JP2007041334A - Liquid crystal display - Google Patents

Abstract

A reflective or transflective liquid crystal display device having sufficient antireflection performance and excellent surface scratch resistance and antifouling properties is provided.
A liquid crystal display device has a liquid crystal cell, an optical anisotropic body, and an exit-side polarizer in this order toward the viewing side. The optical anisotropic body has a ratio Re (450) / Re (550) of an in-plane retardation value Re (550) measured at a wavelength of 550 nm and an in-plane retardation value Re (450) measured at a wavelength of 450 nm of 1. 007 or less. An antireflection body is provided on the side opposite to the optical anisotropic body of the output side polarizer. The antireflective body comprises (A) hollow particles having a particle size of 5 to 2000 nm, (siloxane) oligomers having (meth) acryloyl groups and fluoroalkyl groups, and (C) acrylate compounds having (meth) acryloyl groups. A low refractive index layer made of a cured film formed from a product is provided.
[Selection figure] None

Description

  The present invention relates to a reflective or transflective liquid crystal display device, and more particularly to a reflective or transflective liquid crystal display device having antireflection performance and excellent scratch resistance and antifouling properties.

  In recent years, liquid crystal display devices have been expected to be used as displays for portable information terminals by taking advantage of their thinness and light weight. Since a portable information terminal is normally driven by a battery, it is important to suppress power consumption as much as possible. Therefore, attention is paid to a liquid crystal display device of a portable information terminal that is a reflective type that does not use a backlight with high power consumption or a transflective type that uses a backlight as necessary.

  Since the reflective liquid crystal display device uses external light incident from the display surface side, there is a drawback that the display screen is difficult to see when used in a dark environment. For this reason, in a reflective liquid crystal display device, by using a transflective reflector that transmits a part of incident light instead of a reflector, a transflective display that uses external light together with a backlight A liquid crystal display device has been proposed. Such a transflective liquid crystal display device functions as a reflective type (reflection mode) using external light when the backlight is not lit, and when the backlight is lit in a dark environment. It functions as a transmission type (transmission mode) using light of light.

  Such a liquid crystal display device is required to have a high display quality in the trend of colorization and high definition. For this reason, it has been a problem to improve brightness by capturing light efficiently and to eliminate white blur due to light leakage. However, even if these points are improved, part of the external light may be reflected on the surface of the display device, causing glare on the display screen and deterioration of display quality due to reflection. Therefore, in order to prevent these surface reflections, the display device may be subjected to an antiglare treatment or an antireflection treatment.

  Specifically, as the antiglare treatment, for example, a technique of forming an antiglare layer having a convex shape on the surface of the screen of a liquid crystal display device is used (Patent Document 1). Further, as the antireflection treatment, for example, techniques for forming an antireflection body made of a plurality of inorganic oxides on the surface of the screen (Patent Documents 2 and 3) are disclosed.

JP 2002-318383 A JP 2000-47187 A JP-A-2001-74910

However, as shown in Patent Document 1, when an antiglare layer having a convex shape is formed on the surface of the screen, light scattering occurs at the rear of the screen in the convex portion. Contrast may be reduced.
In addition, the antireflectors as shown in Patent Documents 2 and 3 have a problem that the adverse effect on the contrast can be suppressed, but the light reflection cannot be sufficiently prevented. Furthermore, in this case, since the adhesion between the antireflection body and the substrate may be insufficient, an improvement in the scratch resistance of the surface is required. Further, on the surface of the antireflection body, further improvement in antifouling properties is required.

  An object of the present invention is to provide a reflective or transflective liquid crystal display device having sufficient antireflection performance and excellent surface scratch resistance and antifouling properties.

  As a result of intensive studies in view of the above problems, the present inventor is a liquid crystal display device having a liquid crystal cell, an optical anisotropic body, and an exit-side polarizer in this order toward the viewing side. The rectangular solid has a ratio Re (450) / Re (550) of in-plane retardation value Re (550) measured at a wavelength of 550 nm and in-plane retardation value Re (450) measured at a wavelength of 450 nm of 1.007 or less. An antireflection body is provided on the opposite side of the output side polarizer from the optical anisotropic body, and the antireflection body includes at least a predetermined compound. Based on this finding, it was found that by forming a reflective or transflective liquid crystal display device comprising a low refractive index layer formed of a cured film to be formed, in addition to antireflection performance, it has excellent scratch resistance. The present invention This has led to the formation.

That is, the present invention is a liquid crystal display device having a liquid crystal cell, an optical anisotropic body, and an output side polarizer in this order toward the viewing side, and the optical anisotropic body is a surface measured at a wavelength of 550 nm. The ratio Re (450) / Re (550) of the in-plane retardation value Re (550) and the in-plane retardation value Re (450) measured at a wavelength of 450 nm is 1.007 or less, and On the side opposite to the optical anisotropic body, an antireflection body is provided, and the antireflection body comprises the following components (A), (B), and (C): a composition for forming a low refractive index layer A low-refractive-index layer made of a cured film formed from the above is provided.
(A) Hollow particles having a particle size of 5 to 2000 nm (B) Siloxane oligomer having (meth) acryloyl group and fluoroalkyl group (C) Acrylate compound having (meth) acryloyl group

  Here, it is preferable that the composition for forming a low refractive index layer contains a crosslinkable compound. Moreover, it is preferable that the refractive index of the said low refractive index layer is 1.40 or less, and the refractive index difference with the layer adjacent to the said low refractive index layer is 0.05-0.4.

  The antireflector preferably includes a high refractive index layer laminated on the output side polarizer side of the low refractive index layer, and the refractive index of the high refractive index layer is preferably 1.55 or more. At this time, the high refractive index layer is preferably provided with an antiglare function.

  According to the reflective or transflective liquid crystal display device of the present invention, there are the effects of having sufficient antireflection performance and excellent surface scratch resistance. The liquid crystal display device of the present invention is suitable as a display for a portable information terminal such as a personal computer, a mobile phone, a PDA, or a portable game machine.

The present invention is a liquid crystal display device having a liquid crystal cell, an optical anisotropic body, and an output side polarizer in this order toward the viewing side, wherein the optical anisotropic body has an in-plane letter measured at a wavelength of 550 nm. The ratio Re (450) / Re (550) between the retardation value Re (550) and the in-plane retardation value Re (450) measured at a wavelength of 450 nm is 1.007 or less, and the optical difference of the output side polarizer is An antireflection body is provided on the side opposite to the rectangular parallelepiped, and the antireflection body is formed from a composition for forming a low refractive index layer comprising the following components (A), (B), and (C). The low refractive index layer is provided.
(A) Hollow particles having a particle size of 5 to 2000 nm (B) Siloxane oligomer having (meth) acryloyl group and fluoroalkyl group (C) Acrylate compound having (meth) acryloyl group

<Liquid crystal cell>
The liquid crystal cell used in the present invention includes a transparent electrode substrate having no reflection function (hereinafter sometimes referred to as a first substrate) and a transparent electrode substrate having a reflection function on the entire surface or a portion thereof (hereinafter referred to as a second substrate). And a liquid crystalline compound sealed between these two transparent electrode substrates. When a transparent electrode substrate having a reflective function on the entire surface is used, the obtained liquid crystal display device is a reflective liquid crystal display device, and a substrate having a reflective function is used as a part of the transparent electrode substrate. The obtained liquid crystal display device is a transflective liquid crystal display device.

  In order to form a substrate having such a reflection function, a reflection plate is generally provided on the second substrate. As this reflecting plate, for example, a metal plate is preferable, and in this case, it is more preferable that an uneven structure (see Japanese Patent No. 2756206) is provided on the surface of the metal plate. This is because when the surface of the reflecting plate is smooth, only the regular reflection component is reflected and the viewing angle may be narrowed. In the case of a transflective liquid crystal display device, the second substrate is provided with a function of transmitting light and a function of reflecting light.

  Such a liquid crystal cell is not limited by the type of liquid crystal compound to be sealed, the operation method of the liquid crystal compound, and the like. For example, TN (Twisted Nematic) method, STN (Super Twisted Nematic) method, ECB (Electrically Controlled Birefringence) method, IPS (In-Plane Switching) method, VA (Vertical Alignment) method, OCB (Optically Compensated Birefringence) ) Method, HAN (Hybrid Aligned Nematic) method, ASM (Axially Symmetric Aligned Microcell) method, and the like. Further, various methods such as a halftone gray scale method, a domain division method, a display method using a ferroelectric liquid crystal, and an antiferroelectric liquid crystal can be employed.

<Output-side polarizer>
The output side polarizer of the present invention can extract linearly polarized light from natural light. As the exit side polarizer, for example, an iodine polarizing film, a dye polarizing film using a dichroic dye, or a polyene polarizing film can be used. The iodine-based polarizing film and the dye-based polarizing film are generally produced from a polyvinyl alcohol film. Although there is no restriction | limiting in particular in the thickness of a polarizer, For example, 5-80 micrometers is preferable.

  In the transflective liquid crystal display device, an incident side polarizer is further provided on the second substrate side of the liquid crystal cell. That is, the liquid crystal cell is disposed between the exit side polarizer and the entrance side polarizer. The incident side polarizer has the same function and configuration as the output side polarizer. In the transflective liquid crystal display device, it is preferable that the transmission axis of the exit-side polarizer and the transmission axis of the incident-side polarizer are arranged so as to be substantially perpendicular.

<Optical anisotropic body>
As an optical anisotropic body of the present invention, a ratio Re (450) / Re (550) between an in-plane retardation value Re (550) measured at a wavelength of 550 nm and an in-plane retardation value Re (450) measured at a wavelength of 450 nm. ) Is 1.007 or less, preferably 1.006 or less. The lower limit of the ratio Re (450) / Re (550) is preferably 0.5, more preferably 0.7. By providing the optical anisotropic body in which Re (450) / Re (550) falls within the above range, the liquid crystal display device can obtain a color display with good color development.

  Retardation includes retardation in the film plane (Re) and retardation in the film thickness direction (Rth). Retardation (Re) in the film plane can be obtained by Re = (nx−ny) × d, where the main refractive index in the film plane is nx, ny, and the thickness of the film is d (nm). . Retardation (Rth) in the film thickness direction is defined as follows: Rx = {ny} where ny is the main refractive index in the film plane, nz is the refractive index in the film thickness direction, and d (nm) is the film thickness (Nx + ny) / 2−nz} × d. Re and Rth can be measured using a commercially available automatic birefringence meter (“KOBRA-21ADH” manufactured by Oji Scientific Instruments).

  The optical anisotropic body preferably has an in-plane retardation Re (550) measured at a wavelength of 550 nm of 125 to 150 nm. The optical anisotropic body has a ratio Re (λ) / λ of retardation Re (λ) and wavelength λ at the wavelength λ in the entire visible range, usually 0.22 to 0.28, preferably 0.23. It is -0.27, More preferably, it is the range of 0.24-0.26.

  The optical anisotropic body may have a single-layer structure or a laminated structure as long as it has the above characteristics. For example, a suitable optical anisotropic body includes an optical anisotropic body in which a quarter-wave plate and a half-wave plate are overlapped with their slow axis directions shifted. Here, the quarter-wave plate is an optical anisotropic body having a retardation measured at a wavelength of 550 nm of 125 to 150 nm. The half-wave plate is an optically anisotropic body having a retardation measured at a wavelength of 550 nm and 250 to 300 nm.

  Optical anisotropic bodies such as quarter-wave plates and half-wave plates can be obtained by stretching and orienting a transparent resin film. The slow axis of the optical anisotropic body usually occurs in the stretching direction or a direction perpendicular thereto. The slow axis crossing angle of the quarter-wave plate and half-wave plate obtained by stretching the transparent resin is preferably 56 ° to 62 °, more preferably 57 ° to 61 °. When the slow axis crossing angle is in the above range, an optical anisotropic body excellent in broadband property can be obtained. Note that the slow axis is the direction in which the phase delay becomes maximum when linearly polarized light is incident.

  The transparent resin film used for the quarter wavelength plate or the half wavelength plate is preferably composed of a resin having a total light transmittance of 80% or more at a thickness of 1 mm. Examples of such resins include polymer resins having an alicyclic structure, chain olefin polymers such as polyethylene and polypropylene, polycarbonate polymers, polyester polymers, polysulfone polymers, and polyethersulfone polymers. Polymers and resins having positive intrinsic birefringence such as polyvinyl alcohol polymers; negative polymers such as vinyl aromatic polymers, polyacrylonitrile polymers, polymethyl methacrylate polymers, cellulose ester polymers, etc. A resin having intrinsic birefringence can be mentioned. These can be used alone or in combination of two or more.

  Among the resins having positive intrinsic birefringence, polymer resins and chain olefin polymers having an alicyclic structure are preferable, and particularly excellent in transparency, low hygroscopicity, dimensional stability, light weight, and the like. A polymer resin having a cyclic structure is preferred. Examples of the polymer resin having an alicyclic structure include a norbornene polymer, a monocyclic olefin polymer, and a vinyl alicyclic hydrocarbon polymer. Among these, norbornene-based polymers can be suitably used because they have good transparency and moldability. Examples of the norbornene-based polymer include a ring-opening polymer of a norbornene-based monomer, a ring-opening copolymer of a norbornene-based monomer and another monomer, and a hydrogenated product of these polymers; Examples include addition polymers of monomers, addition copolymers of norbornene monomers and other monomers, and hydrogenated products of these polymers. Among these, a hydrogenated product of a ring-opening polymer or a ring-opening copolymer of a norbornene monomer is particularly preferable because it is excellent in transparency.

  Among the resins having negative intrinsic birefringence, at least one selected from vinyl aromatic polymers, polyacrylonitrile polymers, and polymethyl methacrylate polymers is preferable. Of these, vinyl aromatic polymers are more preferable from the viewpoint of high birefringence. The vinyl aromatic polymer refers to a polymer of a vinyl aromatic monomer or a copolymer of a monomer copolymerizable with a vinyl aromatic monomer. Examples of the vinyl aromatic monomer include styrene; styrene derivatives such as 4-methylstyrene, 4-chlorostyrene, 3-methylstyrene, 4-methoxystyrene, 4-tert-butoxystyrene, α-methylstyrene, and the like. It is done. These may be used alone or in combination of two or more. Monomers copolymerizable with vinyl aromatic monomers include olefins such as propylene and butene; α, β-ethylenically unsaturated nitrile monomers such as acrylonitrile; acrylic acid, methacrylic acid, maleic anhydride, etc. Α, β-ethylenically unsaturated carboxylic acid; acrylic acid ester, methacrylic acid ester; maleimide; vinyl acetate; vinyl chloride; Among vinyl aromatic polymers, a copolymer of styrene or a styrene derivative and maleic anhydride is preferable because of high heat resistance.

  As said transparent resin, that whose glass transition temperature Tg is 90 degreeC or more is preferable from the point which is excellent in the heat resistance of a film, and what is 100 degreeC or more is especially preferable. The method for forming the transparent resin film is not particularly limited, and can be formed by a method such as a solution casting method or a melt extrusion method. Among these, the melt extrusion method that does not use a solvent can reduce the content of volatile components of the film, is easy to produce a film having a large Rth of 100 μm or more, and is preferable from the viewpoint of manufacturing cost. Examples of the melt extrusion method include a method using a T die and an inflation method, and a method using a T die is preferable in terms of excellent productivity and thickness accuracy.

The retardation of the optical anisotropic body can be controlled, for example, by appropriately setting the stretching conditions such as the film material, the thickness of the film before stretching, the stretching ratio and the stretching temperature. When the glass transition temperature of the transparent resin is defined as Tg, the film is preferably stretched in a temperature range of Tg-30 ° C to Tg + 60 ° C, more preferably in a temperature range of Tg-10 ° C to Tg + 50 ° C, preferably 1 Performed at a draw ratio of 01 to 2 times. The stretching speed is preferably 5 to 1000 mm / second, more preferably 10 to 750 mm / second. When the stretching speed is within the above range, stretching control is facilitated, and an optical anisotropic body with small variations in surface accuracy and retardation can be obtained.

  The refractive index nz in the thickness direction of the optical anisotropic body used in the present invention is not particularly limited. For example, nz and other main refractive indexes nx and ny have a relationship of nx> ny> nz, nx> ny = nz, nx> nz> ny, nx = nz> ny, nz> nx> ny. Can be mentioned. The thickness of the optical anisotropic body is preferably 10 to 500 μm, more preferably 20 to 250 μm, and particularly preferably 20 to 120 μm.

  Optical anisotropic bodies such as quarter-wave plates and half-wave plates can also be obtained by aligning and fixing a liquid crystalline compound. The liquid crystalline compound has optical anisotropy, and a film having optical anisotropy can be obtained by arranging and fixing the liquid crystalline compound in a certain direction. Specifically, a low molecular weight or high molecular weight liquid crystalline compound having a property of being polymerized or crosslinked by ultraviolet rays or heat in the presence of a polymerization initiator or a crosslinking agent, or a mixture thereof was aligned substantially uniformly. It can be obtained by immobilization by polymerization or crosslinking reaction.

  Examples of the liquid crystalline compound used for obtaining the optical anisotropic body include a rod-like liquid crystalline compound, a discotic liquid crystalline compound, or a mixture thereof. As rod-like liquid crystalline compounds, azomethines, azoquinones, cyanobiphenyls, cyanophenyl esters, benzoates, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, tolanes, cyano-substituted phenylpyrimidines, alkoxy-substituted compounds Examples thereof include phenylpyrimidines, phenyldioxanes, and alkenylcyclohexylbenzonitriles. Moreover, not only the low molecular liquid crystalline compound as described above but also a polymer rod-shaped liquid crystalline compound can be used. Furthermore, specific examples of the rod-like liquid crystal compound include polymerizable liquid compositions described in JP-A-7-294735, JP-A-2002-174724, and JP-A-8-283748. As an example of an optical anisotropic body using a rod-like liquid crystal compound, a film in which liquid crystal is vertically aligned shows a relationship of nz> nx = ny (including the case where nx and ny are approximated) An example of a tilted film showing a relationship of nz> nx> ny. Commercially available products such as a trade name NH film (manufactured by Nippon Oil Co., Ltd.) can be used as the tilted film.

  As the discotic liquid crystalline compound, various documents (for example, C. Desradade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); edited by the Chemical Society of Japan, Quarterly Chemical Review, No. .22, Chemistry of Liquid Crystals, Chapter 5, Chapter 10, Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm. Page 1794 (1985); and J. Zhang et al., J. Am. Chem. Soc., Vol. 116, page 2655 (1994); The polymerization of discotic liquid crystalline compounds is described in JP-A-8-27284. In order to fix the discotic liquid crystalline compound by polymerization, it is necessary to bond a polymerizable group to the discotic core of the discotic liquid crystalline compound via a linking group. Examples of such discotic liquid crystalline compounds include those described in JP-A No. 2000-284126. Commercially available products such as a trade name WV film (manufactured by Fuji Photo Film Co., Ltd.) can be used as an optical anisotropic body using a discotic liquid crystalline compound.

  The alignment of the liquid crystalline compound can usually be performed by applying the liquid crystalline compound to the alignment film. The alignment film is usually formed of a polymer compound having optical isotropy. Specifically, cellulose resin, polyimide, polyimide amide, polyether imide, polyester, polyarylate, polyvinyl alcohol, gelatin and the like can be mentioned. You may use these in combination of 2 or more types.

  When a discotic liquid crystal is used as the liquid crystalline compound, the discotic liquid crystal molecules are aligned substantially perpendicularly to the plane direction of the film or laminate (average tilt angle in the range of 50 to 90 degrees). Is preferred. For this purpose, the surface energy of the alignment film is lowered by the functional group of the polymer constituting the alignment film, thereby bringing the discotic liquid crystalline compound into a standing state. Preferred examples of the functional group that lowers the surface energy of the alignment film include fluorine atoms and hydrocarbon groups having 10 or more carbon atoms. In order to allow fluorine atoms or hydrocarbon groups to be present on the surface of the alignment film, it is preferable to introduce fluorine atoms or hydrocarbon groups into the side chain rather than the main chain of the polymer. The fluorine atom content of the polymer containing fluorine atoms is preferably 0.05 to 80% by weight, more preferably 0.5 to 65% by weight, and still more preferably 1 to 60% by weight. Examples of the hydrocarbon group include aliphatic groups, aromatic groups, and combinations thereof. The aliphatic group may be cyclic, branched or linear, but is preferably an alkyl group, a cycloalkyl group, an alkenyl group or a cycloalkenyl group. The number of carbon atoms of the hydrocarbon group is preferably 10 to 100, more preferably 10 to 50, still more preferably 10 to 40. The main chain of such a polymer preferably has a polyimide structure or a polyvinyl alcohol structure. Polyimide can generally be synthesized by a condensation reaction of tetracarboxylic acid and diamine. When introducing a hydrocarbon group into polyimide, it is preferable to form a steroid structure in the main chain or side chain of the polyimide. The steroid structure present in the side chain corresponds to a hydrocarbon group having 10 or more carbon atoms, and has a function of vertically aligning the discotic liquid crystalline compound. Examples of the polyvinyl alcohol include fluorine-modified polyvinyl alcohol containing a repeating unit containing a fluorine atom in a range of 5 to 80 mol, and modified polyvinyl alcohol having a hydrocarbon group having 10 or more carbon atoms.

In order to form an alignment film, the polymer compound is formed, and the alignment treatment is performed on the polymer film. A rubbing process is preferably used as the alignment process. The method for rubbing the polymer film is not particularly limited. For example, a method of imparting orientation to the surface of the polymer film by rubbing the surface of the polymer film in a predetermined direction (rubbing) using a cloth or roll such as rayon or nylon can be mentioned. Examples of the alignment treatment other than the rubbing treatment include a method of irradiating light such as linearly polarized ultraviolet light on the polymer film from a predetermined direction, a method of stretching the polymer film, and the like. In addition to the polymer film, an oblique deposition layer such as silicon oxide (SiO ₂ ) can be used as the alignment film. The thickness of the alignment film is usually 0.005 to 10 μm, preferably 0.01 to 1 μm.

  On an optical anisotropic body such as a quarter-wave plate or a half-wave plate, an alignment film that has been subjected to an alignment treatment in a direction in which the angle formed with the slow axis of the optical anisotropic body is 50 to 70 degrees. The liquid crystal compound fixed film (corresponding to a half-wave plate) whose retardation measured at a wavelength of 550 nm is 250 to 300 nm or the retardation measured at a wavelength of 550 nm is 125 to 150 nm. By forming a fixed film (corresponding to a quarter-wave plate) of a liquid crystal compound, an optical anisotropic body corresponding to a superposition of a quarter-wave plate and a half-wave plate can be obtained. . The direction of the alignment treatment intersects with the direction of the slow axis of the optical anisotropic body serving as the substrate in the range of 50 to 70 degrees, preferably 55 to 65 degrees, more preferably 58 to 62 degrees. . The liquid crystalline compound applied on the alignment film is aligned in a direction that coincides with the alignment direction of the alignment film. Therefore, by performing the alignment treatment at the angle as described above, a laminated body in which the slow axis of the optical anisotropic body of the substrate and the optical anisotropic body formed of the liquid crystalline compound intersect at a predetermined angle is obtained. be able to.

  The thickness of the optically anisotropic layer composed of the alignment-fixed film of the liquid crystal compound is not particularly limited, but provides a sufficient function as a quarter-wave plate that gives a quarter-wave retardation to incident light. Above, it is preferable that it is 0.5-50 micrometers normally. By setting the type of the liquid crystal compound immobilization film and the thickness of the liquid crystal compound immobilization film layer to a predetermined one, a quarter wavelength plate composed of the liquid crystal compound immobilization film layer can be obtained. it can.

  In order to form an optical anisotropic body composed of a fixed film of a liquid crystal compound, specifically, it can be carried out as follows. First, on the optical anisotropic body, an alignment film is formed that is aligned in a direction in which an angle formed between the extending direction of the optical anisotropic body and the slow axis of the optical anisotropic body is 50 to 70 degrees. Next, an organic solvent solution of a liquid crystalline compound is applied onto the alignment film of the optical anisotropic body, and the solvent is removed by heating. Next, the liquid crystalline compound can be aligned in a predetermined direction by cooling to a temperature at which the liquid crystalline compound is in a liquid crystal state. Further, when the liquid crystalline compound is polymerized or crosslinked by ultraviolet rays or heat, the liquid crystalline compound is polymerized or crosslinked by ultraviolet rays or heat in the presence of a polymerization initiator or a crosslinking agent in an environment where the liquid crystal state is maintained. A compound-immobilized film can be formed.

  The method of laminating a quarter-wave plate and a half-wave plate is a method of laminating a wave plate, such as a method of laminating with an adhesive, a method of laminating by thermal welding or ultrasonic fusion, or a coextrusion method. Although a method can be used, it is preferable to laminate using an adhesive in order to be able to be used in a wider wavelength region as a broadband wavelength plate and to have excellent durability.

  In the liquid crystal display device of the present invention, for the purpose of widening the viewing angle, in addition to the optical anisotropic body, other films having optical anisotropy are arranged in an arbitrary number and in arbitrary locations. Can do. Examples of the film having optical anisotropy include a uniaxial retardation film, a biaxial retardation film, and a laminate thereof. For example, examples of the uniaxial retardation plate include a C plate and an A plate.

  The C plate is a retardation layer having no retardation or very small in-plane retardation and having a retardation only in the thickness direction, and the optical axis exists in the thickness direction perpendicular to the in-plane direction. The A plate is a retardation layer having no or very small retardation in the thickness direction and having retardation only in the plane, and the optical axis exists in the in-plane direction.

  Examples of the biaxial retardation film include a positive biaxial retardation film (nz> nx> ny) and a negative biaxial retardation film (nx> ny> nz). As a retardation film having uniaxiality or a retardation film having biaxiality, a film obtained by stretching a film made of a material having a positive intrinsic birefringence value, a material having a negative intrinsic birefringence value such as a polystyrene resin, etc. A layered product in which layers made of a material having a positive intrinsic birefringence, such as norbornene-based resin, are stretched on both sides of the layer, or a discotic liquid crystal aligned in parallel or perpendicularly to the surface. Can be mentioned. The in-plane retardation Re of the birefringent layer and the retardation Rth in the direction perpendicular to the surface may be appropriately adjusted according to the liquid crystal mode to be used.

  In the liquid crystal display device of the present invention, an antireflection body is laminated on the surface on the opposite side (viewing side) to the optical anisotropic body of the exit side polarizer. This antireflection body has a low refractive index layer to be described later. The antireflection body may have a high refractive index layer between the exit side polarizer and the low refractive index layer. That is, the high refractive index layer and the low refractive index layer are provided in this order in the direction away from the liquid crystal cell (viewing side).

<Antireflection body>
(High refractive index layer)
The high refractive index layer is a layer provided between the exit side polarizer and the low refractive index layer as necessary. The high refractive index layer is a layer having a high surface hardness, and specifically, a layer having a hardness of “HB” or higher in a pencil hardness test specified in JIS K5600-5-4. The average thickness of the high refractive index layer is not particularly limited, but is usually 0.5 to 30 μm, preferably 3 to 15 μm. Examples of the material forming the high refractive index layer include organic materials such as silicone, melamine, epoxy, acrylic, and urethane acrylate; inorganic materials such as silicon dioxide; and the like. Among these, urethane acrylate-based and polyfunctional acrylate-based materials can be preferably used because of their high adhesive strength and excellent productivity.

  The high refractive index layer is a layer having a higher refractive index than the low refractive index layer described later, and the refractive index is preferably 1.55 or more, and more preferably 1.60 or more. When the refractive index of the high refractive index layer is such a value, there is an advantage that the antireflective performance and scratch resistance in a wide band are improved, and the design of the low refractive index layer laminated on the high refractive index layer becomes easy. . The refractive index can be determined using a known spectroscopic ellipsometer or the like.

  The high refractive index layer may further contain inorganic oxide particles. By adding inorganic oxide particles to the high refractive index layer, it is possible to easily form a high refractive index layer having excellent surface scratch resistance and a refractive index of 1.55 or more. As the inorganic oxide particles used for the high refractive index layer, those having a high refractive index are preferable, and specifically, those having a refractive index of 1.6 or more, particularly 1.6 to 2.3 are preferable. Examples of such inorganic oxide particles include titania (titanium oxide), zirconia (zirconium oxide), zinc oxide, tin oxide, cerium oxide, antimony pentoxide, antimony-doped tin oxide (ATO), and phosphorus dope. Tin oxide (PTO), fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), aluminum-doped zinc oxide (AZO), etc. be able to. Among these, antimony pentoxide is suitable as a component for adjusting the refractive index because it has a high refractive index and an excellent balance between conductivity and transparency.

  The high refractive index layer can be obtained by applying, drying, and curing the above material on the output side polarizer as the base material. Before applying the material, the surface of the substrate may be subjected to plasma treatment, primer treatment, or the like to increase the peel strength of the high refractive index layer. As a curing method, a thermal curing method and an ultraviolet curing method can be used. In addition, the base resin and the material for the high refractive index layer can be co-extruded to form a co-extruded film in which the base resin and the material are laminated. The surface of the high refractive index layer is preferably provided with an antiglare function. For example, the function can be realized by forming a convex shape on the surface.

(Low refractive index layer)
The low refractive index layer is a layer provided on the upper side (viewing side) of the output side polarizer or on the upper side of the high refractive index layer when a high refractive index layer is provided. The low refractive index layer is a layer having a refractive index of 1.40 or less, preferably 1.30 to 1.40, more preferably 1.35 to 1.40. In particular, the refractive index difference between the adjacent exit-side polarizer or high refractive index layer is preferably 0.05 to 0.4. By providing such a low refractive index layer, it is possible to obtain a liquid crystal display device that is excellent in balance between visibility, scratch resistance, and strength and excellent in balance between antireflection performance and scratch resistance. The thickness of the low refractive index layer is preferably 10 to 1000 nm, and more preferably 30 to 500 nm.

  Such a low refractive index layer comprises a hollow particle (A) having a particle size of 5 to 2000 nm, a siloxane oligomer (B) having a (meth) acryloyl group and a fluoroalkyl group, and an acrylate compound having a (meth) acryloyl group. It consists of a cured film formed from the composition for low refractive index layer formation containing (C). In the present invention, (meth) acryloyl means acryloyl and methacryloyl.

[Hollow particles (A)]
The hollow particles used in the present invention are particles having a hollow portion. The hollow particles (A) contained in the low refractive index layer of the present invention have a particle size in the range of 5 to 2000 nm, and preferably in the range of 20 to 100 nm. When the particle size of the hollow particles (A) is smaller than the above value, the refractive index of the low refractive index layer is not sufficiently small. Moreover, when the particle size of a hollow particle (A) exceeds the said value, transparency will deteriorate extremely and there exists a possibility that the contribution by diffuse reflection may become large. The particle size of the hollow particles is a number average particle size as observed with a transmission electron microscope.

  The hollow particles can be produced, for example, based on a method described in JP-A-2001-233611. Commercially available hollow particles may also be used. Although the compounding quantity of a hollow particle is not specifically limited, It is preferable that it is 10-30 weight% with respect to the whole composition for low-refractive-index layer formation using a compound (A)-(C). Within this range, both low refractive index properties and scratch resistance can be achieved.

In the hollow part of the hollow particles, there may be a solvent used when preparing the hollow particles and a gas that enters during drying. Moreover, the empty precursor substance mentioned later for forming the hollow part of a hollow particle may remain | survive in the hollow part. The precursor material is a porous material that remains after removing some of the constituent components of the core particles from the core particles surrounded by the outer shell. As the core particles, porous composite oxide particles made of different types of inorganic oxides are used. The precursor material may remain slightly attached to the outer shell or may occupy most of the interior of the cavity.
The solvent or gas may be present in the pores of the porous material. When the removal amount of the constituent components of the core particles at this time increases, the volume of the hollow portion increases, and hollow particles with a low refractive index are obtained. The transparent coating obtained by blending these hollow particles has a low refractive index and antireflection Excellent performance.

The hollow particles (A) are preferably inorganic hollow particles, particularly silica-based hollow particles. The inorganic compound constituting the inorganic hollow _{particles, SiO 2, Al 2 O 3} , B 2 O 3, TiO 2, ZrO 2, SnO 2, Ce 2 O 3, P 2 O 5, Sb 2 O 3, MoO 3 _{, ZnO 2, WO 3, TiO} 2 -Al 2 O 3, TiO 2 -ZrO 2, In 2 O 3 -SnO 2, Sb 2 O 3 -SnO 2 and the like can be exemplified. These can be used alone or in combination of two or more.

  The outer shell of the hollow particle (A) may be porous having pores, or may be one in which the outside of the pores are closed and the cavity is sealed. The outer shell preferably has a multilayer structure including an inner layer and an outer layer. The outer shell is preferably a plurality of inorganic oxide film layers including an inner first inorganic oxide film layer and an outer second inorganic oxide film layer. By providing the second inorganic oxide coating layer on the outer side, the outer shell can be densified by closing the pores of the outer shell, and hollow particles in which the inner cavity is sealed can be obtained. The thickness of the outer shell of the hollow particles (A) is usually 1 to 50 nm, preferably 5 to 20 nm. The thickness of the outer shell of the hollow particles (A) is preferably in the range of 1/50 to 1/5 of the average particle diameter of the hollow particles.

  When the first inorganic oxide coating layer and the second inorganic oxide coating layer are provided as outer shells as described above, the total thickness of these layers is preferably in the range of 1 to 50 nm. In the formed outer shell, the thickness of the second inorganic oxide coating layer is preferably in the range of 20 to 40 nm.

  Moreover, in order to improve the bonding property with the siloxane oligomer (B) or the acrylate compound (C), the hollow particles are formed on the surface of the hollow particles by a method of reacting the hollow particles with a surfactant or a coupling agent. Hydrophilic groups such as hydroxyl groups and acryloyl groups may be introduced. As the surfactant or coupling agent, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecyl Examples thereof include fluorine-containing organosilicon compounds such as trichlorosilane, heptadecafluorodecyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane.

[Siloxane oligomer (B)]
The siloxane oligomer (B) contained in the low refractive index layer of the present invention has a (meth) acryloyl group and a fluoroalkyl group. The siloxane oligomer (B) includes a compound (b-1) having a (meth) acryloyl group, a fluorine compound (b-2) having a fluoroalkyl group, a general formula X _j SiY _4-j (where X is Represents a monovalent hydrocarbon group which may have a substituent, j represents an integer of 0 to 2, and when j is 2, X may be the same or different. It is preferably a condensate with a silane compound (b-3) having a hydrolyzable group represented by a hydrolyzable group, and Y may be the same or different.

(B-1) Compound having (meth) acryloyl group As the compound (b-1) having (meth) acryloyl group, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl ( Examples thereof include alkyl (meth) acrylates such as (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, and 2-ethylhexyl methacrylate, and organosilanes having a (meth) acryloyl group. Examples of the organosilane having the (meth) acryloyl group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxymethyltrimethoxysilane, 3-methacrylic Loxymethyltriethoxysilane, 3-methacryloxymethylmethyldimethoxysilane, 3-methacryloxymethylmethyldiethoxysilane, 3-acryloxymethyltrimethoxysilane, 3- Examples include acryloxymethyltriethoxysilane, 3-acryloxymethylmethyldimethoxysilane, and 3-acryloxymethylmethyldiethoxysilane. Among these, in terms of handleability, crosslinking density, reactivity, etc., 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropylmethyldimethoxysilane are preferred.

(B-2) Fluorine compound having a fluoroalkyl group As the fluorine compound (b-2) having a fluoroalkyl group, a condensate of a silane compound having a fluoroalkyl group, a monomer having a fluoroalkyl group, and this Examples thereof include a copolymer with a copolymerizable monomer.

  As the condensate of the silane compound having a fluoroalkyl group, it is preferable to use perfluoroalkylalkoxysilane from the viewpoint that a siloxane oligomer can be easily formed by a sol-gel reaction.

Examples of the perfluoroalkylalkoxysilane include, for example, the general formula (2): CF ₃ (CF ₂ ) _n CH ₂ CH ₂ Si (OR ′) ₃ (wherein R ′ is an alkyl having 1 to 5 carbon atoms. And n represents an integer of 0 to 12). Specifically, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane And so on. Among these, the compound whose said n is 2-6 is preferable. These compounds can be used alone or in combination of two or more.

  Examples of the monomer having a fluoroalkyl group include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, and 3,3,3-trifluoropropylene; perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether); Perfluoro (alkyl vinyl ethers) such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); perfluoro (alkoxyalkyl) such as perfluoro (propoxypropyl vinyl ether) Vinyl ethers); other examples. These can be used alone or in combination of two or more.

  Examples of the monomer copolymerizable with the monomer having a fluoroalkyl group include vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether and allyl vinyl ether, vinyl ester compounds such as vinyl acetate and vinyl butyrate, methyl (meth) acrylate, (Meth) acrylate compounds such as ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, styrene compounds such as styrene and p-hydroxymethylstyrene, unsaturated carboxylic acid compounds such as crotonic acid, maleic acid and itaconic acid, and These derivatives can be mentioned.

In (b-3) formula _X j _SiY silane compound having a hydrolyzable group represented by _4-j Formula _X j _SiY silane compound having a hydrolyzable group represented by _4-j, wherein X is The monovalent hydrocarbon group which may have a substituent is represented. Examples of the monovalent hydrocarbon group which may have a substituent include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group; cyclopentyl group and cyclohexyl group A cycloalkyl group such as a phenyl group, a 4-methylphenyl group, an 1-naphthyl group, an aryl group which may have a substituent such as a 2-naphthyl group; an alkenyl group such as a vinyl group or an allyl group; a benzyl group; Aralkyl groups such as phenethyl group and 3-phenylpropyl group; haloalkyl groups such as chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group; alkenylcarbonyloxyalkyl such as γ-methacryloxypropyl group Group: alkyl group having an epoxy group such as γ-glycidoxypropyl group or 3,4-epoxycyclohexylethyl group; γ-mercap It can be mentioned perfluoroalkyl group such as trifluoromethyl group or the like; alkyl groups having an amino group such as 3-aminopropyl group; an alkyl group having a mercapto group and propyl group. Among these, an alkyl group having 1 to 4 carbon atoms, a phenyl group, and a perfluoroalkyl group are preferable from the viewpoint of easy synthesis and availability.

Y represents a hydrolyzable group. The hydrolyzable group is a group that is hydrolyzed in the presence of an acid or a base catalyst as desired to give a — (O—Si) —O— bond. Specific examples of the hydrolyzable group include alkoxyl groups such as methoxy group, ethoxy group and propoxy group; acyloxy groups such as acetoxy group and propionyloxy group; oxime group (—O—N═C—R ¹ (R ² ) ), Enoxy group (—O—C (R ¹ ) = C (R ² ) R ³ ), amino group, aminoxy group (—O—N (R ¹ ) R ² ), amide group (—N (R ¹ )) -C (= O) -R ^2), and the like. In these groups, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent hydrocarbon group. Among these, as Y, an alkoxyl group is preferable from the viewpoint of availability.

The general formula _X j _{SiY 4-j} with a silane compound expressed (b-3), a silicon compound wherein j is an integer of 0 to 2 is preferred. Specific examples thereof include alkoxysilanes, acetoxysilanes, oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are more preferable from the viewpoint of availability.

  Examples of the tetraalkoxysilane in which j is 0 include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane in which j is 1 include methyltrimethoxysilane, methyltriethoxysilane, and methyltriisosilane. Examples include propoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane and the like. Examples of the diorganodialkoxysilane in which j is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.

  Although the compounding quantity of a siloxane oligomer (B) is not specifically limited, It is preferable that it is 3-90 weight% with respect to the whole composition for low refractive index layer formation, and it is more preferable that it is 5-80 weight%. Preferably, it is 10 to 60% by weight. When it is less than 3% by weight, the refractive index of the low refractive index layer becomes high, and there is a possibility that sufficient antireflection effect cannot be obtained. Moreover, when it exceeds 90 weight%, there exists a possibility that the abrasion resistance of a low refractive index layer may not be acquired.

  Although there is no restriction | limiting in particular about the molecular weight of a siloxane oligomer (B), It is preferable that the number average molecular weight by polystyrene conversion measured with the gel permeation chromatograph using a cyclohexane as a solvent is 5000 or more.

  As a method for obtaining the siloxane oligomer (B), the compound (b-1) having the (meth) acryloyl group, the fluorine compound (b-2) having the fluoroalkyl group, and the silane compound (b-3). Can be obtained by condensation. In this condensation, the ratio of each reaction component is not particularly limited, but the molar ratio of the compound (b-1) / the compound (b-2) / the compound (b-3) is 5 to 70/30 to 70. It is preferable to mix | blend so that it may become / 1-50 mol%. Further, in the condensation, each compound may be heated in an alcohol solvent (for example, methanol, ethanol, etc.) in the presence of an organic acid (for example, oxalic acid) or an ester.

[Acrylate compound (C)]
The acrylate compound (C) contained in the low refractive index layer of the present invention has a (meth) acryloyl group. From the viewpoint of effectively increasing the hardness of the antireflective body, the acrylate compound (C) preferably does not contain a fluorine atom and has two or more (meth) acryloyl groups. Such compounds include neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone Examples include modified dipentaerythritol hexa (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate. Kill. These can be used alone or in combination of two or more.

  The acrylate compound (C) may contain a fluorine atom from the viewpoint of effectively reducing the refractive index of the low refractive index layer. Examples of acrylate compounds containing fluorine atoms include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (perfluorobutyl) ethyl. (Meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 2- (Perfluorooctyl) ethyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (Meth) acrylate, 3- (par Fluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl ( (Meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate, 1H, 1H, 3H-tetrafluoro Propyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H -1- (trifluoromethyl) Lifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8, Mention may be made of 9,9-hexadecafluoro-1,10-decandiol-diepoxy (meth) acrylate. These can be used alone or in combination of two or more.

  Although the compounding quantity of an acrylate compound (C) is not specifically limited, It is preferable that it is 5-90 weight% with respect to the whole composition for low refractive index layer formation, and it is more preferable that it is 10-80 weight%. Preferably, it is 15 to 60% by weight. In the case of the above range, the scratch resistance of the low refractive index layer is good, the refractive index of the low refractive index layer is in an appropriate range, and a sufficient antireflection effect is obtained.

  The low refractive index layer of the present invention comprises a composition for forming a low refractive index layer containing the hollow particles (A), the siloxane oligomer (B), and the acrylate compound (C). It can be obtained by coating it on another layer such as a high refractive index layer or the like and then drying and curing it by ionizing radiation and / or heating.

  The composition for forming a low refractive index layer includes the hollow particles (A), the siloxane oligomer (B), and the organic solvent that does not decompose the acrylate compound (C), the (A), (B), and (C) can be mixed and adjusted. Examples of such organic solvents include alcohols such as isopropyl alcohol, methanol, and ethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; toluene, xylene, and the like Or aromatic hydrocarbons thereof; or mixtures thereof. The mixing ratio of the organic solvent and the (A), (B), and (C) is not particularly limited, but when the above (A), (B), and (C) are summed in the coating liquid The concentration of is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight.

  In the composition for forming a low refractive index layer, a polymerization initiator (photo radical initiator or thermal radical initiator) for polymerizing the (A), (B), and (C) in a coating solution. Further, a curing agent, a crosslinking agent, an ultraviolet blocking agent, an ultraviolet absorber, a surface conditioner (leveling agent), or other components may be contained.

The method for applying the composition for forming a low refractive index layer is not particularly limited. Examples of the curing method include heating and actinic ray irradiation. Drying conditions and curing conditions can be appropriately determined according to the type of solvent used, such as boiling point and saturated vapor pressure. In particular, in order to suppress the other layers to be coated from being colored or decomposed, when heating, it is preferable to heat at a temperature in the range of 50 to 150 ° C. for 1 to 180 minutes, More preferably, heating is performed at a temperature in the range of 75 to 105 ° C. for 5 to 60 minutes. Moreover, when irradiating actinic light, an ultraviolet-ray etc. can be used. At this time, the irradiation energy is preferably from 50 to 500 mJ / cm ^2, more preferably 100~450mJ / cm ^2, further preferably 200 to 400 mJ / cm ^2.

  The composition for forming a low refractive index layer for forming the low refractive index layer of the present invention may contain a crosslinkable compound. Examples of the crosslinkable compound include melamine resins, glycols, acrylic resins, azides, and isocyanates. Among these, from the viewpoint of the storage stability of the compound constituting the low refractive index layer, melamine resins such as methylolated melamine, alkoxymethylated melamine or derivatives thereof are preferable. The use ratio of the crosslinkable compound is preferably 70 parts by weight or less, more preferably 30 parts by weight or less, more preferably 100 parts by weight or less with respect to 100 parts by weight of the total of (A), (B) and (C). Preferably it is 5-30 weight part.

  Moreover, in order to improve the antifouling property of the low refractive index layer, an antifouling layer may be further provided on the viewing side of the low refractive index layer. As a material for forming the antifouling layer, usually, a compound having a hydrophobic group can be preferably used. Specifically, a perfluoroalkylsilane compound, a perfluoropolyethersilane compound, or a fluorine-containing silicone compound can be used. As the method for forming the antifouling layer, for example, a physical vapor deposition method such as vapor deposition or sputtering; a chemical vapor deposition method such as CVD; a wet coating method; The thickness of the antifouling layer is not particularly limited, but is usually preferably 20 nm or less, and more preferably 1 to 10 nm.

  In the antireflection body of the present invention, the maximum reflectance of light with an incident angle of 5 degrees and a wavelength of 430 nm to 700 nm from the viewing side is usually 2.0% or less. The reflectance at a wavelength of 550 nm at an incident angle of 5 degrees is usually 1.0% or less. Moreover, the maximum value of the reflectance at a wavelength of 430 nm to 700 nm at an incident angle of 20 degrees is usually 2.0% or less. The reflectance at an incident angle of 20 degrees and a wavelength of 550 nm is usually 1.0% or less. When each reflectance is in the above range, a liquid crystal display device having excellent visibility without reflection of external light and glare can be obtained. The reflectance can be measured using, for example, a spectrophotometer (ultraviolet visible near infrared spectrophotometer V-550, manufactured by JASCO Corporation).

In addition, the antireflection body has a reflectance variation of 20% or less, preferably 10% or less, before and after the steel wool test. If the variation in reflectance exceeds 20%, the screen may be blurred or glaring. The steel wool test is a test in which the surface of the low refractive index layer is rubbed back and forth 10 times with a load of 0.025 MPa applied to steel wool # 0000. The reflectance is measured five times at five arbitrary locations in the plane, and is calculated from the arithmetic average value of these measured values. The change in reflectance before and after the steel wool test was determined by the following formula. Rb represents the reflectance before the steel wool test, and Ra represents the reflectance after the steel wool test.
ΔR = (Rb−Ra) / Rb × 100 (%) (i)

Similarly, the fluctuation of the total light transmittance before and after the steel wool test is usually within 10%, preferably within 8%, more preferably within 6%. The total light transmittance is measured five times at five locations in the plane, and is calculated from the arithmetic average value of these measured values. The fluctuation of the total light transmittance before and after the steel wool test was determined by the following formula. Rc represents the total light transmittance before the steel wool test, and Rd represents the total light transmittance after the steel wool test.
ΔR = (Rc−Rd) / Rc × 100 (%) (ii)

  In the liquid crystal display device of the present invention, in addition to the exit side polarizer, the entrance side polarizer, the optical anisotropic body, the liquid crystal cell, and the antireflection body, other films or layers may be provided, for example, A prism array sheet, a lens array sheet, a light diffusing plate, a light guide plate, a diffusing sheet, a brightness enhancement film, and the like can be arranged in one or more layers at appropriate positions. In the liquid crystal display device of the present invention, a cold cathode tube, a mercury flat lamp, a light emitting diode, electroluminescence, or the like can be used as a backlight.

Here, an outline of the configuration of the transflective liquid crystal display device will be described.
FIG. 1 is a schematic view showing a transflective liquid crystal display device according to the present invention. In FIG. 1, the transflective liquid crystal display device includes a backlight and light guide plate 21, a polarizing plate 20 disposed above the backlight and light guiding plate 21, and a first optical difference disposed above the polarizing plate 20. A rectangular parallelepiped, a semi-transmissive liquid crystal cell disposed above the first optical anisotropic body, a second optical anisotropic body disposed above the semi-transmissive liquid crystal cell, and the second optical anisotropic body The polarizing plate 12 disposed on the upper side of the polarizing plate 12 and the antireflection body 10 disposed on the upper side of the polarizing plate 12 are provided.

  The first optical anisotropic body includes a half-wave plate 19 disposed above the polarizing plate 20 and a quarter-wave plate 18 disposed above the half-wave plate 19. The half-wave plate 19 and the quarter-wave plate 18 have their slow axes intersecting at an angle of about 60 °. The transflective liquid crystal cell includes a transparent electrode 17, a liquid crystal layer 16, and a transparent electrode 15, each having a reflective function, in order from the first optical anisotropic body side. The second optical anisotropic body includes a quarter-wave plate 14 and a half-wave plate 13. The half-wave plate 13 and the quarter-wave plate 14 intersect with the slow axis at an angle of about 60 °. Although illustration is omitted, the antireflective body 10 includes, for example, a high refractive index layer provided on the upper side of the polarizing plate 12 and a low refractive index layer stacked on the high refractive index layer.

Next, an outline of the configuration of the reflective liquid crystal display device will be described.
FIG. 2 is a schematic view showing a reflective liquid crystal display device according to the present invention. In FIG. 2, the reflective liquid crystal display device includes a reflective plate 37, a reflective liquid crystal cell disposed above the reflective plate 37, an optical anisotropic body disposed above the reflective liquid crystal cell, and an optical anisotropic material. A polarizing plate 32 disposed on the upper side of the rectangular parallelepiped and an antireflection body 31 disposed on the upper side of the polarizing plate 32 are provided.

  The reflective liquid crystal cell includes a liquid crystal layer 36, a transparent electrode 35, and a transparent electrode provided on the reflecting plate 37 side. The optical anisotropic body includes a quarter-wave plate 34 and a half-wave plate 33 provided above the quarter-wave plate 34. The half-wave plate 33 and the quarter-wave plate 34 intersect with the slow axis at an angle of about 60 °. Although illustration is omitted, the antireflection body 31 includes, for example, a high refractive index layer provided on the upper side of the polarizing plate 32 and a low refractive index layer laminated on the high refractive index layer. In the case of performing color display, a color filter layer is further provided on the upper side of the liquid crystal cell.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples. Parts and% are based on weight unless otherwise specified. Measurements and evaluations performed in Examples and Comparative Examples are as follows.

(1) Thickness After embedding the target laminate in an epoxy resin, slice it to a thickness of 0.05 μm using a microtome (Daiwa Kogyo Co., Ltd., RUB-2100), and cross section using a transmission electron microscope. The laminate was measured for each layer.

(2) Main refractive index Using an automatic birefringence meter (Oji Scientific Instruments Co., Ltd., KOBRA-21), an optical anisotropic body at a wavelength of 550 nm under a temperature of 20 ° C. ± 2 ° C. and a humidity of 60 ± 5%. The direction of the in-plane slow axis was determined, and the refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction were measured.

(3) Retardation Using a high-speed spectroscopic ellipsometer (JA Woollam, M-2000U), the measurement was performed under conditions of a temperature of 20 ° C. ± 2 ° C. and a humidity of 60 ± 5%.

(4) Reflectance Using a spectrophotometer (manufactured by JASCO Corporation: “UV-visible near-infrared spectrophotometer V-570”), the reflection spectrum was measured at an incident angle of 5 degrees, and the maximum value at a wavelength of 430 to 700 nm, And the reflectance in wavelength 550nm was calculated | required.

(5) Refractive Index of Low Refractive Index Layer and High Refractive Index Layer High-speed spectroscopic ellipsometry (manufactured by JA Woollam, M-2000U) under conditions of temperature 20 ° C. ± 2 ° C. and humidity 60 ± 5% And calculated from the spectrum in the wavelength region of 400 to 1000 nm when the incident angles were measured at 55, 60, and 65 degrees, respectively.

(6) Scratch resistance The surface was reciprocated 10 times in a state where a load of 0.025 MPa was applied to steel wool # 0000, and the surface state after the test was visually observed.
○: Scratch is not recognized ×: Scratch is recognized

(7) Visibility The panel with black display was visually observed and evaluated in two stages.
○: No glare or reflection is seen ×: Glare or reflection is seen

(8) Broadband property The liquid crystal display panel was installed in an environment with an ambient brightness of 500 lux, and the reflected color was visually observed.
○: Reflection color is black ×: Reflection color is blue

(9) Contrast ratio The liquid crystal display panel is installed in an environment with an ambient brightness of 500 lux, and the brightness at a position of 5 degrees from the front during dark display and bright display is colored using a transmissive mode liquid crystal display device. It measured using the luminance meter (The Topcon company make, color luminance meter BM-7). Then, the ratio between the brightness of the bright display and the brightness of the dark display (= the brightness of the bright display / the brightness of the dark display) was calculated, and this was used as the contrast (CR). The greater the contrast (CR), the better the visibility.

(10) Display Evaluation of Reflective Display Device A rectangular wave voltage of 1 kHz was applied to each of the manufactured reflective liquid crystal display devices. Visual evaluation was performed with a white display of 0 V and a black display of 4.5 V.

(11) Antifouling property When a magic ink (trade name: McKee, manufactured by ZEBRA) is attached to the surface of the low refractive index layer, and then wiped with a cellulose nonwoven fabric (trade name: Bencott M-3, manufactured by Asahi Kasei). The state of was visually determined.
○: Can be wiped off completely X: Wipe marks remain

(Production Example 1) Production of raw film 1 A pellet of a norbornene-based polymer (trade name: ZEONOR 1420R, manufactured by Nippon Zeon Co., Ltd., glass transition temperature: 136 ° C., saturated water absorption: less than 0.01% by weight) For 4 hours at 110 ° C. Next, a short shaft having a coat hanger type T-die having an average surface roughness Ra = 0.04 μm and a lip width of 650 mm, in which a leaf disk-shaped polymer filter (filtration accuracy of 30 μm) is installed and the tip of the die lip is chrome-plated Using an extruder, the pellets were melt extruded at 260 ° C. to obtain a raw film 1 having a thickness of 100 μm and a width of 600 mm. The retardation value Re (550) was 3 nm.

(Production Example 2) Production of raw film 2 Layer (II layer) made of norbornene polymer used in Production Example 1, styrene-maleic acid copolymer (manufactured by Nova Chemical Co., Ltd., trade name “Daylark D332”, A layer (I layer) composed of a glass transition temperature of 130 ° C. and an oligomer component content of 3% by weight, and a modified ethylene-vinyl acetate copolymer (manufactured by Mitsubishi Chemical Co., Ltd., trade name “Modic AP A543”, Vicat softening point 80 Of the unstretched laminate of layer II (30 μm) -III layer (6 μm) -I layer (150 μm) -III layer (6 μm) -II layer (30 μm) having an adhesive layer (III layer) consisting of The anti-film 2 was obtained by coextrusion molding.

Production Example 3 Preparation of High Refractive Index Layer Composition H1 Hexafunctional urethane acrylate oligomer (trade name: NK Oligo U-6HA, Shin-Nakamura Chemical Co., Ltd.) 30 parts, butyl acrylate 40 parts, isoboronyl methacrylate ( Product name: NK Ester IB (manufactured by Shin-Nakamura Chemical Co., Ltd.) 30 parts, 5 parts of styrene beads (particle size 3.5 μm), 10 parts of 2,2-diphenylethane-1-one were mixed with a homogenizer, and antimony pentoxide fine particles A 40 wt% MIBK solution (average particle size 20 nm: hydroxyl groups are bonded to the antimony atoms appearing on the surface of the pyrochlore structure at a ratio of 1), and the weight of the antimony pentoxide fine particles is used for forming a high refractive index layer. The composition H1 for forming a high refractive index layer was prepared by mixing at a ratio of 50% by weight of the total solid content of the coating solution.

(Production Example 4) Preparation of composition L1 for forming a low refractive index layer By adding 200 parts of ethanol to a four-necked reaction flask equipped with a reflux tube and adding 120 parts of oxalic acid to this ethanol in small amounts. An ethanol solution of oxalic acid was prepared. Then, this solution was heated to its reflux temperature, and 50 parts of hepadecafluorooctylethyltrimethoxysilane as compound (b-2) and compound (3-acryloxy as b-1) were added to this solution under reflux. A mixture of 50 parts of propyltrimethoxysilane and 10 parts of tetramethoxysilane as compound (b-3) was added dropwise, and after completion of the addition, heating was continued for 5 hours under reflux, followed by cooling.

  Next, 20 parts of dipentaerythritol hexaacrylate as the acrylate compound (C), 5 parts of 2-hydroxy-2-methyl-1-phenylpropan-1-one as a polymerization initiator, and a particle size of 5 parts Hollow silica isopropanol dispersion sol as a hollow particle of 2000 nm (catalyst chemical industry, solid content 20 wt%, average primary particle diameter of about 35 nm, outer shell thickness of about 8 nm), hollow particle ratio of 70 wt. % Was added to the solution, and diluted with methanol so that the solid content was 1% by weight, to prepare a composition L1 for forming a low refractive index layer.

Production Example 5 Preparation of Low Refractive Index Layer Composition L2 Production Example 4 except that 20 parts of 3- (perfluorooctyl) ethyl acrylate, which is a fluorinated acrylate compound, was used instead of dipentaerythritol hexaacrylate. In the same manner as above, a composition L2 for forming a low refractive index layer was prepared.

(Manufacture example 6) Preparation of composition L3 for low-refractive-index layer formation Except having used 60 parts of tetramethoxysilane as a siloxane oligomer which does not have a fluoroalkyl group instead of 50 parts of heptadecafluorooctylethyltrimethoxysilane. In the same manner as in Production Example 4, a composition L3 for forming a low refractive index layer was prepared.

(Production Example 7) Preparation of composition L4 for forming a low refractive index layer 412 parts of methanol was added to 152 parts of tetramethoxysilane, 18 parts of water and 18 parts of 0.01N hydrochloric acid were mixed, and this was used with a disper. And mixed well. The mixture was stirred for 2 hours in a constant temperature bath at 25 ° C., and the weight average molecular weight was adjusted to 850 to obtain a silicone resin. Next, to this silicone resin solution, silica methanol sol (manufactured by Nissan Chemical Industries, Ltd., PMA-ST, average particle size 10 to 20 nm) / silicone resin (condensed compound equivalent) is 80/20 in weight ratio based on solid content. And diluted with methanol so that the total solid content is 3%, to prepare a composition L4 for forming a low refractive index layer.

(Production Example 8) Production of Polarizer A PVA film (Kuraray Vinylon # 7500) having a thickness of 75 μm was mounted on a chuck, and 240 seconds at 30 ° C. in an aqueous solution containing 0.2 g / l iodine and 60 g / l potassium iodide. It was immersed, and then immersed in an aqueous solution having a composition of boric acid 70 g / l and potassium iodide 30 g / l, and simultaneously boric acid treatment was performed for 5 minutes while uniaxially stretching 6.0 times. Finally, it was dried at room temperature for 24 hours to obtain a polarizer. The degree of polarization was 99.993%.

(Production Example 9) Production of Polarizer P One side of a triacetyl cellulose film (KC8UX2M) manufactured by Konica Minolta Co., Ltd. was applied with 25 ml / m ^{2 of} an isopropyl alcohol solution of 1.5 N potassium hydroxide, and 5 at 25 ° C. Dry for 2 seconds. The surface of the film was dried by washing with running water for 10 seconds and blowing air at 25 ° C. In this way, only one surface of the triacetylcellulose film was saponified. The surface of the saponified film is laminated on one side of the polarizer obtained in Production Example 8 by using a roll-to-roll method using a polyvinyl alcohol-based adhesive, and triacetylcellulose is applied to the incident side of the polarizer. Films were laminated to obtain a polarizer P.

(Production Example 10) Production of optical anisotropic bodies C1, C2 and C3 The raw film 1 obtained in Production Example 1 was subjected to oven temperature (preheating temperature, stretching temperature, heat setting temperature) 140 ° C. using a stretching machine. Stretching was performed at a stretching speed of 6 m / min and a longitudinal stretching ratio of 1.5 times and 1.3 times to obtain optical anisotropic bodies C1 and C2, respectively. The retardation values [Re (550)] at a wavelength of 550 nm of the obtained optical anisotropic bodies C1 and C2 were 265 nm and 132.5 nm, respectively. On one side of the optical anisotropic body C1, the optical anisotropic body C2 is passed through an acrylic adhesive (Sumitomo 3M, DP-8005 clear) so that the crossing angle of each slow axis is 59 °. As a result, a bonded optically anisotropic body C3 was obtained. The ratio Re (450) / Re (550) of Re (550) of this optical anisotropic body C3 to the retardation value Re (450) at a wavelength of 450 nm was 1.005.

(Production Example 11) Production of optical anisotropic bodies C4 and C5 Using a tenter stretching machine, the raw film 2 was stretched at a temperature of 138 ° C, a stretching ratio of 1.5 times, and a stretching speed of 115% / min with respect to the width direction. Then, the film was obliquely stretched in the −13 ° direction, and was rolled up over 3000 m to obtain an optical anisotropic body C4. The retardation Re (550) at a wavelength of 550 nm of the obtained optical anisotropic body C4 was measured, and it was 137.2 nm. On one side of the optical anisotropic body C4, the optical anisotropic body C1 obtained in Production Example 10 is crossed with each slow axis via an acrylic adhesive (DP-8005 clear, manufactured by Sumitomo 3M Limited). A bonded optically anisotropic body C5 was obtained so that the angle was 59 °. Re (450) / Re (550) of the optical anisotropic body C5 was 0.81.

(Production Example 12) Production of optical anisotropic bodies C6, C7 and C8 The raw film 1 obtained in Production Example 1 was subjected to oven temperature (preheating temperature, stretching temperature, heat setting temperature) 170 ° C. using a stretching machine. Stretching was performed at a film feed speed of 6 m / min and a longitudinal stretching ratio of 1.75 times and 1.45 times to obtain optical anisotropic bodies C6 and C7, respectively. The retardation values Re (550) of the obtained optical anisotropic bodies C6 and C7 at a wavelength of 550 nm were 265 nm and 132.5 nm, respectively. On one side of the optical anisotropic body C6, the optical anisotropic body C7 is passed through an acrylic adhesive (manufactured by Sumitomo 3M, DP-8005 clear) so that the crossing angle of each slow axis is 59 °. Thus, an optically anisotropic body C8 was obtained. Re (450) / Re (550) of this optical anisotropic body C8 was 1.010.

Production Example 13 Production of Polarizing Plate with Low Refractive Index Layer (TAC Substrate) On one side of a Konica Minolta Triacetyl Cellulose Film (KC8UX2M) m ^{2 was} applied and dried at 25 ° C. for 5 seconds. The surface of the film was dried by washing with running water for 10 seconds and blowing air at 25 ° C. In this way, only one surface of the triacetylcellulose film was saponified. On the other side, a double-sided substrate film having a surface tension of 0.055 N / m is obtained by performing a corona discharge treatment with an output of 0.8 kW using a high-frequency transmitter (high-frequency power supply AGI-024 manufactured by Kasuga Electric Co., Ltd.). Obtained.

Next, the composition H1 for forming a high refractive index layer obtained in Production Example 3 was applied to the surface of the base film that had been subjected to corona discharge treatment using a die coater, and was then dried in an oven at 80 ° C. And dried for 5 minutes to obtain a film. Then, the laminated film 1A which irradiated with the ultraviolet-ray (integrated irradiation amount 300mJ / cm < ₂ >) and laminated | stacked the high refractive index layer of thickness 5 micrometers was obtained. The refractive index of the high refractive index layer was 1.62, and the pencil hardness was 2H.
The low refractive index layer-forming composition L1 obtained in Production Example 4 is applied to the laminated film 1A on the high refractive index layer side using a wire bar coater, and left to stand for 1 hour to dry. Was heat-treated in an oxygen atmosphere at 120 ° C. for 10 minutes to obtain a substrate with a low refractive index layer (TAC substrate) in which a low refractive index layer having a thickness of 100 nm was laminated. Roll-to-roll using a polyvinyl alcohol-based adhesive so that the saponified surface of the obtained base material with a low refractive index layer (TAC base material) overlaps one side of the polarizer obtained in Production Example 8. By laminating by the method, a polarizing plate with a low refractive index layer (TAC substrate) 2A was obtained.

(Production Example 14) Production of Polarizing Plate with Low Refractive Index Layer (COP Base Material) On both sides of the raw film obtained in Production Example 1, a high frequency transmitter (high frequency power supply AGI-024 manufactured by Kasuga Denki Co., Ltd.) was used. Corona discharge treatment was performed at an output of 0.8 KW to obtain a base film having a surface tension of 0.072 N / m. Next, the high refractive index layer-forming composition H1 obtained in Production Example 3 was applied to one side of the base film using a die coater, and dried in an oven at 80 ° C. for 5 minutes. A coating was obtained. Then, the laminated film 1B which irradiated with the ultraviolet-ray (integrated irradiation amount 300mJ / cm < ₂ >) and laminated | stacked the high refractive index layer of thickness 5 micrometers was obtained. The refractive index of the high refractive index layer was 1.62, and the pencil hardness was H.

  On the high refractive index layer side of the laminated film 1B, the low refractive index layer-forming composition L1 obtained in Production Example 4 was applied with a wire bar coater, and allowed to stand for 1 hour to dry. Was heat-treated at 120 ° C. for 10 minutes in an oxygen atmosphere to obtain a substrate with a low refractive index layer (COP substrate) in which a low refractive index layer having a thickness of 100 nm was laminated. Acrylic adhesive so that the surface of the obtained low refractive index layer-attached base material (COP base material) on which the low refractive index layer is not laminated overlaps with one side of the polarizer obtained in Production Example 8. Were bonded together by a roll-to-roll method to obtain a polarizing plate with a low refractive index layer (COP substrate) 2C.

(Production Example 15) Manufacture of observer-side polarizing plate PO1 The optically anisotropic body C3 obtained in Production Example 10 and the polarizing plate 2A with a low refractive index layer obtained in Production Example 13 are combined with the polarizing plate with a low refractive index layer. The crossing angle between the transmission axis of the plate 2A and the slow axis of the optical anisotropic body C1 laminated on the optical anisotropic body C3 is 15 °, and the C1 side of the optical anisotropic body C3 and the polarized light with a low refractive index layer The observer side polarizing plate PO1 was prepared by stacking so that the polarizer side of the plate 2A was in contact therewith.

(Production Example 16) Production of backlight-side polarizing plate PB1 The optical anisotropic body C3 obtained in Production Example 10 and the polarizer P obtained in Production Example 9 were combined with the transmission axis of the polarizer P and the optical anisotropic body. The optically anisotropic body C1 laminated on C3 is laminated so that the crossing angle of the slow axis is 15 °, and the C1 side of the optical anisotropic body C3 and the polarizer side of the polarizer P are in contact with each other. A side polarizing plate PB1 was produced.

Example 1 Fabrication of Liquid Crystal Display Device 1 The TN mode liquid crystal cell used in the liquid crystal display device 1 has a pretilt angle of 2 degrees on the both interfaces of the substrate, a twist angle of 70 degrees to the left twist, and Δnd of 230 nm in the reflective display portion. The transmissive display portion is approximately 262 nm. The liquid crystal film thickness was 3.5 μm in the reflective electrode region (reflective display portion) and 4.0 μm in the transparent electrode region (transmissive display portion). The observer-side polarizing plate PO1 obtained in Production Example 15, the liquid crystal cell, and the backlight-side polarizing plate PB1 obtained in Production Example 16 were laminated in this order, and then the backlight-side polarizing plate PB1. A diffusion sheet, a light guide plate, and a backlight were assembled in this order so as to be in contact with each other, and the liquid crystal display device 1 was produced. The evaluation results of the manufactured liquid crystal display device 1 are shown in Table 1.

(Example 2) Production of liquid crystal display device 2 In Production Example 13, instead of the composition L1 for forming a low refractive index layer, the composition L2 for forming a low refractive index layer obtained in Production Example 5 was used. Then, a polarizing plate with a low refractive index layer (TAC substrate) 2B was obtained in the same manner as in Production Example 13. Subsequently, in place of the polarizing plate 2A with a low refractive index layer in Production Example 15, a polarizing plate PO2 on the observer side in the same manner as in Production Example 15 except that a polarizing plate with a low refractive index layer (TAC substrate) 2B was used. Got. Further, in Example 1, a liquid crystal display device 2 was produced in the same manner as in Example 1 except that the observer side polarizing plate PO2 was used instead of the observer side polarizing plate PO1. The evaluation results of the manufactured liquid crystal display device 2 are shown in Table 1.

(Example 3) Production of liquid crystal display device 3 In Production Example 15, the polarizing plate with a low refractive index layer (COP group) obtained in Production Example 14 was used instead of the polarizing plate with a low refractive index layer (TAC substrate) 2A. Material) An observer side polarizing plate PO3 was obtained in the same manner as in Production Example 15 except that 2C was used. Further, a liquid crystal display device 3 was produced in the same manner as in Example 1, except that the observer side polarizing plate PO3 was used instead of the observer side polarizing plate PO1. The evaluation results of the manufactured liquid crystal display device 3 are shown in Table 1.

Example 4 Production of Liquid Crystal Display 4 Observation was made in the same manner as in Production Example 15 except that the optical anisotropic body C5 obtained in Production Example 11 was used instead of the optical anisotropic body C3 in Production Example 15. A person-side polarizing plate PO4 was obtained. Next, a backlight side polarizing plate PB2 was obtained in the same manner as in Production Example 16, except that the optical anisotropic body C5 obtained in Production Example 11 was used instead of the optical anisotropic body C3 in Production Example 16. . Furthermore, in Example 1, the observer side polarizing plate PO4 is used instead of the observer side polarizing plate PO1, and the backlight side polarizing plate PB2 is used instead of the backlight side polarizing plate PB1. The liquid crystal display device 4 was produced by the method. The evaluation results of the manufactured liquid crystal display device 4 are shown in Table 1.

(Example 5) Production of liquid crystal display device 5 In Production Example 15, instead of the polarizing plate with a low refractive index layer (TAC substrate) 2A, the polarizing plate with a low refractive index layer (COP group) obtained in Production Example 14 Material) 2C was used, and instead of the optical anisotropic body C3, an observer-side polarizing plate PO5 was obtained in the same manner as in Production Example 15 except that the optical anisotropic body C5 obtained in Production Example 11 was used. Next, using the observer side polarizing plate PO5 in place of the observer side polarizing plate PO1 in Example 1, using the backlight side polarizing plate PB2 obtained in Example 4 instead of the backlight side polarizing plate PB1, A liquid crystal display device 5 was produced in the same manner as in Example 1. The evaluation results of the manufactured liquid crystal display device 5 are shown in Table 1.

Comparative Example 1 Production of Liquid Crystal Display Device 6 The optical anisotropic body C8 obtained in Production Example 12 and the polarizing plate 2A with a low refractive index layer obtained in Production Example 13 are combined with the polarizing plate 2A with a low refractive index layer. The crossing angle of the slow axis of the optical anisotropic body C6 laminated on the optical anisotropic body C8 is 15 °, and the C6 side of the optical anisotropic body C8 and the polarizing plate 2A with a low refractive index layer Were laminated so that the polarizer side would be in contact with each other, to produce an observer side polarizing plate PO6.
Next, the optical anisotropic body C6 obtained by stacking the optical anisotropic body C8 obtained in Production Example 12 and the polarizer P obtained in Production Example 9 on the transmission axis of the polarizer P and the optical anisotropic body C8. The backlight side polarizing plate PB3 was manufactured by stacking so that the crossing angle of the slow axis was 15 ° and the C6 side of the optical anisotropic body C8 and the polarizer side of the polarizer P were in contact with each other. Furthermore, in Example 1, the observer side polarizing plate PO6 is used instead of the observer side polarizing plate PO1, and the backlight side polarizing plate PB3 is used instead of the backlight side polarizing plate PB1. A liquid crystal display device 6 was produced by the same method as described above. The evaluation results of the manufactured liquid crystal display device 6 are shown in Table 1.

Comparative Example 2 Production of Liquid Crystal Display Device 7 In the polarizing plate 2A with a low refractive index layer obtained in Production Example 13, the low refractive index obtained in Production Example 6 instead of the low refractive index layer-forming composition L1. A polarizing plate with a low refractive index layer (TAC substrate) 2D was obtained in the same manner as in Production Example 13, except that the layer forming composition L3 was used. Subsequently, in Production Example 15, in place of the polarizing plate 2A with a low refractive index layer, a polarizing plate with a low refractive index layer (TAC substrate) 2D was used in the same manner as in Production Example 15 except that the observer side polarizing plate was used. PO7 was obtained. Further, in Example 1, a liquid crystal display device 7 was produced in the same manner as in Example 1 except that the observer side polarizing plate PO7 was used instead of the observer side polarizing plate PO1. The evaluation results of the manufactured liquid crystal display device 7 are shown in Table 1.

Comparative Example 3 Production of Liquid Crystal Display Device 8 In the polarizing plate 2A with a low refractive index layer obtained in Production Example 13, the low refractive index obtained in Production Example 7 instead of the low refractive index layer-forming composition L1. A polarizing plate with a low refractive index layer (TAC substrate) 2E was obtained in the same manner as in Production Example 13, except that the layer forming composition L4 was used. Subsequently, in place of the polarizing plate 2A with a low refractive index layer in Production Example 15, the polarizing plate PO8 on the observer side is the same as in Production Example 15 except that a polarizing plate with a low refractive index layer (TAC substrate) 2E is used. Got. Further, in Example 1, a liquid crystal display device 8 was produced in the same manner as in Example 1 except that the observer side polarizing plate PO8 was used instead of the observer side polarizing plate PO1. The evaluation results of the manufactured liquid crystal display device 8 are shown in Table 1.

  In Table 1, TAC is an abbreviation for triacetyl cellulose, COP is an abbreviation for alicyclic olefin polymer, and PVA is an abbreviation for polyvinyl alcohol.

  As shown in Table 1 above, according to Examples 1 to 5, it is possible to ensure high contrast and sufficient antireflection performance (visibility) and to be excellent in scratch resistance and antifouling properties. found. On the other hand, in Comparative Example 1, the ratio of Re (450) / Re (550) is 1.01, which is inferior in terms of contrast when it exceeds 1.007. Moreover, in the comparative example 2, it turns out that antifouling property is inadequate by using the siloxane oligomer which does not have a fluoroalkyl group. Moreover, in the comparative example 3, it turns out that scratch resistance is inadequate by not using the hollow particle.

1 is a diagram showing a transflective liquid crystal display device according to the present invention. It is a figure which shows the reflective liquid crystal display device which concerns on this invention.

Explanation of symbols

10, 31 Antireflection body 12, 20, 32 Polarizing plate 13, 19, 33 Half-wave plate 14, 18, 34 1/4 wave plate 15, 35 Transparent electrode 16, 36 Liquid crystal layer 17 Transparent electrode 21 Backlight and Light guide plate 37 Reflector

Claims (4)

A liquid crystal display device having a liquid crystal cell, an optical anisotropic body, and an output side polarizer in this order toward the viewing side,
The optical anisotropic body has a ratio Re (450) / Re (550) of an in-plane retardation value Re (550) measured at a wavelength of 550 nm and an in-plane retardation value Re (450) measured at a wavelength of 450 nm. .007 or less,
An antireflection body is provided on the opposite side of the exit side polarizer from the optical anisotropic body, and the antireflection body includes a low component comprising the following components (A), (B), and (C): A reflective or transflective liquid crystal display device comprising a low refractive index layer made of a cured film formed from a composition for forming a refractive index layer.
(A) Hollow particles having a particle size of 5 to 2000 nm (B) Siloxane oligomer having (meth) acryloyl group and fluoroalkyl group (C) Acrylate compound having (meth) acryloyl group The liquid crystal display device according to claim 1.
The liquid crystal display device, wherein the composition for forming a low refractive index layer further contains a crosslinkable compound. The liquid crystal display device according to claim 1 or 2,
A liquid crystal display, wherein a refractive index of the low refractive index layer is 1.40 or less and a difference in refractive index from a layer adjacent to the low refractive index layer is 0.05 to 0.4. apparatus. The liquid crystal display device according to claim 1,
The antireflection body includes a high refractive index layer laminated on the output side polarizer side of the low refractive index layer, and the refractive index of the high refractive index layer is 1.55 or more. Display device.

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