WO2019065421A1

WO2019065421A1 - Anti-reflection film, anti-reflection article, polarizing plate, and image display device

Info

Publication number: WO2019065421A1
Application number: PCT/JP2018/034676
Authority: WO
Inventors: 考浩加藤; 悠太福島; 竜二実藤
Original assignee: 富士フイルム株式会社
Priority date: 2017-09-29
Filing date: 2018-09-19
Publication date: 2019-04-04
Also published as: JPWO2019065421A1; JP6726809B2

Abstract

Provided are: an anti-reflection film having a base film and an anti-reflection layer, the anti-reflection layer including metal oxide particles and a binder layer, the binder layer being obtained by curing a curable composition including at least a specific curable compound (b-1), a specific curable compound (b-2), and a polymerization initiator, and the anti-reflection layer having a moth-eye structure comprising an uneven shape formed by the metal oxide particles; a polarizing plate having the anti-reflection film; an anti-reflection article; and an image display device.

Description

Antireflective film, antireflective article, polarizing plate, and image display device

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

Image display such as display device using cathode ray tube (CRT), plasma display panel (PDP), electroluminescence display (ELD), fluorescent display (VFD), field emission display (FED), and liquid crystal display (LCD) In the device, an anti-reflection film may be provided to prevent the contrast reduction due to the reflection of external light on the display surface and the reflection of an image. In addition to the image display device such as the glass surface of the showroom, the antireflective film may provide the antireflective function.

As an antireflective film, there is known an antireflective film having a fine uneven shape having a period of less than or equal to the wavelength of visible light on the surface of a substrate, that is, an antireflective film having a so-called moth eye structure. The moth-eye structure makes it possible to create a graded refractive index layer in which the refractive index changes continuously from air to the bulk material inside the base material, thereby preventing light reflection.
As an antireflective film having a motheye structure, Patent Document 1 describes an antireflective film having an antireflective layer having a motheye structure having a concavo-convex shape formed by particles on a base film.

Japanese Patent Application Laid-Open No. 2017-16065

The present inventors apply a composition for forming an antireflective layer containing metal oxide particles and a curable compound which is a compound for forming a binder layer on a substrate film or a hard coat layer to form a coating film. The pressure-sensitive adhesive layer is laminated on the coating film, and a part of the curable compound is diffused (penetrated) into the pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive layer is peeled off to form the metal oxide particles. It has been found that it is possible to form an antireflective layer having a moth-eye structure having a concavo-convex shape.
However, according to the study of the present inventors, when diffusing a part of the curable compound in the coating film formed from the composition for forming an antireflective layer into the pressure-sensitive adhesive layer, the metal oxide in the coating film It has been found that movement of particles may reduce the regularity of the arrangement of particles. The decrease in regularity of the particles may lead to an increase in haze.
Patent Document 1 does not describe the reduction of the regularity of the particles.

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

[1]
An antireflective film comprising a substrate film and an antireflective layer, wherein
The antireflective layer comprises metal oxide particles and a binder layer,
The binder layer is a layer obtained by curing a curable composition containing at least a curable compound (b-1), a curable compound (b-2), and a polymerization initiator,
The antireflection film, wherein the antireflection layer has a moth-eye structure having a concavo-convex shape formed by the metal oxide particles.
Curable compound (b-1): Silane coupling agent having a weight average molecular weight of 10000 or more and having a radical reactive group Curable compound (b-2): Molecular weight of 150 or more, having a radical reactive group And silicon-free compounds [2]
The antireflective film according to [1], wherein the curable composition further comprises a curable compound (b-3).
Curable compound (b-3): Silane coupling agent having a molecular weight of 5000 or less and having a radical reactive group [3]
In [2], the mass ratio of the content of the curable compound (b-1) to the content of the curable compound (b-3) in the curable composition is 0.05 to 0.5. Antireflection film as described.
[4]
An antireflective article having the antireflective film according to any one of [1] to [3] on its surface.
[5]
It is a polarizing plate which has a polarizer and at least one protective film which protects the said polarizer, Comprising: At least one of the said protective film is a reflection as described in any one of [1]-[3] A polarizing plate that is a prevention film.
[6]
An image display device having the antireflective film according to any one of [1] to [3] or the polarizing plate according to [5].

An antireflection film having a moth-eye structure having a concavo-convex shape formed by particles according to the present invention, the antireflection film having high regularity of particles, a polarizing plate having the above-mentioned antireflection film, an antireflection article and an image display Can be provided.

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 reflection preventing film of this invention.

Hereinafter, the present invention will be described in detail.
In the present specification, “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value.
In the present specification, “(meth) acrylate” is used in the meaning of “either or both of acrylate and methacrylate”. The same applies to “(meth) acrylic group”, “(meth) acrylic acid”, “(meth) acrylamide”, “(meth) acryloyl group”, “(meth) acrylic type” and the like.

The antireflective film of the present invention is
An antireflective film comprising a substrate film and an antireflective layer, wherein
The antireflective layer comprises metal oxide particles and a binder layer,
The antireflective film is a layer obtained by curing the curable composition containing at least the curable compound (b-1), the curable compound (b-2), and the polymerization initiator.
Curable compound (b-1): Silane coupling agent having a weight average molecular weight of 10000 or more and having a radical reactive group Curable compound (b-2): Molecular weight of 150 or more, having a radical reactive group And silicon-free compounds

Although the present invention is an antireflection film having a moth-eye structure having a concavo-convex shape formed by particles, the mechanism by which an antireflection film having high regularity of the arrangement of particles is provided is not completely clarified. , Is estimated as follows.
The antireflective film of the present invention is an antireflective film having an antireflective layer on a base film as described later, wherein the antireflective layer includes metal oxide particles and a binder layer, and the binder layer is And a layer obtained by curing the curable composition described below.
The below-mentioned silane coupling group contained in the curable compound (b-1) in the curable composition forms a covalent bond with the hydroxyl group on the surface of the metal oxide particles in the antireflective layer, and the metal oxide particles flow And the regularity of the arrangement of particles (also called regularity of particles). When the weight average molecular weight of the curable compound (b-1) is 10000 or more, the effect of suppressing the aggregation of the metal oxide particles can be enhanced.
Furthermore, the above-mentioned metal oxide particles are immobilized by reacting and immobilizing the radically polymerizable group contained in the curable compound (b-2) with the radically reactive group contained in the curable compound (b-1) Particle regularity can be improved.
Thereby, when diffusing a part of the curable compound in the coating film formed from the above-mentioned curable composition into the pressure-sensitive adhesive layer laminated on the above-mentioned coating film, the metal oxide particles in the above-mentioned coating film It is thought that it becomes difficult to move, and the regularity of particles is improved.

In the antireflection film of the present invention, the integral reflectance is preferably 3% or less, more preferably 2% or less, over the entire wavelength range of 380 to 780 nm.

An example of a preferred embodiment of the antireflective film of the present invention is shown in FIG.
The antireflective film of the present invention may or may not contain a hard coat layer.
FIG. 1 shows an antireflective film of an embodiment including a hard coat layer.
The antireflective film 10 of FIG. 1 has a base film 1, a hard coat layer HC and an antireflective layer 2 in this order. The antireflective film of the present invention may have other layers in addition to these layers. The hard coat layer and the antireflective layer are preferably in contact with each other. The antireflective layer 2 includes metal oxide particles 3 and a binder layer 4. The metal oxide particles 3 protrude from the binder layer 4 to form a concavo-convex shape, and the concavo-convex shape is a moth-eye structure.

(Moss eye structure)
The antireflective layer of the antireflective film of the present invention has a moth-eye structure having a concavo-convex shape formed by metal oxide particles.
The uneven shape is preferably formed on the surface opposite to the interface on the hard coat layer side of the antireflective layer.
The concavo-convex shape formed by the metal oxide particles is preferably such that each metal oxide particle protruding from the binder layer is a convex portion and a portion where the metal oxide particles are not present is a concave portion.
The moth-eye structure having the concavo-convex shape means that the concavo-convex shape is a moth-eye structure.
In addition, as long as a moth-eye structure can be formed, other components, such as binder resin, may exist on the surface of the metal oxide particle which forms a convex part.
The moth-eye structure refers to a processed surface of a substance (material) for suppressing light reflection, and a structure having a periodic microstructured 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. If the period of the fine structure pattern is less than 190 nm, the color of the reflected light is reduced, which is preferable. Moreover, light with a wavelength of 380 nm can recognize a fine | micro structure pattern as the period of the uneven | corrugated shape of a moth-eye structure is 100 nm or more, and since it is excellent in antireflection property, it is preferable. The presence or absence of the moth-eye structure can be confirmed by observing the surface shape with a scanning electron microscope (SEM), an atomic force microscope (AFM) or the like to check whether the above-mentioned microstructure pattern is formed.

The concavo-convex shape of the antireflective layer of the antireflective film of the present invention is B / A which is the ratio of the distance A between the apexes of adjacent convex portions to the distance B between the center between the apexes of adjacent convex portions and the concave portion. Is preferably 0.4 or more. If the B / A is 0.4 or more, the depth of the concave portion becomes larger with respect to the distance between the convex portions, and a graded refractive index layer in which the refractive index changes more gradually from the air to the inside of the antireflective layer As a result, the reflectance can be further reduced.
More preferably, B / A is 0.5 or more. If B / A is 0.5 or more, the distance A between the apexes of adjacent convex portions (convex portions formed by particles) becomes equal to or larger than the particle diameter, and concave portions are formed between the particles. As a result, moth-eye is caused by the presence of both the interface reflection by the steep portion of the refractive index change depending on the curvature on the upper side of the convex and the interface reflection by the steep portion of the refractive index change depending on the curvature of the interparticle recess. In addition to the gradient index layer effect due to the structure, it is presumed that the reflectance is reduced more effectively.
B / A can be controlled by the volume ratio of the binder layer to the metal oxide particles in the antireflective layer. Therefore, it is important to appropriately design the blending ratio of the binder layer and the metal oxide particles.

Furthermore, in order to realize low reflectance and to suppress the generation of haze, it is preferable that the metal oxide particles forming the convex portion be uniformly spread at an appropriate filling rate. From the above viewpoint, the content of the metal oxide particles forming the convex portion is preferably adjusted so as to be uniform throughout the antireflection layer. The filling rate can be measured as the area occupancy rate (particle occupancy rate) of the metal oxide particles located closest to the surface side when the metal oxide particles forming the convex portion from the surface are observed by SEM or the like, 25 % To 64% is preferable, 25 to 50% is more preferable, and 30 to 45% is even more preferable.

The evenness of the surface of the antireflective film can be evaluated by haze. The measurement can be performed according to JIS-K7136 (2000) using a film sample of 40 mm × 80 mm at 25 ° C. and a relative humidity of 60% with Nippon Denshoku Kogyo Co., Ltd. manufactured haze meter NDH4000. Particles that are aggregated and non-uniform have high haze. Lower haze is preferred. The haze value is preferably 0.0 to 3.0%, more preferably 0.0 to 2.5%, and still more preferably 0.0 to 2.0%.

[Base film]
The base film of the antireflection film of the present invention will be described.
The substrate film is preferably a plastic substrate film. The substrate film is not particularly limited as long as it is a translucent substrate generally used as a substrate film of an antireflective film. Various base films can be used. For example, cellulose resins; cellulose acylate (triacetate cellulose, diacetyl cellulose, acetate butyrate cellulose), etc., polyester resins; polyethylene terephthalate, etc., (meth) acrylic resins, polyurethane Base films containing base resins, polycarbonates, polystyrenes, olefin resins, etc. are mentioned, and base films containing cellulose acylate, polyethylene terephthalate, or (meth) acrylic resins are preferable, and cellulose acylate is contained. A substrate film is more preferred.
The thickness of the substrate film is usually about 10 to 1000 μm, but is preferably 15 to 200 μm, more preferably 20 to 200 μm, from the viewpoint of good handleability, high light transmittance and sufficient strength Preferably, 20 to 100 μm is more preferable, and 25 to 100 μm is particularly preferable.
The light transmittance of the base film is preferably 80% or more, and more preferably 90% or more.
The measurement of the total light transmittance shall be performed according to Japanese Industrial Standard (JIS) K7361-1 (1997).

[Anti-reflection layer]
The antireflection layer of the antireflection film of the present invention will be described.
The antireflection layer comprises metal oxide particles and a binder layer, and the binder layer cures a curable composition containing at least a curable compound (b-1), a curable compound (b-2), and a polymerization initiator. The antireflective layer has a moth-eye structure having a concavo-convex shape formed by the metal oxide particles.
Curable compound (b-1): Silane coupling agent having a weight average molecular weight of 10000 or more and having a radical reactive group Curable compound (b-2): Molecular weight of 150 or more, having a radical reactive group And silicon-free compounds

<Binder layer>
The binder layer preferably has a function of binding the metal oxide particles to the base film or the hard coat layer.

<Curable compound (b-1)>
The curable compound (b-1) is preferably a compound having a radical reactive group. As a compound having a radical reactive group, various polymers having a weight average molecular weight of 10000 or more can be used.
Examples of the radical reactive group include polymerizable unsaturated groups (carbon-carbon unsaturated double bond group) such as (meth) acryloyl group, vinyl group, styryl group and allyl group, and the like, among which (meth) An acryloyl group is preferred.

The silane coupling agent as the curable compound (b-1) is a compound containing a silane coupling group. The said silane coupling group represents the group which the alkoxy group or the halogen atom couple | bonded with the silicon atom.
Specifically, the silane coupling group is preferably represented by the following general formula (b).

In the above general formula (b), R ¹ represents an alkoxy group or a halogen atom.
The alkyl group in the alkoxy group when R ¹ represents an alkoxy group is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
When R ¹ represents a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
R ² represents a hydrogen atom or an organic group. The organic group includes an alkyl group and an aryl group, preferably an alkyl group.
As the alkyl group, for example R ¹ described above may include the same alkyl group and the alkyl group in the alkoxy group when it represents an alkoxy group.
The aryl group is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and particularly preferably a phenyl group.
n represents an integer of 1 to 3; n is preferably 2 to 3.
* Represents a bonding position.

When there are a plurality of R ^{1 s} , R ^{1 s} may be each independently the same or different.
When R ² existing in plural numbers, R ² may be the same or different each independently.

The amount of silane coupling group represents the number of silicon atoms to which an alkoxy group or a halogen atom is bonded.

The weight average molecular weight (Mw) of the curable compound (b-1) is preferably 10,000 to 1,000,000, more preferably 15,000 to 500,000, and still more preferably 15,000 to 100,000.
The weight average molecular weight in the present specification is a value measured by gel permeation chromatography (GPC) under the following conditions.
[Eluent] N-methyl-2-pyrrolidone (NMP)
[Equipment name] EcoSEC HLC-8320GPC (made by Tosoh Corporation)
[Column] TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (made by Tosoh Corporation)
[Column temperature] 40 ° C
[Flow rate] 0.35 ml / min

The functional group equivalent (molecular weight / radically reactive group weight) in the curable compound (b-1) is preferably 450 or less, more preferably 400 or less, and still more preferably 350 or less.
The functional group equivalent represents the molecular weight per one functional group, and is the value obtained by dividing the molecular weight of the curable compound (b-1) by the number of radically reactive groups.
The amount of radically reactive groups is the number of radically reactive groups.

The functional group equivalent in the curable compound (b-1) is preferably 50 or more, preferably 80 or more, and more preferably 100 or more.
The ratio of the amount of silane coupling group to the amount of radically reactive group in the curable compound (b-1) (the amount of silane coupling group / the amount of radically reactive group) is preferably 0.01 or more and 0.5 or less, and 0 More than 0.55 and less than 0.3 are more preferable.

The amount of silane coupling group and the amount of radically reactive group in the present specification are values obtained by measurement by ¹ H-NMR.

The synthesis method of the curable compound (b-1) is not particularly limited, and, for example, a silane coupling agent having a radical reactive group synthesized by a known method and a monomer having a protected acryloyl group or methacryloyl group Are polymerized and then deprotected, or by introducing a silane coupling agent site to a polymer having an acryloyl group or a methacryloyl group by a polymer reaction.
The structure of the curable compound of the present invention is not particularly limited, and specific examples thereof include polyester resins, (meth) acrylic resins, polyurethane resins, polycarbonates, polystyrenes, and olefin resins. In addition, dendrimers such as SIRIUS-501 and SUBARU-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) can be preferably used.

<Curable compound (b-2)>
The curable compound (b-2) is a compound having a molecular weight of 150 or more, a radical reactive group, and no silicon. The curable compound (b-2) is preferably a compound having a radical reactive group. As the compound having a radical reactive group, various monomers, oligomers or polymers having a molecular weight of 150 or more can be used.
Examples of the radical reactive group include polymerizable unsaturated groups (carbon-carbon unsaturated double bond group) such as (meth) acryloyl group, vinyl group, styryl group and allyl group, and the like, among which (meth) An acryloyl group is preferred.

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

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

Among them, esters of polyhydric alcohol and (meth) acrylic acid are preferred. More preferably, it is preferable to contain at least one kind of polyfunctional monomer having three or more (meth) acryloyl groups in one 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 trimethylol Propane 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 ) Acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, caprolactone modified dipe Data erythritol Doo hexa (meth) acrylate, 1,2,3-cyclohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate and caprolactone-modified tris (acryloyloxyethyl) isocyanurate.

Specific examples of polyfunctional acrylate compounds having a (meth) acryloyl group include KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, and TPA-, manufactured by Nippon Kayaku Co., Ltd. 330, RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303, Osaka Organic Chemical Industry Co., Ltd. V # 3PA, V Esters of (meth) acrylic acid and polyols such as # 400, V # 36095D, V # 1000, V # 1080 and the like can be mentioned. In addition, purple light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B , UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310B, UV-3500BA , UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2750B (manufactured by Japan Synthetic Chemical Co., Ltd.), UA-306H, UA-306I, UA-306T, UL-503L (Kyoeisha Chemical Co., Ltd.), Unidic 17-806, 17-813, V-4030, V-4000BA (Dainippon Ink & Chemicals, Inc.), EB-1290K, EB-220, EB -5129, EB-1830, EB-4858 (made by Daicel UCB Ltd.), A-TMMT, AD-TMP, A-TMPT, U-4 HA, U-6 HA, U-10 HA, U-15 HA (Shin-Nakamura Chemical Co., Ltd.) Industrial Co., Ltd. product, HI-COP AU-2010, the same AU-2020 (product made by Tokushiki Co., Ltd.), ALONIX M-1960 (product made by Toagosei Co., Ltd.), Art resin UN-3320HA, UN-3320HC, UN-3320HS , UN-904, HDP-4T, etc., trifunctional or higher urethane acrylate compounds, ALONIX M-8100, M-8030, M-905 (Manufactured by Toagosei Co., Ltd., etc. KRM-8307 (manufactured by Daicel-Cytec Co.) three or more functional groups of the polyester compound, such as may also be suitably used.

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

Further, compounds described in JP-A-2005-76005 and JP-A-2005-36105, dendrimers such as SIRIUS-501 and SUBARU-501 (Osaka Organic Chemical Industry Ltd.), JP-A-2005-60425 Also, norbornene ring-containing monomers as described in the above can be used.

The molecular weight of the curable compound (b-2) is 150 or more, preferably 200 or more, and more preferably 400 or more.
The molecular weight of the curable compound (b-2) is preferably 3,000 or less, more preferably 1,000 or less.
When the curable compound (b-2) is an oligomer or a polymer, and the molecular weight is measured by a weight average molecular weight (Mw), the weight average molecular weight is taken as the molecular weight of the curable compound (b-2).

The mass ratio (W ₁ / W ₂ ) of the content (W ₁ ) of the curable compound (b-1) to the content (W ₂ ) of the curable compound (b- ₂ ) in the curable composition is 0.01 to 2.0 is preferable, and 0.05 to 1.0 is more preferable.

<Polymerizable compound (b-3)>
The curable composition preferably contains the following curable compound (b-3). Curable compound (b-3): Silane coupling agent having a molecular weight of 5000 or less and having a radical reactive group As the curable compound (b-3), various monomers, oligomers or polymers having a molecular weight of 5000 or less are used I can do things.
Specific examples of the silane coupling agent having a molecular weight of 5000 or less and having a radical reactive group include, for example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3 -(Meth) acryloxypropyldimethylmethoxysilane, 3- (Meth) acryloxypropylmethyldiethoxysilane, 3- (Meth) acryloxypropyltriethoxysilane, 2- (Meth) acryloxyethyltrimethoxysilane, 2- Examples include (meth) acryloxyethyltriethoxysilane, 4- (meth) acryloxybutyltrimethoxysilane, 4- (meth) acryloxybutyltriethoxysilane and the like. Specifically, KBM-503, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), and silane coupling agents X-12-1048, X-12-1049, X-12 described in JP-A-2014-123091. 1050 (Shin-Etsu Chemical Co., Ltd. product), the compound C3 etc. which are represented by following Structural formula etc. are mentioned.

The molecular weight of the curable compound (b-3) is preferably 5000 or less, preferably 3000 or less, and more preferably 1500 or less.
The molecular weight of the curable compound (b-3) is preferably 200 or more, preferably 250 or more, and more preferably 300 or more.
When the curable compound (b-3) is an oligomer or a polymer and the molecular weight is measured by weight average molecular weight (Mw), the weight average molecular weight is taken as the molecular weight of the curable compound (b-3).

Mass ratio (W ₁ / W ₃ ) of the content (W ₁ ) of the curable compound (b-1) to the content (W ₃ ) of the curable compound (b- ₃ ) in the curable composition Is preferably 0.01 to 0.5, more preferably 0.05 to 0.5, and still more preferably 0.05 to 0.3.
By setting the mass ratio (W ₁ / W ₃ ) in the above range, the coverage of the particle surface with the curable compound while introducing an appropriate amount of the curable compound (b-1) on the surface of the metal oxide particles Can be increased, and sufficient hardness can be imparted after curing while reducing changes in particle regularity before and after curing.

The curable composition may further use a silane coupling agent having a reactive group other than the radical reactive group, as a compound that functions to suppress the aggregation of metal oxide particles described later. Specific examples of the silane coupling agent having a reactive group other than a radical reactive group include KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803 (all are Shin-Etsu Chemical Co., Ltd.). Co., Ltd.).

<Polymerization initiator>
The curable composition contains a polymerization initiator. As the polymerization initiator, an appropriate polymerization initiator may be selected according to the type of the polymerizable compound to be used in combination, and a radical polymerization initiator can be suitably used. As the radical polymerization initiator, either a thermal polymerization initiator or a photopolymerization initiator may be selected according to the type of polymerization treatment (heating or light irradiation) applied in the production 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. Specific examples of the thermal polymerization initiator include an azo compound, a hydroxylamine ester compound, an organic peroxide, hydrogen peroxide and the like. As specific examples of the organic peroxide, those described in Japanese Patent No. 5341155, paragraph 0031 can be mentioned.

The structure of the photopolymerization initiator is not particularly limited. Specifically, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, fluoro Amine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like can be mentioned. Specific examples of the photopolymerization initiator and preferable embodiments, commercial products, and the like are described in paragraphs [0133] to [0151] of JP-A-2009-098658, and they are also suitably used in the present invention as well. it can.

"Latest UV curing technology" {Technical Information Association of Japan} (1991), p. 159, and "UV Curing System", Kiyoyoshi Kato, published by General Technology Center in 1989, p. Various examples are also described at 65 to 148 and are useful for the present invention.

The content of the polymerization initiator in the curable composition is an amount sufficient to polymerize the polymerizable compound contained in the curable composition, and is set such that the starting point is not excessively increased. For the reason, 0.1 to 8% by mass is preferable and 0.5 to 5% by mass is more preferable with respect to the total solid content in the curable composition.

The above-mentioned curable composition is a compound which generates an acid or a base by light or heat to react the above-mentioned curable compound (b-1) and the curable compound (b-3) (hereinafter referred to as a photoacid generator) , A photo base generator, a thermal acid generator, and a thermal base generator may be included.

(solvent)
The curable composition preferably contains a solvent.
It is preferable from a viewpoint of the adhesiveness of a base film and a reflection prevention layer to contain the solvent which has the permeability with respect to a base film as a solvent. The solvent having permeability to the base film is a solvent having a dissolving ability to the base film. Here, a solvent having a dissolving ability to a substrate film means that a substrate film having a size of 24 mm × 36 mm (80 μm in thickness) is put in a 15 ml bottle containing the above solvent at a room temperature (25 ° C.) 24 It means a solvent that is allowed to age for a long time and shake the bottle as appropriate to completely dissolve the substrate film and lose its shape.
When a cellulose acylate film is used as the substrate film, methyl ethyl ketone (MEK), dimethyl carbonate, dimethyl acetate, methyl acetate, acetone, methylene chloride and the like are preferable, and methyl ethyl ketone (MEK), dimethyl carbonate and methyl acetate are more preferable. Although it can be preferably used, it is not limited thereto.
The composition for forming a hard coat layer may contain a solvent (eg, ethanol, methanol, 1-butanol, isopropanol (IPA), methyl isobutyl ketone (MIBK), toluene, etc.) other than the permeable solvent.
In the curable composition, the content of the permeable solvent is preferably 50% by mass or more and 100% by mass or less, and is 70% by mass or more and 100% by mass with respect to the mass of all the solvents contained in the curable composition. It is more preferable that the content is less than%.
When the said curable composition 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 a hydrophilic solvent, lower alcohols such as methanol, ethanol, isopropanol (IPA) and butanol are preferable.
It is preferable that it is 20 to 70 mass%, and, as for solid content concentration of the said curable composition, it is more preferable that it is 30 to 65 mass%.

<Metal oxide particles>
Examples of the metal oxide particles include silica particles, titania particles, zirconia particles, and antimony pentoxide particles. However, since the refractive index is close to that of many binder resins, it is difficult to generate haze, and a moth-eye structure is easily formed. Silica particles are preferred.

The average primary particle diameter of the metal oxide particles is preferably 100 nm or more and 190 nm or less, more preferably 100 nm or more and 180 nm or less, and still more preferably 100 nm or more and 170 nm or less.
As the metal oxide particles, only one type may be used, or two or more types of particles having different average primary particle sizes may be used.

The average primary particle size of the metal oxide particles refers to the cumulative 50% particle size of the volume average particle size. A scanning electron microscope (SEM) can be used to measure the particle size. The powder particles (in the case of a dispersion, dried to evaporate the solvent) are observed by SEM at an appropriate magnification (about 5000 times), and the diameter of each of the 100 primary particles is measured to measure the volume The cumulative 50% particle size can be taken as the average primary particle size. If the particles are not spherical, the average of the major and minor diameters is taken as the diameter of the primary particles. When measuring the particle | grains contained in an anti-reflective film, it observes and calculates an anti-reflective film from the surface side by said SEM similarly. At this time, in order to facilitate observation, the sample may be appropriately subjected to carbon deposition, etching, or the like.

The metal oxide particles are preferably solid particles in terms of strength. The shape of the metal oxide particles is most preferably spherical, but there is no problem if it is other than spherical such as indeterminate form.
For example, the irregular particle in which a part of spherical metal oxide particles is a flat part is used, and the flat part is placed on the lower layer side to suppress the movement of the particles, and from application to drying and curing. Particle aggregation in each of the steps can be prevented, the distance between the projections by the particles can be made uniform, and the transmittance in the short wavelength region can be improved, which is preferable.
In addition, as another example of the irregular shape, particles having a shape in which small particles are further bonded to part of metal oxide particles can be used. The number of small particles bonded to the metal oxide particles may be more than one, but one is more preferable. The particle diameter of the small particles bonded to part of the metal oxide particles is preferably smaller than that of the metal oxide particles, and more preferably 0.5 times or less the particle diameter of the metal oxide particles, and 0. More preferably, it is 25 times or less. The density of the small particles bonded to part of the metal oxide particles is preferably larger than that of the metal oxide particles, more preferably twice or more, and still more preferably three times or more. The small particles are preferably metal oxides, and for example, zirconia, alumina, titania and the like are preferable, but any material that satisfies the above-described density relationship can be used as appropriate. For example, particles in which zirconia particles of 40 nm in diameter are attached to silica particles of 160 nm in diameter are preferable.
The silica particles may be either crystalline or amorphous.

As the metal oxide particles, it is preferable to use surface-treated inorganic fine particles in order to improve the dispersibility in the coating solution, improve the film strength, and prevent aggregation. Specific examples of the surface treatment method and preferable examples thereof are the same as those described in [0119] to [0147] of JP-A-2007-298974.
The metal oxide particles are preferably particles that are surface-modified with a compound having a polymerizable unsaturated group and a functional group having reactivity with the surface of the metal oxide particles.
In particular, from the viewpoint of imparting the binding property with the binder layer and improving the strength of the antireflective layer, the particle surface is a functional group having a polymerizable unsaturated group (preferably unsaturated double bond) and reactivity with the particle surface. It is preferable to carry out surface modification with the compound which has a group, and to provide a polymerizable unsaturated group (preferably unsaturated double bond) to the particle | grain surface. As a compound used for surface modification, the silane coupling agent which has a polymeric group can be used suitably.
Specifically, commercially available KBM-503, KBM-5103 (both are Shine-Etsu Chemical Co., Ltd., X-12-1048, X-12-1049, X-12-1050 described in JP-A-2014-123091). It is preferable to modify the surface of the metal oxide particles with a silane coupling agent containing a (meth) acryloyl group.

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

The metal oxide particles are particularly preferably calcined silica particles because the amount of hydroxyl groups on the surface is moderately large and hard particles.
The calcined silica particles are produced by a known technique of calcining silica particles after obtaining silica particles by hydrolyzing and condensing a hydrolyzable silicon compound in an organic solvent containing water and a catalyst. For example, Japanese Patent Application Laid-Open Nos. 2003-176121 and 2008-137854 can be referred to.
The silicon compound used as a raw material for producing the calcined silica particles is not particularly limited, but chlorosilanes such as tetrachlorosilane, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylvinyldichlorosilane, trimethylchlorosilane and methyldiphenylchlorosilane. Compound; tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, 3-glycidoxypropyltrimethoxysilane, 3-chloro Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane Silane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, Alkoxysilane compounds such as diphenyldimethoxysilane, diphenyldiethoxysilane, dimethoxydiethoxysilane, trimethylmethoxysilane and trimethylethoxysilane; tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane , Acyloxysilane compounds such as trimethylacetoxysilane; dimethylsilanediol, diphenylsilanediol, trico Silanol compounds such as chill silanol; and the like. Among the silane compounds exemplified above, alkoxysilane compounds are particularly preferable because they are more easily available and the obtained calcined silica particles do not contain a halogen atom as an impurity. As a preferable form of the calcined silica particles, it is preferable that the content of the halogen atom is substantially 0% and the halogen atom is not detected.
The firing temperature is not particularly limited, but is preferably 800 to 1300 ° C., and more preferably 1000 ° C. to 1200 ° C.
Further, as an example of the method of producing the above-mentioned irregular shaped particles, adjacent particles are sintered at the time of high temperature firing, and then the sintered particles are pulverized in a pulverizing step to obtain irregularly shaped particles in which a part of the sphere is flat. It can also be done.

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

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

In 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 a larger particle size mainly contribute to the moth-eye structure, and particles of a smaller particle size are mixed between large particles to suppress aggregation of the large particles, and as a result, the reflectance, The haze may improve. In addition, since metal oxide particles having a primary particle diameter of 1 nm or more and less than 70 nm immerse more in the binder resin, convex portions as the antireflective layer are formed of metal oxide particles having a primary particle diameter of 100 nm or more and 190 nm or less Point to something. The number of metal oxide particles having an average primary particle size of 1 nm to 70 nm with respect to metal oxide particles having an average primary particle size of 100 nm or more and 190 nm or less is preferably 1 to 3 times. By setting this range, the aggregation suppressing effect is high, and the reflectance can be lowered. Metal oxide particles having an average primary particle size of 1 nm or more and 70 nm or less preferably have an average primary particle size of 30 nm or more and 50 nm or less because the reflectance can be particularly lowered. When metal oxide particles having different average primary particle sizes are used in combination, it is preferable to make the amount of hydroxyl groups on the surfaces of both particles close to each other, because aggregation is more difficult. However, metal oxide particles having an average primary particle size of 1 nm or more and less than 100 nm are mainly used for suppressing aggregation of metal oxide particles having an average primary particle size of 100 nm or more and 190 nm or less. It is also possible to use metal oxide particles in which the amount of hydroxyl groups is more than 1.00 × 10 ⁻¹ or the indentation hardness is less than 400 MPa.

The antireflective layer may contain components other than these in addition to the binder layer and the metal oxide particles, and for example, contains a dispersant for metal oxide particles, a leveling agent, an antifouling agent, etc. It is also good.

<Dispersant of metal oxide particles>
The metal oxide particle dispersing agent can facilitate the uniform arrangement of the metal oxide particles by reducing the cohesion of the particles. The dispersant is not particularly limited, but anionic compounds such as sulfates and phosphates, cationic compounds such as aliphatic amine salts and quaternary ammonium salts, nonionic compounds and polymer compounds are preferable, and adsorptive groups are preferable. A polymer compound is more preferable because the degree of freedom in selecting each of the steric repulsive group and the steric repulsive group is high. A commercial item can also be used as a dispersing agent. For example, DISPERBYK 160, DISPERBYK 161, DISPERBYK 162, DISPERBYK 163, DISPERBYK 163, DISPERBYK 166, DISPERBYK 166, DISPERBYK 167, DISPERBYK 171, DISPERBYK 180, DISPERBYK 180, DISPERBYK 269, DISPERBYK2 6 0, DISPERBYK2 6 0, DISPERBYK2 6 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Examples include BYK-220S, Anti-Terra 203, Anti-Terra 204, and Anti-Terra 205 (trade names).

A curable compound (b-1) and a curable compound (b-2), and a curable compound (b-3) when the curable composition contains the curable compound (b-3) (B) ”.

<Leveling agent>
The leveling agent can stabilize the liquid after application by lowering the surface tension of the antireflective layer, and facilitate the uniform arrangement of the curable compound (B) and the metal oxide particles.
The composition for forming an antireflective layer used in the present invention can contain at least one leveling agent.
Thereby, the film thickness nonuniformity etc. resulting from the drying variation by the local distribution of a drying wind are suppressed, the repelling of a coating is improved, the said curable compound (B) and metal oxide particle are arrange | positioned uniformly It can be made easy.

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

When the leveling agent is added, the leveling agent moves quickly on the surface of the applied coating film and becomes unevenly distributed, and the leveling agent will be unevenly distributed on the surface even after drying of the coated film, so a film to which the leveling agent is added Surface energy is reduced by the leveling agent. The surface energy of the film is preferably low from the viewpoint of preventing film thickness nonuniformity, repelling, and nonuniformity.

Preferred examples of the silicone-based leveling agent include polymers or oligomers having a plurality of dimethylsilyloxy units as repeating units and having a substituent at the terminal and / or side chain. The polymer or oligomer containing dimethylsilyloxy as a repeating unit may contain structural units other than dimethylsilyloxy. The substituents may be the same or different and are preferably a plurality. Preferred examples of the substituent include groups including polyether group, alkyl group, aryl group, aryloxy group, aryl group, cinnamoyl group, oxetanyl group, fluoroalkyl group, polyoxyalkylene group and the like.

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

As an example of a preferable silicone type leveling agent, as a commercially available silicone type leveling agent which does not have a photopolymerizable group, Shin-Etsu Chemical Co., Ltd. X22-3710, X22-162C, X22-3701E, X22160AS, X22170DX, X224015. X22176DX, X22-176F, X224272, KF8001, X22-2000, etc .; FM4421, FM0425, FMDA26, FS1265 etc. made by Chisso Corporation; BY16-750, BY16880, BY16848, SF8427, made by Toray Dow Corning Corporation. SF8421, SH3746, SH8400, SF3771, SH3749, SH3748, SH8410 etc. TSF series manufactured by Momentive Performance Materials Japan Ltd. (T FIL4400, FWE4400, TFS4445, TSF4446, TSF4453, TSF4452, TSF4730, TSF4770, etc., FGF502, SILWET series (SILWETL77, SILWETL2780, SILWETL7608, SILWETL7002, SILTL7002, SILWETL7087SILT, WEBITG , SILWETL7602, SILWETL7604, SILWETL7604, SILWETL7605, SILWETL7607, SILWETL7622, SILWETL7644, SILW TL7650, SILWETL7657, SILWETL8500, SILWETL8600, SILWETL8610, SILWETL8620, SILWETL720) is not limited thereto but can be exemplified.

As those having a photopolymerizable group, X22-163A, X22-173DX, X22-163C, KF101, X22164A, X24-8201, X22174DX, X22164C, X222426, X222445, X222457, X222245, X22245, X22-163X manufactured by Shin-Etsu Chemical Co., Ltd. , X221602, X221603, X22164E, X22164B, X22164C, X22164D, TM0701 etc .; Silyoplane series (FM0725, FM0721, FM7725, FM7721, FM7726, FM7727 etc.) manufactured by Chisso Corporation; SF8411 manufactured by Toray Dow Corning Co., Ltd. , SF 8413, BY16-152D, BY16-152, BY16-152C, 8388A, etc .; Evonik Degussa Japan ( Made by TEGORad 2010, 2011, 2100, 2200N, 2300, 2500, 2600, 2700, etc .; BYK 3500 manufactured by Bick Chemie Japan Ltd. KNS 5300 manufactured by Shin-Etsu Silicone Co., Ltd. UVHC 1105 manufactured by Momentive Performance Materials Japan Co., Ltd. Although UVHC8550 etc. can be mentioned, it is not limited to this.

The leveling agent is preferably contained in the antireflective layer in an amount of 0.01 to 5.0% by mass, more preferably 0.01 to 2.0% by mass, and further preferably 0.01 to 1.0%. Most preferably, it is contained in%.

The fluorine-based leveling agent comprises a fluoroaliphatic group and a hydrophilic group which contributes to the affinity to various compositions such as coating and molding materials when, for example, this leveling agent is used as an additive. These compounds are compounds having the same molecule, and such compounds can be generally obtained by copolymerizing a monomer having a fluoroaliphatic group and a monomer having a hydrophilic group.
Representative examples of the monomer having a hydrophilic group, which is copolymerized with the monomer having a fluoroaliphatic group, include poly (oxyalkylene) acrylate, poly (oxyalkylene) methacrylate and the like.

As preferable commercially available fluorine-based leveling agents, Megafac series (MCF 350-5, F 472, F 476, F 445, F 444, F 443, F 178, F 470, F 475, F 479, manufactured by DIC Corporation) as having no photopolymerizable group. , F477, F482, F486, TF1025, F478K, F-784-F, etc .; lidosant series manufactured by Neos Co., Ltd. (FTX 218, 250, 245M, 209F, 222F, 245F, 208G, 218G, 240G, 206 D, 240 D, etc.), and those having a photopolymerizable group, for example, OPTOOL DAC manufactured by Daikin Industries, Ltd .; Defensor series manufactured by DIC (TF 3001, TF 3000, TF 3004, TF 3028, TF 3027, TF 3026) , F3025, etc.), RS series (RS71, RS101, RS102, RS103, RS104, RS105, etc.) are exemplified but not limited thereto.

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

<Antifouling agent>
A well-known silicone type or fluorine type antifouling agent, slip agent, etc. can be suitably added to the antireflective layer for the purpose of imparting properties such as antifouling property, water resistance, chemical resistance, and slipperiness. .

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

The antifouling agent is preferably contained in the antireflective layer in an amount of 0.01 to 5.0% by mass, more preferably 0.01 to 2.0% by mass, and further preferably 0.01 to 1.0%. Most preferably, it is contained in%.

The thickness of the binder layer is preferably 10 nm to 500 nm, more preferably 10 nm to 300 nm, and still more preferably 20 nm to 100 nm.

The curing of the curable composition is not particularly limited, but can be carried out by light irradiation. There is no restriction | limiting in particular about the kind of light, Although an X ray, an electron beam, an ultraviolet-ray, visible light, an infrared ray etc. are mentioned, an ultraviolet-ray is used widely. For example, if the coating film is UV curable, it is to cure by irradiation with irradiation dose of ultraviolet rays of ^{10mJ / cm 2 ~ 1000mJ / cm} 2 by an ultraviolet lamp curable compound layer (a) and (B) preferred. It is more preferably 50 mJ / cm ² to 1000 mJ / cm ² and even more preferably 100 mJ / cm ² to 500 mJ / cm ² . At the time of irradiation, the energy may be applied at one time, or may be divided and irradiated. A metal halide lamp, a high pressure mercury lamp, etc. are used suitably as ultraviolet-ray lamp | ramp seed | species.

[Hard coat layer]
The antireflection film of the present invention preferably has a hard coat layer.
The antireflective film of the present invention preferably has at least one hard coat layer between the substrate film and the antireflective layer.
The hard coat layer is not particularly limited, but may be, for example, a layer obtained by curing the same curable compound as the above-mentioned curable compound (b-2).

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

The antireflection film of the present invention can be used in various applications, and can be suitably used, for example, as an antireflection film of an antireflection article or as a polarizing plate protective film.
By applying the antireflective film of the present invention to the surface of an article, an antireflective article can be obtained. Examples of the article include transparent parts for vehicles, meters, windows, displays, substrates for touch panels, lenses, transparent substrates for solar cells, components for backlight units, and the like.
The polarizing plate protective film using the antireflection film of the present invention can be bonded to a polarizer to form a polarizing plate, and can be suitably used for a liquid crystal display device or the like.

[Polarizer]
The polarizing plate of the present invention has a polarizer and the antireflection film of the present invention.
The polarizing plate of the present invention is a polarizing plate having a polarizer and at least one protective film for protecting the polarizer, and preferably at least one of the protective films is the antireflection film of the present invention.

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

[Image display device]
The image display device of the present invention has the antireflection film of the present invention or the polarizing plate of the present invention.
As an image display device, a display device using a cathode ray tube (CRT), a plasma display panel (PDP), an electro luminescence display (ELD), a fluorescent display (VFD), a field emission display (FED), and a liquid crystal display (LCD) In particular, liquid crystal display devices are preferred.
In general, a liquid crystal display device has a liquid crystal cell and two polarizing plates disposed on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates. Furthermore, one optically anisotropic layer may be disposed between the liquid crystal cell and one of the polarizing plates, or two optically anisotropic layers may be disposed between the liquid crystal cell and both of the polarizing plates. As liquid crystal cells, liquid crystal cells of various driving methods such as TN (Twisted Nematic) mode, VA (Vertically Aligned) mode, OCB (Optically Compensatory Bend) mode, and IPS (In-Plane Switching) mode can be applied.

[Method of producing antireflective film]
The method for producing the antireflective film of the present invention is not particularly limited, but when the antireflective film of the present invention has a hard coat layer, preferably,
A hard coat layer is provided on a base film, and the above curable compound (B), a polymerization initiator, and metal oxide particles are formed on the above hard coat layer, the above curable compound (B), a polymerization initiator Providing the metal oxide particles in such a thickness that the metal oxide particles are buried in the layer (a) containing
Step (2): bonding the layer (b) of a pressure-sensitive adhesive film having a support and a layer (b) containing a pressure-sensitive adhesive having a gel fraction of 95.0% or more on the support ,
The metal oxide particles are buried in a layer combining the layer (a) and the layer (b), and protrude from the interface of the layer (a) opposite to the interface on the hard coat layer side Moving the position of the interface between the layer (a) and the layer (b) to the hard coat layer side,
Curing the layer (a) in a state in which the metal oxide particles are buried in the combined layer of the layer (a) and the layer (b),
It is a manufacturing method of an antireflection film which has a process (5) which exfoliates the above-mentioned layer (b) from the above-mentioned layer (a) in this order.

The above-described antireflective film of the present invention can be produced by the above production method.
In the above-mentioned production method, the curable compound (B) described above is preferably used as the curable compound, and the metal oxide particles are also preferably used.
The layer (a) cured in the step (4) corresponds to the above-mentioned binder layer, and the layer including the layer (a) and the metal oxide particles protruding from the layer (a) is an antireflective layer .

An example of a preferred embodiment of the method for producing an antireflective film of the present invention is shown in FIG.
In (1) of FIG. 2, a layer (a) containing a curable compound (B) and a polymerization initiator on the hard coat layer HC provided on the base film 1 in the step (1) (in FIG. 2) A state in which the metal oxide particles (symbol 3 in FIG. 2) are buried in the symbol 4) is schematically shown.

In (2) of FIG. 2, a layer (b) containing a pressure-sensitive adhesive having a gel fraction of 95.0% or more on the support 5 and the support 5 in step (2) (symbol 6 in FIG. 2) The layer (b) of the adhesive film 7 which has these is typically represented with the layer (a) (code | symbol 4 in FIG. 2) bonded together.

In (3) of FIG. 2, in the step (3), the metal oxide particles are buried in the combined layer of the layer (a) and the layer (b), and on the hard coat layer side of the layer (a) A state in which the position of the interface of the layer (a) and the layer (b) is moved to the hard coat layer side so as to protrude from the interface on the opposite side to the interface is schematically shown. In addition, as a method of moving the position of the interface of layer (a) and layer (b) to the hard-coat layer side so that it may mention later, the layer (b) which contains a part of curable compound (B) as an adhesive There is a method of infiltrating the
To move the position of the interface between the layer (a) and the layer (b) to the hard coat layer side also means to bring the position of the interface close to the hard coat layer.

(4) of FIG. 2 schematically shows the step of curing the layer (a) in the state where the metal oxide particles are buried in the layer (a) and the layer (b) in combination in the step (4). In the

(5) of FIG. 2 represents the state (antireflection film 10) after peeling the adhesive film 7 in the step (5) of peeling the adhesive film 7 including the layer (a) to the layer (b) .

In the method for producing an antireflective film of the present invention, the temperature at which the steps (1) to (4) are carried out is preferably 60 ° C. or less, more preferably 40 ° C. or less. By keeping the temperature at the time of performing the steps (1) to (4) at 60 ° C. or less, it is possible to suppress the aggregation of the metal oxide particles and to form a favorable uneven shape.

[Step (1)]
In the step (1), a hard coat layer is provided on the base film, and the above curable compound (B), a polymerization initiator, and metal oxide particles are provided on the above hard coat layer; B) A step of providing the metal oxide particles in such a thickness that the metal oxide particles are buried in the layer (a) containing a polymerization initiator.
In the present invention, “the thickness at which the metal oxide particles are buried in the layer (a)” represents a thickness of 0.8 times or more of the average primary particle diameter of the metal oxide particles.

In the step (1), the method for providing the layer (a) on the hard coat layer is not particularly limited, but it is preferable to provide the layer (a) on the hard coat layer by coating. In this case, the layer (a) is applied with a composition containing the curable compound (B), a polymerization initiator, and metal oxide particles (also referred to as “composition for forming the layer (a)”). It is a layer that The coating method is not particularly limited, and any known method can be used. For example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, die coating method and the like can be mentioned.

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

(Layer (a))
The layer (a) in the step (1) preferably contains the curable compound (B), a polymerization initiator, and metal oxide particles.
Layer (a) is a layer for forming an antireflective layer.
The curable composition containing the curable compound (B) contained in the layer (a) and the polymerization initiator can be cured to become a binder layer of the antireflective layer.
The metal oxide particles contained in the layer (a) are particles which protrude from the surface of the binder layer in the antireflective film and form an uneven shape (moth eye structure).
In addition, since the layer (a) is cured in the step (4), the components contained before curing and after curing are different, but in the present invention, it may be called the layer (a) at any stage for convenience. . The same applies to the hard coat layer.
The film thickness of the layer (a) in the step (1) is preferably 0.8 times or more and 2.0 times or less of the average primary particle diameter of the metal oxide particles, and 0.8 times or more and 1.5 times or less It is more preferable that the ratio is 0.9 times or more and 1.2 times or less.
As described above, since the antireflective layer is finally formed from the composition for forming the layer (a), the composition for forming the layer (a) is the composition for forming the antireflective layer is there.

The base film, the hard coat layer, the curable compound (B), the polymerization initiator, and the metal oxide particles are the same as those described above.

<Solvent>
The composition for forming layer (a) or layer (a) may contain a solvent.
As the solvent, it is preferable to select one having a polarity close to that of the metal oxide particles from the viewpoint of improving the dispersibility. Specifically, for example, alcohol solvents are preferable, and methanol, ethanol, 2-propanol, 1-propanol, butanol and the like can be mentioned. Further, for example, in the case of metal resin particles in which metal oxide particles are surface-modified with hydrophobicity, solvents such as ketones, esters, carbonates, alkanes and aromatics are preferable, and methyl ethyl ketone (MEK), dimethyl carbonate and the like are preferable. Methyl acetate, acetone, methylene chloride, cyclohexanone and the like. These solvents may be used as a mixture of two or more as long as the dispersibility is not significantly deteriorated.

[Step (2)]
The step (2) is a step of laminating a layer (b) of a pressure-sensitive adhesive film having a layer (b) containing a pressure-sensitive adhesive having a gel fraction of 95.0% or more on a support and a layer (a) It is. It does not specifically limit as method to bond together layer (a) and the layer (b) of an adhesive film, A well-known method can be used, for example, the lamination method is mentioned.
It is preferable to bond an adhesive film so that layer (a) and layer (b) may contact.
Before the step (2), the step of drying the layer (a) may be included. The drying temperature of the layer (a) is preferably 20 to 60 ° C., and more preferably 20 to 40 ° C. The drying time is preferably 0.1 to 120 seconds, and more preferably 1 to 30 seconds.
The present inventors bond the layer (b) and the layer (a) of the pressure-sensitive adhesive film in the step (2), and in the step (3) described later, the metal oxide particles are used as the layer (a) and the layer (b). The metal oxide particles are embedded in the combined layer and project from the interface on the opposite side of the interface on the hard coat layer side of the layer (a), and in the step (4) described later, the metal oxide particles By curing the layer (a) in a state of being buried in the combined layer b), aggregation is suppressed by preventing the metal oxide particles from being exposed to the air interface before curing of the layer (a). It has been found that a good asperity shape formed by oxide particles can be produced.

(Adhesive film)
The adhesive film has a support and a layer (b) consisting of an adhesive having a gel fraction of 95.0% or more.

<Layer (b)>
Layer (b) is composed of an adhesive having a gel fraction of 95.0% or more.
When the gel fraction of the pressure-sensitive adhesive is 95.0% or more, the pressure-sensitive adhesive component hardly remains on the surface of the anti-reflection film when peeling off the pressure-sensitive adhesive film to produce an anti-reflection film, even without washing An antireflection film having a sufficiently low reflectance can be obtained.
The gel fraction of the pressure-sensitive adhesive is preferably 95.0% to 99.9%, more preferably 97.0% to 99.9%, and 98.0% to 99.9%. It is more preferable that it is the following.
The gel fraction of the pressure-sensitive adhesive is a ratio of insolubles after the pressure-sensitive adhesive is immersed in tetrahydrofuran (THF) at 25 ° C. for 12 hours, and can be obtained from the following equation.
Gel fraction = (mass of insolubles of the adhesive in THF) / (total mass of the adhesive) x 100 (%)

The weight average molecular weight of the sol component in the pressure-sensitive adhesive is preferably 10000 or less, more preferably 7000 or less, and most preferably 5000 or less. When making the weight average molecular weight of a sol component into the said range, when peeling an adhesive film and manufacturing an anti-reflective film, an adhesive component can be made hard to remain on the anti-reflective film surface.
The sol component of the adhesive represents the content of the adhesive in THF after immersing in tetrahydrofuran (THF) at 25 ° C. for 12 hours. The weight average molecular weight can be analyzed by gel permeation chromatography (GPC).

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

The layer (b) is a pressure-sensitive adhesive layer having a slight adhesive strength and a peel strength (adhesive force) to the surface of an adherend at a peel speed of 0.3 m / min, of about 0.03 to 0.3 N / 25 mm. It is preferable from the viewpoint that it is excellent in the operativity at the time of peeling off an adhesive film from the layer (a) which is an adherend.

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

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

Preferred examples of (meth) acrylate monomers having an aliphatic ring include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, isobornyl (meth) acrylate and the like. Among them, cyclohexyl (meth) acrylate is particularly preferable.

The (meth) acrylic polymer is a copolymer comprising at least one kind of (meth) acrylic acid alkyl ester monomer having 1 to 18 carbon atoms in the alkyl group and at least one kind of another copolymerizable monomer. May be In this case, as another copolymerizable monomer, a copolymerizable vinyl monomer containing at least one group selected from a hydroxyl group, a carboxyl group and an amino group, a copolymerizable vinyl monomer having a vinyl group, an aromatic group Monomers 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) acrylate, 6- Hydroxyhexyl (meth) acrylate, hydroxyl group-containing (meth) acrylic acid esters such as 8-hydroxyoctyl (meth) acrylate, and N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl Examples thereof include hydroxyl group-containing (meth) acrylamides such as (meth) acrylamide, and the like, and it is preferably at least one selected from these compound groups.

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

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

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

Examples of amino group-containing copolymerizable vinyl monomers include monoalkylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoalkylaminopropyl (meth) acrylate and the like monoalkyl And aminoalkyl (meth) acrylates and the like.

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

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

The pressure-sensitive adhesive may include a cured product of a composition for forming a pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive composition).
The pressure-sensitive adhesive composition preferably contains the above-described polymer and a crosslinking agent, and may be crosslinked using heat or ultraviolet light (UV). The crosslinking agent is preferably at least one crosslinking agent selected from the group of compounds consisting of a bifunctional or higher isocyanate-based crosslinking agent, a difunctional or higher epoxy-based crosslinking agent, and an aluminum chelate-based crosslinking agent. When using a crosslinking agent, when peeling an adhesive film and manufacturing an anti-reflective film, from a viewpoint of making an adhesive component hard to remain on the anti-reflective film surface, with respect to 100 mass parts of said polymers, 0. The content is preferably 1 to 15 parts by mass, more preferably 3.5 to 15 parts by mass, and still more preferably 5.1 to 10 parts by mass.

The isocyanate compound having two or more functions may be a polyisocyanate compound having at least two or more isocyanate (NCO) groups in one molecule, and may be hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate. Buret modified product of diisocyanates such as isocyanate (compound having two NCO groups in one molecule), and isocyanurate modified product, trivalent or higher polyol such as trimethylol propane or glycerin (at least 3 in one molecule) The adduct body (polyol modified body) with the compound which has the above OH group, etc. are mentioned.
In addition, the trifunctional or higher functional isocyanate compound is a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule, and in particular isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, It is preferably at least one selected from the group of compounds consisting of adducts of hexamethylene diisocyanate compounds, adducts of isophorone diisocyanate compounds, burettes of hexamethylene diisocyanate compounds, and burettes of isophorone diisocyanate compounds.
The amount of the bifunctional or higher isocyanate-based crosslinking agent is preferably 0.01 to 5.0 parts by mass, and more preferably 0.02 to 3.0 parts by mass with respect to 100 parts by mass of the polymer.

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

As the antistatic agent which is a quaternary onium salt, for example, alkyl dimethyl benzyl ammonium salt having an alkyl group having 8 to 18 carbon atoms, dialkyl methyl benzyl ammonium salt having an alkyl group having 8 to 18 carbon atoms, 8 to 18 carbon atoms Trialkylbenzyl ammonium salt having 18 alkyl groups, tetraalkyl ammonium salt having an alkyl group having 8 to 18 carbon atoms, alkyldimethylbenzyl phosphonium salt having an alkyl group having 8 to 18 carbon atoms, alkyl having 8 to 18 carbon atoms Group-containing dialkylmethylbenzylphosphonium salt, trialkylbenzylphosphonium salt having alkyl group having 8 to 18 carbon atoms, tetraalkylphosphonium salt having alkyl group having 8 to 18 carbon atoms, and alkyl group having 14 to 20 carbon atoms Alkyl trimethi Ammonium salts, alkyl dimethyl ethyl ammonium salt having an alkyl group having 14 to 20 carbon atoms can be used. These alkyl groups may be alkenyl groups having unsaturated bonds.

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. It may be a mixed alkyl group derived from natural fats and oils. Examples of the alkenyl group having 8 to 18 carbon atoms include octenyl group, nonenyl group, decenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, oleyl group, linoleyl group and the like. .
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. It may be a mixed alkyl group derived from natural fats and oils. Examples of the alkenyl group having 14 to 20 carbon atoms include tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, oleyl group, linoleyl group, nonadecenyl group, icocenyl group and the like.

The counter anion of the quaternary onium salt, chloride (Cl ^-), bromide (Br ^-), methylsulfate _(CH ₃ OSO 3 ^-), ethyl sulfate _{_{_{^{(C 2 H 5 OSO 3 -}}}} ), p-toluenesulfonate (p- CH ₃ C ₆ H ₄ SO ₃ ⁻ ) and the like.

Specific examples of quaternary onium salts include dodecyldimethylbenzyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, tetradecyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium bromide, hexadecyl dimethyl benzyl ammonium chloride, hexadecyl dimethyl benzyl ammonium bromide, Octadecyldimethylbenzylammonium chloride, octadecyldimethylbenzylammonium bromide, trioctylbenzylammonium chloride, trioctylbenzylammonium bromide, trioctylbenzylphosphonium chloride, trioctylbenzylphosphonium bromide, tris (decyl) benzylammonium chloride, tris (decyl) benzylamine Monium bromide, tris (decyl) benzylphosphonium chloride, tris (decyl) benzylphosphonium bromide, tetraoctyl ammonium chloride, tetraoctyl ammonium bromide, tetraoctyl phosphonium chloride, tetraoctyl phosphonium bromide, tetranonyl ammonium chloride, tetranonyl ammonium bromide, tetranonyl ammonium bromide Nonyl phosphonium chloride, tetranonyl phosphonium bromide, tetrakis (decyl) ammonium chloride, tetrakis (decyl) ammonium bromide, tetrakis (decyl) phosphonium chloride, tetrakis (decyl) phosphonium bromide, and the like.

“Tris (decyl)” and “tetrakis (decyl)” mean that they have three or four decyl groups each having 10 carbon atoms, and tridecyl groups each having 13 carbon atoms, And a tetradecyl group which is an alkyl group having 14 carbon atoms.

As the antistatic agent, in addition, nonionic, cationic, anionic, amphoteric surfactants, ionic liquids, alkali metal salts, metal oxides, metal fine particles, conductive polymers, carbon, carbon nanotubes, etc. are also used. be able to.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, propylene glycol Fatty acid esters, polyoxyalkylene modified silicones and the like can be mentioned.

As the anionic surfactant, monoalkyl sulfates, alkylpolyoxyethylene sulfates, alkylbenzene sulfonates, monoalkyl phosphates and the like can be mentioned.

Moreover, as an amphoteric surfactant, alkyldimethylamine oxide, alkyl carboxy betaine etc. are mentioned.
The ionic liquid is a non-polymeric substance which comprises an anion and a cation and which is liquid at normal temperature (for example, 25 ° C.). Examples of the cationic moiety include cyclic amidine ions such as imidazolium ion, pyridinium ion, ammonium ion, sulfonium ion, phosphonium ion and the like. As the anion _{_{^{_{moiety, C n H 2n + 1 COO}}}} -, C n F 2n + 1 COO -, NO 3 -, C n F 2n + 1 SO 3 -, (C n F 2n + 1 SO 2) 2 N -, (C n F _{_{_{^{2n + 1 SO 2) 3 C}}}} -, PO 4 2-, AlCl 4 -, Al 2 Cl 7 -, ClO 4 -, BF 4 -, PF 6 -, AsF 6 -, SbF 6 - , and the like.

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

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

The pressure-sensitive adhesive composition may further contain a polyether-modified siloxane compound having an HLB of 7 to 15 as an antistatic aid.
HLB is, for example, a hydrophilic / lipophilic balance (hydrophilic / lipophilic ratio) defined by JIS K 3211 (term of surfactant) or the like.

The pressure-sensitive adhesive composition can further contain a crosslinking accelerator. The crosslinking accelerator may be any substance that functions as a catalyst for the reaction (crosslinking reaction) between the copolymer and the crosslinking agent when the polyisocyanate compound is used as the crosslinking agent, and an amine such as tertiary amine Examples thereof include organic metal compounds such as compounds, metal chelate compounds, organic tin compounds, organic lead compounds, organic zinc compounds and the like. In the present invention, a metal chelate compound or an organic tin compound is preferred as the crosslinking accelerator.

The metal chelate compound is a compound in which one or more polydentate ligands L are bonded to a central metal atom M. The metal chelate compound may or may not have one or more monodentate ligands X bonded to the metal atom M. For example, when a metal chelate compound having one metal atom M is represented by M (L) _m (X) _n , m ≧ 1 and n ≧ 0. When m is 2 or more, m L may be the same ligand or different ligands. When n is 2 or more, n 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. Examples of polydentate ligands L include β-keto esters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, acetylacetone (also known as 2,4-pentanedione), 2 And β-diketones such as 4-hexanedione and benzoylacetone. These are keto-enol tautomeric compounds and in the case of polydentate ligands L may be enolates (eg acetylacetonate) in which the enol is deprotonated.

Examples of the monodentate ligand X include halogen atoms such as chlorine atom and bromine atom, pentanoyl group, hexanoyl group, 2-ethylhexanoyl group, octanoyl group, nonanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, etc. And alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy and butoxy.

Specific examples of metal chelate compounds include tris (2,4-pentanedionato) iron (III), iron trisacetylacetonate, titanium trisacetylacetonate, ruthenium trisacetylacetonate, zinc bis acetylacetonate, aluminum tris Acetylacetonate, zirconium tetrakis acetylacetonate, tris (2,4-hexanedionato) iron (III), bis (2,4-hexanedionato) zinc, tris (2,4-hexanedionato) titanium, tris Examples include (2,4-hexanedionato) aluminum, tetrakis (2,4-hexanedionato) zirconium and the like.

Examples of organic tin compounds include dialkyl tin oxides, fatty acid salts of dialkyl tins, and fatty acid salts of stannous tin. Long chain alkyl tin compounds such as dioctyl tin compounds are preferred. Specific examples of organotin compounds include dioctyltin oxide and dioctyltin dilaurate.

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

<Support>
The support in an adhesive film is demonstrated.
As a support, a plastic film made of a resin having transparency and flexibility is preferably used. The plastic film for the support is preferably a polyester film such as polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate or polybutylene terephthalate, (meth) acrylic resin, polycarbonate resin, polystyrene resin, polyolefin resin Films made of resins, cyclic polyolefin resins, cellulose resins such as cellulose acylate, etc. may be mentioned. However, the (meth) acrylic resin includes a polymer having a lactone ring structure, a polymer having a glutaric anhydride ring structure, and a polymer having a glutarimide ring structure.
Besides these, other plastic films can be used as long as they have the required strength and optical suitability. The support may be a non-oriented film, uniaxial or biaxial orientation, or a stretching ratio or a plastic film in which the angle of the axial method formed along with the crystallization of the orientation is controlled.

As the support, those having UV transparency are preferred. Since it becomes possible to irradiate an ultraviolet ray from the coated layer side when curing the layer (a) in the step (4) by having the ultraviolet ray permeability, it is preferable in terms of manufacturing suitability.
Specifically, the maximum transmittance of the support at a wavelength of 250 nm to 300 nm is preferably 20% or more, more preferably 40% or more, and most preferably 60% or more. When the maximum transmittance at a wavelength of 250 nm to 300 nm is 20% or more, the layer (a) is easily cured by irradiation of ultraviolet rays from the coated layer side, which is preferable.
The maximum transmittance of the pressure-sensitive adhesive film having the layer (b) formed on the support at a wavelength of 250 nm to 300 nm is preferably 20% or more, more preferably 40% or more, and 60% or more. Is most preferred.

The thickness of the support is not particularly limited, but is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm, and still more preferably 10 μm to 40 μm.

A commercially available protective film can be suitably used as an adhesive film which formed layer (b) on the support body. Specifically, Fujimori Kogyo Co., Ltd. AS3-304, AS3-305, AS3-306, AS3-307, AS3-310, AS3-0401, AS3- 0520, AS3-0620, LBO-307, NBO- 0424, ZBO-0421, S-362, TFB-4T3-367AS, and the like.

In the present invention, in the step (4), the layer (a) is cured while maintaining the state in which the metal oxide particles are buried in the layer (a) and the layer (b). It is preferable to have the uneven | corrugated shape formed of the metal oxide particle which protruded from the interface of layer (a) in the front step of). By this, after curing the layer (a) in the step (4), when the layer (b) is peeled off in the step (5), the reflection prevention in the state where the metal oxide particles are protruded from the surface of the layer (a) A film can be obtained.

In the present invention, a step (1-2) of curing a part of the curable compound (B) in the layer (a) between the step (1) and the step (2) to obtain a cured compound (a1c) May be included.
To cure a part of the curable compound (B) means to cure only part of the curable compound (B), not all. By curing only a part of the curable compound (B) in the step (1-2), the metal oxide particles in the step (3) are the interface on the side opposite to the interface on the hard coat layer side of the layer (a) Cohesion of particles when the position of the interface between layer (a) and layer (b) is moved to the hard coat layer side so as to protrude from the surface, and reflection and total light transmittance have good reflection prevention It is preferable to carry out because a film is obtained. Since the optimum curing conditions in the step (1-2) differ depending on the formulation of the layer (a), the optimum curing conditions may be selected appropriately.

[Step (3)]
In the step (3), the metal oxide particles are buried in the combined layer of the layer (a) and the layer (b), and from the interface on the side opposite to the interface on the hard coat layer side of the layer (a) This is a step of moving the position of the interface of the layer (a) and the layer (b) to the hard coat layer side so as to protrude.
In the present invention, "the metal oxide particles are buried in the layer (a) and the layer (b) combined" means that the thickness of the layer (a) and the layer (b) combined is a metal. It represents that it is 0.8 times or more of the average primary particle size of oxide particles.
The step (3) is preferably carried out by penetrating a part of the curable compound (B) into the pressure-sensitive adhesive layer.
When a part of the curable compound (B) is allowed to penetrate the pressure-sensitive adhesive layer in the step (3), the laminate having the base film, the hard coat layer, the layer (a) and the layer (b) is 60 ° C. or less It is preferable to keep the temperature to 40.degree. C. or less. By keeping the temperature at 60 ° C. or lower, the viscosity of the curable compound (B) and the adhesive can be kept high, and the thermal movement of the particles can be suppressed. The effect of preventing the rise of haze and cloudiness is large. The lower limit of the temperature for keeping the laminate having the base film, the hard coat layer, the layer (a) and the layer (b) is not particularly limited, and the temperature lower than room temperature even at room temperature (25 ° C.) It may be

[Step (4)]
The step (4) is a step of curing the layer (a) in a state in which the metal oxide particles are buried in the layer combining the layer (a) and the layer (b).
In the present invention, “the state in which the metal oxide particles are buried in the layer (a) and the layer (b) combined” means that the thickness of the layer (a) and the layer (b) combined is metal oxide It shall represent that it is 0.8 times or more of the average primary particle size of thing particles.
To cure the layer (a) means to cure the curable composition contained in the layer (a), specifically to polymerize the curable compound (B), whereby the reflection of the antireflective film is achieved. The binder layer in the prevention layer can be formed. By maintaining the state in which the metal oxide particles are buried in the layer (a) and the layer (b) in the step (4), the aggregation of the metal oxide particles is suppressed, and a good uneven shape is formed. can do.
As a mechanism by which particle aggregation is suppressed by maintaining the state in which the metal oxide particles are buried in the layer (a) and the layer (b) combined, the metal oxide before the layer (a) hardens When particles are exposed at the air interface, it is known that a large attractive force derived from surface tension, which is called horizontal capillary force, acts, and the metal oxide particles are buried in the layer combining the layers (a) and (b) It is estimated that the attraction can be reduced by letting it do so.

Curing can be performed by irradiating light. There is no restriction | limiting in particular about the kind of light, Although an X ray, an electron beam, an ultraviolet-ray, visible light, an infrared ray etc. are mentioned, an ultraviolet-ray is used widely. For example, if the coating film is UV curable, it is to cure by irradiation with irradiation dose of ultraviolet rays of ^{10mJ / cm 2 ~ 1000mJ / cm} 2 by an ultraviolet lamp curable compound layer (a) and (B) preferred. It is more preferably 50 mJ / cm ² to 1000 mJ / cm ² and even more preferably 100 mJ / cm ² to 500 mJ / cm ² . At the time of irradiation, the energy may be applied at one time, or may be divided and irradiated. A metal halide lamp, a high pressure mercury lamp, etc. are used suitably as ultraviolet-ray lamp | ramp seed | species.

The oxygen concentration at curing is preferably 0 to 1.0% by volume, more preferably 0 to 0.1% by volume, and most preferably 0 to 0.05% by volume. By setting the oxygen concentration at the time of curing to less than 1.0% by volume, it becomes difficult to be affected by the inhibition of curing by oxygen, resulting in a strong film.

In the steps (2) to (4), it is preferable that a plurality of metal oxide particles do not exist in the direction orthogonal to the surface of the base film.

In the steps (2) to (4), the total film thickness of the film thickness of the layer (a) and the film thickness of the layer (b) is preferably larger than the average primary particle size of the metal oxide particles.
When the total film thickness of the film thickness of the layer (a) and the film thickness of the layer (b) is larger than the average primary particle diameter of the metal oxide particles, the particles (a2) form the layer (a) and the layer (b) It can be buried in the combined layers and is preferred.
However, when the pressure-sensitive adhesive film including the layer (b) is peeled off in the step (5) described later, the step (4) is performed because the metal oxide particles protrude from the surface of the layer (a). In the layer (a), the film thickness of the layer (a) is preferably smaller than the average primary particle size of the metal oxide particles, and more preferably half or less of the average primary particle size of the metal oxide particles.
The film thickness of the layer (a) in the step (4) is that the height of the interface on the opposite side to the interface on the hard coat layer side of the layer (ca) obtained by curing it is the average of the metal oxide particles It is preferable to adjust so as to be half or less of the primary particle diameter, and more preferably, the film cross section of the layer (ca) is observed with a scanning electron microscope (SEM), and the film thickness of 100 points is optionally measured When the average value is determined, it is preferable to adjust so as to be 10 nm to 100 nm (more preferably 20 nm to 90 nm, still more preferably 30 nm to 70 nm).

[Step (5)]
The step (5) is a step of peeling the layer (b) from the layer (a).
When the pressure-sensitive adhesive remains on the layer (a) side when the layer (b) is peeled off, a solvent for dissolving the pressure-sensitive adhesive without dissolving the base film, the hard coat layer and the layer (a) after curing You may use and wash.

After the pressure-sensitive adhesive film including the layer (b) is peeled off in the step (5), an antireflective film having a moth-eye structure having a concavo-convex shape formed by metal oxide particles on the surface of the layer (a) is obtained.

Hereinafter, the present invention will be more specifically described by way of examples. Materials, reagents, amounts and proportions of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the following specific examples.

Synthesis Example 1
(Synthesis of Curable Compound (b-1-1))
Sirius-501: Dendrimer-type multifunctional acrylate (Acryl equivalent 110, Osaka Organic Chemical Industry Co., Ltd. product) 20 g, methyl ethyl ketone 20 g of MEK, 0.5 g of (3-mercaptopropyl) trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1 mL of triethylamine were added, and the mixture was stirred at room temperature for 5 hours. To the resulting solution was added 200 g of MEK, and the solution was concentrated under reduced pressure to a solid content concentration of 20% to obtain a MEK solution of a curable compound (b-1-1) of the present invention.
The weight average molecular weight (Mw) of the curable compound (b-1-1) was 30,000, and the amount of silane coupling group / the amount of radically reactive group was 0.05.

Synthesis Example 2
(Synthesis of Curable Compound (b-1-2))
In a 500 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet, 15 g of 2-butanone was charged, and the temperature was raised to 84.degree. Next, a mixed solution consisting of 30 g of BBEM (manufactured by Manac Co., Ltd.), 15 g of 2-butanone and 0.95 g of “V-601” (manufactured by Wako Pure Chemical Industries, Ltd.) is added in 180 minutes so that the addition is completed. It dripped quickly. After completion of the dropwise addition, stirring was continued for further 3 hours, then the temperature was raised to 95 ° C. and stirring was continued for further 2 hours. After cooling to room temperature, 0.03 g of methyl hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.), 49 g of DBU (manufactured by Wako Pure Chemical Industries, Ltd.) and 30 g of MEK were added, and the mixture was stirred at 40 ° C. for 8 hours. After completion of the reaction, desalting was carried out using 1 N hydrochloric acid to separate impurities. The obtained polymer solution was dried over anhydrous magnesium sulfate and filtered, then 2.1 g of (3-mercaptopropyl) trimethoxysilane (manufactured by Tokyo Kasei Co., Ltd.) and 4 mL of triethylamine were added, and the mixture was stirred at room temperature for 5 hours. To the resulting solution was added 200 g of MEK, and the solution was concentrated under reduced pressure to a solid content concentration of 20% to obtain a MEK solution of a curable compound (b-1-2) of the present invention.
The weight average molecular weight (Mw) of the curable compound (b-1-2) was 15,000, and the amount of silane coupling group / the amount of radically reactive group was 0.1.

BBEM and DBU are as follows.
BBEM: Methacrylic acid 2- (2-bromoisobutyryloxy) ethyl DBU: diazabicycloundecene (1,8-diazabicyclo [5.4.0] undec-7-ene)

[Synthesis of silica particle P1]
A 200 L reactor equipped with a stirrer, a dropping device and a thermometer is charged with 67.54 kg of methyl alcohol and 26.33 kg of 28 mass% aqueous ammonia (water and catalyst), and the liquid temperature is 33 ° C. while stirring. Adjusted to On the other hand, a dropping device was charged with a solution of 12.70 kg of tetramethoxysilane dissolved in 5.59 kg of methyl alcohol. While maintaining the liquid temperature in the reactor at 33 ° C., the above solution is dropped from the dropping device over 37 minutes, and after completion of dropping, the solution is stirred for 37 minutes while maintaining the liquid temperature at the above temperature. Hydrolysis and condensation of methoxysilane were performed to obtain a dispersion containing a silica particle precursor. This dispersion is dried by flash drying using a flash vacuum evaporator (CROX SYSTEM CVX-8B manufactured by Hosokawa Micron Corporation) under the conditions of a heating tube temperature of 175 ° C. and a pressure reduction degree of 200 Torr (27 kPa). I got P1.
The average primary particle diameter of the silica particles P1 was 170 nm, the degree of dispersion (CV value) of the particle diameter was 7.0%, and the indentation hardness was 340 MPa.

[Preparation of calcined silica particles P2]
5 kg of silica particles P1 were put in a crucible, calcined at 900 ° C. for 2 hours using an electric furnace, cooled, and then pulverized using a pulverizer to obtain pre-classified calcined silica particles. The mixture was further crushed and classified using a jet pulverizer / classifier (IDS-2 manufactured by Nippon Pneumatic Co., Ltd.) to obtain calcined silica particles P2.

[Preparation of Silane Coupling Agent-treated Silica Particles P3]
5 kg of calcined silica particles P2 were charged in a 20 L Henschel mixer (FM20J manufactured by Mitsui Mining Co., Ltd.) equipped with a heating jacket. While the calcined silica particles P2 were being stirred, a solution of 50 g of 3-acryloxypropyltrimethoxysilane (KBM 5103 manufactured by Shin-Etsu Chemical Co., Ltd.) dissolved in 90 g of methyl alcohol was dropped and mixed. Thereafter, while mixing and stirring, the temperature was raised to 150 ° C. over about 1 hour, and heat treatment was performed by holding at 150 ° C. for 12 hours. In the heat treatment, the scrapes on the wall surface were scraped off while the scraping device was always rotated in the opposite direction to the stirring blade. In addition, scraping off the wall deposit was also performed using a spatula as appropriate. After heating, the resultant was cooled, and crushed and classified using a jet pulverizing classifier to obtain a silane coupling agent-treated silica particle P3.
The average primary particle diameter of the silane coupling agent-treated silica particles P3 was 171 nm, the degree of dispersion (CV value) of the particle diameter was 7.0%, and the indentation hardness was 470 MPa.

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

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

[Synthesis of Copolymer B-1]
In a 500 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet, 10.0 g of cyclohexanone was charged, and the temperature was raised to 84 ° C. Next, a mixed solution of 12.8 g of 2- (perfluorohexyl) ethyl acrylate, 7.2 g of ethyl acrylate, 32 g of cyclohexanone and 0.54 g of "V-601" (manufactured by Wako Pure Chemical Industries, Ltd.) Was dripped at a constant speed so that the dripping was completed in 180 minutes. Stirring was continued for another 3 hours after the addition was completed. Then, the temperature was raised to 95 ° C. and stirring was continued for additional 2 hours to obtain a 32% by mass solution of copolymer B-1 in cyclohexanone.

(Preparation of composition for forming hard coat layer)
Each component is mixed according to the composition described below, and the obtained composition is charged into a mixing tank, stirred, filtered through a polypropylene filter having a pore size of 0.4 μm, and a composition for forming a hard coat layer (hard coat layer Coating solution was used as HC-1.

(Hard coat layer coating solution HC-1)
A-TMMT 24.4 parts by mass AD-TMP 12.0 parts by mass Irgacure 127 1.6 parts by mass Ethanol 3.5 parts by mass Methanol 8.8 parts by mass 1-butanol 6.0 parts by mass Methyl ethyl ketone (MEK) 20.3 Mass part Methyl acetate 21.4 mass parts 32 mass% cyclohexanone solution of copolymer B-1 0.8 mass parts

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

[Preparation of Composition (a-1) (Composition for Forming Antireflection Layer) for Forming Layer (a)]
Each component was charged into a mixing tank so as to have the following composition, stirred for 60 minutes, and dispersed by an ultrasonic disperser for 30 minutes to obtain a composition (a-1).

Composition of Composition (a-1) U-15HA 1.2 parts by mass Compound C3 1.5 parts by mass KBM-4803 5.8 parts by mass Curable compound b-1-1 0.2 parts by mass Irgacure 127 0.2 Parts by mass Compound P 0.1 parts by mass Silica particle dispersion liquid PA-1 32.3 parts by mass Compound A 0.1 parts by mass Ethanol 12.7 parts by mass Methyl ethyl ketone 33.3 parts by mass Acetone 12.7 parts by mass

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

[Preparation of composition (a-2) for forming layer (a)]
Each component was charged into a mixing tank so as to have the following composition, stirred for 60 minutes, and dispersed by an ultrasonic disperser for 30 minutes to obtain a composition (a-2).
Composition of Composition (a-2) U-15HA 1.4 parts by mass Compound C3 1.5 parts by mass KBM-4803 5.8 parts by mass Curable Compound b-1-2 0.14 parts by mass Irgacure 127 0.2 Parts by mass Compound P 0.1 parts by mass Silica particle dispersion liquid PA-1 32.3 parts by mass Compound A 0.1 parts by mass Ethanol 12.7 parts by mass Methyl ethyl ketone 33.3 parts by mass Acetone 12.7 parts by mass

[Preparation of composition (a-3) for forming layer (a)]
Each component was charged into a mixing tank so as to have the following composition, stirred for 60 minutes, and dispersed by an ultrasonic disperser for 30 minutes to obtain a composition (a-3).
Composition of composition (a-3) U-15HA 1.0 part by mass Compound C3 1.6 parts by mass KBM-4803 5.8 parts by mass Compound b-1-1 1.0 parts by mass Irgacure 127 0.2 parts by mass Compound P 0.1 parts by mass Silica particle dispersion liquid PA-1 32.3 parts by mass Compound A 0.1 parts by mass Ethanol 12.7 parts by mass Methyl ethyl ketone 33.3 parts by mass Acetone 12.7 parts by mass

[Preparation of composition (a-4) for forming layer (a)]
Each component was charged into a mixing tank so as to have the following composition, stirred for 60 minutes, and dispersed by an ultrasonic disperser for 30 minutes to obtain a composition (a-4).
Composition of composition (a-4) U-15HA 1.5 parts by mass Compound C3 2.4 parts by mass KBM-4803 5.8 parts by mass Compound b-1-2 0.05 parts by mass Irgacure 127 0.2 parts by mass Compound P 0.1 parts by mass Silica particle dispersion liquid PA-1 32.3 parts by mass Compound A 0.1 parts by mass Ethanol 12.7 parts by mass Methyl ethyl ketone 33.3 parts by mass Acetone 12.7 parts by mass

[Preparation of composition (a-5) for forming layer (a)]
Each component was charged into a mixing tank so as to have the following composition, stirred for 60 minutes, and dispersed by an ultrasonic disperser for 30 minutes to obtain a composition (a-5).
Composition of Composition (a-5) U-15HA 1.0 part by mass Compound C3 1.4 parts by mass KBM-4803 5.8 parts by mass Curable compound b-1-1 0.35 parts by mass Irgacure 127 0.2 Parts by mass Compound P 0.1 parts by mass Silica particle dispersion liquid PA-1 32.3 parts by mass Compound A 0.1 parts by mass Ethanol 12.7 parts by mass Methyl ethyl ketone 33.3 parts by mass Acetone 12.7 parts by mass

[Preparation of composition (c-1) for forming layer (a)]
Each component was charged into a mixing tank so as to have the following composition, stirred for 60 minutes, and dispersed by an ultrasonic disperser for 30 minutes to obtain a composition (c-1).
Composition (c-1) Composition U-15HA 1.4 parts by mass Compound C3 1.5 parts by mass KBM-4803 5.8 parts by mass Irgacure 127 0.2 parts by mass Compound P 0.1 parts by mass Silica particle dispersion PA-1 32.3 parts by mass Compound A 0.1 part by mass Ethanol 12.7 parts by mass Methyl ethyl ketone 33.3 parts by mass Acetone 12.7 parts by mass

Example 1
<Preparation of Antireflection Film 1>
(Formation of hard coat layer)
The hard coat layer coating solution HC-1 was coated on a base film (TJ25, manufactured by Fuji Film Co., Ltd.) using a die coater. A 160 W / cm air-cooled metal halide lamp (I Graphics Co., Ltd.) with nitrogen purge to achieve an atmosphere with an oxygen concentration of approximately 1.3% by volume after drying at 30 ° C. for 90 seconds and then drying at 45 ° C. for 1 minute The coating layer was cured by irradiating an ultraviolet ray having an illuminance of 18 mW / cm ² and an irradiation amount of 10 mJ / cm ² , to form a hard coat layer with a thickness of 5 μm. The substrate with the hard coat layer is HC-1.

(Step (1) Coating of layer (a))
The composition (a-1) was coated on the hard coat layer of the above-mentioned hard coat layer-attached substrate HC-1 using a die coater at 2.8 ml / m ^{2, and} dried at 30 ° C. for 90 seconds. The film thickness of the layer (a) in the step (1) is 170 nm.

(Step (1-2) Step of curing a part of the curable compound (B) in the layer (a) to obtain a cured compound (a1c))
Using a high-pressure mercury lamp (Dr. honle AG, Model: 33351N, part number: LAMP-HOZ 200 D24 U 450 E) while performing nitrogen purge so that the atmosphere has an oxygen concentration of 1.4% by volume (a) (a It irradiated with light with the irradiation amount of 5.0 mJ from the side), and hardened one part of a curable compound (B). In addition, the measurement of the irradiation amount is HEAD SENSER to the eye ultraviolet ray integrated UV light meter UV METER UVPF-A1.
The PD-365 was attached, and measurement was performed at a measurement range of 0.00.

(Step (2) Bonding of adhesive film)
Then, on the layer (a) after drying, a pressure-sensitive adhesive film obtained by peeling a release film from AS 3-304 was attached such that the pressure-sensitive adhesive layer (layer (b)) was on the layer (a) side. . The lamination was carried out at a speed of 1 using a commercial laminator Bio 330 (manufactured by DAE-EL Co.).
AS3-304 refers to a laminate (protective film) composed of a support / adhesive layer / release film, and a laminate composed of a support / adhesive layer from which the release film is peeled off The body is an adhesive film.

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

(Step (3) Penetration of the Curable Compound (B) into the Adhesive Layer)
With the pressure-sensitive adhesive film attached, the film was allowed to stand at 25 ° C. for 5 minutes to permeate a portion of the curable compound (B) into the pressure-sensitive adhesive layer.

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

(Step (5) Peeling of adhesive film)
A pressure-sensitive adhesive film (a film obtained by peeling a release film from AS3-304) including the layer (b) was peeled off from the produced laminate. The layer (a) after peeling the layer (b) was cured to such an extent that the layer was not broken by the peeling of the pressure-sensitive adhesive layer. After peeling off the pressure-sensitive adhesive, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge so that the atmosphere has an oxygen concentration of 0.01 volume% or less, a layer of a plastic substrate From the surface on which (a) was applied, ultraviolet light having an illuminance of 150 mW / cm ² and an irradiation amount of 600 mJ / cm ² was irradiated to cure the layer (a). Thereafter, methyl isobutyl ketone was passed over the adhesive film on which the adhesive film was attached to wash away the residue of the adhesive layer, and dried at 25 ° C. for 10 minutes to obtain an antireflection film 1.

(Particle regularity)
The regularity of the particles was evaluated based on how much the regularity of the particles changed with respect to the standard sample (the standard sample) (.DELTA. Regularity of particles).
-Preparation of reference sample 1-
Prepare a sample that has passed to step (1-2) of anti-reflection film 1 and use a 160 W / cm air-cooled metal halide lamp (I-Graphics (stock) under nitrogen purge so that the atmosphere has an oxygen concentration of 0.01 volume% or less. ), And the layer (a) is cured by irradiation with ultraviolet light having an illuminance of 150 mW / cm ² and an irradiation dose of 600 mJ / cm ² from the surface on which the layer (a) of the base film is applied. Sample 1 was prepared.
-Calculation of particle regularity-
Surface observation was performed on the obtained antireflective film 1 and the sample for reference 1 using a SEM (S-4300 manufactured by Hitachi High-Technologies Corporation). The number of particles in the range of 1280 nm × 830 nm and the average center-to-center distance from the closest particles were calculated, and the regularity of the particles was calculated by the following equation.
(Particle regularity)
= (Average center-to-center distance with closest particles-average primary particle size) / (inter-particle distance in closest packing-average primary particle size) x 100
Here, the interparticle distance in closest packing is represented by the following equation.

(Δ particle regularity) = (particle regularity of reference sample 1) − (particle regularity of antireflective film 1)
The Δ particle regularity was evaluated according to the following criteria.
A: less than 4% B: 4% or more and less than 8% C: 8% or more and less than 10% D: 10% or more In addition, if it is C or more, there is no practical problem.

Table 1 also shows W ₁ / W ₃ and W ₁ / W ₂ .

Examples 2 to 5 and Comparative Example 1
Antireflection films 2 to 5 and C1 were prepared and evaluated in the same manner as in Example 1 except that the composition of the type described in Table 1 below was used instead of the composition (a-1).
The reference samples 2 to 5 corresponding to the antireflective films 2 to 5 and C 1 and C 1 are the same as the reference sample 1 except that the samples after the step (1-2) of each antireflective film are prepared Created. The Δ particle regularity was calculated by subtracting the particle regularity of each antireflective film from the particle regularity of each reference sample as in the following formula.
(Δ particle regularity) = (particle regularity of reference sample) − (particle regularity of antireflective film)

Table 1 also shows W ₁ / W ₃ and W ₁ / W ₂ .

The evaluation results are shown in Table 2 below.

From the comparison of Examples 1 to 5 and Comparative Example 1, the antireflection films of Examples 1 to 5 had a low decrease in particle regularity.
From the comparison of Examples 1 to 2 and 5 with 3 to 4, the antireflective films of Examples 1 to 2 and 5 had a lower reduction in particle regularity.

According to the present invention, an antireflective film having a moth-eye structure having a concavo-convex shape formed by particles, which is a highly antireflective film having high regularity of particles, a polarizing plate having the above antireflective film, an antireflective article and an image A display device can be provided.

Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application (Application No. 2017-191515) filed on Sep. 29, 2017, the contents of which are incorporated herein by reference.

1 substrate film HC hard coat layer 2 antireflection layer 3 metal oxide particles 4 binder layer (layer (a))
5 supports 6 layers (b)
7 adhesive film 10 anti-reflection film A distance between apexes of adjacent projections B distance between center of apexes of adjacent projections and depression UV ultraviolet light

Claims

An antireflective film comprising a substrate film and an antireflective layer, wherein
The antireflective layer comprises metal oxide particles and a binder layer,
The binder layer is a layer obtained by curing a curable composition containing at least a curable compound (b-1), a curable compound (b-2), and a polymerization initiator,
The antireflection film, wherein the antireflection layer has a moth-eye structure having a concavo-convex shape formed by the metal oxide particles.
Curable compound (b-1): Silane coupling agent having a weight average molecular weight of 10000 or more and having a radical reactive group Curable compound (b-2): Molecular weight of 150 or more, having a radical reactive group And silicon-free compounds
The antireflective film according to claim 1, wherein the curable composition further comprises a curable compound (b-3).
Curable compound (b-3): Silane coupling agent having a molecular weight of 5000 or less and having a radical reactive group
The mass ratio of the content of the curable compound (b-1) to the content of the curable compound (b-3) in the curable composition is 0.05 to 0.5. Antireflection film as described.
An antireflective article having the antireflective film according to any one of claims 1 to 3 on its surface.
It is a polarizing plate which has a polarizer and at least one protective film which protects the said polarizer, Comprising: At least one of the said protective film is an anti-reflective film of any one of Claims 1-3. Is a polarizing plate.
An image display device comprising the antireflective film according to any one of claims 1 to 3 or the polarizing plate according to claim 5.