WO2018034126A1

WO2018034126A1 - Antireflective film, antireflective article, polarizing plate, image display device, module, touch panel liquid crystal display device, and method for manufacturing antireflective film

Info

Publication number: WO2018034126A1
Application number: PCT/JP2017/027315
Authority: WO
Inventors: 千裕増田; 美帆朝日; 悠太福島; 竜二実藤
Original assignee: 富士フイルム株式会社
Priority date: 2016-08-15
Filing date: 2017-07-27
Publication date: 2018-02-22

Abstract

The present invention is: an antireflective film having a plastic substrate and an antireflective layer, wherein the antireflective layer includes metal oxide particles and a binder resin, the antireflective layer has a moth-eye structure comprising an uneven shape formed by the metal oxide particles, the total light transmittance of the antireflective film when light is incident from the reverse side of the antireflective layer from the plastic substrate is 88% or greater, and the antireflective film satisfies the expression T₅₈₀ – T₄₈₀ ≤ 3.5%, where T₄₈₀ and T_580} are the transmittance of light at a wavelength of 480 nm and 580 nm, respectively, through the antireflective film when the light is incident from the reverse side of the antireflective layer from the plastic substrate; a method for manufacturing the antireflective film; and an antireflective article, a polarizing plate, an image display device, a module, and a touch panel liquid crystal display device having the antireflective film.

Description

Antireflection film, antireflection article, polarizing plate, image display device, module, liquid crystal display device with touch panel, and production method of antireflection film

The present invention relates to an antireflection film, an antireflection article, a polarizing plate, an image display device, a module, a liquid crystal display device with a touch panel, and a method for producing an antireflection film.

Image display such as a display device using a cathode ray tube (CRT), a plasma display panel (PDP), an electroluminescence display (ELD), a fluorescent display (VFD), a field emission display (FED), and a liquid crystal display (LCD) In an apparatus, an antireflection film may be provided in order to prevent a decrease in contrast and reflection of an image due to reflection of external light on the display surface. Further, a liquid crystal display device with a touch panel may have a structure in which a touch panel and a liquid crystal panel including a liquid crystal cell are arranged via an air gap, but the interface between the touch panel and the air gap, and the air gap and the liquid crystal panel In order to prevent light from being reflected at the interface and lowering the contrast or causing Newton's rings, an antireflection film is placed at the interface between the touch panel and the air gap, and at the interface between the air gap and the liquid crystal panel. How to do is known. Further, there are cases where an antireflection function is imparted by an antireflection film other than an image display device such as a glass surface of a showroom.

As an antireflection film, an antireflection film having a fine unevenness with a period of not more than the wavelength of visible light on the surface of the substrate, that is, an antireflection film having a so-called moth eye structure is known. With the moth-eye structure, it is possible to create a refractive index gradient layer in which the refractive index continuously changes from air to the bulk material inside the substrate, thereby preventing light reflection.

As an antireflection film having a moth-eye structure, Patent Document 1 discloses that a coating liquid containing a transparent resin monomer and fine particles is applied on a transparent substrate and cured to form a transparent resin in which the fine particles are dispersed. An anti-reflection film having a moth-eye structure manufactured by etching a resin is described.

Japanese Unexamined Patent Publication No. 2009-139796

However, it has been found that the antireflection film of Patent Document 1 has a low light transmittance in the short wavelength region of visible light. Specifically, this is expressed by the fact that the transmittance of light having a wavelength of 480 nm is smaller than the transmittance of light having a wavelength of 580 nm. The cause of this is thought to be that light interferes with the concavo-convex period of the moth-eye structure, and more specifically, because diffracted light having a wavelength twice that of the concavo-convex period interferes. If the transmittance of light in the short wavelength region of visible light is low, a change in color tends to occur, and this problem becomes particularly noticeable when two or more antireflection films are used. As a case where two or more antireflection films are used, for example, a liquid crystal display device with a touch panel may be mentioned.

An object of the present invention is to provide an antireflection film having good antireflection performance, high total light transmittance, and high light transmittance in the short wavelength region of visible light, a method for producing the antireflection film, and The object is to provide an antireflection article, a polarizing plate, an image display device, a module, and a liquid crystal display device with a touch panel, each having the antireflection film.

<1>
An antireflection film having a plastic substrate and an antireflection layer,
The antireflection layer includes metal oxide particles and a binder resin,
The antireflection layer has a moth-eye structure having an uneven shape formed by the metal oxide particles,
The total light transmittance of the antireflection film when incident from the side opposite to the plastic substrate of the antireflection layer is 88% or more, and
When the above respective _{T 480} and _{T 580} the transmittance of light having a wavelength of 480nm and 580nm of the antireflection film at the time of entering from the side opposite to the plastic substrate of the anti-reflection _layer, T 580 _{-T 480} ≦ 3. Antireflection film satisfying 5%.
<2>
The concavo-convex shape of the antireflection layer is the antireflection film according to <1>, where X is an average value of distances A between vertices of adjacent convex portions, and X ≦ 190 nm.
<3>
The uneven shape of the antireflection layer is the antireflection film according to <2>, which satisfies X + σ ≦ 190 nm, where σ is a standard deviation representing the distribution of A.
<4>
The antireflection film according to any one of <1> to <3>, wherein the average primary particle size of the metal oxide particles is from 100 nm to 190 nm.
<5>
<1> to <4>, wherein the binder resin includes a compound having 2 or less polymerizable functional groups in one molecule having a viscosity of 1 to 20 mPas at 25 ° C. or a compound having no polymerizable functional group. The antireflection film according to any one of the above.
<6>
The antireflection film according to any one of <1> to <5>, wherein a hard coat layer is provided between the plastic substrate and the antireflection layer.
<7>
The hard coat layer contains a quaternary ammonium salt-containing polymer,
When the surface resistivity of the antireflection layer is SR in the unit Ω / sq, the common logarithm value of SR is 11 or less, and the uneven shape of the antireflection layer is between vertices of adjacent protrusions. <6> satisfying X + σ ≦ 190 nm, where X is the average value of the distance A and σ is the standard deviation representing the distribution of A.
<8>
<1>-<7> Antireflection article which has the antireflection film of any one of <1> on the surface.
<9>
An antireflection according to any one of <1> to <7>, wherein the polarizing plate has a polarizer and at least one protective film for protecting the polarizer, wherein at least one of the protective films is <1> to <7>. A polarizing plate that is a film.
<10>
<1>-<7> The image display apparatus which has an antireflection film of any one of <1>, or the polarizing plate as described in <9>.
<11>
A module comprising two antireflection films according to any one of <1> to <7>, wherein the two antireflection films are disposed to face each other through an air gap.
<12>
The module according to <11>, wherein the two antireflection films have the antireflection layer disposed closer to the air gap than the plastic substrate.
<13>
Including the module according to <12>,
One of the two antireflection films has a touch panel on the side opposite to the antireflection layer side of the plastic substrate of the antireflection film,
A display device with a touch panel, having a liquid crystal cell on the side opposite to the antireflection layer side of the plastic substrate of the other antireflection film.
<14>
On the plastic substrate, a curable compound and metal oxide particles having an average primary particle size of 100 nm or more and 190 nm or less are provided at a thickness at which the metal oxide particles are embedded in the layer (a) containing the curable compound. Step (1),
A step of bonding the layer (b) of the pressure-sensitive adhesive film having the support and the layer (b) containing a pressure-sensitive adhesive having a gel fraction of 95.0% or more on the support (2). ,
The metal oxide particles are embedded in a layer combining the layer (a) and the layer (b), and protrude from the interface on the side opposite to the interface on the plastic substrate side of the layer (a). Step (3) of moving the position of the interface between the layer (a) and the layer (b) to the plastic substrate side,
A step (4) of curing the layer (a) in a state where the metal oxide particles are buried in a layer formed by combining the layer (a) and the layer (b);
Step (5) of peeling the layer (b) from the layer (a);
In this order, and the temperature at which the above steps (1) to (4) are performed is 60 ° C. or less.

According to the present invention, an antireflection film having good antireflection performance, a high total light transmittance, and a high light transmittance in the short wavelength region of visible light, a method for producing the antireflection film, and An antireflection article, a polarizing plate, an image display device, a module, and a liquid crystal display device with a touch panel having the antireflection film 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 module of this invention, and a liquid crystal display device with a touchscreen. It is a schematic diagram for demonstrating an example of the manufacturing method of the antireflection film of this invention.

In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Further, “(meth) acrylate” represents at least one of acrylate and methacrylate, “(meth) acryl” represents at least one of acrylic and methacryl, and “(meth) acryloyl” represents at least one of acryloyl and methacryloyl. .

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

[Antireflection film]
The antireflection film of the present invention is
An antireflection film having a plastic substrate and an antireflection layer,
The antireflection layer includes metal oxide particles and a binder resin, and the antireflection layer has a moth-eye structure having an uneven shape formed by the metal oxide particles,
The total light transmittance of the antireflection film when incident from the side opposite to the plastic substrate of the antireflection layer is 88% or more, and
When the above respective _{T 480} and _{T 580} the transmittance of light having a wavelength of 480nm and 580nm of the antireflection film at the time of entering from the side opposite to the plastic substrate of the anti-reflection _layer, T 580 _{-T 480} ≦ 3. It is an antireflection film satisfying 5%.

The antireflection film of the present invention has a plastic substrate and an antireflection layer, and the plastic substrate and the antireflection layer are laminated. The plastic substrate and the antireflection layer may be directly laminated, or may be laminated via another layer (preferably a hard coat layer).

The total light transmittance of the antireflection film when entering from the side opposite to the plastic substrate of the antireflection layer of the antireflection film of the present invention is 88% or more, preferably 90% or more, more preferably 92. % Or more, more preferably 94% or more.
The antireflection film has a total light transmittance of 88% or more when entering from the side opposite to the plastic substrate of the antireflection layer of the antireflection film, which increases the transparency of the antireflection film. Even if two or more prevention films are used, the visibility is hardly lowered.
The measurement of the total light transmittance is performed according to Japanese Industrial Standard (JIS) K7361-1 (1997).
There are no particular restrictions on the means for increasing the total light transmittance of the antireflection film to 88% or more when it enters from the side opposite to the plastic substrate of the antireflection layer of the antireflection film. For example, the total light transmittance is high. For example, a plastic substrate may be used. In addition, as will be described later, it is also preferable to set the average value X of the distance A between the vertices of adjacent convex portions of the concavo-convex shape of the antireflection layer to 190 nm or less from the viewpoint of preventing a decrease in transmittance in the visible light region.

Furthermore, when the transmittance of light having a wavelength of 480nm and 580nm of the antireflection film when the plastic substrate of the antireflection layer that is incident from the opposite side of the antireflection film of the present invention was T ₄₈₀ and T _580, respectively, T ₄₈₀ and T ₅₈₀ satisfy T ₅₈₀ −T ₄₈₀ ≦ 3.5%, preferably 0% ≦ T ₅₈₀ −T ₄₈₀ ≦ 3.0%, and 0% ≦ T ₅₈₀ −T ₄₈₀ ≦ 2.5% % Is more preferable, and 0% ≦ T ₅₈₀ −T ₄₈₀ ≦ 2.0% is more preferable.
When T ₅₈₀ −T ₄₈₀ ≦ 3.5% is satisfied, that is, T ₅₈₀ −T ₄₈₀ is 3.5% or less, for example, the color change of the display image when an antireflection film is applied to the image display device Can be suppressed. In particular, even when two or more antireflection films are used, the color change hardly occurs.
Measurements of T ₄₈₀ and _{T 580} shall be carried out according to Japanese Industrial Standards (JIS) K0115 (2004 years).
Means for reducing T ₅₈₀ -T ₄₈₀ to 3.5% or less is not particularly limited, but the average value X of the distance A between the vertices of adjacent convex portions of the concavo-convex shape of the antireflection layer should be 190 nm or less. Preferably, when σ is the standard deviation representing the distribution of A, X + σ is more preferably 190 nm or less. By adjusting the concavo-convex shape in this way, even if diffracted light having a wavelength twice the concavo-convex period interferes, it is light that does not fall within the visible light range with a wavelength of 380 nm or more. Can be prevented, the total light transmittance is 88% or more, and T ₅₈₀ -T ₄₈₀ can be 3.5% or less.

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

An example of a preferred embodiment of the antireflection film of the present invention is shown in FIG.
An antireflection film 10 in FIG. 1 includes a plastic substrate 1 and an antireflection layer 2. The antireflection layer 2 includes metal oxide particles 3 and a binder resin 4. The metal oxide particles 3 protrude from the binder resin 4 to form an uneven shape, and this uneven shape has a moth-eye structure.

(Moth eye structure)
The antireflection layer of the antireflection 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 of the antireflection layer on the side opposite to the interface on the plastic substrate side.
The concavo-convex shape formed by the metal oxide particles preferably means that each metal oxide particle protruding from the binder resin film becomes a convex portion, and a portion where no metal oxide particles exist becomes a concave portion. is there.
The moth-eye structure composed of a concavo-convex shape means that the concavo-convex shape is a moth-eye structure.
In addition, as long as the moth-eye structure can be formed, other components such as a binder resin may be present on the surface of the metal oxide particles forming the convex portions.
The moth-eye structure refers to a processed surface of a substance (material) for suppressing light reflection, and a structure having a periodic fine structure pattern. In particular, for the purpose of suppressing the reflection of visible light, it refers to a structure having a fine structure pattern with a period of less than 780 nm. When the period of the fine structure pattern is less than 190 nm, the color of the reflected light is preferably reduced. Moreover, it is preferable that the period of the concavo-convex shape of the moth-eye structure is 100 nm or more because light having a wavelength of 380 nm can recognize a fine structure pattern and has excellent antireflection properties. The presence or absence of the moth-eye structure can be confirmed by observing the surface shape with a scanning electron microscope (SEM), an atomic force microscope (AFM), or the like, and examining whether the fine structure pattern is formed.

The concavo-convex shape of the antireflection layer of the antireflection film of the present invention is B / A, which is a ratio of the distance A between the apexes of adjacent convex portions and the distance B between the center and the concave portion between the apexes of adjacent convex portions. Is preferably 0.4 or more. When B / A is 0.4 or more, the depth of the concave portion increases with respect to the distance between the convex portions, and a refractive index gradient layer in which the refractive index changes more gradually from the air to the inside of the antireflection layer is formed. Therefore, the reflectance can be further reduced.
B / A is more preferably 0.5 or more. If B / A is 0.5 or more, the distance A between the vertices of adjacent convex portions (convex portions formed of particles) becomes equal to or larger than the particle diameter, and concave portions are formed between the particles. As a result, both the interface reflection due to the sharp part of the refractive index change depending on the curvature above the convex part and the interface reflection due to the sharp part of the refractive index change dependent on the curvature of the interparticle concave part exist. In addition to the refractive index gradient layer effect due to the structure, it is presumed that the reflectance is more effectively reduced.

B / A can be controlled by the volume ratio of the binder resin and the metal oxide particles in the antireflection layer. Therefore, it is important to appropriately design the blending ratio between the binder resin and the metal oxide particles.

The concavo-convex shape of the antireflection layer of the antireflection film of the present invention preferably satisfies X ≦ 190 nm, and preferably satisfies X ≦ 180 nm, where X is the average value of the distances A between the vertices of adjacent convex portions. It is more preferable that X ≦ 170 nm is satisfied.
By satisfying X ≦ 190 nm, that is, when X is 190 nm or less, it is possible to prevent a decrease in transmittance in the short wavelength region of visible light as described above.
Further, as will be described later, from the viewpoint of satisfying X + σ ≦ 190 nm when σ is the standard deviation representing the distribution of A, X ≦ 180 nm is more preferable, and X ≦ 170 nm is more preferable.

The means for creating the irregular shape satisfying X ≦ 190 nm is not particularly limited, but (i) using metal oxide particles having an average primary particle size of 190 nm or less, or (ii) aggregation of metal oxide particles. For example, it is possible to suppress the formation of voids between the metal oxide particles. As a method for preventing the aggregation of the metal oxide particles of (ii) above, (ii-1) the metal oxidation accompanying the decrease in the viscosity of the binder resin or convection by setting the temperature at the preparation of the antireflection film to 60 ° C. or lower. And (ii-2) a method of forming a bond between the metal oxide particles and the substrate.

Even when A has a distribution, from the viewpoint of preventing a decrease in transmittance in the short wavelength region of visible light, when σ is a standard deviation representing the distribution of A, X + σ ≦ 240 nm is preferably satisfied, and X + σ ≦ More preferably, 230 nm is satisfied, X + σ ≦ 210 nm is further satisfied, X + σ ≦ 200 nm is particularly preferable, and X + σ ≦ 190 nm is most preferable.
By satisfying X + σ ≦ 190 nm, that is, when X + σ is 190 nm or less, it is possible to prevent a decrease in transmittance in the short wavelength region of visible light as described above.

The means for creating the irregular shape satisfying X + σ ≦ 190 nm is not particularly limited, but (i) using metal oxide particles having an average primary particle size of 190 nm or less, or (ii) aggregation of metal oxide particles Prevention. As a method for preventing aggregation of the metal oxide particles of (ii) above, (ii-1) a method of setting the temperature at the production of the antireflection film to 60 ° C. or lower, or (ii-2) metal oxide particles and Examples thereof include a method of forming a bond with the substrate.

The method for measuring the distance A between the vertices of adjacent convex portions and the distance B (depth of the concave portion) between the center and the concave portion between the vertices of adjacent convex portions will be described more specifically below.
The distance B can be measured by cross-sectional SEM observation of the antireflection film. The antireflection film sample is cut with a microtome to obtain a cross section, and SEM observation is performed at an appropriate magnification (about 5000 times). For easy observation, the sample may be subjected to appropriate processing such as carbon deposition and etching. The distance B is defined as a straight line connecting the vertices of the adjacent protrusions and a perpendicular bisector at the interface between the air and the sample and including the vertices of the adjacent protrusions. The distance from the concave portion that is the point reaching the binder resin is shown. The average value when the distance A between the vertices of adjacent convex portions is measured at 100 points is calculated as X.
Further, the standard deviation indicating the variation in the measured distance A is calculated as σ.
In the SEM photograph, there are cases where the distance A between the vertices of the adjacent convex portions and the distance B between the vertices of the adjacent convex portions and the concave portion B cannot be measured accurately with respect to all the projected and recessed portions. However, in that case, the length may be measured by paying attention to the convex portion and the concave portion shown on the near side in the SEM image.
Note that the concave portion needs to be measured at the same depth as the particles forming the two adjacent convex portions to be measured in the SEM image. This is because if the distance to a particle or the like reflected on the near side is measured as B, B may be estimated small.

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

The uniformity of the surface of the antireflection film can be evaluated by haze. The measurement can be carried out on a film sample of 40 mm × 80 mm at 25 ° C. and a relative humidity of 60% with a haze meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS-K7136 (2000). When the particles are aggregated and non-uniform, the haze increases. A lower haze is preferred. The haze value is preferably 0.0 to 3.0%, more preferably 0.0 to 2.5%, and further preferably 0.0 to 2.0%.

(Plastic substrate)
The plastic substrate of the antireflection film of the present invention will be described.
The plastic substrate is not particularly limited as long as it is a light-transmitting substrate generally used as a substrate for an antireflection film. Various plastic substrates can be used, such as cellulose resin; cellulose acylate (triacetate cellulose, diacetyl cellulose, acetate butyrate cellulose), polyester resin; polyethylene terephthalate, (meth) acrylic resin, polyurethane, etc. Base materials containing polycarbonate resins, polycarbonates, polystyrenes, olefin resins, etc., preferably cellulose acylates, polyethylene terephthalates, or substrates containing (meth) acrylic resins, and substrates containing cellulose acylates Is more preferable, and a cellulose acylate film is particularly preferable. As the cellulose acylate, the base material described in JP 2012-093723 A can be preferably used.
The thickness of the plastic substrate is usually about 10 μm to 1000 μm, but is preferably 15 μm to 200 μm, and preferably 20 μm to 200 μm from the viewpoints of good handleability, high translucency, and sufficient strength. More preferably, 20 μm to 100 μm is more preferable, and 25 μm to 100 μm is particularly preferable.
In particular, when two or more antireflection films are used, a thin plastic substrate can be preferably used. In this case, the thickness of the plastic substrate is preferably 20 μm to 40 μm, and more preferably 25 μm to 40 μm.
As the translucency of the plastic substrate, a material having a total light transmittance of 90% or more is preferable.

(Antireflection layer)
The antireflection layer of the antireflection film of the present invention will be described.
The antireflection layer includes metal oxide particles and a binder resin.

(Binder resin)
The binder resin preferably has a function of binding metal oxide particles to a plastic substrate or a laminate of a plastic substrate and another layer.
The binder resin is preferably a film as shown in FIG.
The binder resin preferably contains a cured product of a curable compound.
The binder resin can be obtained by curing a curable compound.
The curable compound used for forming the binder resin is also referred to as a curable compound (a1).

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

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

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

Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, at least one polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferably contained.
For example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO (ethylene oxide) modified trimethylolpropane tri (meth) acrylate, PO (propylene oxide) modified trimethylol Propane tri (meth) acrylate, EO-modified phosphate tri (meth) acrylate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 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 the polyfunctional acrylate compounds having a (meth) acryloyl group include KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, and TPA- manufactured by Nippon Kayaku Co., Ltd. 330, RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303, V # 3PA, V from Osaka Organic Chemical Industry Co., Ltd. Examples include esterified products of polyols such as # 400, V # 36095D, V # 1000, V # 1080, and (meth) acrylic acid. Purple light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7630B, UV-7640B UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310EA, UV-3310B, UV-3500BA UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2250EA (manufactured by Nippon Synthetic Chemical Co., Ltd.), UA-306H, UA-306I, UA-306T, UL-503L (Kyoeisha Chemical Co., Ltd.), Unidic 17-806, 17-813, V-4030, V-4000BA (Dainippon Ink Chemical Co., Ltd.), EB-1290K, EB-220, EB -5129, EB-1830, EB-4858 (manufactured by Daicel UCB), A-TMMT, A-TMPT, U-4HA, U-6HA, U-10HA, U-15HA (Shin Nakamura Chemical Co., Ltd.) ), High Corp AU-2010, AU-2020 (manufactured by Tokushi Co., Ltd.), Aronix M-1960 (manufactured by Toagosei Co., Ltd.), Art Resin UN-3320HA, UN-3320HC, UN-3320HS, UN-904 Trifunctional or higher urethane acrylate compounds such as HDP-4T, Aronix M-8100, M-8030, M-9050 (Toagosei ( ) Made, like 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 functional groups, such as relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, Also included are oligomers or prepolymers such as polyfunctional compounds such as polyhydric alcohols.

Further, compounds described in JP-A-2005-76005 and JP-A-2005-36105, dendrimers such as SIRIUS-501 and SUBARU-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), JP-A-2005-60425 A norbornene ring-containing monomer as described in 1) can also be used.

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

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

The antireflection layer can further contain a compound other than the curable compound (a1) as a binder-forming compound.
From the viewpoint of ease of penetration into the pressure-sensitive adhesive layer described later, a compound having 2 or less polymerizable functional groups in one molecule may be used as the curable compound (a1). A compound having 3 or more polymerizable functional groups and a compound having 2 or less polymerizable functional groups in one molecule or a compound other than the curable compound (a1) does not have a polymerizable functional group It is preferable to use a compound in combination.
As a compound having 2 or less polymerizable functional groups in one molecule or a compound having no polymerizable functional group, the weight average molecular weight (Mwa) is 40 <Mwa <500, and the SP value (SPa by the Hoy method) ) Is preferably 19 <SPa <24.5 because it easily penetrates into the pressure-sensitive adhesive layer. Moreover, it is preferable that the compound which has 2 or less polymerizable functional groups in 1 molecule is a compound which has 1 polymerizable functional group in 1 molecule.
The SP value (solubility parameter) in the present invention is a value calculated by the Hoy method, and the Hoy method is described in POLYMERHANDBOOKFOURTEDITION.

Further, the compound having 2 or less polymerizable functional groups in one molecule or the compound having no polymerizable functional group preferably has a viscosity at 25 ° C. of 100 mPas or less, more preferably 1 to 50 mPas, 1 to 20 mPas is more preferable. A compound having such a viscosity range is preferable because it easily penetrates into the pressure-sensitive adhesive layer, functions to suppress aggregation of the particles (a2), and can suppress haze and cloudiness. In particular, it is possible to suppress aggregation of the particles (a2) by curing a part of the curable compound (a1) before laminating the pressure-sensitive adhesive layer, as will be described later. By using this, the adhesive layer can be sufficiently infiltrated with a compound having 2 or less polymerizable functional groups in one molecule or a compound not having a polymerizable functional group even in a state where curing has progressed. Is preferable. In particular, a viscosity in the range of 1 to 20 mPas is preferable because it has a large effect of preventing an increase in reflectance and a decrease in total light transmittance caused by the clogging of the binder between the particles.

A compound having 2 or less polymerizable functional groups in one molecule preferably has a (meth) acryloyl group, an epoxy group, an alkoxy group, a vinyl group, a styryl group, an allyl group, or the like as the polymerizable functional group.
As the compound having no polymerizable functional group, an ester compound, an amine compound, an ether compound, an aliphatic alcohol compound, a hydrocarbon compound, or the like can be preferably used, and an ester compound is particularly preferable. More specifically, dimethyl succinate (SP value 20.2, viscosity 2.6 mPas), diethyl succinate (SP value 19.7, viscosity 2.6 mPas), dimethyl adipate (SP value 19.7, viscosity 2) .8 mPas), dibutyl succinate (SP value 19.1, viscosity 3.9 mPas), bis (2-butoxyethyl) adipate (SP value 19.0, viscosity 10.8 mPas), dimethyl suberate (SP value 19. 4, viscosity 3.7 mPas), diethyl phthalate (SP value 22.3, viscosity 9.8 mPas), dibutyl phthalate (SP value 21.4, viscosity 13.7 mPas), triethyl citrate (SP value 22.5, Viscosity 22.6 mPas), acetyltriethyl citrate (SP value 21.1, viscosity 29.7 mPas), diphenyl ether (SP value 21.4, viscosity 3.8) Pas) and the like.

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

<Metal oxide particles>
The metal oxide particles are also referred to as “particles (a2)”.
Examples of the metal oxide particles include silica particles, titania particles, zirconia particles, 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. To silica particles are preferred.

The average primary particle diameter of the metal oxide particles is preferably from 100 nm to 190 nm, more preferably from 100 nm to 180 nm, and still more preferably from 100 nm to 170 nm. By being above the lower limit value, the effect of suppressing the reflection of visible light can be enhanced, and by being below the upper limit value, the average value X of the distances A between the adjacent convex portions of the concavo-convex shape can be easily reduced to 190 nm or less. Become.
As a metal oxide particle, only 1 type may be used and 2 or more types of particle | grains from which an average primary particle diameter differs may be used.

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

The metal oxide particles are preferably solid particles from the viewpoint of strength. The shape of the metal oxide particles is most preferably spherical, but there is no problem even if the shape is not spherical such as indefinite.
For example, by using irregular shaped particles in which some of the spherical metal oxide particles have become flat portions, and by setting the flat portions on the lower layer side, the movement of the particles is suppressed, and after curing from application to drying Particle aggregation in each of these steps can be prevented, the distance between the convex portions by the particles can be made uniform, and the transmittance in the short wavelength region can be improved.
As another example of the irregular shape, particles having a shape in which small particles are further bonded to a part of metal oxide particles can be used. The number of small particles bonded to the metal oxide particles may be plural, but one is more preferable. The particle size of the small particles bonded to a part of the metal oxide particles is preferably smaller than that of the metal oxide particles, more preferably 0.5 times or less than the particle size of the metal oxide particles. More preferably, it is 25 times or less. The density of the small particles bonded to a part of the metal oxide particles is preferably larger than that of the metal oxide particles, more preferably 2 times or more, and further preferably 3 times or more. The small particles are preferably metal oxides, such as zirconia, alumina, and titania. For example, any particles that satisfy the above density relationship can be used. For example, particles in which zirconia particles having a particle diameter of 40 nm are attached to silica particles having a particle diameter of 160 nm are preferable.
The silica particles may be either crystalline or amorphous.

As the metal oxide particles, it is preferable to use inorganic fine particles which have been surface-treated in order to improve dispersibility in a coating solution, improve film strength, and prevent aggregation. Specific examples of the surface treatment method and preferred examples thereof are the same as those described in [0119] to [0147] of JP-A-2007-298974.
In particular, from the viewpoint of imparting binding properties with the curable compound (a1) for forming the binder resin and improving the strength of the antireflection layer, the particle surface is made of a polymerizable unsaturated group (preferably an unsaturated double group). It is preferable to modify the surface with a compound having a bond and a functional group reactive with the particle surface to give a polymerizable unsaturated group (preferably an unsaturated double bond) to the particle surface. As the compound used for the surface modification, the silane coupling agent having a polymerizable functional group described above as the curable compound (a1) can be suitably used.
Specifically, commercially available KBM-503, KBM-5103 (all manufactured by Shin-Etsu Chemical Co., Ltd., X-12-1048, X-12-1049, X-12-1050 described in JP-A-2014-123091) It is preferable to modify the surface of the metal oxide particles with a silane coupling agent containing a (meth) acryloyl group.

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

As the metal oxide particles, fired silica particles are particularly preferable because of the reasonably high amount of hydroxyl groups on the surface and hard particles.
The calcined silica particles are manufactured by a known technique in which silica particles are obtained by hydrolyzing and condensing a hydrolyzable silicon compound in an organic solvent containing water and a catalyst, and then the silica particles are calcined. For example, Japanese Patent Application Laid-Open Nos. 2003-176121 and 2008-137854 can be referred to.
Although it does not specifically limit as a raw material silicon compound which manufactures a burning silica particle, Chlorosilanes, such as tetrachlorosilane, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylvinyldichlorosilane, trimethylchlorosilane, methyldiphenylchlorosilane Compound: Tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, 3-glycidoxypropyltrimethoxysilane, 3-chloro Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, Alkoxysilane compounds such as diphenyldimethoxysilane, diphenyldiethoxysilane, dimethoxydiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane; tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane Acyloxysilane compounds such as trimethylacetoxysilane; dimethylsilanediol, diphenylsilanediol, tri Silanol compounds such as chill silanol; and the like. Of the above-exemplified silane compounds, the alkoxysilane compound is particularly preferred because it is more easily available and the resulting fired silica particles do not contain halogen atoms as impurities. As a preferred form of the calcined silica particles, it is preferable that the content of halogen atoms is substantially 0% and no halogen atoms are detected.
The firing temperature is not particularly limited, but is preferably 800 to 1300 ° C, and more preferably 1000 to 1200 ° C.
Further, as an example of the method for 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 pulverization step to obtain irregular shaped particles in which a part of the sphere is flat. You can also.

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

Consistency of the moth-eye structure is uniform because it contains only one type of monodispersed silica fine particles having an average primary particle size of 100 to 190 nm and a CV (coefficient of variation) value of less than 5%. It is preferable because the reflectance is further lowered. The CV value is usually measured using a laser diffraction particle size measuring device, but other particle size measurement methods may be used, and the particle size distribution may be obtained and calculated by image analysis from the surface SEM image of the antireflection 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 to 190 nm and metal oxide particles having an average primary particle size of 1 nm to less than 70 nm. In this case, particles having a larger particle size mainly contribute to the moth-eye structure, and particles having a smaller particle size are mixed between large particles to suppress aggregation between the large particles. The haze may be improved. In addition, since metal oxide particles having a primary particle size of 1 nm or more and less than 70 nm are more immersed in the binder, the convex portion as the antireflection layer is formed by metal oxide fine particles having a primary particle size of 100 nm or more and 190 nm or less. Point to. The frequency of the number of metal oxide particles having an average primary particle size of 1 nm or more and less than 70 nm with respect to metal oxide fine 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. The metal oxide particles having an average primary particle size of 1 nm or more and 70 nm or less are preferably 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 hydroxyl group amounts on the surfaces of both particles close to each other because aggregation is less likely. However, since the metal oxide particles having an average primary particle size of 1 nm or more and less than 100 nm are mainly used for inhibiting the aggregation of metal oxide particles having an average primary particle size of 100 nm or more and 190 nm or less and separating them, they are available. Metal oxide particles having a hydroxyl group amount that is easily greater than 1.00 × 10 ⁻¹ or an indentation hardness of less than 400 MPa may be used.

The antireflection layer may contain components other than the binder resin and the metal oxide particles, and may contain, for example, a dispersant for the metal oxide particles, a leveling agent, an antifouling agent, and the like.

<Dispersant for metal oxide particles>
The metal oxide particle dispersant can facilitate uniform arrangement of the metal oxide particles by reducing the cohesive force between the particles. The dispersant is not particularly limited, but is preferably an anionic compound such as a sulfate or phosphate, a cationic compound such as an aliphatic amine salt or a quaternary ammonium salt, a nonionic compound or a polymer compound. And a steric repulsion group are more preferred because they have a high degree of freedom in selection. A commercial item can also be used as a dispersing agent. For example, BYK Japan made of (stock) DISPERBYK160, DISPERBYK161, DISPERBYK162, DISPERBYK163, DISPERBYK164, DISPERBYK166, DISPERBYK167, DISPERBYK171, DISPERBYK180, DISPERBYK182, DISPERBYK2000, DISPERBYK2001, DISPERBYK2164, Bykumen, BYK-2009, BYK-P104, BYK-P104S, BYK-220S, Anti-Terra 203, Anti-Terra 204, Anti-Terra 205 (trade name) and the like.

<Leveling agent>
By reducing the surface tension of the antireflection layer, the leveling agent can stabilize the liquid after coating and facilitate the uniform disposition of the curable compound (a1) and the metal oxide particles.
The composition for forming an antireflection layer used in the present invention can contain at least one leveling agent.
As a result, it is possible to suppress unevenness in film thickness due to variation in drying due to local distribution of drying air, to improve the repellency of the coated material, and to uniformly dispose the curable compound (a1) and the metal oxide particles. Can be made easier.

As the leveling agent, specifically, at least one leveling agent selected from a silicone leveling agent and a fluorine leveling agent can be used. In addition, it is preferable that a leveling agent is an oligomer or a polymer rather than a low molecular weight compound.

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

Preferred examples of the silicone leveling agent include polymers or oligomers containing 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 a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include groups containing a polyether group, an alkyl group, an aryl group, an aryloxy group, an aryl group, a cinnamoyl group, an oxetanyl group, a fluoroalkyl group, a polyoxyalkylene group, and the like.

The number average molecular weight of the silicone leveling agent is not particularly limited, but is preferably 100,000 or less, more preferably 50,000 or less, particularly preferably 1000 to 30000, and 1000 to 20000. Is most preferred.

Examples of preferable silicone leveling agents include X22-3710, X22-162C, X22-3701E, X22160AS, X22170DX, and X224015 manufactured by Shin-Etsu Chemical Co., Ltd. as commercially available silicone leveling agents having no ionizing radiation curing group. X22176DX, X22-176F, X224272, KF8001, X22-2000, etc .; Chisso Corporation FM4421, FM0425, FMDA26, FS1265, etc .; Toray Dow Corning Corporation BY16-750, BY16880, BY16848, SF8427, SF8421, SH3746, SH8400, SF3771, SH3749, SH3748, SH8410, etc .; TSF series manufactured by Momentive Performance Materials Japan (TSF4460, TSF4440, TSF4445, TSF4450, TSF4446, TSF4453, TSF4452, TSF4730, TSF4770, etc.), FGF502, SILWET series (SILWETL77, SILWETL2780, SILWETL7608, SILWETL7001, SILWETL7002, SILWETL7087, SILWETL7200, SILWETL7210, SILWETL7220, SILWETL7230, SILWETL7500, SILWETL7510, SILWETL7600, SILWETL7602, SILWETL7604, SILWETL7604, SILWETL7605, SILWETL7607, SILWETL7622, SILWETL7644, S LWETL7650, SILWETL7657, SILWETL8500, SILWETL8600, SILWETL8610, SILWETL8620, SILWETL720) is not limited thereto but can be exemplified.

X22-163A, X22-173DX, X22-163C, KF101, X22164A, X24-8201, X22174DX, X22164C, X222426, X222245, X222457, X222245, manufactured by Shin-Etsu Chemical Co., Ltd., as those having ionizing radiation curing groups , X221602, X221603, X22164E, X22164B, X22164C, X22164D, TM0701, etc .; Chisso Corporation Silaplane series (FM0725, FM0721, FM7725, FM7721, FM7726, FM7727, etc.); Toray Dow Corning S 84 SF8413, BY16-152D, BY16-152, BY16-152C, 8388A, etc .; Evonik Degussaja TEGORad 2010, 2011, 2100, 2200N, 2300, 2500, 2600, 2700, etc. manufactured by Co., Ltd .; BYK3500, manufactured by Big Chemie Japan Co., Ltd .; KNS5300, manufactured by Shin-Etsu Silicone Co., Ltd .; Examples thereof include, but are not limited to, UVHC1105 and UVHC8550.

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

The fluorine-based leveling agent includes a fluoroaliphatic group and a philic group that contributes to affinity for various compositions such as coatings and molding materials when the leveling agent is used as an additive. Such compounds are generally obtained by copolymerizing a monomer having a fluoroaliphatic group and a monomer having a philic group.
Typical examples of the monomer having an amphiphilic group copolymerized with a monomer having a fluoroaliphatic group include poly (oxyalkylene) acrylate and poly (oxyalkylene) methacrylate.

Preferable commercially available fluorine-based leveling agents include those having no ionizing radiation curable groups, Megafac series (MCF350-5, F472, F476, F445, F444, F443, F178, F470, F475, F479, manufactured by DIC Corporation. , F477, F482, F486, TF1025, F478, F178K, F-784-F, etc.) Neos, Inc., Futient series (FTX218, 250, 245M, 209F, 222F, 245F, 208G, 218G, 240G, 206D, 240D, etc.), and having an ionizing radiation curing group, OPTOOL DAC manufactured by Daikin Industries, Ltd .; Defenser series manufactured by DIC Corporation (TF3001, TF3000, TF3004, TF3028, TF3027, T 3026, TF3025, 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.

<Anti-fouling agent>
For the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties and the like, a known silicone-based or fluorine-based antifouling agent, slipping agent, and the like can be appropriately added to the antireflection layer. .

As specific examples of the silicone-based or fluorine-based antifouling agent, those having the ionizing radiation-curing group among the above-mentioned silicone-based or fluorine-based leveling agents can be preferably used, but are not limited thereto. is not.

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

[Hard coat layer]
The antireflection film of the present invention may have other layers between the plastic substrate and the antireflection layer. The other layer is preferably a hard coat layer.
As will be described later, the antireflection film of the present invention includes a quaternary ammonium salt-containing polymer in the hard coat layer, and a common logarithmic value (log SR) of the surface resistivity SR (Ω / sq) of the antireflection layer is 11 or less. In addition, the anti-reflection film satisfying X + σ ≦ 190 nm when the average value of the distance A between the vertices of adjacent convex portions is X and the standard deviation representing the distribution of A is σ. It is preferable that
The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a curable compound (preferably an ionizing radiation curable compound) which is a compound having a polymerizable group. That is, the hard coat layer preferably contains a cured product of a curable compound. For example, the hard coat layer is formed by applying a composition for forming a hard coat layer containing an ionizing radiation curable polyfunctional monomer or a polyfunctional oligomer on a plastic substrate, and crosslinking reaction of the polyfunctional monomer or polyfunctional oligomer, or It can be formed by a polymerization reaction.
The functional group (polymerizable group) of the ionizing radiation-curable polyfunctional monomer and polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

Specifically, the same compound as the above-described curable compound (a1) can be used as the curable compound for forming the hard coat layer.

In particular, when a thin plastic substrate having a thickness of 20 to 40 μm is used, an epoxy group is formed in the molecule as a curable compound for forming a hard coat layer from the viewpoint that curling and wrinkle generation can be suppressed. You may further use the compound which has this. There is no restriction | limiting in the molecular weight of the compound which has an epoxy group in a molecule | numerator, A monomer, an oligomer, or a polymer can be used suitably. Moreover, from the viewpoint of maintaining the surface hardness of the antireflection film, the compound having an epoxy group preferably further contains a polymerizable unsaturated group in the molecule. Examples of the compound having a polymerizable unsaturated group and an epoxy group in the molecule include Daicel Cyclomer M100, but are not limited thereto.

The compound having an epoxy group in the molecule is preferably contained in the hard coat layer in an amount of 12 to 45% by mass, and more preferably 15 to 35% by mass.

From the viewpoint of imparting sufficient durability and impact resistance to the film, the thickness of the hard coat layer is usually about 0.6 μm to 50 μm, preferably 4 μm to 20 μm.
Further, the strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, in a pencil hardness test. Furthermore, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

The hard coat layer is measured as a part where a cured product of ionizing radiation curable compound is detected when the antireflection film is cut with a microtome and the cross section is analyzed with a time-of-flight secondary ion mass spectrometer (TOF-SIMS). Similarly, the film thickness of this region can also be measured from the cross-sectional information of TOF-SIMS.
In addition, the hard coat layer detects another layer between the plastic substrate and the antireflection layer, for example, by cross-sectional observation using a reflection spectral film thickness meter or TEM (transmission electron microscope) using light interference. Can also be measured. As the reflection spectral film thickness meter, FE-3000 (manufactured by Otsuka Electronics Co., Ltd.) or the like can be used.
In this invention, it is preferable to perform a process (1) with respect to the hard-coat layer of a half-cure state. By making the hard coat layer in a half-cured state, it is possible to improve the adhesion between the hard coat layer and the antireflection layer and to form a bond between the hard coat layer and the metal oxide particles provided with unsaturated double bonds on the surface. An effect of suppressing aggregation of the metal oxide particles can be obtained.
For example, if the coating film is UV curable, it can be half cured by appropriately adjusting the oxygen concentration at the time of curing and the amount of UV irradiation. It is preferable to cure by irradiating an ultraviolet ray with an irradiation amount of 1 mJ / cm ² to 300 mJ / cm ^{2 with} an ultraviolet lamp. More preferably ^{5mJ / cm 2 ~ 100mJ / cm} 2, further preferably 10mJ / cm 2 ~ 70mJ / cm 2. At the time of irradiation, the above-mentioned energy may be applied at once, or irradiation may be performed in divided portions. As the ultraviolet lamp type, a metal halide lamp or a high-pressure mercury lamp is preferably used.

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

(solvent)
The composition for forming a hard coat layer preferably contains a solvent.
As a solvent, it is preferable from a viewpoint of the adhesiveness of a plastic base material and a hard-coat layer that the solvent which has the permeability | transmittance with respect to a plastic base material is included. The solvent having permeability to the plastic substrate is a solvent having a dissolving ability to the plastic substrate. Here, the solvent having the ability to dissolve the plastic substrate means that a plastic substrate having a size of 24 mm × 36 mm (thickness 80 μm) is put in a 15 ml bottle containing the above solvent and is 24 at room temperature (25 ° C.). It means a solvent in which the plastic base material completely dissolves and loses its shape by, for example, aging for a while and shaking the bottle as appropriate.
As a permeable solvent when a cellulose acylate film is used as a plastic substrate, methyl ethyl ketone (MEK), dimethyl carbonate, methyl acetate, acetone, methylene chloride, and the like are preferable, and methyl ethyl ketone (MEK), dimethyl carbonate, and methyl acetate are more preferable. Although it can use preferably, it is not limited to these.
The hard coat layer forming composition may contain a solvent other than the osmotic solvent (for example, ethanol, methanol, 1-butanol, isopropanol (IPA), methyl isobutyl ketone (MIBK), toluene, etc.).
In the composition for forming a hard coat layer, the content of the osmotic solvent is preferably 50% by mass or more and 100% by mass or less based on the mass of the total solvent contained in the composition for forming the hard coat layer. More preferably, it is at least 100% by mass.
When the composition for forming a hard coat layer contains a quaternary ammonium salt-containing polymer, it is preferable to contain a hydrophilic solvent as a solvent from the viewpoint of compatibility with the quaternary ammonium salt-containing polymer. As the hydrophilic solvent, lower alcohols such as methanol, ethanol, isopropanol (IPA) and butanol are preferable.
The solid content concentration of the composition for forming a hard coat layer is preferably 20% by mass or more and 70% by mass or less, and more preferably 30% by mass or more and 60% by mass or less.

(Other ingredients)
In addition to the above components, a polymerization initiator, an antistatic agent, an antiglare agent, and the like can be appropriately added to the hard coat layer forming composition. Furthermore, various additives, such as a reactive or non-reactive leveling agent and various sensitizers, may be mixed.

(Polymerization initiator)
If necessary, radicals and cationic polymerization initiators may be appropriately selected and used. These polymerization initiators are decomposed by light irradiation and / or heating to generate radicals or cations to advance radical polymerization and cationic polymerization.
As a polymerization initiator, the thing similar to the polymerization initiator which the composition (A) for forming the layer (a) of the antireflection layer mentioned later may contain is mentioned.
In particular, when the composition for forming a hard coat layer contains a quaternary ammonium salt-containing polymer, it is preferable to use a phosphine oxide polymerization initiator as the polymerization initiator. Since the phosphine oxide polymerization initiator has a photobleaching effect, even if the surface of the hard coat layer is in a half-cured state, the internal curing rate is higher than when other initiators are used, leading to the antireflection layer. Of the quaternary ammonium salt-containing polymer can be suppressed.

(Phosphine oxide polymerization initiator)
As the phosphine oxide-based polymerization initiator, those having an n-π * transition upon light absorption and having a photobleaching effect are preferable. Specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-Trimethylbenzoyl) -phenylphosphine oxide is preferred.
Preferable examples of commercially available phosphine oxide polymerization initiators include Irgacure 819 and DAROCUR TPO manufactured by BASF.
The phosphine oxide polymerization initiator used in the present invention may be one type or two or more types.

(Antistatic agent)
As a specific example of the antistatic agent, a conventionally known antistatic agent such as a quaternary ammonium salt, a conductive polymer, or conductive fine particles can be used. Although not particularly limited, it is inexpensive and easy to handle. Therefore, an antistatic agent having a quaternary ammonium salt is preferable, and a quaternary ammonium salt-containing polymer is more preferable.
When the hard coat layer contains a quaternary ammonium salt-containing polymer, when the quaternary ammonium salt-containing polymer is mixed with the antireflection layer, the metal oxide particles and the quaternary ammonium salt-containing polymer interact to aggregate the metal oxide particles. Since it may accelerate, it is preferable that the quaternary ammonium salt-containing polymer is unevenly distributed on the substrate side of the hard coat layer. A method of unevenly distributing a quaternary ammonium salt-containing polymer is not limited, but a method of forming a hard coat layer by laminating a hard coat layer containing a quaternary ammonium salt-containing polymer and a hard coat layer not containing a quaternary ammonium salt-containing polymer Or a method using phase separation.
The method using phase separation is a hydrophilic and high-boiling solvent (preferably a solvent having a boiling point at 101325 Pa of 80 ° C. or higher, more preferably 90 ° C. or higher and 140 ° C. or lower, and examples thereof include isopropanol and butanol. )) Or by drying at low temperature, the quaternary ammonium salt-containing polymer is unevenly distributed inside the hard coat layer while avoiding the hydrophobic air interface. When the base material is cellulose acylate, the base material is hydrophilic, and therefore, it tends to be unevenly distributed inside the hard coat layer. Further, the uneven distribution also proceeds in the hard coat layer when used in combination with a hydrophobic material. The hydrophobic material preferably has an SP value (SPb) of 19 ≦ SPb ≦ 21, and is preferably a curable compound having a polymerizable unsaturated group from the viewpoint of hardness. Specific examples include DPCA-20 (SPb = 20.6), DPCA-30 (SPb = 20.6), DPCA-60 (SPb = 20.5) manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Chemical Co., Ltd. A-TMMT (SPb = 20.0), A-TMPT (SPb = 20.0), etc. manufactured by the same company may be mentioned.

As the antireflection film of the present invention,
The metal oxide particles used are metal oxide particles provided with a polymerizable unsaturated group on the particle surface,
A hard coat layer formed by curing a composition for forming a hard coat layer containing a curable compound having a polymerizable unsaturated group;
It is preferable that a bond is formed between the metal oxide particles and the hard coat layer.

(Quaternary ammonium salt-containing polymer)
The quaternary ammonium salt-containing polymer can be appropriately selected from known compounds and used, but from the viewpoint of solubility in the coating solution, the following general formulas (I), (II) to (III) Polymers having at least one unit of the structural unit represented are preferred.

In general formula (I), R ₁ represents a hydrogen atom, an alkyl group, a halogen atom, or —CH ₂ COO ⁻ M ⁺ . Y represents a hydrogen atom or —COO ⁻ M ⁺ . M ⁺ represents a proton or a cation. L represents —CONH—, —COO—, —CO— or —O—. J represents an alkylene group or an arylene group. Q represents a group selected from the following group A.

In the formula, R ₂ , R ₂ ′ and R ₂ ″ each independently represents an alkyl group. J represents an alkylene group or an arylene group. X ⁻ represents an anion. p and q each independently represents 0 or 1.

In the general formulas (II) and (III), R ₃ , R ₄ , R ₅ and R ₆ each independently represent an alkyl group, and R ₃ and R ₄ and R ₅ and R ₆ are bonded to each other. A nitrogen-containing heterocycle may be formed.
A, B and D are each independently an alkylene group, an arylene group, an alkenylene group, an arylene alkylene group, —R ₇ COR ₈ —, —R ₉ COOR ₁₀ OCOR ₁₁ —, —R ₁₂ OCR ₁₃ COOR ₁₄ —, — R ₁₅ — (OR ₁₆ ) _m —, —R ₁₇ CONHR ₁₈ NHCOR ₁₉ —, —R ₂₀ OCONHR ₂₁ NHCOR ₂₂ — or —R ₂₃ NHCONHR ₂₄ NHCONHR ₂₅ — is represented. E represents a single bond, an alkylene group, an arylene group, an alkenylene group, an arylene alkylene group, —R ₇ COR ₈ —, —R ₉ COOR ₁₀ OCOR ₁₁ —, —R ₁₂ OCR ₁₃ COOR ₁₄ —, —R ₁₅ — (OR ₁₆ _{_{_{_{) m -, - R 17 CONHR}}}} 18 NHCOR 19 -, - R 20 OCONHR 21 NHCOR 22 - or _-R 23 NHCONHR ₂₄ NHCONHR ₂₅ - or an _-NHCOR 26 CONH-. R ₇ , R ₈ , R ₉ , R ₁₁ , R ₁₂ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₉ , R ₂₀ , R ₂₂ , R ₂₃ , R ₂₅ and R ₂₆ represent an alkylene group. R ₁₀ , R ₁₃ , R ₁₈ , R ₂₁ and R ₂₄ each independently represent a linking group selected from an alkylene group, an alkenylene group, an arylene group, an arylene alkylene group and an alkylene arylene group. m represents a positive integer of 1 to 4. X ⁻ represents an anion.
Z ₁ and Z ₂ represent a non-metallic atomic group necessary for forming a 5-membered or 6-membered ring together with —N═C— group, and are represented by E in the form of a quaternary salt of ≡N ⁺ [X ⁻ ] —. You may connect.
n represents an integer of 5 to 300.

The groups of the general formulas (I) to (III) will be described.
Examples of the halogen atom include a chlorine atom and a bromine atom, and a chlorine atom is preferable.
The alkyl group is preferably a branched or straight chain alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, or a propyl group.
The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably a methylene group, an ethylene group or a propylene group, and particularly preferably an ethylene group.
The arylene group is preferably an arylene group having 6 to 15 carbon atoms, more preferably phenylene, diphenylene, phenylmethylene group, phenyldimethylene group, or naphthylene group, and particularly preferably phenylmethylene group. These groups have a substituent. It may be.
The alkenylene group is preferably an alkylene group having 2 to 10 carbon atoms, and the arylene alkylene group is preferably an arylene alkylene group having 6 to 12 carbon atoms. These groups may have a substituent.
Examples of the substituent that may be substituted for each group include a methyl group, an ethyl group, and a propyl group.

In general formula (I), R ₁ is preferably a hydrogen atom.
Y is preferably a hydrogen atom.
J is preferably a phenylmethylene group.
Q is preferably the following general formula (VI) selected from group A, and R ₂ , R ₂ ′ and R ₂ ″ are each a methyl group.
X ⁻ includes a halogen ion, a sulfonate anion, a carboxylate anion and the like, preferably a halogen ion, and more preferably a chlorine ion.
p and q are preferably 0 or 1, more preferably p = 0 and q = 1.

In general formulas (II) and (III), R ₃ , R ₄ , R ₅ and R ₆ are preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. A methyl group is particularly preferred.
A, B and D are preferably each independently a substituted or unsubstituted alkylene group, arylene group, alkenylene group or arylene alkylene group having 2 to 10 carbon atoms, preferably a phenyldimethylene group.
X ⁻ includes a halogen ion, a sulfonate anion, a carboxylate anion and the like, preferably a halogen ion, and more preferably a chlorine ion.
E is preferably E represents a single bond, an alkylene group, an arylene group, an alkenylene group or an arylene alkylene group.
Examples of the 5-membered or 6-membered ring formed by Z ₁ and Z ₂ together with the —N═C— group include a diazoniabicyclooctane ring.

Specific examples of compounds having units having structures represented by the general formulas (I) to (III) are shown below, but the present invention is not limited thereto. Of the subscripts (m, x, y, r and actual numerical values) in the following specific examples, m represents the number of repeating units of each unit, and x, y, r represents the molar ratio of each unit. .

The compounds exemplified above may be used alone, or two or more compounds may be used in combination.

(Refractive index modifier)
For the purpose of controlling the refractive index of the hard coat layer, a high refractive index monomer or inorganic particles can be added as a refractive index adjusting agent. In addition to the effect of controlling the refractive index, the inorganic particles also have the effect of suppressing cure shrinkage due to the crosslinking reaction. In the present invention, after the hard coat layer is formed, a polymer formed by polymerizing the polyfunctional monomer and / or the high refractive index monomer and the like and inorganic particles dispersed therein are referred to as a binder.

(Leveling agent)
As a specific example of the leveling agent, a conventionally known leveling agent such as fluorine-based or silicone-based can be used. The composition for forming a hard coat layer to which a leveling agent is added can impart coating stability to the coating film surface during coating or drying.

The antireflection film of the present invention can be used for various applications, and for example, can be suitably used as a polarizing plate protective film.
A 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 is a polarizing plate having a polarizer and at least one protective film for protecting the polarizer, and at least one of the protective films is preferably the antireflection film of the present invention.

Examples of the polarizer include an iodine-based polarizer, a dye-based polarizer using a dichroic dye, and a polyene-based polarizer. In general, iodine-based polarizers and dye-based polarizers can be produced using polyvinyl alcohol-based films.

[Anti-reflective article]
The antireflection article of the present invention is an article having the antireflection film of the present invention on the surface. For example, the antireflection film of the present invention can be applied to a cover glass to provide a cover glass having an antireflection function (an example of an antireflection article).

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

[module]
The module of the present invention is a module in which two antireflection films of the present invention are provided, and the two antireflection films are installed facing each other through an air gap (air layer).
In the module of the present invention, the two antireflection films are preferably modules in which the antireflection layer is disposed on the air gap side with respect to the plastic substrate.
FIG. 2 shows a schematic cross-sectional view of an example of the module of the present invention. The module 20 shown in FIG. 2 includes the

antireflection films

10 a and 10 b of the present invention, and two antireflection films are installed to face each other through the air gap 11. Further, the antireflection layer of each of the two

antireflection films

10a and 10b is disposed closer to the air gap 11 than the plastic substrate.
The module of the present invention can be used for various applications, for example, a liquid crystal display device with a touch panel.

[LCD device with touch panel]
The liquid crystal display device with a touch panel of the present invention includes the module of the present invention,
One of the two antireflection films has a touch panel on the side opposite to the antireflection layer side of the plastic substrate of the antireflection film,
It is a liquid crystal display device with a touch panel which has a liquid crystal cell on the opposite side to the antireflection layer side of the plastic substrate of the other antireflection film.
In FIG. 2, the cross-sectional schematic diagram of an example of the liquid crystal display device with a touchscreen of this invention is shown. The liquid crystal display device 30 with a touch panel in FIG. 2 includes the module 20 of the present invention, and the touch panel 12 on the side opposite to the antireflection layer side of the plastic substrate of one of the two antireflection films 10a. And the liquid crystal cell 13 is provided on the side opposite to the antireflection layer side of the plastic substrate of the other antireflection film 10b. The antireflection film 10b also serves as a protective film for the polarizer 15. Another protective film 14 is provided on the opposite side of the polarizer 15 from the antireflection film 10b. The laminate of the antireflection film 10b, the polarizer 15, and the protective film 14 is also the polarizing plate of the present invention.
The liquid crystal display device 30 with a touch panel of the present invention can reduce reflection of external light incident from the side opposite to the interface on the antireflection film 10a side of the touch panel 12 by the antireflection film 10a and the antireflection film 10b. Further, the antireflection film 10a and the antireflection film 10b of the reflection of the present invention have a total light transmittance of 88% or more when incident from the side opposite to the plastic substrate of the antireflection layer, and the antireflection layer When the transmittance of light having a wavelength of 480 nm and 580 nm when incident from the side opposite to the plastic substrate is T ₄₈₀ and T ₅₈₀ , respectively, T ₅₈₀ −T ₄₈₀ ≦ 3.5% is satisfied, so that the backlight (not shown) Can be easily transmitted through the entire visible light region, and the color change of the display image can be suppressed.
In addition, there is no restriction | limiting in particular about the touch panel which can be used, a liquid crystal cell, a protective film, and a polarizer, You may use any well-known thing.
For example, various types of touch panels such as a resistive film type, a capacitance type, an optical type, and an ultrasonic type can be used as the touch panel.

[Method for producing antireflection film]
The production method of the antireflection film of the present invention is as follows:
On the plastic substrate, a curable compound and metal oxide particles having an average primary particle size of 100 nm or more and 190 nm or less are provided at a thickness at which the metal oxide particles are embedded in the layer (a) containing the curable compound. Step (1),
A step of bonding the layer (b) of the pressure-sensitive adhesive film having the support and the layer (b) containing a pressure-sensitive adhesive having a gel fraction of 95.0% or more on the support (2). ,
The metal oxide particles are embedded in a layer combining the layer (a) and the layer (b), and protrude from the interface on the side opposite to the interface on the plastic substrate side of the layer (a). Step (3) of moving the position of the interface between the layer (a) and the layer (b) to the plastic substrate side,
A step (4) of curing the layer (a) in a state where the metal oxide particles are buried in a layer formed by combining the layer (a) and the layer (b);
Step (5) of peeling the layer (b) from the layer (a);
In this order.

By the above production method, the above-described antireflection film of the present invention can be produced.
In the above production method, the above-mentioned curable compound (a1) is preferably used as the curable compound, and the above-mentioned metal oxide particles are preferably used.
The layer (a) cured in the step (4) corresponds to the above-described binder resin film, and the layer including the layer (a) and the metal oxide particles protruding from the layer (a) is an antireflection layer. It is.

An example of a preferred embodiment of the method for producing an antireflection film of the present invention is shown in FIG.
(1) in FIG. 3 shows that in step (1), the average primary particle size is 100 nm or more in the layer (a) (reference numeral 4 in FIG. 3) containing the curable compound (a1) on the plastic substrate 1. A state in which a metal oxide particle of 190 nm or less (also referred to as “particle (a2)”) (reference numeral 3 in FIG. 3) is provided so as to be buried is schematically shown.

(2) of FIG. 3 is 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 the step (2) (reference numeral 6 in FIG. 3). A state in which the layer (b) of the pressure-sensitive adhesive film 7 having the above is bonded to the layer (a) (reference numeral 4 in FIG. 3) is schematically shown.

(3) in FIG. 3 shows that in the step (3), the particles (a2) are buried in the layer including the layer (a) and the layer (b), and the interface on the substrate side of the layer (a) The state which moved the position of the interface of a layer (a) and a layer (b) to the plastic base material side so that it may protrude from the interface on the opposite side is shown typically. As will be described later, as a method of moving the position of the interface between the layer (a) and the layer (b) to the plastic substrate side, the layer (b) containing a part of the curable compound (a1) containing an adhesive. The method of making it penetrate | infiltrate is mentioned.
To move the position of the interface between the layer (a) and the layer (b) toward the plastic substrate means to bring the position of the interface closer to the plastic substrate.

(4) in FIG. 3 schematically shows that the layer (a) is cured in the state where the particles (a2) are embedded in the layer (a) and the layer (b) combined in the step (4). It expresses.

(5) of FIG. 3 represents the state (antireflection film 10) after peeling the adhesive film 7 in the process (5) which peels the adhesive film 7 containing the layer (b) from the layer (a). .

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

[Step (1)]
In step (1), a curable compound and metal oxide particles having an average primary particle size of 100 nm to 190 nm are embedded on a plastic substrate, and the metal oxide particles are embedded in a layer (a) containing the curable compound. It is the process of providing with the thickness to do.
In the present invention, the “thickness in which the metal oxide particles are buried in the layer (a)” represents a thickness of 0.8 times or more the average primary particle diameter of the metal oxide particles.

In step (1), the method for providing the layer (a) on the plastic substrate is not particularly limited, but it is preferable to provide the layer (a) by applying it on the plastic substrate. In this case, the layer (a) is a layer formed by applying a composition (A) containing a curable compound (a1) and particles (a2). A coating method is not particularly limited, and a known method can be used. Examples include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and die coating.

In step (1), it is preferable that a plurality of particles (a2) do not exist in a direction perpendicular to the surface of the plastic substrate. Here, the fact that a plurality of particles (a2) do not exist in the direction perpendicular to the surface of the plastic substrate means that 10 μm × 10 μm in the plane of the plastic substrate is observed with three fields of view with a scanning electron microscope (SEM). The ratio of the number of particles (a2) that do not overlap in the direction perpendicular to the surface is 80% or more, preferably 95% or more.

In the present invention, another layer may be provided on the plastic substrate before the step (1). When another layer is provided on the plastic substrate, in step (1), the layer (a) is provided on this other layer, and the subsequent steps are performed. The other layer is preferably a hard coat layer.

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

The plastic substrate, the curable compound (a1), and the particles (a2) are the same as those described above.

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

<Polymerization initiator>
The layer (a) or the composition (A) for forming the layer (a) may contain a polymerization initiator.
The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator. An appropriate polymerization initiator may be selected according to the type of polymerizable compound used in combination. As the polymerization initiator, either a thermal polymerization initiator or a photopolymerization initiator may be selected according to the type of polymerization treatment (heating, light irradiation) performed in the production process. Moreover, you may use together 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 azo compounds, hydroxylamine ester compounds, organic peroxides, hydrogen peroxide, and the like. Specific examples of the organic peroxide include those described in Japanese Patent No. 5341155, paragraph 0031.

The azo compound may contain at least one azo bond, and may contain various substituents together with the azo bond. Specifically, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylisobutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1- Azonitrile compounds such as [(1-cyano-1-methylethyl) azo] formamide,

dimethyl

2,2′-azobis (2-methylpropionate),

dimethyl

1,1′-azobis (1-cyclohexanecarboxylate), etc. 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis Azoamide compounds such as (N-cyclohexyl-2-methylpropionamide), 2,2′-azobis [2- [1- (2-hydroxyethyl)- -Imidazolin-2-yl] propane] dihydroxychloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] and the like, 2,2′-azobis (2,4,4 -It is also possible to use an azoalkyl compound such as trimethylpentane, an azoamidine compound, or a polymer containing a repeating unit having an azo bond, which is a preferred thermal polymerization initiator because redox decomposition and induced decomposition are unlikely to occur. is there.

Further, examples of the hydroxylamine ester compound include a hydroxylamine ester compound represented by the formula I described in JP-A-2012-521573. Specific compounds are shown below. However, it is not limited to these.

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

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

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

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

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

<Heat acid generator>
Examples of the thermal acid generator include salts composed of an acid and an organic base.
Examples of the acid include organic acids such as sulfonic acid, phosphonic acid, and carboxylic acid, and inorganic acids such as sulfuric acid and phosphoric acid. From the viewpoint of compatibility with the curable compound (a1), organic acids are more preferable, sulfonic acids and phosphonic acids are more preferable, and sulfonic acids are most preferable. Preferred sulfonic acids include p-toluenesulfonic acid (PTS), benzenesulfonic acid (BS), p-dodecylbenzenesulfonic acid (DBS), p-chlorobenzenesulfonic acid (CBS), 1,4-naphthalenedisulfonic acid (NDS). ), Methanesulfonic acid (MsOH), nonafluorobutane-1-sulfonic acid (NFBS), and the like.

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

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

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

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

[Step (2)]
Step (2) is a step of bonding a layer (b) of an 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 and the layer (a). It is. The method for laminating the layer (a) and the layer (b) of the adhesive film is not particularly limited, and a known method can be used, for example, a laminating method.
The adhesive film is preferably bonded so that the layer (a) and the layer (b) are in contact with each other.
You may have the process of drying a layer (a) before a process (2). The drying temperature of the layer (a) is preferably 20 to 60 ° C, more preferably 20 to 40 ° C. The drying time is preferably from 0.1 to 120 seconds, more preferably from 1 to 30 seconds.
The inventors bonded 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 particles (a2) were changed into the layer (a) and the layer (b). In the step (4) to be described later, the particles (a2) are buried in the layers (a) and ( b) curing the layer (a) in a state where it is embedded in the combined layer, so that the particles (a2) are not exposed to the air interface before the layer (a) is cured, thereby suppressing aggregation. It has been found that a good uneven shape formed by (a2) can be produced.

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

<Layer (b)>
The layer (b) is made of an adhesive having a gel fraction of 95.0% or more.
When the gel fraction of the pressure-sensitive adhesive is 95.0% or more, the pressure-sensitive adhesive component hardly remains on the surface of the anti-reflective film when peeling off the pressure-sensitive adhesive film to produce an anti-reflective film. An antireflection film having a sufficiently low reflectance can be obtained.
The gel fraction of the pressure-sensitive adhesive is preferably 95.0% or more and 99.9% or less, more preferably 97.0% or more and 99.9% or less, and 98.0% or more and 99.9%. More preferably, it is as follows.
The gel fraction of the pressure-sensitive adhesive is a ratio of insoluble matter after the pressure-sensitive adhesive is immersed in tetrahydrofuran (THF) at 25 ° C. for 12 hours, and is obtained from the following formula.
Gel fraction = (mass of insoluble matter in adhesive in THF) / (total mass of adhesive) × 100 (%)

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

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

The layer (b) is a pressure-sensitive adhesive layer having a slight adhesive strength with a peel strength (adhesive strength) of about 0.03 to 0.3 N / 25 mm with respect to the surface of the adherend at a peel rate of 0.3 m / min. It is preferable that it is excellent in operability when the adhesive film is peeled off from the layer (a) as the adherend.

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

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

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

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

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

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

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

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

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

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

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

The pressure-sensitive adhesive may include a cured product of a composition for forming the pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive composition).
The pressure-sensitive adhesive composition preferably contains the polymer and a cross-linking agent, and may be cross-linked using heat, ultraviolet light (UV) or the like. As the crosslinking agent, one or more kinds of crosslinking agents selected from the group consisting of a bifunctional or higher functional isocyanate crosslinking agent, a bifunctional or higher epoxy crosslinking agent, and an aluminum chelate crosslinking agent are preferable. When using a crosslinking agent, when peeling an adhesive film and manufacturing an antireflection film, from a viewpoint of making an adhesive component hard to remain on the surface of an antireflection film, it is 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 bifunctional or higher isocyanate compound may be a polyisocyanate compound having at least two isocyanate (NCO) groups in one molecule, such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diene. Burette modified products of diisocyanates such as isocyanate (compounds having two NCO groups in one molecule) and trivalent or higher polyols such as isocyanurate modified products, trimethylolpropane or glycerin (at least 3 in one molecule) And adduct bodies (polyol-modified bodies) with the above-mentioned compounds having an OH group.
Further, the trifunctional or higher functional isocyanate compound is a polyisocyanate compound having at least three isocyanate (NCO) groups in one molecule, in particular, an isocyanurate body of a hexamethylene diisocyanate compound, an isocyanurate body of an isophorone diisocyanate compound, At least one selected from the group consisting of adducts of hexamethylene diisocyanate compounds, adducts of isophorone diisocyanate compounds, burettes of hexamethylene diisocyanate compounds, and burettes of isophorone diisocyanate compounds is preferred.
The bifunctional or higher functional isocyanate-based crosslinking agent is preferably contained in an amount of 0.01 to 5.0 parts by mass, more preferably 0.02 to 3.0 parts by mass with respect to 100 parts by mass of the polymer.

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

Examples of the antistatic agent that is a quaternary onium salt include alkyldimethylbenzylammonium salts having an alkyl group having 8 to 18 carbon atoms, dialkylmethylbenzylammonium salts having an alkyl group having 8 to 18 carbon atoms, and 8 to 8 carbon atoms. Trialkylbenzylammonium salt having 18 alkyl groups, tetraalkylammonium salt having an alkyl group having 8 to 18 carbon atoms, alkyldimethylbenzylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, alkyl having 8 to 18 carbon atoms Having a dialkylmethylbenzylphosphonium salt having a group, a trialkylbenzylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, a tetraalkylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, and an alkyl group having 14 to 20 carbon atoms Alkyl trimethyl Ammonium salts, alkyl dimethyl ethyl ammonium salt having an alkyl group having 14 to 20 carbon atoms can be used. These alkyl groups may be alkenyl groups having an unsaturated bond.

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, octadecyl group and the like. 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, and linoleyl group. .
Examples of the alkyl group having 14 to 20 carbon atoms include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group. It may be a mixed alkyl group derived from natural fats and oils. Examples of the alkenyl group having 14 to 20 carbon atoms include a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, an oleyl group, a linoleyl group, a nonadecenyl group, and an icosenyl group.

Counter anions of quaternary onium salts include chloride (Cl ⁻ ), bromide (Br ⁻ ), methyl sulfate (CH ₃ OSO ₃ ⁻ ), ethyl sulfate (C ₂ H ₅ OSO ₃ ⁻ ), paratoluenesulfonate (p— CH ₃ C ₆ H ₄ SO ₃ ⁻ ) and the like.

Specific examples of the quaternary onium salt include dodecyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium bromide, tetradecyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium bromide, hexadecyldimethylbenzylammonium chloride, hexadecyldimethylbenzylammonium bromide, Octadecyldimethylbenzylammonium chloride, octadecyldimethylbenzylammonium bromide, trioctylbenzylammonium chloride, trioctylbenzylammonium bromide, trioctylbenzylphosphonium chloride, trioctylbenzylphosphonium bromide, tris (decyl) benzylammonium chloride, tris (decyl) benzyla Monium bromide, tris (decyl) benzylphosphonium chloride, tris (decyl) benzylphosphonium bromide, tetraoctylammonium chloride, tetraoctylammonium bromide, tetraoctylphosphonium chloride, tetraoctylphosphonium bromide, tetranonylammonium chloride, tetranonylammonium bromide, tetra Nonylphosphonium chloride, tetranonylphosphonium 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 having 3 or 4 decyl groups, which are alkyl groups having 10 carbon atoms, and a tridecyl group, which is an alkyl group having 13 carbon atoms, And a tetradecyl group which is an alkyl group having 14 carbon atoms.

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

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

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

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

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

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

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

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

The metal chelate compound is a compound in which one or more multidentate ligands L are bonded to the 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 the general formula of a metal chelate compound having one metal atom M is represented by M (L) _m (X) _n , m ≧ 1 and n ≧ 0. When m is 2 or more, the m Ls may be the same ligand or different ligands. When n is 2 or more, the n Xs may be the same ligand or different ligands.

Examples of the metal atom M include Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, and Sn. Examples of the multidentate ligand L include methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, acetylacetone (also known as 2,4-pentanedione), 2 Β-diketones such as 1,4-hexanedione and benzoylacetone. These are ketoenol tautomeric compounds, and the polydentate ligand L may be an enolate (for example, acetylacetonate) in which enol is deprotonated.

The monodentate ligand X includes halogen atoms such as chlorine atom and bromine atom, acyloxy such as pentanoyl group, hexanoyl group, 2-ethylhexanoyl group, octanoyl group, nonanoyl group, decanoyl group, dodecanoyl group and octadecanoyl group. Group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, butoxy group and other alkoxy groups.

Specific examples of the metal chelate compound include tris (2,4-pentandionato) iron (III), iron trisacetylacetonate, titanium trisacetylacetonate, ruthenium trisacetylacetonate, zinc bisacetylacetonate, aluminum tris Acetylacetonate, zirconium tetrakisacetylacetonate, tris (2,4-hexanedionato) iron (III), bis (2,4-hexanedionato) zinc, tris (2,4-hexanedionato) titanium, tris (2,4-hexanedionato) aluminum, tetrakis (2,4-hexanedionato) zirconium and the like.

Examples of the organic tin compound include dialkyl tin oxide, fatty acid salt of dialkyl tin, fatty acid salt of stannous and the like. Long chain alkyl tin compounds such as dioctyl tin compounds are preferred. Specific examples of the organic tin compound include dioctyl tin oxide and dioctyl tin dilaurate.

The 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 the support, a plastic film made of a resin having transparency and flexibility is preferably used. The plastic film for the support is preferably a polyester film such as polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, polybutylene terephthalate, (meth) acrylic resin, polycarbonate resin, polystyrene resin, polyolefin resin. Examples thereof include films made of a resin, a cyclic polyolefin resin, a cellulose resin such as cellulose acylate, and the like. However, the (meth) acrylic resin includes a polymer having a lactone ring structure, a polymer having a glutaric anhydride ring structure, and a polymer having a glutarimide ring structure.
In addition, other plastic films can be used as long as they have necessary strength and optical suitability. The support may be an unstretched film, may be uniaxially or biaxially stretched, and may be a plastic film in which the stretching ratio or the angle of the axial method formed with crystallization of stretching is controlled.

As the support, those having ultraviolet transparency are preferable. By having ultraviolet transparency, when layer (a) is cured in step (4), it becomes possible to irradiate ultraviolet rays from the coating layer side, which is preferable in terms of production suitability.
Specifically, the maximum transmittance of the support at a wavelength of 250 nm to 300 nm is preferably 20% or more, more preferably 40% or more, and most preferably 60% or more. It is preferable that the maximum transmittance at a wavelength of 250 nm to 300 nm is 20% or more because the layer (a) is easily cured by irradiating ultraviolet rays from the coating layer side.
Further, the maximum transmittance at a wavelength of 250 nm to 300 nm of the pressure-sensitive adhesive film having the layer (b) formed on the support is preferably 20% or more, more preferably 40% or more, and 60% or more. Is most preferred.

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

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

In the present invention, in step (4), the layer (a) is cured while maintaining the state in which the particles (a2) are buried in the combined layer (a) and layer (b). It is preferable to have a concavo-convex shape formed by the particles (a2) protruding from the interface of the layer (a) in the previous stage. In this way, after the layer (a) is cured in the step (4) and then the layer (b) is peeled off in the step (5), the antireflection in a state where the particles (a2) protrude from the surface of the layer (a) A film can be obtained.

In the present invention, a part of the curable compound (a1) in the layer (a) is cured between the steps (1) and (2) to obtain a cured compound (a1c) (1-2) May be included.
Curing a part of the curable compound (a1) means that only a part of the curable compound (a1) is cured, not the whole. By curing only a part of the curable compound (a1) in the step (1-2), in the step (3), the particle (a2) is the interface on the side opposite to the interface on the plastic substrate side of the layer (a). Can prevent particle aggregation when the position of the interface between the layer (a) and the layer (b) is lowered to the plastic substrate side so as to protrude from the surface, and antireflection with good reflectance and total light transmittance It is preferable to carry out since a film is obtained. Since the optimal curing conditions in the step (1-2) vary depending on the formulation of the layer (a), the optimal curing conditions may be selected as appropriate.

[Step (3)]
In the step (3), the particles (a2) are embedded in the layer including the layer (a) and the layer (b), and the interface on the side opposite to the interface on the plastic substrate side of the layer (a) is used. In this step, the position of the interface between the layer (a) and the layer (b) is moved toward the plastic substrate so as to protrude.
In the present invention, “the particle (a2) is buried in the layer including the layer (a) and the layer (b)” means that the thickness of the layer including the layer (a) and the layer (b) is the particle. The average primary particle size of (a2) is 0.8 times or more.
The step (3) is preferably performed by allowing a part of the curable compound (a1) to penetrate into the pressure-sensitive adhesive layer.
In the step (3), when a part of the curable compound (a1) is allowed to permeate the pressure-sensitive adhesive layer, the laminate having the plastic substrate, the layer (a), and the layer (b) can be kept at 60 ° C. or lower. It is preferable to keep the temperature at 40 ° C. or lower. By keeping the temperature at 60 ° C. or lower, the viscosity of the curable compound (a1) and the pressure-sensitive adhesive can be kept high and the thermal motion of the particles can be suppressed, so that the antireflection ability is reduced due to aggregation of the particles. The effect of preventing haze and an increase in cloudiness is great. The lower limit of the temperature at which the laminate having the plastic substrate, the layer (a), and the layer (b) is maintained is not particularly limited, and may be room temperature (25 ° C.) or lower than room temperature. Good.

[Step (4)]
Step (4) is a step of curing the layer (a) in a state where the particles (a2) are buried in the layer including the layer (a) and the layer (b).
In the present invention, “the state in which the particle (a2) is embedded in the layer including the layer (a) and the layer (b)” means that the thickness of the layer including the layer (a) and the layer (b) is the particle ( It shall represent that it is 0.8 times or more of the average primary particle diameter of a2).
Curing the layer (a) represents polymerizing the curable compound (a1) contained in the layer (a), whereby the binder resin in the antireflection layer of the antireflection film can be formed. By maintaining the state in which the particles (a2) are embedded in the layer (a) and the layer (b) combined in the step (4), the aggregation of the particles (a2) is suppressed and a favorable uneven shape is formed. can do.
As a mechanism in which particle aggregation is suppressed by maintaining the state in which the particle (a2) is embedded in the layer (a) and the layer (b), the particle (a2) is cured before the layer (a) is cured. ) Is exposed to the air interface, it is known that a large attractive force derived from surface tension called lateral capillary force works, and the particles (a2) are buried in the layer combining the layers (a) and (b). It is presumed that the attractive force can be reduced by letting it be kept.

Curing can be performed by irradiating with ionizing radiation. There is no restriction | limiting in particular about the kind of ionizing radiation, Although an X-ray, an electron beam, an ultraviolet-ray, visible light, infrared rays etc. are mentioned, an ultraviolet-ray is used widely. For example, if the coating film is ultraviolet curable, it is preferable to cure the curable compound (a1) of the layer (a) by irradiating with an ultraviolet lamp with an irradiation amount of 10 mJ / cm ² to 1000 mJ / cm ² . More preferably, it is 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 above-mentioned energy may be applied at once, or irradiation may be performed in divided portions. As the ultraviolet lamp type, a metal halide lamp or a high-pressure mercury lamp is preferably used.

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

In the steps (2) to (4), it is preferable that a plurality of particles (a2) do not exist in a direction perpendicular to the surface of the plastic substrate.

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

[Step (5)]
Step (5) is a step of peeling layer (b) from layer (a).
If the pressure-sensitive adhesive remains on the layer (a) side when the layer (b) is peeled off, the plastic substrate and the cured layer (a) are not dissolved, and are washed with a solvent that dissolves the pressure-sensitive adhesive. May be.

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

The present invention will be described more specifically with reference to the following examples. The amounts, ratios and operations of materials, reagents, and substances shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

<Example 1>
(Preparation of composition for forming hard coat layer)
Each component was mixed with the composition described below, and the resulting composition was put into a mixing tank, stirred, and filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a hard coat layer coating solution HC-1.

(Hard coat layer coating solution HC-1)
A-TMMT 24.4 parts by weight AD-TMP 12.0 parts by weight Irgacure 127 1.6 parts by weight AS-1 2.0 parts by weight Ethanol 3.5 parts by weight Methanol 8.8 parts by weight 1-butanol 6.0 parts by weight Methyl ethyl ketone (MEK) 20.3 parts by mass Methyl acetate 21.4 parts by mass FP-1 0.05 parts by mass

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

AS-1: Compound AS-1 corresponding to (A-6) in the above-mentioned patent document was similarly obtained except that the reaction temperature and time in Synthesis Example 6 of Japanese Patent No. 4678451 were 70 ° C. and 6 hours. Produced. The completed compound AS-1 was a quaternary ammonium salt-containing polymer having an ethylene oxide chain, and the weight average molecular weight measured by GPC was about 60,000.
FP-1: Methyl ethyl ketone solution of a fluorine-containing compound represented by the following formula, solid content concentration is 40% by mass

[Synthesis of Silica Particle P1]
A 200 L reactor equipped with a stirrer, a dropping device and a thermometer was charged with 67.54 kg of methyl alcohol and 26.33 kg of 28% by mass aqueous ammonia (water and catalyst), and the liquid temperature was kept at 33 ° C. while stirring. Adjusted. Meanwhile, a dropping device was charged with a solution prepared by dissolving 12.70 kg of tetramethoxysilane in 5.59 kg of methyl alcohol. While maintaining the liquid temperature in the reactor at 33 ° C., the above solution was dropped from the dropping device over 37 minutes, and after completion of the dropping, stirring was continued for 37 minutes while maintaining the liquid temperature at the above temperature. Hydrolysis and condensation of methoxysilane was performed to obtain a dispersion containing a silica particle precursor. Silica particles were obtained by air-drying this dispersion under the conditions of a heating tube temperature of 175 ° C. and a reduced pressure of 200 torr (27 kPa) using an instantaneous vacuum evaporator (Crox System CVX-8B type manufactured by Hosokawa Micron Corporation). P1 was obtained.
Silica particles P1 had an average primary particle size of 170 nm, a particle size dispersity (CV value) of 7.0%, and an indentation hardness of 340 MPa.

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

[Production of Silane Coupling Agent-treated Silica Particles P3]
5 kg of the fired silica particles P2 were charged into a 20 L Henschel mixer (FM20J type, manufactured by Mitsui Mining Co., Ltd.) equipped with a heating jacket. While the calcined silica particles P2 were being stirred, a solution prepared by dissolving 50 g of 3-acryloxypropyltrimethoxysilane (KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) in 90 g of methyl alcohol was added dropwise and mixed. Then, it heated up to 150 degreeC over about 1 hour, mixing and stirring, and hold | maintained at 150 degreeC for 12 hours, and heat-processed. In the heat treatment, scrapes on the wall surface were scraped while the scraping device was always rotated in the direction opposite to the stirring blade. Moreover, the wall deposits were also scraped off using a spatula as appropriate. After heating, the mixture was cooled, and pulverization and classification were performed using a jet pulverization classifier to obtain silane coupling agent-treated silica particles P3.
The average primary particle diameter of the silane coupling agent-treated silica particles P3 was 171 nm, the dispersion degree (CV value) of the particle diameter was 7.0%, and the indentation hardness was 470 MPa.

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

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

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

Composition (A-1)
U-15HA 1.4 parts by weight Compound C3 1.5 parts by weight Acetyltriethyl citrate 5.8 parts by weight Irgacure 127 0.2 parts by weight Compound P 0.1 parts by weight Silica particle dispersion PA-1 32.3 parts by weight 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 acetyltriethyl citrate are binder compounds, but U-15HA and compound C3 are curable compounds (a1), and acetyltriethyl citrate is a compound having no polymerizable functional group. .
The compounds used are shown below.
U-15HA (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)
Acetyltriethyl citrate: manufactured by Tokyo Chemical Industry Co., Ltd.

<Creation of antireflection film 1>
(Formation of hard coat layer)
The hard coat layer coating solution HC-1 was coated on a plastic substrate (TJ25, manufactured by Fuji Film Co., Ltd.) using a die coater. After drying at 30 ° C. for 90 seconds and then at 45 ° C. for 1 minute, a 160 W / cm air-cooled metal halide lamp (I Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere has an oxygen concentration of approximately 0.3% by volume. The coating layer was cured by irradiating with ultraviolet rays having an illuminance of 200 mW / cm ² and an irradiation amount of 10 mJ / cm ² to form a hard coat layer having a thickness of 5 μm. The base material with a hard coat layer is HC-1.

(Process (1) Coating of layer (a))
On the hard coat layer of the substrate HC-1 with the hard coat layer, 2.8 ml / m ² of the composition (A-1) was applied using a die coater and dried at 30 ° C. for 90 seconds. The film thickness of the layer (a) in the step (1) is 190 nm.

(Step (1-2) Step of curing a part of the curable compound (a1) in the layer (a) to obtain a cured compound (a1c))
Using a high pressure mercury lamp (Model: 33351N, manufactured by Dr. Honle AG, part number: LAMP-HOZ 200 D24 U 450 E) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.5% by volume (a ) Was irradiated with light at an irradiation amount of 5.0 mJ to cure a part of the curable compound (a1). The irradiation amount was measured by attaching a HEAD SENSER PD-365 to an eye ultraviolet integrated illuminometer UV METER UVPF-A1 manufactured by Eye Graphic Co., Ltd. and measuring range 0.00.

(Process (2) Adhesion of adhesive film)
Subsequently, the pressure-sensitive adhesive film obtained by peeling the release film from AS3-304 was bonded onto the dried layer (a) so that the pressure-sensitive adhesive layer (layer (b)) was on the layer (a) side. . Lamination was performed using a commercial laminator Bio330 (manufactured by DAE-EL Co.) at a speed of 1.
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 obtained by peeling the release film from the laminate. The body is an adhesive film.

The detail of the used laminated body (protective film) is shown below.
AS3-304 Fujimori Industry Co., Ltd. Support: Polyester film (thickness 38 μm)
Adhesive layer thickness: 20 μm
Maximum transmittance at a wavelength of 250 nm to 300 nm with the release film peeled off: less than 0.1% The transmittance was measured using an UV-visible near-infrared spectrophotometer UV3150 manufactured by Shimadzu Corporation.

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

(Step (4) Curing of layer (a))
Following the above-described standing, a plastic base material is used using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the atmosphere has an oxygen concentration of 0.01% by volume or less. The layer (a) was cured by irradiating ultraviolet rays having an illuminance of 200 mW / cm ² and an irradiation amount of 300 mJ / cm ² through the adhesive film from the surface on which the layer (a) was applied. The film thicknesses of the layer (a) and the pressure-sensitive adhesive layer (layer (b)) after the step (4) and before the step (5) were 50 nm and 20 μm, respectively.

(Process (5) Peeling of adhesive film)
The pressure-sensitive adhesive film containing the layer (b) (those obtained by peeling off the release film from AS3-304) was peeled from the produced laminate. The layer (a) after peeling off the layer (b) was cured to such an extent that it was not broken by peeling of the pressure-sensitive adhesive layer. After peeling off the pressure-sensitive adhesive, the layer of the plastic substrate is used using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 0.01 vol% or less. The layer (a) was cured by irradiating ultraviolet rays having an illuminance of 200 mW / cm ² and an irradiation amount of 300 mJ / cm ² from the surface coated with (a). Thereafter, methyl isobutyl ketone was poured over the surface to which the adhesive film had been bonded to wash away the residue of the adhesive layer, followed by drying at 25 ° C. for 10 minutes to obtain an antireflection film 1.

<Comparative Example 1>
An antireflection film R1 was obtained in the same manner as in Example 1 except that the standing in the step (3) was 15 minutes at 120 ° C.

(Integral reflectance)
In the obtained antireflection film, the back side of the film (plastic substrate side) is roughened with sandpaper, and then oil-based black ink (filling magic ink: Teranishi Kagaku) is applied to eliminate the backside reflection. The adapter ARV-474 is attached to a photometer V-550 (manufactured by JASCO Corporation), the integrated reflectance at an incident angle of 5 ° is measured in the wavelength region of 380 to 780 nm, and the average reflectance is calculated. Antireflection properties were evaluated.

(Transmittance)
The total light transmittance of the antireflection film when incident from the side opposite to the plastic substrate of the antireflection layer, and the wavelength of 480 nm of the antireflection film when incident from the side opposite to the plastic substrate of the antireflection layer The light transmittance (T ₄₈₀ ) and the light transmittance at 580 nm (T ₅₈₀ ) were measured.
The measurement of the total light transmittance was performed using a Nippon Denshoku Industries Co., Ltd. haze meter NDH4000.
The transmittance of light with a wavelength of 480 nm (T ₄₈₀ ) and the transmittance of light with a wavelength of 580 nm (T ₅₈₀ ) were measured using an ultraviolet-visible near-infrared spectrophotometer UV3150 manufactured by Shimadzu Corporation.

(LogSR)
The surface resistivity of the antireflection layer was measured using an Agilent 4339B High-Resistance meter (manufactured by Agilent Technologies) after placing the antireflection film sample at 25 ° C. and 60% relative humidity for 2 hours. Logarithm (log SR).

(X, X + σ, particle occupancy)
The surface of the antireflection film was observed with an SEM (S-4300, manufactured by Hitachi High-Technologies Corporation), and the particle occupation ratio was determined as the area occupied by the particles / measured area. The magnification was 10,000 times. Further, a cross section was taken by cutting with a microtome, SEM observation was performed at a magnification of 10000, and the distance A between the vertices of adjacent convex portions was measured at 100 points, and an average value X and a standard deviation σ were obtained.

<Examples 2 to 6>
In the same manner as in Example 1, except that the hard coat layer coating solution HC-1 was replaced with the hard coat layer coating solutions HC-2 to HC-6 having the compositions shown in Table 1 below, antireflection films 2 to 6 was created.

<Example 7>
On the hard coat layer of Example 2, a hard coat layer having a thickness of 0.8 μm was further laminated using the hard coat layer coating solution HC-7 having the composition shown in Table 1 below. The drying and curing conditions of the hard coat layer coating solution HC-7 were the same as those of the hard coat layer coating solution HC-1 of Example 1.

DPCA60: Nippon Kayaku Co., Ltd. DPCA-60
irg127: Irgacure 127, photopolymerization initiator (manufactured by BASF Japan Ltd.)
irg819: Irgacure 819, phosphine oxide photopolymerization initiator (manufactured by BASF Japan Ltd.)

[Synthesis of Silica Particle P4]
While maintaining the liquid temperature in the reactor at 33 ° C., the dropping time of the solution from the dropping device is changed to 25 minutes, and after the dropping is completed, the stirring time is changed to 25 minutes while maintaining the liquid temperature at the same temperature. Except that, silica particles P4 were obtained in the same manner as silica particles P1.
Silica particles P4 had an average primary particle size of 150 nm, a particle size dispersity (CV value) of 11.0%, and an indentation hardness of 340 MPa.

[Synthesis of Silica Particle P5]
While maintaining the liquid temperature in the reactor at 33 ° C., the dropping time of the solution from the dropping device was changed to 60 minutes, and after the dropping was completed, the stirring time was changed to 60 minutes while maintaining the liquid temperature at the same temperature. Except that, silica particles P5 were obtained in the same manner as silica particles P1.
Silica particles P5 had an average primary particle size of 205 nm, a particle size dispersity (CV value) of 3.0%, and an indentation hardness of 340 MPa.

[Preparation of calcined silica particles P6]
Fired silica particles P6 were obtained in the same manner as the fired silica particles P2, except that the silica particles P4 were used instead of the silica particles P1.

[Preparation of calcined silica particles P7]
Fired silica particles P7 were obtained in the same manner as the fired silica particles P2, except that the silica particles P5 were used instead of the silica particles P1.

[Production of Silane Coupling Agent-treated Silica Particles P8]
The silane coupling agent-treated silica particles P3 except that the fired silica particles P6 were used instead of the fired silica particles P2 and the amount of 3-acryloxypropyltrimethoxysilane (KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 65 g. In the same manner as above, silane coupling agent-treated silica particles P8 were obtained.
Silane coupling agent-treated silica particles P8 had an average primary particle size of 151 nm, a particle size dispersity (CV value) of 11.0%, and an indentation hardness of 470 MPa.

[Production of Silane Coupling Agent-treated Silica Particles P9]
The silane coupling agent-treated silica particles P3 except that the calcined silica particles P7 were used instead of the calcined silica particles P2, and the amount of 3-acryloxypropyltrimethoxysilane (KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 25 g. In the same manner as above, silane coupling agent-treated silica particles P9 were obtained.
The average primary particle diameter of the silane coupling agent-treated silica particles P9 was 206 nm, the degree of dispersion (CV value) of the particle diameter was 3.0%, and the indentation hardness was 470 MPa.

[Preparation of Silica Particle Dispersion PA-2]
A silica particle dispersion PA-2 (solid content concentration of 20) was prepared in the same manner as the silica particle dispersion PA-1, except that the silane coupling agent treated silica particles P8 were used instead of the silane coupling agent treated silica particles P3. Mass%).

[Preparation of Silica Particle Dispersion PA-3]
A silica particle dispersion PA-3 (solid content concentration of 20) was prepared in the same manner as the silica particle dispersion PA-1, except that the silane coupling agent treated silica particles P9 were used instead of the silane coupling agent treated silica particles P3. Mass%).

<Example 8>
The silica particle dispersion PA-1 of the layer (a) forming composition (A-1) was changed to a silica particle dispersion PA-2 (this layer (a) forming composition is referred to as the composition (A-2)). The antireflection film 8 was prepared in the same manner as in Example 1 except that.

<Example 9>
The acetyltriethyl citrate of the layer (a) forming composition (A-2) was changed to dimethyl suberate (manufactured by Tokyo Chemical Industry Co., Ltd.) (this layer (a) forming composition was changed to the composition (A-3). Then, an antireflection film 9 was prepared in the same manner as in Example 8 except that the irradiation amount in step (1-2) was 7.5 mJ.

<Example 10>
The acetyl triethyl citrate of the layer (a) forming composition (A-2) was changed to dibutyl succinate (manufactured by Tokyo Chemical Industry Co., Ltd.) (this layer (a) forming composition was changed to the composition (A-4) Then, an antireflection film 10 was produced in the same manner as in Example 8 except that the irradiation amount in the step (1-2) was 10 mJ.

<Example 11>
Example 9 except that the composition for forming the layer (a) is changed to (A-5) having the following composition, and heating is performed at 140 ° C. for 15 minutes between the steps (4) and (5). Similarly, an antireflection film 11 was prepared.

Composition (A-5)
U-15HA 1.4 parts by weight Compound C3 1.5 parts by weight Dimethyl suberate 4.1 parts by weight A-TMPT 1.7 parts by weight Irgacure 127 0.2 parts by weight V-601 0.2 parts by weight Compound P-2 0.1 part by mass Silica particle dispersion PA-2 32.3 parts by mass Compound B 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

The compounds used are described below.
A-TMPT: Multifunctional acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
V-601: thermal polymerization initiator,

dimethyl

2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
Compound P-2: Compound having the following structure (manufactured by Wako Pure Chemical Industries, Ltd.)

Compound B has a weight average molecular weight of 17,000.

<Example 12>
The silica particle dispersion PA-1 of the layer (a) forming composition (A-1) was changed to a silica particle dispersion PA-3 (this layer (a) forming composition is referred to as the composition (A-6)). The antireflection film 12 was prepared in the same manner as in Example 1 except that.

Evaluation results are shown in Table 2 below.

The particle occupancy rate of Example 1 was 47.6%.

The antireflection films of Examples 1 to 12 have good antireflection performance, high total light transmittance, and small T ₅₈₀ -T ₄₈₀ , that is, high transmittance of light in the short wavelength region of visible light. It was a film. On the other hand, the antireflection film of Comparative Example 1 had a larger T ₅₈₀ -T ₄₈₀ than the antireflection film of Example 1, and was a film having a low light transmittance in the short wavelength region of visible light.
Since the antireflection films of Examples 1 to 12 have a high transmittance of light in the short wavelength region of visible light, a color change or the like hardly occurs. In particular, it is considered that the occurrence of color change can be suppressed even when two antireflection films are used in a liquid crystal display device with a touch panel.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application consists of a Japanese patent application filed on August 15, 2016 (Japanese Patent Application No. 2016-159295), a Japanese patent application filed on February 16, 2017 (Japanese Patent Application 2017-27380), and an application filed on March 31, 2017. The Japanese patent application (Japanese Patent Application No. 2017-72565) is incorporated herein by reference.

DESCRIPTION OF SYMBOLS 1 Plastic base material 2 Antireflection layer 3 Metal oxide particle (particle (a2))
4 Binder resin (layer (a))
5 support 6 layers (b)
DESCRIPTION OF SYMBOLS 7

Adhesive film

10, 10a, 10b Antireflection film 11 Air gap 12 Touch panel 13 Liquid crystal cell 14 Protective film 15 Polarizer 20 Module 30 Liquid crystal display device with a touch panel A Distance between vertices of adjacent convex parts B The distance between the center and the recess between the UV and UV

Claims

An antireflection film having a plastic substrate and an antireflection layer,
The antireflection layer includes metal oxide particles and a binder resin,
The antireflection layer has a moth-eye structure having an uneven shape formed by the metal oxide particles,
The total light transmittance of the antireflection film when entering from the side opposite to the plastic substrate of the antireflection layer is 88% or more, and
T 580 −T 480 ≦ 3.3, where T 480 and T 580 represent the transmittance of light of wavelengths 480 nm and 580 nm, respectively, when the antireflection layer is incident from the side opposite to the plastic substrate. Antireflection film satisfying 5%.
2. The antireflection film according to claim 1, wherein the uneven shape of the antireflection layer satisfies X ≦ 190 nm, where X is an average value of distances A between apexes of adjacent convex portions.
The concavo-convex shape of the antireflection layer is an antireflection film according to claim 2, wherein X + σ ≦ 190 nm is satisfied, where σ is a standard deviation representing the distribution of A.
The antireflection film according to any one of claims 1 to 3, wherein an average primary particle size of the metal oxide particles is 100 nm or more and 190 nm or less.
5. The binder resin according to claim 1, wherein the binder resin includes a compound having 2 or less polymerizable functional groups or a compound having no polymerizable functional group in one molecule having a viscosity of 1 to 20 mPas at 25 ° C. 2. The antireflection film according to item 1.
The antireflection film according to any one of claims 1 to 5, further comprising a hard coat layer between the plastic substrate and the antireflection layer.
The hard coat layer contains a quaternary ammonium salt-containing polymer,
When the surface resistivity of the antireflection layer is SR in the unit Ω / sq, the common logarithm value of SR is 11 or less, and the uneven shape of the antireflection layer is between the vertices of adjacent protrusions. The antireflection film according to claim 6, wherein X is an average value of the distance A and σ is a standard deviation representing the distribution of A, and satisfies X + σ ≦ 190 nm.
An antireflection article having the antireflection film according to any one of claims 1 to 7 on its surface.
A polarizing plate comprising a polarizer and at least one protective film protecting the polarizer, wherein at least one of the protective films is the antireflection film according to any one of claims 1 to 7. A polarizing plate.
An image display device comprising the antireflection film according to any one of claims 1 to 7 or the polarizing plate according to claim 9.
A module having two antireflection films according to any one of claims 1 to 7, wherein the two antireflection films are disposed to face each other through an air gap.
The module according to claim 11, wherein the two antireflection films have the antireflection layer disposed on the air gap side with respect to the plastic base material.
A module according to claim 12,
One of the two antireflection films has a touch panel on the side opposite to the antireflection layer side of the plastic substrate of the antireflection film,
A display device with a touch panel, having a liquid crystal cell on the side opposite to the antireflection layer side of the plastic substrate of the other antireflection film.
On the plastic substrate, a curable compound and metal oxide particles having an average primary particle size of 100 nm or more and 190 nm or less are provided in such a thickness that the metal oxide particles are buried in the layer (a) containing the curable compound. Step (1),
A step of bonding the layer (b) of the 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 (2). ,
The metal oxide particles are embedded in a layer combining the layer (a) and the layer (b), and project from an interface on the side opposite to the interface on the plastic substrate side of the layer (a). Step (3) of moving the position of the interface between the layer (a) and the layer (b) to the plastic substrate side,
A step (4) of curing the layer (a) in a state in which the metal oxide particles are buried in a combined layer of the layer (a) and the layer (b);
Step (5) of peeling the layer (b) from the layer (a);
In this order, and the temperature at which the steps (1) to (4) are performed is 60 ° C. or less.