CN114761865A - Liquid crystal panel - Google Patents
Liquid crystal panel Download PDFInfo
- Publication number
- CN114761865A CN114761865A CN202080080315.5A CN202080080315A CN114761865A CN 114761865 A CN114761865 A CN 114761865A CN 202080080315 A CN202080080315 A CN 202080080315A CN 114761865 A CN114761865 A CN 114761865A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- film
- layer
- polarizing film
- crystal panel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 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
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- G02F1/1333—Constructional arrangements; Manufacturing methods
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- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
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- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
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- 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
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- G02F2202/00—Materials and properties
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- Physics & Mathematics (AREA)
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- Chemical & Material Sciences (AREA)
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- Mathematical Physics (AREA)
- Inorganic Chemistry (AREA)
- Polarising Elements (AREA)
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- Surface Treatment Of Optical Elements (AREA)
Abstract
The invention provides a liquid crystal panel capable of preventing display defects caused by electrification of a liquid crystal display device and improving the visibility of the liquid crystal display device. The liquid crystal panel is provided with a polarizing film (15) with an antireflection film, and a liquid crystal cell (25), wherein the polarizing film (15) with an antireflection film comprises an antireflection film (10), a polarizing film (20), and an adhesive layer (30) in this order in the stacking direction, and further comprises a conductive layer (40). No conductive layer is provided between the polarizing film with the antireflection film and the liquid crystal cell. The surface resistivity of the conductive layer of the polarizing film with an antireflection film was 1.0X 106Omega/□ or less. The polarizing film with the antireflection film is laminated with alkali-free glass in such a manner that the adhesive layer is in direct contact with the alkali-free glassWhen light from CIE standard light source D65 enters from the surface opposite to the pressure-sensitive adhesive layer in the above state, reflected light having a light reflection ratio Y of 1.1% or less is generated.
Description
Technical Field
The present invention relates to a liquid crystal panel.
Background
The liquid crystal display device includes, for example: the liquid crystal display device includes a liquid crystal panel having a structure in which a polarizing film is disposed on a viewing side of a liquid crystal cell, and an illumination system for irradiating the liquid crystal panel with light. The liquid crystal display device displays an image by applying a voltage to a liquid crystal cell and adjusting the orientation of liquid crystal molecules contained in the liquid crystal cell.
In the liquid crystal display device, static electricity is generated during the production, for example, when a polarizing film is bonded to a liquid crystal cell via an adhesive layer, or during the use, for example, when a user touches the liquid crystal display device. The liquid crystal display device may be charged by the static electricity. If the liquid crystal display device is charged, the alignment of liquid crystal molecules contained in the liquid crystal cell is disturbed, and a display failure occurs. In order to prevent display defects caused by electrification of the liquid crystal display device, it is known to dispose an ITO (indium tin oxide) layer on the surface of the liquid crystal cell on the polarizing film side, for example.
However, the ITO layer may be omitted from the viewpoint of cost. For example, patent documents 1 and 2 disclose a liquid crystal panel in which an ITO layer is not disposed on the surface of a liquid crystal cell on the polarizing film side, and a polarizing film with an adhesive layer is in direct contact with the liquid crystal cell.
Documents of the prior art
Patent literature
Patent document 1: international publication No. 2018/181477
Patent document 2: japanese patent No. 5679337
Disclosure of Invention
Problems to be solved by the invention
In a liquid crystal display device in which an ITO layer is not disposed on the surface of a liquid crystal cell on the polarizing film side, it is difficult to sufficiently prevent display failure due to electrification when the liquid crystal display device is used in an environment in which static electricity is particularly likely to occur, for example, an environment in which other electronic devices are present in the surroundings, such as the inside of a vehicle. In addition, when the liquid crystal display device is used as an in-vehicle display, for example, good visibility is required from the viewpoint of safety.
Accordingly, an object of the present invention is to provide a liquid crystal panel capable of preventing display defects caused by electrification of a liquid crystal display device and improving visibility of the liquid crystal display device.
Means for solving the problems
The invention provides a liquid crystal panel, which comprises a polarizing film with an anti-reflection film and a liquid crystal cell, wherein the polarizing film with the anti-reflection film comprises an anti-reflection film, a polarizing film, an adhesive layer and a conductive layer in sequence in a laminating direction,
no conductive layer is provided between the polarizing film with an antireflection film and the liquid crystal cell,
the surface resistivity of the conductive layer in the polarizing film with an antireflection film is 1.0 × 106Below the value of omega/□, the ratio of omega/□,
in the polarizing film with an antireflection film, when light from CIE standard illuminant D65 is incident from a surface opposite to the pressure-sensitive adhesive layer in a state where the pressure-sensitive adhesive layer is laminated with the alkali-free glass so as to be in direct contact with the alkali-free glass, reflected light having a light reflectance Y of 1.1% or less is generated.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a liquid crystal panel capable of improving visibility of a liquid crystal display device while preventing display defects caused by electrification of the liquid crystal display device.
Drawings
Fig. 1 is a sectional view of a liquid crystal panel according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view showing an example of the antireflection film.
Fig. 3 is a cross-sectional view showing another example of the antireflection film.
Fig. 4 is a cross-sectional view showing a modification of the liquid crystal panel.
Fig. 5 is a cross-sectional view showing another modification of the liquid crystal panel.
FIG. 6 shows a reflection light a from a polarizing film with an antireflection film in examples and comparative examples*Value and b*A graph of the relationship of values.
Detailed Description
The present invention will be described in detail below, but the following description is not intended to limit the present invention to the specific embodiments.
(liquid Crystal Panel embodiment)
As shown in fig. 1, the liquid crystal panel 100 of the present embodiment includes a polarizing film 15 with an antireflection film and a liquid crystal cell 25. No conductive layer, for example, an ITO layer, is provided between the polarizing film 15 with an antireflection film and the liquid crystal cell 25, and the polarizing film 15 with an antireflection film is in direct or indirect contact with the liquid crystal cell 25. Other layers than the conductive layer may be disposed between the polarizing film 15 with the antireflection film and the liquid crystal cell 25 within a range not to impair the effects of the present invention. The antireflection film-equipped polarizing film 15 includes an antireflection film 10, a polarizing film 20, and an adhesive layer 30 in this order in the lamination direction, and further includes a conductive layer 40. The conductive layer 40 is disposed between the polarizing film 20 and the adhesive layer 30, for example, and is in contact with the polarizing film 20 and the adhesive layer 30, respectively. When the conductive layer 40 is disposed between the polarizing film 20 and the pressure-sensitive adhesive layer 30, deterioration of the conductive layer 40 tends to be suppressed. However, the conductive layer 40 may be disposed at a position other than between the polarizing film 20 and the pressure-sensitive adhesive layer 30, and may be disposed between the antireflection film 10 and the polarizing film 20, for example.
In the polarizing film with antireflection film 15, the surface resistivity of the conductive layer 40 was 1.0 × 106Omega/□ or less. The conductive layer 40 having a surface resistivity as low as this can prevent the occurrence of static electricity due to electrification of a liquid crystal display device including the liquid crystal panel 100 even in an environment where static electricity is likely to occurIt was found to be poor. The surface resistivity of the conductive layer 40 can be specified by the following method. First, a laminate in which the surface of the conductive layer 40 is exposed to the outside is prepared. Examples of such a laminate include: a laminate L including a polarizing film 20 and a conductive layer 40. Next, the surface resistivity of the surface of the conductive layer 40 in the prepared laminate was measured. The surface resistivity can be measured according to the method specified in JIS K7194:1994 or JIS K6911: 1995. For example, the surface resistivity of the conductive layer 40 is less than 1.0 × 105In the case of Ω/□, the surface resistivity of the conductive layer 40 can be measured by using Loresta-GP MCP-T600 (manufactured by Mitsubishi Chemical Analyticch Co., Ltd.) according to the method prescribed in JIS K7194: 1994. The surface resistivity of the conductive layer 40 was 1.0X 105In the case of Ω/□ or more, the surface resistivity of the conductive layer 40 can be measured by the method specified in JIS K6911:1995 using Hiresta-UP MCP-HT450 (manufactured by Mitsubishi Chemical Analyticech Co., Ltd.). The measured value obtained by the above measurement can be regarded as the surface resistivity of the conductive layer 40 in the polarizing film 15 with an antireflection film.
The surface resistivity of the conductive layer 40 is preferably 5.0 × 105Omega/□ or less, more preferably 1.0X 105Omega/□ or less, more preferably 1.0X 104Omega/□ or less, particularly preferably 1.0X 103Omega/□ or less. The lower limit of the surface resistivity of the conductive layer 40 is not particularly limited, and is, for example, 1.0 × 102Omega/□. In the case where the liquid crystal panel 100 is used in a liquid crystal display device including a touch sensor or a touch panel, the surface resistivity of the conductive layer 40 may be greater than 5.0 × 10 from the viewpoint of sufficiently ensuring the sensitivity of the touch sensor or the touch panel provided in the liquid crystal display device2Ω/□。
In the antireflection film-equipped polarizing film 15, when light from the CIE standard light source D65 is incident from the surface opposite to the pressure-sensitive adhesive layer 30 (typically, the surface of the antireflection film 10) in a state where the pressure-sensitive adhesive layer 30 is laminated with alkali-free glass so as to be in direct contact with the alkali-free glass, reflected light having a light reflection ratio Y of 1.1% or less is generated. The polarizing film 15 with an antireflection film, which generates such reflected light, can suppress reflection of light on the liquid crystal panel 100, thereby improving visibility of the liquid crystal display device. The light reflectance Y is a Y value of tristimulus values (X, Y and Z) in the XYZ color system (CIE 1931). The tristimulus values are specified in detail in JIS Z8701: 1999.
Specifically, the light reflectance Y can be specified by the following method. First, the polarizing film 15 with the antireflection film is attached to the alkali-free glass by the adhesive layer 30. The alkali-free glass is a glass substantially free of alkali (alkali metal oxide), and specifically, the weight ratio of alkali in the glass is, for example, 1000ppm or less, and further 500ppm or less. The alkali-free glass is, for example, plate-shaped and has a thickness of 0.5mm or more. Next, a black film is attached to the surface of the alkali-free glass opposite to the surface to be attached to the polarizing film 15 with the antireflection film. Next, light from CIE standard light source D65 was incident on the surface of antireflection film-provided polarizing film 15 on the antireflection film 10 side at an incident angle of 5 °. The spectral reflectance in the wavelength range of 360nm to 740nm of the specular reflection light generated in this case can be specified, and the light reflectance Y in the XYZ color system (CIE1931) can be specified based on the spectral reflectance.
The light reflectance Y is preferably 1.0% or less, more preferably 0.9% or less, still more preferably 0.8% or less, and particularly preferably 0.7% or less. The lower limit of the light reflectance Y is not particularly limited, but is, for example, 0.1%.
The above reflected light is at L *a*b*A in the color System (CIE1976)*Value and b*The value is not particularly limited, and preferably satisfies the following relational expressions (1) and (2).
-10≤a*≤10 (1)
-18≤b*≤5 (2)
A above*Value and b*The values can be expressed using tristimulus values (X, Y and Z) of reflected light in XYZ color system and measured by JIS Z8781-4: 2013, and the following formulae (i) and (ii).
[ mathematical formula 1]
a*=500[f(X/Xn)-f(Y/Yn)] (i)
b*=200[f(Y/Yn)-f(Z/Zn)] (ii)
A above*The value is preferably-6 or more and 6 or less, more preferably-3 or more and 3 or less. B above*The value is preferably-15 or more and 3 or less, more preferably-10 or more and 2 or less, further preferably-6 or more and 2 or less, particularly preferably-5 or more and 2 or less. According to circumstances, a*Value and b*The values may satisfy the following relational expressions (3) and (4).
b*≥-1.5a*-15 (3)
b*≤-1.5a*+7.5 (4)
In addition, a*Value and b*The values may satisfy the following relational expressions (5) and (6).
b*≥-1.5a*-5 (5)
b*≤-1.5a*+4.5 (6)
L of the reflected light*The value is, for example, 12 or less, preferably 10 or less, more preferably 8 or less, and further preferably 7 or less. L is*The lower limit of the value is not particularly limited, and is, for example, 3. L is*The values may be determined using the tristimulus values described above and in accordance with JIS Z8781-4: 2013, as defined by the following formula (iii).
[ mathematical formula 2]
L*=116f(Y/Yn)-16 (iii)
Satisfy L*Value of 0, a*Value of 0 and b*The color difference Δ E between the light having a value of 0 (i.e., light having a completely natural hue) and the reflected light is, for example, 22 or less, preferably 18 or less, more preferably 15 or less, still more preferably 10 or less, and particularly preferably 8 or less. The lower limit of the color difference Δ E is not particularly limited, and is, for example, 3. The color difference Δ E may use L of reflected light *Value a*Value and b*The value was calculated based on the following formula (iv).
AE*={(L*)2+(a*)2+(b*)2}1/2 (iv)
[ anti-reflection film ]
As shown in fig. 2, the antireflection film 10 includes a 1 st high refractive index layer 1, a 1 st low refractive index layer 2, a 2 nd high refractive index layer 3, and a 2 nd low refractive index layer 4 in this order in the lamination direction. The 1 st high refractive-index layer 1 is, for example, in contact with a polarizing film 20. The 2 nd low refractive index layer 4 is, for example, located closest to the viewing side among these layers.
The high refractive index layers 1 and 3 are layers having a higher refractive index than the low refractive index layers 2 and 4, and have a refractive index in the range of 1.6 to 3.2, for example. The refractive index of the 1 st high refractive index layer 1 may be the same as or different from that of the 2 nd high refractive index layer 3. In the present specification, unless otherwise specified, "refractive index" means a refractive index measured at a temperature of 25 ℃ using light having a wavelength λ of 550nm in accordance with JIS K0062: 1992, define the values determined.
In a preferred embodiment of the present invention, the high refractive index layers 1 and 3 include, for example, a binder resin and inorganic fine particles dispersed in the binder resin. The binder resin is typically a cured product of an ionizing radiation curable resin, more specifically, a cured product of an ultraviolet curable resin. Examples of the ultraviolet curable resin include resins containing a polymer or oligomer having a substituent capable of radical polymerization, such as a (meth) acrylate resin. The (meth) acrylate resin as the ultraviolet curable resin includes, for example, polymers or oligomers of epoxy (meth) acrylate, polyester (meth) acrylate, acrylic (meth) acrylate, ether (meth) acrylate, and the like. The (meth) acrylate resin may further contain a radical polymerizable monomer (precursor) in addition to the above-mentioned polymer or oligomer. The molecular weight of the monomer is, for example, 200 to 700. Specific examples of the monomer include pentaerythritol triacrylate (PETA: molecular weight 298), neopentyl glycol diacrylate (NPGDA: molecular weight 212), dipentaerythritol hexaacrylate (DPHA: molecular weight 632), dipentaerythritol pentaacrylate (DPPA: molecular weight 578), and trimethylolpropane triacrylate (TMPTA: molecular weight 296). The ionizing radiation-curable resin may contain an initiator, if necessary. Examples of the initiator include: UV radical generators (IRGACURE 907, IRGACURE 127, IRGACURE 192, etc., available from Ciba Specialty Chemicals), and benzoyl peroxide. The binder resin may contain other resins in addition to the cured product of the ionizing radiation-curable resin. The other resin may be a thermosetting resin or a thermoplastic resin. Examples of the other resin include aliphatic resins (for example, polyolefin) and urethane resins.
The refractive index of the binder resin is, for example, 1.40 to 1.60. The amount of the binder resin is, for example, 10 to 80 parts by weight, preferably 20 to 70 parts by weight, based on 100 parts by weight of the high refractive index layer to be formed.
The material of the inorganic fine particles is, for example, a metal oxide. Specific examples of the metal oxide include zirconium oxide (refractive index: 2.19), aluminum oxide (refractive index: 1.56 to 2.62), titanium oxide (refractive index: 2.49 to 2.74), and silicon oxide (refractive index: 1.25 to 1.46). These metal oxides not only have small light absorption but also have a higher refractive index than organic materials such as ionizing radiation-curable resins and thermoplastic resins, and therefore, are suitable for adjusting the refractive index of the high refractive index layers 1 and 3. The inorganic fine particles preferably contain zirconia or titania.
The refractive index of the inorganic fine particles is, for example, 1.60 or more, preferably 1.70 to 2.80, and more preferably 2.00 to 2.80. The inorganic fine particles having a refractive index of 1.60 or more are suitable for adjusting the refractive index of the high refractive index layers 1 and 3. The average particle diameter of the inorganic fine particles is, for example, 1nm to 100nm, preferably 10nm to 80nm, and more preferably 20nm to 70 nm. The average particle diameter of the inorganic fine particles is a particle diameter corresponding to 50% of the volume accumulation in the particle size distribution measured by, for example, a laser diffraction particle sizer (d 50).
The inorganic fine particles may be not surface-modified, but are preferably surface-modified. The inorganic fine particles after surface modification tend to be well dispersed in the binder resin. The surface modification is performed, for example, by coating the surface of the inorganic fine particles with a surface modifier to form a surface modifier layer. Examples of the surface modifier include: coupling agents such as silane coupling agents and titanate coupling agents; surfactants such as fatty acid surfactants. When such a surface modifier is used, the wettability between the binder resin and the inorganic fine particles is improved, and the interface between the binder resin and the inorganic fine particles tends to be stabilized.
The amount of the inorganic fine particles is, for example, 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the high refractive index layer to be formed. When the amount of the inorganic fine particles is within the above range, the antireflection film tends to have sufficient mechanical properties and to sufficiently reduce the light reflectance Y of reflected light.
The high refractive index layers 1 and 3 containing a binder resin and inorganic fine particles have a refractive index of, for example, 1.6 to 2.6, preferably 1.7 to 2.2.
In another preferred embodiment of the present invention, the high refractive index layers 1 and 3 comprise, preferably are substantially formed of, a metal oxide or a metal nitride. Specific examples of the metal oxide include titanium oxide (TiO) 2) Indium/tin oxide (ITO), niobium oxide (Nb)2O5) Yttrium oxide (Y)2O3) Indium oxide (In)2O3) Tin oxide (SnO)2) Zirconium oxide (ZrO)2) Hafnium oxide (HfO)2) Antimony oxide (Sb)2O3) Tantalum oxide (Ta)2O5) Zinc oxide (ZnO), tungsten oxide (WO)3). Specific examples of the metal nitride include silicon nitride (Si)3N4). The high refractive index layers 1 and 3 preferably contain niobium oxide (Nb)2O5) Or titanium oxide (TiO)2). The high refractive index layer made of a metal oxide or a metal nitride has a refractive index of, for example, 2.00 to 2.60, preferably 2.10 to 2.45.
The material of the 1 st high refractive-index layer 1 may be the same as or different from that of the 2 nd high refractive-index layer 3.
The physical film thickness of the 1 st high refractive index layer 1 is, for example, 9nm to 15nm, preferably 11nm to 13 nm. The optical film thickness of the 1 st high refractive index layer 1 is, for example, 20nm to 35nm, preferably 25nm to 30 nm. In the present specification, the optical film thickness is a value represented by the product of the refractive index of light having a wavelength of 550nm and the physical film thickness.
The physical film thickness of the 2 nd high refractive index layer 3 is, for example, 98nm to 124nm, preferably 111nm to 120 nm. The optical film thickness of the 2 nd high refractive index layer 3 is, for example, 230nm to 290nm, preferably 260nm to 280 nm.
The low refractive index layers 2 and 4 are layers having a refractive index lower than that of the high refractive index layers 1 and 3, and the refractive index thereof is, for example, 1.35 to 1.55, preferably 1.40 to 1.50. By appropriately adjusting the difference in refractive index between the low refractive index layers 2 and 4 and the high refractive index layers 1 and 3, reflection of light tends to be suppressed. The refractive index of the 1 st low refractive index layer 2 may be the same as or different from that of the 2 nd low refractive index layer 4.
Examples of the material of the low refractive index layers 2 and 4 include: metal oxides and metal fluorides. Specific examples of the metal oxide include silicon oxide (SiO)2). Specific examples of the metal fluoride include magnesium fluoride and fluorinated silicic acid. The material of the low refractive index layers 2 and 4 is preferably magnesium fluoride or fluorinated silicic acid from the viewpoint of the refractive index, and silicon oxide is preferable from the viewpoint of ease of production, mechanical strength, moisture resistance, and the like, and silicon oxide is preferable if various properties are comprehensively considered. The material of the 1 st low refractive index layer 2 may be the same as or different from that of the 2 nd low refractive index layer 4.
The material of the low refractive index layers 2 and 4 may be a cured product of a curable fluorine-containing resin. The curable fluorine-containing resin has, for example, a structural unit derived from a fluorine-containing monomer and a structural unit derived from a crosslinkable monomer. Specific examples of the fluorine-containing monomer include: fluoroolefins (e.g., vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, and perfluoro-2, 2-dimethyl-1, 3-dioxole), partially or completely fluorinated alkyl (meth) acrylate derivatives (e.g., Viscoat 6FM (manufactured by Osaka Kagaku Co., Ltd.), and M-2020 (manufactured by Daikin Co., Ltd.), and completely or partially fluorinated vinyl ethers). Examples of the crosslinkable monomer include: a (meth) acrylate monomer having a crosslinkable functional group in the molecule, such as glycidyl methacrylate; (meth) acrylate monomers having a functional group such as a carboxyl group, a hydroxyl group, an amino group, or a sulfonic acid group ((meth) acrylic acid, hydroxymethyl (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl (meth) acrylate, etc.). The fluorine-containing resin may have a structural unit derived from a monomer other than the above-mentioned compounds (for example, an olefin monomer, (meth) acrylate monomer, or styrene monomer).
The physical film thickness of the 1 st low refractive index layer 2 is, for example, 26nm to 34nm, preferably 27nm to 31 nm. The optical film thickness of the 1 st low refractive index layer 2 is, for example, 38nm to 50nm, preferably 40nm to 45 nm.
The physical film thickness of the 2 nd low refractive index layer 4 is, for example, 68nm to 88nm, preferably 72nm to 79 nm. The optical film thickness of the 2 nd low refractive index layer 4 is, for example, 100nm to 128nm, preferably 105nm to 115 nm.
The method for producing the high refractive index layer and the low refractive index layer is not particularly limited. In the case where these layers contain a resin, these layers may be formed by a so-called wet process (curing after coating a resin composition). In the case where these layers are composed of a metal oxide, a metal fluoride, a metal nitride, or the like, these layers can be formed by a so-called dry process. Specific examples of the dry process include a PVD (Physical Vapor Deposition) method and a CVD (Chemical Vapor Deposition) method. Examples of the PVD method include: vacuum deposition, reactive deposition, ion beam assisted, sputtering, ion plating. Examples of the CVD method include a plasma CVD method. From the viewpoint of reducing the variation in hue of reflected light, the dry process is preferably a sputtering method.
The antireflection film 10 of fig. 2 may further include other members than the high refractive index layer and the low refractive index layer. Fig. 3 shows another example of the antireflection film. The antireflection film 11 of fig. 3 further includes a substrate 5 and a pressure-sensitive adhesive layer 6. The substrate 5 is disposed between the 1 st high refractive index layer 1 and the polarizing film 20, for example, and is in contact with the 1 st high refractive index layer 1. The pressure-sensitive adhesive layer 6 is disposed, for example, between the substrate 5 and the polarizing film 20, and is in contact with the substrate 5 and the polarizing film 20, respectively.
The substrate 5 includes, for example, a transparent resin film. Examples of the material of such a resin film include: cellulose resins (cellulose triacetate, cellulose diacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, nitrocellulose, etc.), polyamide resins (nylon-6, nylon-66, etc.), polyimide resins, polycarbonate resins, polyester resins (polyethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate 1, 4-cyclohexanedimethanol ester, polyethylene-1, 2-diphenoxyethane-4, 4' -dicarboxylate, polybutylene terephthalate, etc.), polyolefin resins (polyethylene, polypropylene, polymethylpentene, etc.), polysulfone resins, polyethersulfone resins, polyarylate resins, polyetherimide resins, polymethyl methacrylate resins, polyetherketone resins, polystyrene resins, polyether ketone resins, and the like, Polyvinyl chloride resin, polyvinyl alcohol resin, ethylene vinyl alcohol resin, (meth) acrylic acid resin, (meth) acrylonitrile resin, and the like. The substrate 5 may be a single resin film layer, a laminate of a plurality of resin films, or a laminate of a resin film and a hard coat layer described later. The substrate 5 may comprise additives. Specific examples of the additives include antistatic agents, ultraviolet absorbers, plasticizers, lubricants, colorants, antioxidants, flame retardants, and the like.
In a preferred embodiment of the present invention, the substrate 5 is a cellulose Triacetate (TAC) film. The cellulose triacetate film can also function as a protective film for the polarizer. Therefore, by using the antireflection film 11 having the substrate 5 formed of a cellulose triacetate film, the transparent protective film provided on the visible side of the polarizing film 20 may be omitted.
In another preferred embodiment of the present invention, the substrate 5 comprises a hard coating. The substrate 5 may be composed of a hard coat layer, or may be a laminate of a resin film and a hard coat layer. The hard coat layer is a cured layer of, for example, an ionizing radiation-curable resin. Examples of the ionizing radiation include: ultraviolet rays, visible light, infrared rays, and electron beams, and preferably ultraviolet rays. That is, the ionizing radiation-curable resin is preferably an ultraviolet-curable resin. Examples of the ultraviolet curable resin include: (meth) acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, epoxy resins, and the like. Examples of the (meth) acrylic resin include: a cured product (polymer) obtained by curing a (meth) acryloyloxy group-containing polyfunctional monomer with ultraviolet rays. The polyfunctional monomer may be used, for example, in 1 kind or in combination of 2 or more kinds. The polyfunctional monomer may be used, for example, in combination with a photopolymerization initiator.
Inorganic particles or organic particles may be dispersed in the hard coat layer. The average particle diameter (d50) of the fine particles is, for example, 0.01 to 3 μm. The fine particles dispersed in the hard coat layer are preferably silicon oxide (SiO) from the viewpoints of refractive index, stability, heat resistance, and the like2). The hard coating may contain additives. Specific examples of the additives include leveling agents, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antioxidants, and thixotropic agents. In addition, a concave-convex shape may be formed on the surface of the hard coat layer. The hard coat layer having a concavo-convex shape on the surface has a light diffusing function (antiglare).
The physical film thickness of the substrate 5 is not particularly limited. When the substrate 5 is a single resin film layer or a laminate of a plurality of resin films, the physical film thickness of the substrate 5 is, for example, in the range of 10 to 200 μm. When the substrate 5 includes the hard coat layer, the physical film thickness of the hard coat layer is, for example, in the range of 1 μm to 50 μm.
The refractive index of the substrate 5 (in the case where the substrate 5 has a laminated structure, the refractive index of the layer closest to the 1 st high refractive index layer 1) is, for example, 1.3 to 1.8, preferably 1.4 to 1.7.
The adhesive layer 6 is a layer containing an adhesive. Examples of the binder contained in the binder layer 6 include a resin having adhesiveness. Examples of such resins include: acrylic resins, acrylic urethane resins, silicone resins, and the like. The adhesive layer 6 preferably contains an acrylic adhesive composed of an acrylic resin.
Additives may be further contained in the adhesive layer 6 as necessary. Examples of the additives include: crosslinking agent, tackifier, plasticizer, pigment, dye, filler, antiaging agent, conductive material, and ultraviolet rayExternal line absorbent, light stabilizer, peeling regulator, softening agent, surfactant, flame retardant, antioxidant, etc. Examples of the crosslinking agent include: isocyanate crosslinking agents, epoxy crosslinking agents, peroxide crosslinking agents, melamine crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents, urea crosslinking agents, melamine crosslinking agents, urea crosslinking agents, melamine crosslinking agents, urea crosslinking agents, melamine crosslinking agents, urea crosslinking agents, melamine crosslinking agents, urea crosslinking agents, and the like,Oxazoline crosslinking agents, aziridine crosslinking agents, amine crosslinking agents, and the like.
The physical film thickness of the pressure-sensitive adhesive layer 6 is, for example, 5 to 100 μm, preferably 10 to 50 μm.
The antireflection film 11 may further include members other than the substrate 5 and the pressure-sensitive adhesive layer 6. The antireflection film 11 may further include, for example, an antiglare layer disposed between the substrate 5 and the 1 st high refractive index layer 1. The antireflection film 11 may further include an adhesion layer disposed between specific members (for example, between the substrate 5 and the 1 st high refractive index layer 1, or between the antiglare layer and the 1 st high refractive index layer 1). The adhesion layer is a layer for improving adhesion between members, and contains, for example, silicon or SiO x(x < 2). The physical film thickness of the adhesion layer is, for example, 1nm to 10nm, preferably 2nm to 5 nm. The refractive index of the adhesion layer is, for example, 1 to 2.5.
The antireflection films 10 and 11 may further include an antifouling layer disposed on the viewing side of the 2 nd low refractive index layer 4 and in contact with the 2 nd low refractive index layer 4. The antifouling layer is a layer having an antifouling effect and contains at least one selected from a fluorine-based resin and a silicone-based resin, for example. The antifouling layer has a physical film thickness of, for example, 5nm to 13nm, preferably 5nm to 10 nm. The refractive index of the antifouling layer is, for example, 1 to 2.
The reflection light generated when the anti-reflection films 10 and 11 are incident from the CIE standard light source D65 is preferably L*a*b*A in color system1 *Value and b1 *The absolute value of the value is small. a is a1 *The value is, for example, -6 or more and 6 or less, more preferably-3 or more and 3 or less. b is a mixture of1 *The value is, for example, from-15 to 3, preferably from-10 to 2, more preferably from-5 to 2. a is1 *Value and b1 *The values may be specified by the following method. First, the 1 st high refractive index layer 1, the 1 st low refractive index layer 2, the 2 nd high refractive index layer 3, and the 2 nd low refractive index layer 4 of the antireflection film 10 are sequentially laminated on the black film, or the antireflection film 11 is attached to the black film through the adhesive layer 6 of the antireflection film 11. Next, light from CIE standard light source D65 was incident on the surface of antireflection film 10 or 11 on the 2 nd low refractive index layer side at an incident angle of 5 °. The spectral reflectance in the range of 360nm to 740nm is specified for the specular reflection light generated at this time, and the tristimulus values in the XYZ color system are specified based on the spectral reflectance. Using the obtained tristimulus values, specifying a by the above formulae (i) and (ii) 1 *Value and b1 *The value is obtained.
The light reflectance Y of the reflected light1For example, 0.3% or less, preferably 0.2% or less.
[ polarizing film ]
The polarizing film 20 is a laminate including a polarizer and a transparent protective film. The transparent protective film is disposed in contact with, for example, a main surface (surface having the largest area) of the layered polarizer. The polarizer may be disposed between the two transparent protective films. Examples of the polarizer include, but are not particularly limited to, polarizers obtained by uniaxially stretching a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene-vinyl acetate copolymer partially saponified film, to which a dichroic material such as iodine or a dichroic dye is adsorbed; and polyene-based oriented films such as dehydrated polyvinyl alcohol and desalted polyvinyl chloride. The polarizer is preferably formed of a dichroic material such as a polyvinyl alcohol film or iodine.
The thickness of the polarizer is not particularly limited, and is, for example, 80 μm or less. The thickness of the polarizer may be 10 μm or less, preferably 1 to 7 μm. Such a thin polarizer has a small variation in thickness and is excellent in visibility. The size change of the thin polarizer is suppressed, and the durability is excellent. The polarizing film 20 can be thinned by using a thin polarizer.
As the material of the transparent protective film, for example: a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy and the like. Specific examples of such thermoplastic resins include cellulose resins such as cellulose triacetate, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, cyclic polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. The material of the transparent protective film may be a thermosetting resin or an ultraviolet-curable resin such as (meth) acrylic, urethane, acrylic urethane, epoxy, silicone, or the like. In the case where the polarizing film 20 has two transparent protective films, the materials of the two transparent protective films may be the same or different. For example, a transparent protective film made of a thermoplastic resin may be bonded to one main surface of the polarizer by an adhesive, and a transparent protective film made of a thermosetting resin or an ultraviolet curable resin may be bonded to the other main surface of the polarizer. The transparent protective film may contain 1 or more kinds of any additives.
The transparent protective film may have optical characteristics such as an antiglare characteristic and an antireflection characteristic. The transparent protective film may be a film that functions as a retardation film. In the present specification, a retardation film refers to a film having birefringence in the in-plane direction or the thickness direction. Examples of the film functioning as a retardation film include: a film obtained by stretching a polymer film, a film obtained by orienting and fixing a liquid crystal material, and the like.
The adhesive used for bonding the polarizer and the transparent protective film is not particularly limited as long as it is optically transparent, and examples thereof include: water-based, solvent-based, hot-melt, radical-curable, cation-curable, and the like adhesives, and water-based adhesives and radical-curable adhesives are preferred.
The thickness of the polarizing film 20 is, for example, 10 μm to 500 μm. The total light transmittance of the polarizing film 20 is not particularly limited, and is, for example, 30% to 50%. In the present specification, the term "total light transmittance" refers to the transmittance of light having a wavelength in the range of 380nm to 700 nm. The total light transmittance can be measured according to the provisions of JIS K7361-1: 1997. The total light transmittance was measured using CIE standard illuminant D65.
The transmitted light when the polarized film 20 receives light from the CIE standard light source D65 has an a value of preferably-6.0 to 0, more preferably-3.0 to-0.5, and particularly preferably-1.8 to-1.2 in the Hunter Lab color system. The b value of the transmitted light in the Hunter Lab color system is preferably 1.0 to 10, more preferably 1.5 to 5.0, and particularly preferably 2.2 to 4.0. The a-value and b-value of the transmitted light in the hunterlab color system can be specified by the following method. First, the transmittance of light from CIE standard illuminant D65 in the polarizing film 20 was measured using an integrating sphere of a spectrophotometer. The obtained transmittance was subjected to visibility correction (interval of 780-380 nm: 5 nm) by a 2-degree visual field XYZ system defined in JIS Z8701:1999, and the a value and the b value of the transmitted light in the Hunter Lab color system were specified.
[ conductive layer of polarizing film with antireflection film ]
The conductive layer 40 is a layer containing a conductive material. The conductive material may be a material other than ITO, for example, a conductive polymer, a composite of a conductive polymer and a dopant, an ionic surfactant, conductive fine particles, an ionic compound, or the like. From the viewpoint of transparency, total light transmittance, appearance, antistatic effect, and stability of antistatic effect in a high-temperature or high-humidity environment, the conductive layer 40 preferably contains a conductive polymer. In the case where the conductive layer 40 contains a conductive polymer as a conductive material, fogging is less likely to occur even if the thickness of the conductive layer 40 is relatively largely adjusted as compared with the case where conductive fine particles are contained. Therefore, even when the conductive layer 40 is disposed between the liquid crystal cell 25 and the polarizer, the conductive layer 40 including a conductive polymer is less likely to cause polarized light extinction, and the contrast of an image displayed by the liquid crystal display device is less likely to be lowered. When the conductive layer 40 contains a conductive polymer as a conductive material, the refractive index of the conductive layer 40 tends to be lower than that in the case where the conductive fine particles are contained. Therefore, the conductive layer 40 including a conductive polymer is suitable for further reducing the reflectance of light of the liquid crystal panel 100.
Examples of the conductive polymer include: polythiophene, polyaniline, polypyrrole, polyquinoxaline, polyacetylene, polyphenylene ethylene, polynaphthalene and derivatives thereof. The conductive material may contain 1 or 2 or more of these conductive polymers. As the conductive polymer, polythiophene, polyaniline, and derivatives thereof are preferable, and polythiophene derivatives are particularly preferable. Polythiophene, polyaniline, and derivatives thereof function as a conductive polymer having water solubility or water dispersibility, for example. When the conductive polymer is water-soluble or water-dispersible, the conductive layer 40 can be formed using an aqueous solution or an aqueous dispersion of the conductive polymer. In this case, since the conductive layer 40 does not need to be formed using a nonaqueous organic solvent, alteration of the polarizing film 20 or the like by the organic solvent can be suppressed.
The conductive polymer may have a hydrophilic functional group. Examples of the hydrophilic functional group include: sulfo groups, amino groups, amide groups, imine groups, hydroxyl groups, mercapto groups, hydrazine groups, carboxyl groups, sulfate groups, phosphate groups, and salts thereof (e.g., quaternary ammonium salt groups). When the conductive polymer has a hydrophilic functional group, the conductive polymer tends to be easily dissolved in water, or the conductive polymer in a fine particle form tends to be easily dispersed in water.
From the viewpoint of conductivity and chemical stability, the conductive polymer is preferably poly (3, 4-disubstituted thiophene). Examples of the poly (3, 4-disubstituted thiophene) include poly (3, 4-alkylenedioxythiophene) and poly (3, 4-dialkoxythiophene), and poly (3, 4-alkylenedioxythiophene) is preferable. The poly (3, 4-alkylenedioxythiophene) has, for example, a structural unit represented by the following formula (I).
[ chemical formula 1]
In the formula (I), R1For example, 1 to 4 carbon atomsAn alkylene group. The alkylene group may be linear or branched. Examples of the alkylene group include: methylene, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1-methyl-1, 2-ethylene, 1-ethyl-1, 2-ethylene, 1-methyl-1, 3-propylene and 2-methyl-1, 3-propylene, preferably methylene, 1, 2-ethylene, 1, 3-propylene, more preferably 1, 2-ethylene. The conductive polymer is preferably poly (3, 4-methylenedioxythiophene) (PEDOT).
Examples of the dopant include polyanions. In the case where the conductive polymer is polythiophene (or a derivative thereof), the polyanion may form an ion pair with the polythiophene (or a derivative thereof) to stably disperse the polythiophene (or a derivative thereof) in water. The polyanion is not particularly limited, and examples thereof include: carboxylic acid polymers such as polyacrylic acid, polymaleic acid, and polymethacrylic acid; sulfonic acid polymers such as polystyrenesulfonic acid, polyvinylsulfonic acid and polyisoprenesulfonic acid. The polyanion may be a copolymer of a vinylcarboxylic acid or a vinylsulfonic acid with another monomer. Examples of the other monomers include: (meth) acrylate compounds; aromatic vinyl compounds such as styrene and vinylnaphthalene. The polyanion is particularly preferably polystyrene sulfonic acid (PSS). Examples of the composite of the conductive polymer and the dopant include: a complex of poly (3, 4-methylenedioxythiophene) and polystyrene sulfonic acid (PEDOT/PSS).
Examples of the ionic surfactant include: quaternary ammonium salt type,Cationic surfactants such as salt type and sulfonium salt type; anionic surfactants such as carboxylic acid type, sulfonic acid ester type, sulfuric acid ester type, phosphoric acid ester type, and phosphorous acid ester type; sulfobetaine type, alkylbetaine type, alkylimidazoleA betaine-type isozwitterionic surfactant; polyol derivatives, beta-cyclodextrin inclusion compounds, sorbitan fatty acid monoesters, and sorbitan fatty acid monoestersNonionic surfactants such as fatty acid diesters, polyoxyalkylene derivatives, and amine oxides.
Examples of the conductive fine particles include: metal oxide fine particles such as tin oxide, antimony oxide, indium oxide, and zinc oxide, and tin oxide fine particles are preferable. Examples of the material of the tin oxide-based fine particles include: tin oxide, antimony-doped tin oxide, indium-doped tin oxide, aluminum-doped tin oxide, tungsten-doped tin oxide, a titanium oxide-cerium oxide-tin oxide composite, a titanium oxide-tin oxide composite, and the like. The conductive fine particles have an average particle diameter of, for example, 1 to 100nm, preferably 2 to 50 nm. The average particle diameter of the conductive fine particles is, for example, a particle diameter corresponding to 50% of the volume accumulation in the particle size distribution measured by a laser diffraction particle sizer or the like (d 50).
Examples of the ionic compound include: alkali metal salts and/or organic cation-anion salts. Examples of the alkali metal salt include: organic and inorganic salts of alkali metals. In the present specification, the organic cation-anion salt means an organic salt containing an organic cation. The anion contained in the organic cation-anion salt may be an organic anion or an inorganic anion. Organic cation-anion salts are sometimes referred to as ionic liquids or ionic solids.
Examples of the alkali metal ion contained in the alkali metal salt include: lithium ion, sodium ion and potassium ion, and lithium ion is preferable.
Examples of the anion contained in the organic salt of an alkali metal include: CH (CH)3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)3C-、C4F9SO3 -、C3F7COO-、(CF3SO2)(CF3CO)N-、-O3S(CF2)3SO3 -、(CN)2N-And anions represented by the following general formulae (a) to (d).
(a)(CnF2n+1SO2)2N-(wherein n is an integer of 1 to 10)
(b)CF2(CmF2mSO2)2N-(wherein m is an integer of 1 to 10)
(c)-O3S(CF2)lSO3 -(wherein l is an integer of 1 to 10)
(d)(CpF2p+1SO2)N-(CqF2q+1SO2) (wherein p and q are each independently an integer of 1 to 10.)
The anion contained in the organic salt of an alkali metal preferably contains a fluorine atom. The organic salt of an alkali metal functions as an ionic compound having excellent ionic dissociation properties by the anion containing a fluorine atom.
Examples of the anion contained in the inorganic salt of an alkali metal include: cl -、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、AsF6 -、SbF6 -、NbF6 -、TaF6 -、(FSO2)2N-、CO3 2-And so on.
As the anion contained in the alkali metal salt, (CF) is preferred3SO2)2N-、(C2F5SO2)2N-The (perfluoroalkylsulfonyl) imide represented by the above general formula (a) is particularly preferably (CF)3SO2)2N-Bis (trifluoromethanesulfonyl) imide as shown.
Examples of the organic salt of an alkali metal include: sodium acetate, sodium alginate, sodium lignosulfonate, sodium toluenesulfonate, LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2N、Li(CF3SO2)3C、KO3S(CF2)3SO3K、LiO3S(CF2)3SO3K, etc., preferably LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2N、Li(CF3SO2)3C, more preferably Li (CF)3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2And N is added. The organic salt of an alkali metal is preferably a fluorine-containing imide lithium salt, and particularly preferably a (perfluoroalkyl sulfonyl) imide lithium salt.
Examples of the inorganic salt of an alkali metal include: lithium perchlorate and lithium iodide.
Examples of the organic cation contained in the organic cation-anion salt include: pyridine compoundCation, piperidineCation, pyrrolidineCation, cation having pyrroline skeleton, imidazoleCationic, tetrahydropyrimidinesCationic dihydropyrimidinesCationic, pyrazolesCationic pyrazolinesCation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkylCations, and the like.
Examples of the anion contained in the organic cation-anion salt include: cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、(CN)2N-、C4F9SO3 -、C3F7COO-、(CF3SO2)(CF3CO)N-、(FSO2)2N-、-O3S(CF2)3SO3 -And anions represented by the above general formulae (a) to (d). The anion contained in the organic cation-anion salt preferably contains a fluorine atom. The organic cation-anion salt functions as an ionic compound having excellent ionic dissociation properties by the anion containing a fluorine atom.
The ionic compound is not limited to the alkali metal salt and the organic cation-anion salt, and examples thereof include: inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate. The conductive material may contain 1 or 2 or more of the above ionic compounds.
The conductive material is not limited to the above-mentioned materials, and examples thereof include: carbon materials such as acetylene black, ketjen black, natural graphite, and artificial graphite; titanium black; a cationic conductive group such as a quaternary ammonium salt, a zwitterionic conductive group such as a betaine compound, an anionic conductive group such as a sulfonate, a homopolymer of a monomer having a nonionic conductive group such as glycerin, or a copolymer of the monomer and another monomer (for example, a polymer having ionic conductivity such as a polymer having a structural unit derived from an acrylate or methacrylate having a quaternary ammonium salt group); a material (permanent antistatic agent) obtained by alloying a hydrophilic polymer such as a copolymer of ethylene and a methacrylic acid ester with an acrylic resin or the like.
The conductive layer 40 may include other materials such as an adhesive in addition to the conductive material. The adhesive tends to improve the film formability of the conductive material and to improve the adhesion and adhesiveness (anchoring force) of the conductive layer 40 to the polarizing film 20. Examples of the binder include: comprises Oxazoline-based polymers, polyurethane-based resins, polyester-based resins, acrylic-based resins, polyether-based resins, cellulose-based resins, polyvinyl alcohol-based resins, epoxy resins, polyvinyl pyrrolidone, polystyrene-based resins, polyethylene glycol, pentaerythritol and the like, preferably containingOxazoline-based polymers, polyurethane resins, polyester resins, and acrylic resins, and particularly polyurethane resins are preferable. The conductive layer 40 may contain 1 or 2 or more of these binders. The content of the binder in the conductive layer 40 is, for example, 1 wt% to 90 wt%, preferably 10 wt% to 80 wt%.
The thickness of the conductive layer 40 is, for example, 5nm to 180nm, preferably 150nm, more preferably 120nm or less, further preferably 100nm or less, particularly preferably 80nm or less, and particularly preferably 50nm or less. The thickness of the conductive layer 40 may be 10nm or more, or 20nm or more.
In the polarizing film 15 with an antireflection film, the loss a of the total light transmittance due to the conductive layer 40 is, for example, 0.9% or less, preferably 0.8% or less, more preferably 0.6% or less, further preferably 0.5% or less, particularly preferably 0.4% or less, and particularly preferably less than 0.2%. The lower limit of the loss A is not particularly limited, but is, for example, 0.01%. The loss a can be specified by the following method. First, the total light transmittance T1 of the polarizing film 20 and the total light transmittance T2 of the laminate L including the polarizing film 20 and the conductive layer 40 were measured. The total light transmittance T2 of the laminate L is a value when light is incident from the polarizing film 20 side. The difference between the total light transmittance T1 and the total light transmittance T2 (T1 to T2) can be specified as loss a.
In the polarizing film with an antireflection film 15, in the case where the above loss a is more than 0.5%, the surface resistivity of the conductive layer 40 may be a particularly low value. For example, in the polarizing film 15 with an antireflection film, at least one of the following (i) and (ii) may be satisfied: (i) the loss A is 0.5% or less, and the surface resistivity of the conductive layer 40 is 1.0X 106Omega/□ or less; and (ii) the loss A is 0.9% or less, and the surface resistivity of the conductive layer 40 is 1.0X 104Omega/□ or less.
The anchoring force between the conductive layer 40 and the polarizing film 20 is, for example, 10.0N/25mm or more, preferably 12.0N/25mm or more, more preferably 14.0N/25mm or more, and still more preferably 18.0N/25mm or more. The anchoring force can be measured by the following method. First, the polarizing film 15 with an antireflection film to be evaluated was cut out to have a width of 25mm × a length of 150mm to prepare a test piece. Next, the entire surface of the antireflection film 10 included in the test piece was superimposed on a test plate made of stainless steel using a double-sided tape, and a 2kg roller was reciprocated 1 time to press-bond them. Next, the pressure-sensitive adhesive layer 30 included in the test piece was superposed on the evaluation sheet, and a 2kg roller was reciprocated 1 time to press-bond them. The evaluation sheet is not particularly limited as long as it has a size of 30mm in width × 150mm in length and is not peeled from the pressure-sensitive adhesive layer 30 in the test. For example, an ITO film (125Tetlight OES (manufactured by Touchi industries, Ltd.)) can be used as the evaluation sheet. Next, the pressure-sensitive adhesive layer 30 and the conductive layer 40 were peeled from the polarizing film 20 at a peel angle of 180 ° and a tensile speed of 300mm/min while holding the evaluation sheet using a commercially available tensile testing machine, and the average value of the peel forces at this time was specified as the anchoring force between the conductive layer 40 and the polarizing film 20. The above test was carried out in an atmosphere of 23 ℃.
[ adhesive layer ]
The adhesive layer 30 is a layer containing an adhesive. Examples of the binder contained in the binder layer 30 include: rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl pyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, and the like. The pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 30 is preferably an acrylic pressure-sensitive adhesive in view of excellent optical transparency, having suitable adhesive properties such as wettability, cohesiveness and adhesiveness, and being excellent in weather resistance and heat resistance.
The acrylic adhesive contains a (meth) acrylic polymer as a base polymer. The (meth) acrylic polymer contains, for example, a structural unit derived from a (meth) acrylate ester as a main component. In the present specification, "(meth) acrylic acid" means acrylic acid and/or methacrylic acid. "principal component" means the structural unit present in the polymer in the greatest amount on a weight basis.
The number of carbon atoms of an ester moiety (a moiety other than a (meth) acryloyl group) contained in a (meth) acrylate for forming the main skeleton of the (meth) acrylic polymer is not particularly limited, and is, for example, 1 to 18. The ester moiety of the (meth) acrylate may contain an aromatic ring such as a phenyl group or a phenoxy group, or may contain an alkyl group. The alkyl group may be linear or branched. The (meth) acrylic polymer may contain 1 or 2 or more kinds of structural units derived from (meth) acrylic acid esters. In the (meth) acrylic polymer, the average number of carbon atoms of an ester moiety contained in a structural unit derived from a (meth) acrylate ester is preferably 3 to 9. From the viewpoints of adhesion properties, durability, adjustment of retardation, adjustment of refractive index, and the like, the (meth) acrylic polymer preferably has a structural unit derived from a (meth) acrylate containing an aromatic ring. By adjusting the phase difference of the pressure-sensitive adhesive layer 30 with the (meth) acrylate containing an aromatic ring, light leakage of the liquid crystal display device caused by stretching of the pressure-sensitive adhesive layer 30 due to thermal shrinkage of the polarizing film 20 can be suppressed. In addition, the (meth) acrylate is suitable for adjusting the refractive index of the adhesive layer 30 to reduce the difference in refractive index between the adhesive layer 30 and the adherend (liquid crystal cell). If the difference in refractive index is small, reflection of light at the interface between the adhesive layer 30 and the adherend is suppressed, and visibility of the display can be improved.
Examples of the aromatic ring-containing (meth) acrylate include: (meth) acrylates containing a benzene ring such as benzyl (meth) acrylate, phenyl (meth) acrylate, o-phenylphenol (meth) acrylate, phenoxy ester (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, ethylene oxide-modified cresol (meth) acrylate, phenol ethylene oxide-modified (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, methylphenyl (meth) acrylate, and styrene (meth) acrylate; (meth) acrylates containing a naphthalene ring such as hydroxyethylated β -naphthol acrylate, 2-naphthylethyl (meth) acrylate, 2-naphthyloxyethyl acrylate, and 2- (4-methoxy-1-naphthyloxy) ethyl (meth) acrylate; biphenyl ring-containing (meth) acrylates such as biphenyl (meth) acrylates, and the like. Among these, benzyl (meth) acrylate and phenoxyethyl (meth) acrylate are preferable from the viewpoint of improving the adhesive properties and durability of the adhesive layer 30.
When the refractive index of the pressure-sensitive adhesive layer 30 is adjusted by the aromatic ring-containing (meth) acrylate, the content of the structural unit derived from the aromatic ring-containing (meth) acrylate in all the constituent units of the (meth) acrylic polymer is preferably 3 to 25% by weight. The content is more preferably 22% by weight or less, and still more preferably 20% by weight or less. The content is more preferably 8% by weight or more, and still more preferably 12% by weight or more. When the content of the structural unit derived from the aromatic ring-containing (meth) acrylate is 25 wt% or less, light leakage of the liquid crystal display device due to shrinkage of the polarizing film 20 can be suppressed, and the reworkability of the pressure-sensitive adhesive layer 30 tends to be improved. When the content is 3 wt% or more, light leakage of the liquid crystal display device tends to be sufficiently suppressed.
From the viewpoint of improving adhesiveness and heat resistance, the (meth) acrylic polymer may have 1 or more kinds of structural units derived from a comonomer having an unsaturated double bond-containing polymerizable functional group such as a (meth) acryloyl group and a vinyl group, in addition to the structural units derived from the aromatic ring-containing (meth) acrylate. Examples of such comonomers include: hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl acrylate; carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; sulfonic acid group-containing monomers such as styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, (meth) acrylic acid propyl sulfonate, and (meth) acryloyloxynaphthalenesulfonic acid; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate, and the like.
As the above-mentioned comonomers, there may be mentioned, for example: (N-substituted) amide monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide and N-methylol propane (meth) acrylamide; alkylaminoalkyl (meth) acrylate monomers such as aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; alkoxyalkyl (meth) acrylate monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; succinimide monomers such as N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxohexamethylene succinimide, and N- (meth) acryloyl-8-oxooctamethylene succinimide; morpholine monomers such as N-acryloyl morpholine; maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide and N-phenylmaleimide; n-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexyl itaconimide, N-cyclohexylitaconimide, N-lauryl itaconimide, etc.
Examples of the above-mentioned comonomers include: vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinylVinyl monomers such as oxazole, vinyl morpholine, N-vinylcarboxylic acid amides, styrene, alpha-methylstyrene, and N-vinylcaprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; glycol acrylate monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate; acrylic ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine-containing (meth) acrylate, silicone (meth) acrylate, and 2-methoxyethyl acrylate. Further, as the comonomer, for example: olefin monomers such as isoprene, butadiene, and isobutylene; vinyl ethers and the like.
Examples of the above-mentioned comonomers include: silane monomers such as 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-acryloxydecyltrimethoxysilane, 10-methacryloxydecyltriethoxysilane, and 10-acryloxydecyltriethoxysilane.
As the above-mentioned comonomers, for example: esterified products of (meth) acrylic acid and polyhydric alcohols (polyfunctional monomers having 2 or more unsaturated double bonds such as (meth) acryloyl groups and vinyl groups) such as tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol a diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate; and compounds obtained by adding 2 or more compounds having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group to a backbone such as polyester, epoxy, urethane, and the like (for example, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate), and the like.
The content of the structural unit derived from the comonomer in the (meth) acrylic polymer is not particularly limited, and is, for example, 0 to 20 wt%, preferably 0.1 to 15 wt%, and more preferably 0.1 to 10 wt%.
As the comonomer, a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferable from the viewpoint of adhesiveness and durability. As the comonomer, a hydroxyl group-containing monomer and a carboxyl group-containing monomer may be used in combination. For example, in the case where the adhesive composition for forming the adhesive layer 30 contains a crosslinking agent, the comonomer functions as a reaction point with the crosslinking agent. Since the hydroxyl group-containing monomer, the carboxyl group-containing monomer, or the like has excellent reactivity with the intermolecular crosslinking agent, it is suitable for improving the cohesive property and heat resistance of the pressure-sensitive adhesive layer 30 to be obtained. In particular, the hydroxyl group-containing monomer is suitable for improving the reworkability of the adhesive layer 30. The carboxyl group-containing monomer is suitable for achieving both durability and reworkability of the adhesive layer 30.
When a hydroxyl group-containing monomer is used as a comonomer, the content of the structural unit derived from the hydroxyl group-containing monomer in the (meth) acrylic polymer is preferably 0.01 to 15 wt%, more preferably 0.03 to 10 wt%, and still more preferably 0.05 to 7 wt%. When a carboxyl group-containing monomer is used as a comonomer, the content of the structural unit derived from the carboxyl group-containing monomer in the (meth) acrylic polymer is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, and still more preferably 0.2 to 6% by weight.
The weight average molecular weight of the (meth) acrylic polymer is, for example, 50 to 300 ten thousand, and from the viewpoint of durability, particularly heat resistance, it is preferably 70 to 270 ten thousand, and more preferably 80 to 250 ten thousand. When the weight average molecular weight of the (meth) acrylic polymer is 50 ten thousand or more, the pressure-sensitive adhesive layer 30 tends to have heat resistance sufficient for practical use. When the weight average molecular weight of the (meth) acrylic polymer is 300 ten thousand or less, the viscosity of the coating liquid for producing the pressure-sensitive adhesive layer 30 tends to be easily adjusted. If the viscosity of the coating liquid can be easily adjusted, it is not necessary to add a large amount of a diluting solvent to the coating liquid, and therefore, the production cost of the pressure-sensitive adhesive layer 30 can be suppressed. In the present specification, the weight average molecular weight refers to a value obtained by converting a measurement result by GPC (gel permeation chromatography) into polystyrene.
The (meth) acrylic polymer can be produced by a known polymerization reaction such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations. The (meth) acrylic polymer may be a random copolymer, a block copolymer, or a graft copolymer.
The adhesive contained in the adhesive layer 30 may have a structure in which the base polymer is crosslinked by a crosslinking agent. For example, in the case of using a (meth) acrylic polymer as a base polymer, an organic crosslinking agent or a polyfunctional metal chelate compound may be used as the crosslinking agent. Examples of the organic crosslinking agent include: isocyanate crosslinking agents, peroxide crosslinking agents, epoxy crosslinking agents, imine crosslinking agents, and the like. The polyfunctional metal chelate compound is a chelate compound in which a polyvalent metal is covalently bonded or coordinately bonded to an organic compound. Examples of the atom constituting the polyvalent metal include: al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, etc. The organic compound contained in the polyfunctional metal chelate compound contains, for example, an oxygen atom or the like. Examples of the organic compound include: alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, ketone compounds, and the like.
The amount of the crosslinking agent used in the adhesive is preferably 3 parts by weight or less, more preferably 0.01 to 3 parts by weight, still more preferably 0.02 to 2 parts by weight, and particularly preferably 0.03 to 1 part by weight, based on 100 parts by weight of the (meth) acrylic polymer.
The adhesive layer 30 may further contain other materials than adhesives. Examples of the other materials include: conductive materials, silane coupling agents, and other additives. The conductive material is suitable for reducing the surface resistivity of the adhesive layer 30 to prevent display defects caused by electrification of the liquid crystal display device. As the conductive material, the conductive material described above for the conductive layer 40 can be cited. The conductive material contained in the adhesive layer 30 is preferably an ionic compound from the viewpoint of compatibility with the base polymer and transparency of the adhesive layer 30. In particular, when the pressure-sensitive adhesive layer 30 contains an acrylic pressure-sensitive adhesive containing a (meth) acrylic polymer as a base polymer, an ionic compound is preferably used as the conductive material. From the viewpoint of antistatic properties, the ionic compound is preferably an ionic liquid.
The adhesive layer 30 preferably contains 0.05 to 20 parts by weight of a conductive material (e.g., an ionic compound) with respect to 100 parts by weight of a base polymer (e.g., a (meth) acrylic polymer) of the adhesive. When the pressure-sensitive adhesive layer 30 contains 0.05 parts by weight or more of the conductive material, the surface resistivity of the pressure-sensitive adhesive layer 30 tends to be sufficiently reduced, and the antistatic performance of the pressure-sensitive adhesive layer 30 tends to be sufficiently improved. The adhesive layer 30 preferably contains the conductive material in an amount of 0.1 part by weight or more, more preferably 0.5 part by weight or more, based on 100 parts by weight of the base polymer of the adhesive. From the viewpoint of imparting sufficient durability to the adhesive layer 30 for practical use, the adhesive layer 30 preferably contains 20 parts by weight or less, more preferably 10 parts by weight or less, of the conductive material with respect to 100 parts by weight of the base polymer of the adhesive.
Examples of the other additives include polyether compounds such as polyalkylene glycols (for example, polypropylene glycol), colorants, pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic fillers, organic fillers, and metal powders, which are used as appropriate depending on the intended use. The additive may be in the form of powder, particle or foil. The additive may be a redox system by using a reducing agent in a controllable range. By adding a coloring matter such as a colorant to the pressure-sensitive adhesive layer 30, the hue of the reflected light from the liquid crystal panel 100 can be adjusted in some cases. The adhesive layer 30 preferably contains 5 parts by weight or less, more preferably 3 parts by weight or less, and still more preferably 1 part by weight or less of other additives, relative to 100 parts by weight of a base polymer (for example, a (meth) acrylic polymer) of the adhesive.
The thickness of the adhesive layer 30 is not particularly limited, and is, for example, 5 to 100 μm, preferably 10 to 50 μm.
In the polarizing film 15 with an antireflection film, the surface resistivity of the pressure-sensitive adhesive layer 30 is not particularly limited, and is less than 1.0 × 10 14Omega/□, preferably 1.0X 1012Omega/□ or less. The lower limit of the surface resistivity of the pressure-sensitive adhesive layer 30 is not particularly limited, and is, for example, 1.0 × 10 from the viewpoint of durability8Omega/□. The surface resistivity of the adhesive layer 30 can be measured by the following method. First, a laminate in which the surface of the pressure-sensitive adhesive layer 30 is exposed to the outside is prepared. Examples of such a laminate include: a laminate having a pressure-sensitive adhesive layer 30 disposed on a separator such as a polyethylene terephthalate film.Next, the surface resistivity of the surface of the adhesive layer 30 in the prepared laminate was measured. The surface resistivity can be measured by using Hiresta-UP MCP-HT450 (manufactured by Mitsubishi Chemical Analyticech Co., Ltd.) according to the method prescribed in JIS K6911: 1995. The measurement value obtained by this measurement can be regarded as the surface resistivity of the adhesive layer 30.
[ other layers ]
The antireflection film-equipped polarizing film 15 may further include other layers than the antireflection film 10, the polarizing film 20, the conductive layer 40, and the adhesive layer 30. The polarizing film 15 with an antireflection film may contain 1 layer or 2 or more other layers. The other layer is disposed on the visible side of the antireflection film 10 and is in contact with the antireflection film 10, for example. Examples of the other layers include: a surface protective film and a retardation film.
The surface protection film includes, for example, a support film and an adhesive layer disposed on at least one surface of the support film. The adhesive layer of the surface protective film may contain a light release agent, a conductive material, and the like. In the case where the adhesive layer of the surface protective film contains a conductive material, the surface protective film may be attached to the antireflection film 10, and then the surface protective film may be peeled off to contain the conductive material in the antireflection film 10, thereby imparting a conductive function to the surface. As the conductive material, the conductive material described above with respect to the conductive layer 40 can be cited. In order to impart a conductive function to the surface of the antireflection film 10 by peeling off the surface protection film, the pressure-sensitive adhesive layer of the surface protection film preferably contains a light peeling agent in addition to the conductive material. Examples of the light release agent include: silicone resins such as polyorganosiloxane. The conductive function imparted to the surface of the antireflection film 10 can be appropriately adjusted by the amounts of the conductive material and the light release agent used.
The other layer may include an easy adhesion layer for improving adhesion between members. When the other layer is an easy-adhesion layer, the easy-adhesion layer may be disposed on the surface of the polarizing film 20. Instead of the easy-adhesion layer, the surface of the polarizing film 20 may be subjected to an easy-adhesion treatment such as corona treatment or plasma treatment.
[ method for producing polarizing film with antireflection film ]
The polarizing film 15 with an antireflection film having the conductive layer 40 can be produced, for example, by the following method. First, a solution or dispersion of the conductive material is prepared. The solvent of the solution or dispersion is, for example, water, and may further contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include: alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, sec-pentanol, tert-pentanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, and cyclohexanol.
Next, the solution or dispersion of the conductive material is applied to the surface of the polarizing film 20. The conductive layer 40 is formed on the polarizing film 20 by drying the obtained coating film. This provides a laminate L including the polarizing film 20 and the conductive layer 40.
Next, an antireflection film 10 (or 11) was disposed on the polarizing film 20 of the laminate L to produce a laminate L1. Next, a solution containing a binder was prepared. The solution is applied to the surface of a separator to obtain a coating film. The separator is not particularly limited, and for example, a polyethylene terephthalate film treated with a silicone-based release agent can be used. Next, the adhesive layer 30 is formed on the separator by drying the coating film. The obtained adhesive layer 30 was transferred to the conductive layer 40 of the laminate L1, whereby the polarizing film 15 with an antireflection film was produced.
[ liquid Crystal cell ]
The liquid crystal cell 25 includes, for example, a liquid crystal layer 50, a 1 st transparent substrate 60, and a 2 nd transparent substrate 70. The liquid crystal layer 50 is disposed between the 1 st transparent substrate 60 and the 2 nd transparent substrate 70, for example, and is in contact with the 1 st transparent substrate 60 and the 2 nd transparent substrate 70, respectively. The adhesive layer 30 of the antireflection film-equipped polarizing film 15 is, for example, in contact with the 1 st transparent substrate 60 of the liquid crystal cell 25. The liquid crystal panel 100 does not have an ITO layer between the adhesive layer 30 and the 1 st transparent substrate 60, for example.
The liquid crystal layer 50 includes liquid crystal molecules aligned uniformly in the absence of an electric field, for example. The liquid crystal layer 50 including such liquid crystal molecules is suitable for an IPS (In-Plane-Switching) mode. However, the liquid crystal layer 50 may also be used for a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, a pi type, a VA (Vertical Alignment) type, or the like. The thickness of the liquid crystal layer 50 is, for example, 1.5 μm to 4 μm.
Examples of the material of the 1 st transparent substrate 60 and the 2 nd transparent substrate 70 include: glass and polymers. In this specification, a transparent substrate made of a polymer is sometimes referred to as a polymer film. Examples of the polymer constituting the transparent substrate include: polyethylene terephthalate, polycycloolefins, polycarbonates, and the like. The thickness of the transparent substrate made of glass is, for example, 0.1mm to 1 mm. The thickness of the transparent substrate made of a polymer is, for example, 10 to 200 μm.
The liquid crystal cell 25 may further include other layers than the liquid crystal layer 50, the 1 st transparent substrate 60, and the 2 nd transparent substrate 70. Examples of the other layers include: color filter, easy-to-adhere layer and hard coating layer. The color filter is disposed, for example, on the visible side of the liquid crystal layer 50, preferably between the 1 st transparent substrate 60 and the adhesive layer 30 of the antireflection film-attached polarizing film 15. The easy-adhesion layer and the hard coat layer are disposed on the surface of the 1 st transparent substrate 60 or the 2 nd transparent substrate 70, for example.
[ other Components ]
The liquid crystal panel 100 may further include a polarizing film 15 with an antireflection film and other members than the liquid crystal cell 25. For example, the liquid crystal panel 100 may be further electrically connected to a conductive structure (not shown) on the side of the polarization film 15 with an antireflection film. If the conductive structure is grounded, it is easy to prevent the polarizing film 15 with the antireflection film from being electrostatically charged. The conductive structure may cover the entire side surface of the antireflection film-equipped polarizing film 15, or may partially cover the side surface of the antireflection film-equipped polarizing film 15. The ratio of the area of the side surface of the antireflection film-equipped polarizing film 15 covered with the conductive structure to the area of the entire side surface of the antireflection film-equipped polarizing film 15 is, for example, 1% or more, preferably 3% or more.
Examples of the material of the conductive structure include: conductive paste made of metal such as silver and gold; a conductive adhesive; other conductive materials. The conducting structure may be a wiring extending from the side of the polarizing film 15 with the reflection preventing film.
The liquid crystal panel 100 may further include other optical films than the polarizing film 20. Examples of the other optical film include: polarizing films, reflection plates, reflection-transmission plates, phase difference films, viewing angle compensation films, brightness enhancement films, and the like are used for films of liquid crystal display devices. The retardation film includes, for example, 1/2 wave plates, 1/4 wave plates, and the like. The liquid crystal panel 100 may further include 1 or 2 or more kinds of other optical films.
In the case where the other optical film is a polarizing film, the polarizing film is attached to the 2 nd transparent substrate 70 of the liquid crystal cell 25 via an adhesive layer, for example. The polarizing film has, for example, the constitution described above for the polarizing film 20. In the polarizing film as another optical film, the transmission axis (or absorption axis) of the polarizer is orthogonal to, for example, the transmission axis (or absorption axis) of the polarizer in the polarizing film 20. As a material of the adhesive layer for bonding the polarizing film and the 2 nd transparent substrate 70 together, the materials described above for the adhesive layer 30 can be used. The thickness of the adhesive layer is not particularly limited, but is, for example, 1 to 100. mu.m, preferably 2 to 50 μm, more preferably 2 to 40 μm, and still more preferably 5 to 35 μm.
According to the liquid crystal panel 100 of the present embodiment, the surface resistivity of the conductive layer 40 of the polarizing film 15 with the antireflection film is adjusted to 1.0 × 106Omega/□ or less, even in an environment where static electricity is likely to be generated, display failure due to electrification of the liquid crystal display device can be prevented. For example, the liquid crystal panel 100 exhibits a good result when an ESD (Electro-Static Discharge) test is performed. The ESD test is performed by the following method, for example. First, the liquid crystal panel 100 is set in a backlight device. Next, static electricity is applied to the visible side (the antireflection film 10 side) of the liquid crystal panel 100. The application of static electricity was performed using an Electrostatic discharge Gun (Electrostatic discharge Gun) adjusted to have an applied voltage of 10 kV. When static electricity is applied, white spots are generated in a part of the liquid crystal panel 100. The time T until the white spot portion disappeared after static electricity was applied was measured. For the liquid crystal panel 100, the time T isFor example, 10 seconds or less, preferably 1 second or less, and more preferably 0.5 second or less. The ESD test was performed at 23 ℃ and 55% RH.
The present inventors have newly found that reflection of light on the liquid crystal panel 100 can be greatly suppressed by employing a configuration in which no conductive layer such as an ITO layer is provided between the polarizing film 15 with an antireflection film and the liquid crystal cell 25. The liquid crystal panel 100 is suitable for applications requiring good visibility, particularly for applications of in-vehicle displays. Examples of the in-vehicle display include: an instrument panel for a car navigation device, an instrument panel cluster, a mirror display, and the like. The cluster of the dashboard is a panel that displays the running speed of the vehicle, the rotational speed of the engine, and the like. The liquid crystal panel 100 is particularly suitable for applications that do not require touch sensors, such as instrument cluster, mirror displays.
(modification of liquid Crystal Panel)
The polarizing film with an antireflection film 15 provided in the liquid crystal panel 100 may further include other members than the above-described members. As shown in fig. 4, in the liquid crystal panel 110 of the present modification, the antireflection film-attached polarizing film 16 further includes a transparent substrate 45 and an adhesive layer 46 which are disposed between the antireflection film 10 and the polarizing film 20. The liquid crystal panel 110 has the same structure as the liquid crystal panel 100 except for the transparent substrate 45 and the adhesive layer 46. Therefore, the same reference numerals are given to the common elements in the liquid crystal panel 100 and the liquid crystal panel 110 of the modified example, and the description thereof may be omitted. That is, the following descriptions of the respective embodiments can be applied to each other as long as they are not technically contradictory. The following embodiments may be combined with each other as long as they are not technically contradictory.
The transparent substrate 45 is, for example, in contact with the 1 st high refractive index layer 1 of the antireflection film 10. However, the polarizing film 16 with an antireflection film may have the antireflection film 11 illustrated in fig. 3 instead of the antireflection film 10. At this time, the pressure-sensitive adhesive layer 6 of the antireflection film 11 is in contact with the transparent substrate 45. The pressure-sensitive adhesive layer 46 is disposed between the transparent substrate 45 and the polarizing film 20, for example, and is in contact with the transparent substrate 45 and the polarizing film 20, respectively.
As the transparent substrate 45, the transparent substrates described above with respect to the 1 st transparent substrate 60 and the 2 nd transparent substrate 70 can be used, and are preferably made of glass. In this specification, the transparent substrate 45 made of glass is sometimes referred to as "cover glass".
As the adhesive layer 46, the adhesive layer described above with respect to the adhesive layer 30 can be used. It is particularly preferred that Adhesive layer 46 comprise a commercially available Optically Clear Adhesive (OCA). The adhesive layer 46 can be formed using an adhesive tape such as luciac (registered trademark) CS9621T, for example.
(Another modification of the liquid Crystal Panel)
The liquid crystal panel 100 or 110 may further include a touch sensor or a touch panel. Fig. 5 shows a liquid crystal panel 120 provided with the touch panel 80. The structure of the liquid crystal panel 120 is the same as that of the liquid crystal panel 100 except for the touch panel 80.
In the liquid crystal panel 120, the touch panel 80 is disposed on the visible side of the antireflection film 10, for example. The touch panel 80 is not in contact with the antireflection film-equipped polarizing film 15, and a gap (air layer) is formed between the touch panel 80 and the antireflection film-equipped polarizing film 15. The liquid crystal panel 120 is a so-called Out-cell (Out-cell) type liquid crystal panel. The touch panel 80 may be of an optical type, an ultrasonic type, a capacitance type, a resistance film type, or the like. When the touch panel 80 is of the resistive film type, the touch panel 80 has a structure in which, for example, 2 electrode plates having a transparent conductive thin film are arranged so as to face each other with a spacer interposed therebetween. When the touch panel 80 is of the capacitance type, the touch panel 80 is formed of, for example, a transparent conductive film including a transparent conductive thin film having a predetermined pattern shape.
(embodiment of liquid Crystal display device)
The liquid crystal display device of the present embodiment includes, for example, a liquid crystal panel 100 and an illumination system. In the liquid crystal display device, the liquid crystal panel 110 or 120 may be used instead of the liquid crystal panel 100. In the liquid crystal display device, the liquid crystal panel 100 is disposed on the viewing side of the illumination system, for example. The illumination system has, for example, a backlight or a reflector, and irradiates the liquid crystal panel 100 with light.
Examples
The present invention will be described in more detail below with reference to examples. The present invention is not limited to the embodiments described below. In the following, unless otherwise specified, "%" represents "% by weight", "parts" represents "parts by weight", and "thickness" represents "physical film thickness". Unless otherwise specified, the temperature and humidity in the room were 23 ℃ and 65% RH.
< (meth) acrylic polymer weight average molecular weight >
In the following examples, the weight average molecular weight (Mw) of the (meth) acrylic polymer was measured by GPC (gel permeation chromatography). The Mw/Mn of the (meth) acrylic polymer was measured in the same manner as described above.
An analysis device: HLC-8120GPC, manufactured by Tosoh corporation
A chromatographic column: G7000H, manufactured by Tosoh corporationXL+GMHXL+GMHXL
Column size: 90cm each 7.8mm phi x 30cm meter
Column temperature: 40 deg.C
Flow rate: 0.8mL/min
Injection amount: 100 μ L
Eluent: tetrahydrofuran (THF)
The detector: differential Refractometer (RI)
Standard sample: polystyrene
< adhesive layer A >
First, 76.9 parts of butyl acrylate, 18 parts of benzyl acrylate, 5 parts of acrylic acid, and 0.1 part of 4-hydroxybutyl acrylate were placed in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet, and a condenser to obtain a monomer mixture. Further, 0.1 part of 2, 2' -azobisisobutyronitrile as a polymerization initiator was added together with 100 parts of ethyl acetate with respect to 100 parts of the monomer mixture (solid component). While the mixture was slowly stirred, nitrogen gas was introduced into the flask and replaced with nitrogen gas. The polymerization reaction was carried out for 8 hours while maintaining the liquid temperature in the flask at around 55 ℃, thereby preparing a solution of an acrylic polymer having a weight average molecular weight (Mw) of 200 ten thousand and a Mw/Mn of 4.1.
Then, an isocyanate crosslinking agent (Coronate L, trimethylolpropane toluene diisocyanate, manufactured by tokyo corporation) was further added in an amount of 0.45 part, a peroxide crosslinking agent (NYPER BMT, manufactured by japan fat and oil co., ltd.) 0.1 part, and a silane coupling agent (KBM-403, γ -glycidoxypropylmethoxysilane, manufactured by shin-Etsu chemical industries, ltd.) 0.2 part, based on 100 parts of the solid content of the acrylic polymer solution, to prepare a solution of the acrylic pressure-sensitive adhesive composition.
Next, the obtained solution was coated on one surface of a separator (MRF 38 manufactured by mitsubishi chemical polyester film co. The separator is a polyethylene terephthalate film treated with a silicone-based release agent. The obtained coating film was dried at 155 ℃ for 1 minute, and thereby a pressure-sensitive adhesive layer a was formed on the surface of the separator. The thickness of the adhesive layer A was 20 μm.
< adhesive layer B >
An adhesive layer B was produced in the same manner as the adhesive layer a except that 1 part of lithium bis (trifluoromethanesulfonyl) imide (LiTFSI, mitsubishi material corporation) was further added to 100 parts of the solid content of the acrylic polymer solution to prepare a solution of the acrylic adhesive composition.
< adhesive layer C >
First, 94.9 parts of butyl acrylate, 5 parts of acrylic acid, and 0.1 part of 4-hydroxybutyl acrylate were placed in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet, and a condenser to obtain a monomer mixture. Further, 0.1 part of 2, 2' -azobisisobutyronitrile as a polymerization initiator was added together with 100 parts of ethyl acetate with respect to 100 parts of the monomer mixture (solid component). While the mixture was slowly stirred, nitrogen gas was introduced into the flask and replaced with nitrogen gas. The polymerization reaction was carried out for 8 hours while maintaining the liquid temperature in the flask at around 55 ℃, thereby preparing a solution of an acrylic polymer having a weight average molecular weight (Mw) of 210 ten thousand and an Mw/Mn of 4.0.
Then, an isocyanate crosslinking agent (Coronate L, trimethylolpropane toluene diisocyanate, manufactured by tokyo corporation) was further added in an amount of 0.45 part, a peroxide crosslinking agent (NYPER BMT, manufactured by japan fat and oil co., ltd.) 0.1 part, and a silane coupling agent (KBM-403, γ -glycidoxypropylmethoxysilane, manufactured by shin-Etsu chemical industries, ltd.) 0.2 part, based on 100 parts of the solid content of the acrylic polymer solution, to prepare a solution of the acrylic pressure-sensitive adhesive composition.
Next, the obtained solution was applied to one surface of a separator (MRF 38 manufactured by mitsubishi chemical polyester film co. The separator is a polyethylene terephthalate film treated with a silicone-based release agent. The obtained coating film was dried at 155 ℃ for 1 minute, and thereby a pressure-sensitive adhesive layer C was formed on the surface of the separator. The thickness of the adhesive layer C was 12 μm.
< antireflection film AR1 >
First, as a resin for forming the antiglare layer, 50 parts by weight of an ultraviolet-curable urethane acrylate resin (product of mitsubishi chemical corporation, trade name "UV 1700 TL", solid content concentration 80 wt%) and 50 parts by weight of a multifunctional acrylate containing pentaerythritol triacrylate as a main component (product of osaka organic chemical industry, trade name "Viscoat # 300", solid content concentration 100 wt%) were prepared. For 100 parts by weight of the solid content of these resins, 4 parts by weight of particles (product name "Techpolymer SSX504 TNR", product name: 3.0 μm) comprising a copolymer of (meth) acrylic ester and styrene, 1.5 parts by weight of an organoclay, namely synthetic montmorillonite (product name "Smekton SAN", product name: LTD.) as a thixotropy-imparting agent, 3 parts by weight of a photopolymerization initiator (product name "OMNIRAD 907", product name: BASF) and 0.015 part by weight of a leveling agent (product name "GRANDIC PC 4100", product name: DIC corporation, solid content concentration: 10% by weight) were mixed. This mixture was diluted with a toluene/cyclopentanone mixed solvent (weight ratio 80/20) so that the solid content concentration became 50 wt%, to prepare a material (coating liquid) for forming an antiglare layer.
Next, a cellulose Triacetate (TAC) film (product name "TD 60 UL" manufactured by fuji film corporation) was prepared. A material (coating liquid) for forming an antiglare layer was applied to one surface of the transparent plastic film (TAC film) using a wire bar coater to form a coating film. Next, the transparent plastic film on which the coating film was formed was heated at 80 ℃ for 1 minute to dry the coating film. Next, the coating film was irradiated with a high-pressure mercury lamp at a cumulative dose of 300mJ/cm2Thereby performing a curing process. Thus, an anti-glare layer-equipped TAC film having an anti-glare layer formed to a thickness of 8.0 μm was obtained. The haze of the TAC film with the antiglare layer was 8%.
Next, the TAC film with the antiglare layer was introduced into a roll-to-roll sputtering film forming apparatus, and the surface of the antiglare layer was subjected to bombardment treatment (plasma treatment using Ar gas) by running the film. Next, SiO as an adhesion layer having a physical film thickness of 3nm was formed on the surface of the antiglare layerxLayer (x < 2). Then, Nb with a physical film thickness of 12nm was sequentially formed on the adhesion layer2O5Layer (No. 1 high refractive index layer), SiO with a physical film thickness of 29nm2Layer (No. 1 low refractive index layer), Nb with physical film thickness of 116nm 2O5Layer (2 nd high refractive index layer) and SiO with a physical film thickness of 78nm2Layer (2 nd low refractive index layer), laminate a was produced. When these oxide films were formed, the amount of oxygen introduced was adjusted by plasma glow emission monitoring (PEM) control while the pressure in the apparatus was kept constant by adjusting the amount of argon gas introduced and the amount of exhaust gas.
Next, the 2 nd low refractive index layer (SiO) of the laminate a was formed2Layer) as an antifouling layer, a layer made of a fluorine-based resin (physical film thickness: 9 nm). The adhesive layer C was further transferred to the surface of the TAC film of the laminate a, thereby producing an antireflection film AR 1.
< antireflection film AR 2-AR 10 >
Antireflection films AR2 to AR10 were produced in the same manner as the antireflection film AR1 except that the physical film thicknesses of the respective layers were changed to values shown in table 1.
[ Table 1]
< polarizing film P1 >
First, an acrylic film was produced by the following method. 8000g of Methyl Methacrylate (MMA), 2000g of methyl 2- (hydroxymethyl) acrylate (MHMA), 10000g of 4-methyl-2-pentanone (methyl isobutyl ketone, MIBK), and 5g of n-dodecyl mercaptan were charged in a 30-liter tank reactor equipped with a stirrer, a temperature sensor, a condenser, and a nitrogen gas inlet tube. The mixture in the reactor was heated to 105 ℃ and refluxed while introducing nitrogen gas into the reactor. Next, 5.0g of t-butyl peroxyisopropyl carbonate (Kayaku BIC-7, Kayaku Akzo Co., Ltd.) was added as a polymerization initiator, and a solution of 10.0g of t-butyl peroxyisopropyl carbonate and 230g of MIBK was added dropwise thereto over 4 hours to conduct solution polymerization. The solution polymerization is carried out under reflux at about 105 to 120 ℃. After the solution was added dropwise, the mixture was aged for a further 4 hours.
Then, 30g of stearyl phosphate/distearyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry) was added to the obtained polymer solution, and a cyclized condensation reaction was performed at about 90 to 120 ℃ for 5 hours under reflux. The obtained solution was introduced into a vented twin-screw extruder (29.75 mm in diameter and 30 in L/D) having a cylinder temperature of 260 ℃, a rotational speed of 100rpm, a reduced pressure of 13.3 to 400hPa (10 to 300mmHg) and a number of back vents of 1 and a number of front vents of 4 at a processing speed of 2.0kg/h in terms of the amount of resin. Further cyclized condensation reaction and devolatilization are carried out in an extruder. Thus, transparent particles of the lactone ring-containing polymer were obtained.
The dynamic TG measurement was performed on the obtained lactone ring-containing polymer, and as a result, a mass decrease of 0.17 mass% was detected. The lactone ring-containing polymer had a weight average molecular weight of 133000, a melt flow rate of 6.5g/10min and a glass transition temperature of 131 ℃.
The obtained pellets were kneaded and extruded with acrylonitrile-styrene (AS) resin (Toyo AS20, Toyo styrene Co., Ltd.) at a mass ratio of 90/10 using a single-screw extruder (screw 30 mm. phi.) to obtain transparent pellets. The glass transition temperature of the resulting particles was 127 ℃.
The pellets were melt-extruded from a hanger type T-die having a width of 400mm using a 50mm phi single screw extruder, thereby producing a film having a thickness of 120. mu.m. The film was stretched to 2.0 times in the machine direction and 2.0 times in the cross direction at a temperature of 150 ℃ using a biaxial stretching machine, to obtain a stretched film (acrylic film) having a thickness of 30 μm. The optical properties of the stretched film were measured, and as a result, the total light transmittance was 93%, the in-plane retardation Δ nd was 0.8nm, and the thickness direction retardation Rth was 1.5 nm.
Next, a polarizing film P1 was produced by the following method. First, a polyvinyl alcohol film having a thickness of 45 μm was dyed in an iodine solution (temperature 30 ℃) having a concentration of 0.3% for 1 minute between a plurality of rolls having different speed ratios, and stretched to a draw ratio of 3 times. Next, the obtained stretched film was immersed in an aqueous solution (temperature 60 ℃) containing 4% boric acid and 10% potassium iodide for 0.5 minute, and stretched until the total stretch ratio became 6 times. Subsequently, the stretched film was immersed in an aqueous solution (temperature: 30 ℃) containing potassium iodide at a concentration of 1.5% for 10 seconds, and then washed. Next, the stretched film was dried at 50 ℃ for 4 minutes to obtain a polarizer having a thickness of 18 μm. A TAC film (trade name "KC 4 UY" manufactured by Konika Mingda) having a thickness of 40 μm was bonded to one main surface of the polarizer obtained using a polyvinyl alcohol adhesive. The acrylic film having a thickness of 30 μm was bonded to the other principal surface of the polarizer with a polyvinyl alcohol adhesive. Thereby, a polarizing film P1 was obtained.
(example 1)
First, 50 parts of a solution containing PEDOT/PSS (Dentron PT-436 manufactured by Nagase ChemteX Corporation) and 50 parts of water were mixed to prepare a coating liquid having a solid content concentration of 0.5% by weight. Next, the coating liquid was applied to the acrylic film side surface of the polarizing film P1. The obtained coating film was dried at 80 ℃ for 2 minutes to prepare a conductive layer. Thus, a polarizing film with a conductive layer was obtained. The thickness of the conductive layer was 30 nm.
Next, the pressure-sensitive adhesive layer C of the antireflection film AR1 was bonded to the surface of the TAC film of the polarizing film P1. The adhesive layer a was further transferred to the surface of the conductive layer, thereby producing an antireflection film-equipped polarizing film of example 1 having a structure of an antireflection film AR 1/a polarizing film P1/a conductive layer/an adhesive layer a.
(example 2)
A polarizing film with an antireflection film of example 2 was produced in the same manner as in example 1, except that the PEDOT/PSS coating solution was applied to the polarizing film P1 so that the thickness of the conductive layer became 90 nm.
(examples 3 to 12 and comparative examples 1 to 2)
Polarizing films with an antireflection film of examples 3 to 12 and comparative examples 1 to 2 were produced in the same manner as in example 1, except that the antireflection film, the conductive layer, and the adhesive layer were changed to the combinations shown in table 2. In comparative example 2, the pressure-sensitive adhesive layer a was directly bonded to the acrylic film-side surface of the polarizing film P1 without forming a conductive layer on the polarizing film P1.
(example 13)
First, a coating liquid having a solid content concentration of 0.27% by weight was prepared by mixing 9 parts of a solution containing PEDOT/PSS (Dentron P-580W manufactured by Nagase ChemteX Corporation) and 91 parts of water. Next, the coating liquid was applied to the acrylic film side surface of the polarizing film P1. The obtained coating film was dried at 80 ℃ for 2 minutes to prepare a conductive layer. Thereby, a polarizing film with a conductive layer was obtained. The thickness of the conductive layer was 100 nm.
Next, the pressure-sensitive adhesive layer C of the antireflection film AR4 was bonded to the surface of the TAC film of the polarizing film P1. The adhesive layer a was further transferred to the surface of the conductive layer, thereby producing an antireflection film-equipped polarizing film of example 13 having a structure of an antireflection film AR 4/a polarizing film P1/a conductive layer/an adhesive layer a.
Comparative example 3
First, the composition containing PEDOT/PSS8.6 parts of a solution (Dentron P-580W manufactured by Nagase ChemteX Corporation) containingA coating solution (solid content concentration: 0.5 wt%) for forming a conductive layer was prepared by mixing 1 part of a solution of an oxazoline-based acrylic polymer (trade name: EPOCROS WS-700, manufactured by Nippon catalyst) and 90.4 parts of water. The concentration of the polythiophene polymer in the obtained coating liquid was 0.04% by weight, and the content thereof was The concentration of the oxazoline-based acrylic polymer was 0.25 weight percent.
Next, the obtained coating liquid was applied to the acrylic film side main surface of the polarizing film P1. The obtained coating film was dried at 80 ℃ for 2 minutes to prepare a conductive layer. Thus, a polarizing film with a conductive layer was obtained. The thickness of the conductive layer was 60 nm.
Next, the pressure-sensitive adhesive layer C of the antireflection film AR10 was bonded to the surface of the TAC film of the polarizing film P1. The adhesive layer a was further transferred to the surface of the conductive layer, thereby producing an antireflection film-equipped polarizing film of comparative example 3 having a structure of antireflection film AR 10/polarizing film P1/conductive layer/adhesive layer a.
< optical characteristics of polarizing film with antireflection film >
In the polarizing films with an antireflection film obtained in examples and comparative examples, light from CIE standard illuminant D65 was incident from the antireflection film in a state where the pressure-sensitive adhesive layer was laminated with alkali-free glass so as to be in direct contact with the alkali-free glass, and the light reflectance of the reflected light generated at this time was Y, L by the above-described method*Value a*Value and b*A value and satisfies L*Value of 0, a*Value of 0 and b*The color difference Δ E between the light with a value of 0 and the reflected light was evaluated. In this case, the polarizing film with the antireflection film was cut into a 50mm square and used. As the alkali-free glass, EG-XG (thickness: 0.7mm) manufactured by Corning corporation was used. As the black film, black made of polyethylene terephthalate (PET) was used And (5) color films. The spectral reflectance was measured using a spectrophotometer (product name "CM 2600D" manufactured by Konikamet Co., Ltd.). The evaluation sample for evaluating optical characteristics had a structure of a polarizing film with an antireflection film/alkali-free glass/black PET film. In the polarizing film with an antireflection film of comparative example 1, the reflected light was evaluated by using alkali-free glass in which an amorphous ITO layer (thickness 20nm) was not formed on the surface. That is, in comparative example 1, the sample was evaluated to have a structure of a polarizing film with an antireflection film/an ITO layer/alkali-free glass/a black PET film. The ITO layer was fabricated using sputtering. The Sn ratio of ITO contained in the ITO layer was 3 wt%. The Sn ratio was calculated from the weight of Sn atoms/(the weight of Sn atoms + the weight of In atoms) In the ITO.
< optical characteristics of antireflection film >
The antireflection films AR1 to AR10 had a light reflectance Y of reflected light generated when light from the CIE standard light source D65 was incident thereon by the above-described method1、a1 *Value and b1 *The values were evaluated. The same ones as those used in the evaluation of the optical characteristics of the polarizing film with an antireflection film were used for the black film, the spectrophotometer, and the like.
< surface resistivity of adhesive layer >
The surface resistivity (Ω/□) of the adhesive layers a and B was measured at the stage of forming the adhesive layer a or B on the surface of the separator. The surface resistivity was measured by using a resistivity meter (Hiresta-UP MCP-HT450 manufactured by Mitsubishi Chemical Analyticech Co., Ltd.). The measurement conditions were that a voltage of 250V was applied for 10 seconds.
< surface resistivity of conductive layer >
In the examples and comparative examples, the surface resistivity (Ω/□) of the conductive layer was measured at the stage of forming the conductive layer on the surface of the polarizing film P1. In example 13 and comparative example 3, the surface resistivity of the conductive layer was measured by a resistivity meter (Hiresta-UP MCP-HT450 manufactured by Mitsubishi Chemical analysis co., ltd.) according to the method specified in JIS K6911: 1995. The measurement conditions were 10V voltage application and 10 seconds time application. In examples 1 to 12 and comparative example 1, the surface resistivity of the conductive layer was measured by a resistivity meter (Loresta-GP MCP-T600 manufactured by Mitsubishi Chemical Analytech Co., Ltd.) according to the method specified in JIS K7194: 1994. The measurement conditions were 10V voltage application and 10 seconds time application.
< surface resistivity of polarizing film >
In comparative example 2, the surface resistivity of the polarizing film P1 was measured using a resistivity meter (Hiresta-UP MCP-HT450 manufactured by Mitsubishi Chemical analysis Co., Ltd.) according to the method specified in JIS K6911: 1995. The measurement conditions were 10V voltage application and 10 seconds time application. The surface resistivity of the polarizing film P1 is higher than 1.0X 1014Ω/□。
< loss of total light transmittance due to conductive layer A >)
First, the total light transmittance T1 of the polarizing film P1 was measured using a spectrophotometer (V7100 manufactured by japan spectrophotometer corporation) in accordance with JIS K7361-1: 1997. In the same manner, the total light transmittance T2 of the laminate L including the polarizing film P1 and the conductive layer was measured at the stage of forming the conductive layer on the surface of the polarizing film P1. The total light transmittance T2 of the laminate L was measured by allowing light to enter from the polarizing film P1 side. The difference between the total light transmittance T1 and the total light transmittance T2 of the polarizing film P1 (T1 to T2) was calculated, and the calculated value was regarded as the loss a of the total light transmittance due to the conductive layer.
< ESD test >
First, the polarizing films with the antireflection films obtained in examples and comparative examples were bonded to the surface of the liquid crystal cell on the viewing side, and liquid crystal panels were produced. In comparative example 1, a liquid crystal cell having an amorphous ITO layer (thickness 20nm) formed on the surface was used. That is, in comparative example 1, the liquid crystal panel had a structure of a polarizing film with an antireflection film/an ITO layer/a liquid crystal cell. The ITO layer was fabricated using sputtering. The Sn ratio of ITO contained in the ITO layer was 3 wt%. Next, a silver paste was applied to the polarizing film with the antireflection film so as to cover the side surface thereof with a width of 5 mm. The silver paste was dried to form a conductive structure made of silver. The liquid crystal panel is electrically connected to an external ground electrode through the conductive structure. Next, the liquid crystal panel is mounted on the backlight device. Next, static electricity was applied to the visible side (anti-reflection film side) of the liquid crystal panel using an electrostatic discharge (ESD) gun whose applied voltage was adjusted to 10 kV. This causes white spots in a part of the liquid crystal panel. The time T until the white spot portion disappeared after static electricity was applied was measured. In table 2, the results of the ESD test were evaluated based on the following criteria relating to time T. The ESD test was performed at 23 ℃ and 55% RH.
(evaluation criteria)
A: less than 0.5 second
B: more than 0.5 second and less than 1 second
C: more than 1 second and less than 10 seconds
D: for more than 10 seconds
< color tone >
The liquid crystal panel produced in the above-described ESD test was visually observed from the visible side (anti-reflection film side) to evaluate the color tone. In the items of color tones in table 2, a means that no color tone was observed, B means that a very weak color tone was observed, C means that a weak color tone was observed, and D means that a color tone was observed.
As can be seen from Table 2, the sheet had a surface resistivity of 1.0X 106The polarizing films with an antireflection film of examples 1 to 13, which have conductive layers of Ω/□ or less, have better ESD test results than comparative examples 2 and 3, and it is estimated that charging of the liquid crystal panel can be sufficiently suppressed. As is clear from the results of the ESD tests in example 3 and comparative example 1, the use of the adhesive layer to which the conductive material is added together with the conductive layer can sufficiently suppress the electrification of the liquid crystal panel as compared with the case of using the ITO layer.
In addition, the liquid crystal panels including the polarizing films with an antireflection film of examples 1 to 13, in which the light reflectance of the reflected light was sufficiently lower than the value of Y, sufficiently suppressed the reflection of light. These liquid crystal panels are estimated to be suitable for improving visibility of liquid crystal display devices. In contrast, in comparative example 1, the light reflection ratio Y was greatly increased due to the presence of the ITO layer, and the reflection of light on the liquid crystal panel could not be sufficiently suppressed.
Industrial applicability
The liquid crystal panel of the present invention can be used for applications requiring good visibility, for example, applications such as a vehicle-mounted display.
Claims (15)
1. A liquid crystal panel comprising a polarizing film with an antireflection film and a liquid crystal cell, wherein the polarizing film with an antireflection film comprises an antireflection film, a polarizing film, and an adhesive layer in this order in the lamination direction, and further comprises a conductive layer,
no conductive layer is provided between the polarizing film with an antireflection film and the liquid crystal cell,
the polarizing film with an antireflection film has a surface resistivity of the conductive layer of 1.0 × 106Under the condition of omega/□ it can be used,
the antireflection film-equipped polarizing film generates reflected light having a light reflectance Y of 1.1% or less when light from a CIE standard light source D65 is incident from a surface opposite to the pressure-sensitive adhesive layer in a state where the pressure-sensitive adhesive layer and the alkali-free glass are laminated so as to be in direct contact with each other.
2. The liquid crystal panel according to claim 1,
the conductive layer of the antireflection film-equipped polarizing film is disposed between the polarizing film and the adhesive layer.
3. The liquid crystal panel according to claim 1 or 2,
The surface resistivity is 1.0 x 104Omega/□ or less.
4. The liquid crystal panel according to any one of claims 1 to 3,
the surface resistivity is more than 5.0 x 102Ω/□。
5. The liquid crystal panel according to any one of claims 1 to 4,
the light reflectance Y is 0.9% or less.
6. The liquid crystal panel according to any one of claims 1 to 5,
the loss of total light transmittance due to the conductive layer of the polarizing film with an antireflection film is 0.9% or less.
7. The liquid crystal panel according to any one of claims 1 to 6,
said reflected light is at L*a*b*A in color system*Value and b*The values satisfy the following relational expressions (1) and (2),
-10≤a*≤10 (1)
-18≤b*≤5 (2)。
8. the liquid crystal panel according to claim 7,
a is a*The value is-6 or more and 6 or less.
9. The liquid crystal panel according to claim 8,
a is a*The value is-3 or more and 3 or less.
10. The liquid crystal panel according to any one of claims 7 to 9,
b is*The value is-15 or more and 3 or less.
11. The liquid crystal panel according to claim 10,
b is*The value is-10 or more and 2 or less.
12. The liquid crystal panel according to claim 11,
B is described*The value is-6 or more and 2 or less.
13. The liquid crystal panel according to any one of claims 1 to 12,
the antireflection film includes a 1 st high refractive index layer, a 1 st low refractive index layer, a 2 nd high refractive index layer, and a 2 nd low refractive index layer in this order in a lamination direction.
14. The liquid crystal panel according to claim 13,
the optical film thickness of the 1 st high refractive index layer is 20nm to 35nm,
the optical film thickness of the 1 st low refractive index layer is 38nm to 50nm,
the optical film thickness of the 2 nd high refractive index layer is 230nm to 290nm,
the optical film thickness of the 2 nd low refractive index layer is 100nm to 128 nm.
15. The liquid crystal panel according to any one of claims 1 to 14,
the adhesive layer includes a conductive material.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP2019-225878 | 2019-12-13 | ||
JP2019225878A JP7497153B2 (en) | 2019-12-13 | 2019-12-13 | LCD panel |
PCT/JP2020/038059 WO2021117323A1 (en) | 2019-12-13 | 2020-10-07 | Liquid crystal panel |
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Publication Number | Publication Date |
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CN114761865A true CN114761865A (en) | 2022-07-15 |
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Application Number | Title | Priority Date | Filing Date |
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CN202080080315.5A Pending CN114761865A (en) | 2019-12-13 | 2020-10-07 | Liquid crystal panel |
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JP (1) | JP7497153B2 (en) |
KR (1) | KR20220115599A (en) |
CN (1) | CN114761865A (en) |
TW (1) | TW202122886A (en) |
WO (1) | WO2021117323A1 (en) |
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KR20100009472A (en) | 2008-07-18 | 2010-01-27 | 주식회사 엘지화학 | Liquid crystal display |
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2019
- 2019-12-13 JP JP2019225878A patent/JP7497153B2/en active Active
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2020
- 2020-10-07 WO PCT/JP2020/038059 patent/WO2021117323A1/en active Application Filing
- 2020-10-07 KR KR1020227023636A patent/KR20220115599A/en unknown
- 2020-10-07 CN CN202080080315.5A patent/CN114761865A/en active Pending
- 2020-10-13 TW TW109135372A patent/TW202122886A/en unknown
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JP2005121766A (en) * | 2003-10-15 | 2005-05-12 | Koshaku Jo | Transparent antistatic triacetylcellulose film for liquid crystal display |
JP2006126585A (en) * | 2004-10-29 | 2006-05-18 | Fuji Photo Film Co Ltd | Polarizing plate with adhesive and liquid crystal display |
WO2007004818A1 (en) * | 2005-06-30 | 2007-01-11 | Kwang Suck Suh | Anti-reflective film having high surface hardness and antistatic property and method for producing the same |
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TW202122886A (en) | 2021-06-16 |
JP7497153B2 (en) | 2024-06-10 |
WO2021117323A1 (en) | 2021-06-17 |
JP2021096307A (en) | 2021-06-24 |
KR20220115599A (en) | 2022-08-17 |
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