KR20190137917A - Anti-reflection film, polarizer, and image display device - Google Patents

Abstract

According to the present invention, there is provided an antireflection film having a base film, a hard coat layer, and an antireflection layer in this order, wherein the antireflection layer comprises metal oxide particles and a binder resin, and a moss eye having an uneven shape formed of metal oxide particles. And a hard coat layer formed of a composition for forming a hard coat layer comprising a copolymer having a repeating unit having a fluorine atom, a repeating unit having a boronic acid structure or a boronic acid ester structure, and a repeating unit having a photopolymerizable group. An antireflection film as a layer, a polarizing plate having the antireflection film, and an image display device are provided.

Description

Anti-reflection film, polarizer, and image display device

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

Images such as display devices using cathode ray tubes (CRT), plasma display panels (PDP), electro luminescence displays (ELD), fluorescent display displays (VFD), field emission displays (FED), and liquid crystal displays (LCD) In a display apparatus, in order to prevent the fall of the contrast by the reflection of external light in a display surface, and glare of an image, an antireflection film may be provided. Moreover, in addition to image display apparatuses, such as the glass surface of a showroom, an antireflection function may be provided by an antireflection film.

As an antireflection film, the antireflection film which has a fine uneven | corrugated shape whose period is below the wavelength of visible light on the surface of a base material, and the antireflection film which has what is called a moth eye structure are known. By the moth-eye structure, the refractive index gradient layer whose refractive index continuously changes from air to the bulk material inside the base material can be created, and reflection of light can be prevented.

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 formed of irregularities formed by particles on a base film.

Moreover, when coating the composition for forming a hard-coat layer by a coating method, it is known to add the leveling agent which consists of a fluorine-type compound etc. to the composition.

Patent Document 1: Japanese Unexamined Patent Publication No. 2017-016065

MEANS TO SOLVE THE PROBLEM This inventor apply | coats the composition for antireflection layer containing the hardening compound which is a compound for metal oxide particle and binder resin formation on a hard-coat layer, forms a coating film, laminates an adhesive layer on this coating film, and a part of curable compound It was discovered that the antireflection layer having a moth-eye structure composed of irregularities formed by the metal oxide particles was formed by diffusing (penetrating) the pressure-sensitive adhesive layer and then peeling the pressure-sensitive adhesive layer.

However, according to the studies of the present inventors, when a part of the curable compound in the coating film formed of the composition for forming an antireflection layer is diffused in the pressure-sensitive adhesive layer, the metal oxide particles in the coating film move, whereby the regularity of the particles may decrease. I could see that. The decrease in the regularity of these particles may lead to an increase in haze.

In patent document 1, the fall of the regularity of the said particle | grain is not described.

An object of the present invention is to provide an antireflection film having a moth-eye structure composed of irregularities formed by particles, and to provide an antireflection film having high regularity of particles, a polarizing plate having the antireflection film, and an image display device. have.

[One]

As an antireflection film which has 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,

The anti-reflection layer has a moth-eye structure made of irregularities formed by the metal oxide particles,

The said hard coat layer is for hard-coat layer formation containing the copolymer which has a repeating unit represented by the following general formula (I), the repeating unit represented by the following general formula (II), and the repeating unit represented by the following general formula (III). An antireflection film, which is a layer formed of a composition.

[Formula 1]

In general formula (I), R <^1> represents a hydrogen atom or a C1-C20 alkyl group, R <^2> represents the alkyl group which has at least 1 fluorine atom as a substituent, and L represents a bivalent coupling group.

In general formula (II), R <^10> represents a hydrogen atom or a C1-C20 alkyl group, R <^11> and R <^12> may respectively independently represent a hydrogen atom and the aliphatic hydrocarbon group which may have a substituent, and the aryl which may have a substituent. The heteroaryl group which may have a group or a substituent is shown, and R <^11> and R <^12> may be connected. X ¹ represents a divalent linking group.

In 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 as described in [1] whose repeating unit represented by the said General formula (I) is a repeating unit represented by the following general formula (I-2).

[Formula 2]

In 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 as described in [1] or [2] whose repeating unit represented by the said General formula (II) is a repeating unit represented by the following general formula (II-a).

[Formula 3]

In 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 each independently represent a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent or a substituent. It may represent the aryl group which may be sufficient, or the heteroaryl group which may have a substituent, and R <^11> and R <^12> may be connected. X ¹¹ is at least selected from the group consisting of — (C═O) O—, —O (C═O) —, — (C═O) NH—, —O—, —CO—, and —CH ₂ —. The divalent linking group consisting of one is shown. X ¹² is-(C = O) O-, -O (C = O)-,-(C = O) NH-, -O-, -CO-, -NH-, -O (C = O) A divalent linking group 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. . However, the sum total carbon number of said X <^11> and X <^12> is seven or more.

[4]

The antireflection film as described in any one of [1]-[3] whose repeating unit represented by the said General formula (III) is a repeating unit represented by the following general formula (III-a).

[Formula 4]

In 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 represents an integer of 1 to 10, When k represents an integer greater than or equal to 2, some R <^31> may be same or different, and some R <^32> may be same or different. R ³³ represents a hydrogen atom or a methyl group.

[5]

Antireflection as described in any one of [1]-[4] whose content of the repeating unit represented by the said General formula (I) in the said copolymer is 5-40 mol% with respect to all the repeating units which the said copolymer has. film.

[6]

The reflection prevention in any one of [1]-[5] whose content of the repeating unit represented by the said General formula (II) in the said copolymer is 20-60 mol% with respect to all the repeating units which the said copolymer has. film.

[7]

The reflection prevention in any one of [1]-[6] whose content of the repeating unit represented by the said General formula (III) in the said copolymer is 20-65 mol% with respect to all the repeating units which the said copolymer has. film.

[8]

The antireflection film as described in any one of [1]-[7] whose content of the said copolymer in the said composition for hard-coat layer formation is 0.001-20 mass% with respect to the total solid of the said composition for hard-coat layer formation. .

[9]

The antireflection film according to any one of [1] to [8], wherein the metal oxide particles are silica particles.

[10]

The antireflection film as described in any one of [1]-[9] whose average primary particle diameter of the said metal oxide particle is 100-190 nm.

[11]

The said metal oxide particle is a particle | grains whose surface of the said metal oxide particle was surface-modified by the compound which has a polymerizable unsaturated group and the functional group which has reactivity with the surface of the said metal oxide particle, [1]-[10] The antireflective film of any one of Claims.

[12]

The polarizing plate which has a polarizer and the antireflection film in any one of [1]-[11].

[13]

The image display apparatus which has an antireflection film as described in any one of [1]-[11], or a polarizing plate as described in [12].

ADVANTAGE OF THE INVENTION According to this invention, it is an antireflection film which has a moth-eye structure which consists of an uneven | corrugated shape formed by particle | grains, and can provide the antireflection film with a high regularity of particle | grains, the polarizing plate which has the said antireflection film, and an image display apparatus. .

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram 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.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In addition, it is used by the meaning which includes with "-" the numerical value described before and after that as a lower limit and an upper limit in this specification.

In this specification, "(meth) acrylate" is used by the meaning of "any one or both of an acrylate and a methacrylate." "(Meth) acryl group", "(meth) acrylic acid", "(meth) acrylamide", "(meth) acryloyl group", "(meth) acrylic-type", etc. are also the same.

The antireflection film of the present invention,

As an antireflection film which has 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,

The anti-reflection layer has a moth-eye structure made of irregularities formed by the metal oxide particles,

The said hard coat layer is for hard-coat layer formation containing the copolymer which has a repeating unit represented by the following general formula (I), the repeating unit represented by the following general formula (II), and the repeating unit represented by the following general formula (III). Antireflection film, which is a layer formed of a composition.

[Formula 5]

In general formula (I), R <^1> represents a hydrogen atom or a C1-C20 alkyl group, R <^2> represents the alkyl group which has at least 1 fluorine atom as a substituent, or -Si ( ^Ra3 ) ( ^Ra4 ) O-. The group to be included is represented, R ^a3 and R ^a4 each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent, and L represents a divalent linking group.

In general formula (II), R <^10> represents a hydrogen atom or a C1-C20 alkyl group, R <^11> and R <^12> may respectively independently represent a hydrogen atom and the aliphatic hydrocarbon group which may have a substituent, and the aryl which may have a substituent. The heteroaryl group which may have a group or a substituent is shown, and R <^11> and R <^12> may be connected. X ¹ represents a divalent linking group.

In 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.

By this invention, although the mechanism which is an antireflection film which has a moth-eye structure which consists of the uneven | corrugated shape formed by the particle | grains, and is provided with the antireflection film with high regularity of particle | grains was not completely clear, it is estimated as follows.

The antireflection film of the present invention is an antireflection film having a hard coat layer formed of a composition for forming a hard coat layer and an antireflection layer formed of a composition for forming an antireflection layer in this order, as described later. The said composition for hard-coat layer formation is a thing containing the copolymer which has a repeating unit represented by general formula (I), the repeating unit represented by general formula (II), and the repeating unit represented by general formula (III), and a curable compound. It is preferable that the said antireflection layer forming composition contains metal oxide particles and a curable compound.

By the action of the repeating unit represented by General Formula (I), the copolymer is localized near the surface of the hard coat layer (interface with the antireflection layer), and is represented by -BOR ¹¹ OR ¹² of the repeating unit represented by General Formula (II). The boronic acid structure or boronic acid ester structure shown interacts with the metal oxide particles in the antireflection layer to suppress aggregation of the metal oxide particles.

In addition, Y ¹ (photopolymerizable group) of the repeating unit represented by General Formula (III) is polymerized and fixed with the curable compound included in the hard coat layer, whereby the fixing ability of the metal oxide particles can be improved.

In addition, the surface of the metal oxide particles, a polymerizable unsaturated group and in the case where the surface-modified with a compound having a functional group having a surface and reactivity of the metal oxide particles, the repeating unit represented by formula (III) Y ¹ (photopolymerization group ) And the polymerizable unsaturated group on the surface of the metal oxide particles can further increase the fixing ability of the metal oxide particles. Thus, when a part of the curable compound in the coating film formed of the composition for forming an anti-reflection layer described above is diffused in the pressure-sensitive adhesive layer laminated on the coating film, the metal oxide particles in the coating film become difficult to move, and the regularity of the particles is thought to be improved. do.

It is preferable that it is 3% or less, and, as for the antireflection film of this invention over the whole area | region of wavelength 380-780 nm, it is more preferable that it is 2% or less.

An example of preferable embodiment of the antireflection film of this invention is shown in FIG.

The antireflection film 10 of FIG. 1 has the base film 1, the hard-coat layer HC, and the antireflection layer 2 in this order. In addition, the antireflection film of the present invention may have other layers in addition to these layers. It is preferable that the hard coat layer is in contact with the antireflection layer. The antireflection layer 2 contains the metal oxide particles 3 and the binder resin 4. The metal oxide particle 3 protrudes from the binder resin 4, and forms the uneven | corrugated shape, and this uneven | corrugated shape is a moth-eye structure.

(Moss eye structure)

The antireflection layer of the antireflection film of the present invention has a moth-eye structure composed of an uneven shape formed of metal oxide particles.

The uneven shape is preferably formed on the surface on the side opposite to the interface on the hard coat layer side of the antireflection layer.

The uneven shape formed by the metal oxide particles is preferably one in which the metal oxide particles protruding from the film of the binder resin become convex portions, and the portions in which the metal oxide particles do not exist are concave portions.

The moth-eye structure which consists of an uneven | corrugated shape shows that the uneven | corrugated shape becomes a motheye structure.

Moreover, as long as the moth-eye structure can be formed, other components, such as binder resin, may exist in the surface of the metal oxide particle which forms a convex part.

The moth-eye structure is a processed surface of a material (material) for suppressing reflection of light, and refers to a structure having a periodic fine structure pattern. In particular, for the purpose of suppressing the reflection of visible light, it refers to a structure having a fine structure pattern with a period of less than 780 nm. When the period of the fine structure pattern is less than 190 nm, the color of the reflected light is small, which is preferable. Moreover, when the period of the uneven | corrugated shape of a moth-eye structure is 100 nm or more, since the light of wavelength 380nm can recognize a fine structure pattern, and is excellent in antireflection property, it is preferable. The presence or absence of a moth-eye structure can be confirmed by observing the surface shape by a scanning electron microscope (SEM), an atomic force microscope (AFM), etc. and examining whether the said microstructure pattern has arisen.

As for the uneven | corrugated shape of the antireflection layer of the antireflection film of this invention, it is preferable that B / A which is ratio of the distance A between the vertices of adjacent convex parts, and the center B between the vertices of adjacent convex parts, and the distance B of a recessed part is 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 thus the refractive index inclined layer in which the refractive index changes more smoothly from the air to the inside of the antireflection layer can be made, so that the reflectance can be further reduced. have.

As for B / A, it is more preferable that it is 0.5 or more. If B / A is 0.5 or more, the distance A between the vertices of adjacent convex portions (convex portions formed by particles) becomes larger than the particle diameter, and concave portions are formed between the particles. As a result, both of the interfacial reflection caused by the region having a high refractive index change depending on the curvature above the convex portion and the interfacial reflection caused by the region having a large refractive index change depending on the curvature of the intergranular concave portion exist. In addition to the gradient layer effect, it is assumed that the reflectance is more effectively reduced.

B / A can be controlled by the volume ratio of binder resin and metal oxide particle in an antireflection layer. For this reason, it is important to design the compounding ratio of binder resin and metal oxide particle suitably.

Moreover, when realizing a low reflectance and suppressing generation | occurrence | production of a haze, it is preferable that the metal oxide particle which forms a convex part is spread | distributed uniformly at an appropriate filling rate. From the above viewpoint, the content of the metal oxide particles forming the convex portions is preferably adjusted to be uniform in the entire antireflection layer. The filling rate can be measured as the area occupancy (particle occupancy) of the metal oxide particles located on the most surface side when the metal oxide particles forming the convex portions on the surface are observed by SEM or the like, and preferably 25% to 64%. , 25-50% is more preferable, and 30-45% is more preferable.

The uniformity of the surface of the antireflection film can be evaluated by haze. The measurement can measure 40 mm x 80 mm of film samples with the haze meter NDH4000 by Nippon Denshoku Kogyo Co., Ltd. at 25 degreeC and 60% of a relative humidity according to JIS-K7136 (2000). Haze increases that particle | grains aggregate and are nonuniform. It is preferable that the haze is low. 0.0-3.0% is preferable, as for the value of haze, 0.0-2.5% is more preferable, 0.0-2.0% is more preferable.

[Hard coat layer]

The hard coat layer of the antireflection film of this invention is demonstrated.

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 for forming a hard coat layer containing a copolymer having at least a repeating unit represented by General Formula (I), a repeating unit represented by General Formula (II), and a repeating unit represented by General Formula (III). Layer formed from the composition.

Hereinafter, the copolymer which has a repeating unit represented by the said General formula (I), the repeating unit represented by the said General formula (II), and the repeating unit represented by the said General formula (III) is also called "copolymer (a)."

<Copolymer (a)>

Copolymer (a) is a copolymer which has at least the repeating unit represented by the said General formula (I), the repeating unit represented by the said General formula (II), and the repeating unit represented by the said General formula (III). The copolymer (a) may have a function as a leveling agent.

(Repeat unit represented by general formula (I))

The repeating unit represented by general formula (I) is demonstrated.

[Formula 6]

In general formula (I), R <^1> represents a hydrogen atom or a C1-C20 alkyl group, R <^2> represents the alkyl group which has at least 1 fluorine atom as a substituent, or -Si ( ^Ra3 ) ( ^Ra4 ) O-. The group to be included is represented, R ^a3 and R ^a4 each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent, and L represents a divalent linking group.

R ¹ in General Formula (I) represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. And it is more preferable to represent a hydrogen atom or a methyl group.

R ² in General Formula (I) represents an alkyl group having at least one fluorine atom as a substituent, or a group containing —Si (R ^a3 ) (R ^a4 ) O—, and an alkyl group substituted with at least one fluorine atom (fluoro Alkyl group), more preferably represents a fluoroalkyl group of 1 to 20 carbon atoms, more preferably represents a fluoroalkyl group of 1 to 18 carbon atoms, and particularly represents a fluoroalkyl group of 2 to 15 carbon atoms. desirable. In addition, 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 General Formula (I) is preferably an alkyl group having at least one fluorine atom as a substituent. As another embodiment, R ² in General Formula (I) is —Si (R ^a3 ) (R ^The group containing ^a4 ) O- may be shown, and in this case, it is preferable to have a repeating unit (polysiloxane structure) containing the siloxane bond represented by -Si ( ^Ra3 ) ( ^Ra4 ) O-. R ^a3 and R ^a4 each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent. In this case, it is preferable that a copolymer (a) is a graft copolymer in which the polysiloxane structure was introduce | transduced into the side chain. As for the compound which has a siloxane bond for obtaining this graft copolymer, it is more preferable that it is a compound represented with the following general formula (IV).

[Formula 7]

R ^a3 and R ^a4 each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent. R ^a1 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 10-1000.

Nn R ^a3 in General Formula (IV) may be the same or different, and nn R ^a4 may be the same or different.

As an alkyl group in the case where R ^a3 and R ^a4 in General formula (IV) represent an alkyl group, a C1-C12 alkyl group is preferable, A C1-C10 alkyl group is more preferable, For example, a methyl group, an ethyl group, and a hexyl group Can be mentioned. The said alkyl group may have a substituent and a halogen atom is preferable as a substituent. When the said alkyl group is a haloalkyl group which has a halogen atom as a substituent, as a haloalkyl group, a C1-C12 fluoroalkyl group is preferable, A C1-C10 fluoroalkyl group is more preferable, For example, trifluoro Methyl group and pentafluoroethyl group are mentioned.

As an aryl group in case R <^a3> and R <^a4> represent an aryl group, a C6-C20 aryl group is preferable and a phenyl group and a naphthyl group are mentioned, for example.

Especially, it is preferable that R <^a3> and R <^a4> represent a methyl group, a trifluoromethyl group, or a phenyl group, and it is especially preferable to represent a methyl group.

R ^a1 in General Formula (IV) represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, it represents a hydrogen atom or a methyl group.

R ^a5 in 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.

In general formula (IV), nn represents 10-1000, it is preferable to represent 20-500, and it is more preferable to represent 30-200.

As a compound which has a siloxane bond for graft copolymerization, a single-terminal (meth) acryloyl group containing polysiloxane macromer (for example, silaplane 0721, copper 0725 (above, brand names, JNC Corporation make), AK- 5, AK-30, AK-32 (above, brand name, product made by Toagosei Co., Ltd.), KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X- 22-164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (above, brand name, Shin-Etsu Chemical Co., Ltd. make), etc. Can be mentioned.

Although it does not specifically limit as bivalent coupling group which L in general formula (I) shows, -O-,-(C = O) O-, -O (C = O)-,-(C = O) NH-, -NH (C = O)-, a divalent aromatic group which may have a substituent, the divalent aliphatic chain group which may have a substituent, and the at least 1 chosen from the group which consists of a divalent aliphatic cyclic group which may have a substituent. It is preferable to represent the bivalent coupling group used.

In addition, with respect to L in General formula (I),-(C = O) O- shows that C = O couple | bonds on the R <^1> side, and O couple | bonds on the R <^2> side. -O (C = O) - is, O is bonded at the R ¹ side, and indicates that the C = O bond in the R ² side. - (C = O) NH-, in the R ¹ side is C = O bond, indicating that the NH is engaged in the R ² side. -NH (C = O) - is, NH is engaged in the R ¹ side, and indicates that the C = O bond in the R ² side.

As a bivalent aromatic group, a divalent aromatic hydrocarbon group may be sufficient, a divalent aromatic heterocyclic group may be sufficient, a C6-C20 divalent aromatic group is preferable, and a C6-C12 divalent aromatic group is more preferable.

As a divalent aliphatic chain machine, a C1-C20 alkylene group is preferable and a C1-C10 alkylene group is more preferable.

As a bivalent aliphatic cyclic group, a C3-C20 cycloalkylene group is preferable, and a C3-C15 cycloalkylene group 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. It is preferable not to have a substituent from a viewpoint of the ease of synthesis.

As L,-(C = O) O- or -O (C = O)-is preferable and-(C = O) O- is more preferable.

It is especially preferable that the repeating unit represented with general formula (I) is a repeating unit represented with the following general formula (I-2) from a surface locality viewpoint and radical polymerizable viewpoint.

[Formula 8]

In 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.

R ¹ in the general formula (I-2) is R ¹ and consent of the general formula (I), the preferred range is also the same.

Ma and na in general formula (I-2) respectively independently represent the integer of 1-20. From a viewpoint of surface ubiquitous, and a viewpoint of raw material acquisition and the ease of manufacture, it is preferable that ma is an integer of 1-8, It is more preferable that it is an integer of 1-5, It is more preferable that it is 1 or 2. Moreover, it is preferable that na is an integer of 1-15, It is more preferable that it is an integer of 1-12, It is more preferable that it is an integer of 2-10, The integer of 5-7 is the most preferable.

In General Formula (I-2), X represents a hydrogen atom or a fluorine atom, and preferably represents a fluorine atom.

The repeating unit represented by general formula (I) can be obtained by superposition | polymerization of a corresponding monomer, As a preferable monomer, it is 2,2,2- trifluoroethyl (meth) acrylate, 2,2,3, for example. , 3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluoro Lococtyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro -5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H- 1- (tri Fluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3- Perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxy Hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (Meth) acrylate etc. are mentioned.

(Repeat unit represented by general formula (II))

The repeating unit represented by general formula (II) is demonstrated.

[Formula 9]

In general formula (II), R <^10> represents a hydrogen atom or a C1-C20 alkyl group, R <^11> and R <^12> may respectively independently represent a hydrogen atom and the aliphatic hydrocarbon group which may have a substituent, and the aryl which may have a substituent. The heteroaryl group which may have a group or a substituent is shown, and R <^11> and R <^12> may be connected. X ¹ represents a divalent linking group.

R ¹⁰ in General Formula (II) represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, it represents a hydrogen atom or a methyl group.

As an aliphatic hydrocarbon group when R <^11> and R <^12> in general formula (II) represents an aliphatic hydrocarbon group, it is preferable that it is a C1-C20 aliphatic hydrocarbon group, and it is more preferable that it is a C1-C10 aliphatic hydrocarbon group. Do.

As an aliphatic hydrocarbon group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group is mentioned.

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl and octadecyl groups Linear, such as, eicosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-methylhexyl group or A branched alkyl group is mentioned.

As a specific example of a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, 2-norbornyl group, etc. are mentioned.

Specific examples of the alkenyl group include linear or branched alkenyl groups such as vinyl group, 1-propenyl group, 1-butenyl group, and 1-methyl-1-propenyl group.

As a specific example of a cycloalkenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group, etc. are mentioned.

As an example of the said alkynyl group, an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-octaynyl group, etc. are mentioned.

As an aryl group in case R <^11> and R <^12> represents an aryl group, it is preferable that it is a C6-C20 aryl group, and it is more preferable that it is a C6-C12 aryl group.

A phenyl group is mentioned as a specific example of an aryl group. Moreover, the thing which two to four benzene rings formed the condensed ring, and the thing where the benzene ring and the unsaturated 5-membered ring formed the condensed ring are mentioned, As a specific example, a naphthyl group, anthryl group, a phenanthryl group, an indenyl group, an acena Butenyl group, fluorenyl group, pyrenyl group and the like.

As a heteroaryl group in the case where R ¹¹ and R ¹² represent a heteroaryl group, one hydrogen atom of a heteroaromatic ring containing at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom is removed, and hetero And aryl groups. Specific examples of the heteroaromatic ring containing at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom include pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole, isoxazole, Oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thianaphthene, dibenzothiophene, indazole benzimidazole, anthranyl, benzisoxazole, benzoxazole , Benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroline, pterazine, etc. Can be mentioned.

R ¹¹ and R ¹² may be linked, in which case R ¹¹ and R ¹² are each independently an alkyl group or an aryl group, and they are preferably linked to each other, and R ¹¹ and R ¹² are alkyl groups, and these are It is more preferable that they are connected to each other.

As a bivalent coupling group represented by X <^1> in General formula (II),-(C = O) O-, -O (C = O)-,-(C = O) NH-, -NH (C = O)- At least one linker selected from -O-, -CO-, -NH-, -O (C = O) -NH-, -O (C = O) -O-, and -CH _2- Moreover, it is preferable that carbon number is seven or more.

In addition, with respect to X <^1> in General formula (II),-(C = O) O- shows that C = O couple | bonds on the R <^10> side, and O couple | bonds on the B side. -O (C = O)-represents that O is bonded at the R ¹⁰ side and C = O is bonded at the B side. -(C = O) NH- represents that C = O is bonded at the R ¹⁰ side and NH is bonded at the B side. -NH (C = O)-shows that NH couple | bonds with R <^10> side, and C = O couple | bonds with B side.

R ¹¹ , R ¹² and X ¹ may be substituted with one or more substituents if possible. As a substituent, the monovalent nonmetallic atom group except a hydrogen atom is mentioned, 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-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkyl sulfoxy group, aryl sulfoxy group, acyl thio group , Acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkyl ureido group, N ', N'-dialkyl ureido group, N'-aryl ureido group, N', N'- Diaryl ureido group, N'-alkyl-N'- aryl ureido group, N-alkyl ureido group, N-aryl ureido group, N'-alkyl-N-alkyl ureido group, N'-alkyl-N-aryl ureido group , N ', N'- Alkyl-N-alkyl ureido group, N ', N'-dialkyl-N-aryl ureido group, N'-aryl-N-alkyl ureido group, N'-aryl-N-aryl ureido group, N', N ' -Diaryl-N-alkylureido group, N ', N'- diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl -N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonyl Amino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugated base group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkyl carbamoyl group, N-aryl carbamoyl group, N, N- diaryl carbamoyl group, N-alkyl-N-aryl carbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl sulfone group, a sulfo group (-SO ₃ H) and its conjugated salts device, alkoxy sulfonic group, ah Oxofonyl group, sulfinamoyl group, N-alkyl sulfinamoyl group, N, N-dialkyl sulfinamoyl group, N-aryl sulfinamoyl group, N, N- diaryl sulfinamoyl group, N-alkyl-N-aryl Sulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfa Moyl group, N-acyl sulfamoyl group and its conjugated base group, N-alkylsulfonyl sulfamoyl group (-SO ₂ NHSO ₂ (alkyl)) and its conjugated base group, N-arylsulfonyl sulfamoyl group (-SO ₂ NHSO ₂ (aryl)) and its conjugated base group, N-alkylsulfonylcarbamoyl group (-CONHSO ₂ (alkyl)) and its conjugated base group, N-arylsulfonylcarbamoyl group (-CONHSO ₂ (aryl) ) And its conjugated base group, alkoxysilyl group (-Si (Oalkyl) ₃ ), aryloxysilyl group (-Si (Oaryl) ₃ ), hydroxysilyl group (-Si (OH) ₃ ) and its conjugated base group, a phosphono group (-PO ₃ H ₂₎ and its conjugated salts device, dialkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphonate Group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated salts device, monoaryl Phosphono group (-PO ₃ H (aryl)) and its conjugated base group, phosphonooxy group (-OPO ₃ H ₂ ) and its conjugated base group, dialkylphosphonooxy group (-OPO ₃ (alkyl) ₂ ) , Diarylphosphonooxy group (-OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (-OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (-OPO ₃ H (alkyl)) And conjugated base groups thereof, monoarylphosphonooxy groups (-OPO ₃ H (aryl)) and conjugated base groups thereof, cyano groups, nitro groups, aryl groups, alkenyl groups and alkynyl groups.

Moreover, if possible, these substituents may combine with each other or the substituted hydrocarbon group, and may form a ring.

R ¹¹ and R ¹² in General Formula (II) each independently represent a hydrogen atom or an alkyl group, or both are alkyl groups, and are preferably bonded to each other to form a ring, and R ¹¹ and R ¹² are both hydrogen atoms, Or it is all an alkyl group, and it is preferable to combine with each other and to form the ring.

From the viewpoint of more easily interacting with the metal oxide particles in the antireflection layer and being superior due to the regularity of the metal oxide particles, the repeating unit represented by the general formula (II) is a repeating unit represented by the following general formula (II-a). desirable.

[Formula 10]

In 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 each independently represent a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent or a substituent. It may represent the aryl group which may be sufficient, or the heteroaryl group which may have a substituent, and R <^11> and R <^12> may be connected. X ¹¹ is at least selected from the group consisting of — (C═O) O—, —O (C═O) —, — (C═O) NH—, —O—, —CO—, and —CH ₂ —. The divalent linking group consisting of one is shown. X ¹² is-(C = O) O-, -O (C = O)-,-(C = O) NH-, -O-, -CO-, -NH-, -O (C = O) A divalent linking group 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. . However, the sum total carbon number of said X <^11> and X <^12> is seven or more.

As X ¹¹ in general formula (II-a),-(C = O) O-, -O (C = O)-,-(C = O) NH- is preferable, and-(C = O) O- Most preferred.

It is preferable that X <^12> in general formula (II-a) contains 1-5 aromatic rings, It is more preferable to have 2-4 aromatic rings, It is most preferable to have 2-3 aromatic rings Do.

Formula (II-a) of the R ^10, the preferred range of R ¹¹ and R ¹² are the same as R ^10, R ¹¹ and R ¹² in each of the general formula (II).

As for the repeating unit represented by general formula (II) or (II-a), it is more preferable that it is a repeating unit represented with the following general formula (II-b).

[Formula 11]

In general formula (II-b), R <^10> represents a hydrogen atom or a C1-C20 alkyl group, R <^11> and R <^12> respectively independently has a hydrogen atom and the aliphatic hydrocarbon group which may have a substituent, and a substituent It may represent the aryl group which may be sufficient, or the heteroaryl group which may have a substituent, and R <^11> and R <^12> may be connected. 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)- A divalent linking group comprising at least one linking group selected from the group consisting of NH—, —O (C═O) —O—, and —CH ₂ —, and X ²² includes an aromatic ring which may have a substituent; You may be.

Formula (II-b) of the R ^10, the preferred range of R ¹¹ and R ¹² are the same as R ^10, R ¹¹ and R ¹² in each of the general formula (II).

The repeating unit represented by General formula (II) can be obtained by superposition | polymerization of a corresponding monomer. Although the repeating unit shown below is mentioned as a repeating unit represented by General formula (II), for example, It is not limited to these.

[Formula 12]

[Formula 13]

[Formula 14]

(Repeating unit represented by general formula (III))

The repeating unit represented by General formula (III) is demonstrated.

[Formula 15]

In 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 General Formula (III) represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. And it is more preferable to represent a hydrogen atom or a methyl group.

Although it does not specifically limit as bivalent coupling group which L <^2> in general formula (III) shows, -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 at least one selected from the group consisting of a divalent aliphatic cyclic group which may have a substituent. It is preferable to represent the bivalent coupling group comprised.

Further, with respect to L ² in the general formula (III), - (C = O) O- , in side R ²⁰ C = O and the bond indicates that the bond from O Y ¹ side. -O (C = O)-represents that O is bonded at the R ²⁰ side and C = O is bonded at the Y ¹ side. -(C = O) NH- represents that C = O is bonded at the R ²⁰ side and NH is bonded at the Y ¹ side. -NH (C = O)-represents that NH couple | bonds with the R <^20> side, and C = O couple | bonds with the Y <^1> side.

As a bivalent aromatic group, a divalent aromatic hydrocarbon group may be sufficient, a divalent aromatic heterocyclic group may be sufficient, a C6-C20 divalent aromatic group is preferable, and a C6-C12 divalent aromatic group is more preferable.

As a divalent aliphatic chain machine, a C1-C20 alkylene group is preferable and a C1-C10 alkylene group is more preferable.

As a bivalent aliphatic cyclic group, a C3-C20 cycloalkylene group is preferable, and a C3-C15 cycloalkylene group is more preferable.

Although the bivalent aromatic group, the divalent aliphatic chain group, and the divalent aliphatic cyclic group may have a substituent, respectively, it is preferable not to have a substituent from a viewpoint of the ease of synthesis.

As L <^2> , it is preferable to represent the bivalent coupling group comprised from at least 1 selected from the group which consists of -O-,-(C = O) O-, and a bivalent aliphatic chain group which may have a substituent.

The photopolymerizable group represented by Y ¹ in General Formula (III) is not particularly limited as long as it is a group which is polymerized by being irradiated with light when used with a suitable initiator, but is preferably a group which is polymerized by a radical or an acid, and more preferably. Preferably a group that polymerizes better than radicals. In addition, "light" shall also include an electron beam. Examples of the "light" include infrared rays, visible light, ultraviolet rays, X-rays, electron beams, and the like, and are preferably ultraviolet rays. As a photopolymerizable group, 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 is preferable, and it is more preferable that it is an acryloyl group or a methacryloyl group desirable.

It is preferable that the repeating unit represented by general formula (III) is a repeating unit represented with the following general formula (III-a).

[Formula 16]

In 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 represents an integer of 1 to 10, When k represents an integer greater than or equal to 2, some R <^31> may be same or different, and some R <^32> may be same or different. R ³³ represents a hydrogen atom or a methyl group.

R <^20> in general formula (III-a) is synonymous with R <^20> in general formula (III), and its preferable range is also the same.

As a substituent in the case where R <^31> and R <^32> in general formula (III-a) represents a substituent, an alkyl group, a hydroxyl group, etc. are mentioned.

The repeating unit represented by General formula (III) is a method synthesize | combined by superposition | polymerization of the corresponding monomer, the method synthesize | combining by polymerizing the monomer which has a protected acryloyl group or a methacryloyl group, and then deprotecting, a hydroxyl group, or a carboxyl And a method of synthesizing by introducing a photopolymerizable group into a polymer having a reactive group such as a group by a polymer reaction.

Although the specific example of the repeating unit represented by General formula (III) is shown below, it is not limited to these.

[Formula 17]

(Other repeating units)

The copolymer (a) has a repeating unit represented by General Formula (I), a repeating unit represented by General Formula (II) and a repeating unit represented by General Formula (III), but in addition to these, other repeating units You may have more.

Other repeating units can be obtained by polymerization of a corresponding monomer. As a monomer which gives another repeating unit, a general purpose monomer is mentioned, For example, the thing of Polymer Handbook 2nd ed., J. Brandrup, Wiley lnterscience (1975) Chapter 1-483 can be used. For example, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylic amide, allyl compound, vinyl ether, vinyl ester, itaconic acid dialkyl, and dialkyl ester of fumaric acid The compound etc. which have one addition polymeric unsaturated bond selected from the group or the monoalkyl ester, etc. are mentioned.

Specifically as a monomer which gives another repeating unit, the following monomers are mentioned.

Acrylic esters:

Methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylol propane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, phenoxyethyl acrylate, purfuryl acryl Ethylene, tetrahydrofurfuryl acrylate, 2-acryloyloxyethyl succinate, 2-carboxyethyl acrylate, etc.,

Methacrylic esters:

Methyl methacrylate, ethyl methacrylate, propyl methacrylate, crawlethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate Latex, phenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol monoacetoacetate monomethacrylate, 2-methacryloyloxyethyl phthalate, 2-methacrylo Monooxyethyl succinate, 2-methacryloyloxyethyl hexahydrophthalic acid, methacrylic acid 2-carboxyethyl, and the like,

Acrylamides:

Acrylamide, N-alkylacrylamide (as alkyl group having 1 to 3 carbon atoms, for example, methyl group, ethyl group, propyl group), N, N-dialkylacrylamide (as alkyl group having 1 to 6 carbon atoms), N- Hydroxyethyl-N-methylacrylamide, N-2-acetamideethyl-N-acetylacrylamide and the like.

Methacrylic amides:

Methacrylamide, N-alkyl methacrylamide (as alkyl group having 1 to 3 carbon atoms, for example, methyl group, ethyl group, propyl group), N, N-dialkyl methacrylate (as alkyl group having 1 to 6 carbon atoms) ), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamide ethyl-N-acetylmethacrylamide, and the like.

Allyl compound:

Allyl esters (e.g. allyl acetate, allyl caproic acid, allyl caprylic acid, allyl laurate, allyl palmitic acid, allyl stearate, allyl benzoate, allyl acetoacetic acid, allyl lactate, etc.), allyloxyethanol, etc.

Vinyl ethers:

Alkyl vinyl ethers (e.g., hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, crawlethyl vinyl ether, 1 -Methyl-2,2-dimethylpropylvinylether, 2-ethylbutylvinylether, hydroxyethylvinylether, diethyleneglycolvinylether, dimethylaminoethylvinylether, 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 valerate, vinyl caproate, vinyl crawl acetate, vinyl diacetate, vinyl methoxy acetate, vinyl butyl acetate, vinyl Lactate, vinyl-β-phenylbutyrate, vinylcyclohexyl carboxylate and the like.

Itaconic acid dialkyls:

Itaconic acid dimethyl, itaconic acid diethyl, itaconic acid dibutyl, etc.

Dialkyl esters or monoalkyl esters of fumaric acid: dibutyl fumarate and the like.

As a monomer which gives another repeating unit, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleonitrile, styrene, 4-vinyl benzoic acid, styrene macromer (AS-made by Toagosei Co., Ltd.) 6S), methyl methacrylate macromer (AA-6 by Toagosei Co., Ltd.), etc. are mentioned. It is also possible to convert the structure of the polymer after polymerization into a polymer reaction.

(Content of Each Repeating Unit in Copolymer (a))

It is preferable that it is 5-45 mol% with respect to the all the repeating units which the copolymer (a) has, and, as for content of the repeating unit represented by general formula (I) in a copolymer (a), it is more preferable that it is 5-40 mol%. It is preferable, It is more preferable that it is 10-40 mol%, It is especially preferable that it is 15-35 mol%.

It is preferable that it is 15-60 mol% with respect to the all the repeating units which the copolymer (a) has, and, as for content of the repeating unit represented by general formula (II) in a copolymer (a), it is 20-60 mol% more It is preferable and it is more preferable that it is 25-50 mol%.

It is preferable that it is 15-65 mol% with respect to the all the repeating units which a copolymer (a) has, and, as for content of the repeating unit represented by general formula (III) in a copolymer (a), it is more preferable that it is 20-65 mol%. It is preferable and it is more preferable that it is 25-55 mol%.

When it has another repeating unit in a copolymer (a), it is preferable that it is 15 mol% or less with respect to all the repeating units which the copolymer (a) has, and, as for content of another repeating unit, it is more preferable that it is 10 mol% or less. Do.

By setting the content of each repeating unit in the above range, when forming the antireflection layer on the hard coat layer, the antireflection layer can be satisfactorily formed without cissing, and the copolymer (a) is reflected by the hard coat layer. It can be localized near the surface (interface of a hard coat layer and an antireflection layer) on the prevention layer side, and the rubbing resistance of an antireflection layer is not impaired, and the regularity of the metal oxide particle in an antireflection layer can be improved further. In addition, it goes without saying that the sum total of content of each said repeating unit does not exceed 100 mol%.

(Weight Average Molecular Weight of Copolymer (a))

It is preferable that the weight average molecular weights (Mw) of a copolymer (a) are 1000-200000, It is more preferable that it is 5000-100000, It is more preferable that it is 10000-80000.

By making the weight average molecular weight of the copolymer (a) in the above range, the time to polymerize the photopolymerizable group represented by Y ¹ in the repeating unit represented by formula (III), the polymerization reaction is efficiently carried out.

In addition, the weight average molecular weight of a copolymer (a) is the value measured on condition of the following by gel permeation chromatography (GPC).

[Eluent] N-methyl-2-pyrrolidone (NMP)

[Device name] EcoSEC HLC-8320GPC (made by Tosoh Corporation)

[Column] TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation)

[Column Temperature] 40 ℃

[Flow rate] 0.35ml / min

The copolymer (a) can be polymerized by a known method. For example, a solution polymerization method, suspension polymerization method, emulsion polymerization method, melt polymerization method, etc. are mentioned. Especially, it is preferable to synthesize | combine by the solution polymerization method.

In order to prevent insolubilization by gelation during synthesis, the molecular weight of the copolymer (a) can be appropriately adjusted. As a method for adjusting the molecular weight, there is a change in the amount of the initiator, a change in the monomer concentration, the use of a chain transfer agent, etc., but it is preferable to change the initiator amount or the monomer concentration to adjust it.

Although the specific example of a copolymer (a) is shown below, it is not limited to these.

[Formula 18]

[Formula 19]

It is preferable that n in said A-17 is 10-60.

Although content of the copolymer (a) in the composition for hard-coat layer formation is not specifically limited, It is preferable that it is 0.001-20 mass% with respect to the total solid of the composition for hard-coat layer formation, and it is more preferable that it is 0.005-10 mass%. It is preferable and it is more preferable that it is 0.01-5 mass%. The copolymer (a) has a repeating unit represented by General Formula (III), and since Y ¹ (photopolymerizable group) in General Formula (III) polymerizes, a decrease in the scratch resistance of the antireflection layer can be prevented. There is an advantage that the content can be increased more than that of the leveling agent. In addition, all solid content is all components other than the solvent in a composition.

The hard coat layer of the antireflection film of this invention is a layer formed from the composition for hard-coat layer formation containing a copolymer (a). When forming a hard coat layer from the composition for hard-coat layer formation, or when forming an anti-reflection layer on a hard-coat layer, etc., the repeating unit represented by general formula (III) of a copolymer (a) by light irradiation. In order to polymerize Y ¹ (photopolymerizable group), a polymer chain comprising a repeating unit represented by General Formula (I) and a repeating unit represented by General Formula (II) is crosslinked in the hard coat layer by polymerization of Y ¹ . Crosslinked polymers having a structure (also referred to as "polymer of copolymer (a)") may be included. The copolymer (a) may be contained in the hard coat layer. That is, the hard coat layer may include a copolymer (a) or a polymer of the copolymer (a).

In the antireflection film of the present invention, it is preferable that the copolymer (a) or the polymer of the copolymer (a) is localized near the surface (the interface between the hard coat layer and the antireflection layer) on the antireflection layer side of the hard coat layer. . The localization of the copolymer (a) or the polymer of the copolymer (a) near the surface (the interface between the hard coat layer and the antireflection layer) on the antireflection layer side of the hard coat layer is obtained by cutting the antireflection film with a microtome and This can be confirmed by analyzing time-of-flight secondary ion mass spectrometry (TOF-SIMS). More specifically, the repeating unit represented by general formula (I) containing a fluorine atom or a polysiloxane structure, the repeating unit represented by general formula (II) containing a boronic acid structure or a boronic acid ester structure, and a photopolymerizable group are contained. It can confirm by whether the repeating unit represented by General formula (III) or the structure after the superposition | polymerization to be detected is detected.

In addition, although the antireflection film of this invention contains the polymer of a copolymer (a) or a copolymer (a) in a hard-coat layer, at least the polymer of a copolymer (a) or a copolymer (a) is included in a hard-coat layer. What is necessary is just to include and may also contain the polymer of a copolymer (a) or a copolymer (a) also in layers other than a hard-coat layer.

<Other components of the hard coat layer>

In addition to the copolymer (a) or the polymer of the copolymer (a), the hard coat layer preferably contains other components.

It is preferable that a hard-coat layer is formed by the polymerization reaction of the curable compound which is a compound which has a polymeric group. That is, it is preferable that a hard-coat layer contains the hardened | cured material of a curable compound.

As a curable compound for forming a hard-coat layer, the compound similar to curable compound (a1) for forming binder resin of an antireflection layer mentioned later can be used specifically ,.

Although content of the curable compound in the composition for hard-coat layer formation is not specifically limited, It is preferable that it is 20-99.9 mass% with respect to the total solid of the composition for hard-coat layer formation.

When a hard coat layer cuts an antireflection film with a microtome and analyzes a cross section by TOF-SIMS, it can measure as a part which hardened | cured material of a curable compound is detected, and the film thickness of a hard coat layer is also similar to TOF-SIMS. It can be measured from cross-sectional information of.

The hard coat layer can also be measured by detecting another layer in the middle of the base film and the antireflection layer, for example, by cross-sectional observation using a reflectance spectrometer or a TEM (transmission electron microscope) using light interference. Can be. As the reflection spectroscopic film thickness gauge, FE-3000 (manufactured by Otsuka Denshi Co., Ltd.) or the like can be used.

In the manufacturing method of the antireflection film of this invention, it is preferable to perform the process (1) mentioned later with respect to the hard-coat layer of a half-cure state. By setting the hard coat layer to a half-cure state, it is possible to improve the adhesion between the hard coat layer and the antireflection layer and to suppress the aggregation of the metal oxide particles by forming a bond with the metal oxide particles provided with the hard coat layer and the unsaturated double bond on the surface. Effect is obtained.

For example, if a coating film is ultraviolet curable, it can be set as the half cure by adjusting oxygen concentration and ultraviolet irradiation amount at the time of hardening suitably. To cure by irradiating ultraviolet irradiation dose of ^{1mJ / cm 2 ~ 300mJ / cm} 2 by an ultraviolet lamp it is preferred. More preferably from ^{5mJ / cm 2 ~ 100mJ / cm} 2 , and more preferably of ^{10mJ / cm 2 ~ 70mJ / cm} 2. At the time of irradiation, the said energy may be irradiated at once, and can also irradiate separately. As an ultraviolet lamp type, a metal halide lamp, a high pressure mercury lamp, etc. are used suitably.

It is preferable that the oxygen concentration at the time of hardening is 0.05-5.0 volume%, It is more preferable that it is 0.1-2 volume%, It is most preferable that it is 0.1-1 volume%.

(menstruum)

It is preferable that the composition for hard-coat layer formation contains a solvent.

As a solvent, it is preferable from the viewpoint of the adhesiveness of a base film and a hard-coat layer to contain the solvent which has permeability with respect to a base film. The solvent which has permeability with respect to a base film is a solvent which has the solubility with respect to a base film. Here, the solvent which has a solubility with respect to a base film is put the base film of 24 mm x 36 mm (thickness 80 micrometers) in the 15 ml bottle containing the said solvent, and time-lapses at room temperature (25 degreeC) for 24 hours, By shaking, it means the solvent which a base film melt | dissolves completely and removes a form.

As a permeable solvent in the case of using a cellulose acylate film as a base film, methyl ethyl ketone (MEK), dimethyl carbonate, methyl acetate, acetone, methylene chloride, etc. are preferable, methyl ethyl ketone (MEK), dimethyl carbonate, acetic acid Although methyl can be used more preferably, it is not limited to these.

The composition for hard coat layer formation may contain solvents other than a 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 the hard coat layer, and is 70% by mass or more and 100% by mass. It is more preferable that it is the following.

When the composition for hard-coat layer formation contains a quaternary ammonium salt containing polymer, it is preferable to contain a hydrophilic solvent as a solvent from a viewpoint of compatibility with a quaternary ammonium salt containing polymer. As the hydrophilic solvent, lower alcohols such as methanol, ethanol, isopropanol (IPA) and butanol are preferable.

It is preferable that it is 20 mass% or more and 70 mass% or less, and, as for solid content concentration of the composition for hard-coat layer formation, it is more preferable that they are 30 mass% or more and 65 mass% or less.

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

(Polymerization initiator)

You may use suitably selecting a radical, a cationic polymerization initiator, etc. as needed. These polymerization initiators are decomposed by light irradiation and / or heating to generate radicals or cations to advance radical polymerization and cationic polymerization.

As a polymerization initiator, the thing similar to the polymerization initiator which the composition for forming the layer (a) mentioned later may contain is mentioned.

In particular, when the composition for hard coat layer formation 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-cure state, the internal curing rate is higher than when using other initiators, and the quaternary ammonium salt is contained in the antireflection layer. Incorporation of the polymer can be suppressed.

Although content of the polymerization initiator in the composition for hard-coat layer formation is not specifically limited, It is preferable that it is 0.5-8 mass% with respect to the total solid of the composition for hard-coat layer formation.

(Antistatic agent)

As a specific example of an antistatic agent, conventionally well-known antistatic agents, such as a quaternary ammonium salt, a conductive polymer, electroconductive fine particles, can be used, It is although it does not specifically limit, It is an inexpensive and antistatic agent which has a quaternary ammonium salt from the ease of handling. It is preferable and it is more preferable that it is a quaternary ammonium salt containing polymer.

As the antireflection film of the present invention,

The metal oxide particles to be used are metal oxide particles provided with a polymerizable unsaturated group on the particle surface,

It has a hard coat layer which hardens the composition for hard-coat layer formation containing the curable compound which has a polymerizable unsaturated group,

It is preferable that a bond is formed between the said metal oxide particle and the said hard-coat layer.

(Refractive index adjuster)

For the purpose of controlling the refractive index of the hard coat layer, a high refractive index monomer or inorganic particles can be added as the refractive index regulator. In addition to the effect of controlling the refractive index, the inorganic particles also have an effect of suppressing curing shrinkage due to a polymerization reaction. In this invention, after formation of a hard-coat layer, it is called a binder including the polymer produced by superposing | polymerizing the said polyfunctional monomer and / or high refractive index monomer, etc., and the inorganic particle dispersed in it.

(Leveling Agents Other Than Copolymer (a))

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

(Film thickness of the hard coat layer)

It is preferable that the thickness of a hard-coat layer is about 0.6-50 micrometers, More preferably, it is 4-20 micrometers.

It is preferable that it is H or more, and, as for the strength of a hard-coat layer by a pencil hardness test, it is more preferable that it is 2H or more. In the taper test according to JIS K5400, the smaller the amount of abrasion of the test pieces before and after the test, the more preferable.

[Substrate film]

The base film of the antireflection film of this invention is demonstrated.

It is preferable that a base film is a plastic base film. There is no restriction | limiting in particular as a base film as long as it is a base material which has light transmittance generally used as a base film of an antireflection film. As a base film, it can use variously, For example, Cellulose-type resin; Polyester resins such as cellulose acylate (triacetate cellulose, diacetyl cellulose, acetate butyrate cellulose); The base film containing (meth) acrylic-type resin, polyurethane-type resin, polycarbonate, polystyrene, an olefin resin etc., such as polyethylene terephthalate, is mentioned, Cellulose acylate, polyethylene terephthalate, or (meth) acrylic-type resin The base film containing is preferable, and the base film containing cellulose acylate is more preferable.

Although the thickness of a base film is about 10-1000 micrometers normally, 15-200 micrometers is preferable, 20-200 micrometers is more preferable, and 20-100 micrometers is from a viewpoint that handleability is favorable, high light transmittance, and sufficient strength is obtained. More preferably, 25-100 micrometers is especially preferable.

As light transmittance of a base film, it is preferable that total light transmittance is 80% or more, and it is more preferable that it is 90% or more.

The measurement of total light transmittance shall be performed according to Japanese Industrial Standard (JIS) K7361-1 (1997).

Antireflection 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>

It is preferable that binder resin has a function which binds metal oxide particle to a hard-coat layer.

It is preferable that binder resin is a film | membrane as shown to the code | symbol 4 of FIG.

It is preferable that binder resin contains the hardened | cured material of a curable compound.

The binder resin can be obtained by curing the curable compound.

The curable compound used for formation of binder resin is also called curable compound (a1).

<Curable Compound (a1)>

As curable compound (a1), the compound which has a polymeric group is preferable. As the compound having a polymerizable group, various monomers, oligomers or polymers can be used, and the polymerizable group is preferably photopolymerizable.

As a photopolymerizable group, polymerizable unsaturated groups (carbon-carbon unsaturated double bond groups), such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group, etc. are mentioned, Especially, a (meth) acryloyl group desirable.

Specific examples of the compound having a polymerizable unsaturated group include alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, and propylene glycol di (meth) acrylate ( Meth) acrylic acid diesters;

Polyoxy, such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethyleneglycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate (Meth) acrylic acid diesters of alkylene glycols;

(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;

Ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxydiethoxy) phenyl} propane and 2-2-bis {4- (acryloxypolypropoxy) phenyl} propane (Meth) acrylic acid diesters; Etc. can be mentioned.

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

Especially, ester of polyhydric alcohol and (meth) acrylic acid is preferable. More preferably, it is preferable to contain at least 1 type of polyfunctional monomer which has three or more (meth) acryloyl groups in 1 molecule.

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 trimethylolpropane tri (meth) acrylate, EO modified phosphoric acid tri (meth) acrylate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, capro Lactone-modified dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane poly Acrylate, polyester polyacrylate, caprolactone modified tris (acryloxyethyl) isocyanurate, etc. are mentioned.

As a specific compound of the polyfunctional acrylate type compounds which have a (meth) acryloyl group, Nippon Kayaku Co., Ltd. KAYARAD DPHA, copper DPHA-2C, copper PET-30, copper TMPTA, copper TPA-320, copper TPA -330, East RP-1040, East T-1420, East D-310, East DPCA-20, East DPCA-30, East DPCA-60, East GPO-303, Osaka Yuki Kagaku Kogyo Co., Ltd.V # 3PA And esters of polyols such as V # 400, V # 36095D, V # 1000, V # 1080 and (meth) acrylic acid. Shiko UV-1400B, copper UV-1700B, copper UV-6300B, copper UV-7550B, copper UV-7600B, copper UV-7605B, copper UV-7610B, copper UV-7620EA, copper UV-7630B, copper UV-7640B , Copper UV-6630B, copper UV-7000B, copper UV-7510B, copper UV-7461TE, copper UV-3000B, copper UV-3200B, copper UV-3210EA, copper UV-3310EA, copper UV-3310B, copper UV-3500BA , Copper UV-3520TL, copper UV-3700B, copper UV-6100B, copper UV-6640B, copper UV-2000B, copper UV-2010B, copper UV-2250EA, copper UV-2750B (product made by Nippon Kosei Kagaku Co., Ltd.) , UA-306H, UA-306I, UA-306T, UL-503LN (manufactured by Kyoeisha Kagaku Co., Ltd.), Unidyk 17-806, East 17-813, East V-4030, East V-4000BA (Die Nippon ink Kagaku Kogyo Co., Ltd.), EB-1290K, EB-220, EB-5129, EB-1830, EB-4858 (made by Daicel UCB Co., Ltd.), A-TMMT, AD-TMP, A- TMPT, U-4HA, U-6HA, U-10HA, U-15HA (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.), Hicorp AU-2010, East AU-2020 (Dokushiki Co., Ltd.), aronix Urethane acrylate more than trifunctional, such as M-1960 (made by Toagosei Co., Ltd.), art resin UN-3320HA, UN-3320HC, UN-3320HS, UN-904, HDP-4T Polyester compounds more than trifunctional, such as a compound, an Aronix M-8100, M-8030, M-9050 (made by Toagosei Co., Ltd.), and KRM-8307 (made by Daicel Cytec Co., Ltd.), etc. can also be used suitably. .

Further, resins having three or more polymerizable groups, for example, relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, and polybutadienes And oligomers or prepolymers such as polyfunctional compounds such as resins, polythiolpolyene resins, and polyhydric alcohols.

Moreover, dendrimers, such as the compound of Unexamined-Japanese-Patent No. 2005-076005, 2005-036105, SIRIUS-501, SUBARU-501 (manufactured by Osaka Yuki Chemical Co., Ltd.), and Japanese Unexamined Patent Publication 2005- Norbornene ring-containing monomers as described in 060425 can also be used.

Moreover, you may use the silane coupling agent which has a polymeric group as curable compound (a1) in order to combine a metal oxide particle and a curable compound (a1), and to make it a firm film | membrane.

As a specific example of the silane coupling agent which has a polymeric group, 3- (meth) acryloxypropyl trimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryl Oxypropyldimethylmethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2- (meth) acryloxyethyltrimethoxysilane Phosphorus, 2- (meth) acryloxyethyl triethoxysilane, 4- (meth) acryloxybutyl trimethoxysilane, 4- (meth) acryloxybutyl triethoxysilane, and the like. . Specifically, the silane coupling agent X-12-1048, X-12-1049, X of KBM-503, KBM-5103 (made by Shin-Etsu Chemical Co., Ltd.), Unexamined-Japanese-Patent No. 2014-123091. The compound C3 etc. which are represented by -12-1050 (made by Shin-Etsu Chemical Co., Ltd.), and the following structural formula are mentioned.

[Formula 20]

The compound which has a polymeric group may use two or more types together. Polymerization of these compounds having a polymerizable group can be carried out by irradiation of light or heating in the presence of an optical radical initiator or a thermal radical initiator.

The antireflection layer may further include compounds other than the curable compound (a1) as the compound for forming the binder resin.

From the viewpoint of ease of penetration into the pressure-sensitive adhesive layer described later, a compound having two or less polymerizable groups in one molecule may be used as the curable compound (a1), and in particular, a compound having three or more polymerizable groups in one molecule and It is preferable to use together the compound which does not have a polymeric group as a compound which has two or less polymeric groups in 1 molecule, or a compound other than curable compound (a1).

As a compound which has two or less polymeric groups in 1 molecule, or a compound which does not have a polymeric group, a weight average molecular weight (Mwa) is 40 <Mwa <500, and SP value (SPa) by Hoy method is 19 <SPa < It is preferable that the compound which is 24.5 easily penetrates into an adhesive layer. Moreover, it is preferable that the compound which has two or less polymeric groups in 1 molecule is a compound which has one polymeric group in 1 molecule.

In addition, SP value (soluble parameter) in this invention is a value computed by the Hoy method, and the Hoy method is described in POLYMER HANDBOOK FOURTH EDITION.

Moreover, it is preferable that the viscosity in 25 degreeC is 100 mPas or less, the compound which has two or less polymeric groups in 1 molecule, or the compound which does not have a polymeric group, 1-50 mPas is more preferable, and 1-20 mPas is more desirable. The compound in such a viscosity range is preferable because it easily penetrates into the pressure-sensitive adhesive layer, and acts to suppress aggregation of the particles (a2) and can suppress haze and turbidity. In particular, aggregation of the particles (a2) can be suppressed by curing a part of the curable compound (a1) before laminating the pressure-sensitive adhesive layer as described below, but even when the curing is advanced by using a compound in such a viscosity range. Since the compound which has two or less polymeric groups in one molecule, or the compound which does not have a polymeric group can fully permeate | transmit the adhesive layer, it is preferable. In particular, when it exists in the viscosity range of 1-20 mPas, since the effect which prevents a raise of reflectance or fall of total light transmittance which generate | occur | produces by blocking a binder in the clearance gap of particle | grains is large, it is preferable.

It is preferable that the compound which has two or less polymeric groups in 1 molecule has a (meth) acryloyl group, an epoxy group, an alkoxy group, a vinyl group, a styryl group, an allyl group, etc. as a polymeric group.

As a compound which does not have a polymeric group, an ester type compound, an amine type compound, an ether type compound, an aliphatic alcohol type compound, a hydrocarbon type compound, etc. can be used preferably, and an ester type compound is especially preferable. More specifically, dimethyl succinate (SP value 20.2, viscosity 2.6 mPas), diethyl succinate (SP value 19.7, viscosity 2.6 mPas), adipic acid dimethyl (SP value 19.7, viscosity 2.8 mPas), succinic acid Dibutyl (SP value 19.1, viscosity 3.9 mPas), adipic bis (2-butoxyethyl) (SP value 19.0, viscosity 10.8 mPas), dimethyl suverate (SP value 19.4, viscosity 3.7 mPas), phthalic acid die Ethyl (SP value 22.3, viscosity 9.8 mPas), phthalic acid dibutyl (SP value 21.4, viscosity 13.7 mPas), triethyl citrate (SP value 22.5, viscosity 22.6 mPas), acetyl triethyl citrate (SP value 21.1, viscosity 29.7 mPas) And diphenyl ether (SP value 21.4, viscosity 3.8 mPas) and the like.

Moreover, you may use the silane coupling agent which has reactive groups other than a radical reactive group as a compound which acts to suppress aggregation of particle | grains (a2). As a specific example of the silane coupling agent which has reactive groups other than a radical reactive group, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803 (above, Shin-Etsu Chemical Co., Ltd.) 1) can be mentioned.

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

<Metal Oxide Particles>

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, and the like. Silica particles are difficult to generate haze due to the close refractive index of many binder resins, and also to form a moth-eye structure. Is preferred.

It is preferable that the average primary particle diameter of a metal oxide particle is 100 nm or more and 190 nm or less, It is more preferable that it is 100 nm or more and 180 nm or less, It is more preferable that it is 100 nm or more and 170 nm or less.

As the metal oxide particles, only one kind may be used, or two or more kinds of particles having different average primary particle diameters may be used.

The average primary particle diameter of a metal oxide particle points out 50% of the cumulative volume average particle diameter. A scanning electron microscope (SEM) can be used for the measurement of a particle diameter. Powder particles (in the case of dispersion, dried and volatilized solvent) were observed at an appropriate magnification (about 5000 times) by SEM observation, and the diameters of each of the 100 primary particles were measured and the volume thereof was calculated. A 50% particle size can be made into an average primary particle size. If the particles are not spherical, the average value of the long and short diameters is regarded as the diameter of the primary particles. When measuring the particle | grains contained in an antireflection film, an antireflection film is observed and calculated by SEM in the same manner to the above from the surface side. At this time, carbon sample, an etching process, etc. may be suitably given to a sample so that it may be easy to observe.

It is preferable that a metal oxide particle is a solid particle from a viewpoint of intensity | strength. Although the spherical shape is most preferable for the shape of a metal oxide particle, even if it is other than spherical shapes, such as an amorphous form, there is no problem.

For example, by using irregular particles in which a part of spherical metal oxide particles are planar portions, and providing a planar portion at the lower layer side, the movement of the particles is suppressed, and in each step from application to drying and curing. Agglomeration of particles can be prevented, the distance between the convex portions caused by the particles can be made uniform, and the transmittance of the short wavelength region can be improved, which is preferable.

Moreover, as another example of an amorphous form, the particle | grains of the shape which the small particle couple | bonded with a part of metal oxide particle further can be used. Although the number of the small particles couple | bonded with the metal oxide particle may be multiple, one is more preferable. It is preferable that the particle diameter of the small particle couple | bonded with a part of metal oxide particle is smaller than metal oxide particle, It is more preferable that it is 0.5 times or less of the particle diameter of metal oxide particle, It is more preferable that it is 0.25 times or less. It is preferable that the density of the small particle couple | bonded with a part of metal oxide particle is larger than metal oxide particle, It is more preferable that it is 2 times or more, It is more preferable that it is 3 times or more. It is preferable that a small particle is a metal oxide, For example, zirconia, alumina, titania, etc. are preferable, but if it satisfy | fills the relationship of the said density, it can use suitably. 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.

Moreover, about a silica particle, crystalline may be sufficient and any of an amorphous may be sufficient.

As the metal oxide particles, it is preferable to use surface-treated inorganic fine particles for improving dispersibility, film strength, and preventing aggregation in the coating liquid. Specific examples and preferred examples of the surface treatment method are the same as those described in [0119] to [0147] of JP-A-2007-298974.

It is preferable that a metal oxide particle is particle | grains surface-modified by the compound which has a functional group which has reactivity with the surface of a polymerizable unsaturated group and a metal oxide particle.

In particular, from the viewpoint of imparting binding properties with the curable compound (a1) for forming the binder resin and improving the strength of the antireflection layer, the particle surface is formed from a polymerizable unsaturated group (preferably unsaturated double bond) and the particle surface. It is preferable to surface-modify with the compound which has a reactive functional group, and to give a polymerizable unsaturated group (preferably unsaturated double bond) to the particle surface. As a compound used for surface modification, the silane coupling agent which has a polymeric group mentioned above as a curable compound (a1) can be used suitably.

Specifically, commercially available KBM-503 and KBM-5103 (both manufactured by Shin-Etsu Chemical Co., Ltd.) and Japanese Patent Application Laid-Open No. 2014-123091, X-12-1048, X-12-1049, and X- It is preferable to modify the silane coupling agent containing a (meth) acryloyl group such as 12-1050 to the metal oxide particle surface.

As a specific example of the particle | grains whose average primary particle diameters are 100 nm or more and 190 nm or less, Shihostar KE-P10 (average primary particle diameter 150 nm, amorphous silica by Nippon Shokubai Co., Ltd.) etc. can be used preferably.

As metal oxide particle | grains, it is especially preferable that they are calcined silica particle | grains from the reason that the amount of hydroxyl groups of a surface is suitably large and it is a hard particle | grain.

Calcined silica particles can be produced by known techniques such as calcining silica particles after hydrolysis and condensation of a hydrolyzable silicone compound in an organic solvent containing water and a catalyst, followed by calcining. For example, refer to Unexamined-Japanese-Patent No. 2003-176121, Unexamined-Japanese-Patent No. 2008-137854, etc. can be referred.

Although it does not specifically limit as a silicone compound of the raw material which manufactures calcined silica particle, tetrachlorosilane, methyl trichlorosilane, phenyl trichlorosilane, dimethyldichlorosilane, diphenyl dichlorosilane, methyl vinyl die Chlorosilane compounds such as chlorosilane, trimethylchlorosilane and methyldiphenylchlorosilane; Tetramethoxysilane, Tetraethoxysilane, Tetraisopropoxysilane, Tetrabutoxysilane, Methyltrimethoxysilane, Methyltriethoxysilane, Trimethoxyvinylsilane, Triethoxyvinyl Silane, 3-glycidoxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane Phosphorus, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy Propylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethoxydiethoxysilane, trimethylmethoxysilane , Trimethylethoxysilane, etc. An alkoxy silane compound; Acyloxysilane compounds such as tetraacetoxy silane, methyl triacetoxy silane, phenyl triacetoxy silane, dimethyl diacetoxy silane, diphenyl diacetoxy silane and trimethyl acetoxy silane; Silanol compounds such as dimethylsilinadiol, diphenylsilinadiol and trimethylsilanol; Etc. can be mentioned. Among the silane compounds of the above examples, the alkoxysilane compound is particularly preferred because it is easier to obtain and no halogen atoms are contained in the calcined silica particles obtained as impurities. As a preferable form of calcined silica particle, content of a halogen atom is substantially 0%, and it is preferable that a halogen atom is not detected.

Although baking temperature is not specifically limited, 800-1300 degreeC is preferable and 1000 degreeC-1200 degreeC is more preferable.

Moreover, as an example of the manufacturing method of the said amorphous particle, adjacent particle | grains are sintered at the time of high temperature baking, and the sintered particle is then grind | pulverized by a grinding | pulverization process, and the amorphous particle which a part of spherical form became flat can also be obtained.

The content of the metal oxide particles in the antireflection ^{layer, 50mg / m 2 ~ 200mg /} m 2 are ^{preferred, 100mg / m 2 ~ 180mg /} m 2 is more preferred, and most preferably ^{130mg / m 2 ~ 170mg / m} 2 . Above the lower limit, since many convex portions of the moth eye structure can be formed, the antireflection property is more easily improved, and if it is below the upper limit, aggregation hardly occurs, and a favorable moth eye structure is easily formed.

When the average primary particle diameter of the metal oxide particles is 100 nm or more and 190 nm or less and contains only one type of monodisperse silica fine particles having a CV (coefficient of variation) value of less than 5%, the height of the unevenness of the moth-eye structure becomes uniform. It is preferable because the reflectance is further lowered. Although CV value is measured using a laser diffraction type particle size measuring apparatus normally, another particle diameter measuring system may be sufficient and it can also calculate and calculate a particle size distribution by image analysis from the surface SEM image of an antireflection layer. As for CV value, it is more preferable that it is less than 4%.

As still another aspect, the metal oxide fine particles preferably 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, particles of larger particle size mainly contribute to the moth-eye structure, and particles of smaller particle size are mixed between the larger particles to suppress aggregation of the larger particles, resulting in better reflectance and haze. It may become. In addition, since the metal oxide particle whose primary particle diameter is 1 nm or more and less than 70 nm is immersed a lot in binder resin, the convex part as an antireflection layer shows that it is formed by the metal oxide fine particle whose primary particle diameter is 100 nm or more and 190 nm or less. It is preferable to include the frequency of the number of the metal oxide particle whose average primary particle diameter is 1 nm or more and less than 70 nm with respect to the metal oxide microparticles whose average primary particle diameter is 100 nm or more and 190 nm or less at the frequency of 1-3 times. By setting it as this range, the aggregation suppression effect is high and a reflectance can be made low. The metal oxide particles having an average primary particle size of 1 nm or more and 70 nm or less are preferably those having an average primary particle size of 30 nm or more and 50 nm or less because the reflectance can be made particularly low. When using together metal oxide particles from which an average primary particle diameter differs, it is preferable to make hydroxyl amount of the surface of both particle | grains close, since it is hard to aggregate more. 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 and space agglomeration of metal oxide particles having an average primary particle size of 100 nm or more and 190 nm or less, so that an easily available hydroxyl group amount is 1.00. You may use the metal oxide particle more than x10-1, or less than 400 MPa of indentation hardness.

In addition to binder resin and metal oxide particle, the antireflection layer may contain components other than these, for example, may contain the dispersing agent, leveling agent, antifouling agent, etc. of a metal oxide particle.

<Dispersant of Metal Oxide Particles>

The dispersing agent of a metal oxide particle can make it easy to arrange | position a metal oxide particle uniformly by reducing the cohesion force of particle | grains. Although it does not specifically limit as a dispersing agent, Cationic compounds, such as anionic compounds, such as a sulfate and a phosphate, an aliphatic amine salt, and a quaternary ammonium salt, a nonionic compound, and a high molecular compound are preferable, The freedom degree of selection of an adsorption group and a three-dimensional repulsive group is preferable. Since is high, a high molecular compound is more preferable. A commercial item can also be used as a dispersing agent. For example, DISPERBYK160, DISPERBYK161, DISPERBYK162, DISPERBYK163, DISPERBYK164, DISPERBYK166, DISPERBYK167, DISPERBYK171, DISPERBYK180, DISPERBYK182, DISPERBYK2000, DISPERBYK2001, DISPERBYK2K-104, Bykumen -P104S, BYK-220S, Anti-Terra203, Anti-Terra204, Anti-Terra205 (above trade name), etc. are mentioned.

<Leveling agent>

By lowering the surface tension of the antireflection layer, the leveling agent can stabilize the liquid after coating and make it easy to uniformly arrange the curable compound (a1) and the metal oxide particles.

The composition for antireflection layer formation used in the present invention may contain at least one leveling agent.

Thereby, the film thickness variation etc. resulting from the dry imbalance by the local distribution of a dry wind, etc. can be suppressed, the sieve of a coating material can be improved, or a curable compound (a1) and metal oxide particle can be arrange | positioned easily.

As the leveling agent, at least one leveling agent selected from silicon-based leveling agents and fluorine-based leveling agents can be used. Moreover, it is preferable that a leveling agent is an oligomer or a polymer rather than a low molecular weight compound.

When the leveling agent is added, the leveling agent is quickly moved and localized on the surface of the applied coating film, and since the leveling agent is unevenly distributed on the surface even after drying of the coating film, the surface energy of the film to which the leveling agent is added is lowered by the leveling agent. do. It is preferable that the surface energy of the film is low from the viewpoint of preventing film thickness variability, sheeting, and nonuniformity.

As a preferable example of a silicone type leveling agent, the polymer or oligomer which contains two or more dimethylsilyloxy units as a repeating unit, and has a substituent in the terminal and / or a side chain is mentioned. In the polymer or oligomer containing dimethylsilyloxy as a repeating unit, structural units other than dimethylsilyloxy may be included. The substituents may be the same or different and preferably have a plurality of substituents. Examples of preferred substituents include groups including polyether groups, alkyl groups, aryl groups, aryloxy groups, aryl groups, cinnamoyl groups, oxetanyl groups, fluoroalkyl groups, polyoxyalkylene groups and the like.

Although there is no restriction | limiting in particular in the number average molecular weight of a silicone type leveling agent, It is preferable that it is 100,000 or less, It is more preferable that it is 50,000 or less, It is especially preferable that it is 1000-30000, It is most preferable that it is 1000-20000.

As an example of a preferable silicone leveling agent, it is a commercially available silicone-type leveling agent which does not have a photopolymerizable group, X22-3710, X22-162C, X22-3701E, X22160AS, X22170DX, X224015, X22176DX, X22 by Shin-Etsu Chemical Co., Ltd. -176F, X224272, KF8001, X22-2000 and the like; Chiso Co., Ltd. FM4421, FM0425, FMDA26, FS1265, etc .; Toray Dow Corning Co., Ltd. BY16-750, BY16880, BY16848, SF8427, SF8421, SH3746, SH8400, SF3771, SH3749, SH3748, SH8410, etc .; TSF Series (TSF4460, TSF4440, TSF4445, TSF4450, TSF4446, TSF4453, TSF442, TSF4453, TSF4453, etc.), FGF502, SILWETL7700, SILWEILWE7002, SILWEILWE , SILWETL7200, SILWETL7210, SILWETL7220, include SILWETL7230, SILWETL7500, SILWETL7510, SILWETL7600, SILWETL7602, SILWETL7604, SILWETL7604, SILWETL7605, SILWETL7607, SILWETL7622, SILWETL7644, SILWETL7650, SILWETL7657, SILWETL8500, SILWETL8600, SILWETL8610, such SILWETL8620, SILWETL720), but limited to, It doesn't happen.

As having a photopolymerizable group, X22-163A, X22-173DX, X22-163C, KF101, X22164A, X24-8201, X22174DX, X22164C, X222426, X222445, X222457, X222459, X22245, manufactured by Shin-Etsu Chemical Co., Ltd. X221602, X221603, X22164E, X22164B, X22164C, X22164D, TM0701 and the like; Silaplane series (FM0725, FM0721, FM7725, FM7721, FM7726, FM7727, etc.) by Chiso Corporation; Toray Dow Corning Co., Ltd. SF8411, SF8413, BY16-152D, BY16-152, BY16-152C, 8388A, etc .; TEGORad 2010, 2011, 2100, 2200N, 2300, 2500, 2600, 2700, etc. made by Evonik Degussa Japan; BYK3500 by Big Chemie Japan Co., Ltd .; KNS5300 made by Shin-Etsu Silicone; Although UVHC1105, UVHC8550, etc. made by Momentive Performance Materials Japan Corporation are mentioned, It is not limited to this.

It is preferable to contain 0.01-5.0 mass% in a reflection prevention layer, It is more preferable to contain 0.01-2.0 mass%, It is most preferable to contain 0.01-1.0 mass%.

A fluorine-type leveling agent is a compound which has a fluoro aliphatic group and a lipophilic group which contributes to affinity with respect to various compositions, such as for coating and molding materials, when this leveling agent is used as an additive, for example, Generally, the same compound can be obtained by copolymerizing a monomer having a fluoroaliphatic group and a monomer having a lipophilic group.

As a typical example of the monomer which has a lipophilic group copolymerized with the monomer which has a fluoro aliphatic group, poly (oxyalkylene) acrylate, poly (oxyalkylene) methacrylate, etc. are mentioned.

As a preferable commercial fluorine-type leveling agent, it does not have a photopolymerizable group, and it is Megapak series (MCF350-5, F472, F476, F445, F444, F443, F178, F470, F475, F479, F477, F482, made by DIC Corporation). F486, TF1025, F478, F178K, F-784-F, etc.); Neos Co., Ltd. P aftergent series (FTX218, 250, 245M, 209F, 222F, 245F, 208G, 218G, 240G, 206D, 240D, etc.) is mentioned, Daikin High School Co., Ltd. has a photopolymerizable group. Opoptal DACs; DIC Corporation's Defencer Series (TF3001, TF3000, TF3004, TF3028, TF3027, TF3026, TF3025, etc.), RS Series (RS71, RS101, RS102, RS103, RS104, RS105, etc.) may be mentioned. no.

Moreover, the compound etc. which were described in Unexamined-Japanese-Patent No. 2004-331812, Unexamined-Japanese-Patent No. 2004-163610 can also be used.

<Antifouling agent>

A well-known silicone type or fluorine type antifouling agent, a sliding agent, etc. can be added to an antireflection layer suitably in order to provide characteristics, such as antifouling property, water resistance, chemical resistance, and sliding property.

As a specific example of a silicone type or fluorine-type antifouling agent, what has a photopolymerizable group can be used suitably among the silicone type or fluorine-type leveling agent mentioned above, It is not limited to these.

It is preferable to contain 0.01-5.0 mass% of antifouling agents in an antireflection layer, It is more preferable to contain 0.01-2.0 mass%, It is most preferable that 0.01-1.0 mass% is contained.

The antireflection film of this invention can be used for various uses, For example, it can use suitably as a polarizing plate protective film.

The polarizing plate protective film using the antireflection film of this invention can be bonded together with a polarizer, and can be used as a polarizing plate, and can be used suitably for a liquid crystal display device.

[Polarizing Plate]

The polarizing plate of this invention has a polarizer and the antireflection film of this invention.

The polarizing plate of this invention is a polarizing plate which has a polarizer and at least 1 protective film which protects a polarizer, It is preferable that at least 1 sheet of a protective film is an antireflection film of this invention.

The polarizer includes an iodine polarizer, a dye polarizer using a dichroic dye, or a polyene polarizer. An iodine type polarizer and a dye type polarizer can be manufactured generally using a polyvinyl alcohol-type film.

[Image display device]

The image display device of the present invention includes the antireflection film of the present invention or the polarizing plate of the present invention.

As the image display device, a display device using a cathode ray tube (CRT), a plasma display panel (PDP), an electroluminescence display (ELD), a fluorescent display display (VFD), a field emission display (FED), and a liquid crystal display ( LCD), and especially a liquid crystal display device is preferable.

Generally, a liquid crystal display device has a liquid crystal cell and two polarizing plates arrange | positioned at the both sides, and the liquid crystal cell carries a liquid crystal between two electrode substrates. In addition, one optically anisotropic layer may be arrange | positioned between a liquid crystal cell and one polarizing plate, or two sheets may be arrange | positioned between a liquid crystal cell and both polarizing plates. The liquid crystal cell may be a liquid crystal cell of various driving methods such as twisted nematic (TN) mode, vertically aligned (VA) mode, optimally compensated bend (OCB) mode, and in-plane switching (IPS) mode.

[Method for Producing Antireflection Film]

Although the manufacturing method of the antireflection film of this invention is not specifically limited, Preferably,

On the base film, the composition for hard-coat layer formation containing the said copolymer (a) is apply | coated, a hard-coat layer is provided, and a curable compound and a metal oxide particle contain the said curable compound on the said hard-coat layer. A step (1) of providing the metal oxide particles with a thickness buried in the layer (a)

A step (2) of bonding the layer (b) of the pressure-sensitive adhesive film having the support and the layer (b) comprising a pressure-sensitive adhesive having a gel fraction of at least 95.0% on the support (2),

The layer so that the metal oxide particles are buried in the combined layer of the layer (a) and the layer (b) and protrude from an interface on the side opposite to the interface on the side of the hard coat layer of the layer (a). (3) moving the position of the interface between (a) and the layer (b) to the hard coat layer side;

(4) the step of curing the layer (a) while the metal oxide particles are buried in the layer in which the layer (a) and the layer (b) are combined,

It is a manufacturing method of the antireflection film which has the process (5) which peels the said layer (b) from the said layer (a) in this order.

By the said manufacturing method, the antireflection film of this invention mentioned above can be manufactured.

In the above production method, the curable compound (a1) described above is preferably used as the curable compound, and the metal oxide particles are also preferably used as described above.

Moreover, the layer (a) hardened | cured at the process (4) is corresponded to the film | membrane of the binder resin mentioned above, and it is an antireflection layer containing the metal oxide particle which protruded from layer (a) and layer (a).

An example of preferable embodiment of the manufacturing method of the antireflection film of this invention is shown in FIG.

FIG.2 (1) shows the layer (a) (symbol 4 in FIG. 2) which contains a curable compound (a1) on the hard-coat layer HC provided on the base film 1 in process (1). ), A state in which a metal oxide particle (also referred to as "particle (a2)") (symbol 3 in FIG. 2) is provided to a thickness to be buried is schematically shown.

FIG.2 (2) has the layer (b) (symbol 6 in FIG. 2) which consists of an adhesive whose gel fraction is 95.0% or more on the support body 5 and the said support body 5 in a process (2). The state which bonded the layer (b) of the adhesive film 7 with the layer (a) (symbol 4 in FIG. 2) is typically shown.

2 (3) shows that in the step (3), the particles (a2) are buried in the layer in which the layers (a) and (b) are combined, and the interface on the hard coat layer side of the layer (a) and Shows the state which moved the position of the interface of layer (a) and layer (b) to the hard-coat layer side so that it may protrude from the interface of the opposite side. Moreover, as mentioned later, as a method of moving the position of the interface of a layer (a) and a layer (b) to the hard-coat layer side, the method of making a part of curable compound (a1) penetrate into the layer (b) containing an adhesive. Can be mentioned.

To move the position of the interface between the layer (a) and the layer (b) toward the hard coat layer side is to bring the position of the interface closer to the hard coat layer.

FIG. 2 (4) schematically shows that in the step (4), the particle (a2) is cured in the state in which the particle (a2) is buried in the layer in which the layer (a) and the layer (b) are combined. have.

(5) is a state after peeling the adhesive film 7 in the process (5) of peeling the adhesive film 7 containing the layer (b) from a layer (a) (Anti-reflection film ( 10)).

In the manufacturing method of the antireflection film of this invention, it is preferable that the temperature at the time of performing process (1)-(4) is 60 degrees C or less, and it is more preferable that it is 40 degrees C or less. By keeping the temperature at the time of performing process (1)-(4) at 60 degrees C or less, aggregation of metal oxide particle can be suppressed and favorable uneven | corrugated shape can be formed.

[Step (1)]

In the step (1), the composition for forming a hard coat layer containing the copolymer (a) is applied onto a base film to provide a hard coat layer, and the curable compound and the metal oxide particles are formed on the hard coat layer. It is a process of providing with the thickness in which a metal oxide particle is embedded in the layer (a) containing a curable compound.

In the present invention, "thickness in which the metal oxide particles are embedded in the layer (a)" means 0.8 times or more of the average primary particle diameter 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 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 curable compound (a1) and a composition (also referred to as "composition for forming layer (a)") containing particles (a2). As a coating method, it does not specifically limit but a well-known method can be used. For example, the dip coating method, the air knife coating method, the curtain coating method, the roller coating method, the wire bar coating method, the gravure coating method, the die coating method, etc. are mentioned.

In a process (1), it is preferable that two or more particle | grains (a2) do not exist in the direction orthogonal to the surface of a base film. Here, when two or more 10 micrometers x 10 micrometers in surface inside of a base film are observed by a scanning electron microscope (SEM), when two or more particle | grains (a2) do not exist in the direction orthogonal to the surface of a base film, orthogonal to a surface, It shows that the ratio of the number of the particle | grains (a2) of the state which does not exist in multiple superimposition in the direction is 80% or more, Preferably it is 95% or more.

(Layer (a))

It is preferable that the layer (a) in a process (1) contains a curable compound (a1) and particle | grains (a2).

Layer (a) is a layer for forming an antireflection layer.

Curable compound (a1) contained in layer (a) is what can become binder resin of an antireflection layer by hardening.

The particle (a2) contained in the layer (a) is a particle which protrudes from the surface of the film made of the binder resin in the antireflection film to form an uneven shape (moss eye structure).

In addition, since the layer (a) is cured in the step (4), the components to be contained before curing and after curing are different. However, in the present invention, the layer (a) may be called at any stage for convenience. The same applies to the hard coat layer.

It is preferable that the film thickness of the layer (a) in a process (1) is 0.8 times or more and 2.0 times or less of the average primary particle diameter of particle | grains (a2), It is more preferable that they are 0.8 times or more and 1.5 times or less, 0.9 times or more It is more preferable that it is 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 a composition for forming an antireflection layer.

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

<Solvent>

The composition for forming a layer (a) or a layer (a) may contain the solvent.

As a solvent, it is preferable to select the thing with polarity close to particle | grains (a2) from a viewpoint of improving dispersibility. Specifically, an alcohol solvent is preferable, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, etc. are mentioned. For example, in the case of the metal resin particle whose particle | grain (a2) became the hydrophobization surface modification, solvents, such as a ketone system, ester type, a carbonate type, an alkane, and an aromatic type, are preferable, and methyl ethyl ketone (MEK), Dimethyl carbonate, methyl acetate, acetone, methylene chloride, cyclohexanone, etc. are mentioned. You may use these solvent in mixture of multiple types in the range which does not remarkably deteriorate dispersibility.

<Polymerization initiator>

The composition for forming layer (a) or layer (a) may contain the polymerization initiator.

The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator. What is necessary is just to select the suitable polymerization initiator according to the kind of polymeric compound used together. As a polymerization initiator, what is necessary is just to select either a thermal polymerization initiator or a photoinitiator according to the kind (heating, light irradiation) of the polymerization process performed in a manufacturing process. Moreover, you may use together with a thermal polymerization initiator and a photoinitiator.

The structure of the thermal polymerization initiator is not particularly limited. As a specific aspect of a thermal polymerization initiator, an azo compound, a hydroxylamine ester compound, an organic peroxide, hydrogen peroxide, etc. are mentioned. As a specific example of an organic peroxide, the thing of Unexamined-Japanese-Patent No. 5331155 Paragraph 0031 is mentioned.

When curable compound (a1) is a photopolymerizable compound, it is preferable to contain a photoinitiator.

The structure of the photopolymerization initiator is not particularly limited. Specific examples include acetophenones, benzoin, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, and disulfides. Compounds, fluoroamine compounds, aromatic sulfoniums, ropindimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like can be given. Specific examples of the photopolymerization initiator, preferred embodiments, commercial products, and the like are described in paragraphs [0133] to [0151] of JP-A-2009-098658, and can be suitably used in the present invention as well.

"The Latest UV Curing Technology" {Kijutsu Joho Kyokai Co., Ltd.} (1991), p. 159, and "Ultraviolet Curing System" by Kiyoshi Kato (issued by Sogo Kijutsu Center, 1989), p. Various examples are also described in 65 to 148 and are useful in the present invention.

The content of the polymerization initiator in the layer (a) is an amount sufficient to polymerize the polymerizable compound contained in the layer (a), and the total amount of the polymerization initiator in the layer (a) is set to prevent the excessive increase in the starting point. 0.1-8 mass% is preferable with respect to, and 0.5-5 mass% is more preferable.

In the layer (a), a compound which generates an acid or a base by light or heat in order to react the silane coupling agent having a polymerizable group (hereinafter, referred to as photoacid generator, photobase generator, thermal acid generator, and thermal base generation) May be called zero).

<Mine generator>

Examples of the photoacid generator include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenium salts, and arsonium salts, organic halogen compounds, organic metal / organic halogenates, and photo-degraded, sulfonic acid-producing compounds, disulfone compounds, diazoketosulfones, diazodisulfone compounds, and the like, represented by photoacid generators having an o-nitrobenzyl type protecting group, iminosulfonates, and the like. In addition, triazines (eg 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc.), quaternary ammonium salts, diazo Methane compound, an imide sulfonate compound, and an oxime sulfonate compound can also be mentioned.

Moreover, the compound which introduce | transduced the group which generate | occur | produces an acid by light, or the compound into the main chain or side chain of a polymer can be used.

See also V. N. R. Pillai, Synthesis, (1), 1 (1980), A. Abad et al., Tetrahedron Lett., (47) 4555 (1971), D. H. R. Barton et al., J. Chem. Compounds which generate an acid by light described in Soc., (C), 329 (1970), US Patent No. 3,779,778, European Patent No. 126,712 and the like can also be used.

<Thermal Acid Generator>

As a thermal acid generator, the salt which consists of an acid and an organic base is mentioned.

Examples of the acid include organic acids such as sulfonic acid, phosphonic acid and carboxylic acid, and inorganic acids such as sulfuric acid and phosphoric acid. From the viewpoint of compatibility with the curable compound (a1), an organic acid is more preferable, sulfonic acid and phosphonic acid are more preferable, and sulfonic acid is most preferred. Preferred sulfonic acids include p-toluenesulfonic acid (PTS), benzenesulfonic acid (BS), p-dodecylbenzenesulfonic acid (DBS), p-chlorobenzenesulfonic acid (CBS), 1,4-naphthalenedisulfonic acid (NDS), methanesulfonic acid (MsOH), nonafluorobutane-1-sulfonic acid (NFBS), etc. are mentioned.

As an example of an acid generator, the thing of Unexamined-Japanese-Patent No. 2016-000803 can be used suitably.

<Photobase Generator>

As a photobase generator, the substance which produces | generates a base by action of an active energy ray is mentioned. More specifically, (1) salts of organic acids and bases which are decarbonized and decomposed by irradiation with ultraviolet rays, visible light or infrared rays, (2) compounds which are decomposed by intranucleophilic substitution reactions or dislocation reactions and release amines; Or (3) It can be used to cause any chemical reaction by irradiation of ultraviolet light, visible light or infrared light and release the base.

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, what is described in Unexamined-Japanese-Patent No. 2010-243773 can be used suitably.

The content of the compound which 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 reason why the starting point is set so as not to increase excessively. In the above, 0.1 to 8% by mass is preferable and more preferably 0.1 to 5% by mass based on the total solids in the layer (a).

The composition for forming layer (a) or layer (a) may further contain the dispersing agent, leveling agent, antifouling agent, etc. of particle | grain (a2), and these are the same as that mentioned above.

[Step (2)]

Step (2) is a step of bonding the layer (b) of the pressure-sensitive adhesive film having the layer (b) containing the pressure-sensitive adhesive on the support and the support with a gel fraction of 95.0% or more, with the layer (a). It does not specifically limit as a method of bonding a layer (a) and the layer (b) of an adhesion film, A well-known method can be used, For example, a laminating method is mentioned.

It is preferable to bond an adhesive film so that a layer (a) and a layer (b) may contact.

You may have the process of drying layer (a) before a process (2). 20-60 degreeC is preferable and, as for the drying temperature of a layer (a), 20-40 degreeC is more preferable. 0.1-120 second is preferable and, as for drying time, 1-30 second is more preferable.

The present inventors bonded the layer (b) and layer (a) of the adhesion film in the process (2), and combined the layer (a) and the layer (b) with the particle (a2) in the process (3) described later. The particles (a2) are embedded in the layer and protrude from the interface on the side opposite to the interface on the hard coat layer side of the layer (a), so that the particles (a2) form the layer (a) and the layer (b) in the step (4) described later. By curing the layer (a) in the state of being buried in the combined layers, the particles (a2) are not exposed to the air interface before curing of the layer (a), the aggregation is suppressed, and the good irregularities formed by the particles (a2) are formed. Found that can be produced.

(Adhesive film)

An adhesive film has a layer (b) which consists of an adhesive whose support body and a gel fraction are 95.0% or more.

<Layer (b)>

Layer (b) consists of an adhesive whose gel fraction is 95.0% or more.

When the gel fraction of the pressure-sensitive adhesive is 95.0% or more, when the pressure-sensitive adhesive film is peeled off to produce an anti-reflection film, the pressure-sensitive adhesive component is hard to remain on the surface of the anti-reflection film, and an antireflection film having a sufficiently low reflectance can be obtained even without washing. .

It is preferable that the gel fraction of an adhesive is 95.0% or more and 99.9% or less, It is more preferable that they are 97.0% or more and 99.9% or less, It is more preferable that they are 98.0% or more and 99.9% or less.

The gel fraction of an adhesive is a ratio of the insoluble content after immersing an adhesive in tetrahydrofuran (THF) for 12 hours at 25 degreeC, and is calculated | required from the following formula.

Gel fraction = (mass of insoluble matter to THF of adhesive) / (total mass of adhesive) * 100 (%)

It is preferable that the weight average molecular weight of the sol component in an adhesive is 10000 or less, It is more preferable that it is 7000 or less, It is most preferable that it is 5000 or less. By peeling an adhesive film and making an antireflection film by making the weight average molecular weight of a sol component into the said range, an adhesive component can make it hard to remain on the antireflection film surface.

The sol component of an adhesive shows the melt | dissolution with respect to THF after immersing an adhesive in tetrahydrofuran (THF) for 12 hours at 25 degreeC. The weight average molecular weight can be analyzed by gel permeation chromatography (GPC).

It is preferable that the film thickness of a layer (b) is 0.1 micrometer or more and 50 micrometers or less, It is more preferable that they are 1 micrometer or more and 30 micrometers or less, It is more preferable that they are 1 micrometer or more and 20 micrometers or less.

The layer (b) is a layer (a), which is an adhesive layer, in which the peel strength (adhesive force) to the surface of the adherend at a peeling rate of 0.3 m / min is a pressure-sensitive adhesive layer having a non-adhesive force of about 0.03 to 0.3 N / 25 mm. It is preferable at the point which is excellent in the operability at the time of peeling an adhesive film from.

As an adhesive, what contains a polymer is preferable and what contains a (meth) acrylic-type polymer is more preferable. In particular, the polymer (in the case of 2 or more types of monomers) of at least 1 type of monomer among the (meth) acrylic-acid alkylester monomers of C1-C18 of an alkyl group is preferable. It is preferable that the weight average molecular weights of a (meth) acrylic-type polymer are 200,000-2 million.

Examples of the (meth) acrylic acid alkyl ester monomer having 1 to 18 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth). Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isomyristyl (meth) acrylate, isocetyl (Meth) acrylate, isostearyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, tetradecyl (meth) acrylate, pen Decyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) (meth) acrylate monomers, such as acrylate. The alkyl group of the alkyl (meth) acrylate monomer may be any of linear, branched and cyclic. 2 or more types of said monomers may be used together.

Suitable 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. have. Especially, it is especially preferable that it is cyclohexyl (meth) acrylate.

The (meth) acrylic polymer may be a copolymer composed of at least one of the (meth) acrylic acid alkyl ester monomers having 1 to 18 carbon atoms of the alkyl group and at least one of the other copolymerizable monomers. In this case, as another copolymerizable monomer, the copolymerizable vinyl monomer containing at least 1 group chosen from a hydroxyl group, a carboxyl group, and an amino group, the copolymerizable vinyl monomer which has a vinyl group, an aromatic monomer, etc. are mentioned.

As a copolymerizable vinyl monomer containing a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth Hydroxyl group-containing (meth) acrylic acid esters such as) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, and N-hydroxy (meth) acrylamide, N-hydroxy Hydroxyl group-containing (meth) acrylamides such as oxymethyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide; and the like, and are preferably at least one kind selected from these compound groups.

It is preferable to contain 0.1-15 mass parts of copolymerizable vinyl monomers containing a hydroxyl group with respect to 100 mass parts of a (meth) acrylic-type polymer.

As a copolymerizable vinyl monomer containing a carboxyl group, (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, etc. are mentioned, These compounds are mentioned. It is preferable that it is at least 1 sort (s) chosen from the group.

It is preferable to contain 0.1-2 mass parts of copolymerizable vinyl monomers containing a carboxyl group with respect to 100 mass parts of a (meth) acryl copolymer.

Examples of the copolymerizable vinyl monomer containing an amino group include monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, and monoethylaminopropyl (meth) acrylate. Monoalkyl aminoalkyl (meth) acrylates; and the like.

As an aromatic monomer, styrene etc. are mentioned besides aromatic group containing (meth) acrylic acid ester, such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.

Examples of the 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.

An adhesive may contain the hardened | cured material of the composition (also called adhesive composition) for forming an adhesive.

It is preferable that an adhesive composition contains the said polymer and a crosslinking agent, and you may crosslink using heat, an ultraviolet-ray (UV), etc. As the crosslinking agent, at least one crosslinking agent selected from the group consisting of bifunctional or higher functional isocyanate crosslinking agents, bifunctional or higher functional epoxy crosslinking agents, and aluminum chelate crosslinking agents is preferable. When using a crosslinking agent, when peeling an adhesive film and manufacturing an antireflection film, it contains 0.1-15 mass parts with respect to 100 mass parts of said polymer from a viewpoint which makes it difficult to remain an adhesive component on the antireflection film surface. It is more preferable to contain 3.5-15 mass parts, and it is more preferable to contain 5.1-10 mass parts.

As a bifunctional or more isocyanate type compound, what is necessary is just a polyisocyanate compound which has at least 2 or more isocyanate (NCO) group in 1 molecule, and is hexamethylene diisocyanate and isophorone diisocyanate. Burette modified substance of diisocyanates (compound which has two NCO groups in 1 molecule), such as a nitrate, diphenylmethane diisocyanate, tolylene diisocyanate, and xylylene diisocyanate And adducts (polyol modified substances) with trivalent or higher polyols (compounds having at least three or more OH groups in one molecule) such as isocyanurate modified substance, trimethylolpropane or glycerin. .

Moreover, the trifunctional or more isocyanate compound is a polyisocyanate compound which has at least 3 or more isocyanate (NCO) groups in 1 molecule, and especially isocyanurate of the hexamethylene diisocyanate compound. Sieve, Isocyanurate body of isophorone diisocyanate compound, Adduct body of hexamethylene diisocyanate compound, Adduct body of isophorone diisocyanate compound, Hexamethylene diisocyanate It is preferable that it is at least 1 sort (s) chosen from the compound group which consists of a burette body of a compound and the burette body of an isophorone diisocyanate compound.

It is preferable that 0.01-5.0 mass parts is contained with respect to 100 mass parts of polymers, and, as for a bifunctional or more isocyanate type crosslinking agent, it is more preferable that 0.02-3.0 mass parts are contained.

In order to provide antistatic performance, an adhesive composition may contain an antistatic agent. The antistatic agent is preferably an ionic compound, more preferably a quaternary onium salt.

As an antistatic agent which is a quaternary onium salt, For example, the alkyldimethylbenzyl ammonium salt which has a C8-C18 alkyl group, the dialkylmethylbenzyl ammonium salt which has a C8-C18 alkyl group, and the trialkyl which has a C8-C18 alkyl group Benzyl ammonium salt, tetraalkylammonium salt having a C8-C18 alkyl group, alkyldimethylbenzylphosphonium salt having a C8-C18 alkyl group, dialkylmethylbenzylphosphonium salt having a C8-C18 alkyl group, C8-C8 Trialkylbenzylphosphonium salt having an alkyl group of 18, tetraalkylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, alkyltrimethylammonium salt having an alkyl group having 14 to 20 carbon atoms, alkyldimethyl having an alkyl group having 14 to 20 carbon atoms Ethyl ammonium salt etc. 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 octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group. The mixed alkyl group derived from a natural fat or oil may be sufficient. Examples of the alkenyl group having 8 to 18 carbon atoms include octenyl group, nonenyl group, deceenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, oleyl group and li Nole group etc. are mentioned.

Examples of the alkyl group having 14 to 20 carbon atoms include tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and icosyl group. The mixed alkyl group derived from a natural fat or oil may be sufficient. Examples of the alkenyl group having 14 to 20 carbon atoms include tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadesenyl group, octadecenyl group, oleyl group, linoleyl group, nonadesenyl group, and icosenyl group.

Quaternary onium As the salt counter anion, chloride (Cl ^-), bromide (Br ^-), methyl sulphate (CH ₃ OSO ₃ ^-), ethyl sulfate ^{_{(C 2 H 5 OSO 3 -}} ), p-toluene sulfonate (p-CH and the ^{_{like) - 3 C 6 H 4 SO}} 3.

Specific examples of the quaternary onium salts include dodecyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium bromide, tetradecyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium bromide, hexadecyldimethylbenzylammonium chloride, hexadecyldi Methylbenzylammonium bromide, octadecyldimethylbenzylammonium chloride, octadecyldimethylbenzylammonium bromide, trioctylbenzylammonium chloride, trioctylbenzylammonium bromide, trioctylbenzylphosphonium chloride, trioctylbenzylphosphonium bromide, tris (decyl Benzylammonium chloride, tris (decyl) benzylammonium bromide, tris (decyl) benzylphosphonium chloride, tris (decyl) benzylphosphonium bromide, tetraoctylammonium chloride, tetraoctylammonium bromide, tetraoctylfo Sponium chloride, tetraoctylphosphonium bromide, tetranonylammonium chloride, tetranonylammonium bromide, tetranonylphosphonium chloride, tetranonylphosphonium bromide, tetrakis (decyl) ammonium chloride, tetrakis (decyl) ammonium bromide, tetrakis (Decyl) phosphonium chloride, tetrakis (decyl) phosphonium bromide, etc. are mentioned.

In addition, "tris (decyl)" and "tetrakis (decyl)" mean having three or four decyl groups which are C10 alkyl groups, the tridecyl group which is an C13 alkyl group, and the C14 alkyl group It is distinguished from the phosphorus tetradecyl group.

As the antistatic agent, nonionic, cationic, anionic, amphoteric surfactants, ionic liquids, alkali metal salts, metal oxides, metal fine particles, conductive polymers, carbon, carbon nanotubes, and the like can also be used.

Examples of 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 fatty acid esters, polyoxyalkylene-modified silicones, and the like.

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

Moreover, as an amphoteric surfactant, alkyl dimethylamine oxide, alkyl carboxy betaine, etc. are mentioned.

As an ionic liquid, it is a non-polymeric substance which consists of an anion and a cation and is liquid at normal temperature (for example, 25 degreeC). Examples of the cation moiety include cyclic amidine ions such as imidazolium ions, pyridinium ions, ammonium ions, sulfonium ions and phosphonium ions. In addition, as the anionic _{portion, 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 - Etc. can be mentioned.

As an alkali metal salt, the metal salt etc. which consist of lithium, sodium, and potassium are mentioned, You may add the compound containing polyoxyalkylene structure for stabilization of an ionic substance.

It is preferable to contain 0.1-10 mass parts of antistatic agents with respect to 100 mass parts of polymers.

The pressure-sensitive adhesive composition may further contain a polyether modified siloxane compound having an HLB of 7 to 15 as an antistatic assistant.

HLB is hydrophilic lipophilic balance (hydrophilic lipophilic ratio) prescribed | regulated, for example by JISK3211 (surfactant term).

The pressure-sensitive adhesive composition may further contain a crosslinking accelerator. In the case where the polyisocyanate compound is used as a crosslinking agent, the crosslinking accelerator may be a substance which functions as a catalyst for the reaction (crosslinking reaction) between the copolymer and the crosslinking agent, and may be an amine compound such as a tertiary amine or a metal chelate Organometallic compounds, such as a compound, an organotin compound, an organic lead compound, and an organozinc compound, etc. are mentioned. In this invention, a metal chelate compound or an organic tin compound is preferable as a crosslinking promoter.

As a metal chelate compound, it is a compound which 1 or more polydentate ligand L couple | bonded with the center metal atom M. The metal chelate compound may or may not have one or more single-site ligands X bonded to the metal atom M. For example, when the general formula of the metal chelate compound having one metal atom M is represented by M (L) _m (X) _n , m ≧ 1 and _n ≧ 0. When m is two or more, m pieces of L may be the same ligand or different ligands. When n is two or more, n pieces of X 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. As the multidentate ligand L, β-ketoesters such as methyl acetoacetic acid, ethyl acetoacetic acid, acetoacetic acid octyl, acetoacetic acid oleyl, acetoacetic acid lauryl, acetoacetic acid stearyl, and acetylacetone (alias 2,4-pentane ion (Beta) -diketone, such as 2) and 2, 4- hexanedione, and benzoyl acetone. These are ketoenol tautomer compounds, and in the multidentate ligand L, enolate (e.g., acetylacetonate) which is deprotonated with enol may be used.

As the single ligand, X, halogen atoms such as a chlorine atom and a bromine atom, a pentane oil group, a hexane oil group, a 2-ethylhexane oil group, an octane oil group, a nonan oil group, a decane oil group, a dodecane oil group, and an octadecane And alkoxy groups such as acyloxy groups such as oil groups, methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups and butoxy groups.

Specific examples of the metal chelate compound include tris (2,4-pentanedionate) iron (III), iron trisacetylacetate, titanium trisacetylacetonate, ruthenium trisacetylacetate, zinc bisacetylacetate, and aluminum trisacetyl Acetate, zirconium tetrakisacetylacetonate, tris (2,4-hexanedionate) iron (III), bis (2,4-hexanedionate) zinc, tris (2,4-hexanedionate) Titanium, tris (2, 4-hexanedionate) aluminum, tetrakis (2, 4-hexanedionate) zirconium, etc. are mentioned.

Examples of the organic tin compound include dialkyl tin oxide, fatty acid salts of dialkyl tin, fatty acid salts of first tin, and the like. Long-chain alkyl tin compounds such as dioctyl tin compounds are preferred. Dioctyl tin oxide, dioctyl tin dilaurate, etc. are mentioned as a specific organic tin compound.

It is preferable that 0.001-0.5 mass part is contained with respect to 100 mass parts of copolymers with a crosslinking promoter.

<Support>

The support body in an adhesive film is demonstrated.

As a support body, the plastic film which consists of resin which has transparency and flexibility is used preferably. As the plastic film for the support, preferably, a polyester film such as polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, polybutylene terephthalate, (meth) acrylic resin, polycarbonate resin, polystyrene resin, polyolefin resin And films made of cellulose resins such as resins, cyclic polyolefin resins, and cellulose acylates. However, the said (meth) acrylic-type resin contains the polymer which has a lactone ring structure, the polymer which has a glutaric anhydride ring structure, and the polymer which has a glutarimide ring structure.

In addition, other plastic films can also be used as long as they have the required strength and optical aptitude. The support may be a non-stretched film, may be uniaxially or biaxially stretched, or may be a plastic film in which the angle of the axial method formed in accordance with the draw ratio or crystallization of stretching is controlled.

As a support body, what has ultraviolet permeability is preferable. Since ultraviolet irradiation is possible from the coating layer side at the time of hardening a layer (a) in a process (4) by having ultraviolet transmittance | permeability, it is preferable on manufacture suitability.

Specifically, the maximum transmittance at a wavelength of 250 nm to 300 nm of the support is preferably 20% or more, more preferably 40% or more, and most preferably 60% or more. If the maximum transmittance in wavelength 250nm-300nm is 20% or more, it is easy to irradiate an ultraviolet-ray from the coating layer side, and to harden | cure the layer (a), and it is preferable.

Moreover, it is preferable that the maximum transmittance in wavelength 250nm-300nm of the adhesive film which formed the layer (b) on the support body is 20% or more, It is more preferable that it is 40% or more, It is most preferable that it is 60% or more.

Although the film thickness of a support body is not specifically limited, It is preferable that they are 10 micrometers or more and 100 micrometers or less, It is more preferable that they are 10 micrometers or more and 50 micrometers or less, It is more preferable that they are 10 micrometers or more and 40 micrometers or less.

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

In the present invention, in the step (4), the particles (a2) are cured in the layer (a) while being buried in the combined layer of the layers (a) and (b), but the step before the step (4) In this case, it is preferable to have a concave-convex shape formed by the particles (a2) protruding from the interface of the layer (a). By doing so, after curing the layer (a) in the step (4), when the layer (b) is peeled off in the step (5), the antireflection film of the state in which the particles (a2) protrude from the surface of the layer (a). You can get it.

In this invention, you may include the process (1-2) which hardens a part of curable compound (a1) in layer (a), and obtains hardened compound (a1c) between process (1) and process (2). .

Curing a part of the curable compound (a1) means curing only part of the curable compound (a1), not all of it. By curing only a part of the curable compound (a1) in the step (1-2), in the step (3), the layer (a2) protrudes from the interface on the side opposite to the interface on the side of the hard coat layer of the layer (a) ( It is preferable to carry out since the aggregation of the particle | grains when moving the position of the interface of a) and the layer (b) to the hard-coat layer side can be suppressed, and the antireflection film with favorable reflectance and total light transmittance is obtained. Since the optimal hardening conditions in a process (1-2) differ by prescription of a layer (a), what is necessary is just to select the optimal hardening conditions suitably.

[Step (3)]

The step (3) is such that the particles (a2) are buried in the layer in which the layers (a) and (b) are combined and protrude from the interface on the side opposite to the interface on the hard coat layer side of the layer (a), It is a process of moving the position of the interface of a layer (a) and a layer (b) to the hard-coat layer side.

In the present invention, "the particle (a2) is buried in the layer which combined the layer (a) and the layer (b)" means that the thickness of the layer which combined the layer (a) and the layer (b) is the average of the particle (a2) It shall show that it is 0.8 times or more of a primary particle diameter.

It is preferable that a process (3) is performed by making a part of curable compound (a1) penetrate into an adhesive layer.

In the step (3), when injecting a part of the curable compound (a1) into the pressure-sensitive adhesive layer, the laminate having the base film, the hard coat layer, the layer (a), and the layer (b) is kept at 60 ° C. or less. It is preferable, and it is more preferable to keep it at 40 degrees C or less. By maintaining the temperature at 60 ° C. or lower, the viscosity 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 performance due to aggregation of the particles decreases, haze and The effect of preventing an increase in turbidity is great. The lower limit of the temperature for holding the laminate having the base film, the hard coat layer, the layer (a), and the layer (b) is not particularly limited, and may be room temperature (25 ° C.) or a temperature lower than room temperature.

[Step (4)]

Process (4) is a process of hardening layer (a) in the state in which particle | grain (a2) was buried in the layer which combined layer (a) and layer (b).

In the present invention, "the state in which the particles (a2) are buried in the layer of the layer (a) and the layer (b)" means that the thickness of the layer of the layer (a) and the layer (b) is the average of the particles (a2). It shall show that it is 0.8 times or more of a primary particle diameter.

Curing the layer (a) indicates polymerizing the curable compound (a1) contained in the layer (a), whereby the binder resin in the antireflection layer of the antireflection film can be formed. By maintaining the state in which the particle (a2) is buried in the layer in which the layer (a) and the layer (b) are combined in the step (4), aggregation of the particle (a2) can be suppressed and a good uneven shape can be formed.

As a mechanism in which particle agglomeration is suppressed by keeping the particles (a2) buried in the combined layers of the layers (a) and (b), when the particles (a2) are exposed to the air interface until the layer (a) is cured It is known that a large attraction force derived from surface tension called a transverse tube force acts, and the attraction force can be reduced by embedding the particles (a2) in the combined layer (a) and (b). We estimate that it is possible.

Curing can be performed by irradiating light. There is no restriction | limiting in particular about the kind of light, X-ray, an electron beam, an ultraviolet-ray, visible light, an infrared ray etc. are mentioned, Ultraviolet ray is widely used. For example, if the coating is UV-curing, it is preferred by the ultraviolet lamp is irradiated with a dose of UV light of ^{10mJ / cm 2 ~ 1000mJ / cm} 2 to cure the curable compound (a1) in layer (a). More preferably ^{50mJ / cm 2 ~ 1000mJ / cm} 2 , and more preferably of ^{100mJ / cm 2 ~ 500mJ / cm} 2. At the time of irradiation, the said energy may be irradiated at once, and can also irradiate separately. As an ultraviolet lamp type, a metal halide lamp, a high pressure mercury lamp, etc. are used suitably.

It is preferable that the oxygen concentration at the time of hardening is 0 to 1.0 volume%, It is more preferable that it is 0 to 0.1 volume%, It is most preferable that it is 0 to 0.05 volume%. By making oxygen concentration at the time of hardening less than 1.0 volume%, it becomes hard to be influenced by hardening inhibition by oxygen, and it becomes a firm film.

In process (2)-(4), it is preferable that two or more particle | grains (a2) do not exist in the direction orthogonal to the surface of a base film.

In process (2)-(4), it is preferable that the film thickness of the sum total of the film thickness of layer (a) and the film thickness of layer (b) is larger than the average primary particle diameter of particle | grain (a2).

When the film thickness of the sum of the film thickness of the layer (a) and the film thickness of the layer (b) is larger than the average primary particle diameter of the particle (a2), the layer (a2) is the layer in which the layer (a) and the layer (b) are combined. It can be made to be buried in the inside, and is preferable.

However, when peeling the adhesive film containing a layer (b) in the process (5) mentioned later, it is a reason for obtaining the shape (moss eye structure) which the particle | grains a2 protruded from the surface of the layer (a). In (4), it is preferable that the film thickness of layer (a) is smaller than the average primary particle diameter of particle | grain (a2), and it is more preferable that it is half or less of the average primary particle diameter of particle | grain (a2).

As for the film thickness of the layer (a) in a process (4), the height of the interface on the opposite side to the interface on the hard-coat layer side of the layer (ca) obtained by hardening this has an average primary particle diameter of particle | grain (a2). It is preferable to adjust so that it may become less than half, More preferably, when the film cross section of the layer (ca) is observed with a scanning electron microscope (SEM), and 100 film thicknesses are measured arbitrarily and the average value is calculated | required. It is preferable to adjust so that it may become 10 nm-100 nm (more preferably, 20 nm-90 nm, more preferably 30 nm-70 nm).

[Step (5)]

Process (5) is a process of peeling layer (b) from layer (a).

When an adhesive remains on the layer (a) side when peeling a layer (b), a base film, a hard-coat layer, and the layer (a) after hardening may not melt | dissolve, You may wash | clean using the solvent which melt | dissolves an adhesive.

After peeling the adhesive film containing a layer (b) by a process (5), the antireflective film which has a moth-eye structure which consists of an uneven | corrugated shape formed by particle | grains (a2) on the surface of layer (a) is obtained. .

Example

An Example is given to the following and this invention is demonstrated to it further more concretely. The amounts of materials, reagents, substances, proportions thereof, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit 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 introduce | transduced into the 500 milliliter 3-necked flask provided with the stirrer, the thermometer, the reflux cooling tube, and the nitrogen gas introduction tube, and it heated up to 84 degreeC. 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" (made by Wako Junyaku Co., Ltd.) The mixed solution which mixed 0.54g of was dripped at constant speed so that dripping may be completed in 180 minutes. After completion of the dropwise addition, stirring was further continued for 3 hours, the temperature was raised to 95 ° C, and further stirring was continued for 2 hours. After cooling to room temperature, 0.41 g of methylhydroquinone, 4.26 g of glycidyl methacrylate, 1.55 g of tetrabutylammonium bromide, and 20 g of cyclohexanone were added, followed by stirring at 80 ° C. for 8 hours. Hexane solution was obtained.

[Formula 21]

Except having changed the monomer used by the synthesis example 1, and its composition ratio suitably, copolymer B-2-B-18 of the structure shown in following Table 1 were synthesize | combined.

<Example 1>

(Preparation of the composition for hard coat layer formation)

Each component is mixed by the composition described below, the obtained composition is thrown into a mixing tank, it stirred, it filtered with a polypropylene filter of 0.4 micrometer of pore diameters, and the composition for hard-coat layer formation (hard coat layer coating liquid) HC- I made it 1.

(Hard Coat Layer Coating Liquid HC-1)

A-TMMT 24.4 parts by mass

12.0 parts by mass of AD-TMP

Irgacure 127 1.6 parts by mass

3.5 parts by mass of ethanol

8.8 parts by mass of methanol

6.0 parts by mass of 1-butanol

Methyl ethyl ketone (MEK) 20.3 parts by mass

21.4 parts by mass of methyl acetate

0.8 parts by mass of copolymer B-1

A-tmmt: pentaerythritol tetraacrylate (made by shinnakamura kagaku high school)

AD-TMP: ditrimethylolpropane tetraacrylate (NK ester made by Shin-Nakamura Kagaku Kogyo Co., Ltd.)

Irgacure 127: photopolymerization initiator (manufactured by BASF Japan Co., Ltd.)

Copolymer B-1 is a compound synthesized in Synthesis Example 1, having a repeating unit shown in Table 1 as the content (mol%) shown in Table 1, and having a weight average molecular weight (Mw) shown in Table 1 to be.

TABLE 1

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

[Formula 22]

II-1 to II-12 and III-1 to III-6 in the said Table 1 are the structures as mentioned above.

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

[Formula 23]

N of AS-6 is about 60.

[Synthesis of Silica Particles P1]

67.54 kg of methyl alcohol and 26.33 kg of 28 mass% ammonia water (water and catalyst) were introduced into a 200 L reactor equipped with a stirrer, a dropping device, and a thermometer, and the temperature of the liquid was adjusted to 33 ° C while stirring. On the other hand, the solution which melt | dissolved 12.70 kg of tetramethoxysilane in 5.59 kg of methyl alcohol was introduce | transduced into the dripping apparatus. Tetramethoxysilane by dropping the solution from the dripping apparatus for 37 minutes while maintaining the temperature of the liquid in the reactor at 33 ° C, and after completion of dropping, by stirring while maintaining the temperature of the liquid at the temperature for 37 minutes. Was hydrolyzed and condensed to obtain a dispersion containing silica particle precursor. Silica particle P1 was obtained by air-drying this dispersion liquid on the conditions of a heating tube temperature of 175 degreeC, and pressure reduction degree 200torr (27kPa) using the instantaneous vacuum evaporator (Chox system CVX-8B type | mold by Hosokawa Micron Co., Ltd.). .

The average primary particle diameter of silica particle P1 was 170 nm, the dispersion degree (CV value) of the particle diameter was 7.0%, and the indentation hardness was 340 Mpa.

[Production of Plastic Silica Particles P2]

5 kg of silica particles P1 were placed in a crucible, calcined at 900 ° C. for 2 hours using an electric furnace, cooled, and then ground using a grinder to obtain classified pre-fired silica particles. Furthermore, calcined silica particle P2 was obtained by pulverizing and classifying using a jet grinding classifier (IDS-2 type by Nippon Pneumatic Co., Ltd.).

[Production of Silane Coupling Agent Treated Silica Particles P3]

5 kg of calcined silica particles P2 were introduced into a 20L Henschel mixer (model FM20J manufactured by Mitsui Gozan Co., Ltd.) equipped with a heating jacket. Where the calcined silica particles P2 were stirred, a solution of 50 g of 3-acryloxypropyltrimethoxysilane (KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) in 90 g of methyl alcohol was added dropwise and mixed. Then, it heated up to 150 degreeC for about 1 hour, stirring and mixing, and it heated and maintained at 150 degreeC for 12 hours. In the heat treatment, the scraping device was scraped while constantly rotating the scraping device in the direction opposite to the stirring blade. Moreover, scraping the wall surface adherend was also appropriately performed using a spatula. After heating, the mixture was cooled, pulverized and classified using a jet mill classifier to obtain silane coupling agent treated silica particles P3.

The average primary particle diameter of the silane coupling agent treated silica particle P3 was 171 nm, the dispersion degree (CV value) of the particle diameter was 7.0%, and the indentation hardness was 470 Mpa.

[Production of Silica Particle Dispersion PA-1]

50 g of silane coupling agent treated silica particles P3, 200 g of MEK, and 600 g of 0.05 mm zirconia beads were placed in a 1 L bottle container having a diameter of 12 cm, and set in a ball mill V-2M (Iri Shokai), and at 10 10 revolutions per minute. Time dispersed. Thus, silica particle dispersion PA-1 (solid content concentration 20 mass%) was produced.

[Synthesis of Compound C3]

In a flask equipped with a reflux condenser and thermometer, 19.3 g of 3-isocyanatepropyltrimethoxysilane, 3.9 g of glycerin 1,3-bisacryrate, 6.8 g of 2-hydroxyethyl acrylate, and dilauric acid 0.1 g of dibutyl tin and 70.0 g of toluene were added, and it stirred at room temperature for 12 hours. After stirring, 500 ppm of methylhydroquinone was added and distilled off under reduced pressure to obtain Compound C3.

[Formula 24]

[Preparation of composition (composition for antireflection layer formation) for forming layer (a)]

Each component was put into the mixing tank so that it might become the following composition, it stirred for 60 minutes, it disperse | distributed with the ultrasonic disperser for 30 minutes, and it was set as the coating liquid.

Composition (A-1)

1.4 parts by mass of U-15HA

1.5 parts by mass of compound C3

KBM-4803 5.8 parts by mass

Irgacure 127 0.2 parts by mass

0.1 parts by mass of compound P

32.3 parts by mass of silica particle dispersion PA-1

0.1 parts by mass of compound A

12.7 parts by mass of ethanol

Methyl ethyl ketone 33.3 parts by mass

Acetone 12.7 parts by mass

U-15HA, Compound C3, and KBM-4803 are compounds for forming a binder resin, but U-15HA and Compound C3 are curable compounds (a1), and KBM-4803 is a silane coupling agent having a reactive group other than a radical reactive group.

The compound used, respectively, is shown below.

U-15HA (made by Shin-Nakamura Kagaku Kogyo Co., Ltd.): urethane acrylate

Irgacure 127: photopolymerization initiator (manufactured by BASF Japan Co., Ltd.)

Compound P: 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine (photoacid generator, Tokyo Kasei Kogyo Co., Ltd. make)

Compound A: F-784-F (manufactured by DIC Corporation)

KBM-4803: Silane Coupling Agent Having a Reactive Group Other Than a Radical Reactive Group (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Production of anti-reflection film 1>

(Formation of the hard coat layer)

The hard coat layer coating liquid HC-1 was apply | coated on the base film (TJ25, Fujifilm Co., Ltd. product) using the die coater. After drying for 90 seconds at 30 DEG C and for 1 minute at 45 DEG C, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the oxygen concentration is approximately 1.3% by volume, An irradiance of 18 mW / cm ² and an ultraviolet ray having an irradiation amount of 10 mJ / cm ² were irradiated to cure the coating layer to form a hard coat layer having a thickness of 5 μm. The said hard-coat layer containing base material is HC-1.

(Coating of Step (1) Layer (a))

On the hard-coat layer of the said base material HC-1 containing a hard-coat layer, 2.8 ml / m <^{2> was} apply | coated using the die coater, and it dried at 30 degreeC for 90 second. The film thickness of the layer (a) in the step (1) is 170 nm.

(Step (1-2) A step of curing a part of the curable compound (a1) in the layer (a) to obtain a cured compound (a1c))

Irradiation from the layer (a) side using a high pressure mercury lamp (model: 33351N part number: LAMP-HOZ 200 D24 U 450 E) while purging with nitrogen so that the oxygen concentration is 1.4% by volume. It was irradiated at 5.0mJ to harden a part of curable compound (a1). In addition, the measurement of dosage is made by I graphics company

HEAD SENSER to child ultraviolet integrating light meter UV METER UVPF-A1

PD-365 was mounted and measured with a measurement range of 0.00.

(Adhesion of Process (2) Adhesive Film)

Next, on the layer (a) after drying, the adhesive film obtained by peeling a peeling film from AS3-304 was bonded together so that an adhesive layer (layer (b)) may become a layer (a) side. For bonding, it carried out at speed 1 using the commercial laminator Bio330 (made by DAE-EL Co.).

In addition, AS3-304 points out the laminated body (protective film) comprised from a support body / adhesive layer / peeling film, and the laminated body comprised from a support body / adhesive layer which peeled the peeling film from this laminated body is an adhesive film.

The detail of the used laminated body (protective film) is shown below.

AS3-304 Fujimori High School Co., Ltd.

Support: Polyester film (38 μm thick)

Adhesive layer thickness: 20μm

Maximum transmittance in wavelength 250nm-300nm in the state which peeled the peeling film: Less than 0.1%

The transmittance | permeability was measured using the ultraviolet visible near-infrared spectrophotometer UV3150 by Shimadzu Corporation.

(Infiltration into the pressure-sensitive adhesive layer of step (3) the curable compound (a1))

It left still for 5 minutes at 25 degreeC, bonding an adhesive film, and a part of curable compound (a1) penetrated into an adhesive layer.

(Hardening of step (4) layer (a))

Subsequent to the above standing, the layer (a) of the base film is coated using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the oxygen concentration becomes 0.01 vol% or less. The layer (a) was hardened | cured by irradiating the ultraviolet-ray of roughness 150mW / cm <^2> and irradiation amount 600mJ / cm <^2> over the adhesive film from the obtained surface. After the step (4), the film thicknesses of the layer (a) and the pressure-sensitive adhesive layer (layer (b)) before the step (5) were 50 nm and 20 µm, respectively.

(Step (5) Peeling of Adhesive Film)

The adhesive film (thing which peeled the peeling film from AS3-304) containing the layer (b) was peeled from the produced laminated body. The layer (a) after peeling off the layer (b) was hardened so that it might not be broken by peeling of an adhesive layer. The surface on which the layer (a) of the plastic base material was apply | coated using 160 W / cm of air-cooled metal halide lamps (made by Eye Graphics Co., Ltd.), purging nitrogen so that oxygen concentration might be 0.01 volume% or less after peeling of an adhesive. The ultraviolet-ray of illumination intensity 150mW / cm <^2> and irradiation amount 600mJ / cm <^2> was irradiated from the, and the layer (a) was hardened. Then, methyl isobutyl ketone was put on the surface where the adhesive film was bonded, the residue of the adhesive layer was wash | cleaned, it dried at 25 degreeC for 10 minutes, and the antireflection film 1 was obtained.

(Regularity of particles)

The regularity of the particles was evaluated according to how much the particle regularity was changed (Δparticle regularity) with respect to the reference sample (reference sample).

Production of Sample 1 for Reference

A sample having passed up to step (1-2) of the antireflection film 1 was prepared, and a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was purged with nitrogen to purge the oxygen concentration to 0.01% by volume or less. The sample 1 for reference | standard was produced by irradiating the ultraviolet-ray of illumination intensity 150mW / cm <^2> and irradiation amount 600mJ / cm <^2> from the surface to which the layer (a) of the base film was apply | coated using it, and hardening layer (a).

Calculation of particle regularity

About the obtained antireflection film 1 and the reference sample 1, surface observation by SEM (S-4300 by Hitachi High Technologies, Ltd.) was performed. The number of particles in the range of 1280 nm x 830 nm and the average center-to-center distance with the nearest particles were calculated, and the regularity of the particles was calculated by the following formula.

(Particle regularity)

= (Average distance between average centers with nearest particle-average primary particle size) / (distance between particles in average charge-average primary particle size) x 100

Here, (distance between particles in closest filling) = √ (4 / (√3) × 1280 × 830/2 / number of particles) × 10.

(Δparticle regularity) = (particle regularity of sample 1 for reference)-(particle regularity of antireflection film 1)

(DELTA) particle regularity was evaluated based on the following criteria.

A: less than 4%

B: 4% or more but less than 8%

C: 8% or more but less than 10%

D: more than 10%

<Examples 2-18, and Comparative Example 1>

The hard coat layer coating liquid HC-2-HC-18, and it carried out similarly to the hard coat layer coating liquid HC-1 except having used the copolymer of the kind shown in following Table 2 instead of copolymer B-1, and HC-R1 was prepared.

Instead of the hard coat layer coating liquid HC-1, the hard coat layer coating liquids HC-2 to HC-18, and HC-R1 were used in the same manner as in Example 1, except that the antireflective films 2 to 18 and R1 were used. Produced and evaluated.

In addition, the antireflection films 2-18 and the reference samples 2-8 corresponding to R1, and R1 are the same as the reference sample 1 except preparing the sample which passed until the process (1-2) of each antireflection film. Made by. (DELTA) particle regularity was computed by subtracting the particle regularity of each antireflection film from the particle regularity of each reference sample, like the following formula.

(Δparticle regularity) = (particle regularity of sample for reference)-(particle regularity of antireflection film)

TABLE 2

Copolymers B-2 to B-18 have a repeating unit shown in Table 1 above as a content (mass%) shown in Table 1, and are copolymers having Mw shown in Table 1 below.

Copolymer B-R1 is a compound of the following structure, and the ratio of each repeating unit is molar ratio.

[Formula 25]

The evaluation results are shown in Table 3 below.

TABLE 3

Although the average reflectances of the antireflection films obtained in Examples 1 to 18 and Comparative Example 1 were all 1% or less, it could be confirmed that they had a moth-eye structure by SEM observation, but when observed with the naked eye in the light source, the reflection of the Examples On the other hand, the anti-reflection film obtained in Comparative Example 1 felt cloudy, while the anti-reflection film was very small.

In the antireflection films of Examples 1 to 18, the regularity drop of the particles due to the formation of the moth-eye structure was small. On the other hand, the antireflection film of Comparative Example 1 had a large drop in regularity of the particles due to the formation of the moth-eye structure as compared with the antireflection film of the example, and became an antireflection film having a haze compared with the antireflection film of the example.

Industrial availability

ADVANTAGE OF THE INVENTION According to this invention, it is an antireflection film which has a moth-eye structure which consists of an uneven | corrugated shape formed by particle | grains, and can provide the antireflection film with a high regularity of particle | grains, the polarizing plate which has the said antireflection film, and an image display apparatus. .

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

This application is based on the JP Patent application (Japanese Patent Application No. 2017-129822) of an application on June 30, 2017, The content is taken in here as a reference.

1 base film
HC hard coat layer
2 antireflective layer
3 metal oxide particles (particles (a2))
4 binder resin (layer (a))
5 support
6 layers (b)
7 adhesive film
10 antireflection film
A Distance between vertices of adjacent convexities
B Distance between concave and center between apex of adjacent convex
UV ultraviolet

Claims (13)

As an antireflection film which has 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,
The anti-reflection layer has a moth-eye structure made of irregularities formed by the metal oxide particles,
The said hard coat layer is for hard-coat layer formation containing the copolymer which has a repeating unit represented by the following general formula (I), the repeating unit represented by the following general formula (II), and the repeating unit represented by the following general formula (III). An antireflection film, which is a layer formed of a composition.
[Formula 1]

In general formula (I), R <^1> represents a hydrogen atom or a C1-C20 alkyl group, R <^2> represents the alkyl group which has at least 1 fluorine atom as a substituent, and L represents a bivalent coupling group.
In general formula (II), R <^10> represents a hydrogen atom or a C1-C20 alkyl group, R <^11> and R <^12> may respectively independently represent a hydrogen atom and the aliphatic hydrocarbon group which may have a substituent, and the aryl which may have a substituent. The heteroaryl group which may have a group or a substituent is shown, and R <^11> and R <^12> may be connected. X ¹ represents a divalent linking group.
In 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 method according to claim 1,
The antireflection film whose repeating unit represented by said general formula (I) is a repeating unit represented by the following general formula (I-2).
[Formula 2]

In 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 method according to claim 1 or 2,
The antireflection film whose repeating unit represented by the said General formula (II) is a repeating unit represented by the following general formula (II-a).
[Formula 3]

In 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 each independently represent a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent or a substituent. It may represent the aryl group which may be sufficient, or the heteroaryl group which may have a substituent, and R <^11> and R <^12> may be connected. X ¹¹ is at least selected from the group consisting of — (C═O) O—, —O (C═O) —, — (C═O) NH—, —O—, —CO—, and —CH ₂ —. The divalent linking group consisting of one is shown. X ¹² is-(C = O) O-, -O (C = O)-,-(C = O) NH-, -O-, -CO-, -NH-, -O (C = O) A divalent linking group 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. . However, the sum total carbon number of said X <^11> and X <^12> is seven or more. The method according to any one of claims 1 to 3,
The antireflection film whose repeating unit represented by the said General formula (III) is a repeating unit represented by the following general formula (III-a).
[Formula 4]

In 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 represents an integer of 1 to 10, When k represents an integer greater than or equal to 2, some R <^31> may be same or different, and some R <^32> may be same or different. R ³³ represents a hydrogen atom or a methyl group. The method according to any one of claims 1 to 4,
Antireflection film whose content of the repeating unit represented by the said General formula (I) in the said copolymer is 5-40 mol% with respect to all the repeating units which the said copolymer has. The method according to any one of claims 1 to 5,
The antireflection film whose content of the repeating unit represented by the said General formula (II) in the said copolymer is 20-60 mol% with respect to all the repeating units which the said copolymer has. The method according to any one of claims 1 to 6,
The antireflection film whose content of the repeating unit represented by the said General formula (III) in the said copolymer is 20-65 mol% with respect to all the repeating units which the said copolymer has. The method according to any one of claims 1 to 7,
Content of the said copolymer in the said composition for hard-coat layer formation is 0.001-20 mass% with respect to the total solid of the said composition for hard-coat layer formation. The method according to any one of claims 1 to 8,
The antireflection film, wherein the metal oxide particles are silica particles. The method according to any one of claims 1 to 9,
The antireflection film of which the average primary particle diameter of the said metal oxide particle is 100-190 nm. The method according to any one of claims 1 to 10,
The anti-reflection film of which the said metal oxide particle is particle | grains surface-modified by the compound which has a polymerizable unsaturated group and the functional group which has reactivity with the surface of the said metal oxide particle. The polarizing plate which has a polarizer and the antireflective film of any one of Claims 1-11. The image display apparatus which has an antireflection film of any one of Claims 1-11, or the polarizing plate of Claim 12.

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