regularity can lead to increased haze.
Patent Document 1 does not describe the decrease in regularity of the particles.

An object of the present invention is an antireflection film having a moth-eye structure having a concavo-convex shape formed by particles, an antireflection film having high particle regularity, a polarizing plate having the antireflection film, and an image display device. To provide.

[1]
An antireflection film having a base film, a hard coat layer, and an antireflection layer in this order.
The antireflection layer contains metal oxide particles and a binder resin, and contains metal oxide particles and a binder resin.
The antireflection layer has a moth-eye structure having an uneven shape formed by the metal oxide particles.
The hard coat layer is a copolymer having a repeating unit represented by the following general formula (I), a repeating unit represented by the following general formula (II), and a repeating unit represented by the following general formula (III). An antireflection film, which is a layer formed from a composition for forming a hard coat layer containing.

In the general formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ² represents an alkyl group having at least one fluorine atom as a substituent, and L represents a divalent linking group. Represent.
In the general formula (II), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are aliphatic hydrocarbon groups which may independently have a hydrogen atom and a substituent, respectively. , An aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R ¹¹ and R ¹² may be linked. X ¹ represents a divalent linking group.
In the general formula (III), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, L ² represents a divalent linking group, and Y ¹ represents a photopolymerizable group.
[2]
The antireflection film according to [1], wherein the repeating unit represented by the general formula (I) is a repeating unit represented by the following general formula (I-2).

In the general formula (I-2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ma and na each independently represent an integer of 1 to 20, and X represents a hydrogen atom or a fluorine atom. ..
[3]
The antireflection film according to [1] or [2], wherein the repeating unit represented by the general formula (II) is a repeating unit represented by the following general formula (II-a).

In the general formula (II-a), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are aliphatic hydrocarbons which may independently have a hydrogen atom and a substituent, respectively. It represents a hydrogen group, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R ¹¹ and R ¹² may be linked. X ¹¹ is - (C = O) O - , - O (C = O) -, - (C = O) NH -, - O -, - CO-, and -CH ₂ - is selected from the group consisting of Represents a divalent linking group composed of at least one. X ¹² is − (C = O) O−, −O (C = O) −, − (C = O) NH−, −O−, −CO−, −NH−, −O (C = O) A divalent containing at least one linking group selected from -NH-, -O (C = O) -O-, and -CH _2- and containing at least one aromatic ring which may have a substituent. Represents the linking group of. However, the total number of carbon atoms of ^{X 11} and X ^{12 is 7 or more.}
[4]
The antireflection film according to any one of [1] to [3], wherein the repeating unit represented by the general formula (III) is a repeating unit represented by the following general formula (III-a).

In the general formula (III-a), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ³¹ and R ³² each independently represent a hydrogen atom or a substituent, and k is an integer of 1 to 10. When k represents an integer of 2 or more, the plurality of R ^31s may be the same or different, and the plurality of R ^32s may be the same or different. R ³³ represents a hydrogen atom or a methyl group.
[5]
The content of the repeating unit represented by the general formula (I) in the copolymer is 5 to 40 mol% with respect to all the repeating units of the copolymer [1] to [4]. The antireflection film according to any one of the above items.
[6]
The content of the repeating unit represented by the general formula (II) in the copolymer is 20 to 60 mol% with respect to all the repeating units of the copolymer [1] to [5]. The antireflection film according to any one of the above items.
[7]
The content of the repeating unit represented by the general formula (III) in the copolymer is 20 to 65 mol% with respect to all the repeating units of the copolymer [1] to [6]. The antireflection film according to any one of the above items.
[8]
The content of the copolymer in the composition for forming a hard coat layer is 0.001 to 20% by mass with respect to the total solid content of the composition for forming a hard coat layer [1] to [7]. ], The antireflection film according to any one of the items.
[9]
The antireflection film according to any one of [1] to [8], wherein the metal oxide particles are silica particles.
[10]
The antireflection film according to any one of [1] to [9], wherein the metal oxide particles have an average primary particle size of 100 to 190 nm.
[11]
The metal oxide particles are particles in which the surface of the metal oxide particles is surface-modified with a compound having a polymerizable unsaturated group and a functional group reactive with the surface of the metal oxide particles [1]. The antireflection film according to any one of [10].
[12]
A polarizing plate having a polarizer and an antireflection film according to any one of [1] to [11].
[13]
An image display device having the antireflection film according to any one of [1] to [11] or the polarizing plate according to [12].

INDUSTRIAL APPLICABILITY The present invention provides an antireflection film having a moth-eye structure having a concavo-convex shape formed by particles, an antireflection film having high particle regularity, a polarizing plate having the antireflection film, and an image display device. be able to.

It is sectional drawing which shows an example of the antireflection film of this invention. It is a schematic diagram for demonstrating an example of the manufacturing method of the antireflection film of this invention.

Hereinafter, the present invention will be described in detail.
In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.
As used herein, "(meth) acrylate" is used to mean "one or both of acrylate and methacrylate". The same applies to "(meth) acrylic group", "(meth) acrylic acid", "(meth) acrylamide", "(meth) acryloyl group", "(meth) acrylic group" and the like.

The antireflection film of the present invention
An antireflection film having a base film, a hard coat layer, and an antireflection layer in this order.
The antireflection layer contains metal oxide particles and a binder resin, and contains metal oxide particles and a binder resin.
The antireflection layer has a moth-eye structure having an uneven shape formed by the metal oxide particles.
The hard coat layer is a copolymer having a repeating unit represented by the following general formula (I), a repeating unit represented by the following general formula (II), and a repeating unit represented by the following general formula (III). It is an antireflection film which is a layer formed from the composition for forming a hard coat layer containing.

In the general formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ² is an alkyl group having at least one fluorine atom as a substituent, or −Si (R ^a3 ) (R ^a4). ) Represents a group containing O−, R ^a3 and R ^a4 each represent an alkyl group which may independently have a substituent or an aryl group which may have a substituent, and L represents a divalent linkage. Represents a group.
In the general formula (II), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are aliphatic hydrocarbon groups which may independently have a hydrogen atom and a substituent, respectively. , An aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R ¹¹ and R ¹² may be linked. X ¹ represents a divalent linking group.
In the general formula (III), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, L ² represents a divalent linking group, and Y ¹ represents a photopolymerizable group.

According to the present invention, the mechanism for providing an antireflection film having a moth-eye structure having a moth-eye structure formed by particles and having high particle regularity has not been completely clarified. It is estimated as.
As will be described later, the antireflection film of the present invention includes a hard coat layer formed from a composition for forming a hard coat layer and an antireflection layer formed from a composition for forming an antireflection layer on a base film. The antireflection film having the above in this order, the composition for forming a hard coat layer is a repeating unit represented by the general formula (I), a repeating unit represented by the general formula (II), and a general formula (III). It contains a copolymer having a repeating unit represented by (1) and a curable compound, and the composition for forming an antireflection layer preferably contains metal oxide particles and a curable compound. ..
Due to the action of the repeating unit represented by the general formula (I), the copolymer is unevenly distributed near the surface of the hard coat layer (the interface with the antireflection layer), and the repeating unit represented by the general formula (II)- BOR ^{11 The} boronic acid structure or boronic acid ester structure represented by OR ¹² interacts with the metal oxide particles in the antireflection layer to suppress the aggregation of the metal oxide particles.
^{Further, the repeating unit Y 1} (photopolymerizable group) represented by the general formula (III) is polymerized and immobilized with the curable compound contained in the hard coat layer to immobilize the metal oxide particles. It is possible to improve the power of polymerization.
When the surface of the metal oxide particles is surface-modified with a compound having a polymerizable unsaturated group and a functional group reactive with the surface of the metal oxide particles, it is represented by the general formula (III). ^{By polymerizing Y 1} (photopolymerizable group) of the repeating unit and the polymerizable unsaturated group on the surface of the metal oxide particles, the immobilization power of the metal oxide particles can be further enhanced. As a result, when a part of the curable compound in the coating film formed from the above-mentioned antireflection layer forming composition is diffused into the pressure-sensitive adhesive layer laminated on the coating film, the metal in the coating film is used. It is considered that the oxide particles become difficult to move and the regularity of the particles is improved.

The antireflection film of the present invention preferably has an integrated reflectance of 3% or less, more preferably 2% or less, over the entire wavelength range of 380 to 780 nm.

An example of a preferred embodiment of the antireflection film of the present invention is shown in FIG.
The antireflection film 10 of FIG. 1 has a base film 1, a hard coat layer HC, and an antireflection layer 2 in this order. The antireflection film of the present invention may have other layers in addition to these layers. It is preferable that the hard coat layer and the antireflection layer are in contact with each other. The antireflection layer 2 contains the metal oxide particles 3 and the binder resin 4. The metal oxide particles 3 project from the binder resin 4 to form an uneven shape, and the uneven shape has a moth-eye structure.

(Moss eye structure)
The antireflection layer of the antireflection film of the present invention has a moth-eye structure having an uneven shape formed by metal oxide particles.
The uneven shape is preferably formed on the surface of the antireflection layer opposite to the interface on the hard coat layer side.
The uneven shape formed by the metal oxide particles preferably means that each metal oxide particle protruding from the binder resin film has a convex portion, and the portion where the metal oxide particle does not exist has a concave portion. is there.
The moth-eye structure having a concavo-convex shape means that the concavo-convex shape is a moth-eye structure.
As long as the moth-eye structure can be formed, other components such as a binder resin may be present on the surface of the metal oxide particles forming the convex portion.
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 microstructure pattern with a period of less than 780 nm. When the period of the fine structure pattern is less than 190 nm, the tint of the reflected light becomes small, which is preferable. Further, when the period of the uneven shape of the moth-eye structure is 100 nm or more, light having a wavelength of 380 nm can recognize the fine structure pattern and is excellent in antireflection property, which is preferable. The presence or absence of the moth-eye structure can be confirmed by observing the surface shape with a scanning electron microscope (SEM), an atomic force microscope (AFM), or the like and examining whether or not the fine structure pattern is formed.

The uneven shape of the antireflection layer of the antireflection film of the present invention is B / A, which is the ratio of the distance A between the vertices of adjacent convex portions and the distance B between the center and the concave portion between the vertices of adjacent convex portions. Is preferably 0.4 or more. When the B / A is 0.4 or more, the depth of the concave portion increases with respect to the distance between the convex portions, and a refractive index inclined layer in which the refractive index changes more slowly from the air to the inside of the antireflection layer is formed. Therefore, the reflectance can be further reduced.
The B / A is more preferably 0.5 or more. When the B / A is 0.5 or more, the distance A between the vertices of the adjacent convex portions (convex portions formed by the particles) is equal to or larger than the particle diameter, and the concave portions are formed between the particles. As a result, there are both interfacial reflection due to the steep part of the refractive index change depending on the curvature of the upper side of the convex portion and interfacial reflection due to the steep part of the refractive index change depending on the curvature of the interparticle concave part. In addition to the refractive index gradient layer effect due to the structure, it is presumed that the reflectance is reduced more effectively.
B / A can be controlled by the volume ratio of the binder resin and the metal oxide particles in the antireflection layer. Therefore, it is important to properly design the blending ratio of the binder resin and the metal oxide particles.

Further, in order to realize low reflectance and suppress the occurrence of haze, it is preferable that the metal oxide particles forming the convex portions are uniformly spread with an appropriate filling rate. From the above viewpoint, it is preferable that the content of the metal oxide particles forming the convex portion is adjusted so as to be uniform in the entire antireflection layer. The filling rate can be measured as the area occupancy rate (particle occupancy rate) of the metal oxide particles located on the most surface side when observing the metal oxide particles forming the convex portion from the surface by SEM or the like. It is preferably% to 64%, more preferably 25 to 50%, still more preferably 30 to 45%.

The surface uniformity of the antireflection film can be evaluated by haze. The measurement can be performed on a film sample of 40 mm × 80 mm at 25 ° C. and a relative humidity of 60% with a haze meter NDH4000 manufactured by Nippon Denshoku Kogyo Co., Ltd. according to JIS-K7136 (2000). If the particles are agglomerated and non-uniform, the haze will be high. The lower the haze, the better. The haze value is preferably 0.0 to 3.0%, more preferably 0.0 to 2.5%, and even more preferably 0.0 to 2.0%.

[Hard coat layer]
The hard coat layer of the antireflection film of the present invention will be described.
The antireflection film of the present invention has at least one hard coat layer between the base film and the antireflection layer.
The hard coat layer is a copolymer having at least a repeating unit represented by the general formula (I), a repeating unit represented by the general formula (II), and a repeating unit represented by the general formula (III). It is a layer formed from the composition for forming a hard coat layer containing.
Hereinafter, a copolymer having a repeating unit represented by the general formula (I), a repeating unit represented by the general formula (II), and a repeating unit represented by the general formula (III) will be referred to as "copolyweight". Also called "coalescence (a)".

<Copolymer (a)>
The copolymer (a) is composed of at least a repeating unit represented by the general formula (I), a repeating unit represented by the general formula (II), and a repeating unit represented by the general formula (III). It is a copolymer having. The copolymer (a) can have a function as a leveling agent.

(Repeating unit represented by general formula (I))
The repeating unit represented by the general formula (I) will be described.

In the general formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ² is an alkyl group having at least one fluorine atom as a substituent, or −Si (R ^a3 ) (R ^a4). ) Represents a group containing O−, R ^a3 and R ^a4 each represent an alkyl group which may independently have a substituent or an aryl group which may have a substituent, and L represents a divalent linkage. Represents a group.

^{R 1} in the general formula (I) 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, and has a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is more preferable to represent an alkyl group, and even more preferably to represent a hydrogen atom or a methyl group.

^{R 2} in the general formula (I) represents an alkyl group having at least one fluorine atom as a substituent, or a group containing −Si ( ^Ra3 ) ( ^Ra4 ) O−, and is substituted with at least one fluorine atom. It is preferable to represent an alkyl group (fluoroalkyl group), more preferably to represent a fluoroalkyl group having 1 to 20 carbon atoms, further preferably to represent a fluoroalkyl group having 1 to 18 carbon atoms, and 2 to 2 carbon atoms. It is particularly preferred to represent 15 fluoroalkyl groups. The number of fluorine atoms in the fluoroalkyl group is preferably 1 to 25, more preferably 3 to 21, and even more preferably 5 to 21.

^{As described above, R 2} in the general formula (I) is preferably an alkyl group having at least one fluorine atom as a substituent, but as another embodiment, R 2 in the general formula (I) is used. ² can also represent a ^{-Si (R a3) (R a4} ) group containing O-, and in this ^{case, -Si (R a3) (R a4} ) O- repeating units containing a siloxane bond represented by ( It is preferable to have a polysiloxane structure). R ^a3 and R ^a4 represent an alkyl group which may independently have a substituent or an aryl group which may have a substituent. In this case, the copolymer (a) is preferably a graft copolymer in which a polysiloxane structure is introduced into the side chain. The compound having a siloxane bond for obtaining this graft copolymer is more preferably a compound represented by the following general formula (IV).

R ^a3 and R ^a4 represent an alkyl group which may independently have a substituent or an aryl group which may have a substituent. ^Ra1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ^a5 represents an alkyl group having 1 to 12 carbon atoms. nn represents 10 to 1000.
^{The nn R a3s} in the general formula (IV) may be the same or different, and the nn R ^a4s may be the same or different.

^{When R a3} and R ^a4 in the general formula (IV) represent an alkyl group, the alkyl group having 1 to 12 carbon atoms is preferable, and the alkyl group having 1 to 10 carbon atoms is more preferable, for example, methyl. Examples include a group, an ethyl group, and a hexyl group. The alkyl group may have a substituent, and a halogen atom is preferable as the substituent. When the alkyl group is a haloalkyl group having a halogen atom as a substituent, the haloalkyl group is preferably a fluoroalkyl group having 1 to 12 carbon atoms, more preferably a fluoroalkyl group having 1 to 10 carbon atoms, for example, tri. Fluoromethyl group and pentafluoroethyl group can be mentioned.
When R ^a3 and R ^a4 represent an aryl group, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
Among them, ^Ra3 and ^Ra4 preferably represent a methyl group, a trifluoromethyl group, or a phenyl group, and particularly preferably represent a methyl group.

The general formula (IV) R ^a1 in represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a hydrogen atom or 1 to 4 carbon atoms It is more preferable to represent an alkyl group, and even more preferably to represent a hydrogen atom or a methyl group.

^Ra5 in the general formula (IV) represents an alkyl group having 1 to 12 carbon atoms, and preferably represents an alkyl group having 1 to 4 carbon atoms.
The nn in the general formula (IV) represents 10 to 1000, preferably 20 to 500, and more preferably 30 to 200.

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

The divalent linking group represented by L in the general formula (I) is not particularly limited, but is −O−, − (C = O) O−, −O (C = O) −, − (C = O). ) NH-, -NH (C = O)-, having a divalent aromatic group which may have a substituent, a divalent aliphatic chain group which may have a substituent, and a substituent. It is preferable to represent a divalent linking group composed of at least one selected from the group consisting of optionally divalent aliphatic cyclic groups.
Note that L in the general formula (I), - (C = O) O- is, C = O is attached at ^{R 1} side, indicating that O is attached at ^{R 2} side. -O (C = O) - indicates that in ^{R 1} side O is attached, C = O is attached at ^{R 2} side. - (C = O) NH- is, C = O is attached at ^{R 1} side, indicating that the NH is attached at ^{R 2} side. -NH (C = O) - denotes that the NH is attached at ^{R 1} side, C = O is attached at ^{R 2} side.
The divalent aromatic group may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group, and a divalent aromatic group having 6 to 20 carbon atoms is preferable. , A divalent aromatic group having 6 to 12 carbon atoms is more preferable.
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.
The divalent aromatic group, the divalent aliphatic chain group, and the divalent aliphatic cyclic group may each have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. From the viewpoint of ease of synthesis, it is preferable to have no substituent.
As L, − (C = O) O− or −O (C = O) − is preferable, and − (C = O) O− is more preferable.

From the viewpoint of surface uneven distribution and radical polymerization, the repeating unit represented by the general formula (I) is particularly preferably the repeating unit represented by the following general formula (I-2).

In the general formula (I-2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ma and na each independently represent an integer of 1 to 20, and X represents a hydrogen atom or a fluorine atom. ..

Formula (I-2) ^{R 1} in the general formula (I) in the same meaning as ^{R 1,} and preferred ranges are also the same.
Ma and na in the general formula (I-2) each independently represent an integer of 1 to 20. From the viewpoint of uneven distribution of the surface and the ease of obtaining and manufacturing the raw material, ma is preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and further preferably 1 or 2. preferable. Further, na is preferably an integer of 1 to 15, more preferably an integer of 1 to 12, further preferably an integer of 2 to 10, and most preferably an integer of 5 to 7.
X in the general formula (I-2) represents a hydrogen atom or a fluorine atom, and preferably represents a fluorine atom.

The repeating unit represented by the general formula (I) can be obtained by polymerizing the corresponding monomer, and preferred monomers include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2, 2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (Meta) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate , 2- (Perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H-1- (trifolomethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluoro Butyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate , 3- (Perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (Perfluoro-7-) Methyloctyl) -2-hydroxypropyl (meth) acrylate and the like can be mentioned.

(Repeating unit represented by general formula (II))
The repeating unit represented by the general formula (II) will be described.

In the general formula (II), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are aliphatic hydrocarbon groups which may independently have a hydrogen atom and a substituent, respectively. , An aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R ¹¹ and R ¹² may be linked. X ¹ represents a divalent linking group.

^{R 10} in the general formula (II) 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, and has a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is more preferable to represent an alkyl group, and even more preferably to represent a hydrogen atom or a methyl group.

^{When R 11} and R ¹² in the general formula (II) represent an aliphatic hydrocarbon group, the aliphatic hydrocarbon group preferably has an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and has 1 carbon number. More preferably, it is an aliphatic hydrocarbon group of 10 to 10.
Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, and an alkynyl group.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group and a hexadecyl group. Linear or branched such as 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. Alkyl group of.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-norbornyl group and the like.
Specific examples of the alkenyl group include a linear or branched alkenyl group such as a vinyl group, a 1-propenyl group, a 1-butenyl group and a 1-methyl-1-propenyl group.
Specific examples of the cycloalkenyl group include 1-cyclopentenyl group, 1-cyclohexenyl group and the like.
Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-octynyl group and the like.

When R ¹¹ and R ¹² represent an aryl group, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms.
Specific examples of the aryl group include a phenyl group. Further, examples thereof include those in which two to four benzene rings form a condensed ring and those in which a benzene ring and an unsaturated five-membered ring form a condensed ring. Specific examples thereof include a naphthyl group and an anthryl group. Examples thereof include a phenylyl group, an indenyl group, an acenabutenyl group, a fluorenyl group, a pyrenyl group and the like.

When R ¹¹ and R ¹² represent a heteroaryl group, the heteroaryl group is obtained by removing one hydrogen atom of a heteroaromatic ring containing one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. However, a heteroaryl group can be mentioned. Specific examples of a 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, isoxazole and oxazole. , Thiazol, thiazazole, indole, carbazole, benzofuran, dibenzofuran, thianaften, dibenzothiophene, indazole benzimidazole, anthranil, benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, acrydin, Examples thereof include isoquinolin, phthalazine, quinazoline, quinoxalin, naphthylidine, phenanthrolin, pteridine and the like.

R ¹¹ and R ¹² may be linked, and in this case, R ¹¹ and R ¹² are each independently an alkyl group or an aryl group, and it is preferable that they are linked to each other. ^{More preferably, 11} and R ¹² are alkyl groups, which are linked to each other.

^{The divalent linking group represented by X 1} in the general formula (II) includes-(C = O) O-, -O (C = O)-,-(C = O) NH-, and -NH. (C = O)-, -O-, -CO-, -NH-, -O (C = O) -NH-, -O (C = O) -O-, and -CH _2- It preferably contains at least one linking group and has 7 or more carbon atoms.
^{Regarding X 1} in the general formula (II), − (C = O) O − indicates ^{that C = O is bonded on the R 10} side and O is bonded on the B side. -O (C = O) - ^indicates that in ^{R 10} side O is attached, C = O is attached on the B side. - (C = O) NH- ^represents that C = O are linked by ^{R 10} side, NH binds the B side. -NH (C = O) - ^denotes that the NH is attached at ^{R 10} side, C = O is attached on the B side.

R ¹¹ , R ¹² and X ¹ may be substituted with one or more substituents where possible. Examples of the substituent include a monovalent non-metal atomic group excluding a hydrogen atom, and for example, it is selected from the following substituent group Z.
Substituent group Z:
Halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group , N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-ally Lucarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N -Alkylacylacylamino group, N-arylacylamino group, carbonyl group, N'-alkylureido group, N', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureide group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N', N '-Dialkyl-N-alkyl carboxylic group, N', N'-dialkyl-N-aryl walide group, N'-aryl-N-alkyl aldehyde group, N'-aryl-N-aryl ureido group, N', N '-Diaryl-N-alkyl ureido group, N', N'-diaryl-N-aryl ureido group, N'-alkyl-N'-aryl-N-alkyl ureido group, N'-alkyl-N'-aryl- N-arylureid group, alkoxycarbonylamino group, allyloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group , N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugate base group, alkoxycarbonyl group, allyloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkyl Carbonyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfoni Group, a sulfo group (-SO 3 _H) and its conjugated base group, alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N- dialkyl sulfinamoyl group, N- aryl Sulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N- Aryl sulfamoyl group, N, N-diaryl sulfamoyl group, N-alkyl-N-aryl sulfamoyl group, N-acyl sulfamoyl group and its conjugate base group, N-alkylsulfonyl sulfamoyl group ( -SO ₂ NHSO ₂ (alkyl) and its conjugate base group, N-arylsulfonylsulfamoyl group (-SO ₂ NHSO ₂ (aryl)) and its conjugate base group, N-alkylsulfonylcarbamoyl group (-CONHSO ₂ (-CONHSO 2)) Alkyl)) and its conjugate base group, N-arylsulfonylcarbamoyl group (-CONHSO ₂ (aryl)) and its conjugate base group, alkoxysilyl group (-Si (Oalkyl) ₃ ), aryloxysilyl group (-Si (Oaryl)) ₃ ), hydroxysilyl group (-Si (OH) ₃ ) and its conjugate base group, phosphono group (-PO ₃ H ₂ ) and its conjugate base group, dialkylphosphono group (-PO ₃ (alkyl) ₂ ), Diarylphosphono groups (-PO ₃ (aryl) ₂ ), alkylarylphosphono groups (-PO ₃ (alkyl) (aryl)), monoalkylphosphono groups (-PO ₃ H (alkyl)) and their conjugate base groups. , Monoarylphosphono group (-PO ₃ H (aryl)) and its conjugate base group, phosphonooxy group (-OPO ₃ H ₂ ) and its conjugate base group, dialkylphosphonooxy group (-OPO ₃ (alkyl) ₂ ) , Diarylphosphonooxy groups (-OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy groups (-OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy groups (-OPO ₃ H (alkyl)) and a conjugated base group thereof, monoarylphosphono group _(-OPO 3 H _(aryl)) and its conjugated base group, a cyano group, a nitro group, an aryl group, an alkenyl group and alkynyl group.
Further, these substituents may form a ring by bonding with each other or with a hydrocarbon group substituted, if possible.

It is preferred formula (II) R ¹¹ and R ¹² in the that each independently represent a hydrogen atom or an alkyl group, or together form a ring together an alkyl radical, R ¹¹ and R ¹² It is preferable that both are hydrogen atoms or both are alkyl groups and are bonded to each other to form a ring.

From the viewpoint that it is easier to interact with the metal oxide particles in the antireflection layer and is more excellent in the regularity of the metal oxide particles, the repeating unit represented by the general formula (II) is the following general formula (II-a). It is preferably a repeating unit represented by.

In the general formula (II-a), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are aliphatic hydrocarbons which may independently have a hydrogen atom and a substituent, respectively. It represents a hydrogen group, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R ¹¹ and R ¹² may be linked. X ¹¹ is - (C = O) O - , - O (C = O) -, - (C = O) NH -, - O -, - CO-, and -CH ₂ - is selected from the group consisting of Represents a divalent linking group composed of at least one. X ¹² is − (C = O) O−, −O (C = O) −, − (C = O) NH−, −O−, −CO−, −NH−, −O (C = O) A divalent containing at least one linking group selected from -NH-, -O (C = O) -O-, and -CH _2- and containing at least one aromatic ring which may have a substituent. Represents the linking group of. However, the total number of carbon atoms of ^{X 11} and X ^{12 is 7 or more.}

^{As X 11} in the general formula (II-a), − (C = O) O−, −O (C = O) −, − (C = O) NH− are preferable, and − (C = O) O. -Is most preferable.
^{X 12} in the general formula (II-a) preferably contains 1 to 5 aromatic rings, more preferably 2 to 4 aromatic rings, and 2 to 3 aromatic rings. Most preferably.
Each general formula (II-a) the preferred range of ^{R 10, R 11} and ^{R 12} in is the same as ^{R 10, R 11} and ^{R 12} in the general formula (II).

The repeating unit represented by the general formula (II) or (II-a) is more preferably the repeating unit represented by the following general formula (II-b).

In the general formula (II-b), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are aliphatic hydrocarbons which may independently have a hydrogen atom and a substituent, respectively. It represents a hydrogen group, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R ¹¹ and R ¹² may be linked. X ²¹ represents − (C = O) O− or − (C = O) NH−. X ²² is − (C = O) O−, −O (C = O) −, − (C = O) NH−, −O−, −CO−, −NH−, −O (C = O) − It is a divalent linking group containing at least one linking group selected from the group consisting of NH-, -O (C = O) -O-, and -CH _2- ^{, and X 22} has a substituent. It may also contain a good aromatic ring.

^{The preferred ranges of R 10} , R ¹¹ and R ^{12 in} the general formula (II-b) are similar to those ^{of R 10} , R ¹¹ and R ^{12 in} the general formula (II), respectively.

The repeating unit represented by the general formula (II) can be obtained by polymerizing the corresponding monomers. Examples of the repeating unit represented by the general formula (II) include, but are not limited to, the repeating units shown below.

(Repeating unit represented by general formula (III))
The repeating unit represented by the general formula (III) will be described.

In the general formula (III), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, L ² represents a divalent linking group, and Y ¹ represents a photopolymerizable group.

^{R 20} in the general formula (III) 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, and has a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is more preferable to represent an alkyl group, and even more preferably to represent a hydrogen atom or a methyl group.

^{The divalent linking group represented by L 2} in the general formula (III) is not particularly limited, but is −O−, − (C = O) O−, −O (C = O) −, − (C = O) NH-, -NH (C = O)-, a divalent aromatic group which may have a substituent, a divalent aliphatic chain group which may have a substituent, and a substituent. It is preferable to represent a divalent linking group composed of at least one selected from the group consisting of a divalent aliphatic cyclic group which may be possessed.
^{Regarding L 2} in the general formula (III), − (C = O) O − indicates ^{that C = O is bound on the R 20} side and O is bound on the Y ¹ side. -O (C = O) - ^indicates that in ^{R 20} side O is attached, C = O are bound by ^{Y 1} side. - (C = O) NH- ^represents that C = O are linked by ^{R 20} side, NH binds with ^{Y 1} side. -NH (C = O) - ^denotes that the NH is attached at ^{R 20} side, C = O are bound by ^{Y 1} side.
The divalent aromatic group may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group, and a divalent aromatic group having 6 to 20 carbon atoms is preferable. , A divalent aromatic group having 6 to 12 carbon atoms is more preferable.
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.
The divalent aromatic group, the divalent aliphatic chain group, and the divalent aliphatic cyclic group may each have a substituent, but from the viewpoint of ease of synthesis, they have a substituent. It is preferable not to.
L ² is composed of at least one selected from the group consisting of −O−, − (C = O) O−, and a divalent aliphatic chain group which may have a substituent (2). It preferably represents a valent linking group.

Formula (III) a photopolymerizable group represented by Y ¹ in is not particularly limited as long as it is a group that polymerizes by being irradiated with light when used with a suitable initiator, preferably a radical or an acid It is a group that polymerizes by radicals, and more preferably a group that polymerizes by radicals. In addition, "light" shall include an electron beam. Examples of the "light" include infrared rays, visible light, ultraviolet rays, X-rays, electron beams, and the like, and ultraviolet rays are preferable. Specifically, the photopolymerizable group is preferably an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a styryl group, an epoxy group, an alicyclic epoxy group, or an oxetanyl group, and is preferably an acryloyl group or a methacryloyl group. More preferred.

The repeating unit represented by the general formula (III) is preferably a repeating unit represented by the following general formula (III-a).

In the general formula (III-a), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ³¹ and R ³² each independently represent a hydrogen atom or a substituent, and k is an integer of 1 to 10. When k represents an integer of 2 or more, the plurality of R ^31s may be the same or different, and the plurality of R ^32s may be the same or different. R ³³ represents a hydrogen atom or a methyl group.

Formula (III-a) ^{R 20} in is the same meaning as in formula (III) ^{R 20} in the preferred ranges are also the same.
^{Examples of the substituent when R 31} and R ³² in the general formula (III-a) represent a substituent include an alkyl group and a hydroxyl group.

The repeating unit represented by the general formula (III) is synthesized by a method of synthesizing by polymerization of the corresponding monomer, polymerizing a monomer having a protected acryloyl group or a methacryloyl group, and then deprotecting. There are a method, a method of synthesizing by introducing a photopolymerizable group by a polymer reaction into a polymer having a reactive group such as a hydroxyl group or a carboxyl group, and the like.
Specific examples of the repeating unit represented by the general formula (III) are shown below, but the present invention is not limited thereto.

(Other repeating units)
The copolymer (a) has a repeating unit represented by the general formula (I), a repeating unit represented by the general formula (II), and a repeating unit represented by the general formula (III). , In addition to these, it may have other repeating units.
Other repeating units can be obtained by polymerization of the corresponding monomers. Examples of the monomer giving the other repeating unit include general-purpose monomers, for example, PolymerHandbook 2nd ed. , J. Brandrup, Wiley literscience (1975) Chapter2 Pages 1-483 can be used. For example, acrylic acid, methacrylic acid, methacrylic acid esters, methacrylic acid esters, acrylamides, methacrylicamides, allyl compounds, vinyl ethers, vinyl esters, dialkyl itaconates, dialkyl esters of fumaric acid or monoalkyl esters. Examples thereof include a compound having one addition-polymerizable unsaturated bond selected from the above.

Specific examples of the monomer giving the other repeating unit include the following monomers.
Acrylic acid esters:
Methyl acrylate, ethyl acrylate, propyl acrylate, chlorethyl acrylate, 2-hydroxyethyl acrylate, trimethylpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, phenoxyethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 2- Acryloyloxyethyl succinate, 2-carboxyethyl acrylate, etc.,
Methacrylic acid esters:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, phenoxyethyl methacrylate, flufuryl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol Monoacetacetate monomethacrylate, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-carboxyethyl methacrylate, etc.

Acrylamides:
Acrylamide, N-alkylacrylamide (alkyl groups having 1 to 3 carbon atoms, for example, methyl group, ethyl group, propyl group), N, N-dialkylacrylamide (alkyl groups having 1 to 6 carbon atoms), N-Hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, etc.
Methacrylamides:
Methacrylamide, N-alkylmethacrylamide (alkyl groups having 1 to 3 carbon atoms, for example, methyl group, ethyl group, propyl group), N, N-dialkylmethacrylamide (alkyl groups having 1 to 6 carbon atoms) ), N-Hydroxyethyl-N-methylmethacrylamide, N-2-acetamide ethyl-N-acetylmethacrylamide, etc.
Allyl compound:
Allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol, etc.

Vinyl ethers:
Alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl 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, tetrahydrofurfuryl vinyl ether, etc. Vinyl esters:
Vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrete, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl- β-Phenylbutyrate, vinylcyclohexylcarboxylate, etc.

Dialkyl itaconic acid:
Dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc.
Dialkyl esters or monoalkyl esters of fumaric acid: dibutyl fumarate and the like.

Other monomers that give repeating units include crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleironitrile, styrene, 4-vinylbenzoic acid, styrene macromer (AS-6S manufactured by Toa Synthetic Co., Ltd.), and methyl methacrylate. Macromer (AA-6 manufactured by Toa Synthetic Co., Ltd.) and the like can also be mentioned. It is also possible to convert the structure of the polymer after polymerization by a polymer reaction.

(Content of each repeating unit in the copolymer (a))
The content of the repeating unit represented by the general formula (I) in the copolymer (a) is preferably 5 to 45 mol% with respect to all the repeating units of the copolymer (a). It is more preferably 5 to 40 mol%, further preferably 10 to 40 mol%, and particularly preferably 15 to 35 mol%.
The content of the repeating unit represented by the general formula (II) in the copolymer (a) is preferably 15 to 60 mol% with respect to all the repeating units of the copolymer (a). It is more preferably 20 to 60 mol%, further preferably 25 to 50 mol%.
The content of the repeating unit represented by the general formula (III) in the copolymer (a) is preferably 15 to 65 mol% with respect to all the repeating units of the copolymer (a). It is more preferably 20 to 65 mol%, further preferably 25 to 55 mol%.
When the copolymer (a) has other repeating units, the content of the other repeating units is preferably 15 mol% or less with respect to all the repeating units contained in the copolymer (a). More preferably, it is 10 mol% or less.
By setting the content of each repeating unit in the above range, when the antireflection layer is formed on the hard coat layer, the antireflection layer can be formed well without being repelled, and the copolymer (a) is hard coated. It can be unevenly distributed near the surface of the layer on the antireflection layer side (the interface between the hard coat layer and the antireflection layer), and the rules of the metal oxide particles in the antireflection layer without impairing the abrasion resistance of the antireflection layer. The sex can be further improved. Needless to say, the total content of each of the above repeating units does not exceed 100 mol%.

(Weight average molecular weight of copolymer (a))
The weight average molecular weight (Mw) of the copolymer (a) is preferably 1000 to 20000, more preferably 5000 to 100,000, and even more preferably 1000 to 80000.
The weight average molecular weight of the copolymer (a) is within the above range, when polymerizing the photopolymerizable group represented by Y ¹ in the repeating unit represented by formula (III), effectively The polymerization reaction proceeds.
The weight average molecular weight of the copolymer (a) is a value measured by gel permeation chromatography (GPC) under the following conditions.
[Eluent] N-methyl-2-pyrrolidone (NMP)
[Device name] EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)
[Column] TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation)
[Column temperature] 40 ° C
[Flow velocity] 0.35 ml / min

The copolymer (a) can be polymerized by a known method. For example, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a melt polymerization method and the like can be mentioned. Of these, it is preferably synthesized by a solution polymerization method.
In order to prevent insolubilization due to gelation during synthesis, the molecular weight of the copolymer (a) can be appropriately adjusted. The method for adjusting the molecular weight includes changing the initiator amount, changing the monomer concentration, using a chain transfer agent, and the like, but it is preferable to change the initiator amount or the monomer concentration for adjustment.

Specific examples of the copolymer (a) are shown below, but the copolymer (a) is not limited thereto.

It is preferable that n in the above A-17 is 10 to 60.

The content of the copolymer (a) in the composition for forming a hard coat layer is not particularly limited, but may be 0.001 to 20% by mass with respect to the total solid content of the composition for forming a hard coat layer. It is preferably 0.005 to 10% by mass, more preferably 0.01 to 5% by mass. The copolymer (a) has a repeating unit represented by the general formula (III), and the antireflection layer is resistant to the polymerization of ^{Y 1 (photopolymerizable group) in the general formula (III).} Since it is possible to prevent a decrease in rubbing property, there is an advantage that the content can be increased as compared with the conventional leveling agent. The total solid content is all components other than the solvent in the composition.

The hard coat layer of the antireflection film of the present invention is a layer formed from a composition for forming a hard coat layer containing the copolymer (a). When the hard coat layer is formed from the composition for forming the hard coat layer, or when the antireflection layer is formed on the hard coat layer, the copolymer (a) is represented by the general formula (III) by light irradiation. Since the repeating unit Y ¹ (photopolymerizable group) is polymerized, the hard coat layer contains a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II). polymer chain (also referred to as "polymer of the copolymer (a)".) crosslinked polymer having a structure crosslinked by polymerization of Y ¹ may include. The hard coat layer may contain the copolymer (a). That is, the hard coat layer may contain the copolymer (a) or the polymer of the copolymer (a).
In the antireflection film of the present invention, the copolymer (a) or the polymer of the copolymer (a) is unevenly distributed near the surface of the hard coat layer on the antireflection layer side (the interface between the hard coat layer and the antireflection layer). It is preferable to do so. The fact that the copolymer (a) or the polymer of the copolymer (a) is unevenly distributed near the surface of the hard coat layer on the antireflection layer side (the interface between the hard coat layer and the antireflection layer) is an antireflection film. Can be confirmed by cutting with a microtome and analyzing the cross section with a time-of-flight secondary ion mass spectrometry (TOF-SIMS: Time-of-Flight Interface Ion Mass Spectrometry). More specifically, a repeating unit represented by the general formula (I) containing a fluorine atom or a polysiloxane structure, a repeating unit represented by the general formula (II) containing a boronic acid structure or a boronic acid ester structure, It can be confirmed by checking whether the repeating unit represented by the general formula (III) containing the photopolymerizable group or the structure after the polymerization is detected.
The antireflection film of the present invention contains a polymer (a) or a polymer of the copolymer (a) in the hard coat layer, but at least the copolymer (a) or the copolymer weight is contained in the hard coat layer. The polymer of the coalescence (a) may be contained, and the layer other than the hard coat layer may also contain the polymer of the copolymer (a) or the polymer (a).

<Other components of the hard coat layer>
The hard coat layer preferably contains other components in addition to the copolymer (a) or the polymer of the copolymer (a).
The hard coat layer is preferably formed by a polymerization reaction of a curable compound which is a compound having a polymerizable group. That is, the hard coat layer preferably contains a cured product of a curable compound.
As the curable compound for forming the hard coat layer, specifically, the same compound as the curable compound (a1) for forming the binder resin of the antireflection layer described later can be used.
The content of the curable compound in the composition for forming a hard coat layer is not particularly limited, but is preferably 20 to 99.9% by mass with respect to the total solid content of the composition for forming a hard coat layer.

The hard coat layer can be measured as a portion where a cured product of a curable compound is detected when the antireflection film is cut with a microtome and the cross section is analyzed with TOF-SIMS, and the film thickness of the hard coat layer is also the same. It can be measured from the cross-sectional information of TOF-SIMS.
Further, for the hard coat layer, another layer is detected between the base film and the antireflection layer by, for example, cross-sectional observation with a reflection spectroscopic film thickness meter using light interference or a TEM (transmission electron microscope). Can also be measured by. As the reflection spectroscopic film thickness meter, FE-3000 (manufactured by Otsuka Electronics Co., Ltd.) or the like can be used.
In the method for producing an antireflection film of the present invention, the step (1) described later is preferably performed on the hard coat layer in a half-cured state. By putting the hard coat layer in a half-cured state, the adhesion between the hard coat layer and the antireflection layer is improved, and the bond between the hard coat layer and the metal oxide particles having unsaturated double bonds on the surface is formed. The effect of suppressing aggregation of metal oxide particles can be obtained.
For example, if the coating film is ultraviolet curable, half-cure can be achieved by appropriately adjusting the oxygen concentration at the time of curing and the amount of ultraviolet irradiation. Preferably cured by an irradiation of ^1mJ / cm ^{2 ~300mJ} / cm 2 by an ultraviolet lamp. More preferably ^{5mJ / cm 2 ~100mJ / cm 2} , further preferably ^{10mJ / cm 2 ~70mJ / cm 2} . At the time of irradiation, the above energy may be applied all at once, or may be divided and irradiated. As the ultraviolet lamp type, a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used.

The oxygen concentration at the time of curing is preferably 0.05 to 5.0% by volume, more preferably 0.1 to 2% by volume, and most preferably 0.1 to 1% by volume.

(solvent)
The composition for forming a hard coat layer preferably contains a solvent.
The solvent preferably contains a solvent having permeability to the base film from the viewpoint of adhesion between the base film and the hard coat layer. The solvent having permeability to the base film is a solvent having the ability to dissolve in the base film. Here, the solvent having a dissolving ability for the base film is 24 mm at room temperature (25 ° C.) by placing a base film having a size of 24 mm × 36 mm (thickness 80 μm) in a 15 ml bottle containing the above solvent. It means a solvent in which the base film is completely dissolved and loses its shape by shaking the bottle as appropriate over time.
When a cellulose acylate film is used as the base film, methyl ethyl ketone (MEK), dimethyl carbonate, methyl acetate, acetone, methylene chloride and the like are preferable, and methyl ethyl ketone (MEK), dimethyl carbonate and methyl acetate are more preferable. It can be preferably used, but is not limited thereto.
The composition for forming a hard coat layer may contain a solvent other than the permeable solvent (for example, ethanol, methanol, 1-butanol, isopropanol (IPA), methyl isobutyl ketone (MIBK), toluene, etc.).
In the composition for forming a hard coat layer, the content of the permeable solvent is preferably 50% by mass or more and 100% by mass or less with respect to the mass of all the solvents contained in the composition for forming a hard coat layer. More preferably, it is by mass% or more and 100% by mass or less.
When the composition for forming a hard coat layer contains a quaternary ammonium salt-containing polymer, it is preferable to contain a hydrophilic solvent as the solvent from the viewpoint of compatibility with the quaternary ammonium salt-containing polymer. As the hydrophilic solvent, lower alcohols such as methanol, ethanol, isopropanol (IPA) and butanol are preferable.
The solid content concentration of the composition for forming a hard coat layer is preferably 20% by mass or more and 70% by mass or less, and more preferably 30% by mass or more and 65% by mass or less.

In addition to the above components, a polymerization initiator, an antistatic agent, an antiglare agent, and the like can be appropriately added to the composition for forming a hard coat layer. Further, various additives such as a leveling agent and various sensitizers other than the above-mentioned copolymer (a) may be mixed.

(Polymerization initiator)
If necessary, radical and cationic polymerization initiators and the like may be appropriately selected and used. These polymerization initiators are decomposed by light irradiation and / or heating to generate radicals or cations to promote radical polymerization and cationic polymerization.
Examples of the polymerization initiator include those similar to those of the polymerization initiator which may be contained in the composition for forming the layer (a) described later.
In particular, when the composition for forming a hard coat layer contains a quaternary ammonium salt-containing polymer, it is preferable to use a phosphine oxide-based polymerization initiator as the polymerization initiator. Since the phosphine oxide-based polymerization initiator has a photobleaching effect, even if the surface of the hard coat layer is in a half-cured state, the internal curing rate is higher than when other initiators are used, and the antireflection layer is formed. It is possible to suppress the contamination of the quaternary ammonium salt-containing polymer.
The content of the polymerization initiator in the composition for forming a hard coat layer is not particularly limited, but is preferably 0.5 to 8% by mass with respect to the total solid content of the composition for forming a hard coat layer.

(Antistatic agent)
As a specific example of the antistatic agent, a conventionally known antistatic agent such as a quaternary ammonium salt, a conductive polymer, or a conductive fine particle can be used, and the antistatic agent is not particularly limited, but is inexpensive and easy to handle. Therefore, it is preferably an antistatic agent having a quaternary ammonium salt, and more preferably a quaternary ammonium salt-containing polymer.

The antireflection film of the present invention includes
The metal oxide particles used are metal oxide particles having a polymerizable unsaturated group added to the particle surface.
It has a hard coat layer obtained by curing a composition for forming a hard coat layer containing a curable compound having a polymerizable unsaturated group.
It is preferable that a bond is formed between the metal oxide particles and the hard coat layer.

(Refractive index adjuster)
A high refractive index monomer or inorganic particles can be added as a refractive index adjusting agent for the purpose of controlling the refractive index of the hard coat layer. Inorganic particles have the effect of suppressing curing shrinkage due to the polymerization reaction, in addition to the effect of controlling the refractive index. In the present invention, after the formation of the hard coat layer, the polymer produced by polymerizing the polyfunctional monomer and / or the high refractive index monomer and the like, and the inorganic particles dispersed therein are referred to as a binder.

(Leveling agents other than copolymer (a))
As a specific example of the leveling agent other than the copolymer (a), a conventionally known leveling agent such as a fluorine-based or silicone-based agent can be used.

(Thickness of hard coat layer)
The thickness of the hard coat layer is preferably about 0.6 to 50 μm, more preferably 4 to 20 μm.
The strength of the hard coat layer is preferably H or more, and more preferably 2H or more in the pencil hardness test. Further, in the Taber test according to JIS K5400, it is preferable that the amount of wear of the test piece before and after the test is small.

[Base film]
The base film of the antireflection film of the present invention will be described.
The base film is preferably a plastic base film. The base film is not particularly limited as long as it is a light-transmitting base material generally used as a base film for an antireflection film. Various types of base films can be used, for example, cellulose-based resin; cellulose acylate (triacetate cellulose, diacetyl cellulose, acetate butyrate cellulose) and the like, polyester resin; polyethylene terephthalate and the like, (meth) acrylic resin, polyurethane. Examples thereof include a base film containing a base resin, a polycarbonate, a polystyrene, an olefin resin and the like, and a base film containing a cellulose acylate, a polyethylene terephthalate, or a (meth) acrylic resin is preferable and contains a cellulose acylate. The base film is more preferable.
The thickness of the base film is usually about 10 to 1000 μm, but is preferably 15 to 200 μm, more preferably 20 to 200 μm, from the viewpoint of good handleability, high translucency, and sufficient strength. Preferably, 20 to 100 μm is more preferable, and 25 to 100 μm is particularly preferable.
The light transmittance of the base film is preferably 80% or more, more preferably 90% or more.
The total light transmittance shall be measured in accordance with Japanese Industrial Standards (JIS) K7361-1 (1997).

[Anti-reflective layer]
The antireflection layer of the antireflection film of the present invention will be described.
The antireflection layer contains metal oxide particles and a binder resin.

<Binder resin>
The binder resin preferably has a function of binding metal oxide particles to the hard coat layer.
The binder resin is preferably a film as shown by reference numeral 4 in FIG.
The binder resin preferably contains a cured product of a curable compound.
The binder resin can be obtained by curing a curable compound.
The curable compound used for forming the binder resin is also referred to as a curable compound (a1).

<Curable compound (a1)>
As the curable compound (a1), a compound having a polymerizable group is preferable. As the compound having a polymerizable group, various monomers, oligomers or polymers can be used, and as the polymerizable group, a photopolymerizable one is preferable.
Examples of the photopolymerizable group include polymerizable unsaturated groups (carbon-carbon unsaturated double-bonding groups) such as (meth) acryloyl group, vinyl group, styryl group and allyl group, and among them, (meth). Acryloyl groups are preferred.

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

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

Of these, esters of a polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, one molecule contains at least one polyfunctional monomer having three or more (meth) acryloyl groups.
For example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO (ethylene oxide) modified trimethylolpropane tri (meth) acrylate, PO (propylene oxide) modified trimethylol Propanetri (meth) acrylate, EO-modified tri (meth) phosphate, trimethylolethanetri (meth) acrylate, trimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate ) Acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol tohexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate, Examples thereof include caprolactone-modified tris (acetyloxyethyl) isocyanurate.

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

Furthermore, resins having three or more polymerizable 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, many Also mentioned are oligomers such as polyfunctional compounds such as valent alcohols or prepolymers.

Further, the compounds described in JP-A-2005-76005 and JP-A-2005-36105, dendrimers such as SIRIUS-501 and SUBARU-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), JP-A-2005-60425. Norbornene ring-containing monomers as described in 1.

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

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

The antireflection layer can further contain a compound other than the curable compound (a1) as a binder resin forming compound.
From the viewpoint of easy penetration into the pressure-sensitive adhesive layer, which will be described later, a compound having two or less polymerizable groups in one molecule may be used as the curable compound (a1), but in particular, in one molecule. A compound having 3 or more polymerizable groups, a compound having 2 or less polymerizable groups in one molecule, or a compound having no polymerizable group as a compound other than the curable compound (a1) is used in combination. Is preferable.
As a compound having two or less polymerizable groups in one molecule or a compound having no polymerizable group, the weight average molecular weight (Mwa) is 40 <Mwa <500, and the SP value (SPa) by the Hoy method is A compound having 19 <SPa <24.5 is preferable because it easily penetrates into the pressure-sensitive adhesive layer. Further, the compound having two or less polymerizable groups in one molecule is preferably a compound having one polymerizable group in one molecule.
The SP value (solubility parameter) in the present invention is a value calculated by the Hoy method, and the Hoy method is described in POLYMER HANDBOOK FOURTH EDITION.

Further, the compound having two or less polymerizable groups in one molecule or the compound having no polymerizable group preferably has a viscosity at 25 ° C. of 100 mPas or less, more preferably 1 to 50 mPas, and 1 to 1 to 50 mPas. 20 mPas is even more preferable. A compound in such a viscosity range is preferable because it easily penetrates into the pressure-sensitive adhesive layer, works to suppress aggregation of particles (a2), and can suppress haze and cloudiness. In particular, as will be described later, it is possible to suppress the aggregation of the particles (a2) by curing a part of the curable compound (a1) before laminating the pressure-sensitive adhesive layer, but the compound in such a viscosity range. By using, a compound having two or less polymerizable groups in one molecule or a compound having no polymerizable group can be sufficiently permeated into the pressure-sensitive adhesive layer even in a cured state. Therefore, it is preferable. In particular, when the viscosity is in the range of 1 to 20 mPas, the effect of preventing an increase in reflectance or a decrease in total light transmittance caused by clogging of the gaps between particles is large, which is preferable.

The compound having two or less polymerizable 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 group.
As the compound having no polymerizable group, an ester compound, an amine compound, an ether compound, an aliphatic alcohol compound, a hydrocarbon compound and the like can be preferably used, and an ester compound is particularly preferable. More specifically, dimethyl succinate (SP value 20.2, viscosity 2.6 mPas), diethyl succinate (SP value 19.7, viscosity 2.6 mPas), dimethyl adipate (SP value 19.7, viscosity 2). .8 mPas), dibutyl succinate (SP value 19.1, viscosity 3.9 mPas), bis adipate (2-butoxyethyl) (SP value 19.0, viscosity 10.8 mPas), dimethyl sverate (SP value 19. 4, viscosity 3.7 mPas), diethyl phthalate (SP value 22.3, viscosity 9.8 mPas), dibutyl phthalate (SP value 21.4, viscosity 13.7 mPas), triethyl citrate (SP value 22.5, Viscosity 22.6 mPas), acetyltriethyl citrate (SP value 21.1, viscosity 29.7 mPas), diphenyl ether (SP value 21.4, viscosity 3.8 mPas) and the like.

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

The content of the binder resin contained in the antireflection layer is ^{preferably 100mg / m 2 ~800mg / m 2} , more preferably ^{100mg / m 2 ~600mg / m 2} , 100mg / m 2 ~400mg / m 2 and most preferably ..

<Metal oxide particles>
The metal oxide particles are also referred to as "particles (a2)".
Examples of the metal oxide particles include silica particles, titania particles, zirconia particles, antimony pentoxide particles, etc., but since the refractive index is close to that of many binder resins, haze is unlikely to occur and a moth-eye structure is easily formed. Therefore, silica particles are preferable.

The average primary particle size of the metal oxide particles is preferably 100 nm or more and 190 nm or less, more preferably 100 nm or more and 180 nm or less, and further preferably 100 nm or more and 170 nm or less.
Only one kind of metal oxide particles may be used, or two or more kinds of particles having different average primary particle diameters may be used.

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

The metal oxide particles are preferably solid particles from the viewpoint of strength. The shape of the metal oxide particles is most preferably spherical, but there is no problem even if the shape of the metal oxide particles is other than spherical such as amorphous.
For example, by using amorphous particles in which a part of spherical metal oxide particles is a flat surface and placing the flat surface on the lower layer side, the movement of the particles is suppressed, and from application to drying and hardening. It is preferable that particle aggregation in each step of the above can be prevented, the distance between the convex portions due to the particles can be made uniform, and the transmittance in the short wavelength region can be improved.
Further, as another example of the amorphous shape, particles having a shape in which small particles are further bonded to a part of the metal oxide particles can be used. The number of small particles bonded to the metal oxide particles may be plural, but one is more preferable. The particle size of the small particles bonded to a part of the metal oxide particles is preferably smaller than that of the metal oxide particles, and more preferably 0.5 times or less the particle size of the metal oxide particles. It is more preferably 25 times or less. The density of the small particles bonded to a part of the metal oxide particles is preferably higher than that of the metal oxide particles, more preferably 2 times or more, and further preferably 3 times or more. The small particles are preferably metal oxides, for example, zirconia, alumina, titania and the like, but can be appropriately used as long as they satisfy the above density relationship. For example, particles in which zirconia particles having a particle size of 40 nm are attached to silica particles having a particle size of 160 nm are preferable.
Further, the silica particles may be either crystalline or amorphous.

As the metal oxide particles, it is preferable to use surface-treated inorganic fine particles in order to improve dispersibility in the coating liquid, improve film strength, and prevent 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.
The metal oxide particles are preferably particles whose surface is modified with a compound having a polymerizable unsaturated group and a functional group having reactivity with the surface of the metal oxide particles.
In particular, from the viewpoint of imparting binding property to the curable compound (a1) for forming the binder resin and improving the strength of the antireflection layer, the particle surface is subjected to a polymerizable unsaturated group (preferably unsaturated double). It is preferable to surface-modify with a compound having a functional group reactive with the particle surface (bond) and impart a polymerizable unsaturated group (preferably an unsaturated double bond) to the particle surface. As the compound used for surface modification, the above-mentioned silane coupling agent having a polymerizable group as the curable compound (a1) can be preferably used.
Specifically, commercially available KBM-503 and KBM-5103 (all manufactured by Shin-Etsu Chemical Co., Ltd., X-12-1048, X-12-1049, X-12-1050 described in JP-A-2014-123091) It is preferable to modify the surface of the metal oxide particles with a silane coupling agent containing such a (meth) acryloyl group.

As a specific example of particles having an average primary particle diameter of 100 nm or more and 190 nm or less, Seahoster KE-P10 (average primary particle diameter of 150 nm, amorphous silica manufactured by Nippon Shokubai Co., Ltd.) can be preferably used.

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

The content of the metal oxide particles of the antireflection layer is ^{preferably 50mg / m 2 ~200mg / m 2} , more preferably ^{100mg / m 2 ~180mg / m 2} , 130mg / m 2 ~170mg / m 2 and most preferable. Above the lower limit, many convex portions of the moth-eye structure can be formed, so that the antireflection property is more likely to be improved, and when it is below the upper limit, aggregation is less likely to occur and a good moth-eye structure is easily formed.

Containing only one type of monodisperse silica fine particles having an average primary particle size of 100 nm or more and 190 nm or less and a CV (coefficient of variation) value of less than 5% of the metal oxide particles makes the height of the unevenness of the moth-eye structure uniform. This is preferable because the reflectance is further lowered. The CV value is usually measured using a laser diffraction type particle size measuring device, but other particle size measuring methods may be used, and the particle size distribution can be calculated by image analysis from the surface SEM image of the antireflection layer. it can. More preferably, the CV value is less than 4%.

As another aspect, it is also preferable that the metal oxide fine particles include both metal oxide fine particles having an average primary particle size of 100 nm or more and 190 nm or less and metal oxide particles having an average primary particle size of 1 nm or more and less than 70 nm. In this case, the larger particle size particles mainly contribute to the moth-eye structure, and the smaller particle size particles are mixed between the large particles to suppress the aggregation of the large particles, resulting in the reflectance. Haze may improve. Since the metal oxide particles having a primary particle size of 1 nm or more and less than 70 nm are more immersed in the binder resin, the convex portion as the antireflection layer is formed by the metal oxide fine particles having a primary particle size of 100 nm or more and 190 nm or less. Refers to things. The frequency of the number of metal oxide particles having an average primary particle size of 1 nm or more and less than 70 nm with respect to the metal oxide fine particles having an average primary particle size of 100 nm or more and 190 nm or less is preferably included as a frequency of 1 to 3 times. Within this range, the agglutination suppressing effect is high and the reflectance can be lowered. For metal oxide particles having an average primary particle size of 1 nm or more and 70 nm or less, it is preferable that the average primary particle size is 30 nm or more and 50 nm or less because the reflectance can be particularly lowered. When metal oxide particles having different average primary particle sizes are used in combination, it is preferable that the amounts of hydroxyl groups on the surfaces of both particles are close to each other because they are less likely to aggregate. However, metal oxide particles having an average primary particle size of 1 nm or more and less than 100 nm are mainly used to suppress aggregation of metal oxide particles having an average primary particle size of 100 nm or more and 190 nm or less, and are therefore available. Metal oxide particles having an easy hydroxyl group amount of ^{more than 1.00 × 10 -1} or an indentation hardness of less than 400 MPa may be used.

The antireflection layer may contain components other than these in addition to the binder resin and the metal oxide particles, and may contain, for example, a dispersant for the metal oxide particles, a leveling agent, an antifouling agent, and the like. May be good.

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

<Leveling agent>
By lowering the surface tension of the antireflection layer, the leveling agent can stabilize the liquid after coating and facilitate uniform arrangement of the curable compound (a1) and the metal oxide particles.
The antireflection layer forming composition used in the present invention can contain at least one leveling agent.
As a result, unevenness in film thickness due to drying variation due to the local distribution of dry air can be suppressed, repelling of the coating material can be improved, and the curable compound (a1) and metal oxide particles can be uniformly arranged. It can be made easier.

Specifically, as the leveling agent, at least one leveling agent selected from a silicone-based leveling agent and a fluorine-based leveling agent can be used. The leveling agent is preferably an oligomer or a polymer rather than a low molecular weight compound.

When a leveling agent is added, the leveling agent rapidly moves to the surface of the applied coating film and becomes unevenly distributed, and the leveling agent is unevenly distributed on the surface as it is even after the coating film is dried. The surface energy of the surface energy is reduced by the leveling agent. From the viewpoint of preventing film thickness non-uniformity, repelling, and unevenness, it is preferable that the surface energy of the film is low.

Preferred examples of the silicone-based leveling agent include polymers or oligomers containing a plurality of dimethylsilyloxy units as repeating units and having substituents at the ends and / or side chains. The polymer or oligomer containing dimethylsilyloxy as a repeating unit may contain structural units other than dimethylsilyloxy. The substituents may be the same or different, and it is preferable that there are a plurality of substituents. Examples of preferable substituents include groups containing a polyether group, an alkyl group, an aryl group, an aryloxy group, an aryl group, a cinnamoyl group, an oxetanyl group, a fluoroalkyl group, a polyoxyalkylene group and the like.

The number average molecular weight of the silicone-based leveling agent is not particularly limited, but is preferably 100,000 or less, more preferably 50,000 or less, particularly preferably 1,000 to 30,000, and 1,000 to 20,000. Is the most preferable.

As an example of a preferable silicone-based leveling agent, as a commercially available silicone-based leveling agent having no photopolymerizable group, X22-3710, X22-162C, X22-3701E, X22160AS, X22170DX, X224015 manufactured by Shin-Etsu Chemical Co., Ltd. , X22176DX, X22-176F, X224272, KF8001, X22-2000, etc .; FM4421, FM0425, FMDA26, FS1265, etc. manufactured by Chisso Corporation; BY16-750, BY16880, BY16848, BY16848, SF8427 manufactured by Toray Dow Corning Co., Ltd. SF8421, SH3746, SH8400, SF3771, SH3749, SH3748, SH8410, etc .; TSF series manufactured by Momentive Performance Materials Japan (TSF4460, TSF4440, TSF4445, TSF4450, TSF4446, TSF4453, TSF4452, TSF4730, TSF4770, etc.) , SILWET series (SILWETL77, SILWETL2780, SILWETL7608, SILWETL7001, SILWETL7002, SILWETL7087, SILWETL7200, SILWETL7210, SILWETL7220, SILWETL7230, SILWETL7500, SILWETL7510, SILWETL7600, SILWETL7602, SILWETL7604, SILWETL7604, SILWETL7605, SILWETL7607, SILWETL7622, SILWETL7644, SILWETL7650, SILWETL7657, SILWETL8500, SILWETL8600, SILWETL8610, SILWETL8620, SILWETL720) and the like can be mentioned, but the present invention is not limited thereto.

As those having a photopolymerizable group, X22-163A, X22-173DX, X22-163C, KF101, X22164A, X24-8201, X22174DX, X22164C, X222426, X222445, X222457, X222459, X222245 manufactured by Shin-Etsu Chemical Co., Ltd. , X221602, X221603, X22164E, X22164B, X22164C, X22164D, TM0701 etc.; Chisso Co., Ltd. silaplane series (FM0725, FM0721, FM7725, FM7721, FM7726, FM7727, etc.); Toray Dow Corning Co., Ltd. , SF8413, BY16-152D, BY16-152, BY16-152C, 8388A, etc .; TEGORad 2010, 2011, 2100, 2200N, 2300, 2500, 2600, 2700, etc. manufactured by Evonik Degusa Japan Co., Ltd .; BYK3500; KNS5300 manufactured by Shin-Etsu Silicone Co., Ltd .; UVHC1105, UVHC8550 manufactured by Momentive Performance Materials Japan Co., Ltd., etc., but are not limited thereto.

The leveling agent is preferably contained in the antireflection layer in an amount of 0.01 to 5.0% by mass, more preferably 0.01 to 2.0% by mass, and 0.01 to 1.0% by mass. % Is most preferably contained.

The fluoroaliphatic group contains a fluoroaliphatic group and a copolymeric group that contributes to the affinity for various compositions such as for coatings and molding materials when this leveling agent is used as an additive. It is a compound contained in the same molecule, and such a compound can generally be obtained by copolymerizing a monomer having a fluoroaliphatic group and a monomer having a remedial group.
Typical examples of a monomer having an amphipathic group that is copolymerized with a monomer having a fluoroaliphatic group include poly (oxyalkylene) acrylate and poly (oxyalkylene) methacrylate.

Preferred commercially available fluorine-based leveling agents include those having no photopolymerizable group, such as Megafuck series (MCF350-5, F472, F476, F445, F444, F443, F178, F470, F475, F479) manufactured by DIC Corporation. , F477, F482, F486, TF1025, F478, F178K, F-784-F, etc.); Fluorent series manufactured by Neos Co., Ltd. (FTX218, 250, 245M, 209F, 222F, 245F, 208G, 218G, 240G, 206D, 240D, etc.), and examples having a photopolymerizable group include Optool DAC manufactured by Daikin Industries, Ltd .; Defensa series manufactured by DIC Corporation (TF3001, TF3000, TF3004, TF3028, TF3027, TF3026). , TF3025, etc.), RS series (RS71, RS101, RS102, RS103, RS104, RS105, etc.), but are not limited thereto.

Further, the compounds described in JP-A-2004-331812 and JP-A-2004-163610 can also be used.

<Anti-fouling agent>
A known silicone-based or fluorine-based antifouling agent, slipper, or the like can be appropriately added to the antireflection layer for the purpose of imparting properties such as antifouling property, water resistance, chemical resistance, and slipperiness. ..

As a specific example of the silicone-based or fluorine-based antifouling agent, those having a photopolymerizable group among the above-mentioned silicone-based or fluorine-based leveling agents can be preferably used, but are limited thereto. is not it.

The antifouling agent is preferably contained in the antireflection layer in an amount of 0.01 to 5.0% by mass, more preferably 0.01 to 2.0% by mass, and 0.01 to 1.0% by mass. % Is most preferably contained.

The antireflection film of the present invention can be used for various purposes, and can be suitably used as, for example, a polarizing plate protective film.
The polarizing plate protective film using the antireflection film of the present invention can be bonded to a polarizing element to form a polarizing plate, and can be suitably used for a liquid crystal display device or the like.

[Polarizer]
The polarizing plate of the present invention has a polarizing element and an antireflection film of the present invention.
The polarizing plate of the present invention is a polarizing plate having a polarizing element and at least one protective film that protects the polarizing element, and it is preferable that at least one of the protective films is the antireflection film of the present invention.

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

[Image display device]
The image display device of the present invention has the antireflection film of the present invention or the polarizing plate of the present invention.
The image display device includes a display device using a cathode ray tube (CRT), a plasma display panel (PDP), an electroluminescence display (ELD), a fluorescent display (VFD), a field emission display (FED), and a liquid crystal display (LCD). ), And a liquid crystal display device is particularly preferable.
Generally, a liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides of the liquid crystal cell, and the liquid crystal cell supports a liquid crystal between two electrode substrates. Further, one optically anisotropic layer may be arranged between the liquid crystal cell and one polarizing plate, or two layers may be arranged between the liquid crystal cell and both polarizing plates. As the liquid crystal cell, a liquid crystal cell of various drive methods such as a TN (Twisted Nematic) mode, a VA (Virtually Aligned) mode, an OCB (Optically Compensatory Bend) mode, and an IPS (In-Plane Switching) mode can be applied.

[Manufacturing method of antireflection film]
The method for producing the antireflection film of the present invention is not particularly limited, but is preferable.
A composition for forming a hard coat layer containing the copolymer (a) is applied onto a base film to provide a hard coat layer, and a curable compound and metal oxide particles are placed on the hard coat layer. Step (1) of providing the layer (a) containing the curable compound with a thickness at which the metal oxide particles are embedded.
Step (2) of laminating the layer (b) of the pressure-sensitive adhesive film having the support and the layer (b) containing the pressure-sensitive adhesive having a gel fraction of 95.0% or more on the support with the layer (a). ,
The metal oxide particles are buried in the combined layer of the layer (a) and the layer (b), and protrude from the interface of the layer (a) opposite to the interface on the hard coat layer side. The step (3) of moving the position of the interface between the layer (a) and the layer (b) to the hard coat layer side so as to be performed.
Step (4) of curing the layer (a) in a state where the metal oxide particles are buried in a layer in which the layer (a) and the layer (b) are combined.
Step (5) of peeling the layer (b) from the layer (a),
Is a method for producing an antireflection film.

By the above manufacturing method, the above-mentioned antireflection film of the present invention can be manufactured.
In the above production method, the above-mentioned curable compound (a1) is preferably used as the curable compound, and the above-mentioned metal oxide particles are also preferably used.
Further, the layer (a) cured in the step (4) corresponds to the above-mentioned binder resin film, and the layer (a) and the metal oxide particles protruding from the layer (a) are included in the antireflection layer. Is.

FIG. 2 shows an example of a preferred embodiment of the method for producing an antireflection film of the present invention.
FIG. 2 (1) shows the inside of the layer (a) (reference numeral 4 in FIG. 2) containing the curable compound (a1) on the hard coat layer HC provided on the base film 1 in the step (1). The state in which the metal oxide particles (also referred to as “particles (a2)”) (reference numeral 3 in FIG. 2) are provided with a thickness to be buried is schematically shown.

FIG. 2 (2) shows a layer (b) containing an adhesive having a gel fraction of 95.0% or more on the support 5 and the support 5 in the step (2) (reference numeral 6 in FIG. 2). The state in which the layer (b) of the adhesive film 7 having the above is bonded to the layer (a) (reference numeral 4 in FIG. 2) is schematically shown.

In FIG. 2 (3), in the step (3), the particles (a2) are buried in the combined layer of the layer (a) and the layer (b), and the hard coat layer side of the layer (a) is formed. A state in which the position of the interface between the layers (a) and the layer (b) is moved to the hard coat layer side so as to protrude from the interface on the opposite side to the interface is schematically shown. As will be described later, as a method of moving the position of the interface between the layers (a) and the layer (b) to the hard coat layer side, a layer (b) containing a part of the curable compound (a1) with an adhesive is used. There is a method of infiltrating into.
Moving the position of the interface between the layer (a) and the layer (b) toward the hard coat layer also brings the position of the interface closer to the hard coat layer.

FIG. 2 (4) schematically shows a place where the layer (a) is cured in the step (4) with the particles (a2) buried in the combined layer of the layer (a) and the layer (b). It is represented as.

FIG. 2 (5) shows a state (antireflection film 10) after the adhesive film 7 is peeled off in the step (5) of peeling the adhesive film 7 including the layer (b) from the layer (a). ..

In the method for producing an antireflection film of the present invention, the temperature at which steps (1) to (4) are performed is preferably 60 ° C. or lower, more preferably 40 ° C. or lower. By keeping the temperature at which the steps (1) to (4) are performed at 60 ° C. or lower, the aggregation of the metal oxide particles can be suppressed, and a good uneven shape can be formed.

[Step (1)]
In the step (1), a composition for forming a hard coat layer containing the copolymer (a) is applied onto a base film to provide a hard coat layer, and a curable compound and a metal are placed on the hard coat layer. This is a step of providing the oxide particles with a thickness at which the metal oxide particles are embedded in the layer (a) containing the curable compound.
In the present invention, the "thickness in which the metal oxide particles are embedded in the layer (a)" means a thickness of 0.8 times or more the average primary particle size of the metal oxide particles.

In the step (1), the method of providing the layer (a) on the hard coat layer is not particularly limited, but it is preferably provided by applying the layer (a) on the hard coat layer. In this case, the layer (a) is a layer formed by applying a composition containing the curable compound (a1) and the particles (a2) (also referred to as "composition for forming the layer (a)"). Is. The coating method is not particularly limited, and a known method can be used. For example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method and the like can be mentioned.

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

(Layer (a))
The layer (a) in the step (1) preferably contains the curable compound (a1) and the particles (a2).
The layer (a) is a layer for forming an antireflection layer.
The curable compound (a1) contained in the layer (a) can become a binder resin for the antireflection layer by being cured.
The particles (a2) contained in the layer (a) are particles in the antireflection film that protrude from the surface of the film made of the binder resin to form an uneven shape (moth-eye structure).
Since the layer (a) is cured in the step (4), the components contained before and after the curing are different, but in the present invention, it may be referred to as the layer (a) at any stage for convenience. .. The same applies to the hard coat layer.
The film thickness of the layer (a) in the step (1) is preferably 0.8 times or more and 2.0 times or less, and 0.8 times or more and 1.5 times or less the average primary particle size of the particles (a2). It is more preferable that it is 0.9 times or more and 1.2 times or less.
As described above, since the antireflection layer is finally formed from the composition for forming the layer (a), the composition for forming the layer (a) is an antireflection layer forming composition. is there.

The base film, the hard coat layer, the curable compound (a1), and the particles (a2) are the same as those described above.

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

<Polymerization initiator>
The composition for forming the layer (a) or the layer (a) may contain a polymerization initiator.
The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator. An appropriate polymerization initiator may be selected according to the type of the polymerizable compound used in combination. As the polymerization initiator, either a thermal polymerization initiator or a photopolymerization initiator may be selected depending on the type of polymerization treatment (heating, light irradiation) performed in the production process. Further, the thermal polymerization initiator and the photopolymerization initiator may be used in combination.

The structure of the thermal polymerization initiator is not particularly limited. Specific embodiments of the thermal polymerization initiator include azo compounds, hydroxylamine ester compounds, organic peroxides, hydrogen peroxide and the like. Specific examples of the organic peroxide include those described in paragraph 0031 of Japanese Patent No. 5341155.

When the curable compound (a1) is a photopolymerizable compound, it preferably contains a photopolymerization initiator.
The structure of the photopolymerization initiator is not particularly limited. Specific embodiments include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, and fluorocarbon compounds. Examples thereof include amine compounds, aromatic sulfoniums, loffin dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes and coumarins. Specific examples of the photopolymerization initiator, preferred embodiments, commercially available products, and the like are described in paragraphs [0133] to [0151] of JP-A-2009-098658, and can be preferably used in the present invention as well. it can.

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

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

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

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

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

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

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

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

The composition for forming the layer (a) or the layer (a) may further contain a dispersant, a leveling agent, an antifouling agent, etc. of the particles (a2), which are the same as those described above. is there.

[Step (2)]
The step (2) is a step of laminating the layer (b) of the pressure-sensitive adhesive film having the support and the layer (b) containing the pressure-sensitive adhesive having a gel fraction of 95.0% or more on the support with the layer (a). Is. The method of laminating the layer (a) and the layer (b) of the adhesive film is not particularly limited, and a known method can be used, and examples thereof include a laminating method.
It is preferable to attach the adhesive film so that the layer (a) and the layer (b) are in contact with each other.
Before the step (2), there may be a step of drying the layer (a). The drying temperature of the layer (a) is preferably 20 to 60 ° C, more preferably 20 to 40 ° C. The drying time is preferably 0.1 to 120 seconds, more preferably 1 to 30 seconds.
In the step (2), the present inventors attach the layer (b) and the layer (a) of the adhesive film, and in the step (3) described later, the particles (a2) are formed into the layer (a) and the layer (b). The particles (a2) are buried in the combined layers and protrude from the interface of the layer (a) opposite to the interface on the hard coat layer side, and the particles (a2) are formed in the layer (a) and the layer (a) in the step (4) described later. By curing the layer (a) while being buried in the combined layer of b), the particles (a2) are not exposed to the air interface before the layer (a) is cured, so that aggregation is suppressed and the particles It has been found that a good uneven shape formed by (a2) can be produced.

(Adhesive film)
The pressure-sensitive adhesive film has a support and a layer (b) made of a pressure-sensitive adhesive having a gel fraction of 95.0% or more.

<Layer (b)>
The layer (b) is made of an adhesive having a gel fraction of 95.0% or more.
When the gel content of the pressure-sensitive adhesive is 95.0% or more, the pressure-sensitive adhesive component does not easily remain on the surface of the anti-reflection film when the pressure-sensitive adhesive film is peeled off to produce an anti-reflection film, and even if cleaning is not performed. , An antireflection film having a sufficiently low reflectance can be obtained.
The gel fraction of the pressure-sensitive adhesive is preferably 95.0% or more and 99.9% or less, more preferably 97.0% or more and 99.9% or less, and 98.0% or more and 99.9%. The following is more preferable.
The gel fraction of the pressure-sensitive adhesive is the ratio of the insoluble content after immersing the pressure-sensitive adhesive in tetrahydrofuran (THF) at 25 ° C. for 12 hours, and is calculated from the following formula.
Gel fraction = (mass of adhesive insoluble in THF) / (total mass of adhesive) x 100 (%)

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

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

The layer (b) is an adhesive layer having a slight adhesive strength, in which the peel strength (adhesive strength) with respect to the surface of the adherend at a peeling speed of 0.3 m / min is about 0.03 to 0.3 N / 25 mm. This is preferable because it is excellent in operability when the adhesive film is peeled off from the layer (a) which is an adherend.

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 the (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 18 carbon atoms (a copolymer in the case of two or more kinds of monomers) is preferable. The weight average molecular weight of the (meth) acrylic polymer is preferably 200,000 to 2,000,000.

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

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

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

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

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

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

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

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

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

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

The pressure-sensitive adhesive may contain a cured product of a composition for forming the pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive composition).
The pressure-sensitive adhesive composition preferably contains the above polymer and a cross-linking agent, and may be cross-linked using heat, ultraviolet rays (UV), or the like. As the cross-linking agent, one or more cross-linking agents selected from the compound group consisting of a bifunctional or higher functional isocyanate-based cross-linking agent, a bifunctional or higher functional epoxy-based cross-linking agent, and an aluminum chelate-based cross-linking agent are preferable. When a cross-linking agent is used, when the adhesive film is peeled off to produce an antireflection film, from the viewpoint of making it difficult for the adhesive component to remain on the surface of the antireflection film, 0. It is preferably contained in an amount of 1 to 15 parts by mass, more preferably 3.5 to 15 parts by mass, and even more preferably 5.1 to 10 parts by mass.

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

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

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

Examples of the alkyl group having 8 to 18 carbon atoms include an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. It may be a mixed alkyl group derived from natural fats and oils. Examples of the alkenyl group having 8 to 18 carbon atoms include an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, an oleyl group and a linoleyl group. ..
Examples of the alkyl group having 14 to 20 carbon atoms include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group and an icosyl group. It may be a mixed alkyl group derived from natural fats and oils. Examples of the alkenyl group having 14 to 20 carbon atoms include a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, an oleyl group, a linoleyl group, a nonadesenyl group and an icosenyl group.

Counter anions for the quaternary onium salt include chloride (Cl ⁻ ), bromide (Br ⁻ ), methyl sulfate (CH ₃ OSO ₃ ⁻ ), ethyl sulfate (C ₂ H ₅ OSO ₃ ⁻ ), and paratoluene sulfonate (p −). _{CH 3 C 6 H 4 SO 3} -) and the like.

Specific examples of the quaternary onium salt include dodecyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium bromide, tetradecyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium bromide, hexadecyldimethylbenzylammonium chloride, hexadecyldimethylbenzylammonium bromide, Octadecyldimethylbenzylammonium chloride, octadecyldimethylbenzylammonium bromide, trioctylbenzylammonium chloride, trioctylbenzylammonium bromide, trioctylbenzylphosphonium chloride, trioctylbenzylphosphonium bromide, tris (decyl) benzylammonium chloride, tris (decyl) benzylammonium Bromid, Tris (decyl) benzylphosphonium chloride, Tris (decyl) benzylphosphonium bromide, Tetraoctylammonium chloride, Tetraoctylammonium bromide, Tetraoctylphosphonium chloride, Tetraoctylphosphonium bromide, Tetranonylammonium chloride, Tetranonylammonium bromide, Tetranonyl Examples thereof include phosphonium chloride, tetranonyl phosphonium bromide, tetrakis (decyl) ammonium chloride, tetrakis (decyl) ammonium bromide, tetrakis (decyl) phosphonium chloride, and tetrakis (decyl) phosphonium bromide.

In addition, "tris (decyl)" and "tetrakis (decyl)" mean having 3 or 4 decyl groups which are alkyl groups having 10 carbon atoms, and tridecyl groups which are alkyl groups having 13 carbon atoms. And the tetradecyl group, which is an alkyl group having 14 carbon atoms.

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

Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, and propylene glycol. Examples thereof include fatty acid esters and polyoxyalkylene-modified silicones.

Examples of the anionic surfactant include monoalkyl sulfates, alkyl polyoxyethylene sulfates, alkylbenzene sulfonates, monoalkyl phosphates and the like.

Further, examples of the amphoteric surfactant include alkyldimethylamine oxide and alkylcarboxybetaine.
The ionic liquid is a non-polymeric substance composed of anions and cations and is a liquid at room temperature (for example, 25 ° C.). Examples of the cation portion include cyclic amidin ions such as imidazolium ions, pyridinium ions, ammonium ions, sulfonium ions, phosphonium ions and the like. The anion portions include C _n H _{2n + 1} COO ⁻ , C _n F _{2n + 1} COO ⁻ , NO ₃ ⁻ , C _n F _{2n + 1} SO ₃ ⁻ , (C _n F _{2n + 1} SO ₂ ) ₂ N ⁻ , (C _n F). _{2n + 1} SO ₂ ) ₃ C ⁻ , PO ₄ ^{2 −} , AlCl ₄ −, Al ₂ Cl ₇ ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ^{− and the} like.

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

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

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

The pressure-sensitive adhesive composition may further contain a cross-linking accelerator. The cross-linking accelerator may be a substance that functions as a catalyst for the reaction (cross-linking reaction) between the copolymer and the cross-linking agent when the polyisocyanate compound is used as the cross-linking agent, and is an amine-based substance such as a tertiary amine. Examples thereof include organic metal compounds such as compounds, 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 cross-linking accelerator.

The metal chelate compound is a compound in which one or more polydentate ligands L are bonded to the central metal atom M. The metal chelate compound may or may not have one or more bidentate ligands X that bind to the metal atom M. For example, when the general formula of a metal chelate compound having one metal atom M is _{represented by M (L) m} (X) _n , m ≧ 1 and n ≧ 0. When m is 2 or more, m L may be the same ligand or may be different ligands. When n is 2 or more, n Xs may be the same ligand or different ligands.

Examples of the metal atom M include Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, Sn and the like. Examples of the polydentate ligand L include β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetic acid, lauryl acetoacetic acid, and stearyl acetoacetic acid, and acetylacetone (also known as 2,4-pentandione), , 4-Hexanedione, β-diketone such as benzoylacetone. These are keto-enol tautomeric compounds and may be enol-deprotonated enolates (eg, acetylacetonate) in the polydentate ligand L.

The monodentate ligand X includes halogen atoms such as chlorine atom and bromine atom, pentanoyl group, hexanoyl group, 2-ethylhexanoyl group, octanoyl group, nonanoyl group, decanoyyl group, dodecanoyl group, octadecanoyl group and other acyloxy. Examples thereof include an alkoxy group such as a group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group and a butoxy group.

Specific examples of the metal chelate compound include tris (2,4-pentandionato) iron (III), iron tris acetylacetonate, titanium trisacetylacetonate, ruthenium trisacetylacetonate, zinc bisacetylacetonate, and aluminum tris. Acetylacetonate, Zirconite Tetrakis Acetylacetonate, Tris (2,4-Hexanedionate) Iron (III), Bis (2,4-HexaneZionato) Zinc, Tris (2,4-Hexanedionate) Titanium, Tris Examples thereof include (2,4-hexane dionat) aluminum and tetrakis (2,4-hexane dionate) zirconium.

Examples of the organic tin compound include dialkyltin oxide, a fatty acid salt of dialkyltin, and a fatty acid salt of first tin. Long-chain alkyl tin compounds such as dioctyl tin compounds are preferred. Specific examples of the organic tin compound include dioctyl tin oxide and dioctyl tin dilaurate.

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

<Support>
The support in the adhesive film will be described.
As the support, a plastic film made of a transparent and flexible resin is preferably used. Suitable plastic films for the support include polyester films such as polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, and polybutylene terephthalate, (meth) acrylic resin, polycarbonate resin, polystyrene resin, and polyolefin resin. Examples thereof include a film made of a resin, a cyclic polyolefin resin, a 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 the required strength and optical suitability. The support may be a non-stretched film, uniaxially or biaxially stretched, or may be a plastic film in which the stretching ratio or the angle of the axial method formed by the crystallization of stretching is controlled.

As the support, one having ultraviolet transparency is preferable. Having ultraviolet light transmission makes it possible to irradiate the layer (a) with ultraviolet rays from the coating layer side when curing the layer (a) in the step (4), which is preferable in terms of manufacturing suitability.
Specifically, the maximum transmittance of the support at a wavelength of 250 nm to 300 nm is preferably 20% or more, more preferably 40% or more, and most preferably 60% or more. When the maximum transmittance at a wavelength of 250 nm to 300 nm is 20% or more, it is preferable that the layer (a) is easily cured by irradiating ultraviolet rays from the coating layer side.
Further, the maximum transmittance of the pressure-sensitive adhesive film having the layer (b) formed on the support at a wavelength of 250 nm to 300 nm is preferably 20% or more, more preferably 40% or more, and more preferably 60% or more. Is the most preferable.

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

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

In the present invention, in the step (4), the layer (a) is cured while maintaining the state in which the particles (a2) are buried in the combined layer of the layer (a) and the layer (b). ), It is preferable to have a concavo-convex shape formed by particles (a2) protruding from the interface of the layer (a). By doing so, when the layer (a) is cured in the step (4) and then the layer (b) is peeled off in the step (5), the antireflection in a state where the particles (a2) protrude from the surface of the layer (a). You can get the film.

In the present invention, a step (1-2) of obtaining a cured compound (a1c) by curing a part of the curable compound (a1) in the layer (a) between the steps (1) and (2). May include.
Curing a part of the curable compound (a1) means curing only a part of the curable compound (a1), not all of the curable compound (a1). By curing only a part of the curable compound (a1) in the step (1-2), the particles (a2) are the interface opposite to the interface on the hard coat layer side of the layer (a) in the step (3). It is possible to suppress the aggregation of particles when the position of the interface between the layers (a) and the layer (b) is moved to the hard coat layer side so as to protrude from the surface, and the reflectance and the total light transmittance are good antireflection. It is preferable to carry out because a film can be obtained. Since the optimum curing conditions in the step (1-2) differ depending on the formulation of the layer (a), the optimum curing conditions may be appropriately selected.

[Step (3)]
In the step (3), the particles (a2) are buried in the combined layer of the layer (a) and the layer (b), and from the interface opposite to the interface on the hard coat layer side of the layer (a). This is a step of moving the position of the interface between the layer (a) and the layer (b) toward the hard coat layer side so as to protrude.
In the present invention, "the particles (a2) are buried in the combined layer of the layer (a) and the layer (b)" means that the thickness of the combined layer of the layer (a) and the layer (b) is the particle. It means that it is 0.8 times or more the average primary particle size of (a2).
The step (3) is preferably carried out by infiltrating a part of the curable compound (a1) into the pressure-sensitive adhesive layer.
In the step (3), when a part of the curable compound (a1) is infiltrated into the pressure-sensitive adhesive layer, the laminate having the base film, the hard coat layer, the layer (a), and the layer (b) is heated to 60 ° C. or lower. It is preferable to keep the temperature at 40 ° C. or lower, and it is more preferable to keep the temperature below 40 ° C. By keeping the temperature below 60 ° C., the viscosities of the curable compound (a1) and the pressure-sensitive adhesive can be kept high, and the thermal motion of the particles can be suppressed, so that the antireflection ability due to the aggregation of the particles is lowered. , Has a great effect of preventing an increase in haze and cloudiness. The lower limit of the temperature at which the laminate having the base film, the hard coat layer, the layer (a), and the layer (b) is maintained is not particularly limited, and even at room temperature (25 ° C.), the temperature is lower than room temperature. It may be.

[Step (4)]
The step (4) is a step of curing the layer (a) in a state where the particles (a2) are buried in the combined layer of the layer (a) and the layer (b).
In the present invention, "a state in which the particles (a2) are buried in the combined layer of the layer (a) and the layer (b)" means that the thickness of the combined layer of the layer (a) and the layer (b) is the particle ( It shall indicate that it is 0.8 times or more the average primary particle size of a2).
Curing the layer (a) means polymerizing the curable compound (a1) contained in the layer (a), whereby a binder resin in the antireflection layer of the antireflection film can be formed. By maintaining the state in which the particles (a2) are buried in the combined layer of the layer (a) and the layer (b) in the step (4), the aggregation of the particles (a2) is suppressed and a good uneven shape is formed. can do.
As a mechanism for suppressing particle agglutination by maintaining the state in which the particles (a2) are buried in the combined layer of the layer (a) and the layer (b), the particles (a2) are suppressed by the time the layer (a) is cured. ) Is exposed to the air interface, it is known that a large attractive force derived from surface tension called lateral capillary force acts, and the particles (a2) are buried in the layer (a) and the layer (b) combined. It is presumed that the above-mentioned attractive force can be reduced by keeping it.

Curing can be performed by irradiating with light. The type of light is not particularly limited, and examples thereof include X-rays, electron beams, ultraviolet rays, visible light, and infrared rays, but ultraviolet rays are widely used. For example, if the coating film is ultraviolet-curable, preferably to cure the curable compound (a1) of the layer by irradiation with irradiation dose of ultraviolet rays of 10mJ ^/ cm ² ~1000mJ ^/ cm 2 by an ultraviolet lamp (a). More preferably ^{50mJ / cm 2 ~1000mJ / cm 2} , further preferably ^{100mJ / cm 2 ~500mJ / cm 2} . At the time of irradiation, the above energy may be applied all at once, or may be divided and irradiated. As the ultraviolet lamp type, a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used.

The oxygen concentration at the time of curing is preferably 0 to 1.0% by volume, more preferably 0 to 0.1% by volume, and most preferably 0 to 0.05% by volume. By making the oxygen concentration at the time of curing smaller than 1.0% by volume, the film is less susceptible to the inhibition of curing by oxygen, and a strong film is formed.

In steps (2) to (4), it is preferable that a plurality of particles (a2) are not present in the direction orthogonal to the surface of the base film.

In steps (2) to (4), it is preferable that the total film thickness of the film thickness of the layer (a) and the film thickness of the layer (b) is larger than the average primary particle size of the particles (a2).
When the total film thickness of the film thickness of the layer (a) and the film thickness of the layer (b) is larger than the average primary particle size of the particles (a2), the particles (a2) form the layers (a) and the layer (b). It can be buried in the combined layers, which is preferable.
However, the step (4) is for the reason that when the adhesive film containing the layer (b) is peeled off in the step (5) described later, a shape (moss eye structure) in which the particles (a2) protrude from the surface of the layer (a) is obtained. ), The film thickness of the layer (a) is preferably smaller than the average primary particle size of the particles (a2), and more preferably half or less of the average primary particle size of the particles (a2).
The film thickness of the layer (a) in the step (4) is such that the height of the interface of the layer (ca) obtained by curing the layer (ca) opposite to the interface on the hard coat layer side is the average of the particles (a2). It is preferable to adjust the particle size so that it is less than half of the primary particle size, and more preferably, the film cross section of the layer (ca) is observed with a scanning electron microscope (SEM), and the film thickness at 100 points is arbitrarily measured. When the average value is determined, it is preferable to adjust the value to 10 nm to 100 nm (more preferably 20 nm to 90 nm, still more preferably 30 nm to 70 nm).

[Step (5)]
The step (5) is a step of peeling the layer (b) from the layer (a).
If the adhesive remains on the layer (a) side when the layer (b) is peeled off, the base film, the hard coat layer and the cured layer (a) are not dissolved, but a solvent that dissolves the adhesive is used. May be used for cleaning.

After the adhesive film containing the layer (b) is peeled off by the step (5), an antireflection film having a moth-eye structure having an uneven shape formed by particles (a2) on the surface of the layer (a) is obtained.

Hereinafter, the present invention will be described in more detail with reference to examples. The amounts, ratios, operations, etc. of the materials, reagents, and substances shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

<Synthesis example 1>
(Synthesis of copolymer B-1)
10.0 g of cyclohexanone was charged into a 500 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, and the temperature was raised to 84 ° C. Next, 6.28 g of 2- (perfluorohexyl) ethyl acrylate, 11.54 g of compound MII-1, 2.16 g of acrylic acid, 32 g of cyclohexanone and "V-601" (manufactured by Wako Pure Chemical Industries, Ltd.). 0.54 g of the mixed solution was added dropwise at a constant velocity so that the addition was completed in 180 minutes. After the dropping was completed, stirring was continued for another 3 hours, the temperature was raised to 95 ° C., and stirring was continued for another 2 hours. After cooling to room temperature, 0.41 g of methyl hydroquinone, 4.26 g of glycidyl methacrylate, 1.55 g of tetrabutylammonium bromide, and 20 g of cyclohexanone are added and stirred at 80 ° C. for 8 hours to prepare a cyclohexanone solution of the copolymer B-1. Obtained.

Copolymers B-2 to B-18 having the structures shown in Table 1 below were synthesized in the same manner except that the monomers used in Synthesis Example 1 and their composition ratios were appropriately changed.

<Example 1>
(Preparation of composition for forming hard coat layer)
Each component is mixed according to the composition described below, the obtained composition is put into a mixing tank, stirred, and filtered through a polypropylene filter having a pore size of 0.4 μm to form a hard coat layer composition (hard coat layer). Coating liquid) HC-1.

(Hard coat layer coating liquid HC-1)
A-TMMT 24.4 parts by mass AD-TMP 12.0 parts by mass Irgacure 127 1.6 parts by mass Ethanol 3.5 parts by mass Methanol 8.8 parts by mass 1-butanol 6.0 parts by mass Methyl ethyl ketone (MEK) 20.3 Parts by mass Methyl acetate 21.4 parts by mass Copolymer B-1 0.8 parts by mass

A-TMMT: Pentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
AD-TMP: Ditrimethylolpropane tetraacrylate (NK ester manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
Irgacure 127: Photopolymerization Initiator (manufactured by BASF Japan Ltd.)

The copolymer B-1 was synthesized in the above Synthesis Example 1, has the repeating unit shown in Table 1 below at the content (mol%) shown in Table 1, and has the weight shown in Table 1. It is a copolymer having an average molecular weight (Mw).

C6FA, C8FA, and C6FHA in Table 1 above are repeating units having the following structure.

II-1 to II-12 and III-1 to III-6 in Table 1 above have the structures as described above.

St, PhEA, AA, and AS-6 in Table 1 above are repeating units having the following structure.

The n of AS-6 is about 60.

[Synthesis of silica particles P1]
67.54 kg of methyl alcohol and 26.33 kg of 28% by mass aqueous ammonia (water and catalyst) were charged into a 200 L reactor equipped with a stirrer, a dropping device and a thermometer, and the liquid temperature was adjusted to 33 ° C. while stirring. Adjusted to. On the other hand, a solution prepared by dissolving 12.70 kg of tetramethoxysilane in 5.59 kg of methyl alcohol was charged into the dropping device. While maintaining the liquid temperature in the reactor at 33 ° C., the above solution is added dropwise from the dropping device over 37 minutes, and after the completion of the dropping, stirring is performed while maintaining the liquid temperature at the above temperature for another 37 minutes. Hydrolysis and condensation of methoxysilane were carried out to obtain a dispersion containing a silica particle precursor. Silica particles are dried by airflow of this dispersion using an instantaneous vacuum evaporator (Cracks system CVX-8B type manufactured by Hosokawa Micron Co., Ltd.) under the conditions of a heating tube temperature of 175 ° C. and a reduced pressure of 200 torr (27 kPa). Obtained P1.
The average primary particle size of the silica particles P1 was 170 nm, the particle size dispersion (CV value) was 7.0%, and the indentation hardness was 340 MPa.

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

[Preparation of Silane Coupling Agent-treated Silane Particles P3]
5 kg of calcined silica particles P2 were charged into a 20 L Henschel mixer (FM20J type manufactured by Mitsui Mining Co., Ltd.) equipped with a heating jacket. While stirring the calcined silica particles P2, 50 g of 3-acryloxypropyltrimethoxysilane (KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise by dissolving a solution in 90 g of methyl alcohol and mixed. Then, the temperature was raised to 150 ° C. over about 1 hour while mixing and stirring, and the temperature was maintained at 150 ° C. for 12 hours for heat treatment. In the heat treatment, the scraping device was constantly rotated in the direction opposite to that of the stirring blade to scrape off the deposits on the wall surface. In addition, a spatula was used to scrape off the deposits on the wall surface as appropriate. After heating, it was cooled and crushed and classified using a jet pulverization classifier to obtain silica particles P3 treated with a silane coupling agent.
The average primary particle size of the silane coupling agent-treated silica particles P3 was 171 nm, the particle size dispersion (CV value) was 7.0%, and the indentation hardness was 470 MPa.

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

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

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

Composition (A-1)
U-15HA 1.4 parts by mass Compound C3 1.5 parts by mass KBM-4803 5.8 parts by mass Irgacure 127 0.2 parts by mass Compound P 0.1 parts by mass Silica particle dispersion PA-1 32.3 parts by mass Compound A 0.1 parts by mass Ethanol 12.7 parts by mass Methyl ethyl ketone 33.3 parts by mass Ease 12.7 parts by mass

U-15HA, compound C3, and KBM-4803 are binder resin forming compounds, while U-15HA and compound C3 are curable compounds (a1), and KBM-4803 contains reactive groups other than radical reactive groups. It is a silane coupling agent having.
The compounds used for each are shown below.
U-15HA (manufactured by Shin Nakamura Chemical Industry Co., Ltd.): Urethane acrylate Irgacure 127: Photopolymerization initiator (manufactured by BASF Japan Ltd.)
Compound P: 2- (4-Methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine (photoacid generator, manufactured by Tokyo Chemical Industry Co., Ltd.)
Compound A: F-784-F (manufactured by DIC Corporation)
KBM-4803: Silane coupling agent having a reactive group other than radical reactive group (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Creation of antireflection film 1>
(Formation of hard coat layer)
The hard coat layer coating liquid HC-1 was applied onto a base film (TJ25, manufactured by FUJIFILM Corporation) using a die coater. After drying at 30 ° C. for 90 seconds and then at 45 ° C. for 1 minute, a 160 W / cm air-cooled metal halide lamp (Igraphics Co., Ltd.) while purging nitrogen so that the atmosphere has an oxygen concentration of about 1.3% by volume. The coating layer was cured by irradiating ultraviolet rays having an illuminance of 18 mW / cm ² and an irradiation volume of 10 mJ / cm ² to form a hard coat layer having a thickness of 5 μm. The base material with the hard coat layer is HC-1.

(Process (1) Coating of layer (a))
The composition (A-1) was applied to the hard coat layer of the base material HC-1 with a hard coat layer at 2.8 ^{ml / m 2} using a die coater, and dried at 30 ° C. for 90 seconds. The film thickness of the layer (a) in the step (1) is 170 nm.

(Step (1-2) Step of curing a part of the curable compound (a1) in the layer (a) to obtain the cured compound (a1c))
A layer (a) using a high-pressure mercury lamp (Dr. honle AG model: 33351N part number: LAMP-HOZ 200 D24 U 450 E) while purging nitrogen so that the atmosphere has an oxygen concentration of 1.4% by volume. ) Was irradiated with light at an irradiation volume of 5.0 mJ to cure a part of the curable compound (a1). In addition, the irradiation amount is measured by HEAD SENSER on the eye ultraviolet integrated illuminance meter UV METER UVPF-A1 manufactured by Eye Graphic Co., Ltd.
PD-365 was attached and measurement was performed in a measurement range of 0.00.

(Process (2) Adhesive film bonding)
Next, an adhesive film obtained by peeling the release film from AS3-304 was bonded onto the dried layer (a) so that the adhesive layer (layer (b)) was on the layer (a) side. .. For bonding, a commercial laminator Bio330 (manufactured by DAE-EL Co.) was used, and the bonding was performed at a speed of 1.
In addition, AS3-304 refers to a laminate (protective film) composed of a support / adhesive layer / release film, and the release film is peeled off from this laminate, and the laminate composed of a support / adhesive layer is formed. The body is an adhesive film.

Details of the laminate (protective film) used are shown below.
-AS3-304 Fujimori Kogyo Co., Ltd. Support: Polyester film (thickness 38 μm)
Adhesive layer thickness: 20 μm
Maximum transmittance at wavelengths of 250 nm to 300 nm with the release film peeled off: less than 0.1% The transmittance was measured using an ultraviolet-visible near-infrared spectrophotometer UV3150 manufactured by Shimadzu Corporation.

(Step (3) Permeation of curable compound (a1) into the pressure-sensitive adhesive layer)
With the pressure-sensitive adhesive film attached, the mixture was allowed to stand at 25 ° C. for 5 minutes to allow a part of the curable compound (a1) to penetrate into the pressure-sensitive adhesive layer.

(Step (4) Curing of layer (a))
Following the above standing, a base film using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging nitrogen so that the atmosphere has an oxygen concentration of 0.01% by volume or less. The layer (a) was cured by irradiating the surface coated with the layer (a) with ultraviolet rays having an ^{illuminance of 150 mW / cm 2} and an irradiation volume of 600 mJ / cm ^{2 through the adhesive film.} The film thicknesses of the layer (a) and the pressure-sensitive adhesive layer (layer (b)) after the step (4) and before the step (5) were 50 nm and 20 μm, respectively.

(Step (5) Peeling of adhesive film)
The adhesive film containing the layer (b) (the release film was peeled off from AS3-304) was peeled off from the prepared laminate. The layer (a) after the layer (b) was peeled off was hardened to the extent that it was not broken by the peeling of the pressure-sensitive adhesive layer. After peeling off the adhesive, use a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging nitrogen so that the oxygen concentration becomes 0.01% by volume or less, and layer the plastic base material. The layer (a) was cured by irradiating the surface coated with (a) with ^{ultraviolet rays having an illuminance of 150 mW / cm 2} and an irradiation amount of 600 mJ / cm ^2. Then, methyl isobutyl ketone was poured over the surface to which the pressure-sensitive adhesive film was bonded to wash away the residue of the pressure-sensitive adhesive layer, and the film was dried at 25 ° C. for 10 minutes to obtain an antireflection film 1.

(Particle regularity)
The regularity of the particles was evaluated by how much the regularity of the particles changed with respect to the reference sample (sample for reference) (Δ particle regularity).
-Preparation of reference sample 1-
Prepare a sample that has passed the steps (1-2) of the antireflection film 1, and while purging nitrogen so that the oxygen concentration becomes 0.01% by volume or less, an air-cooled metal halide lamp of 160 W / cm (I Graphics Co., Ltd.) The layer (a) is cured by irradiating the surface coated with the layer (a) of the base film ^{with ultraviolet rays having an illuminance of 150 mW / cm 2} and an irradiation volume of 600 mJ / cm ^2. Sample 1 for use was prepared.
-Calculation of particle regularity-
The surface of the obtained antireflection film 1 and the reference sample 1 was observed by SEM (S-4300 manufactured by Hitachi High-Technologies Corporation). The number of particles in the range of 1280 nm × 830 nm and the average distance between the centers with the closest particles were calculated, and the regularity of the particles was calculated by the following formula.
(Particle regularity)
= (Average center-to-center distance with closest particles-Average primary particle size) / (Distance between particles in closest packing-Average primary particle size) x 100
Here, (distance between particles in the closest packing) = √ (4 / (√3) × 1280 × 830/2 / number of particles) × 10.
(Δ particle regularity) = (particle regularity of reference sample 1)-(particle regularity of antireflection film 1)
The delta baryon regularity was evaluated according to the following criteria.
A: Less than 4% B: 4% or more and less than 8% C: 8% or more and less than 10% D: 10% or more

<Examples 2 to 18 and Comparative Example 1>
Hard coat layer coating liquids HC-2 to HC- in the same manner as the hard coat layer coating liquid HC-1 except that the types of copolymers shown in Table 2 below were used instead of the copolymer B-1. 18 and HC-R1 were prepared.
The antireflection films 2 to 18 and the antireflection films 2 to 18 in the same manner as in Example 1 except that the hard coat layer coating liquids HC-2 to HC-18 and HC-R1 were used instead of the hard coat layer coating liquid HC-1. R1 was prepared and evaluated.
The antireflection films 2 to 18 and the reference samples 2 to 8 and R1 corresponding to R1 are the same as those of the reference sample 1 except that the samples that have undergone the steps (1-2) of each antireflection film are prepared. Created. The Δparticle regularity was calculated by subtracting the particle regularity of each antireflection film from the particle regularity of each reference sample as shown in the following formula.
(Δ particle regularity) = (particle regularity of reference sample)-(particle regularity of antireflection film)

The copolymers B-2 to B-18 are copolymers having the repeating units shown in Table 1 in the content (mass%) shown in Table 1 and having Mw shown in Table 1.
The copolymer B-R1 is a compound having the following structure, and the ratio of each repeating unit is a molar ratio.

The evaluation results are shown in Table 3 below.

The average reflectances of the antireflection films obtained in Examples 1 to 18 and Comparative Example 1 were all 1% or less, and it was confirmed by SEM observation that they had a moth-eye structure, but when they were visually observed through a light source. In addition, the antireflection film of the example had a very small cloudiness, whereas the antireflection film obtained in Comparative Example 1 had a cloudiness.
In the antireflection films of Examples 1 to 18, the decrease in regularity of particles due to the formation of the moth-eye structure was small. On the other hand, the antireflection film of Comparative Example 1 has a larger decrease in regularity of particles due to the formation of the moth-eye structure than the antireflection film of the example, and is an antireflection film having a cloudy feeling as compared with the antireflection film of the example. It was.

INDUSTRIAL APPLICABILITY The present invention provides an antireflection film having a moth-eye structure having a concavo-convex shape formed by particles, an antireflection film having high particle regularity, a polarizing plate having the antireflection film, and an image display device. be able to.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on June 30, 2017 (Japanese Patent Application No. 2017-129822), the contents of which are incorporated herein by reference.

1 Base film HC hard coat layer 2 Antireflection layer 3 Metal oxide particles (particles (a2))
4 Binder resin (layer (a))
5 support 6 layers (b)
7 Adhesive film 10 Anti-reflection film A Distance between the vertices of adjacent convex parts B Distance between the center and concave part between the vertices of adjacent convex parts UV UV

Claims (13)

An antireflection film having a base film, a hard coat layer, and an antireflection layer in this order.
The antireflection layer contains metal oxide particles and a binder resin, and contains metal oxide particles and a binder resin.
The antireflection layer has a moth-eye structure having an uneven shape formed by the metal oxide particles.
The hard coat layer is a copolymer having a repeating unit represented by the following general formula (I), a repeating unit represented by the following general formula (II), and a repeating unit represented by the following general formula (III). An antireflection film, which is a layer formed from a composition for forming a hard coat layer containing.

In the general formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ² represents an alkyl group having at least one fluorine atom as a substituent, and L represents a divalent linking group. Represent.
In the general formula (II), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are aliphatic hydrocarbon groups which may independently have a hydrogen atom and a substituent, respectively. , An aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R ¹¹ and R ¹² may be linked. X ¹ represents a divalent linking group.
In the general formula (III), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, L ² represents a divalent linking group, and Y ¹ represents a photopolymerizable group. The antireflection film according to claim 1, wherein the repeating unit represented by the general formula (I) is a repeating unit represented by the following general formula (I-2).

In the general formula (I-2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ma and na each independently represent an integer of 1 to 20, and X represents a hydrogen atom or a fluorine atom. .. The antireflection film according to claim 1 or 2, wherein the repeating unit represented by the general formula (II) is a repeating unit represented by the following general formula (II-a).

In the general formula (II-a), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are aliphatic hydrocarbons which may independently have a hydrogen atom and a substituent, respectively. It represents a hydrogen group, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R ¹¹ and R ¹² may be linked. X ¹¹ is - (C = O) O - , - O (C = O) -, - (C = O) NH -, - O -, - CO-, and -CH ₂ - is selected from the group consisting of Represents a divalent linking group composed of at least one. X ¹² is − (C = O) O−, −O (C = O) −, − (C = O) NH−, −O−, −CO−, −NH−, −O (C = O) A divalent containing at least one linking group selected from -NH-, -O (C = O) -O-, and -CH _2- and containing at least one aromatic ring which may have a substituent. Represents the linking group of. However, the total number of carbon atoms of ^{X 11} and X ^{12 is 7 or more.} The antireflection film according to any one of claims 1 to 3, wherein the repeating unit represented by the general formula (III) is a repeating unit represented by the following general formula (III-a).

In the general formula (III-a), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ³¹ and R ³² each independently represent a hydrogen atom or a substituent, and k is an integer of 1 to 10. When k represents an integer of 2 or more, the plurality of R ^31s may be the same or different, and the plurality of R ^32s may be the same or different. R ³³ represents a hydrogen atom or a methyl group. Any of claims 1 to 4, wherein the content of the repeating unit represented by the general formula (I) in the copolymer is 5 to 40 mol% with respect to all the repeating units of the copolymer. The antireflection film according to item 1. Any of claims 1 to 5, wherein the content of the repeating unit represented by the general formula (II) in the copolymer is 20 to 60 mol% with respect to all the repeating units of the copolymer. The antireflection film according to item 1. Any of claims 1 to 6, wherein the content of the repeating unit represented by the general formula (III) in the copolymer is 20 to 65 mol% with respect to all the repeating units of the copolymer. The antireflection film according to item 1. Claims 1 to 7, wherein the content of the copolymer in the composition for forming a hard coat layer is 0.001 to 20% by mass with respect to the total solid content of the composition for forming a hard coat layer. The antireflection film according to any one of the following items. The antireflection film according to any one of claims 1 to 8, wherein the metal oxide particles are silica particles. The antireflection film according to any one of claims 1 to 9, wherein the metal oxide particles have an average primary particle size of 100 to 190 nm. The invention according to any one of claims 1 to 10, wherein the metal oxide particles are particles surface-modified with a compound having a polymerizable unsaturated group and a functional group reactive with the surface of the metal oxide particles. Anti-reflection film. A polarizing plate having a polarizer and an antireflection film according to any one of claims 1 to 11. An image display device having the antireflection film according to any one of claims 1 to 11 or the polarizing plate according to claim 12.

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