CN110036311B - Antireflection film, antireflection element, polarizing plate, and display device - Google Patents
Antireflection film, antireflection element, polarizing plate, and display device Download PDFInfo
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- CN110036311B CN110036311B CN201780074312.9A CN201780074312A CN110036311B CN 110036311 B CN110036311 B CN 110036311B CN 201780074312 A CN201780074312 A CN 201780074312A CN 110036311 B CN110036311 B CN 110036311B
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- Surface Treatment Of Optical Elements (AREA)
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Abstract
The present invention relates to an antireflection film, an antireflection element, a polarizing plate, and a display device having excellent antireflection property and steel wool abrasion resistance, and thus can provide an antireflection film including at least two or more stacked layers having different refractive indices, wherein the uppermost layer includes: a binder comprising a crosslinked product obtained by crosslinking a polymer comprising a photoreactive fluorine-containing compound a and a polymer comprising a monomer B having at least one or more hydroxyl groups and two or more photoreactive functional groups; hollow silica particles dispersed in the binder; and a photoreactive fluoropolymer and a polymer having a main chain a bonded through siloxane, the polymer being distributed on the uppermost surface.
Description
Technical Field
The invention relates to an antireflection film, an antireflection element, a polarizing plate and a display device.
Background
In general, a display device, such as a liquid crystal display or an organic electroluminescent (organic EL) display, is configured to prevent contrast deterioration or image overlapping due to external light reflection. For this reason, a low-reflectance film is provided for the lowermost surface of the display device.
However, when a typical low-reflectance film having a light reflectance of more than 1% is applied to a product requiring high contrast, the anti-reflection property of the product may be insufficient due to an excessive increase in reflectance.
For example, patent document 1 discloses a sheet-like low reflectance member having a high steel wool load capacity of 500g/cm2This is an index of the wear resistance of steel wool. However, since the low-reflectance element has a light reflectance of more than 1%, the low-reflectance element has a problem of insufficient antireflection.
On the other hand, the low-reflectance film having a light reflectance of less than 0.3% has poorer steel wool abrasion resistance than the low-reflectance film having a light reflectance of more than 1%. An antireflection element disclosed in patent document 2 has a light reflectance of less than 0.3% by lamination of three layers having different refractive indices. However, the antireflection element has a density of 200g/cm2Low steel wool load bearing capacity. Therefore, the conventional anti-reflection element has a trade-off relationship between the light reflectance and the wear resistance of the steel wool, and thus cannot achieve good performance in terms of both the light reflectance and the wear resistance of the steel wool.
< Prior document >
< patent document >
< patent document 1> patent publication No. 5723625
< patent document 2> publication laid-open No. 2015-227934
Disclosure of Invention
Technical problem
An object of the present invention is to provide an antireflection film, an antireflection element, a polarizing plate, and a display device, which have good antireflection properties and steel wool abrasion resistance.
Technical scheme
One aspect of the present invention relates to an antireflection film including at least two layers having different refractive indices, wherein an uppermost layer of the antireflection film includes: an adhesive comprising a crosslinked product obtained by crosslinking a polymer comprising a photoreactive fluorine-containing compound a and a polymer comprising a monomer B having at least one hydroxyl group and at least two photoreactive functional groups; hollow silica particles dispersed in the binder; a photoreactive fluoropolymer, and a polymer having a main chain a bonded through siloxane, and the polymer having the main chain a bonded through siloxane is dispersed on the surface of the uppermost layer together with the photoreactive fluoropolymer.
In one embodiment, the polymer having the main chain a bonded through siloxane may be a photoreactive modified silicone polymer.
In one embodiment, the adhesive may include a polymer C having a siloxane-bonded main chain b represented by formula (1), the unit constituting the siloxane-bonded main chain b may have a methoxy group directly connected to a silicon atom and a methyl group directly connected to the silicon atom, and the polymer C may be a polymer having a siloxane-bonded main chain a.
(wherein n is an integer of 2 to 10)
In one embodiment, the refractive index of the uppermost layer may be less than about 1.310.
In one embodiment, the surface of the uppermost layer may have a light reflectance of less than about 0.20%.
In one embodiment, the steel wool load bearing capacity of the uppermost layer may be about 300g/cm2Or higher.
In one embodiment, the uppermost layer may be stacked on the hard coating layer, and the refractive index of the hard coating layer may be about 1.500 to 1.650.
Another aspect of the present invention relates to an antireflection element comprising a transparent substrate and the above-described antireflection film formed on the transparent substrate, wherein the antireflection film comprises a hard coat layer and an uppermost layer stacked in this order on the transparent substrate.
Still another aspect of the present invention relates to a polarizing plate including the antireflection film as described above or the antireflection element at the uppermost layer thereof as described above.
Still another aspect of the present invention relates to a display device including the polarizing plate as described above.
Advantageous effects
The present invention provides an antireflection film, an antireflection element, a polarizing plate, and a display device having good antireflection properties and steel wool abrasion resistance.
Drawings
Fig. 1 is a sectional view of an antireflection film according to a first embodiment of the present invention.
Fig. 2 is a sectional view of an antireflection film according to a second embodiment of the present invention.
Fig. 3 is a sectional view of an antireflection film according to a third embodiment of the present invention.
Fig. 4 is a cross-sectional view of an antireflective element according to a fourth embodiment of the invention.
Fig. 5 is a cross-sectional view of a polarizing plate according to a fourth embodiment of the present invention.
Fig. 6 is a sectional view of a display device according to a sixth embodiment of the present invention.
Fig. 7 is a sectional view of a display device according to a seventh embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
[ embodiment 1]
(anti-reflection film)
Hereinafter, the antireflection film 1 according to the first embodiment will be described with reference to the drawings. Fig. 1 is a sectional view of an antireflection film according to a first embodiment of the present invention.
Referring to fig. 1, the antireflection film 1 includes a hard coat layer (high refractive index layer) 2 and a low refractive index layer 3, which have different refractive indices and are sequentially stacked in the above order. In the antireflection film 1, the low refractive index layer 3 is the uppermost layer.
The low refractive index layer 3 as the uppermost layer contains a binder 4, hollow silica particles 5, a photoreactive fluoropolymer 6, and a photoreactive modified silicone polymer 7.
The binder 4 in the low refractive index layer 3 includes a crosslinked product obtained by crosslinking a polymer including the photoreactive fluorine-containing compound a and a polymer including the monomer B. Monomer B includes at least one hydroxyl group and at least two photoreactive functional groups.
The photoreactive fluoropolymer 6 has a proximal end attached to the adhesive 4 and a distal end extending beyond the low refractive index layer 3 relative to the adhesive 4. Further, the photoreactive modified silicone polymer 7 has a proximal end connected to the adhesive 4 and a distal end extending out of the low refractive index layer 3 with respect to the adhesive 4. More specifically, the photoreactive fluoropolymer 6 is distributed on the surface 3a of the low refractive index layer 3, similarly to the fluorine atoms (F) existing outside the surface 3a of the low refractive index layer 3. Also, the photoreactive modified silicone polymer 7 is distributed on the surface 3a of the low refractive index layer 3, similarly to silicon atoms (Si) existing outside the surface 3a of the low refractive index layer 3. Further, the photoreactive fluoropolymer 6 and the photoreactive modified silicone polymer 7 are substantially uniformly distributed on the surface 3a of the low refractive index layer 3. The content of the photoreactive fluoropolymer 6 on the surface 3a of the low refractive index layer 3 can be appropriately adjusted by the content of the photoreactive fluoropolymer 6 in the low refractive index layer 3. Further, by the content of the photoreactive modified silicone polymer 7 in the low refractive index layer 3, the content of the photoreactive modified silicone polymer 7 on the surface 3a of the low refractive index layer 3 can be appropriately adjusted.
The distribution of the photoreactive fluoropolymer 6 and the photoreactive modified silicone polymer 7 on the surface 3a of the low refractive index layer 3 can be measured by the following method. For example, methods of Auger Electron Spectroscopy (AES) and argon (Ar) ion etching may be used. Specifically, the low refractive index layer 3 is etched from the surface 3a to the hard coat layer 2 (in the thickness direction) using an argon ion etching method. During the etching of the low refractive index layer 3, the distribution of fluorine and silicon atoms in the low refractive index layer 3 in the thickness direction thereof was analyzed by auger electron spectroscopy. As a result of this analysis, if the distribution satisfies the following condition, it is determined that the photoreactive fluoropolymer 6 and photoreactive modified silicone polymer 7 are distributed on the surface 3a of the low refractive index layer 3. The analysis results showed that fluorine and silicon atoms were distributed more near the surface 3a of the low refractive index layer 3, and less to the hard coat layer 2.
The low refractive index layer 3 may have a refractive index of less than about 1.310, more preferably about 1.300 or less. When the refractive index of the low refractive index layer 3 is less than about 1.310, the antireflection film 1 has sufficient antireflection property to be applied to a display device requiring high contrast.
The refractive index of the low refractive index layer 3 can be measured by the following method.
1) Black ink was deposited on the rear surface (surface on which the antireflection film 1 was not formed) of the substrate (antireflection element including the antireflection film 1 formed thereon) to remove light reflected from the rear surface of the antireflection element. Alternatively, the black member may be bonded to the rear surface of the antireflection member by a transparent adhesive or the like.
2) The diffuse light incident at 8 degrees was focused on the surface of the antireflection element using a commercially available spectrophotometer, and the specular reflectance and diffuse reflectance at wavelengths of 380nm to 740nm were measured for the 8-degree received light beam.
3) For example, a commercially available spectrophotometer may be CM-2600d or CM-3600A (Konica Minolta, Inc.). This spectrophotometer can obtain a specular reflectance Y value (SCI) and a diffuse reflectance Y value (SCE) at 2 degrees incidence under a D light source, and a value required for Y ═ SCI-SCE is defined as a light reflectance value.
4) The thickness and refractive index of the thin layer are adjusted to obtain a light reflectance spectrum and a film optically calculated reflectance spectrum having the same radius of curvature, and are defined as the refractive index of the low refractive index layer 3.
The surface 3a of the low refractive index layer 3 may have a light reflectance of less than about 0.20%, preferably about 0.19% or less, more preferably about 0.17% or less. The light reflectance refers to reflectance corresponding to the lightness (Y) of the product color in the XYZ colorimetry. Further, the light reflectance of the surface 3a of the low refractive index layer 3 is the light reflectance of the surface 1a of the antireflection film 1. When the light reflectance of the low refractive index layer 3 is less than 0.20%, the antireflection film 1 has sufficient antireflection resistance to be applied to a display device requiring high contrast.
The light reflectance of the surface 3a of the low refractive index layer 3 can be measured by the following method.
1) Black ink was deposited on the rear surface (surface on which the antireflection film 1 was not formed) of the substrate (antireflection element including the antireflection film 1 formed thereon) to remove light reflected from the rear surface of the antireflection element. Alternatively, the black member may be bonded to the rear surface of the antireflection member by a transparent adhesive or the like.
2) The diffuse light incident at 8 degrees was focused on the surface of the antireflection element using a commercially available spectrophotometer, and the specular reflectance and diffuse reflectance at wavelengths of 380nm to 740nm were measured for the 8-degree received light beam.
3) For example, a commercially available spectrophotometer may be CM-2600d or CM-3600A (Konica Minolta, Inc.). This spectrophotometer can obtain a specular reflectance Y value (SCI) and a diffuse reflectance Y value (SCE) at 2 degrees incidence under a D light source, and a value required for Y ═ SCI-SCE is defined as a light reflectance value.
Preferably, the steel wool carrying capacity of the low refractive index layer 3 may be about 300g/cm2Or higher. The steel wool carrying capacity due to the low refractive index layer 3 is about 300g/cm2Or higher, and thus, the antireflection film 1 applied to the display device can sufficiently protect the display surface of the display device. Specifically, the steel wool carrying capacity of the low refractive index layer 3 may be about 300g/cm2To about 400g/cm2Or about 350g/cm2To about 400g/cm2。
The steel wool load bearing capacity of the low refractive index layer 3 can be measured by the following method. # 0000: 1cm above the low refractive index layer 32The steel wool reciprocates 10 times at a sliding speed of 100mm/s within the contact area and the sliding distance of 100 mm. After the steel wool was reciprocated on the low refractive index layer 3, the surface of the low refractive index layer 3 was observed with the naked eyeAnd (5) kneading. Here, the maximum load that causes less than 10 scratches on the surface of the low refractive index layer is defined as the steel wool load-bearing capacity.
The hollow silica particles 5 may be surface-treated to improve compatibility with acrylic resin or solvent.
The average primary particle diameter of the hollow silica particles 5 is about 50nm to about 100nm, preferably about 60nm to about 90 nm. When the average primary particle diameter of the hollow silica particles 5 is 50nm or more, the low refractive index layer 3 may be formed to have a refractive index of less than about 1.310 without excessively increasing the refractive index of the hollow silica particles 5. On the other hand, the hollow silica particles 5 have an average primary particle diameter of about 100nm or less and can prevent an excessive decrease in strength. Therefore, the low refractive index layer 3 does not suffer from deterioration in steel wool abrasion resistance or pencil hardness. Therefore, the low refractive index layer 3 can be formed to a thickness of about 100 nm.
The average primary particle diameter thereof can be obtained according to a Scanning Electron Microscope (SEM) of the hollow silica particles 5.
In the low refractive index layer 3, the amount of the hollow silica particles 5 is preferably about 45 parts by mass to about 56 parts by mass. When the amount of the hollow silica particles 5 is about 45 parts by mass or more, the refractive index of the low refractive index layer 3 may be less than about 1.310, and the light reflectance is less than about 0.20%. On the other hand, when the content of the hollow silica particles 5 is less than or equal to about 56 parts by mass, there is no problem that the content of the binder 4 in the low refractive index layer 3 is excessively reduced. Therefore, sufficient steel wool abrasion resistance is ensured while ensuring sufficient strength of the low refractive index layer 3.
The hard coat layer 2 is made of a resin such as triacetyl cellulose (TAC), polyethylene terephthalate (PET), cycloolefin polymer (COP), poly (methyl methacrylate) (PMMA), or the like. The hard coat layer 2 may be an element composed of resin.
Alternatively, the hard coat layer 2 may be formed of an acrylic resin, a urethane resin, an epoxy resin, or a mixture thereof on a resin-made member. With this structure, the hard coat layer 2 having high surface hardness can be formed.
As the refractive index of the hard coat layer 2 increases, the light reflectance of the surface 3a of the low refractive index layer 3 decreases. However, an increase in the refractive index of the hard coat layer 2 may result in a decrease in the strength of the hard coat layer 2. An increase in the content of the high-refractive-index material in the hard coat layer 2 may lead to an increase in manufacturing cost. Therefore, the refractive index of the hard coat layer 2 is adjusted according to these factors.
According to the antireflection film 1 of this embodiment, in the two-layer structure in which the low refractive index layer 3 is stacked on the hard coat layer 2, the refractive index of the hard coat layer 2 is preferably about 1.500 to about 1.650. More preferably, the refractive index of the hard coat layer 2 is about 1.550 to about 1.650. When the refractive index of the hard coat layer 2 is about 1.500 or more, the refractive index of the low refractive index layer 3 may be less than about 1.310. In addition, the steel wool load-bearing capacity of the low refractive index layer 3 may be about 300g/cm2Or more. On the other hand, when the refractive index of the hard coat layer 2 is about 1.650 or less, the surface 3a of the low refractive index layer 3 can be prevented from suffering an increase in reflectance at low and high wavelengths. Therefore, the light reflected by the surface 3a of the low refractive index layer 3 can be prevented from appearing in color.
Preferably, the hard coating layer 2 has a thickness of about 1 μm to about 10 μm, but is not limited thereto.
The antireflection film 1 according to this embodiment is formed by stacking a hard coat layer 2 and a low refractive index layer 3 having different refractive indices. Alternatively, the low refractive index layer 3 as the uppermost layer contains a binder 4, hollow silica particles 5, a photoreactive fluoropolymer 6, and a photoreactive modified silicone polymer 7. Further, hollow silica particles 5 are dispersed in the binder 4. Furthermore, the photoreactive fluoropolymer 6 and the photoreactive modified silicone polymer 7 are distributed on the surface (uppermost surface) 3a of the low refractive index layer 3. Therefore, the surface 3a of the low refractive index layer 3 is slidable, thereby making the antireflection film have good performance in terms of steel wool abrasion resistance and antireflection.
(method for producing antireflection film)
Next, a method of manufacturing the antireflection film 1 according to the first embodiment will be described.
The method of manufacturing the antireflection film 1 according to the first embodiment includes at least the process a, the process B, the process C, and the process D.
Process a is a process of preparing a coating solution for forming the low refractive index layer 3.
Process B is a process of forming a coating layer as a precursor of the low refractive index layer 3 using the coating solution prepared in process a.
Process C is a process of drying the coating layer formed in process B.
Process D includes a polymerization process of the photoreactive fluorine-containing compound A and the monomer B contained in the coating dried in Process C. Further, process D includes a process of crosslinking a polymer including the photoreactive fluorine-containing compound a and a polymer including the monomer B.
In the process a, the coating liquid is prepared by uniformly stirring and mixing the components of the coating liquid in a predetermined content (mixing ratio).
The coating liquid contains a photoreactive fluorine-containing compound A, a monomer B, hollow silica particles 5, a photoreactive fluorine-containing polymer, a photoreactive modified silicone polymer, a solvent, and a photopolymerization initiator.
The photoreactive fluorine-containing compound a may be a fluorine-containing monomer, a fluorine-containing oligomer, or a fluorine-containing polymer, which contains 30 to 60 mass% of fluorine and a photoreactive group. Within this range, a coating liquid of the photoreactive fluorine-containing compound A can be prepared at an appropriate mixing ratio. The photoreactive fluorine-containing compound a is distributed throughout the uppermost layer, i.e., throughout the low refractive index layer.
The amount of the photoreactive fluorine-containing compound a may be about 20 parts by mass to about 40 parts by mass, specifically about 25 parts by mass to about 35 parts by mass, relative to 100 parts by mass of the coating liquid in terms of solid content. When the amount of the photoreactive fluorine-containing compound a is about 20 parts by mass or more, the low refractive index layer 3 may be formed, which has a refractive index of less than about 1.310. As a result, the low refractive index layer 3 may have a light reflectance of less than about 0.20%. On the other hand, at an amount of the photoreactive fluorine-containing compound a of about 40 parts by mass or less, the low refractive index layer 3 can be prevented from deteriorating in surface hardness due to an excessive increase in fluorine component. As a result, the low refractive index layer does not suffer from deterioration in steel wool abrasion resistance or pencil hardness. Further, there is no problem of deterioration in compatibility with other components forming the low refractive index layer 3.
The photoreactive fluorine-containing compound a is different from the photoreactive fluorine-containing polymer described below. The photoreactive fluorine-containing compound a may be a monomer.
Examples of the monomer B having at least one hydroxyl group and at least two photoreactive functional groups may include 2-hydroxy-1, 3-dimethacryloxypropane, dipentaerythritol hexaacrylate, epoxidized dipentaerythritol hexaacrylate, propoxylated dipentaerythritol hexaacrylate, pentaerythritol triacrylate, epoxidized pentaerythritol triacrylate, propoxylated pentaerythritol triacrylate, isocyanurate diacrylate, and the like. Specifically, isocyanureyl diacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, or the like can be used.
The amount of the monomer B may be about 5 to about 20 parts by mass, specifically about 5 to about 15 parts by mass, or about 5 to about 10 parts by mass, or about 10 to about 20 parts by mass, relative to 100 parts by mass of the coating liquid in terms of solid content. When the amount of the monomer B is 5 parts by mass or more, the low refractive index layer 3 having sufficient strength can be formed. Further, the photoreactive fluoropolymer 6 and the photoreactive modified silicone polymer 7 may be sufficiently distributed on the surface 3a of the low refractive index layer 3. As a result, the surface 3a of the low refractive index layer 3 can have sufficient smoothness. On the other hand, when the amount of the monomer B is about 20 parts by mass or less, the low refractive index layer 3 may be formed, which has a refractive index of less than about 1.310. As a result, the light reflectance of the low refractive index layer 3 may be less than about 0.20%.
The amount of the hollow silica particles 5 may be about 45 parts by mass to about 56 parts by mass, specifically about 45 parts by mass to about 55 parts by mass, about 45 parts by mass to about 50 parts by mass, or about 50 parts by mass to about 55 parts by mass, relative to 100 parts by mass of the coating liquid in terms of solid content. When the amount of the hollow silica particles 5 is about 45 parts by mass or more, the refractive index of the low refractive index layer 3 may be less than about 1.310. As a result, the light reflectance of the low refractive index layer 3 may be less than about 0.20%. On the other hand, when the amount of the hollow silica particles 5 is about 56 parts by mass or less, the low refractive index layer 3 can be prevented from suffering an excessive decrease in the content of the binder 4 while ensuring sufficient strength thereof. In addition, sufficient steel wool abrasion resistance can be ensured.
The photoreactive fluoropolymer may be a polymer comprising perfluoropolyether having a weight average molecular weight of about 2,000 to about 10,000 as a backbone. The polymer including perfluoropolyether as a main chain has a terminal functional group at one end or both ends thereof. The functional group of the photoreactive fluoropolymer is a photoreactive group. The photoreactive fluoropolymer is distributed only on the surface of the low refractive index layer as the uppermost layer.
The amount of the photoreactive fluoropolymer may be about 1 part by mass to about 10 parts by mass, specifically about 1 part by mass to about 5 parts by mass, or about 5 parts by mass to about 10 parts by mass, relative to 100 parts by mass of the coating liquid in terms of solid content. When the amount of the photoreactive fluoropolymer is about 1 part by mass or more, the surface 3a of the low refractive index layer 3 may have sufficient smoothness and improve steel wool abrasion resistance. On the other hand, at an amount of the photoreactive fluoropolymer of about 10 parts by mass or less, the low refractive index layer 3 can be prevented from decreasing in surface hardness due to an excessive increase in fluorine content. In addition, sufficient steel wool abrasion resistance can be ensured.
The photoreactive modified silicone polymer may be a polymer including dimethylsiloxane having a weight average molecular weight of about 10,000 to about 50,000 and at least one photoreactive functional group as a main chain a. In other words, the photoreactive modified silicone polymer is a polymer having a main chain a bonded through siloxane. Preferably, the functional group of the photoreactive modified silicone polymer provides not only the terminal (side) but also a side chain of the main chain a. The functional group of the photoreactive modified silicone polymer is a photoreactive group.
The amount of the photoreactive modified silicone polymer may be about 1 part by mass to about 3 parts by mass in terms of solid content with respect to 100 parts by mass of the coating liquid. When the amount of the photoreactive modified silicone polymer is about 1 part by mass or more, the low refractive index layer 3 may have sufficient steel wool abrasion resistance. On the other hand, when the amount of the photoreactive modified silicone polymer is 3 parts by mass or less, the increase of haze (haze) of the low refractive index layer 3 can be prevented.
Examples of the solvent may include methyl isobutyl ketone (MIBK), Methyl Ethyl Ketone (MEK), isopropyl alcohol (IPA), Propylene Glycol Monomethyl Ether (PGME), Propylene Glycol Monomethyl Ether Acetate (PGMEA), and the like. These solvents may be used alone or together as a mixture thereof. The solvent should be selected in consideration of dispersibility of other materials or compatibility with other materials to form the low refractive index layer 3.
In the coating liquid, the mixing ratio of the solvents is adjusted to achieve a solid concentration suitable for the coating apparatus or the coating rate. For example, in the slit coating, the mixing ratio of the solvent may be adjusted to about 1% by mass to about 3% by mass according to 100% by mass of the coating liquid. As a result, the low refractive index layer 3 can be formed to a thickness of about 100 nm.
Examples of the photopolymerization initiator include 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropynyl) -benzyl ] phenyl } -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1-hydroxy-cyclohexyl-phenylketone and the like.
Preferably, the amount of the photopolymerization initiator may be about 1 part by mass to about 5 parts by mass relative to 100 parts by mass of the coating liquid in terms of solid content.
When the amount of the photopolymerization initiator is about 1 part by mass or more, the polymer including the photoreactive fluorine-containing compound a and the polymer including the monomer B may be sufficiently crosslinked. As a result, the low refractive index layer 3 can have sufficient steel wool abrasion resistance. On the other hand, when the amount of the photopolymerization initiator is about 5 parts by mass or less, the low refractive index layer 3 may be formed, which has a refractive index of less than about 1.310. As a result, the light reflectance of the low refractive index layer 3 may be less than about 0.20%.
For example, in the process B, a coating layer corresponding to the precursor of the low refractive index layer 3 is formed by applying the coating liquid on the hard coat layer 2 formed on the transparent substrate. The coating liquid is uniformly coated on the hard coating 2, so that the thickness of the coating formed on the hard coating 2 is uniform.
For example, the coating liquid may be applied using micro gravure coating, slit coating, knife coating, or spray coating without being limited to rain.
In process C, the coating is dried to evaporate the solvent in the coating. The drying temperature (heating temperature) and drying time (heating time) at which the solvent is sufficiently evaporated are appropriately determined depending on the kind of the solvent and the like. For example, the drying temperature may be set in the range of about 30 ℃ to about 150 ℃, and the drying time may be set in the range of about 20 seconds to about 5 minutes. The coating may be dried by natural drying or heat drying.
Further, during the drying of the coating of process C, the photoreactive fluoropolymer and photoreactive modified silicone polymer are distributed on the surface of the coating. On the other hand, it is assumed that the reason why the photoreactive fluoropolymer and photoreactive modified silicone polymer are distributed on the coating surface is as follows. These polymers exhibit relative hydrophobicity and have low specific gravity. Therefore, phase separation occurs between these polymers and a binder composed of a polymer including a photoreactive fluorine-containing compound a having a hydrophilic hydroxyl group and a polymer including a monomer B. As a result, these polymers are likely to float on the adhesive.
In Process D, the dried coating is irradiated with light to polymerize the photoreactive fluorochemical A and monomer B in the coating. In addition, in process D, the polymer including the photoreactive fluorine-containing compound a is crosslinked with the polymer including the monomer B to form the low refractive index layer 3. On the other hand, the photoreactive fluoropolymer and photoreactive modified silicone polymer are distributed on the coating surface after drying. As a result, the photoreactive fluoropolymer and photoreactive modified silicone polymer are distributed on the surface 3a of the low refractive index layer 3.
For example, the coating may be irradiated by ultraviolet light, visible light, electron beam, ionizing radiation, or the like.
For example, the coating can be irradiated with ultraviolet light using a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon lamp, a metal halide lamp, or the like. Further, for example, ultraviolet irradiation amount means cumulative irradiation amount at a wavelength of 365nm, and may be at about 100mJ/cm2To about 1,000mJ/cm2Within the range of (1).
In addition, in order to prevent deterioration upon oxygen curing, irradiation of the coating is preferably performed in a nitrogen atmosphere of about 1,000ppm or less.
By these processes, the antireflection film 1 according to this embodiment can be obtained.
[ embodiment 2]
(anti-reflection film)
Next, an antireflection film 10 according to a second embodiment will be described with reference to the drawings. Fig. 2 is a sectional view of the antireflection film 10 according to the second embodiment of the present invention. In fig. 2, the same components of the antireflection film are denoted by the same reference numerals and repeated description thereof is omitted, compared with the components of the antireflection film 1 according to the first embodiment shown in fig. 1.
Referring to fig. 2, the antireflection film 10 includes a hard coat layer 2 and a low refractive index layer 3, which are sequentially stacked in the above order. In the antireflection film 10, the low refractive index layer 3 is the uppermost layer. The low refractive index layer 3 as the uppermost layer contains a binder 4, hollow silica particles 5, and a photoreactive fluoropolymer 6. Hollow silica particles 5 are dispersed in the binder 4. The photoreactive fluoropolymer 6 is distributed on the surface (uppermost surface) 3a of the low refractive index layer 3.
The binder 4 in the low refractive index layer 3 includes the same crosslinked product as the first embodiment and a polymer C having a main chain b bonded through siloxane as shown in formula (1). In other words, the adhesive 4 is composed of a mixture of a crosslinked product obtained by crosslinking a polymer including the photoreactive fluorine-containing compound a with a polymer including the monomer B and the polymer C. Further, the polymer C constitutes the uppermost layer of the low refractive index layer 3 together with the fluorine-containing polymer 6 having photoreactivity.
The polymer C has a main chain b represented by formula (1) bonded through a siloxane bond, and a linear structure, a three-dimensional structure, or a combination thereof. On the other hand, the main chain b in formula (1) bonded through siloxane is a structure shown in parentheses.
In the formula (1), n is an integer of 2 to 10, preferably 3 to 5.
In formula (1), the unit constituting the main chain has one methoxy group directly bonded to a silicon atom and one methyl group directly bonded to a silicon atom. In the formula (1), the unit constituting the main chain has a structure in parentheses.
Specifically, the polymer C may be a siloxane compound, wherein n represents the degree of polymerization of the structure in parentheses of the formula (1), and is in the range of 3 to 4, 5 or 9.
Polymer C has a lower refractive index than the polymer comprising monomer B. Therefore, by adding the polymer C to the binder 4 to reduce the content of the monomer B in the binder 4, the refractive index of the low refractive index layer 3 can be further reduced.
Polymer C can increase steel wool abrasion resistance while reducing light reflectance by reducing the refractive index.
In the antireflection film 10 according to this embodiment, the binder 4 constituting the low refractive index layer 3 includes the same crosslinked product and polymer C as those of the first embodiment. Further, the polymer C constitutes the uppermost layer of the low refractive index layer 3 together with the fluorine-containing polymer 6 having photoreactivity. Therefore, although the surface 3a of the low refractive index layer 3 is slidable, the antireflection film having good performance in terms of steel wool abrasion resistance and antireflection property can be obtained. The antireflection film 10 according to this embodiment can be manufactured more easily than the antireflection film 1 having a three-layer structure, an inorganic deposition film, or an inorganic sputtering film, and can secure a low refractive index at a lower manufacturing cost.
(method for producing antireflection film)
Next, a method of manufacturing the antireflection film 10 according to the second embodiment will be described.
The method of manufacturing the antireflection film 10 according to the second embodiment is the same as the method of manufacturing the antireflection film 1 according to the first embodiment except for the process a of preparing the coating liquid.
In the process a, the coating liquid is prepared by uniformly stirring and mixing the components of the coating liquid in a predetermined content (mixing ratio). The coating liquid contains a photoreactive fluorine-containing compound A, a monomer B, hollow silica particles 5, a photoreactive fluorine-containing polymer, a solvent, and a photopolymerization initiator.
According to this embodiment, the mixing ratio of the photoreactive fluorine-containing compound a, the monomer B and the polymer C in the coating liquid is different from that of the coating liquid according to the first example. On the other hand, the mixing ratio of the other components in the coating liquid according to the present embodiment is the same as that of the coating liquid according to the first embodiment.
The amount of the photoreactive fluorine-containing compound a may be about 10 parts by mass to about 30 parts by mass, specifically about 15 parts by mass to about 30 parts by mass, or about 20 parts by mass to about 30 parts by mass with respect to 100 parts by mass of the coating liquid in terms of solid content. When the amount of the photoreactive fluorine-containing compound a is about 10 parts by mass or more, the low refractive index layer 3 may be formed, which has a refractive index of less than about 1.310. As a result, the light reflectance of the low refractive index layer 3 may be less than about 0.20%. On the other hand, at an amount of the photoreactive fluorine-containing compound a of about 30 parts by mass or less, the low refractive index layer 3 can be prevented from deteriorating in surface hardness due to an excessive increase in fluorine component. As a result, the low refractive index layer does not suffer from deterioration in the wear resistance of steel wool. In addition, there is no problem of deterioration in compatibility with other components forming the low refractive index layer 3.
The amount of the monomer B may be about 3 to 10 parts by mass, specifically about 3 to about 5 parts by mass, relative to 100 parts by mass of the coating liquid in terms of solid content. When the amount of the monomer B is 3 parts by mass or more, the low refractive index layer 3 having sufficient strength can be formed. Further, the photoreactive fluoropolymer 6 is sufficiently distributed on the surface 3a of the low refractive index layer 3, whereby the polymer C can be sufficiently exposed to the surface 3a of the low refractive index layer 3. As a result, the surface 3a of the low refractive index layer 3 can have sufficient smoothness. On the other hand, when the amount of the monomer B is about 10 parts by mass or less, the low refractive index layer 3 may be formed, which has a refractive index of less than about 1.310. As a result, the light reflectance of the low refractive index layer 3 may be less than about 0.20%.
The amount of the polymer C may be about 5 to 15 parts by mass, specifically about 5 to 10 parts by mass, relative to 100 parts by mass of the coating liquid in terms of solid content (when the amount of the polymer C is 5 parts by mass or more, the low refractive index layer 3 may be formed with sufficient strength. further, the photoreactive fluoropolymer 6 is sufficiently distributed on the surface 3a of the low refractive index layer 3 while the polymer C is sufficiently exposed to the surface 3a of the low refractive index layer 3. as a result, the surface 3a of the low refractive index layer 3 may have sufficient smoothness.
By the above-described process according to the above-described embodiment, the antireflection film 10 can be manufactured using the above-described coating liquid.
[ embodiment 3]
(anti-reflection film)
Next, an antireflection film 20 according to a third embodiment will be described with reference to the drawings.
Fig. 3 is a sectional view of an antireflection film 20 according to a third embodiment of the present invention. In fig. 3, the same components of the antireflection film are denoted by the same reference numerals and repeated description thereof is omitted, compared with the components of the antireflection film 1 according to the first embodiment shown in fig. 1.
Referring to fig. 3, the anti-reflection film 20 includes a hard coat layer 2, a high refractive index layer 21, and a low refractive index layer 3, which have different refractive indices and are sequentially stacked in this order.
In the three-layer structure of the antireflection film 20 according to this embodiment, the refractive index of the high refractive index layer 21 is about 1.650 to about 1.800, preferably about 1.700 to about 1.750.
When the refractive index of the high refractive index layer 21 is in the range of about 1.650 to about 1.800, it is possible to obtain an optimum condition in which the anti-reflection film 20 has the lowest reflectance determined based on the thicknesses or refractive indices of its three layers. On the other hand, in this refractive index range, it is difficult to form the antireflection film 20 having a light reflectance of less than 0.2%.
The high refractive index layer 21 is formed of a mixture of an organic high refractive index material having a fluorine main chain or high refractive index nanoparticles (such as zirconia and titania) and an acrylic resin.
The high refractive index nanoparticles may have an average primary particle diameter of about 3nm to 30 nm.
For example, the high refractive index layer 21 may have a thickness of about 130nm to about 160 nm. When the thickness of the high refractive index layer 21 is in the range of about 130nm to about 160nm, the anti-reflection film may have a further reduced reflectance, and the light reflected by the anti-reflection film is substantially colorless.
According to this embodiment, in the antireflection film 20 having a three-layer structure including the high refractive index layer 21, the high refractive index layer 21 is formed, the refractive index of which is higher than that of the two-layer structure. Therefore, the light reflectance of the surface 3a of the low refractive index layer 3 can be reduced.
On the other hand, according to the antireflection film 1 of the first embodiment or the antireflection film 10 of the second embodiment, the low refractive index layer 3 can be realized.
[ embodiment 4]
(antireflection element)
Next, an antireflection element 30 according to a fourth embodiment is described with reference to the drawings.
Fig. 4 is a cross-sectional view of an antireflective element 30 according to a fourth embodiment of the invention. In fig. 4, the same components of the antireflection element as compared with the components of the antireflection film 1 according to the first embodiment shown in fig. 1 are denoted by the same reference numerals and repeated description thereof is omitted.
Referring to fig. 4, the anti-reflection member 30 is a sheet-like or plate-like member including a transparent substrate 31 and an anti-reflection film 1 formed on the transparent substrate 31.
In the antireflection element 30, the hard coat layer 2 and the low refractive index layer 3 are stacked on the transparent substrate 31 in this order.
The transparent substrate 31 is formed of a resin such as triacetyl cellulose (TAC), polyethylene terephthalate (PET), cycloolefin polymer (COP), poly (methyl methacrylate) (PMMA), and the like.
For example, the thickness of the transparent substrate 31 may be about 20 μm to about 200 μm, but is not limited thereto.
According to this embodiment, the antireflection element 30 includes the above-described antireflection film 1. Therefore, as in the antireflection film 1, the surface 3a of the low refractive index layer 3 is slidable, and an antireflection element having good performance in terms of steel wool abrasion resistance and antireflection can be obtained.
On the other hand, the antireflection element 30 according to this embodiment may use the antireflection film 10 according to the second embodiment instead of the antireflection film 1.
[ embodiment 5]
(polarizing plate)
Next, a polarizing plate 40 according to a fifth embodiment is described with reference to the drawings. Fig. 5 is a cross-sectional view of a polarizing plate 40 according to a fifth embodiment of the present invention. In fig. 5, the same components of the polarizing plate are denoted by the same numerals and the repeated description thereof is omitted, compared to the components of the antireflection film 1 according to the first embodiment shown in fig. 1.
Referring to fig. 5, the polarizing plate 40 includes a polarizing plate body 41 and an anti-reflection film 1 formed on a surface of the polarizing plate body 41.
The polarizing plate body 41 may be a general viewing angle-improved polarizing plate or a circular polarizing plate, but is not limited thereto.
Further, the polarizing plate 40 according to this embodiment may use the antireflection film 10 according to the second embodiment or the antireflection element 30 according to the fourth example instead of the antireflection film 1.
According to the antireflection film 1 described above, the polarizing plate 40 according to this embodiment can have sufficient antireflection resistance suitable for a display device requiring high contrast.
[ embodiment 6]
(display device: liquid Crystal display)
Next, a display device 50 according to a sixth embodiment is described with reference to the drawings. Fig. 6 is a sectional view of a display device 50 according to a sixth embodiment of the present invention. In fig. 6, the same components of the display device are denoted by the same reference numerals and repeated description thereof is omitted, compared to the components of the antireflection film 1 according to the first embodiment shown in fig. 1 and the polarizing plate 40 according to the fifth embodiment shown in fig. 5.
As the display device 50 according to this embodiment, a liquid crystal display will be described by way of example.
Referring to fig. 6, the display device 50 includes a liquid crystal display device 51, a polarizing plate (first polarizing plate) 40, and a polarizing plate (second polarizing plate) 52, which are combined on both sides of the liquid crystal display device 51. The polarizing plate 40 is disposed to the display surface 51a side of the liquid crystal display device 51 such that the polarizing plate body 41 of the polarizing plate 40 abuts the display surface.
The liquid crystal display device 51 may be a typical liquid crystal display device, and is not limited to a specific liquid crystal display device.
The polarizing plate 52 may be a typical circular polarizing plate, and is not limited to a specific circular polarizing plate.
The display device 50 according to this embodiment includes the polarizing plate 40, thereby obtaining a liquid crystal display having excellent anti-reflection rate.
[ embodiment 7]
(display device: organic EL display)
Next, a display device 60 according to a seventh embodiment is described with reference to the drawings. Fig. 7 is a sectional view of a display device 60 according to a sixth embodiment of the present invention. In fig. 7, the same components of the display device are denoted by the same reference numerals and repeated description thereof is omitted, compared to the components of the antireflection film 1 according to the first embodiment shown in fig. 1 and the polarizing plate 40 according to the fifth embodiment shown in fig. 5.
As the display device 60 according to this embodiment, an organic EL display will be described by way of example.
Referring to fig. 7, the display device 60 includes an organic EL device 61 and a polarizing plate 40 disposed on the organic EL device 61. The polarizing plate 40 is a circular polarizing plate having a retardation of λ/4, and is provided to the display surface 61a of the organic EL device 61 so that the polarizing plate body 41 abuts the display surface.
The organic EL device 61 may be a typical organic EL device, but is not limited to a specific organic EL device.
The display device 60 according to this embodiment includes the polarizing plate 40, thereby obtaining an organic EL display having excellent anti-reflectance.
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, it should be understood that the present invention is not limited thereto.
[ example 1]
A photoreactive fluorine-containing compound A, a monomer B, hollow silica particles, a photoreactive fluorine-containing polymer, a photoreactive modified silicone polymer, and a photopolymerization initiator were mixed. These components were mixed in a solid content ratio (mass ratio) as shown in table 1.
Then, a solvent was added to the mixture, and uniformly stirred and mixed with the solvent, thereby preparing a coating liquid of example 1.
According to 100 mass% of the coating liquid, 97 mass% of a solvent was added.
As the photoreactive fluorine-containing compound A ("fluorine compound A" in Table 1), a product containing 50 mass% of fluorine (AR-110, DAIKIN) was used.
As monomer B, isocyanuric acid diacrylate was used.
As the hollow silica particles, a product having an average primary particle diameter of 75nm (Thruya 5320, JGC catalysts and Chemicals) was used.
As the photoreactive fluoropolymer ("fluoropolymer" in Table 1), a product having a weight average molecular weight of 5,000 (KY-1203, Shin-Etsu Chemical Co., Ltd.) was used.
As the photoreactive modified silicone polymer ("siloxane polymer" in table 1), a product (TEGORad2700, EVONIK) having a weight average molecular weight of 30,000 was used.
As the photopolymerization initiator, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) -benzyl ] phenyl } -2-methyl-propan-1-one (product name: IRGACURE 127, BASF) was used.
As solvent, methyl isobutyl ketone was used.
Then, a hard coat substrate including a transparent substrate formed of TAC and a hard coat layer formed on the transparent substrate was prepared. The hard coat layer was mainly composed of a transparent acrylic resin, had a refractive index of 1.580 and a thickness of 5 μm. The hardcoat substrate had a total light transmittance of 91.9% and a haze of 0.30%.
The coating liquid was coated on the hard coat layer of the hard coat base material to form a coating layer having a thickness of 3.3 μm.
Thereafter, the coating was dried in an oven at 80 ℃ for 2min to evaporate the solvent in the coating.
Thereafter, the dried coating layer is irradiated with ultraviolet light to polymerize the photoreactive fluorine-containing compound a and the monomer B. Further, a polymer including the photoreactive fluorine-containing compound a is crosslinked with a polymer including the monomer B to form a low refractive index layer. As a result, an antireflection element of example 1 was obtained.
At about 200mJ/cm2At a wavelength of 365nm, ultraviolet radiation is performed.
[ example 2]
An antireflection element of example 2 was obtained by the same method as example 1, except that dipentaerythritol hexaacrylate was used as the monomer B.
[ example 3]
An antireflection element of example 3 was obtained by the same method as example 1, except that pentaerythritol triacrylate was used as the monomer B.
Comparative example 1
An antireflection element of comparative example 1 was obtained in the same manner as in example 1, except that trimethylolpropane acrylate was used instead of the isocyanuryldiacrylate.
Comparative example 2
An antireflection element of comparative example 2 was obtained by the same method as in example 1 except that the photoreactive fluorine-containing compound a was mixed by 35 parts by mass, the isocyanureyl diacrylate was mixed by 15 parts by mass, and the hollow silica particles were mixed by 40 parts by mass in terms of solid content, as shown in table 1.
[ comparative example 3]
An antireflection element of comparative example 3 was obtained by the same method as in example 1 except that the photoreactive fluorine-containing compound a was mixed by 20 parts by mass, the isocyanureyl diacrylate was mixed by 10 parts by mass, and the hollow silica particles were mixed by 60 parts by mass in terms of solid content, as shown in table 1.
[ comparative example 4]
An antireflective element of comparative example 4 was obtained by the same method as example 1, except that a product (CN990, ARKEMA) having a weight average molecular weight of 9000 was used as the photoreactive modified silicone polymer.
[ comparative example 5]
An antireflective member of comparative example 5 was obtained by the same method as example 1, except that the product (Solvay, MT70) having a weight average molecular weight of 800 was used as the photoreactive modified silicone polymer.
[ evaluation ]
(1) Refractive index of low refractive index layer
The refractive index of the low refractive index layer of each of the antireflective elements of examples 1 to 3 and comparative examples 1 to 5 was measured. The refractive index of the low refractive index layer can be measured by the following method.
1) The black ink is deposited on the rear surface (surface on which the antireflection film is not formed) of the substrate (antireflection element including the antireflection film formed thereon) to remove light reflected from the rear surface of the antireflection element.
2) The diffuse light incident at 8 degrees was focused on the surface of the antireflection element using a commercially available spectrophotometer, and the specular reflectance and diffuse reflectance at wavelengths of 380nm to 740nm were measured for the 8-degree received light beam.
3) As a commercially available spectrophotometer, a spectrophotometer CM-2600d (Konica Minolta) was used.
This spectrophotometer can obtain a specular reflectance Y value (SCI) and a diffuse reflectance Y value (SCE) at 2 degrees incidence under a D light source, and a value required for Y ═ SCI-SCE is defined as a light reflectance value.
4) The thickness and refractive index of the thin layer are adjusted to obtain a light reflectance spectrum and a film optically calculated reflectance spectrum having the same radius of curvature, and are defined as the refractive index of the low refractive index layer. The results are shown in Table 2.
(2) Light reflectance of surface of low refractive index layer
The light reflectance of the surface of the low refractive index layer of each of the antireflective members of examples 1 to 3 and comparative examples 1 to 5 was measured. The light reflectance of the low refractive index layer can be measured by the following method.
1) The black ink was deposited on the rear surface (surface on which the antireflection film 1 was not formed) of the substrate (antireflection element including the antireflection film formed thereon) to remove the light reflected from the rear surface of the antireflection element.
2) The diffuse light incident at 8 degrees was focused on the surface of the antireflection element using a commercially available spectrophotometer, and the specular reflectance and diffuse reflectance at wavelengths of 380nm to 740nm were measured for the 8-degree received light beam.
3) As a commercially available spectrophotometer, a spectrophotometer CM-2600d (Konica Minolta) was used.
This spectrophotometer can obtain a specular reflectance Y value (SCI) and a diffuse reflectance Y value (SCE) at 2 degrees incidence under a D light source, and a value required for Y ═ SCI-SCE is defined as a light reflectance value. The results are shown in Table 2.
(3) Steel wool carrying capacity of low refractive index layer
The steel wool load bearing capacity of the surface of the low refractive index layer of each of the antireflective members of examples 1 to 3 and comparative examples 1 to 5 was measured. The steel wool load bearing capacity of the low refractive index layer can be measured by the following method. # 0000: 1cm above the low refractive index layer2The steel wool reciprocates 10 times at a sliding speed of 100mm/s within the contact area and the sliding distance of 100 mm. After the steel wool was reciprocated on the low refractive index layer, the surface of the low refractive index layer was observed with naked eyes. Here, the maximum load that causes less than 10 scratches on the surface of the low refractive index layer is defined as the steel wool load-bearing capacity. The results are shown in Table 2.
[ Table 1]
[ Table 2]
As a result shown in table 2, the anti-reflection elements of examples 1 to 3, which showed good performance in terms of steel wool abrasion resistance and anti-reflection rate, were analyzed.
On the other hand, the antireflective member of comparative example 1 in which trimethylolpropane acrylate was substituted for isocyanureyl diacrylate to deteriorate the wear resistance of steel wool was analyzed.
An antireflection element of comparative example 2 was obtained using 35 parts by mass of the photoreactive fluorine-containing compound a, 15 parts by mass of isocyanurate diacrylate and 40 parts by mass of hollow silica particles in terms of solid content. As a result, the antireflection element of comparative example 2 was deteriorated in the refractive index of the low refractive index layer and the light reflectance of the surface of the low refractive index layer.
The antireflective member of comparative example 3 obtained using a composition outside the scope of the present invention and deteriorated in abrasion resistance of steel wool was analyzed.
The anti-reflective element of comparative example 4, which was obtained using a photoreactive modified silicone polymer having a weight average molecular weight of 9,000 and deteriorated abrasion resistance at steel wool, was analyzed.
The antireflective member of comparative example 5, which was obtained using a photoreactive fluoropolymer having a weight average molecular weight of 800 and deteriorated in abrasion resistance of steel wool, was analyzed.
[ example 4]
A photoreactive fluorine-containing compound A, a monomer B, a polymer C, hollow silica particles, a photoreactive fluorine-containing polymer and a photopolymerization initiator were mixed. These components were mixed in a solid content ratio (mass ratio) as shown in table 3.
Then, a solvent was added to the mixture, and uniformly stirred and mixed with the solvent, thereby preparing a coating liquid of example 4.
According to 100 mass% of the coating liquid, 97 mass% of a solvent was added.
As the photoreactive fluorine-containing compound A ("fluorine compound A" in Table 3), a product containing 50 mass% of fluorine (AR-110, DAIKIN) was used.
As monomer B, isocyanuric acid diacrylate was used.
As the polymer C, a silicone compound (KR-515, Shin-Etsu Chemical Co., Ltd.) was used, wherein n represents the degree of polymerization of the structure in parentheses of the formula (1) in the range of 3 to 4.
As the hollow silica particles, a product having an average primary particle diameter of 75nm (Thruya 5320, JGC catalysts and Chemicals) was used.
As the photoreactive fluoropolymer ("fluoropolymer" in Table 3), a product (FS-7024, Fluoro Technology) having a weight average molecular weight of 5,000 was used.
As the photopolymerization initiator, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) -benzyl ] phenyl } -2-methyl-propan-1-one (product name: IRGACURE 127, BASF) was used.
As solvent, methyl isobutyl ketone was used.
Thereafter, an antireflection element of example 4 was obtained by the same method as in example 1.
[ example 5]
As the photoreactive fluoropolymer ("fluoropolymer" in Table 3), a product (KY-1203, Shin-Etsu Chemical Co., Ltd.) having a weight average molecular weight of 5,000 was used. A coating liquid was prepared by the same method as in example 4.
Then, a hard coat substrate including a transparent substrate formed of TAC, a hard coat layer formed on the transparent substrate, and a hard high refractive index layer formed on the hard coat layer was prepared.
The hard coat layer was mainly composed of a transparent acrylic resin, had a refractive index of 1.580 and a thickness of 5 μm.
The high refractive index layer was formed by crosslinking zirconia particles and an acrylic resin binder, and had a refractive index of 1.73 and a thickness of 150 nm. The hardcoat substrate had a total light transmittance of 91.9% and a haze of 0.50%. Thereafter, an antireflection element of example 5 was obtained by the same method as in example 1.
[ comparative example 6]
An antireflection element was obtained by the same method as in example 4, except that the composition of the antireflection element was changed as listed in table 3.
[ comparative example 7]
An antireflection element was obtained by the same method as in example 4, except that the composition of the antireflection element was changed as listed in table 3.
[ comparative example 8]
An antireflection element was obtained by the same method as in example 4, except that the composition of the antireflection element was changed as listed in table 3.
[ evaluation ]
(1) Refractive index of low refractive index layer
The refractive index of the surface of the low refractive index layer of each of the antireflective members of examples 4 to 5 and comparative examples 6 to 8 was measured.
The refractive index of the low refractive index layer was measured by the same method as in examples 1 to 3 and comparative examples 1 to 5. The results are shown in Table 4.
(2) Light reflectance of surface of low refractive index layer
The light reflectance of the surface of the low refractive index layer of each of the antireflective members of examples 4 to 5 and comparative examples 6 to 8 was measured. The light reflectance of the low refractive index layer was measured by the same method as in examples 1 to 3 and comparative examples 1 to 5. The results are shown in Table 4.
(3) Steel wool carrying capacity of low refractive index layer
The steel wool load bearing capacity of the surface of the low refractive index layer of each of the antireflective members of examples 4 to 5 and comparative examples 6 to 8 was measured. The steel wool load bearing capacity of the low refractive index layer was measured by the same method as in examples 1 to 3 and comparative examples 1 to 5. The results are shown in Table 4.
[ Table 3]
[ Table 4]
As can be seen from the results of table 4, the analysis showed that the antireflective members of examples 4 and 5 had better antireflective properties than the antireflective members of examples 1 to 3.
Furthermore, the analysis showed that the antireflective element of example 5 had better antireflective properties than the antireflective elements of examples 1 to 3.
(list of reference numerals)
1: an antireflection film which is formed on a substrate,
2: a hard coating layer is coated on the surface of the substrate,
3: low refractive index layer
4: an adhesive agent is added to the mixture of the components,
5: the hollow silica particles are formed by the reaction of a hollow silica,
6: a photoreactive fluoropolymer, which is a fluoropolymer,
7: a modified silicone polymer that is photoreactive,
10: an antireflection film which is formed on a substrate,
20: an antireflection film which is formed on a substrate,
21: a high-refractive-index layer having a refractive index,
30: an anti-reflection element is provided on the substrate,
31: a transparent base material, a transparent substrate,
40: a polarizing plate having a plurality of polarizing plates,
41: a polarizing plate body having a plurality of polarizing plates,
50: a display device for displaying the image of the object,
51: a liquid crystal display device is provided with a liquid crystal layer,
52: a polarizing plate having a plurality of polarizing plates,
60: a display device for displaying the image of the object,
61: an organic EL device.
Claims (10)
1. An antireflection film comprising at least two layers having different refractive indices,
wherein the uppermost layer of the anti-reflection film comprises: a binder comprising a crosslinked product obtained by crosslinking a polymer comprising a photoreactive fluoromonomer A and a polymer comprising a monomer B having at least one hydroxyl group and at least two photoreactive functional groups; hollow silica particles dispersed in the binder; a photoreactive fluoropolymer; and a polymer having a main chain a bonded through siloxane, the photoreactive fluoropolymer and the polymer having a main chain a bonded through siloxane being dispersed on an uppermost surface of the uppermost layer,
the refractive index of the uppermost layer is less than 1.310,
the surface of the uppermost layer has a light reflectance of less than 0.20%,
the bearing capacity of the steel wool at the uppermost layer is 300g/cm2Or higher.
2. The antireflective film of claim 1 wherein the polymer having a main chain a bonded through a siloxane is a photoreactive modified silicone polymer.
3. The antireflection film as described in claim 1, wherein the binder comprises a polymer C having a main chain bonded through siloxane represented by formula (1), a unit constituting the main chain bonded through siloxane has one methoxy group directly bonded to a silicon atom and one methyl group directly bonded to the silicon atom, and the polymer C is to be a polymer having a main chain a bonded through siloxane:
< formula 1>
Wherein n is an integer from 2 to 10.
4. The antirefiective film of claim 1 wherein the uppermost layer is stacked on a hardcoat layer having a refractive index of 1.500-1.650.
5. The antireflection film according to claim 2, wherein the uppermost layer is formed using a coating liquid containing, in terms of solid content, 20 to 40 parts by mass of the photoreactive fluorine-containing monomer a, 5 to 20 parts by mass of the monomer B having at least one hydroxyl group and at least two photoreactive functional groups, 45 to 56 parts by mass of the hollow silica particles, 1 to 10 parts by mass of the photoreactive fluorine-containing polymer, 1 to 3 parts by mass of the photoreactive modified silicone polymer, and 1 to 5 parts by mass of a photopolymerization initiator, compared to 100 parts by mass of the coating liquid.
6. The antireflective film of claim 5 wherein the photoreactive fluoropolymer has a weight average molecular weight of 2,000 to 10,000 and the photoreactive modified silicone polymer has a weight average molecular weight of 10,000 to 50,000.
7. The antireflection film according to claim 3, wherein the uppermost layer is formed using a coating liquid containing, in terms of solid content, 10 to 30 parts by mass of the photoreactive fluorine-containing monomer a, 3 to 10 parts by mass of the monomer B having at least one hydroxyl group and at least two photoreactive functional groups, 45 to 56 parts by mass of the hollow silica particles, 1 to 10 parts by mass of the photoreactive fluorine-containing polymer, 5 to 15 parts by mass of polymer C, and 1 to 5 parts by mass of a photopolymerization initiator, compared to 100 parts by mass of the coating liquid.
8. An antireflection element comprising a transparent substrate and the antireflection film according to any one of claims 1 to 7 formed on the transparent substrate, wherein the antireflection film comprises a hard coat layer and the uppermost layer stacked in this order on the transparent substrate.
9. A polarizing plate comprising the antireflection film described in any one of claims 1 to 7 formed on an uppermost surface thereof.
10. A display device comprising the polarizing plate according to claim 9.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016232908A JP2018091906A (en) | 2016-11-30 | 2016-11-30 | Antireflection film, antireflection member, polarizer, and display device |
| JP2016-232908 | 2016-11-30 | ||
| KR1020170092282A KR102097801B1 (en) | 2016-11-30 | 2017-07-20 | Antireflection film, member comprising the same, polarizing plate comprising the same and display comprising the same |
| KR10-2017-0092282 | 2017-07-20 | ||
| PCT/KR2017/012575 WO2018101629A1 (en) | 2016-11-30 | 2017-11-08 | Antireflective film, antireflective member, polarizing plate, and display device |
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| CN110036311A CN110036311A (en) | 2019-07-19 |
| CN110036311B true CN110036311B (en) | 2021-03-05 |
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| CN201780074312.9A Active CN110036311B (en) | 2016-11-30 | 2017-11-08 | Antireflection film, antireflection element, polarizing plate, and display device |
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| Country | Link |
|---|---|
| JP (2) | JP2018091906A (en) |
| KR (1) | KR102097801B1 (en) |
| CN (1) | CN110036311B (en) |
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| JP2004333901A (en) * | 2003-05-08 | 2004-11-25 | Optimax Technology Corp | Method for manufacturing glare-proof antireflection film |
| JP2010092003A (en) * | 2008-09-11 | 2010-04-22 | Toppan Printing Co Ltd | Antireflection film |
| JP5062509B2 (en) * | 2006-06-30 | 2012-10-31 | 大日本印刷株式会社 | Anti-reflection laminate |
| CN102998723A (en) * | 2012-11-29 | 2013-03-27 | 法国圣戈班玻璃公司 | Antireflection optical assembly and manufacturing method thereof |
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| KR101092573B1 (en) | 2010-04-06 | 2011-12-13 | 주식회사 엘지화학 | Anti-reflective coating composition, anti-reflection film and method for manufacturing the same |
| JP5723625B2 (en) | 2011-02-15 | 2015-05-27 | 富士フイルム株式会社 | Antireflection film manufacturing method, antireflection film |
| KR101548313B1 (en) * | 2012-05-25 | 2015-08-28 | 주식회사 엘지화학 | Anti-reflective coating composition having improved scratch-resistant, and anti-reflective coating film using the same |
| JP6155850B2 (en) | 2013-05-30 | 2017-07-05 | 凸版印刷株式会社 | Antireflection film |
| JP6689564B2 (en) | 2014-05-30 | 2020-04-28 | 大日本印刷株式会社 | Antireflection film, polarizing plate, and image display device |
| JP6661286B2 (en) | 2014-06-30 | 2020-03-11 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Resin film, optical member and polarizing member |
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- 2016-11-30 JP JP2016232908A patent/JP2018091906A/en active Pending
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- 2017-07-20 KR KR1020170092282A patent/KR102097801B1/en active IP Right Grant
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Patent Citations (4)
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|---|---|---|---|---|
| JP2004333901A (en) * | 2003-05-08 | 2004-11-25 | Optimax Technology Corp | Method for manufacturing glare-proof antireflection film |
| JP5062509B2 (en) * | 2006-06-30 | 2012-10-31 | 大日本印刷株式会社 | Anti-reflection laminate |
| JP2010092003A (en) * | 2008-09-11 | 2010-04-22 | Toppan Printing Co Ltd | Antireflection film |
| CN102998723A (en) * | 2012-11-29 | 2013-03-27 | 法国圣戈班玻璃公司 | Antireflection optical assembly and manufacturing method thereof |
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| Publication number | Publication date |
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| JP7101673B2 (en) | 2022-07-15 |
| KR102097801B1 (en) | 2020-04-06 |
| JP2018091906A (en) | 2018-06-14 |
| KR20180062326A (en) | 2018-06-08 |
| CN110036311A (en) | 2019-07-19 |
| JP2020516922A (en) | 2020-06-11 |
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