JP2018072807A - Glare and reflection preventing film and image display device having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glare and reflection preventing film which can increase the visibility that a person actually feels in a display screen and attains an excellent resistance to abrasion by suppressing a luminous reflectance.SOLUTION: A glare-preventing hard-coat layer, a high refractive-index layer, and a low refractive-index layer are deposited in this order on a transparent base material film. The index of refraction of the glare-preventing hard-coat layer (nAG) is in the region of 1.49 to 1.65, the index of refraction of the low refractive-index layer is in the range of 1.29 to 1.37, and the film thickness is in the range of 0.06 to 0.12 μm. In that case, when the index of refraction of the high refractive index layer is nH and the film thickness is dH, the following conditions (1) and (2) are satisfied: 0.03≤nH-nAG≤0.20 (1); 0.12 μm≤dH≤0.30 μm (2). As a result, the luminous reflectance Rof the film is 1.0% or lower.SELECTED DRAWING: None

Description

  The present invention includes an antiglare antireflection film for an image display device, which is used by being attached to the outermost surface on the image display side, such as a liquid crystal display, an organic EL display, a touch panel display, and a car navigation system, and the like. The present invention relates to an image display device.

  Conventionally, various image display devices such as a liquid crystal display, a touch panel display, and a car navigation system have a drawback that light from the outside is reflected on a screen (display) and it is difficult to see a display image. For this reason, an antiglare film is disposed on the display surface in order to diffuse light from the outside. Particularly in recent years, the display resolution has been increasing. In connection with this, the necessity to prevent reflection of external light more than the conventional anti-glare film has increased.

  As such an antiglare antireflection film for an image display device, for example, Patent Document 1 is disclosed. In Patent Document 1, for the purpose of improving the black density of an image, suppressing the haze value, and improving the visibility of the image, an antiglare hard coat layer, a high refractive index layer, a low refractive index layer are provided on the transparent substrate film. In the antiglare antireflection film in which the refractive index layers are laminated in this order, the antiglare hard coat layer is made of an active energy ray-curable resin, a photopolymerization initiator, and a translucency having an average particle size of 6 μm or more and less than 30 μm. It is formed by a composition for forming an antiglare hard coat layer containing organic fine particles. In addition, the refractive index n1 of the cured product of the active energy ray-curable resin and the refractive index n2 of the translucent organic fine particles satisfy the relationship of 0 ≦ | n1−n2 | <0.020, and the antiglare hard coat layer The ratio a / A of the average particle diameter (a) of the translucent organic fine particles to the film thickness (A) is set to 0.2 to 1.0. Further, in the variable light intensity at which the light incident on the antiglare antireflection film at an incident angle of 45 ° is reflected on the surface, the reflected light intensity at the reflection angle of 45 ° is R (45 °), and the reflected light intensity at the reflection angle of 53 °. Is R (53 °), the value of R (53 °) / R (45 °) is 0 or more and less than 0.04, and the minimum reflectance of the integrating sphere for surface reflection is 0 to 1.8%. ing.

  In addition, finger input is possible because of the development of a display capable of touch panel input operations. Since it is possible to perform finger input in this way, in recent years, the need to increase the scratch resistance of the display surface has been increasing.

JP 2010-78698 A

  As described above, in order to improve image visibility, particularly color reproducibility including black density, it is necessary to reduce the reflectance in the display. Therefore, in Patent Document 1, good image visibility is achieved by disposing an antiglare antireflection film on the display surface to reduce the reflectance. However, the reflectance here is based on the “integral sphere minimum reflectance”. In this case, even if the minimum reflectance of the integrating sphere is low, if the minimum reflectance wavelength is greatly deviated from human visual sensitivity, the human eye may end up feeling dazzling reflected light. Therefore, when the “integral sphere minimum reflectance” is used as a reference, there is a possibility that the image visibility that a person actually feels does not necessarily match.

On the other hand, as a reference for the reflectance, there is also a “luminous reflectance” calculated by weighting the human visibility to the reflectance. This corresponds to a quantitative value that directly represents the intensity of reflected light that humans feel. Therefore, in order to reliably improve the image visibility actually felt by humans, it is necessary to design based on the luminous reflectance (R _SCI ). In Patent Document 1, attention is not paid to luminous reflectance.

  Further, although this type of antiglare antireflection film is also required to have scratch resistance, Patent Document 1 does not pay attention to the scratch resistance.

  Accordingly, an object of the present invention is to provide an antiglare antireflection film that can reliably improve the visibility of images actually felt by humans by suppressing the luminous reflectance, and also has good scratch resistance. It is providing an image display apparatus provided with.

For this purpose, the present invention adopts the following means.
[1] An antiglare hard coat layer, a high refractive index layer, and a low refractive index layer are laminated in this order on a transparent substrate film,
The refractive index (nAG) of the antiglare hard coat layer is 1.49 to 1.65,
The low refractive index layer has a refractive index of 1.29 to 1.37, a film thickness of 0.06 to 0.12 μm,
An antiglare antireflection film that satisfies the following conditions (1) and (2), where nH is a refractive index of the high refractive index layer and dH is a film thickness.
0.03 ≦ nH−nAG ≦ 0.20 (1)
0.12 μm ≦ dH ≦ 0.30 μm (2)
[2] The antiglare antireflection film according to [1], wherein the luminous reflectance R _SCI is 1.0% or less.
[3] An image display device comprising the antiglare antireflection film according to [1] or [2] on the outermost surface on the display side of the display.

The luminous reflectance R _SCI is the reflectance of the Y value (tristimulus value) of the XYZ color system, and is a reflectance measured according to JIS Z 8701. In the present invention or specification, “XX to XX” indicating a numerical range means “XX or more and XX or less” unless otherwise specified.

In this invention, it has anti-glare property and the antireflection effect is acquired by the intensity | strength of reflected light being reduced. Further, the luminous reflectance R _SCI is 1.0% or less, and the visibility of the image is improved. In particular, the luminous reflectance corresponds to a quantitative value that directly expresses the intensity of reflected light felt by humans, so that the image visibility actually felt by humans can be reliably improved.

  The antiglare antireflection film of the present invention (hereinafter also simply referred to as an antiglare film) is an antiglare hard coat layer, a high refractive index layer, and a low refractive index layer on a transparent substrate film (one side). Are laminated in this order from the transparent substrate film side. This anti-glare film is disposed on the outermost surface on the side of displaying an image on the display in the image display device. Examples of the image display device include a high-definition liquid crystal display, a touch panel display, an organic EL display, or a car navigation system.

[Transparent substrate film]
The material for forming the transparent substrate film is not particularly limited as long as it has good transparency and excellent light transmittance, and known materials conventionally used in this type of film can be used. For example, derivatives such as triacetyl cellulose (TAC), diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose, polyethylene terephthalate (PET), cycloolefin polymer (COP), cycloolefin copolymer (COC), polycarbonate A single-layer or double-layer sheet made of (PC), polymethyl methacrylate (PMMA) or the like can be used. Among these, triacetyl cellulose (TAC) is preferable because it has no optical anisotropy and good light transmittance.

  The thickness of the transparent substrate is usually 10 to 500 μm. If this thickness is too thin, the handleability of the antiglare film tends to deteriorate and the strength tends to decrease. On the other hand, if the thickness is too large, the film becomes unnecessarily thick and the handleability of the antiglare film is also deteriorated.

[Anti-glare hard coat layer]
The antiglare hard coat layer has the required strength and hardness as a hard coat layer, and has irregularities on the surface thereof. Anti-glare property is exhibited by external light being reflected and diffused on the surface irregularities (surface diffusibility). The antiglare hard coat layer is formed by curing an antiglare hard coat layer composition containing at least an active energy ray-curable resin, a photopolymerization initiator, and translucent organic fine particles.

The refractive index (nAG) of the antiglare hard coat layer is 1.49 to 1.65, preferably 1.52 to 1.60. If the refractive index of the antiglare hard coat layer is greater than 1.49 less than or 1.65, luminous reflectance R _SCI antiglare film may exceed 1.0, the image display visibility is reduced . The film thickness of the antiglare hard coat layer is usually set to 10 to 30 μm, preferably 15 to 25 μm.

(Active energy ray-curable resin)
The active energy ray curable resin is a base component of the antiglare hard coat layer composition, and includes a monofunctional monomer, a polyfunctional monomer, an oligomer having a vinyl group or a (meth) acryloyl group, a vinyl group, 1 type (s) or 2 or more types can be used from the polymer which has a (meth) acryloyl group. In particular, urethane (meth) acrylate is preferable in that a cured film having characteristics of a urethane resin such as flexibility and rubber elasticity, good followability to a transparent base film, and excellent flexibility is obtained. The (meth) acryloyl group means an acryloyl group or a methacryloyl group. (Meth) acrylate means acrylate or methacrylate.

  Examples of the urethane (meth) acrylate include monofunctional urethane (meth) acrylate, bifunctional urethane (meth) acrylate, and trifunctional urethane (meth) acrylate. Among these, bifunctional urethane (meth) acrylate or trifunctional urethane (meth) acrylate is preferable, and trifunctional urethane (meth) acrylate having a (meth) acryloyl group at the terminal is more preferable.

(Photopolymerization initiator)
The photopolymerization initiator is used for initiating polymerization by irradiating an active energy ray-curable resin with active energy rays such as ultraviolet rays. As the photopolymerization initiator, one or more of benzophenones, acetophenones, α-amyloxime ester, Michler benzoyl benzoate, tetramethylchuram monosulfide, thioxanthones and the like can be used. Specifically, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy-1,2-diphenylethane-1 -One, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, α-amyloxime ester, mihilaben Examples include zoylbenzoate and tetramethylchuram monosulfide.

  The content of the photopolymerization initiator is a total of 100 parts by mass of the active energy ray-curable resin and the photopolymerization initiator (in the case of containing metal oxide fine particles described later, the active energy ray-curable resin and the photopolymerization initiator). 0.1 to 20 parts by mass is preferable, and 1 to 10 parts by mass is more preferable. If the content of the photopolymerization initiator is too small, curing of the antiglare hard coat layer is insufficient, and if it is excessive, it is unnecessarily large and wasted.

(Translucent organic fine particles)
The translucent organic fine particles are contained in order to positively form a light diffusion function in the antiglare hard coat layer, that is, surface irregularities. As the translucent organic fine particles, styrene-acrylic copolymer resin, (meth) acrylic resin (refractive index 1.49), vinyl chloride resin (refractive index 1.54), polystyrene resin (refractive index 1.59), polyethylene One or more resin fine particles selected from resin (refractive index 1.53), melamine resin (refractive index 1.57 to 1.60), polycarbonate resin (refractive index 1.59) and the like can be used. Among these, a (meth) acrylic resin or a styrene-acrylic copolymer resin is preferable because the refractive index can be easily adjusted. Styrene-acrylic copolymer resin is more preferable in that the refractive index can be arbitrarily adjusted by changing the copolymer composition of both monomers.

  The difference (n1-n2) between the refractive index n1 of the cured product of the active energy ray-curable resin and the refractive index n2 of the translucent organic fine particles preferably satisfies 0 ≦ | n1-n2 | <0.02. When the refractive index difference (n1-n2) is within this range, light scattering inside the antiglare hard coat layer can be suppressed, and light transmittance can be improved. When this refractive index difference (n1-n2) is too large, light scattering inside the antiglare hard coat layer becomes large, and the transmission of light is hindered to deteriorate the image definition. When the refractive index difference is adjusted, it is mainly performed by specifying the type of translucent organic fine particles and changing the refractive index. However, the active energy ray-curable resin has additional components such as inorganic fine particles. The method of changing the refractive index of the cured product of the active energy ray-curable resin by adding an additive is also possible as long as the deterioration of physical properties due to the addition of an additional component does not become a problem.

  The light-transmitting organic fine particles are preferably monodispersed with a uniform particle diameter as much as possible in order to uniformly diffuse or scatter light in the antiglare hard coat layer and on the surface thereof. The average particle size of the translucent organic fine particles is preferably 6 to 30 μm, more preferably 6 to 25 μm. When the average particle diameter of the light-transmitting organic fine particles is too small, the effect of diffusing reflected light generated at the interface inside the antiglare film becomes small. On the other hand, if the average particle diameter of the translucent organic fine particles is excessive, the surface irregularities become too large and the haze value becomes large, or in order to avoid this, it is necessary to increase the film thickness of the antiglare hard coat layer. Therefore, there arises a problem that the antiglare film is curled or wrinkled due to curing shrinkage of the film.

  The average particle size described in the present specification is a value calculated from the particle number distribution obtained by converting the distribution measured by the Coulter counter method into a particle number distribution. The Coulter counter method is a particle size measurement method using electrical resistance, and is a method of measuring an average particle size by measuring a change in electrical resistance between two electrodes that occurs when particles pass through pores.

  In addition, the ratio (a / A) of the average particle diameter (a) of the translucent organic fine particles to the film thickness (A) of the antiglare hard coat layer is preferably 0.2 to 1.0. More preferably, it is 3 to 0.8. When this ratio (a / A) is too small, it is difficult to form significant unevenness by the translucent organic fine particles, and the antiglare property is insufficient. On the other hand, if (a / A) is excessive, the surface irregularities become too large, the haze value increases, and the glare also increases.

  The compounding amount of the translucent organic fine particles is a total of 100 parts by mass of the active energy ray curable resin and the photopolymerization initiator (when the metal oxide fine particles described later are also included, the active energy ray curable resin and the photopolymerization start 1 to 20 parts by mass is preferable, and 3 to 10 parts by mass is more preferable with respect to 100 parts by mass in total of the agent and the metal oxide fine particles. If the blending amount of the translucent organic fine particles is too small, it is difficult to obtain a sufficient antiglare property. On the other hand, if the compounding amount of the light-transmitting organic fine particles is excessive, the haze value of the antiglare hard coat layer becomes too high, and when the antiglare film is placed on the display surface, whitening occurs and the image visibility is reduced. descend.

  In addition to the active energy ray-curable resin, the photopolymerization initiator, and the translucent organic fine particles that are essential components, the antiglare hard coat layer composition includes other components as long as the effects of the present invention are not impaired. Can also be added. Examples thereof include metal oxide fine particles, surfactants, photosensitizers, stabilizers, ultraviolet absorbers, infrared absorbers, antioxidants, surface conditioners, and particle dispersants.

  The metal oxide fine particles are arbitrarily blended in order to adjust the refractive index of the antiglare hard coat layer. Examples of the metal oxide fine particles include fine particles of silica, zinc oxide, zinc antimonate, titanium oxide (titania), zirconium oxide (zirconia), antimony oxide, cerium oxide, aluminum oxide, tin oxide and the like. When the metal oxide fine particles are blended, the content thereof is 10 to 80 parts by mass depending on a desired refractive index in a total of 100 parts by mass of the active energy ray-curable resin, the photopolymerization initiator, and the metal oxide fine particles. It may be adjusted within the range.

[High refractive index layer]
The high refractive index layer has a higher refractive index than the antiglare hard coat layer, and constitutes an antireflection layer together with the low refractive index layer, and exhibits an antireflection function by a relative relationship with the low refractive index layer. It is. The high refractive index layer is formed by curing a composition for a high refractive index layer containing an active energy ray-curable resin as a base, a photopolymerization initiator, and metal oxide fine particles.

  The active energy ray-curable resin and the photopolymerization initiator may be the same type as that used in the antiglare hard coat layer. 0.1-20 mass% is preferable in the composition for high refractive index layers, and, as for content of a photoinitiator, 1-10 mass% is more preferable.

  The metal oxide fine particles are an essential component to be incorporated in order to increase the refractive index of the high refractive index layer more actively than the antiglare hard coat layer. The metal oxide fine particles may be basically the same type as that used in the antiglare hard coat layer. Among them, zinc antimonate, indium tin oxide (ITO), zirconium oxide, titanium oxide, etc. However, it is preferable because of its high refractive index. In addition, when metal oxide fine particles are blended in the antiglare hard coat layer, the refractive index is higher than that used in the antiglare hard coat layer in order to increase the refractive index than the antiglare hard coat layer. High metal oxide fine particles are used, or the same kind of metal oxide fine particles are blended more than the antiglare hard coat layer. What is necessary is just to adjust content of a metal oxide fine particle in the range for 1-80 mass% in a composition for high refractive index layers according to a desired refractive index.

The refractive index (nH) of the high refractive index layer is set to 1.56 to 1.80 on the assumption that it is higher than the antiglare hard coat layer. At this time, the difference (nH-nAG) between the refractive index (nH) of the high refractive index layer and the refractive index (nAG) of the antiglare hard coat layer is 0.03 to 0.20, preferably 0.04 to Set to be 0.15. If the refractive index difference between the two layers (nH-NAG) is greater than 0.03 less than or 0.20, luminous reflectance _{R SCI} antiglare film may exceed 1.0, image visibility of the display descend.

The film thickness (dH) of the high refractive index layer is 0.12 to 0.30 μm, preferably 0.14 to 0.25 μm. If the film thickness of the high refractive index layer (dH) is larger than 0.12 less than or 0.30, luminous reflectance _{R SCI} antiglare film may exceed 1.0, lowering image visibility of the display To do.

[Low refractive index layer]
The low refractive index layer has a lower refractive index than the antiglare hard coat layer, and constitutes an antireflection layer together with the high refractive index layer, and exhibits an antireflection function by a relative relationship with the high refractive index layer. It is. The low refractive index layer comprises (a) (meth) acrylate containing a C2-C7 perfluoroalkyl chain, (b) polyester-modified polydimethylsiloxane having an acrylic group, (c) component (a), and (b Curing a composition for a low refractive index layer comprising a fluorine-containing compound having a polymerizable double bond copolymerizable with the component, (d) hollow silica fine particles, and (e) a photopolymerization initiator. It is formed.

((A) component)
The (meth) acrylate containing a C2-C7 perfluoroalkyl chain can weaken the adhesion of a fingerprint when the surface of the low refractive index layer is touched. Specific examples of the (meth) acrylate containing a C2-C7 perfluoroalkyl chain include OPTOOL DAC-HP manufactured by Daikin Industries, Ltd., and MegaFac RS-75 manufactured by DIC Corporation. The (meth) acrylate containing a C2 to C7 perfluoroalkyl chain is contained in the composition for a low refractive index layer in an amount of 3 to 15% by mass, preferably 5 to 10% by mass.

((B) component)
The polyester-modified polydimethylsiloxane having an acrylic group can improve the wiping property of fingerprints attached to the surface of the low refractive index layer. Specific examples of the polyester-modified polydimethylsiloxane having an acrylic group include BYK-UV3500, BYK-UV3530, BYK-UV3570 manufactured by Big Chemie Japan Co., Ltd.

  The polyester-modified polydimethylsiloxane having an acrylic group is contained in the composition for a low refractive index layer in an amount of 1 to 8% by mass, preferably 2 to 6% by mass.

(Component (c))
The fluorine-containing compound having a polymerizable double bond copolymerizable with the component (a) and the component (b) can impart hardness to the low refractive index layer. This fluorine-containing compound is contained in the composition for a low refractive index layer in an amount of 7 to 70% by mass, preferably 6 to 50% by mass. When the content is less than 7% by mass, the scratch resistance is lowered due to insufficient hardness of the low refractive index layer. On the other hand, when it exceeds 70 mass%, the luminous reflectance of an anti-glare film will fall.

  Examples of the fluorine-containing compound having a polymerizable double bond copolymerizable with component (a) and component (b) include fluorine-containing monofunctional (meth) acrylate, fluorine-containing polyfunctional (meth) acrylate, and fluorine-containing itaconic acid. Examples thereof include monomers such as esters and fluorine-containing maleates, polymers thereof, and fluorine-containing reactive polymers having a polymerizable double bond.

  Examples of the fluorine-containing monofunctional (meth) acrylate include 1- (meth) acryloyloxy-1-perfluoroalkylmethane, 1- (meth) acryloyloxy-2-perfluoroalkylethane, and the like. Examples of the perfluoroalkyl group include linear, branched or cyclic groups having 1 to 8 carbon atoms.

  As the fluorine-containing polyfunctional (meth) acrylate, fluorine-containing bifunctional (meth) acrylate, fluorine-containing trifunctional (meth) acrylate and fluorine-containing tetrafunctional (meth) acrylate are preferable. Examples of the fluorine-containing bifunctional (meth) acrylate include 1,2-di (meth) acryloyloxy-3-perfluoroalkylbutane, 2-hydroxy-1H, 1H, 2H, 3H, 3H-perfluoroalkyl-2 ′. , 2′-bis {(meth) acryloyloxymethyl} propionate, α, ω-di (meth) acryloyloxymethyl perfluoroalkane and the like. The perfluoroalkyl group is preferably a linear, branched or cyclic group having 1 to 11 carbon atoms, and the perfluoroalkane group is preferably a linear group. These fluorine-containing bifunctional (meth) acrylates can be used alone or as a mixture when used.

  Examples of the fluorine-containing trifunctional (meth) acrylate include, for example, 2- (meth) acryloyloxy-1H, 1H, 2H, 3H, 3H-perfluoroalkyl-2 ′, 2′-bis {(meth) acryloyloxy Methyl} propionate. The perfluoroalkyl group is preferably a linear, branched or cyclic group having 1 to 11 carbon atoms.

  Examples of fluorine-containing tetrafunctional (meth) acrylates include α, β, ψ, ω-tetrakis {(meth) acryloyloxy} -αH, αH, βH, γH, γH, χH, χH, ψH, ωH, ωH- Perfluoroalkane and the like are preferable. The perfluoroalkane group is preferably a linear one having 1 to 14 carbon atoms. In use, the fluorine-containing tetrafunctional (meth) acrylate can be used alone or as a mixture.

  The fluorine-containing reactive polymer having a polymerizable double bond has a main chain derived from a fluorine-containing ethylenic monomer and has a reactive group for crosslinking and curing. Examples of the reactive group include a (meth) acryloyloxy group, an α-fluoroacryloyloxy group, and an epoxy group. Such a fluorine-containing reactive polymer that is soluble in a solvent and has a polymerizable double bond has a high molecular weight, so it has good film forming properties while containing fluorine, and is crosslinked and cured using reactive groups after film formation. By doing so, a cured layer can be obtained.

The fluorine-containing reactive polymer having a polymerizable double bond has a content of a group having a polymerizable double bond of usually 1 to 20% by mass, preferably 5 to 15% by mass, and the weight average molecular weight is usually normal. It is 1,000 to 500,000, preferably 3,000 to 200,000. Specific examples of the fluorine-containing reactive polymer include perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanone represented by the following general formula (1). Is obtained by reacting α-fluoroacrylic acid fluoride: CH ₂ ═CFCOF with a homopolymer obtained by polymerizing a diol with a peroxide represented by the following general formula (2) to substitute a hydroxyl group with a fluoroacrylate. Is mentioned.

(Component (d))
The hollow silica fine particles are blended to actively lower the refractive index. The refractive index of the hollow silica fine particles varies depending on the production method, but is preferably 1.25 to 1.37. The hollow silica fine particles are not particularly limited as long as the refractive index is lowered, and known hollow silica fine particles can be used. Specific examples include acrylic modified hollow silica fine particle through rear 4320 manufactured by JGC Catalysts & Chemicals Co., Ltd.

  The hollow silica fine particles are contained in the low refractive index layer composition in an amount of 10 to 85% by mass, preferably 30 to 85% by mass. When the content of the silica fine particles is less than 10% by mass, the refractive index of the low refractive index layer cannot be significantly lowered, and the luminous reflectance of the antiglare film is lowered. On the other hand, when the content of the silica fine particles is more than 85% by mass, the coating film strength becomes weak, so that the scratch resistance of the antiglare film is lowered.

((E) component)
As the photopolymerization initiator, the same kind as that used in the antiglare hard coat layer and the high refractive index layer can be used. The photopolymerization initiator is contained in the composition for a low refractive index layer in an amount of 1 to 10% by mass, preferably 2.5 to 7.5% by mass. The total content of the components (a) to (e) is 100% by mass.

The refractive index (nL) of the low refractive index layer is set to 1.29 to 1.37 on the assumption that it is lower than the antiglare hard coat layer. When the refractive index (nL) of the low refractive index layer is smaller than 1.29, the scratch resistance of the antiglare and antireflection film is lowered. On the other hand, when it exceeds 1.37 luminous reflectance R _SCI antiglare film may exceed 1.0, the image display visibility is reduced.

The film thickness (dL) of the low refractive index layer is 0.06 to 0.12 μm, preferably 0.08 to 0.10 μm. If the film thickness of the low refractive index layer (dL) is greater than 0.06μm less than or 0.12 .mu.m, luminous reflectance _{R SCI} antiglare film may exceed 1.0, lowering image visibility of the display To do.

[Formation of hard coat layer, high refractive index layer, and low refractive index layer]
In order to form the hard coat layer, the high refractive index layer, and the low refractive index layer, it is possible to employ a method of curing by applying a composition for each layer and irradiating and curing with an active energy ray.

  When applying the composition for each layer, it is diluted with a diluent solvent as necessary to adjust the viscosity. Examples of the diluent solvent include toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, Examples include diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, heptane, octane, decane, dodecane, propylene glycol monomethyl ether, and 3-methoxybutanol.

  In particular, regarding the antiglare hard coat layer, it is preferable to use a non-swelling solvent for the light-transmitting organic fine particles in order to make the surface of the antiglare hard coat layer free from defects and uniform. The non-swelling solvent is a solvent that does not swell the translucent organic fine particles, and specifically includes an alcohol solvent.

  As the coating method, the wet coating method is particularly preferable in terms of productivity and production cost. The wet coating method may be a known method, for example, roll coating method, spin coating method, dip coating method, brush coating method, spray coating method, bar coating method, knife coating method, die coating method, gravure coating method, curtain flow coating method. Any known method such as a reverse coating method, a kiss coating method, or a comma coating method may be employed. When applying, it is also preferable to pre-treat the surface of the transparent substrate film such as a corona discharge treatment in order to improve adhesion.

As an active energy ray source used for irradiation of active energy rays, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, an electron beam accelerator, a radioactive element or the like is used. It is preferable that the irradiation amount of an active energy ray is 50-5000 mJ / cm < ² > as an integrated light quantity in ultraviolet wavelength 365nm. When the irradiation amount is less than 50 mJ / cm ² , curing of the composition for forming an antiglare hard coat layer becomes insufficient, which is not preferable. On the other hand, when it exceeds 5000 mJ / cm ² , the active energy ray-curable resin tends to be colored, which is not preferable.

[Image display device]
The anti-glare antireflection film configured as described above is used by being disposed on the outermost surface on the side of displaying an image of a display such as a liquid crystal display, a touch panel display, or an organic EL display in the image display device. Thereby, anti-glare property and anti-reflective property can be exhibited, and the visibility of an image improves. In particular, the effect is large in a high-definition display. Here, high definition means that the pixels forming the image are small and the resolution of the displayed image is high. Specifically, the pixel density per inch of the image is 150 ppi (Pixel Per Inch) or more. An image display apparatus provided with such a display is provided with an antiglare antireflection film, so that reflection of an outside scene is suppressed and the image visibility is good.

  Specifically, the display of the image display device includes a personal computer, a word processor, a television, a mobile phone, a portable terminal, a game machine, an automatic cash withdrawal depositing device, a cash dispenser, a vending machine, a car navigation device, and a security system. A display for displaying an image in a terminal or the like can be used.

  Examples of the display include a liquid crystal display, a touch panel display, an organic EL display, a toner display used for plasma display, field emission display, projection display, electronic paper, CRT (CRT), and the like. Furthermore, the display can be applied to a display for display, for example, a glass case such as a showcase or a show window, or a plastic case.

Specific examples of the present invention will be described below with reference to production examples, examples and comparative examples.
(Preparation of antiglare hard coat composition: AG1)
As active energy ray-curable resin, urethane acrylate [molecular weight 1400, viscosity at 60 ° C. is 2500 to 4500 Pa · s, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., “purple light UV7600B”] 95 parts by mass, photopolymerization initiator [Ciba Specialty -"Irgacure 184 (I-184)" manufactured by Chemicals Co., Ltd.] 5 parts by mass, fine particles of cross-linked acrylic-styrene copolymer resin as translucent organic fine particles ["SXX-108LXE" manufactured by Sekisui Plastics Co., Ltd. ( (Monodispersed fine particles having a uniform particle diameter), average particle diameter of 8.0 μm, refractive index of 1.545] A composition for antiglare hard coat comprising 5 parts by mass was mixed with 95 parts by mass of methyl ethyl ketone as a diluent solvent.

(Preparation of AG2 to AG5)
The materials shown in Table 1 were mixed at the ratio shown in Table 1 and prepared in the same manner as AG1. In addition, the amount of the metal oxide fine particles shown in Table 1 is a solid content conversion value. The details of each material shown in Table 1 are as follows.
DPHA: Dipentaerythritol hexaacrylate “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.
Silica fine particles: “MIBK-ST” (methyl isobutyl ketone-dispersed silica sol) manufactured by Nissan Chemical Industries, Ltd.
Zirconium oxide: "ZRMEK 25% -F47" (Zirconium oxide fine particle dispersion) manufactured by CI Kasei Co., Ltd.
XX-22V: Fine particles of crosslinked acrylic-styrene copolymer resin [“XX22V” manufactured by Sekisui Plastics Co., Ltd., monodispersed fine particles having a uniform particle size, average particle size of 8.0 μm, refractive index of 1.525]
Through rear 2320: “Thru rear 2320” manufactured by Nikko Catalysts & Chemicals, Inc., hollow silica fine particles having a particle diameter of 50 nm OD2H2A: 1,10-diacryloyloxy-2,9-dihydroxy- represented by the following general formula (3) 4,4,5,5,6,6,7,7-octafluorodecane

About the composition of obtained AG1-AG5, the refractive index after the hardening was measured as follows. The results are also shown in Table 1.
<Measurement of refractive index>
(1) On the TAC film [trade name “TD80UL”, manufactured by FUJIFILM Corporation], the thickness of each layer is such that the coating liquid for each layer is 100 to 1000 nm in thickness after drying and curing by a bar coater. Was adjusted and applied. After drying, the film was cured by irradiating with 400 mJ / cm ² of ultraviolet rays using a 120 W high-pressure mercury lamp in a nitrogen atmosphere with an ultraviolet irradiation device (manufactured by Iwasaki Electric Co., Ltd.) to prepare a film for refractive index measurement.
(2) The reflection spectrum was measured with a reflection spectral film thickness meter [“FE-3000”, manufactured by Otsuka Electronics Co., Ltd.] after the back surface of the produced film was roughened with sandpaper and painted with black paint.
(3) From the reflectance read from the reflection spectrum, the constant of the wavelength dispersion formula (Formula 1) of n-Cauchy shown below was obtained, and the refractive index at the wavelength of 589 nm was obtained.
N (λ) = a / λ4 + b / λ2 + c (Formula 1)
Note that the refractive index of the antiglare hard coat layer is such that, among the compositions constituting the antiglare hard coat layer, a composition excluding the translucent organic fine particles is cured to form a cured film, and the cured film It was calculated by measuring the reflection spectrum.

(Composition for high refractive index layer: Preparation of H1)
As active energy ray-curable resin, urethane acrylate (molecular weight 1400, viscosity at 60 ° C. is 2500 to 4500 Pa · s, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., “purple UV7600B”), 50% by mass, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., “Irgacure 184 (I-184)” 5 mass%, and zinc antimonate [Nissan Chemical Industry Co., Ltd. “Selnax CX-603M-F2” zinc antimonate fine particle dispersion] 45 IPA as a diluent solvent was mixed with a composition for a high refractive index layer composed of mass% (in terms of solid content) so that the solid content concentration would be 10%.

(Preparation of H2 to H5)
The materials shown in Table 2 were mixed at the ratio shown in Table 2 and prepared in the same manner as H1. In addition, the compounding quantity shown in Table 2 is a solid content conversion value. Moreover, the detail of each material shown only in Table 2 is as follows.
Zinc antimonate: “CELNAX CX-603M-F2” manufactured by Nissan Chemical Industries, Ltd. (Zinc antimonate fine particle dispersion)
Titanium oxide: "RTTMBK15WT% -N24" (titanium oxide fine particle dispersion) manufactured by CI Kasei Co., Ltd.

About the obtained composition of H1-H5, the refractive index after the hardening was measured similarly to the composition for AG layers. The results are also shown in Table 2.

((C) Production of fluorine-containing compound δ1)
In a four-necked flask, 104 parts by mass of perfluoro- (1,1,9,9-tetrahydro-2,5-bisfluoromethyl-3,6-dioxanonenol) and bis (2,2,3, 3,4,45,5,6,6,7,7-dodecafluoroheptanoyl) peroxide 11 mass parts of 8 mass% perfluorohexane solution was added. The hollow portion was purged with nitrogen, and then stirred at 20 ° C. for 24 hours under a nitrogen stream to obtain a highly viscous solid. The obtained solid dissolved in diethyl ether was poured into perfluorohexane, separated and vacuum dried to obtain a colorless and transparent polymer which was a hydroxyl group-containing fluorine-containing allyl ether polymer.

When this polymer was analyzed by ¹⁹ F-NMR (nuclear magnetic resonance spectrum), ¹ H-NMR, IR (infrared absorption spectrum), it was composed of a structural unit of a colorless and transparent polymer which is a hydroxyl group-containing fluorine-containing allyl ether polymer. It was a fluorine-containing polymer having a hydroxyl group at the end of the side chain. The number average molecular weight measured by GPC (gel permeation chromatograph) was 72,000, and the weight average molecular weight was 118,000.

  5 parts by mass of the obtained hydroxyl group-containing fluorine-containing allyl ether polymer, 43 parts by mass of methyl ethyl ketone (MEK), and 1 part by mass of pyridine were charged into a four-necked flask and cooled to 5 ° C. or less with ice. And what melt | dissolved 1 mass part of alpha-fluoroacrylic acid fluoride in 9 mass parts of MEK was dripped over 10 minutes, stirring under nitrogen stream. Thereby, a solution of the fluorine-containing compound δ1 having a polymerizable double bond copolymerizable with the component (a) and the component (b) was obtained.

(Composition for low refractive index layer: preparation of L1)
(A) (Meth) acrylate containing a C2-C7 perfluoroalkyl chain (“DAC-” manufactured by Shin-Etsu Chemical Co., Ltd.) using isopropyl alcohol (IPA) as a solvent so that the solid content concentration is 5% by mass. HP ”] 5.0 mass%, (b) polyester-modified polydimethylsiloxane having an acrylic group [“ BYKUV-3570 ”manufactured by Big Chemie Japan Co., Ltd.] 4.0 mass%, and (c) fluorine-containing compound ( (1) 43.0% by mass in terms of solid content, (d) hollow silica fine particles having a particle diameter of 60 nm [“Thruria 4320” manufactured by Nikko Catalysts & Chemicals, Ltd.] 43.0% by mass, and (e) It was obtained by mixing 5% by mass with a photopolymerization initiator [“Irgacure 907 (I-907)” manufactured by BASF Japan Ltd.].

(Preparation of L2 to L7)
The materials shown in Table 3 were mixed at the ratio shown in Table 3 and prepared in the same manner as L1. In addition, the compounding quantity shown in Table 3 is a solid content conversion value. The details of each material shown only in Table 3 are as follows.
Through rear 2320: “Thru rear 2320” manufactured by Nikko Catalysts & Chemicals, Inc., hollow silica fine particles having a particle diameter of 50 nm OD2H2A: 1,10-diacryloyloxy-2,9-dihydroxy- represented by the general formula (3) 4,4,5,5,6,6,7,7-octafluorodecane

About the obtained composition of L1-L7, the refractive index after the hardening was measured similarly to the composition for AG layers. The results are also shown in Table 3.

Example 1
Prepared by mixing 35 parts by mass of ethyl acetate (EtOAc) and 22 parts by mass of 2-propanol [IPA] with the anti-glare hard coat layer composition AG1 to prepare a coating liquid for forming an anti-glare hard coat layer. did. This anti-glare hard coat layer forming coating solution was applied as a transparent substrate film onto a triacetyl cellulose (TAC) film having a thickness of 80 μm with a roll coater so that the dry film thickness was 18 μm. Dried for 2 minutes. Thereafter, ultraviolet rays were irradiated with a 120 W high-pressure mercury lamp (manufactured by Nippon Battery Co., Ltd.) (integrated light amount 400 mJ / cm ² ) and cured to form an antiglare hard coat layer.

On this antiglare hard coat layer, the high refractive index layer composition H1 was applied so as to have a dry film thickness of 0.16 μm, and then irradiated with ultraviolet rays using a 120 W high-pressure mercury lamp (manufactured by Eye Graphics) in a nitrogen atmosphere. Irradiated (integrated light amount 400 mJ / cm ² ) and cured to form a high refractive index layer.

Further, the low refractive index layer composition L1 was applied on the high refractive index layer so as to have a dry film thickness of 0.10 μm, and then irradiated with ultraviolet rays using a 120 W high pressure mercury lamp (manufactured by Eye Graphics) in a nitrogen atmosphere. (Integrated light quantity 400 mJ / cm ² ) and cured to form a low refractive index layer, and the antiglare antireflection film of Example 1 was produced.

(Examples 2-11, Comparative Examples 1-11)
The materials shown in Tables 4 and 5 were applied at the film thicknesses shown in Tables 4 and 5 and dried and cured in the same manner as in Example 1 to obtain the antiglare antireflection films of Examples 2 to 11 and Comparative Examples 1 to 11. Produced.

About each obtained anti-glare antireflection film, luminous reflectance R _SCI (Y value) and scratch resistance were measured as follows. The results are also shown in Tables 4 and 5.
<Visual reflectance>
In order to remove the back surface reflection of the measurement surface, the back surface of the film was roughened with sandpaper and adjusted with a black paint. The measured surface of the adjusted film is measured by “SD6000” manufactured by Nippon Denshoku Co., Ltd., and the tristimulus value Y of the object color due to reflection in the XYZ color system (CIE standard illuminant D65) defined in JISZ 8701 is obtained. Calculated.
<Abrasion resistance>
The surface of the antireflection film was subjected to 10 reciprocal rubbings with a stroke width of 25 mm and a speed of 30 mm / sec by applying a load of 250 gf to # 0000 steel wool, and the surface was visually observed and evaluated according to the following criteria. Steel wool was gathered to about 10 mmφ, and was cut and rubbed so as to have a uniform surface.
○: 0 to 10 scratches Δ: 11 to 20 scratches ×: 21 or more scratches

From the results of Table 4, it was confirmed that in all of Examples 1 to 11, the luminous reflectance _RSCI was 1.0 or less, good image visibility was obtained, and the scratch resistance was compatible.

On the other hand, from the results in Table 5, since the refractive index of the AG layer is low in Comparative Example 1, the refractive index of the AG layer is high in Comparative Example 2, and thus the refractive index difference between the H layer and the AG layer is small in Comparative Example 3. Therefore, in Comparative Example 4, the refractive index difference between the H layer and the AG layer is large. In Comparative Example 6, the refractive index of the L layer is high. In Comparative Example 7, the thickness of the H layer is small. Since the film thickness of the H layer is large, the film thickness of the L layer is large in Comparative Example 9, and the film thickness of the L layer is small in Comparative Example 10, so the luminous reflectance _RSCI exceeds 1.0 respectively. It was confirmed that good image visibility could not be obtained. Moreover, in Comparative Example 5 and Comparative Example 11, the crosslink density was lowered to reduce the refractive index of the L layer, so that the scratch resistance was deteriorated.

Claims (3)

On the transparent base film, an antiglare hard coat layer, a high refractive index layer, and a low refractive index layer are laminated in this order,
The refractive index (nAG) of the antiglare hard coat layer is 1.49 to 1.65,
The low refractive index layer has a refractive index of 1.29 to 1.37, a film thickness of 0.06 to 0.12 μm,
An antiglare antireflection film that satisfies the following conditions (1) and (2), where nH is a refractive index of the high refractive index layer and dH is a film thickness.
0.03 ≦ nH−nAG ≦ 0.20 (1)
0.12 μm ≦ dH ≦ 0.30 μm (2) The antiglare antireflection film according to claim 1, wherein the luminous reflectance R _SCI is 1.0% or less. The image display apparatus provided with the anti-glare antireflection film of Claim 1 or Claim 2 in the outermost surface of the side which displays the image of a display.