JP2016122140A - Anti-glare anti-reflection film and image display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-glare anti-reflection film which suppresses glare of a display, offers good slidability for flicking with fingers and superior stain resistance, and allows fingerprints thereon to be easily wiped off.SOLUTION: An anti-glare anti-reflation film includes: a low refractive index layer laminated as an outer most layer on a transparent base material film; and an anti-glare layer, having a refractive index higher than that of the low refractive index layer, laminated between the transparent base material film and the low refractive index layer. The anti-glare layer contains large diameter particles and small diameter fine particles having a specific gravity of 2.7-6.0 times that of the large diameter particles in a specific volumetric proportion, and a ratio of a diameter of the large diameter particles to a thickness of the anti-glare layer is defined. The low refractive index layer is formed by curing a composition containing, in a specific proportion, (a) a (meth)acrylate containing a perfluoroalkyl chain of C2-C7, (b) a polyether-modified polydimethylsiloxane having an acrylic group or a polyester-modified polydimethylsiloxane having an acrylic group, (c) an ultraviolet-curable resin that is copolymerizable with (a) and (b), (d) hollow silica fine particles, and (e) photopolymerization initiator.SELECTED DRAWING: None

Description

  The present invention is an antiglare antireflection film that has little display glare, good flicking of fingers during flicking, excellent antifouling properties, and easy wiping of fingerprints. The present invention relates to a dazzling antireflection film. The present invention also relates to an image display device using the antiglare antireflection film.

  A display such as a car navigation system, a smartphone, or a television is required to reflect less light emitted from an external light source such as a fluorescent lamp or sunlight in order to improve the visibility. This is because when the light is reflected on the surface of the display, an image in front of the light is reflected on the display, making it difficult to see the display image. Therefore, by providing an antiglare film having fine irregularities on the surface, the reflected light is scattered to make the reflection inconspicuous.

  Conventionally, the number of pixels of a normal display is about 100 to 150 per 25.4 mm (= 1 inch) in length and width of the screen, and if a conventional anti-glare film is used, it is possible to view images without problems. Become. However, the number of pixels per inch, such as car navigation systems, smartphones, and 8K televisions, is increasing, and the number of displays that display high-definition images is increasing. For example, the number of pixels is about 300 per 25.4 mm in length and width of the screen. In some cases, a high-definition display more than twice that of a normal display. One of the purposes is to make the image of a display for normal use more precise. However, when a conventional antiglare film is applied to a display in which the number of pixels is doubled as described above, the visibility is remarkably impaired. That is, when a conventional anti-glare film is provided on the surface of the display, a black mask (or a black matrix, for example, a black line portion provided vertically and horizontally) at the boundary of each pixel of the display, and prevention. There is no particular problem at the location where the concave and convex portions of the glare film overlap, but at the location where the black mask and the concave portion of the antiglare film overlap, the image light is scattered, This is because a scintillation phenomenon that glitters and glitters occurs. When a conventional anti-glare film is applied to a display with the number of pixels doubled as described above, scintillation (surface glare) phenomenon becomes prominent, and characters, lines, pictures, photographs, etc., especially characters and lines Visibility is significantly impaired.

  In this connection, Patent Document 1 discloses an antiglare antireflection film that reduces scintillation (surface glare). This anti-glare antireflection film has a structure in which an anti-glare layer and a low refractive index layer are laminated in this order on a transparent base film, and each layer varies depending on the refractive index difference between the anti-glare layer and the low refractive index layer. The reflected light on the surface of the lens interferes and cancels out, thereby reducing the reflected light and scattering the reflected light by the fine unevenness of the antiglare layer. The antiglare layer is a light whose refractive index is increased by dispersing metal oxide fine particles having a primary particle diameter of 0.01 to 0.1 μm and a refractive index of 1.90 to 2.90 in a binder resin. Unevenness is formed by using a transparent resin as a matrix resin and containing particles having an average particle diameter of 0.1 to 5 μm, which is called a light-transmitting diffusing agent. In this antiglare antireflection film, in order to suppress scintillation (surface glare), particles having a refractive index difference of 0.01 to 0.5 with a light transmissive resin are used as a transmissive diffusing agent, and The haze value on the surface of the antiglare layer (the surface not on the transparent base film side) is 7 to 30, and the haze value inside the antiglare layer is 1 to 30.

JP 2003-4904 A

  The above-mentioned conventional anti-glare anti-reflective film is difficult to wipe off the attached fingerprint, the finger does not slip during flicking, and has a feeling of being caught, and furthermore, the effect of suppressing scintillation (glare) is small, so a high-definition touch panel When applied to the viewing side of the display, fingerprints are accumulated, the operability of the touch panel is poor, and it is difficult to view an excellent image due to glare.

  Such a problem has become apparent since car navigation systems and mobile phones equipped with a capacitive touch panel having a multi-touch function have become popular in recent years. The trend of performance requirements for surface films has changed, and new needs that have not existed in the past to suppress finger slipperiness and adhesion of fingerprints to the touch panel surface are increasing, as well as demands for antireflection functions. However, conventional anti-glare anti-reflection films are specialized in anti-reflection functions and no countermeasures are taken against fingerprint adhesion, so they can meet the needs of finger slipperiness and fingerprint adhesion prevention. Not.

  Therefore, the object of the present invention is to provide an anti-glare reflection that has less glare on the display, good finger slipperiness during flicking, excellent antifouling properties, and easy fingerprint wiping. It is to provide a prevention film.

  In the antiglare antireflection film of the present invention, a low refractive index layer is laminated on the outermost layer of one surface of a transparent substrate film, and the low refractive index layer is interposed between the transparent substrate film and the low refractive index layer. An antiglare layer having a refractive index higher than that of the refractive index layer is laminated. The antiglare layer includes large-sized fine particles and small-sized fine particles having a specific gravity larger than the large-sized fine particles and a smaller particle diameter. The large-sized fine particles have a particle diameter Pdia of 0.1 μm ≦ Pdia ≦ 5 μm, and a ratio t / Pdia between the film thickness t of the antiglare layer and the particle diameter Pdia is 0.05 ≦ t / Pdia ≦ 1. 7. The particle diameter Mdia of the small-sized fine particles is 0.01 μm ≦ Mdia ≦ 0.1 μm. The ratio Mden / Pden of the specific gravity Mden of the small particle and the specific gravity Pden of the large particle is 6.0 ≧ Mden / Pden ≧ 2.7, and the volume ratio of the large particle to the total volume of the antiglare layer Is 0.5% or more and 40% or less, and the volume ratio of the small-diameter fine particles in the total volume of the antiglare layer is 15% or more and 65% or less. The low refractive index layer comprises (a) 5.0 to 15.0% by mass of (meth) acrylate containing a C2 to C7 perfluoroalkyl chain, and (b) a polyether-modified polydimethylsiloxane or acrylic having an acrylic group. Polyester-modified polydimethylsiloxane having a group of 2.0 to 8.0% by mass, (c) UV curable resin copolymerizable with (a) and (b) 9.0 to 70.0% by mass, (d) Hollow silica fine particles 22.0-83.0% by mass, (e) a photopolymerization initiator 1.0-10.0% by mass, and (b) the mass% of which is less than the mass% of (a). It is formed by curing the rate layer resin composition (however, the total of (a), (b), (c), (d), and (e) is 100% by mass).

  The ratio t / Pdia between the film thickness t of the antiglare layer and the particle diameter Pdia of the large fine particles is more preferably 0.05 ≦ t / Pdia ≦ 1.3.

  The volume ratio of the small-sized fine particles in the total volume of the antiglare layer is more preferably 15% or more and 55% or less.

  The small-diameter fine particles are preferably at least one selected from the group consisting of zirconium oxide, titanium oxide, zirconia, zinc oxide, zinc antimonate, tin-doped indium oxide, antimony-doped tin oxide, and silica.

  The large-diameter fine particles are preferably acrylic resin, polystyrene, polymethacrylstyrene, cross-linked acrylic-styrene copolymer resin, silica, benzoguanamine formaldehyde condensate, benzoguanamine / melamine / formaldehyde condensate, melamine / formaldehyde condensate, polyethylene resin, It is at least one selected from the group consisting of epoxy resins, silicone resins, polyvinylidene fluoride, and polyfluorinated ethylene resins.

  A hard coat layer may be laminated between the transparent substrate film and the antiglare layer.

  The antiglare antireflection film of the present invention is provided on the surface of an image display device.

  According to the present invention, there is provided an antiglare antireflection film that has less glare on the display, is easy to slip a finger at the time of flicking, has excellent antifouling property, and can easily wipe off fingerprints. be able to.

<Anti-glare anti-reflection film>
The antiglare antireflection film is based on a transparent base film, and a low refractive index layer is laminated on the outermost layer on at least one surface thereof, and at least the antiglare layer is provided between the transparent base film and the low refractive index layer. Are stacked. In this antiglare antireflection film, a hard coat layer can be appropriately laminated between the transparent substrate film and the antiglare layer.

≪Transparent substrate film≫
The transparent substrate film is not particularly limited as long as it is colorless and transparent. Examples of the material for forming such a transparent substrate film include polyesters such as triacetyl cellulose and polyethylene terephthalate, cycloolefin polymers, polycarbonate resins, or polymethyl methacrylate resins, polyarylate, and polyether sulfone. Of these, triacetyl cellulose and polyethylene terephthalate are preferable in terms of high versatility. These transparent base films have a refractive index of about 1.47 to 1.70 for light of 589 nm.

  The thickness of the transparent substrate film is preferably about 25 to 400 μm, more preferably about 50 to 200 μm. When the thickness of the transparent substrate film is thinner than 25 μm or thicker than 400 μm, the handleability during the production and use of the antiglare antireflection film is lowered.

≪Anti-glare layer≫
The antiglare layer has light transmittance. The antiglare layer has a higher refractive index than the low refractive index layer, and the reflected light on the surface of each layer cancels out due to the difference in refractive index between the transparent base film and the antiglare layer, thereby reducing the reflected light. It has an antireflection effect. The antiglare layer has fine irregularities on the surface, and the irregularities scatter reflected light to reduce glare and improve finger slipping.

  The difference in refractive index of the antiglare layer with respect to light of 589 nm is preferably 0.10 or more, and preferably 1.47 to 1.85, with respect to the low refractive index layer. When the refractive index exceeds 1.85, the strength of the surface may be lowered. Further, when the refractive index is less than 1.47, it is difficult to effectively reduce the reflectance.

  The antiglare layer includes at least a large particle and a small particle having different particle diameters and specific gravity, and a binder resin. The antiglare layer can be formed by curing a resin composition for an antiglare layer containing large fine particles, small fine particles, a binder resin, and a photopolymerization initiator as appropriate.

<Large diameter fine particles>
Large diameter fine particles are spherical and have a larger particle size and a lower specific gravity than small diameter fine particles. Concave and convex shapes are formed on the surface of the antiglare and antireflection film by the large diameter fine particles. The particle diameter Pdia of the large-sized fine particles is 0.1 μm ≦ Pdia ≦ 5 μm. When the particle diameter Pdia is less than 0.1 μm, the surface unevenness (≈Ra) becomes too small, and thus no antiglare property is exhibited. On the other hand, when the particle diameter Pdia exceeds 5 μm, the surface irregularity interval (≈Sm) becomes large, and the glare-suppressing action is reduced. Moreover, since the contact area with a finger becomes large, finger slipperiness also falls. Preferably, 0.5 μm ≦ Pdia ≦ 3 μm. By controlling to 0.5 μm ≦ Pdia ≦ 3 μm, the size of the surface unevenness (≈Ra) and the surface unevenness interval (≈Sm) can be adjusted more appropriately.

  As long as the particle diameter Pdia of the large-diameter fine particles is a method for measuring the average particle diameter of the particles, any measuring method can be applied. Preferably, the particle diameter Pdia is measured with a transmission electron microscope (magnification of 20,000 to 2,000,000 times). Observation is performed to observe 100 particles, and the average value is defined as the (average) particle diameter.

  Within the above range, the particle diameter Pdia of the large-sized fine particles satisfies the ratio t / Pdia with the film thickness t of the antiglare layer satisfies 0.05 ≦ t / Pdia ≦ 1.7. Here, the film thickness t of the anti-glare layer is the thickness of the portion of the anti-glare layer where there is no protrusion (convex) due to particles. As long as the film thickness t of the antiglare layer is a method for measuring the film thickness, any measurement method can be applied, but preferably, the reflection spectrum of the portion without protrusion (convex) due to particles is measured by a spectral film thickness meter. Then, it is calculated from the obtained reflection spectrum by the peak valley method. When t / Pdia> 1.7, the particle size of the large-sized fine particles is small with respect to the film thickness t and the size of the surface irregularities is small, so that the antiglare property is lowered. When 0.05 ≦ t / Pdia ≦ 1.7, the antiglare property and the glare suppressing action are excellent, and the finger slipping property is good. When t / Pdia ≦ 1.3, the glare-suppressing action is further improved. Further, when t / Pdia ≦ 1, the surface hardness of the antiglare antireflection film can be increased. The film thickness t is preferably 0.1 μm ≦ t ≦ 5 μm. If the thickness is 0.1 μm> t, the strength of the antiglare layer tends to decrease. When t> 5 μm, the gap between the surface irregularities tends to increase, and the glare tends to increase.

  The material of the large-sized fine particles is not particularly limited as long as the ratio of the specific gravity with the small-sized fine particles is within the range described below, but as a guide, a specific gravity having a specific gravity Pden of Pden ≦ 3.0 can be selected. Examples of such a material include resin and silica. Resins include acrylic resin, polystyrene, polymethacrylstyrene, cross-linked acrylic-styrene copolymer resin, benzoguanamine formaldehyde condensate, benzoguanamine / melamine / formaldehyde condensate, melamine / formaldehyde condensate, polyethylene resin, epoxy resin, silicone resin, polyfluoride. And vinylidene chloride and polyfluoroethylene-based resin. Of these, acrylic, polystyrene, and a cross-linked acrylic-styrene copolymer resin are preferable because they have a low specific gravity and easily exhibit antiglare properties. The large-sized fine particles may be used alone or in combination of two or more.

  The ratio of the volume of the large-sized fine particles to the total volume of the antiglare layer is 0.5% or more and 40% or less. If the volume ratio of the large fine particles is less than 0.5%, sufficient antiglare property cannot be obtained. On the other hand, if the volume ratio of the large-sized fine particles exceeds 40%, the surface irregularities become too large, so that the antiglare property becomes too strong and the visibility is lowered.

<Small particle size>
Small-sized fine particles have a smaller particle size and a higher specific gravity than large-sized fine particles. The small-sized fine particles are typically spherical and segregate the large-sized fine particles to the upper layer portion of the antiglare layer. The particle diameter Mdia of the small-sized fine particles is 0.01 μm ≦ Mdia ≦ 0.1 μm. When the particle diameter Mdia is less than 0.01 μm, the particles are likely to aggregate and it may be difficult to achieve uniform antiglare properties. On the other hand, if the particle diameter Mdia exceeds 0.1 μm, visible light is likely to be scattered, and thus haze may increase. When the particle diameter Mdia is controlled to 0.02 μm ≦ Mdia ≦ 0.07 μm, it is preferable because an effect of segregating large-sized fine particles uniformly on the upper layer portion of the antiglare layer is preferable.

  As the particle size of the small-sized fine particles, any measuring method can be applied as long as it is a method for measuring the average particle size of the particles. Preferably, the particles are observed with a transmission electron microscope (magnification of 20,000 to 2,000,000 times). And 100 particles are observed, and the average value is defined as the (average) particle diameter.

  The specific gravity Mden of the small-sized fine particles is such that the ratio Mden / Pden with the specific gravity Pden of the large-sized fine particles is 6.0 ≧ Mden / Pden ≧ 2.7. When Mden / Pden <2.7, it is difficult to segregate large-diameter fine particles in the upper layer portion of the antiglare layer, so that antiglare property is hardly exhibited. If Mden / Pden> 6.0, the types of small-diameter particles are limited, and the degree of freedom in selecting a material is reduced, for example, expensive particles such as gold fine particles have to be selected.

  The material of the small-diameter fine particles is not particularly limited as long as the ratio of the specific gravity to the large-diameter fine particles falls within the above range, but as a guide, one having a specific gravity Mden of Mden ≧ 2.5 can be selected. Examples of such a material include metal oxide and silica. Examples of the metal oxide include zirconium oxide, titanium oxide, zirconia, zinc oxide, zinc antimonate, tin-doped indium oxide, and antimony-doped tin oxide. Of these, titanium oxide and zirconium oxide are preferable because of their high refractive index and large specific gravity. The small-diameter fine particles may be used alone or in combination of two or more.

  The content of the small-sized fine particles in the anti-glare layer is such that the proportion of the volume of the small-sized fine particles in the total volume of the anti-glare layer is 15% or more and 65% or less. If the volume ratio of the small-diameter fine particles is less than 15%, the surface irregularity interval (≈Sm) becomes large, and the glare-suppressing action decreases. Moreover, since the contact area with a finger becomes large, finger slipperiness also falls. On the other hand, when the volume ratio of the small-diameter fine particles exceeds 65%, the content of the binder resin is relatively reduced, and the surface hardness of the antiglare antireflection film tends to be lowered. More preferably, the volume ratio of the small-diameter fine particles is 55% or less. In this case, the surface hardness of the antiglare antireflection film can be increased.

<Binder resin>
Binder resins include monomers, oligomers, and prepolymers having radical polymerizable functional groups such as acryloyl group, methacryloyl group, acryloyloxy group, and methacryloyloxy group, and cationic polymerizable functional groups such as epoxy group, vinyl ether group, and oxetane group. Are used alone, or a composition obtained by appropriately mixing them. Examples of monomers include methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and the like. it can. As oligomers and prepolymers, polyester acrylate, polyurethane acrylate, polyfunctional urethane acrylate, epoxy acrylate, polyether acrylate, acrylate compounds such as alkit acrylate, melamine acrylate, silicone acrylate, unsaturated polyester, tetramethylene glycol diglycidyl ether, Epoxy compounds such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether and various alicyclic epoxies, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3- Examples include oxetane compounds such as ethyl-3-oxetanyl) methoxy] methyl} benzene and di [1-ethyl (3-oxetanyl)] methyl ether. Door can be. These can be used alone or in combination.

  The binder resin content in the antiglare layer is preferably such that the volume ratio of the binder resin in the total volume of the antiglare layer is 83.5% or less. If it exceeds 83.5%, the content of the large-sized fine particles and the small-sized fine particles decreases, so that the surface unevenness becomes small and the antiglare property is hardly exhibited. Further, the volume ratio of the binder resin is preferably 5% or more. If it is less than 5%, voids are generated in the film and the strength is lowered. More preferably, the volume ratio of the binder resin is 30% or more. In this case, the hardness of the antiglare layer can be increased.

<Photopolymerization initiator>
The photopolymerization initiator is used as a polymerization initiator when the antiglare hard coat layer resin composition is cured by active energy rays such as ultraviolet rays (UV) to form a coating film. The photopolymerization initiator is not particularly limited as long as it initiates polymerization upon irradiation with active energy rays, and known compounds can be used. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, acetophenone polymerization initiators such as 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy 1,2 -Benzoin polymerization initiators such as diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4' -Benzophenone polymerization initiators such as tetra (t-butylperoxycarbonyl) benzophenone, 2-chlorothio Sandton, such thioxanthone type polymerization initiators such as 2,4-diethyl thioxanthone, and the like.

  The volume ratio of the photopolymerization initiator in the total volume of the antiglare layer is preferably 1% or more and 25%. When the photopolymerization initiator is less than the above range, the polymerization becomes insufficient and the adhesion cannot be exhibited. On the other hand, when the amount is more than the above range, the cross-linking density of the film is lowered, and thus the strength is weakened.

<Additives>
The antiglare layer resin composition may be prepared by adding conventionally known additives such as a surface preparation agent, a leveling agent, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, an antistatic agent, and an antifoaming agent as necessary. You may contain in the range which does not impair the effect of invention.

≪Low refractive index layer≫
The low refractive index layer has optical transparency. The low refractive index layer has a refractive index lower than that of the antiglare layer, and exhibits an antireflection effect together with other layers such as the antiglare layer. The refractive index of the low refractive index layer with respect to 589 nm light is preferably 1.49 or less. When the refractive index exceeds 1.49, it is difficult to obtain sufficient visibility reflectance. Further, as described later, the refractive index of the low refractive index layer is lowered by containing hollow silica, and the refractive index is adjusted by adjusting the content of the hollow silica within a range described later. . When the content of the hollow silica is adjusted within the range described later, the lower limit of the refractive index of the low refractive index layer is about 1.25.

When the refractive index of the low refractive index layer is nL and the film thickness is dL, the following (I) is preferably established.
380 nm / 4 nL <dL <780 nm / 4 nL (I)
When dL is 380 nm / 4 nL or less, the minimum reflectance wavelength (the wavelength of light that minimizes the reflectance) becomes 380 nm or less when the low refractive index layer is provided, and when the low refractive index layer is provided. It becomes difficult to effectively reduce the reflectance in the visible light region. On the other hand, when dL is 780 nm / 4 nL or more, when the low refractive index layer is provided, the minimum reflectance wavelength (the wavelength of light that minimizes the reflectance) becomes 780 nm or more, and the low refractive index layer is provided. In this case, it is difficult to effectively reduce the reflectance in the visible light region.

[Resin composition for low refractive index layer]
The low refractive index layer can be formed by curing the resin composition for the low refractive index layer. The resin composition for a low refractive index layer comprises (a) (meth) acrylate containing a C2-C7 perfluoroalkyl chain, and (b) a polyether-modified polydimethylsiloxane having an acrylic group or a polyester-modified having an acrylic group. It comprises polydimethylsiloxane, (c) an ultraviolet curable resin copolymerizable with the components (a) and (b), (d) hollow silica fine particles, and (e) a photopolymerization initiator. In addition, content of (b) component is less than content of (a) component. In this specification, “(meth) acrylate” refers to acrylate and methacrylate. Similarly, the “(meth) acryloyl group” described later refers to an acryloyl group and a methacryloyl group.

[(A) component]
(A) A (meth) acrylate containing a C2-C7 perfluoroalkyl chain is for expressing an antifouling function, and has an adhesion property of a fingerprint attached when the surface of a low refractive index layer is touched. Can weaken. Specific examples of (meth) acrylates containing C2-C7 perfluoroalkyl chains include those represented by the following chemical formula (1) and those represented by the following chemical formula (2).

(In the formula, n is an integer of 0 to 100, and X is H or CH _3. )

(Wherein X represents a perfluoroalkyl group or a perfluoropolyether)

  (A) The (meth) acrylate containing a C2-C7 perfluoroalkyl chain is contained in the resin composition for a low refractive index layer in an amount of 5.0 to 15.0 mass%. When the content is less than 5.0% by mass, the adhesion of fingerprints when touching the surface of the low refractive index layer cannot be effectively reduced. On the other hand, when it exceeds 15.0 mass%, the wiping property of the fingerprint is deteriorated.

[Component (b)]
(B) The polyether-modified polydimethylsiloxane having an acrylic group or the polyester-modified polydimethylsiloxane having an acrylic group is for improving the wiping property of fingerprints attached to the surface of the low refractive index layer.

The basic skeleton (polydiorganosiloxane) of a polyether-modified polydimethylsiloxane having an acrylic group or a polyester-modified polydimethylsiloxane having an acrylic group is represented by the following general formula (3), and a polymerizable reactive group is contained in one molecule. Are compounds having at least 2, preferably 2-8.

  A and B in the general formula (3) are linear or branched organic groups, an alkyl chain (C1-30), a perfluoroalkyl chain (C1-10), an arylalkyl chain, Aliphatic to aromatic (poly) ester chains (partial molecular weight of the organic chain 100 to 3000), aliphatic to aromatic (poly) ether chains (partial molecular weight of the organic chain 100 to 3000) and aliphatic Or at least one skeleton selected from the group consisting of aromatic (poly) urethane chains (partial molecular weight of the organic chain 100 to 3000), and a polymerizable reactive group is introduced into the organic group In the molecule, A and B may be the same or different, and A or B may be the same or different. However, the number of polymerizable reactive groups introduced into A and B is a compound having two, preferably 2 to 8, per molecule. Furthermore, it is more preferable that the polymerizable reactive group is introduced into B for the convenience of synthesis. C in the general formula (3) represents the length of the polysiloxane skeleton in the form of c + 1, and is preferably an integer of 3 to 250, more preferably 6 to 100.

  As the polymerizable reactive group, at least an acrylic group is introduced. The acryl group to be introduced is preferably an acryloyloxy group in terms of excellent reactivity. In addition to the acryloyloxy group, a (meth) acryloyloxy group, an α-fluoroacryloyloxy group, and the like can also be introduced. As a bonding method between the polymerizable reactive group and the polysiloxane skeleton, a conventionally known bonding method, for example, (poly) ether type, (poly) ester type, (poly) ester type and (poly) urethane type are combined. All of the bonding methods such as a bonding method combining a (poly) ether type and a (poly) urethane type, a bonding method combining a (poly) ester type and a (poly) ether type, and the like can be employed.

  For example, in the case of a bonding method combining a polyester type and a polyurethane type, the structure of the polydiorganosiloxane molecule has a basic skeleton as shown in the following general formula (4) and extends from the polysiloxane site. A polymerizable reactive group is bonded to the ends of three or more side chains of the chain.

  X in the general formula (4) is an integer of 3 to 250, preferably an integer of 6 to 100, and Y and Z are integers satisfying that Y + Z is 3 or more, preferably 4 to 20, m and n are both integers of 1-10. m and n may be the same or different, but the same is preferable in that a polyether-modified polydimethylsiloxane having an acrylic group or a polyester-modified polydimethylsiloxane having an acrylic group can be easily prepared.

R ₁ in the general formula (4) is a linear alkyl group (1 to 30 carbon atoms), a perfluoroalkyl group (1 to 10 carbon atoms), an arylalkyl group or a polyester group (partial side chain). It has a molecular weight of 200 to 2000, and is bonded to the Si atom via an alkyl chain), a polyether group (partial molecular weight of the side chain is 200 to 2000, and is bonded to the Si atom via an alkyl chain). Any one). In the molecule, R ₁ may be the same or different, but the same one is more preferable because the preparation of the polyether-modified polydimethylsiloxane having an acrylic group or the polyester-modified polydimethylsiloxane having an acrylic group is simple. . Further, from the viewpoint of compatibility with the resin at the time of use, it is most general and preferable that R ₁ is a methyl group.

R ₂ in the general formula (4) is a linear or branched chain having 3 to 30 carbon atoms, preferably 3 to 15 carbon atoms, and has at least two urethane bonds on the chain. It is bonded to the polysiloxane skeleton and R ₃ (provided that R ₃ is bonded so that three or more are included in one molecule of the polydiorganosiloxane). R ₂ may be the same or different in the molecule, but the same is more preferable because the preparation of the polyether-modified polydimethylsiloxane having an acrylic group or the polyester-modified polydimethylsiloxane having an acrylic group is simple. .

R ₃ in the general formula (4) is a site having a polyester skeleton, preferably a polyester skeleton containing three or more ester bonds, and has a polymerizable reactive group as described above, preferably (meth) acryloyl at the terminal. A group is attached. R ₃ may be the same or different in the molecule, but the same is more preferable because the preparation of the polyether-modified polydimethylsiloxane having an acrylic group or the polyester-modified polydimethylsiloxane having an acrylic group is simple. Further, from the viewpoint of compatibility with the resin at the time of use, it is most general and preferable that R ₃ has a polycaprolactone skeleton composed of 3 or more caprolactones.

R ₄ in the general formula (4) is any one of hydrogen, fluorine and methyl groups, and R ₄ may be the same or different in the molecule, but the polyether-modified polydimethylsiloxane or acrylic having an acrylic group The same is more preferable because the preparation of the polyester-modified polydimethylsiloxane having a group is simple.

  Next, some more specific examples in the case of using the bonding method combining the polyester type and the polyurethane type as described above will be described together with an example of the manufacturing method. However, the following examples of the production method do not mean that the polyether-modified polydimethylsiloxane having an acrylic group or the polyester-modified polydimethylsiloxane having an acrylic group is limited to the following examples.

  For example, by ring-opening polymerization of ε-caprolactone using polydimethylsiloxane represented by average formula (5) obtained by a conventionally known method, triisocyanate represented by general formula (6), and ethylene glycol monomethacrylate. Using the prepared polymerizable reactive group-containing polyester represented by the general formula (7) in a molar ratio of 1: 2: 4, a polycrystal represented by the average formula (8) is obtained by a conventionally known urethane bond forming reaction. A dimethylsiloxane compound is obtained. At this time, after adding polydimethylsiloxane (5) to triisocyanate (6) and forming urethane bonds at both ends of polydimethylsiloxane (5), urethane with polymerizable reactive group-containing polyester (7) By forming a bond, a by-product [for example, a by-product composed only of polydimethylsiloxane (5) and triisocyanate (6), or a polymerizable reactive group-containing polyester (7) and triisocyanate (6) only. The desired polydimethylsiloxane (8) can be obtained in a high yield by suppressing the production of by-products and the like].

  Here, d in the average formulas (5) and (8) is an integer of 15 to 20, e is an integer of 1 to 5, f in the general formula (6) is an integer of 4 to 8, and the general formula (7) And g in average formula (8) is an integer of 3-5. In the average formulas (5) and (8), Me represents a methyl group.

  In addition, for example, polydimethylsiloxane represented by the average formula (9) obtained by a conventionally known method, diisocyanate represented by the general formula (10), and ε-caprolactone using pentaerythritol triacrylate By using a polymerizable reactive group-containing polyester represented by the general formula (11) prepared by ring-opening polymerization in a molar ratio of 1: 2: 2, an average formula (12) is obtained by a conventionally known urethane bond forming reaction. The polydimethylsiloxane compound represented by these is obtained. At this time, after adding polydimethylsiloxane (9) to diisocyanate (10) and forming urethane bonds at both ends of polydimethylsiloxane (9), urethane bonds with polymerizable reactive group-containing polyester (11) By forming a by-product [for example, a by-product consisting of only polydimethylsiloxane (9) and diisocyanate (10), or a by-product consisting only of polymerizable reactive group-containing polyester (11) and diisocyanate (10) Etc.] and the desired polydimethylsiloxane (12) can be obtained in high yield.

  Here, h in the average formula (9) is an integer of 25 to 35, i is an integer of 1 to 5, j in the general formula (10) is an integer of 5 to 10, and k in the general formula (11). Is an integer of 3-5. In the average formula (12), h is 29, i is 5, j is 6, and k is 5.

  Further, for example, the above two examples are combined to react polydimethylsiloxane represented by the average formula (9), triisocyanate (6), and polymerizable reactive group-containing polyester (11) at a molar ratio of 1: 2: 4. (12) polydimethylsiloxane having an acryloyloxy group can also be obtained.

  In addition to this, polydimethylsiloxane is synthesized by a method in which a polyester portion having a polymerizable reactive group and a polyurethane portion are bonded and then introduced into a siloxane skeleton, or a method in which a polymerizable reactive group is finally introduced. It is also possible. Usually, the compound represented by General formula (3) can be used individually or in combination of 2 or more types.

  In addition, organopolysiloxane having one polymerizable reactive group in one molecule, for example, one-end (meth) acryloyloxy-modified polydimethylsiloxane, polydiorganosiloxane having the above specific structure (polyether-modified polydimethyl having an acrylic group) A siloxane or a polyester-modified polydimethylsiloxane having an acrylic group can also be used in combination.

  (B) The polyether-modified polydimethylsiloxane having an acrylic group or the polyester-modified polydimethylsiloxane having an acrylic group is contained in an amount of 2.0 to 8.0% by mass in the composition for a low refractive index layer. When the content is less than 2.0% by mass, the wiping property of the fingerprint attached to the surface of the low refractive index layer is not improved. On the other hand, if it exceeds 8.0% by mass, the adhesion of fingerprints when touching the surface of the low refractive index layer cannot be weakened.

[(C) component]
(C) The ultraviolet curable resin copolymerizable with the component (a) and the component (b) can impart hardness to the low refractive index layer. (C) The ultraviolet curable resin copolymerizable with the component (a) and the component (b) is contained in an amount of 9.0 to 70.0% by mass in the resin composition for the low refractive index layer. When the content is less than 9.0% by mass, the low refractive index layer is insufficient in hardness or the transmittance is lowered. On the other hand, when it exceeds 70.0 mass%, the wiping property of fingerprints is not improved.

  (C) The ultraviolet curable resin copolymerizable with the component (a) and the component (b) has a functional group containing a polymerizable double bond copolymerizable with the component (a) and the component (b). Examples of such functional groups include radical polymerizable functional groups such as acryloyl group, methacryloyl group, acryloyloxy group, and methacryloyloxy group, and cationic polymerizable functional groups such as epoxy group, vinyl ether group, and oxetane group. Examples of the ultraviolet curable resin copolymerizable with the component (c) (a) and the component (b) include urethane (meth) acrylate (oligomer), epoxy (meth) acrylate (oligomer), polyester (meth) acrylate ( Oligomer), polyether (meth) acrylate (oligomer), (meth) acrylate (oligomer), and fluorine-containing compounds thereof.

[Component (d)]
(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.

  (D) 22.0-83.0 mass% of hollow silica fine particles are contained in the low refractive index layer. (D) When the content of the hollow silica fine particles is less than 22.0% by mass, the refractive index of the low refractive index layer is not sufficiently lowered. On the other hand, when the content of the hollow silica fine particles (d) is more than 83.0% by mass, the coating film strength becomes weak, which is not preferable.

[(E) component]
(E) The photopolymerization initiator is used as a polymerization initiator when a coating film is formed by curing the resin composition for a low refractive index layer with active energy rays such as ultraviolet rays (UV). (E) As a photoinitiator, if a polymerization is started by active energy ray irradiation, it will not specifically limit, A well-known compound can be used. For example, acetophenone-based polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin, 2,2-dimethoxy 1,2-diphenylethane-1 Benzoin-based polymerization initiators such as -one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4'-tetra (t- Examples thereof include benzophenone polymerization initiators such as (butylperoxycarbonyl) benzophenone, and thioxanthone polymerization initiators such as 2-chlorothioxanthone and 2,4-diethylthioxanthone.

  (E) 1.0-10.0 mass% of photoinitiators are contained in the resin composition for low refractive index layers. (E) If content of a photoinitiator is less than 1.0 mass%, hardening of a low refractive index layer will become inadequate. On the other hand, if the content of (e) the photopolymerization initiator exceeds 10.0% by mass, the photopolymerization initiator is undesirably increased. The total content of the components (a) to (e) is 100% by mass.

≪Hard coat layer≫
A hard coat layer can be provided between the transparent base film and the antiglare layer in order to increase the surface hardness of the antiglare antireflection film. The refractive index nh of the hard coat layer is not particularly limited and can be appropriately applied. However, it is preferable that the difference | nb−nh | from the refractive index nb of the transparent base film does not exceed 0.35. If the difference | nb−nh | between the refractive index nb of the transparent substrate film and the refractive index nh of the hard coat layer exceeds 0.35, the reflectance at the transparent substrate film / hard coat layer interface increases. Transmittance decreases. More preferably, the refractive index nh of the hard coat layer is not less than the refractive index nb of the base material and not more than the refractive index na of the antiglare layer. When the refractive index nh of the hard coat layer is lower than the refractive index nb of the transparent substrate film, the reflectance at the hard coat layer / antiglare layer interface increases, and the transmittance decreases. Further, when the refractive index nh of the hard coat layer is higher than the refractive index na of the antiglare layer, the reflectance at the substrate / hard coat layer interface increases, and the transmittance decreases. The refractive index of the hard coat layer is preferably 1.49 to 1.85. When the refractive index exceeds 1.85, interference unevenness may appear due to interference caused by the difference in refractive index between the transparent base film and the hard coat layer.

  The film thickness of the hard coat layer is preferably 1 μm or more. A film thickness of less than 1 μm is not preferable because the surface hardness cannot be increased effectively. Further, the film thickness of the hard coat layer is preferably 3 μm or more. When the thickness exceeds 20 μm, problems such as a decrease in flex resistance occur, which is not preferable.

  The material for the hard coat layer is not particularly limited as long as it is a known material conventionally used for an antireflection film or the like. For example, a reactive silicon compound such as tetraethoxysilane or an active energy ray curable resin can be used, and these may be mixed. And the hard-coat layer can be formed by irradiating and hardening | curing active energy rays, such as an ultraviolet-ray and an electron beam, to the coating liquid for hard-coat layers prepared by adding a photoinitiator to these.

  Examples of the active energy ray-curable resin include monofunctional (meth) acrylate and polyfunctional (meth) acrylate. Specifically as monofunctional (meth) acrylate, (meth) acrylic acid alkyl ester, (meth) acrylic acid (poly) ethylene glycol group-containing (meth) acrylic acid ester and the like are preferable. Examples of the polyfunctional (meth) acrylate include ester compounds of polyhydric alcohol and (meth) acrylic acid, polyfunctional polymerizable compounds containing two or more (meth) acryloyl groups such as urethane-modified acrylate, and the like.

  Among these, from the viewpoint of achieving both productivity and hardness, a cured product of a composition containing an active energy ray-curable resin having a pencil hardness (evaluation method: JIS-K5600-5-4) of H or higher is preferable. . The composition containing such an active energy ray curable resin is not particularly limited. For example, a known active energy ray curable resin or a mixture of two or more known active energy ray curable resins may be mixed. And those commercially available as ultraviolet curable hard coat materials.

  The photopolymerization initiator is used as a polymerization initiator when a coating film is formed by curing the hard coat layer coating liquid with an active energy ray such as ultraviolet (UV). The photopolymerization initiator is not particularly limited as long as it initiates polymerization upon irradiation with active energy rays, and known compounds can be used. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, acetophenone polymerization initiators such as 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy 1,2 -Benzoin polymerization initiators such as diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4' -Benzophenone polymerization initiators such as tetra (t-butylperoxycarbonyl) benzophenone, 2-chlorothio Xanthone, such thioxanthone type polymerization initiators such as 2,4-diethyl thioxanthone, and the like.

  The solvent of the coating solution is not particularly limited as long as it is a known one that has been conventionally used for the coating solution for forming each layer in this type of antireflection film, and examples thereof include alcohol-based, ketone-based, and ester-based solvents. Can be selected in a timely manner.

  Furthermore, the hard coat layer may contain other additives. Other additives include inorganic particles for adjusting the refractive index, antistatic agents, surface adjusting agents, and the like. As the antistatic agent, conductive metal oxide fine particles such as ATO fine particles and ITO fine particles, conductive polymers such as PEDOT, and surfactants such as quaternary ammonium salts can be used. As the surface conditioner, a silicon leveling agent such as polydimethylsiloxane or an acrylic leveling agent can be used.

≪Formation of each layer≫
The formation method of the antiglare layer, the low refractive index layer, and the hard coat layer is not particularly limited. For example, each of the resin compositions for each layer is adjusted by appropriately diluting with a solvent by a coating method such as a dry coating method or a wet coating method. A method in which the coating liquid is applied to a transparent substrate film and cured can be employed. 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, and typical examples include a roll coating method, a die coating method, a spin coating method, and a dip coating method. In these, the method which can form a coating film continuously, such as a roll coat method, is preferable from the point of productivity. The formed coating film can form a cured film by performing a curing reaction by heating, irradiation with active energy rays such as ultraviolet rays and electron beams.

<Image display device provided with antiglare antireflection film on surface>
The image display device provided with the antiglare antireflection film on the surface of the screen can suppress reflection of light on the screen, suppress glare, and can easily slide a finger during flicking. In addition, it is excellent in antifouling property and easy to wipe off fingerprints. Examples of the image display device include a car navigation system, a smartphone, a mobile PC, and an electronic blackboard display. The antiglare antireflection film is attached to the observation side surface of the image display device via an OCA (optical clear adhesive) or attached to the observation side surface as a polarizing film. In the case of using an antiglare antireflection film as a polarizing film, the polarizing film is generally protected on at least one side of a polarizer composed of a polyvinyl alcohol-based resin film adsorbed and oriented with iodine or a dichroic dye. Although many films are laminated, if the antiglare antireflection film is bonded to one surface of such a polarizing film, a polarizing film having an antiglare antireflection effect is obtained. The antiglare reflection can also be achieved by using the antiglare antireflection film also as a protective film and pasting it on one side of the polarizer so that one surface on which the low refractive index layer or the like is laminated is on the outside. It can be set as the polarizing film with the prevention effect.

  Hereinafter, the embodiment will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the scope of these examples.

[Transparent substrate film]
In each Example and Comparative Example, the following were used as the transparent substrate film.
Triacetyl cellulose (TAC)
“TD80UL” manufactured by FUJIFILM Corporation 80 μm, refractive index 1.48
Polyethylene terephthalate (PET)
“U403” 100 μm manufactured by Toray Industries, Inc., refractive index 1.65
Cycloolefin polymer (COP)
“ZEONOR FILM” manufactured by Nippon Zeon Co., Ltd. 80 μm, refractive index 1.53

[Resin composition for anti-glare layer]
As the resin composition for the antiglare layer, the following raw materials were used, and the respective raw materials were mixed in the compositions described in Tables 1 to 6 below to prepare resin compositions AG-1 to AG-39 for the antiglare layer. . In addition, the volume ratio of each raw material shows the ratio of the volume of the said raw material in the resin composition whole volume for glare-proof layers.

<Small particle size>
Titanium oxide fine particles (dispersion)
“RTTMEK25WT% -F02” manufactured by CIK Nanotech Co., Ltd., particle size 0.015 μm
Zirconia (dispersion)
"ZRMEK25% -F47" manufactured by CII Kasei Co., Ltd., particle size 0.015μm
Zinc antimonate fine particles (AZO) (dispersion)
“CELNAX CX-603M-F2” manufactured by Nissan Chemical Industries, Ltd., particle diameter 0.05 μm
ITO fine particles (dispersion)
“Conductive EI-3NMHR3, 35%” manufactured by Dainippon Paint Co., Ltd., particle size 0.05 μm
Silica ultrafine particles (dispersion)
“IPA-ST, 30%” manufactured by Nissan Chemical Co., Ltd., particle size 0.03 μm
Silica ultrafine particle “SIMIBK15WT% -H58” manufactured by CIK Nanotech Co., Ltd., particle size 0.1 μm
Antimony-tin oxide fine particles (ATO)
Product name: ATO, particle size 0.05 μm, manufactured by Nissan Chemical Industries, Ltd.
Zinc oxide Air Brown Co., Ltd. “TECNAPOW-ZNO”, particle size 0.02μm

<Large diameter fine particles>
Acrylic (PMMA), particle size 0.8μm “MX-80H3wT” by Soken Chemical Co., Ltd.
Acrylic (PMMA), particle size 3μm “MX-300” manufactured by Soken Chemical Co., Ltd.
Acrylic (PMMA), particle size 5μm “MX-500” manufactured by Soken Chemical Co., Ltd.
Acrylic (PMMA), particle size 8μm “SSX-108” manufactured by Sekisui Plastics Co., Ltd.
Polystyrene (PS), particle size 3.5 μm “Made by Soken Chemical Co., Ltd., SX-350H”
Cross-linked acrylic-styrene copolymer resin (MS), particle size 0.8μm
"SSX1008QXE" manufactured by Sekisui Plastics Co., Ltd.
Cross-linked acrylic-styrene copolymer resin (MS), particle size 5 μm
"SSX1055QXE" manufactured by Sekisui Plastics Co., Ltd. Monodispersed fine particle silica with uniform particle size, particle size 0.8μm "Sicastar 43-00-802" manufactured by Corefront Co., Ltd.

<Binder resin>
Dipentaerythritol hexaacrylate, “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.
Urethane acrylate, “Shikko UV7600B” manufactured by Nippon Synthetic Chemical Industry Co., Ltd., molecular weight 1400, viscosity at 60 ° C. is 2500 to 4500 Pa · s
Pentaerythritol triacrylate (PE3A), “PET30” manufactured by Nippon Kayaku Co., Ltd.

<Photopolymerization initiator>
“IRGACURE 184 (I-184)” manufactured by Ciba Specialty Chemicals Co., Ltd.

[Resin composition for low refractive index layer]
As the resin composition for a low refractive index layer, the following raw materials are used, and the respective raw materials are mixed in the compositions described in Tables 7 to 10 below, and the resin compositions for low refractive index layers LL1-1 to 1-18, LL2-1 to LL2-12 were prepared. In addition, the compounding quantity of each material has described the mass% of solid content. The raw materials for the resin composition for the low refractive index layer are as follows.

<(A) component>
(Meth) acrylate containing C2-C7 perfluoroalkyl chain "OPTOOL DAC-HP" manufactured by Daikin Industries, Ltd.
(Meth) acrylate containing C2-C7 perfluoroalkyl chain "Megafac RS-75" manufactured by DIC Corporation
An oligomer containing a C2-C7 perfluoroalkyl chain and containing no (meth) acrylate "Megafac F-558" manufactured by DIC Corporation

<(B) component>
Polyether-modified polydimethylsiloxane having an acrylic group "BYK-UV 3500" manufactured by Big Chemie Japan Co., Ltd.
Polyether-modified polydimethylsiloxane having an acrylic group "BYK-UV 3530" manufactured by Big Chemie Japan Co., Ltd.
Polyester-modified polydimethylsiloxane having an acrylic group "BYK-UV 3570" manufactured by Big Chemie Japan Co., Ltd.
Polyether-modified polydimethylsiloxane having no acrylic group "BYK331" manufactured by Big Chemie Japan Co., Ltd.

<(C) component>
Dipentaerythritol hexaacrylate “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.
OD2H2A

<(D) Hollow silica fine particles>
“Acrylic modified hollow silica fine particles through rear NAU” manufactured by JGC Catalysts & Chemicals Co., Ltd.
“Acrylic modified hollow silica fine particles through rear V8208” manufactured by JGC Catalysts & Chemicals Co., Ltd.

<(E) Photopolymerization initiator>
“IRGACURE907 (I-907)” manufactured by Ciba Specialty Chemicals Co., Ltd.

[Resin composition for hard coat layer]
The following commercially available products were used as the resin composition for the hard coat layer.
Hard coat "Rioduras LAS1303NL" manufactured by Toyo Ink Co., Ltd.

(Example 1-1)
On one side of FUJIFILM TAC film “TD80UL, 80 μm”, the film thickness after curing the resin composition for anti-glare (AG-1) with a bar coater (the film thickness of the part where particles are not present) is 0.2 μm. The antiglare layer was formed by irradiating with a 120 W high-pressure mercury lamp and irradiating with 400 mJ ultraviolet rays.

  Next, on this antiglare layer, a low refractive index layer coating solution prepared by mixing a resin composition for low refractive index layer (LL1-1) and a solvent (methyl isobutyl ketone) at a ratio of 1: 5 is applied to a bar coater. Then, it was applied so that the film thickness after curing was 0.1 μm, and an anti-glare antireflection film was produced by irradiating and curing 400 mJ ultraviolet rays with a 120 W high pressure mercury lamp in a nitrogen atmosphere.

(Examples 1-2 to 1-19, 1-21 to 46, Comparative Examples 1-1 to 1-25)
Using the materials shown in Tables 11 to 18, antiglare and antireflection films were prepared in the same manner as in Example 1-1.

(Example 1-20)
On one side of a TAC film “TD80UL, 80 μm” manufactured by Fuji Film, a hard coat resin composition was applied with a bar coater so that the film thickness after curing (the film thickness of the part where no particles exist) was 4 μm. A clear hard coat layer was formed by curing by irradiating 400 mJ ultraviolet rays with a high-pressure mercury lamp. Next, an antiglare layer and a low refractive index layer were provided on the clear hard coat layer by the same method as in Example 1-1.

  About the obtained anti-glare antireflection film of each Example and Comparative Example, various characteristics were measured and evaluated by the following methods. The results are also shown in Tables 11-18.

<Refractive index of transparent substrate film>
It measured by the method of JISK7142-2014.

<The refractive index of each layer composition after curing>
(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 of ultraviolet light 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 roughening the back surface of the produced film with sandpaper and painting 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 / λ ⁴ + b / λ ² + c (Formula 1)
The refractive index of the antiglare layer is calculated by curing a composition excluding the large particles among the compositions constituting the antiglare layer to form a cured film, and measuring the reflection spectrum of the cured film. did.

<Film thickness of antiglare layer>
Measure the reflection spectrum of the part without protrusions (convex) due to particles with a spectroscopic film thickness meter (FE3000, manufactured by Otsuka Electronics), and calculate it from the obtained reflection spectrum by the peak valley method.

<Surface roughness>
Arithmetic average roughness in accordance with the provisions of JIS B 0601-1994, using a surface roughness measuring machine manufactured by Kosaka Laboratory Co., Ltd., Surfcorder SE500, under conditions of a scanning range of 4 mm and a scanning speed of 0.2 mm / s. Ra (μm) and the average interval Sm (mm) of the irregularities were measured.

<Visibility reflectance>
In order to remove the back surface reflection of the measurement surface, the back surface was roughened with sandpaper and painted with a black paint, and a light wavelength of 380 nm to 780 nm was measured with a spectrophotometer [trade name: U-best 560 manufactured by JASCO Corporation]. The 5 ° and −5 ° specular reflection spectra were measured. Viewing the tristimulus value Y of the object color due to reflection in the XYZ color system assumed in JIS Z8701, using the spectral reflectance of the obtained light with a wavelength of 380 nm to 780 nm and the relative spectral distribution of the CIE standard illuminant D65. Sensitivity reflectance (%) was used.

<All haze>
A haze meter (Nippon Denshoku Industries Co., Ltd., NDH2000) was used, and the haze value (%) as an optical characteristic was measured.

<Internal haze>
The internal haze value is a haze value measured by dropping water droplets on the surface of the antiglare hard coat layer and pressing glass there.

<External haze>
External haze = total haze-calculated by internal haze.

<(1) Antiglare property>
(1) -1 <Reflection image blur>
When the fluorescent lamp light is reflected so that the fluorescent lamp distance is 3 m and the incident angle is 10 ° on the surface on which the antiglare hard coat layer is laminated, how much the outline of the fluorescent lamp reflected regularly at 10 ° is blurred. Was evaluated according to the following evaluation criteria. As the fluorescent lamp, FHF32EXNH manufactured by Panasonic Corporation was used.
○: Blurred so that the outline cannot be confirmed.
X: The outline is not blurred or blurred so that the outline cannot be confirmed, but the visibility of the image is poor.
(1) -2 <Transparent image definition, reflected image definition>
A value of image definition (transmission image definition) through an optical comb having a width of 1 mm using an image definition measuring device based on JIS K 7105-1981 (image clarity measuring device manufactured by Suga Test Instruments Co., Ltd., ICM-1T). (Degree) (%) and the value of image sharpness (reflection image sharpness) (%) measured by 45 ° reflection. The criteria for determination of the measurement results are as follows.
Transmission image definition: "100% to 90% ... no antiglare property", "less than 90% 15% or more ... good antiglare effect", "less than 15% less than 0% ... prevention The dazzling effect is too strong. ''
Reflected image sharpness: "100% to 80% ... no antiglare property", "less than 80%, 5% or more ... good antiglare effect", "less than 5%, less than 0% ... prevention The dazzling effect is too strong. ''

<Glitter>
An anti-glare film was placed on the outermost surface on the image display side of a high-definition liquid crystal touch panel as a high-definition liquid crystal display, and the glare was measured visually and evaluated in the following three stages.
A: No glare, B: Slight glare, but not worrisome, X: Glitter as worrisome.

<Fingerprint wiping>
The attached fingerprint was wiped with Toray-made Toraysee at a load of 200 gf / cm 2 and the number of times of wiping necessary to make the fingerprint invisible was counted.
○: 20 round trips or less, x: 21 round trips or more.

<Finger slipperiness>
The coefficient of dynamic friction with respect to an artificial skin model of urethane elastomer material (trade name: Bio Skin Plate Plate #BS Color 1, manufactured by Beaulux Co., Ltd.) was measured by a measurement method based on JIS K 7125-1999.
The coefficient of friction evaluated by this evaluation method correlates with the slipperiness when flicking with a human finger. The smaller the coefficient of friction, the easier the finger slides, and the higher the coefficient of friction, the less sensitive the finger is. It was evaluated. In addition, when the friction coefficient is such that the friction coefficient ≦ 0.5, 90% or more of the evaluators (N = 30) determined that the finger is easy to slip when flicking.

<Surface hardness>
The load was set to 750 g and evaluated according to JIS K 5600.

  From the results of the examples, the particle diameter Pdia of the large-sized fine particles contained in the antiglare layer is 0.1 μm ≦ Pdia ≦ 5 μm, and the ratio t / Pdia of the film thickness t of the antiglare layer and the particle diameter Pdia is 0. 0.05 ≦ t / Pdia ≦ 1.7, the particle diameter Mdia of the small particle is 0.01 μm ≦ Mdia ≦ 0.1 μm, and the ratio Mden / Pden of the specific gravity Mden of the small particle and the specific gravity Pden of the large particle is 6.0 ≧ Mden / Pden ≧ 2.7, and the volume ratio of the large diameter fine particles occupying the total volume of the antiglare layer is 0.5% to 40%, and the small diameter fine particles occupying the total volume of the antiglare layer When the volume ratio is 15% or more and 65% or less, moderate unevenness is formed on the antiglare and antireflection film, the antiglare property is excellent, the glare is small, and the ease of finger slipping during flicking is good. The outermost low refractive index layer is (a) 5.0 to 15.0% by mass of (meth) acrylate containing a C2 to C7 perfluoroalkyl chain, and (b) a polyether-modified poly having an acrylic group. 2.0 to 8.0% by mass of polyester-modified polydimethylsiloxane having dimethylsiloxane or acrylic group, and 9.0 to 70.0% by mass of UV curable resin copolymerizable with (c) (a) and (b) , (D) 22.0-83.0% by mass of hollow silica fine particles, (e) 1.0-10.0% by mass of a photopolymerization initiator, and (b) is% by mass of (a). When it is a cured product of a resin composition for a low refractive index layer (provided that the total of (a), (b), (c), (d), and (e) is 100% by mass), fingerprint wiping properties Excellent.

  On the other hand, in Comparative Examples 1-1, 1-4, 1-12, and 1-13, the volume ratio of the small-diameter fine particles in the total volume of the antiglare layer is small, and the antiglare property is inferior. In Comparative Example 1-2, the volume ratio of the large-sized fine particles in the total volume of the antiglare layer is small, and the antiglare property is inferior. In Comparative Example 1-3, the volume ratio of the large-sized fine particles occupying the entire volume of the antiglare layer is large, and since appropriate unevenness is not formed, the antiglare property is inferior and the haze is large. In Comparative Example 1-5, since the particle diameter of the large-sized fine particles is small with respect to the film thickness, moderate unevenness is not formed and the antiglare property is inferior. In Comparative Examples 1-6 to 1-10, since the difference in specific gravity between the large-sized fine particles and the small-sized fine particles is small, the antiglare property is inferior and the glare is large. Moreover, finger slipperiness is also inferior. In Comparative Example 1-11, the particle diameter of the large-sized fine particles is large and the glare is large.

  Moreover, in Comparative 1-13-1-25, the fingerprint wiping property is inferior for the following reason in the composition of the low refractive index layer. In Comparative Examples 1-13 and 1-14, the component (a) is small. In Comparative Example 1-15, the component (a) is large. In Comparative Examples 1-16 and 1-17, the component (b) is absent or small. In Comparative Examples 1-18 and 1-19, the component (b) is large. In Comparative Examples 1-20 to 1-22, the masses of the component (a) and the component (b) are equal or the mass of the component (b) is larger. Comparative Example 1-23 does not contain a polymerization initiator. In Comparative Examples 1-24 and 1-25, the component (a) and the component (b) do not react.

Claims (7)

A low refractive index layer is laminated on one surface of the transparent substrate film, and an antiglare layer having a higher refractive index than the low refractive index layer is laminated between the transparent substrate film and the low refractive index layer. Has been
The antiglare layer includes large-sized fine particles, and small-sized fine particles having a specific gravity larger than the large-sized fine particles and a small particle size,
The large-sized fine particles have a particle diameter Pdia of 0.1 μm ≦ Pdia ≦ 5 μm, and a ratio t / Pdia between the film thickness t of the antiglare layer and the particle diameter Pdia is 0.05 ≦ t / Pdia ≦ 1. 7 and the particle diameter Mdia of the small particle is 0.01 μm ≦ Mdia ≦ 0.1 μm,
The ratio Mden / Pden of the specific gravity Mden of the small particle and the specific gravity Pden of the large particle is 6.0 ≧ Mden / Pden ≧ 2.7,
The volume ratio of the large-sized fine particles in the total volume of the anti-glare layer is 0.5% or more and 40% or less, and the volume ratio of the small-sized particles in the total volume of the anti-glare layer is 15% or more and 65% or less. And
The low refractive index layer is
(A) 5.0 to 15.0 mass% of (meth) acrylate containing a C2 to C7 perfluoroalkyl chain,
(B) Polyether-modified polydimethylsiloxane having an acrylic group or polyester-modified polydimethylsiloxane having an acrylic group, 2.0 to 8.0% by mass,
(C) 9.0 to 70.0% by mass of an ultraviolet curable resin copolymerizable with (a) and (b),
(D) 22.0-83.0 mass% of hollow silica fine particles,
(E) Photoinitiator 1.0-10.0 mass%
Consists of
The resin composition for a low refractive index layer in which the mass% of (b) is less than the mass% of (a) (however, the total of (a) (b) (c) (d) (e) is 100 mass%. is there.)
An anti-glare antireflection film formed by curing.   2. The antiglare antireflection film according to claim 1, wherein a ratio t / Pdia of a film thickness t of the antiglare layer and a particle diameter Pdia of the large fine particles satisfies 0.05 ≦ t / Pdia ≦ 1.3.   3. The antiglare antireflection film according to claim 1, wherein a volume ratio of the small-diameter fine particles occupying the entire volume of the antiglare layer is 15% or more and 55% or less.   The small-sized fine particles are at least one selected from the group consisting of zirconium oxide, titanium oxide, zirconia, zinc oxide, zinc antimonate, tin-doped indium oxide, antimony-doped tin oxide, and silica. The antiglare antireflection film according to any one of the above.   The large-sized fine particles are acrylic resin, polystyrene, polymethacrylstyrene, crosslinked acrylic-styrene copolymer resin, silica, benzoguanamine formaldehyde condensate, benzoguanamine / melamine / formaldehyde condensate, melamine / formaldehyde condensate, polyethylene resin, epoxy resin, The antiglare antireflection film according to any one of claims 1 to 4, wherein the antiglare antireflection film is at least one selected from the group consisting of a silicone resin, a polyvinylidene fluoride, and a polyvinyl fluoride resin.   The antiglare antireflection film according to any one of claims 1 to 5, wherein a hard coat layer is laminated between the transparent substrate film and the antiglare layer.   An image display device comprising the antiglare antireflection film according to any one of claims 1 to 6 on a surface thereof.