JP6520114B2 - Antiglare antireflective film and image display device using the same - Google Patents

Description

  The present invention is an antiglare antireflective film, which has less glare of a display, good slipperiness of a finger at the time of flicking, excellent antifouling property, and easy wiping of fingerprints. The present invention relates to an antiglare film. The present invention also relates to an image display using the antiglare antireflection film.

  Displays such as car navigation systems, smart phones, and televisions are required to have less reflection of light emitted from external light sources such as fluorescent lamps and sunlight in order to enhance their visibility. When 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 displayed image. Therefore, by providing an antiglare film having fine asperities on the surface on the surface of the display, the reflected light is scattered to make the reflection less noticeable.

  Conventionally, the number of pixels of a normal display is about 100 to 150 per 25.4 mm (= 1 inch) in the vertical and horizontal directions of the screen, and it becomes possible to view an image without any problem if a conventional antiglare film is used. Become. However, displays that display high-definition images with a large number of pixels per inch, such as car navigation systems, smartphones, and 8K televisions, are increasing. For example, the number of pixels is approximately 300 per 25.4 mm in the screen, ie, the above It may be twice as high definition as normal displays. One of the purposes is to make the image of the 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 rather impaired. When a conventional antiglare film is provided on the surface of a display, it is used to prevent a black mask (or black matrix, for example, black lines provided longitudinally and laterally) at the boundaries of each pixel of the display. There is no particular problem in the place where the convex part of the unevenness of the glare film overlaps, but in the place where the concave parts of the black mask and the antiglare film overlap, that part is scattered because the image light is scattered. This is because a scintillating and sparkling scintillation phenomenon occurs. When a conventional antiglare film is applied to a display in which the number of pixels is doubled as described above, the scintillation (surface glaring) phenomenon becomes remarkable, and characters, lines, pictures, photographs, etc., in particular characters or lines It seriously impairs the visibility.

  Related to this, Patent Document 1 discloses an antiglare antireflection film aiming to reduce scintillation (surface girder). This antiglare antireflection film has a structure in which an antiglare layer and a low refractive index layer are laminated in this order on a transparent substrate film, and each layer is formed by the difference in refractive index between the antiglare layer and the low refractive index layer. The reflected light on the surface of the lens interferes with each other to cancel out each other, 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 enhanced 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. 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 referred to as a light transmitting diffuser, irregularities are formed. In this antiglare antireflection film, particles having a refractive index difference of 0.01 to 0.5 with respect to the light transmitting resin are used as the light transmitting diffusion agent in order to suppress scintillation (surface glaring), and The haze value of the surface of the antiglare layer (the surface which is not the transparent substrate film side) is 7 to 30, and the haze value of the inside of the antiglare layer is 1 to 30.

Japanese Patent Application Publication No. 2003-4904

  The above-mentioned conventional anti-glare antireflective film is difficult to wipe off the attached fingerprint, and the finger does not slip easily at the time of flicking and has a feeling of being caught, and furthermore, the suppression effect of scintillation (glare) is small, so a high definition touch panel When applied to the observation side of the display, there are problems such as fingerprint contamination is accumulated, the operability of the touch panel is poor, and it is difficult to appreciate an excellent image due to the occurrence of glare.

  Such problems are manifested in recent years because car navigation systems and mobile phones equipped with a capacitive touch panel having a multi-touch function have become widespread. The trend of the required performance for the surface film is changing, and not only the demand for the reflection preventing function but also the new need which has not been in the past to suppress the slipperiness of the finger and the adhesion of the fingerprint on the touch panel surface is increasing. However, the conventional antiglare antireflective film is specialized in the function of anti-reflection, and since no measures for adhesion of fingerprints are applied, it can meet the needs for suppressing the slipperiness of fingers and adhesion of fingerprints. Not.

  Therefore, the object of the present invention is to prevent glare on the display, to make the finger slippery at the time of flicking good, to be excellent in anti-staining properties, and to facilitate fingerprint wiping. It is in providing 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 the transparent base film, and the low refractive index layer is formed between the transparent base 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 diameter fine particles and small diameter fine particles having a larger specific gravity and smaller particle size than the large diameter fine particles. The large diameter fine particles have a particle diameter Pdia of 0.1 μm ≦ Pdia ≦ 5 μm, and a ratio t / Pdia of the film thickness t of the antiglare layer to the particle diameter Pdia of 0.05 ≦ t / Pdia ≦ 1. 7 The particle diameter Mdia of the small-diameter fine particles is 0.01 μm ≦ Mdia ≦ 0.1 μm. The ratio Mden / Pden of the specific gravity Mden of the small-diameter fine particles to the specific gravity Pden of the large-diameter fine particles is 6.0denMden / Pden ≧ 2.7, and the volume ratio of the large-diameter fine particles occupies the entire 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 entire volume of the antiglare layer is 15% or more and 65% or less. The low refractive index layer is (a) 5.0 to 15.0% by mass of (meth) acrylate containing a C 2 to C 7 perfluoroalkyl chain, (b) polyether modified polydimethylsiloxane having acrylic group or acrylic group Group-modified polyester-modified polydimethylsiloxane 2.0 to 8.0% by mass, (c) (a) and (b) UV curable resin copolymerizable with 9.0 to 70.0% by mass (d) Low refractive index consisting of 22.0 to 83.0% by mass of hollow silica fine particles, (e) 1.0 to 10.0% by mass of a photopolymerization initiator, and the% by mass of (b) being less than the% by mass of (a) It is formed by curing the resin composition for rate layer (however, the total of (a), (b), (c), (d) and (e) is 100% by mass).

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

  It is more preferable that the volume ratio of the small diameter fine particles in the entire volume of the antiglare layer is 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, polymethacrylic styrene, crosslinked 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 an epoxy resin, a silicone resin, polyvinylidene fluoride and a polyfluorinated ethylene-based resin.

  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, it is possible to provide an antiglare antireflective film having less glare of a display, good finger slipperiness at the time of flicking, excellent antifouling property, and easy wiping of fingerprints. be able to.

<Anti-glare antireflective film>
The antiglare antireflection film is based on a transparent substrate film, a low refractive index layer is laminated on the outermost layer of at least one of the surfaces, and at least an antiglare layer is provided between the transparent substrate film and the low refractive index layer. It is stacked. In the 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, polyarylates, and polyether sulfones. Among these, triacetyl cellulose and polyethylene terephthalate are preferable in terms of high versatility. The refractive index to light of 589 nm of these transparent substrate films is approximately 1.47 to 1.70.

  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 at the time of production and use of the antiglare antireflection film is lowered.

«Antiglare layer»
The antiglare layer is light transmissive. The antiglare layer has a refractive index higher than that of the low refractive index layer, and the reflected light on the surface of each layer cancels each other out due to the difference in refractive index between the transparent base film and the antiglare layer, thereby reducing reflected light. It plays an antireflective effect. In addition, the antiglare layer has fine unevenness on the surface, and the unevenness scatters the reflected light to reduce glare and improve finger slipperiness.

  The refractive index of the antiglare layer to light of 589 nm is preferably such that the difference from the low refractive index layer is 0.10 or more, and preferably 1.47 to 1.85. If the refractive index exceeds 1.85, the surface strength may be low. In addition, when the refractive index is less than 1.47, it is difficult to effectively reduce the reflectance.

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

<Large particle size>
The large diameter fine particles are spherical, and the particle diameter is large and the specific gravity is small compared to the small diameter fine particles. An irregular shape is formed on the surface of the antiglare antireflection film by the large diameter fine particles. The particle diameter Pdia of the large diameter fine particles is 0.1 μm ≦ Pdia ≦ 5 μm. When the particle diameter Pdia is less than 0.1 μm, the surface asperity (≒ Ra) becomes too small, so that the antiglare property is not expressed. On the other hand, when the particle diameter Pdia exceeds 5 μm, the unevenness interval (間隔 Sm) on the surface becomes large, so that the antiglare effect decreases. In addition, since the contact area with the finger increases, the finger slipperiness also decreases. Preferably, 0.5 μm ≦ Pdia ≦ 3 μm. By controlling to 0.5 μm ≦ Pdia ≦ 3 μm, the size of the surface asperity (≒ Ra) and the surface asperity interval (≒ Sm) can be adjusted more appropriately.

  The particle diameter Pdia of the large diameter fine particles may be any measurement method as long as it is a method of measuring the average particle diameter of the particles, but preferably, the particles of the particles are transmitted electron microscope (magnification 20,000 to 2,000,000) Observation is performed, 100 particles are observed, and the average value is taken as the (average) particle diameter.

  In the above-described range, the ratio t / Pdia to the film thickness t of the antiglare layer satisfies 0.05 ≦ t / Pdia ≦ 1.7 within the above range of the particle diameter Pdia of the large-diameter fine particles. Here, the film thickness t of the antiglare layer is the thickness of a portion where there is no protrusion (convex) by the particles in the antiglare layer. The film thickness t of the antiglare layer can be any measurement method as long as it measures the film thickness, but preferably, the reflection film of the portion without protrusion (convex) due to the particles is measured by a spectrophotometer Then, it is calculated by the peak valley method from the obtained reflection spectrum. When t / Pdia> 1.7, the particle diameter of the large-diameter fine particles is small relative to the film thickness t, and the size of the surface unevenness is small, so that the antiglare property is lowered. When 0.05 ≦ t / Pdia ≦ 1.7, the antiglare property and the glare suppressing effect are excellent, and the finger slipperiness is good. When t / Pdia ≦ 1.3, the glare suppressing action is further excellent. Moreover, the surface hardness of an antiglare antireflection film can be raised as it is t / Pdia <= 1. The film thickness t is preferably 0.1 μm ≦ t ≦ 5 μm. If 0.1 μm> t, the strength of the antiglare layer tends to decrease. When t> 5 μm, the distance between the surface irregularities tends to be large, and the glare tends to be strong.

  The material of the large-diameter fine particles is not particularly limited as long as the ratio of the specific gravity to the small-diameter fine particles is in the range described later, but one having a specific gravity Pden of Pden ≦ 3.0 can be selected as a standard. Such materials include resins and silica. As the resin, acrylic resin, polystyrene, polymethacryl styrene, crosslinked acrylic-styrene copolymer resin, benzoguanamine formaldehyde condensate, benzoguanamine-melamine-formaldehyde condensate, melamine-formaldehyde condensate, polyethylene resin, epoxy resin, silicone resin, polyfluorocarbon Examples include vinylidene fluoride and polyethylene fluoride-based resins. Among them, acrylic, polystyrene and cross-linked acryl-styrene copolymer resins are preferable because they have a low specific gravity and easily exhibit antiglare properties. The large-diameter fine particles may be used alone or in combination of two or more.

  The ratio of the volume of the large diameter fine particles to the total volume of the antiglare layer is 0.5% or more and 40% or less. When the volume fraction of the large-diameter fine particles is less than 0.5%, sufficient antiglare property can not be obtained. On the other hand, when the volume ratio of the large-diameter fine particles exceeds 40%, the surface asperity becomes too large, so the antiglare property becomes too strong, and the visibility decreases.

<Small particle size>
The small diameter particles have a smaller particle size and a higher specific gravity than large diameter particles. The small-diameter particles are typically spherical, and segregate the large-diameter particles to the upper layer of the antiglare layer. The particle diameter Mdia of the small-diameter fine particles is 0.01 μm ≦ Mdia ≦ 0.1 μm. When the particle size Mdia is less than 0.01 μm, the particles are likely to be aggregated and it may be difficult to exhibit uniform antiglare properties. On the other hand, when the particle size Mdia exceeds 0.1 μm, visible light tends to be scattered, and the haze may increase. When the particle diameter Mdia is controlled to 0.02 μm ≦ Mdia ≦ 0.07 μm, the effect of causing the large-diameter fine particles to be uniformly segregated in the upper layer portion of the antiglare layer appears, which is preferable.

  As long as the particle diameter of the small-diameter fine particles is a method of measuring the average particle diameter of the particles, any measurement method can be applied, but preferably, observation of the particles with a transmission electron microscope (magnification 20,000 to 2,000,000) Then, 100 particles are observed, and the average value is taken as the (average) particle diameter.

  The specific gravity Mden of the small-diameter particles is such that the ratio Mden / Pden of the specific gravity Pden of the large-diameter particles is 6.0 ≧ Mden / Pden ≧ 2.7. When Mden / Pden <2.7, it becomes difficult to segregate the large diameter fine particles in the upper layer portion of the antiglare layer, so that it becomes difficult to express the antiglare property. If Mden / Pden> 6.0, the type of small-diameter particles is limited, and it is not preferable because the degree of freedom in selecting materials is lowered, such as selection of expensive particles such as gold fine particles.

  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 is in the above-mentioned range, but one having a specific gravity Mden of Mden ≧ 2.5 can be selected as a standard. Such materials include metal oxides and silica. Examples of metal oxides include zirconium oxide, titanium oxide, zirconia, zinc oxide, zinc antimonate, tin-doped indium oxide, and antimony-doped tin oxide. Among them, titanium oxide and zirconium oxide are preferable because they have a high refractive index and a large specific gravity. The small-diameter fine particles may be used alone or in combination of two or more.

  In the content of the small diameter fine particles in the antiglare layer, the volume ratio of the small diameter fine particles in the entire volume of the antiglare layer is 15% or more and 65% or less. If the volume ratio of the small-diameter fine particles is less than 15%, the unevenness interval (≒ Sm) on the surface becomes large, and the antiglare effect decreases. In addition, since the contact area with the finger increases, the finger slipperiness also decreases. On the other hand, when the proportion of the volume of the small diameter fine particles exceeds 65%, the content of the binder resin relatively decreases, and the surface hardness of the antiglare antireflection film tends to decrease. More preferably, the proportion of the volume 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>
As the binder resin, monomers, oligomers and prepolymers having radically 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 The composition is used alone or in combination. Examples of monomers include methyl acrylate, methyl methacrylate, methoxypolyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate and the like. it can. Oligomers and prepolymers include polyester acrylates, polyurethane acrylates, polyfunctional urethane acrylates, epoxy acrylates, polyether acrylates, acrylate acrylates, melamine acrylates, acrylate compounds such as silicone acrylates, unsaturated polyesters, tetramethylene glycol diglycidyl ether, Epoxy compounds such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether and various alicyclic epoxy compounds, 3-ethyl-3-hydroxymethyl oxetane, 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 of two or more.

  The content of the binder resin in the antiglare layer is preferably such that the ratio of the volume of the binder resin to the total volume of the antiglare layer is 83.5% or less. If it exceeds 83.5%, the content of the large diameter fine particles and the small diameter fine particles decreases, so the surface unevenness becomes small, and it becomes difficult to express the antiglare property. The volume ratio of the binder resin is preferably 5% or more. If it is less than 5%, voids occur in the membrane and the strength is reduced. 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.

<Photoinitiator>
A photoinitiator is used as a polymerization initiator at the time of hardening the resin composition for anti-glare hard-coat layers by active energy rays, such as an ultraviolet-ray (UV), and forming a coating film. The photopolymerization initiator is not particularly limited as long as it initiates polymerization by active energy ray irradiation, 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-morphorinopropane-1 Acetophenone-based polymerization initiators such as N-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy-1,2 Benzoin-based polymerization initiators such as diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4' Benzophenone series 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 proportion of the volume of the photopolymerization initiator in the total volume of the antiglare layer is preferably 1% or more and 25%. If the photopolymerization initiator is less than the above range, the polymerization is insufficient and adhesion can not be exhibited. On the other hand, if the amount is more than the above range, the crosslink density of the membrane is low, so the strength is weak.

<Additives>
The resin composition for the antiglare layer contains, if necessary, conventionally known additives such as surface preparation agents, leveling agents, ultraviolet light absorbers, ultraviolet light stabilizers, antioxidants, antistatic agents, antifoaming agents and the like. You may contain in the range which does not impair the effect of invention.

«Low refractive index layer»
The low refractive index layer is light transmissive. The low refractive index layer has a refractive index lower than that of the antiglare layer, and exhibits an antireflective effect along with other layers such as the antiglare layer. The refractive index to light of 589 nm of the low refractive index layer is preferably 1.49 or less. When the refractive index exceeds 1.49, it is difficult to obtain a sufficient luminous 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 hollow silica within the range described later. . When adjusting the content of hollow silica 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, preferably, the following (I) is established.
380 nm / 4 nL <dL <780 nm / 4 nL (I)
When dL is set to 380 nm / 4 nL or less, the minimum reflectance wavelength (the wavelength of light for which the reflectance is minimum) when the low refractive index layer is provided is 380 nm or less, and the low refractive index layer is provided. It is difficult to effectively reduce the reflectance of 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 for which the reflectance is minimum) becomes 780 nm or more, and the low refractive index layer is provided. In this case, it is difficult to effectively reduce the reflectance of the visible light region.

[Resin composition for low refractive index layer]
The low refractive index layer can be formed by curing the low refractive index layer resin composition. The resin composition for a low refractive index layer comprises (a) a (meth) acrylate containing a C2-C7 perfluoroalkyl chain, and (b) a polyether-modified polydimethylsiloxane having an acrylic group or a polyester-modified acrylic group. It consists of polydimethylsiloxane, an ultraviolet-curable resin copolymerizable with (c) the component (a) and the component (b), (d) hollow silica fine particles, and (e) a photopolymerization initiator. The content of the component (b) is less than the content of the component (a). Also, as used herein, "(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 to C7 perfluoroalkyl chain is for expressing an antifouling function, and the adhesion of a fingerprint to be attached when the surface of the low refractive index layer is touched It can be weakened. Specific examples of the (meth) acrylate containing a C2 to C7 perfluoroalkyl chain include those represented by the following chemical formula (1) and those represented by the following chemical formula (2).

(Wherein, n is an integer of 0 to 100, and X is H or CH ₃ )

(Wherein, X 1 represents a perfluoroalkyl group or perfluoropolyether)

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

[(B) component]
(B) The polyether-modified polydimethylsiloxane having an acryl group or the polyester-modified polydimethylsiloxane having an acryl group is for improving the wiping properties 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 one polymerizable reactive group is contained in one molecule. Are compounds having at least two, preferably two to eight.

  A and B in the general formula (3) are linear or branched organic groups, and an alkyl chain (1 to 30 carbon atoms), a perfluoroalkyl chain (1 to 10 carbon atoms), an arylalkyl chain, Aliphatic to aromatic (poly) ester chain (partial molecular weight 100 to 3000 of the organic chain), aliphatic to aromatic (poly) ether chain (partial molecular weight 100 to 3000 of the organic chain) and aliphatic And at least one skeleton selected from the group consisting of an aromatic (poly) urethane chain (partial molecular weight 100 to 3000 of the organic chain), 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 to 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 ease 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.

  At least an acrylic group is introduced as the polymerizable reactive group. As an acryl group introduce | transduced, an acryloyloxy group is preferable at the point which is excellent in the reactivity. In addition to the acryloyloxy group, a (meth) acryloyloxy group or an α-fluoroacryloyloxy group can also be introduced. As a bonding system between the polymerizable reactive group and the polysiloxane skeleton, a bonding system known in the related art, for example, a combination of (poly) ether type, (poly) ester type, (poly) ester type and (poly) urethane type The bonding method, the bonding method combining the (poly) ether type and the (poly) urethane type, and the bonding method combining the (poly) ester type and the (poly) ether type can all be adopted.

  For example, in the case of a combination of 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 the side extending from the polysiloxane moiety A polymerizable reactive group is bound to the end of three or more side chains in 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 such that Y + Z is 3 or more, preferably 4 to 20, Each of m and n is an integer of 1 to 10. m and n may be the same or different, but the same is preferable because polyether-modified polydimethylsiloxane having an acryl group or polyester-modified polydimethylsiloxane having an acryl group can be easily prepared.

R ₁ in the general formula (4) is a linear alkyl group (having 1 to 30 carbon atoms), a perfluoroalkyl group (having 1 to 10 carbon atoms), an arylalkyl group, a polyester group (partially the side chain It has a molecular weight of 200 to 2,000 and is bonded to a Si atom via an alkyl chain, a polyether group (a partial molecular weight of the side chain is 200 to 2000, and is bonded to a Si atom via an alkyl chain) It is either). R ₁ in the molecule may be the same or different, but it is more preferable that they be identical because preparation of polyether-modified polydimethylsiloxane having an acryl group or polyester-modified polydimethylsiloxane having an acryl group is simple . Further, from the viewpoint of compatibility with the resin at the time of use, etc., the case where R ₁ is a methyl group is the most versatile and preferable.

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

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

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

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

  For example, by ring-opening polymerization of ε-caprolactone using polydimethylsiloxane represented by the average formula (5), triisocyanate represented by the general formula (6), and ethylene glycol monomethacrylate obtained by a conventionally known method The polyester represented by the general formula (7) to be prepared is used at a molar ratio of 1: 2: 4, and the poly represented by the average formula (8) is formed by a conventionally known urethane bond forming reaction. A dimethylsiloxane compound is obtained. At this time, after polydimethylsiloxane (5) is added to triisocyanate (6) to form urethane bonds at both ends of polydimethylsiloxane (5), urethane with the polymerizable reactive group-containing polyester (7) is formed. By forming a bond, by-products [for example, by-products consisting only of polydimethylsiloxane (5) and triisocyanate (6), or polyesters containing polymerizable reactive group (7) and triisocyanate (6) are formed. It is possible to obtain the target polydimethylsiloxane (8) in high yield while suppressing the formation of by-products etc.].

  Here, d in the average formula (5), (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, the general formula (7) And g in average Formula (8) is an integer of 3-5. Moreover, in average formula (5) * (8), Me represents a methyl group.

  Besides, 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 Using a polymerizable reactive group-containing polyester represented by the general formula (11) prepared by ring-opening polymerization at a molar ratio of 1: 2: 2, an average formula (12) can be obtained by a conventionally known urethane bond forming reaction. The polydimethylsiloxane compound represented by these is obtained. At this time, after polydimethylsiloxane (9) is added to diisocyanate (10) to form urethane bonds at both ends of polydimethylsiloxane (9), urethane bond with the polymerizable reactive group-containing polyester (11) Forming a by-product [for example, a by-product consisting only of polydimethylsiloxane (9) and diisocyanate (10), or a by-product consisting only of the polymerizable reactive group-containing polyester (11) and diisocyanate (10) Etc.] can be suppressed, and the target 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 to 5. In the average formula (12), h is 29, i is 5, j is 6, and k is 5.

  Furthermore, for example, the polydimethylsiloxane represented by the average formula (9), the triisocyanate (6), and the polymerizable reactive group-containing polyester (11) are reacted at a molar ratio of 1: 2: 4 by combining the above two examples. It is also possible to obtain a polydimethylsiloxane having an acryloyloxy group of (12).

  Other than this, polydimethylsiloxane is synthesized by a method in which a polyester portion having a polymerizable reactive group and a polyurethane portion are combined and then introduced into the siloxane skeleton, or a method in which the introduction of the polymerizable reactive group is finally performed. It is also possible. Usually, the compounds represented by the general formula (3) can be used singly or in combination of two or more.

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

  (B) Polyether-modified polydimethylsiloxane having an acryl group or polyester-modified polydimethylsiloxane having an acryl group is contained in an amount of 2.0 to 8.0% by mass in the composition for a low refractive index layer. If the content is less than 2.0% by mass, the wiping properties of fingerprints attached to the surface of the low refractive index layer do not improve. On the other hand, if it exceeds 8.0% by mass, the adhesion of the fingerprint when touching the surface of the low refractive index layer can not be weakened.

[(C) component]
The ultraviolet curable resin copolymerizable with the (c) component and the (b) component can impart hardness to the low refractive index layer. The ultraviolet curable resin copolymerizable with the (c) component and the (b) component is contained in an amount of 9.0 to 70.0% by mass in the low refractive index layer resin composition. If the content is less than 9.0% by mass, insufficient hardness of the low refractive index layer and a decrease in transmittance occur. On the other hand, if it exceeds 70.0% by mass, the wiping property of the fingerprint does not improve.

  The ultraviolet curable resin copolymerizable with the (c) component and the (b) component has a functional group containing a polymerizable double bond which is copolymerizable with the (a) component and the (b) component. 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 UV curable resin copolymerizable with the (c) component and the (b) component include, for example, urethane (meth) acrylate (oligomer), epoxy (meth) acrylate (oligomer), polyester (meth) acrylate ( Oligomers), polyether (meth) acrylates (oligomers), (meth) acrylates (oligomers) and their fluorine-containing compounds.

[(D) component]
(D) Hollow silica fine particles are blended to positively 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 they can reduce the refractive index, and known hollow silica fine particles can be used. Specifically, acrylic modified hollow silica fine particle through rear 4320 and the like manufactured by JGC Catalysts Chemical Co., Ltd. can be mentioned.

  The hollow silica fine particles (d) are contained in an amount of 22.0 to 83.0 mass% in the low refractive index layer. (D) If the content of the hollow silica fine particles is less than 22.0% by mass, the refractive index of the low refractive index layer does not become sufficiently low. 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 is undesirably reduced.

[(E) component]
(E) A photopolymerization initiator is used as a polymerization initiator at the time of hardening the resin composition for low refractive index layers by active energy rays, such as an ultraviolet ray (UV), and forming a coating film. The photopolymerization initiator (e) is not particularly limited as long as the polymerization is initiated by active energy ray irradiation, and known compounds can be used. For example, acetophenone-based polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin, 2,2-dimethoxy 1,2-diphenylethane-1 Benzoin-based polymerization initiators such as benzophenone, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4'-tetra (t- Benzophenone-based polymerization initiators such as butylperoxycarbonyl) benzophenone and thioxanthone-based polymerization initiators such as 2-chlorothioxanthone and 2,4-diethylthioxanthone can be mentioned.

  The photopolymerization initiator (e) is contained in an amount of 1.0 to 10.0% by mass in the low refractive index layer resin composition. (E) When the content of the photopolymerization initiator is less than 1.0% by mass, the curing of the low refractive index layer becomes insufficient. On the other hand, if the content of the photopolymerization initiator (e) exceeds 10.0% by mass, the amount of the photopolymerization initiator is unnecessarily increased, which is not preferable. In addition, the total content of the said (a)-(e) component is 100 mass%.

«Hard coat layer»
A hard coat layer can be provided between the transparent substrate 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 may be suitably applied, but it is preferable that the difference | nb-nh | with the refractive index nb of the transparent substrate film does not exceed 0.35. If the difference between the refractive index nb of the transparent substrate film and the refractive index nh of the hardcoat layer exceeds | nb−nh |, the reflectance at the interface between the transparent substrate film and the hardcoat layer increases, Transmittance decreases. Still more preferably, the refractive index nh of the hard coat layer is not less than the refractive index nb of the base material, and is preferably 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 interface of the hard coat layer / the antiglare layer increases, and the transmittance decreases. In addition, 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 interface of the base material / hard coat layer 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 resulting from the difference in refractive index between the transparent substrate film and the hard coat layer.

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

  The material of the hard coat layer is not particularly limited as long as it is a known material conventionally used for an antireflective film or the like. For example, reactive silicon compounds such as tetraethoxysilane and active energy ray curable resins can be used, and these may be mixed. Then, a hard coat layer coating solution prepared by adding a photopolymerization initiator thereto is irradiated with an active energy ray such as an ultraviolet ray or an electron beam to be cured to form a hard coat layer.

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

  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 more is preferable. . The composition containing such active energy ray curable resin is not particularly limited, but, for example, a known active energy ray curable resin or a mixture of two or more known active energy ray curable resins And those marketed as UV curable hard coat materials can be used.

  A photoinitiator is used as a polymerization initiator at the time of hardening the coating liquid for hard-coat layers by active energy rays, such as an ultraviolet-ray (UV), and forming a coating film. The photopolymerization initiator is not particularly limited as long as it initiates polymerization by active energy ray irradiation, 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-morphorinopropane-1 Acetophenone-based polymerization initiators such as N-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy-1,2 Benzoin-based polymerization initiators such as diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4' Benzophenone-based polymerization initiators such as tetra- (t-butylperoxycarbonyl) benzophenone, 2-chlorothione Xanthone, such thioxanthone type polymerization initiators such as 2,4-diethyl thioxanthone, and the like.

  The solvent for the coating solution is not particularly limited as long as it is a publicly known one conventionally used in the coating solution for forming each layer in this type of antireflective film etc. For example, alcohol solvents, ketone solvents, ester solvents You can choose in a timely manner.

  Furthermore, the hard coat layer may contain other additives. Other additives include inorganic particles for refractive index adjustment, antistatic agents, surface conditioners, 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 a surface conditioner, silicon-based leveling agents such as polydimethylsiloxane and acrylic-based leveling agents can be used.

«Formation of each layer»
The method for forming the antiglare layer, the low refractive index layer and the hard coat layer is not particularly limited, and each is prepared by appropriately diluting the resin composition for each layer with a solvent by a coating method such as dry coating method or wet coating method. The method of apply | coating a coating liquid to a transparent base film and hardening it is employable. As a coating method, a wet coating method is particularly preferable in terms of productivity and production cost. The wet coating method may be a known method such as roll coating method, die coating method, spin coating method, dip coating method and the like. Among these, the method which can form a coating film continuously, such as a roll coating method, is preferable from the point of productivity. The formed coating film can form a cured film by performing a curing reaction by heating or irradiation with active energy rays such as ultraviolet rays and electron beams.

<Image display device having antiglare antireflective film on the surface>
The image display apparatus having the above antiglare antireflection film on the surface of the screen can suppress reflection of light on the screen and can suppress glare, and the finger is easily slippery at the time of flicking. At the same time, 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 a display of an electronic blackboard. The antiglare antireflection film is attached to the surface on the observation side of the image display device via OCA (optical clear adhesive) or attached to the surface on the observation side as a polarizing film. The mode of using the antiglare antireflection film as a polarizing film will be described. In general, the polarizing film is protected on at least one side of a polarizer made of a polyvinyl alcohol resin film on which iodine or a dichroic dye is adsorbed and oriented. There are many films in the form of laminated films, but if the above-mentioned antiglare antireflection film is bonded to one side of such a polarizing film, it becomes a polarizing film having an antiglare antireflection effect. The antiglare reflection may also be achieved by bonding the antiglare antireflective film also as a protective film and bonding it to one side of the polarizer such that the low refractive index layer or the like is laminated on one side. It can be set as a polarizing film with a prevention effect.

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

[Transparent substrate film]
The following were used as a transparent base film in each Example and a comparative example.
Triacetyl cellulose (TAC)
Fuji Film Co., Ltd. "TD80UL" 80μm, refractive index 1.48
Polyethylene terephthalate (PET)
Toray Industries, Inc. "U403" 100 μm, refractive index 1.65
Cycloolefin polymer (COP)
Nippon Zeon Co., Ltd. "Zeonor film" 80 μm, refractive index 1.53

[Resin composition for antiglare layer]
The following raw materials were used as a resin composition for antiglare layer, and each raw material was mixed by the composition described in the following Tables 1-6, and resin composition AG-1-AG-39 for antiglare layers were prepared. . In addition, the volume ratio of each raw material shows the ratio of the volume of the said raw material in the whole resin composition for anti-glare layers.

<Small particle size>
Titanium oxide fine particles (dispersion liquid)
CIK Nanotech Co., Ltd. "RTTM EK 25 WT%-F02", particle size 0.015 μm
Zirconia (dispersion liquid)
CI Kasei Co., Ltd. product "ZRMEK 25%-F47", particle diameter 0.015 micrometer
Zinc antimonate fine particles (AZO) (dispersion liquid)
Nissan Chemical Industries Co., Ltd. "CELLNAX CX-603 M-F2", particle diameter 0.05 μm
ITO fine particles (dispersion liquid)
Dainippon Paint Co., Ltd. “Conductive EI-3 NMHR3, 35%”, particle diameter 0.05 μm
Silica ultrafine particles (dispersion liquid)
Nissan Chemical Industries, Ltd. "IPA-ST, 30%", particle diameter 0.03 μm
Ultrafine particles of silica "SIMIBK15WT% -H58" manufactured by CIK Nanotech Co., Ltd., particle size 0.1 μm
Antimony-tin oxide fine particles (ATO)
Nissan Chemical Industries Ltd. product name: ATO, particle diameter 0.05 μm
Zinc oxide Air Brown Co., Ltd. “TECNAPOW-ZNO”, particle diameter 0.02 μm

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

<Binder resin>
Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd. "KAYARAD DPHA"
Urethane acrylate, "Nippon Synthetic Chemical Industry Co., Ltd.""purpleUV7600B" molecular weight 1400, viscosity at 60 ° C is 2500 to 4500 Pa · s
Pentaerythritol triacrylate (PE3A), manufactured by Nippon Kayaku Co., Ltd. "PET 30"

<Photoinitiator>
"IRGACURE 184 (I-184)" manufactured by Ciba Specialty Chemicals Co., Ltd.

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

<(A) component>
(Meth) Acrylate Containing a C2-C7 Perfluoroalkyl Chain "Optool DAC-HP" manufactured by Daikin Industries, Ltd.
(Meth) Acrylate Containing C2-C7 Perfluoroalkyl Chain "Megafuck RS-75" manufactured by DIC Corporation
An oligomer containing a C 2 to C 7 perfluoroalkyl chain and containing no (meth) acrylate “Megafuck F-558” manufactured by DIC Corporation

<(B) component>
Polyether modified polydimethyl siloxane having an acrylic group "BYK-UV 3500" manufactured by BIC Chemie Japan Ltd.
Polyether modified polydimethylsiloxane having an acrylic group "BYK-UV 3530" manufactured by BIC Chemie Japan Ltd.
Polyester-modified polydimethylsiloxane having an acrylic group "BYK-UV 3570" manufactured by Big Chemie Japan Ltd.
Polyether modified polydimethyl siloxane which does not have an acryl group "BYK331" made by BIC Chemie Japan Ltd.

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

<(D) Hollow silica fine particles>
JGC Catalysts & Chemicals Co., Ltd. “Acryl-Modified Hollow Silica Fine Particles, Sururia NAU”
JGC Catalysts & Chemicals Co., Ltd. “Acryl-Modified Hollow Silica Fine Particles, Sururia V8208”

<(E) Photopolymerization initiator>
"IRGACURE 907 (I-907)" manufactured by Ciba Specialty Chemicals Co., Ltd.

[Resin composition for hard coat layer]
The following commercial item was used as a resin composition for hard-coat layers.
Toyo Ink Co., Ltd. hard coat "Liodurasu LAS1303NL"

Example 1-1
The film thickness of the antiglare resin composition (AG-1) after curing with a bar coater on one surface of a TAC film “TD 80 UL, 80 μm” made by Fuji Film (film thickness of a portion without particles) is 0.2 μm The antiglare layer was formed by curing by irradiation with ultraviolet light of 400 mJ with a 120 W high pressure mercury lamp.

  Next, using a bar coater, a coating solution for a low refractive index layer in which a resin composition for low refractive index layer (LL1-1) and a solvent (methyl isobutyl ketone) are mixed in a ratio of 1: 5 on this antiglare layer The coating was applied so that the film thickness after curing was 0.1 μm, and was irradiated with ultraviolet light of 400 mJ with a 120 W high pressure mercury lamp in a nitrogen atmosphere to be cured, thereby producing an antiglare antireflection film.

(Examples 1-2 to 1-19, 1-21 to 46, Comparative examples 1-1 to 1-25)
An antiglare antireflection film was produced in the same manner as in Example 1-1 using the materials shown in Tables 11-18.

(Example 1-20)
A hard coat resin composition is applied by a bar coater on one surface of a TAC film “TD 80 UL, 80 μm” made by Fujifilm so that the film thickness after curing (film thickness of the portion without particles) becomes 4 μm, 120 W A clear hard coat layer was formed by curing by irradiation with ultraviolet light of 400 mJ with a high pressure mercury lamp. Then, an antiglare layer and a low refractive index layer were provided on the clear hard coat layer in the same manner as in Example 1-1.

  The various properties of the antiglare antireflection films of the respective Examples and Comparative Examples obtained 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 JISK 7142-2014.

<Refractive index of each layer composition after curing>
(1) On a TAC film (trade name "TD80UL", manufactured by Fujifilm Corporation), using a bar coater, the coating solution for each layer is dried and cured to a thickness of 100 to 1000 nm. Was adjusted and applied. After drying, it was irradiated with ultraviolet light of 400 mJ and cured 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 back surface of the produced film was roughened with sand paper, and the reflection spectrum was measured with a reflection spectrophotometer (“FE-3000”, manufactured by Otsuka Electronics Co., Ltd.) filled with a 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 determined, and the refractive index at a wavelength of 589 nm of light was determined.
N (λ) = a / λ ⁴ + b / λ ² + c (Equation 1)
The refractive index of the antiglare layer is calculated by curing the composition excluding the large diameter particles in the composition constituting the antiglare layer to form a cured film, and measuring the reflection spectrum of the cured film. did.

<Thickness of antiglare layer>
The reflection spectrum of the part without protrusion (convex) by the particles was measured by a spectral film thickness meter (FE3000, manufactured by Otsuka Electronics), and calculated from the obtained reflection spectrum by the peak valley method.

<Surface roughness>
Using a surface roughness tester, Surfcoder SE500, manufactured by Kosaka Laboratory Ltd., under the conditions of a scanning range of 4 mm and a scanning speed of 0.2 mm / s, the arithmetic average rough according to the definition of JIS B 0601-1994. The average Ra (μm) and the average interval Sm (mm) of the asperities were measured.

<Visibility Reflectivity>
In order to remove the back reflection of the measurement surface, the back surface is roughened with sand paper and the one coated with black paint is a light of 380 nm to 780 nm wavelength by a spectrophotometer (manufactured by JASCO Corporation, trade name: U-best 560). The specular reflection spectrum of 5 ° and -5 ° was measured. The tristimulus value Y of the object color due to reflection in the XYZ color system assumed in JIS Z 8701 is viewed using the spectral reflectance of the wavelength 380 nm to 780 nm of the obtained light and the relative spectral distribution of the CIE standard illuminant D65. The sensitivity reflectance (%) was used.

<All haze>
The haze value (%) as an optical characteristic was measured using a haze meter (NDH 2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

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

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

<(1) Antiglare property>
(1) -1 <image non-sharpness of reflection>
How much the outline of the fluorescent lamp that is specularly reflected at 10 ° is blurred if the fluorescent light is reflected on the surface on which the antiglare hard coat layer is laminated so that the fluorescent light distance is 3 m and the incident angle is 10 ° Were evaluated according to the evaluation criteria shown below. The fluorescent lamp used FHF32 EXNH manufactured by Panasonic Corporation.
○: The image is blurred so that the contour can not be confirmed.
X: The outline is not blurred or blurred so that the outline can not be confirmed, but the visibility of the image is poor.
(1)-2 <transmission image definition, reflection image definition>
Image sharpness value through an optical comb having a width of 1 mm using an image sharpness measurement device (image measurement device manufactured by Suga Test Instruments Co., Ltd., ICM-1T) based on JIS K 7105-1981 (transmission image sharpness Values (%) of the image definition (reflected image definition) (%) measured at 45 ° reflection and 45% reflection. The judgment criteria of the measurement result are as follows.
Transmission image sharpness ... "100% to 90% ... no antiglare property", "less than 90% less than 15% ... 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% ... antiglare The dazzling effect is too strong "

<Glare>
An antiglare film was placed on the outermost surface of the image display side of a high definition liquid crystal touch panel as a high definition liquid crystal display, glare was measured visually, and evaluated in the following three steps.
◎: No glare, ○: Some glare, but not bothersome, x: There is enough glare to be anxious.

<Fingerprint wipeability>
The attached fingerprints were wiped empty with a load of 200 gf / cm 2 by Toray Industries, Inc., Toray Industries, Ltd., and the number of blanking wipes necessary for the fingerprints to disappear visually was counted.
○: not more than 20 reciprocations, x: not less than 21 reciprocations.

<Finger slippery>
The dynamic friction coefficient of the urethane elastomer material against an artificial skin model (trade name: Bioskin plate plate #BS color 1, manufactured by Beaulux Co., Ltd.) was measured by a measurement method according to JIS K 7125-1999.
The coefficient of friction evaluated by this evaluation method correlates with the slipperiness when flicking with a human finger, and the smaller the coefficient of friction, the easier the finger slips, and the greater the coefficient of friction, the harder the finger is slippery and sensory Was rated. In addition, when the coefficient of friction was equal to or less than 0.5, 90% or more of the evaluators (N = 30) judged that the finger was slippery at the time of flicking.

<Surface hardness>
The load was 750 g and was evaluated in accordance with JIS K 5600.

  From the results of Example, the particle diameter Pdia of the large diameter fine particles contained in the antiglare layer is 0.1 μm ≦ Pdia ≦ 5 μm, and the ratio t / Pdia of the thickness t of the antiglare layer to the particle diameter Pdia is 0 .05 ≦ t / Pdia ≦ 1.7, the particle diameter Mdia of the small-diameter fine particles is 0.01 μm ≦ Mdia ≦ 0.1 μm, and the ratio Mden / Pden of the specific gravity Mden of the small-diameter particles and the specific gravity Pden of the large-diameter particles is 6.0 ≧ Mden / Pden ≧ 2.7, the volume ratio of the large diameter fine particles in the entire volume of the antiglare layer is 0.5% or more and 40% or less, and the small diameter fine particles in the entire volume of the antiglare layer When the volume proportion of the film is 15% or more and 65% or less, appropriate unevenness is formed on the antiglare antireflection film, the antiglare property is excellent, the glare is small, and the finger slipperiness at the time of flicking is improved. In addition, the outermost low refractive index layer is (a) 5.0 to 15.0 mass% of (meth) acrylate containing a C 2 to C 7 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 an acryl group, 9.0 to 70.0% by mass of an ultraviolet curable resin copolymerizable with (c), (a) and (b) (D) hollow silica fine particles 22.0 to 83.0% by mass, (e) photopolymerization initiator 1.0 to 10.0% by mass, the mass% of (b) being the mass% of (a) When it is a cured product of less resin composition for low refractive index layer (however, the total of (a), (b), (c), (d) and (e) is 100% by mass) fingerprint wiping performance 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 to the entire volume of the antiglare layer is small, and the antiglare property is inferior. In Comparative Example 1-2, the volume ratio of the large diameter fine particles in the entire volume of the antiglare layer is small, and the antiglare property is poor. In Comparative Example 1-3, the volume ratio of the large-diameter fine particles to the entire volume of the antiglare layer is large, and since adequate irregularities are not formed, the antiglare property is inferior and the haze is large. In Comparative Example 1-5, since the particle diameter of the large-diameter fine particles is smaller than the film thickness, appropriate unevenness is not formed and the antiglare property is inferior. In Comparative Examples 1-6 to 1-10, since the specific gravity difference between the large diameter fine particles and the small diameter fine particles is small, the antiglare property is inferior, and there is much glare. In addition, finger slipperiness is also inferior. In Comparative Example 1-11, the particle diameter of the large-diameter fine particles is large, and the glare is large.

  Moreover, in the comparison 1-13-1-25, in the composition of a low refractive index layer, fingerprint wiping property is inferior by the following reason. In Comparative Examples 1-13 and 1-14, the amount of the component (a) is small. In Comparative Example 1-15, there are many (a) components. In Comparative Examples 1-16 and 1-17, the component (b) is absent or small. There are many (b) components in comparative examples 1-18 and 1-19. In Comparative Examples 1-20 to 1-22, the mass of the components (a) and (b) is 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 components (a) and (b) do not react.

Claims (7)

A low refractive index layer is laminated on one surface of a transparent substrate film, and an antiglare layer having a refractive index higher than that of 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-diameter fine particles and small-diameter fine particles having a specific gravity larger than that of the large-diameter fine particles and having a smaller particle size.
The large diameter fine particles have a particle diameter Pdia of 0.1 μm ≦ Pdia ≦ 5 μm, and a ratio t / Pdia of the film thickness t of the antiglare layer to the particle diameter Pdia of 0.05 ≦ t / Pdia ≦ 1. And the particle diameter Mdia of the small-diameter fine particles is 0.01 μm ≦ Mdia ≦ 0.1 μm,
The ratio Mden / Pden of the specific gravity Mden of the small diameter fine particles to the specific gravity Pden of the large diameter fine particles is 6.06.0Mden / Pden ≧ 2.7,
The volume ratio of the large diameter fine particles in the entire volume of the antiglare layer is 0.5% or more and 40% or less, and the volume ratio of the small diameter particles in the entire volume of the antiglare layer is 15% or more and 65% or less And
The low refractive index layer is
(A) 5.0 to 15.0% by mass of (meth) acrylate containing a C 2 to C 7 perfluoroalkyl chain,
(B) 2.0 to 8.0% by mass of polyether modified polydimethylsiloxane having an acrylic group or polyester modified polydimethylsiloxane having an acrylic group,
(C) 9.0 to 70.0% by mass of an ultraviolet curable resin copolymerizable with (a) and (b),
(D) hollow silica fine particles 22.0 to 83.0 mass%,
(E) 1.0 to 10.0 mass% of a photopolymerization initiator
Consists of
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.)
Antiglare antireflective film formed by curing of   The antiglare antireflection film according to claim 1, wherein a ratio t / Pdia of the film thickness t of the antiglare layer to the particle diameter Pdia of the large diameter fine particles is 0.05 ≦ t / Pdia ≦ 1.3.   The antiglare antireflection film according to claim 1 or 2, wherein a volume ratio of the small diameter fine particles in the entire volume of the antiglare layer is 15% or more and 55% or less.   The small-diameter 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-diameter fine particles may be acrylic resin, polystyrene, polymethacrylic styrene, 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, which is at least one selected from the group consisting of silicone resins, polyvinylidene fluoride and polytetrafluoroethylene resins.   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.   The image display apparatus equipped with the antiglare antireflection film as described in any one of Claims 1-6 on the surface.