WO2011001836A1 - 接着層を有する輝度向上フィルム、偏光板、それらを備える液晶表示装置 - Google Patents
接着層を有する輝度向上フィルム、偏光板、それらを備える液晶表示装置 Download PDFInfo
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- WO2011001836A1 WO2011001836A1 PCT/JP2010/060339 JP2010060339W WO2011001836A1 WO 2011001836 A1 WO2011001836 A1 WO 2011001836A1 JP 2010060339 W JP2010060339 W JP 2010060339W WO 2011001836 A1 WO2011001836 A1 WO 2011001836A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- G02B1/105—
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/04—Prisms
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
- G02F1/133536—Reflective polarizers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
Definitions
- the present invention relates to a brightness enhancement film, a manufacturing method thereof, a polarizing plate, and a liquid crystal display device.
- a display device such as a liquid crystal display device
- various optical members in order to improve the performance.
- a brightness enhancement film as a method for effectively using light from a backlight to improve brightness and increase luminous efficiency.
- a brightness enhancement film for example, a film in which a resin layer having cholesteric regularity (hereinafter referred to as “cholesteric resin layer” as appropriate) and a quarter wavelength plate are laminated in this order via an adhesive layer or the like is used. (Patent Document 1).
- a method has been proposed in which a cholesteric resin layer formed on a coating substrate having an alignment film is peeled off and transferred onto another translucent substrate (Patent Document 2).
- Such a brightness enhancement film can separate the roles of the alignment substrate and the translucent substrate, has a small number of films, and can be directly laminated with a polarizing plate, which is advantageous in terms of thickness reduction and cost. .
- the present invention provides a brightness enhancement film having a cholesteric resin layer, which makes the cholesteric resin layer less susceptible to deformation and scratches, and forms a liquid crystal display device that is excellent in thinness, brightness, and display characteristics when used as a liquid crystal display device. Development of a polarizing member that can be obtained is an issue.
- the present inventor has found that the above problems can be solved by providing a transparent film on at least one surface of the cholesteric resin layer via a specific active energy ray-curable adhesive layer.
- the headline and the present invention were completed. That is, according to the present invention, the following [1] to [9] are provided.
- a brightness enhancement film in which a transparent film is provided on at least one surface of a resin layer having cholesteric regularity via an active energy ray-curable adhesive layer,
- the active energy ray curable adhesive layer is formed by curing an active energy ray curable adhesive composition,
- the adhesive composition is in an uncured state (A) an oligomer-type polyfunctional (meth) acrylate having 3 or less functional groups, and (B) a viscosity at a temperature of 20 ⁇ 1.0 ° C. is 10 mPa ⁇ s or more and less than 500 mPa ⁇ s.
- a brightness enhancement film comprising at least a mono (meth) acrylate having at least one hydroxyl group in a molecule.
- a polarizing plate wherein a transparent protective film is provided on both surfaces of a polarizer, and the brightness enhancement film according to any one of [1] to [5] is bonded to one surface.
- a polarizing plate characterized in that a transparent protective film is provided on one surface of a polarizer and the brightness enhancement film according to any one of [1] to [5] is bonded to the other surface.
- a liquid crystal display device comprising the brightness enhancement film according to any one of [1] to [5].
- a liquid crystal display device in which the polarizing plate according to [6] or [7] is bonded to a lighting device side of a liquid crystal cell.
- the brightness enhancement film of the present invention is less damaged and less deformed by the cholesteric resin layer, is integrated with the polarizing plate, and can be improved in thickness, brightness and brightness uniformity when used in a liquid crystal display device, A lightweight and low-cost device can be obtained.
- FIG. 1 is a longitudinal sectional view conceptually showing an embodiment of the brightness enhancement film of the present invention.
- FIG. 2 is a longitudinal sectional view conceptually showing a state before being produced on a coated substrate and before peeling when producing the brightness enhancement film of the present invention.
- FIG. 3 is a longitudinal sectional view conceptually showing an embodiment of the polarizing plate of the present invention.
- FIG. 4 is a longitudinal sectional view conceptually showing another embodiment of the polarizing plate of the present invention, and shows that one of the protective films of the polarizing plate can be substituted with a brightness enhancement film as compared with the embodiment of FIG. ing.
- Luminance-enhancing film of the present invention includes a cholesteric resin layer.
- the brightness enhancement film of the present invention includes a transparent film on at least one surface of the cholesteric resin layer via an active energy ray-curable adhesive layer.
- the transparent film may be provided on both surfaces of the cholesteric resin layer.
- Transparent film examples include a quarter wave plate (sometimes referred to as “ ⁇ / 4 plate”), a protective film, and the like.
- (1 ⁇ 4 wavelength plate) As the quarter wavelength plate, for example, a stretched film formed by stretching a film-like polymer can be used.
- a transparent resin can be preferably used.
- the transparent resin for example, a 1 mm thick plate having a total light transmittance of 80% or more can be used. Examples thereof include polymethyl methacrylate, polystyrene, polycarbonate, polyether sulfone, amorphous polyethylene, triacetyl cellulose, and a resin having an alicyclic structure.
- Preferable examples include a quarter wavelength plate formed by stretching a resin film including a styrene resin layer and a quarter wavelength plate formed by stretching a resin film having an alicyclic structure. More preferable examples include the optically anisotropic elements described below.
- the quarter-wave plate can set the retardation Re (hereinafter, abbreviated as “Re”) in the front direction to a substantially quarter wavelength of transmitted light.
- the wavelength range of the transmitted light can be a desired range required for the composite optical member, and specifically, for example, 400 nm to 700 nm.
- the retardation Re in the front direction is approximately 1 ⁇ 4 wavelength of transmitted light, and the Re value is ⁇ 65 nm from the 1 ⁇ 4 value of the center value in the center value of the wavelength range of transmitted light, preferably It means ⁇ 30 nm, more preferably ⁇ 10 nm.
- the quarter-wave plate has a thickness direction retardation Rth (hereinafter sometimes abbreviated as “Rth”) of less than 0 nm.
- the value of retardation Rth in the thickness direction can be preferably ⁇ 30 nm to ⁇ 1000 nm, more preferably ⁇ 50 nm to ⁇ 300 nm, in the central value of the wavelength range of transmitted light.
- Ny represents a refractive index in a direction perpendicular to the thickness direction (in-plane direction) and perpendicular to nx
- d represents a film thickness.
- the retardation Re in the front direction and the retardation Rth in the thickness direction are measured using a commercially available phase difference measuring apparatus with a quarter-wave plate in the longitudinal direction and the width direction at intervals of 100 mm (longitudinal or lateral length). If the distance is less than 200 mm, three points are specified at equal intervals in that direction), and measurement is performed in a lattice point shape over the entire surface, and the average value is obtained.
- the material of the optically anisotropic element constituting the quarter-wave plate is not particularly limited, but a material having a layer made of a styrene resin can be preferably used.
- the styrene resin is a polymer resin having a styrene structure as a part or all of the repeating units, and a polystyrene or a copolymer of styrene and maleic anhydride can be preferably used.
- the molecular weight of the styrenic resin used for the optically anisotropic element is appropriately selected according to the purpose of use, but is the weight average molecular weight (Mw) of polyisoprene measured by gel permeation chromatography using cyclohexane as a solvent. Usually, it is 10,000 or more and 300,000 or less, preferably 15,000 or more and 250,000 or less, more preferably 20,000 or more and 200,000 or less.
- the optically anisotropic element preferably has a laminated structure of a layer made of the styrenic resin and a layer containing another thermoplastic resin.
- a laminated structure By having the laminated structure, it is possible to provide an element that has both the optical characteristics of the styrene resin and the mechanical strength of other thermoplastic resins.
- the other thermoplastic resin a resin having an alicyclic structure or a methacrylic resin can be suitably used.
- Examples of the resin having an alicyclic structure include alicyclic olefin polymers.
- the alicyclic olefin polymer is an amorphous olefin polymer having a cycloalkane structure or a cycloalkene structure in the main chain and / or side chain.
- the methacrylic resin is a polymer mainly composed of a methacrylic acid ester, and examples thereof include a homopolymer of methacrylic acid ester and a copolymer of methacrylic acid ester and other monomers.
- methacrylic acid ester alkyl methacrylate is usually used.
- acrylic acid esters, aromatic vinyl compounds, vinylcyan compounds, etc. are used as other monomers copolymerized with methacrylic acid esters.
- a multilayer film formed by laminating a film (b layer) made of another thermoplastic resin on both surfaces of a film (a layer) made of polystyrene resin is stretched.
- a stretched multilayer film can be mentioned.
- polystyrene resin constituting the a layer the same “styrene resin” as described above can be used.
- the method of laminating the polystyrene resin that is the material of the a layer and the other thermoplastic resin that is the material of the b layer to form a multilayer film is not particularly limited, but is a coextrusion T-die method, coextrusion inflation
- Known methods such as a method of forming by coextrusion such as a method, a coextrusion lamination method, a film lamination forming method such as dry lamination, and a coating forming method may be appropriately used.
- a molding method by coextrusion is preferable from the viewpoints of production efficiency and that volatile components such as a solvent do not remain in the film.
- the extrusion temperature can be appropriately selected according to the type of the polystyrene resin used and the other thermoplastic resin.
- the multilayer film is formed by laminating the b layer on both sides of the a layer.
- An adhesive layer can be provided between the a layer and the b layer, but the a layer and the b layer are directly laminated (that is, a laminate having a three-layer structure of b layer / a layer / b layer). Is preferred.
- the thicknesses of the a layer and the b layer laminated on both surfaces thereof are not particularly limited, but can be preferably 10 ⁇ m or more and 300 ⁇ m or less and 10 ⁇ m or more and 400 ⁇ m or less, respectively.
- the stretched multilayer film is formed by stretching the multilayer film.
- the stretching can be preferably performed by uniaxial stretching or oblique stretching, and more preferably by uniaxial stretching or oblique stretching by a tenter.
- the thickness of the optically anisotropic element is preferably 50 ⁇ m or more and 1000 ⁇ m or less, more preferably 50 ⁇ m or more and 600 ⁇ m or less.
- the quarter wavelength plate itself may also have a function as an optical compensation layer, but may have an optical compensation layer separately in addition to the quarter wavelength plate.
- an optical compensation layer the same optical anisotropic element as described above can be used, and a homeotropic liquid crystal alignment film obtained by homeotropic alignment of liquid crystal molecules on a substrate and curing (Japanese Patent No. 399969). ), A nematic hybrid liquid crystal alignment film (US Pat. No. 6,294,229) obtained by curing a state in which liquid crystal molecules are nematic hybrid aligned on a substrate can be used.
- a transparent resin film can be used as the protective film for protecting the cholesteric resin layer.
- the transparent resin the same resin as that used for the quarter-wave plate can be used.
- a resin film having an unstretched alicyclic structure with good heat resistance and transparency can be used.
- the protective film can be provided with irregularities on the surface opposite to the surface facing the cholesteric resin layer. By providing the unevenness, it is possible to prevent sticking to other backlight members (that is, members other than the brightness enhancement film constituting the backlight) and to improve the slipperiness, thereby preventing damage.
- Examples thereof include a method of providing irregularities by coating, drying and curing the solution on the surface of the transparent resin film by a bar coating method, a gravure coating method, a die coating method, a spray coating method, a dip coating method, and a spin coating method.
- a method of coating a surface of a transparent resin film with a solution in which translucent particles are dispersed in a resin solution, which is excellent in production suitability in a long length, is preferable.
- the surface roughness of the protective film having irregularities on the surface can be measured according to JIS B0601-1994.
- the 10-point average roughness and the average length of the contour curve elements are measured at a measurement length of 5 ⁇ m, and the average of the 10-point measurement values is used as the 10-point average roughness Rz and the contour curve of the measurement object.
- the average element length Sm can be calculated.
- the ratio Rz / Sm of the preferred ten-point average roughness Rz to the average length Sm of the uneven surface is in the range of 2 ⁇ 10 ⁇ 4 to 7 ⁇ 10 ⁇ 3 , more preferably 3 ⁇ 10 ⁇ 4 to It is 5 ⁇ 10 ⁇ 3 , more preferably 5 ⁇ 10 ⁇ 4 to 4.5 ⁇ 10 ⁇ 3 .
- a cholesteric resin layer (that is, a resin layer having cholesteric regularity) is a resin layer obtained by providing a coating film of a cholesteric liquid crystal composition on a substrate for forming a resin layer and curing the coating film.
- Cholesteric regularity means that the molecular axes are aligned in a certain direction on one plane, but the direction of the molecular axis is slightly shifted on the next plane, and the angle is further shifted on the next plane. This is a structure in which the angle of the molecular axis is shifted (twisted) as it advances through a plane in which molecules are arranged in a certain direction. Thus, the structure in which the direction of the molecular axis is twisted becomes an optically chiral structure.
- the brightness enhancement film according to the present invention preferably includes a cholesteric resin layer that exhibits this circularly polarized light separation function over the entire wavelength region of visible light.
- a cholesteric resin layer having a circularly polarized light separation function is preferable for light in any wavelength range of blue (wavelength 410 to 470 nm), green (wavelength 520 to 580 nm), and red (wavelength 600 to 660 nm).
- the cholesteric resin layer can be obtained, for example, by polymerizing a cholesteric liquid crystal composition (X) containing a polymerizable liquid crystal compound in a curing process described later. Such a layer becomes a non-liquid crystalline resin layer cured while exhibiting the molecular orientation of the liquid crystalline compound.
- a liquid crystal composition here for convenience includes not only a mixture of two or more substances but also a material made of a single substance.
- the cholesteric liquid crystal composition (X) contains a compound represented by the following general formula (1) and a rod-like liquid crystal compound as a polymerizable liquid crystal compound.
- R 1X and R 2X each independently represent a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched chain having 1 to 20 carbon atoms. And a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a (meth) acryl group, an epoxy group, a mercapto group, an isocyanate group, an amino group, and a cyano group.
- (meth) acryl means acryl and methacryl.
- the alkyl group and alkylene oxide group may be unsubstituted or substituted with one or more halogen atoms.
- the halogen atom, hydroxyl group, carboxyl group, (meth) acryl group, epoxy group, mercapto group, isocyanate group, amino group, and cyano group are bonded to an alkyl group having 1 to 2 carbon atoms or an alkylene oxide group. May be.
- R 1X and R 2X include a halogen atom, a hydroxyl group, a carboxyl group, a (meth) acryl group, an epoxy group, a mercapto group, an isocyanate group, an amino group, and a cyano group.
- R 1X and R 2X are a reactive group.
- the compound represented by the general formula (1) is fixed in the liquid crystal composition layer at the time of curing, and a stronger film can be formed.
- the reactive group include a carboxyl group, a (meth) acryl group, an epoxy group, a mercapto group, an isocyanate group, and an amino group.
- a 1X and A 2X are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, 4,4′-biphenylene group, 4, A group selected from the group consisting of a 4′-bicyclohexylene group and a 2,6-naphthylene group.
- the 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, 4,4′-biphenylene group, 4,4′-bicyclohexylene group, and 2,6-naphthylene group are , It may be unsubstituted or substituted with one or more halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, amino groups, alkyl groups having 1 to 10 carbon atoms, or halogenated alkyl groups. In each of A 1X and A 2X , when two or more substituents are present, they may be the same or different.
- a 1X and A 2X include groups selected from the group consisting of 1,4-phenylene group, 4,4′-biphenylene group, and 2,6-naphthylene group.
- aromatic ring skeletons are relatively rigid as compared with the alicyclic skeletons, have high affinity with the mesogens of rod-like liquid crystalline compounds described later, and have higher alignment uniformity.
- Z include a single bond, —OCO—, and —CH ⁇ N—N ⁇ CH—.
- the compound of General formula (1) it is preferable that at least 1 type has liquid crystallinity, and it is preferable to have chirality.
- the cholesteric liquid crystal composition (X) preferably contains a mixture of a plurality of optical isomers as the compound of the general formula (1). For example, a mixture of plural kinds of enantiomers and / or diastereomers can be contained. At least one of the compounds of the general formula (1) preferably has a melting point in the range of 50 ° C to 150 ° C.
- the refractive index anisotropy ⁇ n is preferably high.
- At least one ⁇ n of the compound of the general formula (1) is preferably 0.20 or more, more preferably 0.22 or more.
- the thickness may be less than 1 ⁇ m. If the thickness is less than 1 ⁇ m, the optical characteristics are sensitively influenced by variations in film thickness, which tends to make manufacture difficult. Therefore, in such a case, the upper limit of ⁇ n is preferably set to 0.4.
- Particular preferred compounds of the general formula (1) include the following compounds (A1) to (A9):
- the cholesteric liquid crystal composition (X) preferably contains a rod-like liquid crystal compound having at least two or more reactive groups in one molecule.
- Examples of the rod-like liquid crystalline compound include compounds represented by the general formula (2). R 3X -C 3X -D 3X -C 5X -MC 6X -D 4X -C 4X -R 4X Formula (2)
- R 3X and R 4X are reactive groups, each independently (meth) acryl group, (thio) epoxy group, oxetane group, thietanyl group, aziridinyl group, pyrrole group, vinyl group, It represents a group selected from the group consisting of an allyl group, a fumarate group, a cinnamoyl group, an oxazoline group, a mercapto group, an iso (thio) cyanate group, an amino group, a hydroxyl group, a carboxyl group, and an alkoxysilyl group.
- D 3X and D 4X are a single bond, a divalent saturated hydrocarbon group such as a linear or branched methylene group and alkylene group having 1 to 20 carbon atoms, and a carbon atom.
- C 3X to C 6X are a single bond, —O—, —S—, —SS—, —CO—, —CS—, —OCO—, —CH 2 —, —OCH 2.
- M represents a mesogenic group, specifically, azomethines, azoxys, phenyls, biphenyls, terphenyls, naphthalenes, which may be unsubstituted or substituted.
- Anthracenes benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, alkenylcyclohexylbenzonitriles
- Two to four skeletons are represented by —O—, —S—, —SS—, —CO—, —CS—, —OCO—, —CH 2 —, —OCH 2 —, —CH ⁇ N—.
- N CH -, - NHCO - , - OCOO -, - CH 2 COO-, and coupled by a linking group of -CH 2 OCO-, etc. Is a group formed by.
- the rod-like liquid crystalline compound preferably has an asymmetric structure.
- the asymmetric structure is a structure in which R 3X -C 3X -D 3X -C 5X -and -C 6X -D 4X -C 4X -R 4X are different in the general formula (2) with the mesogenic group M as the center. That means.
- the rod-like liquid crystalline compound may have at least two reactive groups in one molecule.
- the reactive group include an epoxy group, a thioepoxy group, an oxetane group, a thietanyl group, an aziridinyl group, a pyrrole group, a fumarate group, a cinnamoyl group, an isocyanate group, an isothiocyanate group, an amino group, a hydroxyl group, and a carboxyl group.
- the weight ratio of (total weight of the compound of the general formula (1)) / (total weight of the rod-like liquid crystal compound) is preferably 0.05 to 1. It is more preferably 1 to 0.65, and further preferably 0.15 to 0.45. If the weight ratio is less than 0.05, the alignment uniformity may be insufficient. On the other hand, if it is more than 1, the alignment uniformity is lowered, the stability of the liquid crystal phase is lowered, or ⁇ n as the liquid crystal composition is lowered, so that desired optical performance (for example, circularly polarized light separation characteristics) cannot be obtained. There is a case.
- the total weight indicates the weight when one kind is used and the total weight when two or more kinds are used.
- the cholesteric liquid crystal composition can optionally contain a chiral agent.
- a specific chiral agent the compounds represented by the following (C1) and (C2) having an isosorbide skeleton in which the chiral group is divalent can be used.
- LC756 of BASF Corporation Paliocolor can be obtained.
- the chiral agent can be included in a range that does not deteriorate the desired optical performance.
- the content of the chiral agent is usually 1 to 60% by weight in the cholesteric liquid crystal composition.
- the cholesteric liquid crystal composition can further contain other optional components as necessary.
- the other optional components include solvents, photopolymerization initiators, surfactants, crosslinking agents, polymerization inhibitors for improving pot life, antioxidants for improving durability, ultraviolet absorbers, and light stability. And the like. These optional components can be included in a range that does not deteriorate the desired optical performance.
- the method for producing the cholesteric liquid crystal composition is not particularly limited, and can be produced by mixing the above components.
- the cholesteric liquid crystal composition is applied onto a base material layer directly or through an alignment film to obtain a coating film, and then subjected to light irradiation and / or application one or more times.
- a cholesteric resin layer can be obtained by performing a temperature treatment to cure the coating film. More specifically, the cholesteric resin layer can be produced by the following methods (M1) and (M2).
- a transparent film such as a quarter-wave plate can be used, and a cholesteric resin layer can be directly provided thereon.
- a laminated structure of a quarter wavelength plate and a cholesteric resin layer can be obtained by using a quarter wavelength plate as a base material layer and forming a cholesteric resin layer thereon.
- M2 An arbitrary base material layer is used, a cholesteric resin layer is formed thereon, the cholesteric resin layer is transferred to a transparent film via an adhesive composition, and the base material layer is peeled off. A resin layer may be provided.
- a transparent resin substrate can be preferably used as the substrate layer.
- the same transparent resin substrate as that used for the quarter-wave plate can be used.
- alicyclic olefin polymers or chain olefin polymers are preferable, and alicyclic olefin polymers are particularly preferable from the viewpoints of transparency, low hygroscopicity, dimensional stability, lightness, and the like.
- An alignment film can be provided on the base material layer as necessary.
- the cholesteric liquid crystal composition applied thereon can be aligned in a desired direction.
- the alignment film is subjected to corona discharge treatment or the like on the surface of the base material layer, if necessary, and then a solution obtained by dissolving the alignment film material in water or a solvent is used for reverse gravure coating, direct gravure coating, die It can be formed by applying and drying using a known method such as coating or bar coating, and then subjecting the dried coating film to rubbing treatment.
- the material for the alignment film is preferably a modified polyamide from the viewpoint of durability and the like.
- polyvinyl alcohol is particularly preferable from the viewpoint of easy transfer in the method (M2).
- the modified polyamide include those obtained by modifying an aromatic polyamide or an aliphatic polyamide, and those obtained by modifying an aliphatic polyamide are preferred.
- an orientation treatment may be performed as necessary.
- the orientation treatment is performed, for example, by heating the coating film at 50 to 150 ° C. for 0.5 to 10 minutes.
- a substance capable of exhibiting a cholesteric liquid crystal phase in the coating film can be well aligned.
- the curing step is performed by, for example, one or more times of light irradiation, heating treatment, or a combination thereof.
- the heating conditions are, for example, a temperature of 40 to 200 ° C., preferably 50 to 200 ° C., more preferably 50 to 140 ° C., and a time of 1 second to 3 minutes, preferably 5 to 120 seconds.
- the light used for light irradiation includes not only visible light but also ultraviolet rays and other electromagnetic waves.
- the light irradiation can be performed, for example, by irradiating light having a wavelength of 200 to 500 nm for 0.01 second to 3 minutes.
- a weakly irradiated ultraviolet ray of 0.01 to 50 mJ / cm 2 and heating may be alternately repeated a plurality of times to obtain a circularly polarized light separating element having a wide reflection band.
- a relatively strong ultraviolet ray of 50 to 10,000 mJ / cm 2 is irradiated to completely polymerize the liquid crystalline compound to form a cholesteric resin layer. It can.
- the expansion of the reflection band and the irradiation with strong ultraviolet rays may be performed in the air, or a part or all of the process may be performed in an atmosphere in which the oxygen concentration is controlled (for example, in a nitrogen atmosphere). .
- the dry film thickness of the cholesteric resin layer is preferably 10 ⁇ m or less, more preferably 2 ⁇ m or more and 7 ⁇ m or less, and even more preferably 3 ⁇ m or more and 6 ⁇ m or less.
- the dry film thickness refers to the total film thickness of each layer when the cholesteric resin layer is two or more layers, and the film thickness when the cholesteric resin layer is one layer.
- the transfer in the method (M2) can be performed by transferring a cholesteric resin layer formed on a substrate for forming a resin layer or an alignment film onto a layer to be transferred. Such transfer can be performed such that the layer to be transferred and the cholesteric resin layer are attached via an adhesive layer.
- the layer to be transferred can be a transparent film, specifically a quarter wave plate, for example.
- the adhesive layer can be provided in advance on either one or both of the surfaces to be transferred and the opposing surfaces on both sides of the cholesteric resin layer.
- the cholesteric resin layer is formed on the alignment film, only the cholesteric resin layer may be transferred, or both the cholesteric resin layer and the alignment film may be transferred. From the viewpoint of easy peeling and prevention of orientation failure of the cholesteric resin layer, it is preferable to transfer both the cholesteric resin layer and the alignment film.
- the adhesive layer (active energy ray-curable adhesive layer) used in the present invention is an adhesive layer obtained by curing an active energy ray-curable adhesive composition (also referred to as an adhesive layer composition).
- the adhesive composition has an uncured (A) oligomer type polyfunctional (meth) acrylate having 3 or less functional groups, and (B) a viscosity at a temperature of 20 ⁇ 1.0 ° C. of 10 mPa ⁇ s to 500 mPa ⁇ s. mono (meth) acrylate having at least one hydroxyl group of less than s.
- (meth) acrylate means acrylate and / or methacrylate.
- the active energy ray-curable adhesive composition refers to an adhesive composition that cures when irradiated with active energy rays such as ultraviolet rays, X-rays, and electron beams. Since an inexpensive apparatus can be used, an adhesive composition that is cured by ultraviolet rays is preferable.
- the light source used for irradiating with ultraviolet rays is not particularly limited, and examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp.
- the irradiation intensity is not particularly limited, but the irradiation intensity in the wavelength region effective for activating the polymerization initiator is preferably 50 to 5000 mW / cm 2 . More preferably, it is 100 to 3000 mW / cm 2 , and further preferably 300 to 2000 mW / cm 2 .
- the light irradiation intensity is less than 50 mW / cm 2 , the reaction time becomes too long and the curing is insufficient. If it exceeds 5000 mW / cm 2 , the adhesive composition may be yellowed due to radiant heat from the lamp, heat of polymerization reaction, or the like, and the shrinkage of the adhesive layer may increase, resulting in a decrease in adhesive strength.
- the light irradiation time is appropriately selected according to the curing state and is not particularly limited.
- the integrated light amount expressed as the product of the irradiation intensity and the irradiation time is 10 to 5,000 mJ / cm 2. It is preferable to set to. More preferably 100 ⁇ 3000mJ / cm 2, more preferably from 500 ⁇ 2000mJ / cm 2.
- the oligomer type polyfunctional (meth) acrylate having 3 or less functional groups used in the present invention preferably has 2 and 3 functional groups.
- the oligomer-type polyfunctional (meth) acrylate include radical polymerization such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, and silicone (meth) acrylate. Examples thereof include acrylic oligomers having various functional groups of 3 or less, or a mixture thereof.
- the functional group refers to a group having an unsaturated bond.
- the functional group include the following (r-1) to (r-8), among which (meth) acryloyl group including (r-1) to (r-5) is preferable.
- only one type of functional group may be used, or two or more types may be used in combination at any ratio.
- Et represents an ethyl group
- n-Pr represents an n-propyl group.
- the molecular weight of the oligomer type polyfunctional (meth) acrylate is 500 to 10,000 in terms of the weight average molecular weight (Mw) in terms of polyisoprene measured by gel permeation chromatography.
- the polyester (meth) acrylate is obtained by reacting a terminal hydroxyl group of a polyester obtained from a polybasic acid and a polyhydric alcohol with (meth) acrylic acid.
- the polybasic acid include phthalic acid, adipic acid, maleic acid, itaconic acid, succinic acid, and terephthalic acid.
- the polyhydric alcohol include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol.
- EBECRYL 851,852,853,884,885 manufactured by Daicel Cytec
- Olester manufactured by Mitsui Chemicals
- Aronix M-6100,6200,6250,6500 manufactured by Toagosei Co., Ltd.
- Epoxy (meth) acrylate is a reaction product obtained by ring-opening addition reaction of (meth) acrylic acid to an epoxy resin.
- Epoxy resins include bisphenol A type consisting of bisphenol A and epichlorohydrin, novolak type consisting of phenol novolac and epichlorohydrin, aliphatic type, and alicyclic type.
- Aliphatic epoxy resins include ethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylol Propane diglycidyl ether, polyethylene glycol diglycidyl ether, and the like can be used, and unsaturated fatty acid epoxy resins such as butadiene-based epoxy resins and isoprene-based epoxy resins can also be used.
- Alicyclic epoxy resins include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9-diepoxysilimonene, 3,4-epoxycyclohexenylmethyl-3 ′, 4 ′.
- -Epoxycyclohexenecarboxylate and the like can be used.
- EBECRYL600, 860, 3105, 3420, 3700, 3701, 3702, 3703, 3708, 6040 (manufactured by Daicel Cytec), Neopole 8101, 8250, 8260, 8270, 8355, 8351, 8335, 8414, 8190, 8195, 8316 , 8317, 8318, 8319, 8371 (manufactured by Iupika Japan), Denacol acrylate DA212, 250, 314, 721, 722, DM201 (manufactured by Nagase ChemteX), Van Beam (manufactured by Harima Chemicals), Miramer PE210, PE230, EA2280 (manufactured by Toyo Chemicals) and the like can be mentioned.
- Urethane (meth) acrylate is a reaction product having a urethane skeleton at the center by reaction of a (meth) acrylic monomer having a hydroxyl group, a polyfunctional isocyanate and a polyhydric alcohol.
- a (meth) acrylic monomer having a hydroxyl group examples include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
- polyfunctional isocyanate examples include tolylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylolpropane tolylene diisocyanate, and diphenylmethane triisocyanate. Among them, hexamethylene diisocyanate having good weather resistance is preferably used. As a polyhydric alcohol, what can be used for polyester (meth) acrylate can be used.
- EBECRYL 204, 210, 220, 230, 270, 4858, 8200, 8201, 8402, 8804, 8807, 9260, 9270, KRM 8098, 7735, 8296 (manufactured by Daicel Cytec Co., Ltd.), UX2201, 2301, 3204, 3301, 4101, 6101, 7101, 8101, 0937 (manufactured by Nippon Kayaku Co., Ltd.), UV6640B, 6100B, 3700B, 3500BA, 3520TL, 3200B, 3000B, 3310B, 3210EA, 7000B, 6630B, 7461TE (manufactured by Nippon Synthetic Chemical Co., Ltd.), Iupika 8921, 8932 , 8940, 8936, 8937, 8980, 8975, 8976 (manufactured by Nippon Yupica), Miramer PU240, PU340 (manufact
- Polyether (meth) acrylate is a reaction product of polyether polyol and (meth) acrylic acid. Examples thereof include ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and EBECRYL81 (manufactured by Daicel Cytec).
- polyester (meth) acrylate epoxy (meth) acrylate, and urethane (meth) acrylate is preferred.
- the number of functional groups is 3 or less, the curing shrinkage of the cured product when the adhesive composition is cured with active energy rays can be reduced, and the glass transition temperature of the cured product can be lowered, and the cholesteric resin layer and Good adhesion to the transparent film can be maintained.
- the term “viscosity” means that the measured value of the viscosity satisfies 10 mPa ⁇ s or more and less than 500 mPa ⁇ s at at least one point within the range of the temperature condition.
- mono (meth) acrylate having at least one hydroxyl group having a viscosity of 10 mPa ⁇ s or more and less than 500 mPa ⁇ s at a temperature of 20 ⁇ 1.0 ° C. used in the present invention include 2-hydroxypropyl acrylate (10.9 mPa ⁇ s).
- the coating composition of the adhesive composition is good and the adhesive layer exhibits a stronger adhesive force. Therefore, it is preferable.
- the viscosity range is more preferably 50 mPa ⁇ s to 400 mPa ⁇ s, still more preferably 70 mPa ⁇ s to 350 mPa ⁇ s.
- the mono (meth) acrylate is preferably 35 parts by weight or more and 85 parts by weight or less in 100 parts by weight of (meth) acrylate contained in the uncured adhesive composition. By being within this range, a stronger adhesive force can be obtained.
- the adhesive composition includes a polymerization initiator, a crosslinking agent, an inorganic filler, a polymerization inhibitor, a color pigment, a dye, an antifoaming agent, a leveling agent, a dispersant, as long as the effect of the present invention is not impaired as necessary.
- a light diffusing agent, a plasticizer, an antistatic agent, a surfactant, a non-reactive polymer (inactive polymer), a viscosity modifier, a near-infrared absorbing material, an adhesion promoter, and the like can also be included.
- a polymerization initiator it can select suitably according to the kind of active energy ray.
- one or more photopolymerization initiators can be used.
- a photosensitizer can be used arbitrarily.
- Photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, methylbenzoyl formate, 2,2-diethoxyacetophenone, ⁇ -ionone, ⁇ -bromostyrene, diazoaminobenzene, ⁇ -Amylcinnaldehyde, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, p, p'-bisdiethylaminobenzophenone, benzoin ethyl ether, be
- the amount (addition part) of the photopolymerization initiator is preferably 0.5 parts by weight or more and 10 parts by weight or less, more preferably 100 parts by weight of (meth) acrylate contained in the uncured adhesive composition.
- the range is from 1 part by weight to 5 parts by weight.
- n-butylamine, triethylamine, poly-n-butylphosphine or the like can be added as a photosensitizer to control curability.
- the antifoaming agent can be added to such an extent that the adhesive strength of the adhesive layer does not decrease, and is 0.1 parts by weight or more and 1.0 part by weight or less based on the solid content of the uncured adhesive composition. Preferably, it is 0.1 parts by weight or more and 0.5 parts by weight or less.
- cross-linking agent a bifunctional or higher (meth) acrylate monomer having a molecular weight of less than 500 can be mixed.
- the amount (addition part) of the crosslinking agent is preferably 0.5 parts by weight or more and 10 parts by weight or less, more preferably 100 parts by weight of (meth) acrylate contained in the uncured adhesive composition. 1 part by weight or more and 5 parts by weight or less.
- the adhesive layer is excessively cured, and the adhesive force between the cholesteric resin layer and the transparent film is lowered. If it is less than 0.5 part by weight, the effect of the crosslinking agent is not exhibited.
- a slurry in which metal oxide nanoparticles of several nm to several hundred nm are dispersed in a solvent can be used.
- the metal oxide include silica, aluminum hydroxide, aluminum oxide, titanium oxide, zinc oxide, barium sulfate, magnesium silicate, and a mixture thereof.
- Organosilica Sol Methanol Silica Sol IPA-ST, IPA-ST-UP, IPA-ST-ZL, EG-ST, NPC-ST-30, DMAC-ST, MEK-ST, MIBK-ST, XBA -ST, PMA-ST, PGM-ST, PL-1-IPA, PL-1-TOL, PL-2L-PGME, and PL-2L-MEK manufactured by Fuso Chemical.
- a preferable amount (added part) is in the range of 1 to 15 parts by weight, more preferably 5 to 5 parts by weight, based on 100 parts by weight of (meth) acrylate contained in the uncured adhesive composition. 10 parts by weight. When the amount is less than 1 part by weight, the effect is not observed, and when the amount is more than 15 parts by weight, the adhesive strength is reduced.
- the light diffusing agent is a particle having a property of diffusing light, and can be roughly classified into an inorganic filler and an organic filler.
- the inorganic filler include glass, silica, aluminum hydroxide, aluminum oxide, titanium oxide, zinc oxide, barium sulfate, magnesium silicate, and a mixture thereof.
- the organic filler examples include acrylic resin, polyurethane resin, polyvinyl chloride resin, polystyrene resin, polyacrylonitrile resin, polyamide resin, polysiloxane resin, melamine resin, benzoguanamine resin, fluorine resin, polycarbonate resin, silicone resin, polyethylene resin, Examples thereof include an ethylene-vinyl acetate copolymer, acrylonitrile, and a cross-linked product thereof.
- an acrylic resin, a polystyrene resin, a polysiloxane resin, and fine particles made of a crosslinked product thereof are preferable in terms of high dispersibility, high heat resistance, and no coloration (yellowing) during molding. .
- fine particles made of a crosslinked product of an acrylic resin are more preferable in terms of more excellent transparency.
- what consists of 2 or more types of raw materials as a light-diffusion agent may be used, and 2 or more types of light-diffusion agents may be mixed and used.
- the amount (added part) of the light diffusing agent is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the solid content contained in the uncured adhesive composition.
- the amount (added part) of the light diffusing agent is a value determined by a desired haze value and a film thickness of the adhesive layer.
- An inert polymer means inert to polymerization and curing by active energy rays, and when a film thickness is designed to be 5 ⁇ m or more in order to achieve a desired haze value by adding a light diffusing agent, and When the film thickness of the adhesive layer is designed to be 5 ⁇ m or more in order to make the total thickness of the brightness enhancement film a desired thickness, it can be added to keep the film thickness of the adhesive layer stable even in an unpolymerized state. .
- the glass transition temperature of the inert polymer is preferably from ⁇ 10 ° C. to 80 ° C., more preferably from ⁇ 5 ° C. to 50 ° C. By setting this glass transition temperature, the adhesive force after polymerization and curing can be maintained.
- the inert polymer examples include urethane resin, methyl methacrylate polymer, styrene polymer, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate, polyester, polycarbonate resin, triacetyl cellulose resin, and butyral resin.
- examples thereof include a random copolymer obtained by copolymerizing at least species, a block copolymer, a graft copolymer obtained by grafting a molecule having a carboxylic acid, a sulfonic acid, an ester thereof, a hydroxyl group or a mercapto group in the side chain.
- the amount (addition part) of the inert polymer is preferably 20 parts by weight or more and 70 parts by weight or less, more preferably 30 parts by weight or more, in 100 parts by weight of the solid content contained in the uncured adhesive composition. 60 parts by weight or less.
- the adhesive layer thickness is designed to be 5 ⁇ m or more, the viscosity of the adhesive layer is low in an uncured state, the film thickness is not stable, the film thickness blurring increases, and a diffusing agent is mixed. In this case, the haze value is not stable.
- the amount is more than 60 parts by weight, the adhesive layer film hardness in an uncured state increases, and bubbles are frequently mixed during bonding.
- the adhesion-imparting agent a dual cure type monomer can be suitably used.
- laromar manufactured by BASF Japan
- Karenz MOI manufactured by AOI
- BEI manufactured by Showa Denko KK
- the amount (addition part) of the adhesion imparting agent is preferably 1 part by weight or more and 30 parts by weight or less, more preferably 5 parts by weight or more and 20 parts by weight or less in 100 parts by weight of the solid content contained in the uncured adhesive composition. Less than parts by weight.
- a roll coating method, a curtain coating method, and a slot coating method which are commonly applied to continuous films, are used.
- a die coating method such as a spray coating method or the like can be used, and is not particularly limited.
- the thickness of the adhesive composition to be applied is usually 0.5 ⁇ m or more and 100 ⁇ m or less, preferably 1 ⁇ m or more and 50 ⁇ m or less. If it is thicker than necessary, the curing rate of the adhesive composition will decrease and curing may be insufficient. If it is too thin, the adhesive strength is insufficient, which is not preferable.
- the lamination of the cholesteric resin layer and the transparent film after the adhesive composition is applied can be performed by a commonly used laminating means, but it is performed so as to thoroughly eliminate bubbles mixed in during the lamination.
- a commonly used laminating means it is possible to increase the clamping pressure between the rolls paired with the lami roll, to decrease the laminating speed, and in the batch laminating process, the surface pressure is increased or the vacuum pressure is applied. It is possible to suppress mixing of bubbles at the time of matching.
- Curing of the adhesive layer after coating and laminating can be performed by uniformly irradiating ultraviolet rays or electron beams in the width direction of the long laminating film under appropriate conditions depending on the adhesive composition to be used. .
- Polarizing plate and liquid crystal display device of the present invention comprise the brightness enhancement film of the present invention.
- the liquid crystal display device of the present invention has the polarizing plate of the present invention including the brightness enhancement film of the present invention.
- the polarizing plate in this case can further be provided with a transparent protective film.
- the transparent protective film the same resin as the protective film for protecting the cholesteric resin layer can be used, and among these, polymethyl methacrylate and triacetyl cellulose are preferable, and the durability of the display device From the viewpoint of improving display performance, polymethyl methacrylate is particularly preferable.
- thermoplastic resin as a transparent material which is a material of a transparent protective film.
- polymethyl methacrylate include homopolymers of alkyl methacrylate such as methyl methacrylate and ethyl methacrylate; or alkyl methacrylate and styrene, vinyl acetate, ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid, vinyl toluene, Mention may be made of a copolymer with a vinyl monomer having an unsaturated bond such as ⁇ -methylstyrene. Among these, only 1 type may be used and 2 or more types may be combined.
- the polymethyl methacrylate preferably has a glass transition temperature in the range of 80 to 120 ° C. Furthermore, polymethyl methacrylate has a high surface hardness when formed into a film, specifically, a pencil hardness (according to JIS K5600-5-4 except that the test load is 500 g) exceeding 2H. Is preferred.
- the resin constituting the transparent protective film is, for example, a 1 mm thick plate having a total light transmittance of 80% or more, preferably 85%, like the resin constituting the protective film for protecting the cholesteric resin layer. More preferably, 90% or more can be used.
- the transparent protective film has a moisture permeability at a thickness of 100 ⁇ m of usually 20 to 500 g / m 2 ⁇ 24 h, preferably 50 to 200 g / m 2 ⁇ 24 h, more preferably 120 to 170 g / m 2 ⁇ 24 h.
- the thickness of the transparent protective film is preferably 100 ⁇ m or less, more preferably 1 ⁇ m or more and 60 ⁇ m or less, and further preferably 5 ⁇ m or more and 40 ⁇ m or less. By setting the thickness within the above range, the polarizing plate and the display device can be thinned.
- the method for integrating the polarizing plate and the transparent protective film is not particularly limited. For example, a method of plasma-treating these surfaces and then pressure-bonding them, a method of laminating via an adhesive layer or an adhesive layer, etc. Can be mentioned.
- the pressure-sensitive adhesive and adhesive can be applied directly at the time of lamination, but after applying the adhesive or pressure-sensitive adhesive on the separator, laminating and peeling the separator, the pressure-sensitive adhesive layer or adhesive Layers can also be formed.
- a transparent protective film may be provided on both sides of the polarizer, and the brightness enhancement film of the present invention may be bonded to one side (see the embodiment of FIG. 3), or the transparent protective film on one side of the polarizer. And the brightness enhancement film of the present invention can be bonded to the other surface (see the embodiment of FIG. 4).
- the transparent protective film is provided only on one side of the polarizer and the brightness enhancement film is provided on one side, the polarizer can be protected with a small number of films, and the display device can be thinned.
- a polarizing plate contained in the composite laminate (also referred to as a composite) is combined with a liquid crystal cell and another polarizing plate, whereby a polarizing plate-liquid crystal cell- A laminated structure called a polarizing plate is formed, and thereby the display of images is controlled.
- a polarizing plate included in the composite is used as a first polarizing plate, and a liquid crystal cell is sandwiched between the first polarizing plate and another second polarizing plate.
- the first polarizing plate can be incorporated into the display device by attaching the first polarizing plate to the liquid crystal cell with the light source side (that is, the lighting device side) and the second polarizing plate as the display surface side.
- the material of the polarizer (second polarizer) included in the second polarizing plate is not particularly limited, and the same material as the polarizer (first polarizer) included in the first polarizing plate may be used. it can.
- the liquid crystal cell is not particularly limited and can be appropriately selected from those used in known liquid crystal display devices. Specifically, the polarized light that has passed through the first polarizer is controlled by the liquid crystal cell so that the polarized light passes through the second polarizer and is emitted from the display surface or is not emitted, and as a result, an image is displayed on the display surface.
- Various types of liquid crystal cells and polarizers can be used.
- a driving method of the liquid crystal cell for example, a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, a HAN (Hybrid Alignment Nematic) type, an IPS (In Plane Switching) type, a VA (Vertical Agate type) Examples include a Multiple Vertical Alignment type and an OCB (Optical Compensated Bend) type.
- TN Transmission Nematic
- STN Super Twisted Nematic
- HAN Hybrid Alignment Nematic
- IPS In Plane Switching
- VA Very Agate type
- a driving method of the liquid crystal cell for example, a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, a HAN (Hybrid Alignment Nematic) type, an IPS (In Plane Switching) type, a VA (Vertical Agate type) Examples include a Multiple Vertical Alignment type and an OCB (Optical Compensated Bend) type.
- the liquid crystal display device of the present invention can further include a backlight as a lighting device, and can have a configuration in which a brightness enhancement film is disposed between the backlight and the liquid crystal cell. More specifically, the brightness enhancement film of the present invention is arranged between the backlight of the liquid crystal display device and the liquid crystal cell so that the cholesteric resin layer is on the backlight side of the ⁇ / 4 plate, thereby improving the brightness. Can be achieved.
- liquid crystal display device of the present invention is not particularly limited, and can be used as a television, a display device for computers, a display device for other electronic devices, and the like. In particular, it can be suitably used in applications that require high display quality over a wide viewing angle.
- the test was conducted in accordance with the JIS K5600-5-4 scratch hardness test method except that the load was 500 g, the scanning distance was 30 mm, and the stamping speed was 20 mm / min. The hardness of the cholesteric resin layer surface of the brightness enhancement film was measured.
- Evaluation was made by cutting the surface of the cholesteric resin layer of the brightness enhancement film according to JIS K5600-5-6 cross-cut method. Evaluation 5: Small peeling of the coating film at the intersection of cuts. Evaluation 4: The coating film is peeled along the edge of the cut and / or at the intersection. Evaluation 3: The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eyes are partially or completely peeled off. Evaluation 2: The coating film is partially or completely peeled along the edge of the cut, and / or several eyes are partially or completely peeled off. Evaluation 1: When the degree of peeling exceeds Evaluation 2.
- Example 1> (I. Production of substrate-cholesteric resin layer laminate)
- a sheet-like substrate (trade name “Zeonor ZF14-100”, manufactured by Nippon Zeon Co., Ltd.) was subjected to corona discharge treatment so that the wetting index was 56 mN / m.
- Polyvinyl alcohol (trade name “Poval PVA203”, manufactured by Kuraray Co., Ltd.) is applied to the corona discharge treated surface with a # 2 bar coater and dried at 120 ° C. for 5 minutes to produce a dry film having a thickness of 0.2 ⁇ m. did. By rubbing the dry film in one direction, a substrate having an alignment film was obtained.
- This cholesteric liquid crystal composition was applied to the surface having the alignment film of the base material having the alignment film prepared above with a die coater.
- the coating film is subjected to an orientation treatment at 100 ° C. for 5 minutes, and the coating film is subjected to a process of irradiation with weak ultraviolet rays of 0.1 to 45 mJ / cm 2 and subsequent heating treatment at 100 ° C. for 1 minute.
- ultraviolet rays of 800 mJ / cm 2 were irradiated in a nitrogen atmosphere to form a cholesteric resin layer having a dry film thickness of 5.3 ⁇ m to obtain a substrate-cholesteric resin layer laminate.
- Rubber particles were produced according to Example 3 of JP-B-55-27576. This rubber particle has a spherical three-layer structure, the core inner layer is a crosslinked polymer of methyl methacrylate and a small amount of allyl methacrylate, and the inner layer is composed of butyl acrylate and styrene as main components and a small amount of acrylic acid.
- the outer layer is a hard polymer of methyl methacrylate and a small amount of ethyl acrylate.
- the average particle size of the inner layer was 0.19 ⁇ m, and the particle size including the outer layer was 0.22 ⁇ m.
- methacrylic acid ester polymer composition A glass transition temperature 105 ° C.
- the methacrylic acid ester polymer composition A (b layer) and the styrene maleic anhydride copolymer (glass transition temperature 130 ° C.) (a layer) are coextruded at a temperature of 280 ° C.
- a multilayer film having a three-layer structure of -b layers, each layer having an average thickness of 45-70-45 ( ⁇ m) was obtained.
- This multilayer film was tenter uniaxially stretched at a stretching temperature of 128 ° C., a stretching ratio of 1.4 times, and a stretching speed of 10 m / min to obtain a quarter-wave plate as a stretched multilayer film. Further, one side of this quarter-wave plate was subjected to corona discharge treatment so that the wetting index was 56 dyne / cm. Regarding the retardation value of the obtained quarter-wave plate at a wavelength of 550 nm, the retardation Rth in the thickness direction was ⁇ 118 nm, and the retardation Re in the in-plane direction was 140 nm.
- Substrate-Cholesteric resin layer laminate produced by mixing and dissolving 0.9 parts (trade name “IRGACURE651”, manufactured by Ciba Specialty Chemicals) the corona discharge treatment (treatment conditions: 150W ⁇ min / m 2) was It was coated using a # 6 bar corona discharge treated surface, and dried for 1 minute at 65 ° C., a substrate having an adhesive layer having a thickness of 3.4 .mu.m - cholesteric resin layer - to produce a laminate of the adhesive layer.
- the base material was peeled from the laminate to obtain a brightness enhancement film 1 having a layer configuration of a quarter-wave plate, an adhesive layer, and a cholesteric resin layer.
- the evaluation results of the brightness enhancement film 1 are shown in Table 1.
- Example 2 ⁇ Example 2> 18.2 parts urethane acrylate (trade name “UV-7000B”, manufactured by Nippon Synthetic Chemical Co., Ltd.) as oligomer-type polyfunctional (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate (product) as (meth) acrylate
- the brightness enhancement film 2 was obtained in the same manner as in Example 1 except that the ratio was changed to 72.7 parts (name “DA141”, manufactured by Nagase Chemitech, viscosity 373 mPa ⁇ s).
- the evaluation results of the brightness enhancement film 2 are shown in Table 1.
- Example 3 A brightness enhancement film is obtained in the same manner as in Example 2 except that (meth) acrylate is changed to 72.7 parts of monohydroxyalkyl acrylate (trade name “PA500”, manufactured by Toho Chemical Co., Ltd., viscosity 71.8 mPa ⁇ s). 3 was obtained. The evaluation results of the brightness enhancement film 3 are shown in Table 1.
- Example 4 Luminance improvement in the same manner as in Example 1 except that the oligomer type polyfunctional (meth) acrylate was changed to 54.5 parts of epoxy acrylate (trade name “Evekryl EB3708”, manufactured by Daicel-Cytech, 2 functional groups). Film 4 was obtained. The evaluation results of the brightness enhancement film 4 are shown in Table 1.
- urethane acrylate (trade name “UV-7000B”, manufactured by Nippon Synthetic Chemical Co., Ltd., 2 to 3 functional groups), 72.7 parts of 2-hydroxy-3-phenoxypropyl acrylate as (meth) acrylate ( Trade name “DA141”, manufactured by Nagase Chemitech Co., Ltd., viscosity 373 mPa ⁇ s), 9.1 parts of 4-hydroxybutyl acrylate, 71.9 parts of methyl ethyl ketone, other photopolymerization initiator (trade name “DAROCURE TPO”, Ciba 2.7 parts by Specialty Chemicals), 332.2 parts urethane resin (trade name “Yuriano 5242”, Arakawa Chemical Industries, Ltd.) as an inert polymer, and crosslinked polystyrene particles (trade name “SX130H”, Soken Chemical Co., Ltd.) 13.8 parts of the adhesive solution prepared by mixing and dissolving the above (i.
- UV-7000B manufactured by Nippon Synthetic Chemical Co.
- the surface of the cholesteric resin layer produced in step 1) was applied to the corona discharge treated surface subjected to corona discharge treatment (treatment condition: 150 W ⁇ min / m 2 ) using a blade and at 65 ° C.
- the substrate was dried for 2 minutes to produce a laminate of a base material-cholesteric resin layer-adhesive layer having an adhesive layer with a thickness of 10.5 ⁇ m.
- Subsequent steps were carried out in the same manner as in Example 1 to obtain the brightness enhancement film 5.
- the evaluation results of the brightness enhancement film 5 are shown in Table 1.
- the brightness enhancement film 6 was placed on a prism sheet of a liquid crystal monitor LCD-DTV 191X (sheet configuration: diffusion sheet / prism sheet) manufactured by IO DATA, and observed with white display. The glare caused by the prism sheet was not observed, and the cholesteric resin layer was not lifted, and the display was uniform in brightness.
- LCD-DTV 191X sheet configuration: diffusion sheet / prism sheet
- Example 8> (Ix. Manufacture of liquid crystal display devices)
- the surface on the quarter wavelength plate side of the brightness enhancement film 1 produced in Example 1 was subjected to corona treatment so as to have a wetting index of 56 dyne / cm, and PVA (trade name “GOHSEFIMAR Z200”, manufactured by Nippon Synthetic Chemical Co., Ltd. ) PVA adhesive solution consisting of 3.0 parts, glyoxal (trade name “Glyoxal”, Nippon Synthetic Chemical Co., Ltd.) 0.05 part, and pure water 97.0 parts was applied with a # 8 bar and protected on one side of the polarizer.
- the laminate was bonded to the other side of the polarizing plate to which the film was adhered and dried at 100 ° C. for 2 minutes to obtain a laminate.
- IO DATA company LCD monitor LCD-DTV191X LCD panel light source side polarizing plate is peeled off, and the laminated body manufactured above is laminated so that the brightness enhancement film side faces the light source side, and then installed again, with white display Observations were made.
- the display was uniform in brightness with no point defects in the surface and no cholesteric resin layer floating.
- Example 9 (X. Production of brightness enhancement film) Corona treatment was performed so that the single-sided wetting index of the quarter-wave plate manufactured in (ii) was 56 dyne / cm, the diffusion adhesive layer manufactured in (v) was bonded, and the separator was peeled off.
- the produced cholesteric resin layer of the laminate was subjected to corona treatment (treatment condition: 150 W ⁇ min / m 2 ), and bonded to the diffusion adhesive layer, and the substrate was peeled off. Corona treatment (treatment condition: 150 W ⁇ min / m 2 ) is performed on the surface of the cholesteric resin layer opposite to the surface in contact with the diffusion adhesive layer, and the adhesive solution used in Example 1 is the same as in Example 1.
- the coating layer was dried by the method described above to obtain an adhesive layer-cholesteric resin layer-diffusion adhesive layer-1 / 4 wavelength plate laminate.
- Zeonor film (trade name “ZF14-100”, manufactured by Nippon Zeon Co., Ltd.) as a transparent film was subjected to corona treatment so that the wetting index was 56 dyne / cm, and the adhesive layer of the laminate obtained in (x) was obtained. In the same manner as in Example 1, the adhesive layer was cured by UV irradiation.
- the diffusion adhesive layer of the separator-diffusion adhesive layer laminate produced in (v) above was bonded to the quarter-wave plate side, the separator was peeled off, and a ZEONOR film (trade name “ZF14-100”, Japan) Zeon Co., Ltd.) was bonded to produce a brightness enhancement film 7 of ZEONOR film-diffusion adhesive layer-1 / 4 wavelength plate-diffusion adhesive layer-cholesteric resin layer-adhesion layer-ZEONOR film.
- the brightness enhancement film 7 was placed on a prism sheet of a liquid crystal monitor LCD-DTV 191X (sheet configuration: diffusion sheet / prism sheet) manufactured by IO DATA, and observed with a white display. The glare caused by the prism sheet was not observed, and the brightness enhancement film 2 was not swelled by heat when the backlight was lit, and the display was uniform in brightness.
- Example 2 except that the oligomer-type polyfunctional (meth) acrylate was changed to 18.2 parts of urethane acrylate (trade name “UV-7640B”, manufactured by Nippon Synthetic Chemical Co., Ltd., 6 or more functional groups). Thus, a brightness enhancement film 9 was obtained.
- the evaluation results of the brightness enhancement film 9 are shown in Table 1. It was found that when an oligomer type polyfunctional (meth) acrylate having a functional group number of 6 or more was used, the adhesive strength was lowered.
- the brightness enhancement film 10 was obtained in the same manner as in Example 2 except that (meth) acrylate was changed to 72.7 parts of HEA (2-hydroxyethyl acrylate, manufactured by Toho Chemical Co., Ltd., viscosity 9.0 mPa ⁇ s). It was. When the viscosity of (meth) acrylate was lowered, coating suitability was deteriorated, and it was found that there was a problem in the production of a brightness enhancement film.
- Example 6 A liquid crystal monitor was prepared in the same manner as in Example 7 except that the brightness enhancement film was changed to that manufactured in Comparative Example 1, and observation was performed with white display. Point defects, scratches, and floating of the cholesteric resin layer were observed in the surface.
- Example 7 A liquid crystal monitor was prepared in the same manner as in Example 8 except that the brightness enhancement film was changed to that produced in Comparative Example 1, and observation was performed with white display. Point defects, scratches, and floating of the cholesteric resin layer were observed in the surface.
- the brightness enhancement film 12 was placed on a prism sheet of a liquid crystal monitor LCD-DTV 191X (sheet configuration: diffusion sheet / prism sheet) manufactured by IO DATA and observed with a white display. Although glare caused by the prism sheet was not observed, the brightness enhancement film 3 was swelled by heat when the backlight was turned on, and an in-plane distribution of color was observed.
- LCD-DTV 191X sheet configuration: diffusion sheet / prism sheet
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Abstract
Description
また、配向膜を有する塗工基材上に形成されたコレステリック樹脂層を剥離して、他の透光性基材上に転写する際、コレステリック樹脂層にかかる応力によって、樹脂層に容易にクラックが発生するという問題があった。
さらに、コレステリック樹脂層を支持する基材とコレステリック樹脂層を貼り合せる際に使用する粘着剤によっては、自己支持性が不十分であり、バックライト点灯時の熱や環境試験において変形が見られるという問題があった。
即ち、本発明によれば、下記〔1〕~〔9〕が提供される。
活性エネルギー線硬化型接着層は、活性エネルギー線硬化型の接着剤組成物を硬化させてなり、
接着剤組成物が未硬化状態で
(A)官能基数が3以下のオリゴマー型多官能(メタ)アクリレート、及び
(B)温度20±1.0℃における粘度が10mPa・s以上500mPa・s未満の分子内に水酸基を少なくともひとつ有するモノ(メタ)アクリレート
を少なくとも含むことを特徴とする輝度向上フィルム。
〔2〕 未硬化状態の接着剤組成物に含まれる(メタ)アクリレート100重量部中、(B)の含有量が35~85重量部の範囲にある〔1〕記載の輝度向上フィルム。
〔3〕 (A)がウレタン(メタ)アクリレート、エポキシ(メタ)アクリレート、ポリエステル(メタ)アクリレートからなる群より選択される少なくとも1種のオリゴマー型(メタ)アクリレートである〔1〕または〔2〕に記載の輝度向上フィルム。
〔4〕未硬化状態の接着剤組成物がさらに
(C)ガラス転移温度が-10℃以上80℃以下の不活性重合体を含むことを特徴とする〔1〕~〔3〕に記載の輝度向上フィルム。
〔5〕透明フィルムがλ/4板である〔1〕~〔4〕のいずれかに記載の輝度向上フィルム。
〔6〕偏光子の両面に透明保護フィルムを設け、一方の面に、〔1〕~〔5〕のいずれかに記載の輝度向上フィルムを貼り合せたことを特徴とする偏光板。
〔7〕偏光子の片面に透明保護フィルムを設け、他方の面に〔1〕~〔5〕のいずれかに記載の輝度向上フィルムを貼り合せたことを特徴とする偏光板。
〔8〕〔1〕~〔5〕のいずれかに記載の輝度向上フィルムを備えた液晶表示装置。
〔9〕〔6〕または〔7〕に記載の偏光板を液晶セルの照明装置側に貼り合せた液晶表示装置。
本発明の輝度向上フィルムは、コレステリック樹脂層を備える。また、本発明の輝度向上フィルムは、コレステリック樹脂層の少なくとも一方の面に、活性エネルギー線硬化型接着層を介して、透明フィルムを備える。なお、透明フィルムは、コレステリック樹脂層の両方の面に設けられていてもよい。
透明フィルムとしては、1/4波長板(「λ/4板」ということもある。)、保護フィルム等が例示できる。
(1/4波長板)
1/4波長板としては、例えば、フィルム状のポリマーを延伸してなる延伸フィルムを用いることができる。ポリマーとしては、透明樹脂を好ましく用いることができ、前記透明樹脂は例えば1mm厚板で全光透過率80%以上のものを使用することができる。例えば、ポリメチルメタクリレート、ポリスチレン、ポリカーボネート、ポリエーテルスルホン、アモルファスポリエチレン、トリアセチルセルロース、脂環式構造を有する樹脂などを挙げることができる。好ましい例として、スチレン系樹脂層を含む樹脂フィルムを延伸してなる1/4波長板、脂環式構造を有する樹脂フィルムを延伸してなる1/4波長板を挙げることができる。より好ましくは、以下に述べる光学異方性素子を挙げることができる。
なお、前記正面方向のリターデーションRe及び厚み方向のリターデーションRthは、市販の位相差測定装置を用いて、1/4波長板を長手方向及び幅方向に100mm間隔(長手方向又は横方向の長さが200mmに満たない場合は、その方向へは等間隔に3点指定する)で、全面にわたり、格子点状に測定を行い、その平均値とする。
コレステリック樹脂層を保護する保護フィルムとしては、透明樹脂フィルムを用いることができる。透明樹脂としては、1/4波長板に使用したものと同じものを使用することができる。特に好ましくは、耐熱性、透明性が良好な未延伸の脂環式構造を有する樹脂フィルムを用いることができる。
これらの中で、長尺での製造適性に優れている、透光性粒子を樹脂溶液中に分散した溶液を透明樹脂フィルム表面に塗工する方法が好ましい。
凹凸を設けた表面の好ましい十点平均粗さRzと平均長さSmの比Rz/Smは、2×10-4~7×10-3の範囲であり、より好ましくは3×10-4~5×10-3、さらに好ましくは5×10-4~4.5×10-3である。
(コレステリック樹脂層)
コレステリック樹脂層(すなわち、コレステリック規則性を有する樹脂層)とは、樹脂層形成用の基材上にコレステリック液晶組成物の塗膜を設け、塗膜を硬化させてなる、樹脂層である。
コレステリック規則性とは、一平面上では分子軸が一定の方向に並んでいるが、次の平面では分子軸の方向が少し角度をなしてずれ、さらに次の平面ではさらに角度がずれるという具合に、分子が一定方向に配列している平面を進むに従って分子軸の角度がずれて(ねじれて)いく構造である。このように分子軸の方向がねじれてゆく構造は光学的にカイラルな構造となる。
R1X-A1X-Z-A2X-R2X (1)
一般式(1)の化合物の少なくとも一種は、その融点が、50℃~150℃の範囲内であることが好ましい。
R3X-C3X-D3X-C5X-M-C6X-D4X-C4X-R4X 式(2)
一般式(2)において、D3X及びD4Xは単結合、炭素原子数1~20個の直鎖状又は分岐鎖状のメチレン基およびアルキレン基などの二価の飽和炭化水素基、並びに炭素原子数1~20個の直鎖状又は分岐鎖状のアルキレンオキサイド基からなる群より選択される基を表す。
一般式(2)において、Mはメソゲン基を表し、具体的には、非置換又は置換基を有していてもよい、アゾメチン類、アゾキシ類、フェニル類、ビフェニル類、ターフェニル類、ナフタレン類、アントラセン類、安息香酸エステル類、シクロヘキサンカルボン酸フェニルエステル類、シアノフェニルシクロヘキサン類、シアノ置換フェニルピリミジン類、アルコキシ置換フェニルピリミジン類、フェニルジオキサン類、トラン類、アルケニルシクロヘキシルベンゾニトリル類の群から選択された2~4個の骨格を、-O-、-S-、-S-S-、-CO-、-CS-、-OCO-、-CH2-、-OCH2-、-CH=N-N=CH-、-NHCO-、-OCOO-、-CH2COO-、及び-CH2OCO-等の結合基によって結合されて形成される基を表す。
(M2)任意の基材層を用い、この上にコレステリック樹脂層を形成し、接着剤組成物等を介してコレステリック樹脂層を透明フィルムに転写し基材層を剥離して、透明フィルムにコレステリック樹脂層を設けてもよい。こうすることで、例えば、接着層を介して1/4波長板とコレステリック樹脂層の基材レスの積層構造を得ることができる。
前記変性ポリアミドとしては、芳香族ポリアミド又は脂肪族ポリアミドに変性を加えたものを挙げることができ、脂肪族ポリアミドに変性を加えたものが好ましい。
接着層は、転写に先立ち、転写対象の層及びコレステリック樹脂層の両側の向き合う面のうち、どちらか一方又は両方に予め設けることができる。
コレステリック樹脂層を配向膜上に形成した場合、コレステリック樹脂層のみを転写してもよいが、コレステリック樹脂層および配向膜を共に転写してもよい。剥離の容易さ及びコレステリック樹脂層の配向不良発生防止の観点からは、コレステリック樹脂層及び配向膜を共に転写することが好ましい。
本発明で使用される接着層(活性エネルギー線硬化型接着層)は、活性エネルギー線硬化型の接着剤組成物(接着層組成物ともいう。)を硬化させてなる接着層である。前記の接着剤組成物は、未硬化状態で(A)官能基数が3以下のオリゴマー型多官能(メタ)アクリレート、及び(B)温度20±1.0℃における粘度が10mPa・s以上500mPa・s未満の水酸基を少なくともひとつ有するモノ(メタ)アクリレートを含む。ここで、(メタ)アクリレートとは、アクリレート及び/またはメタクリレートの意味である。
(A)官能基数が3以下のオリゴマー型多官能(メタ)アクリレート
本発明で用いる官能基数が3以下のオリゴマー型多官能(メタ)アクリレートは、好ましくは官能基数が2および3である。前記オリゴマー型多官能(メタ)アクリレートとしては、例えば、ポリエステル(メタ)アクリレート、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレート、ポリエーテル(メタ)アクリレート、シリコーン(メタ)アクリレートなどのラジカル重合性を示す各種の官能基数が3以下のアクリル系オリゴマーの単独またはこれらの混合物が例示される。
多塩基酸としては、フタル酸、アジピン酸、マレイン酸、イタコン酸、コハク酸、テレフタル酸などが挙げられる。
多価アルコールとしては、エチレングリコール、1,4-ブタンジオール、1,6-ヘキサンジオール、ジエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、などが挙げられる。
例えば、EBECRYL 851,852,853,884,885(ダイセルサイテック社製)、オレスター(三井化学社製)、アロニックスM-6100,6200,6250,6500(東亞合成社製)などを挙げることができる。
エポキシ樹脂としては、ビスフェノールAとエピクロロヒドリンからなるビスフェノールA型、フェノールノボラックとエピクロロヒドリンからなるノボラック型、脂肪族型、脂環型のものがある。脂肪族型エポキシ樹脂としては、エチレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,4-ブタンジオールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、トリメチロールプロパンジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテルなどを用いることができ、またブタジエン系エポキシ樹脂、イソプレン系エポキシ樹脂などの不飽和脂肪酸エポキシ樹脂も用いることができる。脂環型エポキシ樹脂は、ビニルシクロヘキセンモノオキサイド、1,2-エポキシ-4-ビニルシクロヘキサン、1,2:8,9-ジエポキシシリモネン、3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレートなどを用いることができる。
温度20±1.0℃における粘度が10mPa・s以上500mPa・s未満とは、温度条件の範囲内の少なくとも1点で粘度の測定値が10mPa・s以上500mPa・s未満を満たすことをいう。本発明で用いる温度20±1.0℃における粘度が10mPa・s以上500mPa・s未満の水酸基を少なくともひとつ有するモノ(メタ)アクリレートの具体例としては、2-ヒドロキシプロピルアクリレート(10.9mPa・s)、4-ヒドロキシブチルアクリレート(17mPa・s)、2-ヒドロキシ-3-フェノキシプロピルアクリレート(373mPa・s)、グリセリンモノメタクリレート:ブレンマーGLM(150mPa・s、日油社製)、ポリエチレングリコールモノメタクリレート:ブレンマーPE-90(15mPa・s、日油社製)、PE-200(30mPa・s、日油社製)、PE-350(45mPa・s、日油社製)、ポリプロピレングリコールモノメタクリレート:ブレンマーPP-1000(50mPa・s、日油社製)、PP-500(75mPa・s、日油社製)、ポリ(エチレン・プロピレングリコール)モノメタクリレート:ブレンマー50PEP-300(55mPa・s、日油社製)、ポリエチレングリコール・ポリプロピレングリコールモノメタクリレート:ブレンマー70PEP-350B(79mPa・s、日油社製)、プロピレングリコール・ポリブチレングリコールモノメタクリレート:ブレンマー10PPB-500B(48mPa・s、日油社製)、ポリエチレングリコールモノアクリレート:ブレンマーAE-200(15mPa・s、日油社製)、ポリプロピレングリコールモノアクリレート:ブレンマーAP-400(48mPa・s、日油社製)、脂肪族エポキシアクリレート:EBECRYL112(55mPa・s、ダイセルサイテック)、PA500(71.8mPa・s、東邦化学社製)等が挙げられる。
必要に応じて本発明の効果を損なわない範囲で、接着剤組成物には、重合開始剤、架橋剤、無機フィラー、重合禁止剤、着色顔料、染料、消泡剤、レベリング剤、分散剤、光拡散剤、可塑剤、帯電防止剤、界面活性剤、非反応性ポリマー(不活性重合体)、粘度調整剤、近赤外線吸収材、密着付与剤等を含むことも可能である。
光硬化を行う場合、光重合開始剤を1種類以上使用することができる。また、任意に光増感剤を用いることができる。
また、光増感剤として例えば、n-ブチルアミン、トリエチルアミン、ポリ-n-ブチルホスフィンなどを添加して硬化性をコントロールすることもできる。
消泡剤は、接着層の接着力が低下しない程度に添加することが可能であり、未硬化状態の接着剤組成物固形分に対して、0.1重量部以上1.0重量部以下が好ましく、より好ましくは0.1重量部以上0.5重量部以下である。
金属酸化物としては、シリカ、水酸化アルミニウム、酸化アルミニウム、酸化チタン、酸化亜鉛、硫酸バリウム、マグネシウムシリケート、およびこれらの混合物などが挙げられる。例えば、日産化学社製 オルガノシリカゾル メタノールシリカゾル,IPA-ST,IPA-ST-UP,IPA-ST-ZL,EG-ST,NPC-ST-30,DMAC-ST,MEK-ST,MIBK-ST,XBA-ST,PMA-ST,PGM-ST、扶桑化学社製 PL-1-IPA,PL-1-TOL,PL-2L-PGME,PL-2L-MEKなどを挙げることができる。
光拡散剤の量(添加部)は、未硬化状態の接着剤組成物に含まれる固形分100重量部に対して、好ましくは0.5~20重量部である。光拡散剤の量(添加部)は、所望のヘイズ値と接着層の膜厚で決定される値である。
密着付与剤の量(添加部)は、未硬化状態の接着剤組成物に含まれる固形分100重量部中、好ましくは1重量部以上30重量部以下であり、より好ましくは5重量部以上20重量部以下である。
本発明の偏光板、液晶表示装置は、前記本発明の輝度向上フィルムを備える。好ましい態様として、本発明の液晶表示装置は、前記本発明の輝度向上フィルムを含む前記本発明の偏光板を有する。この場合の偏光板はさらに透明保護フィルムを設けることができる。透明保護フィルムとしては、前記のコレステリック樹脂層を保護するための保護フィルムと同様の樹脂を使用することができ、これらの中でもポリメチルメタクリレート、トリアセチルセルロースであることが好ましく、表示装置の耐久性や表示性能を向上させることができる観点から、ポリメチルメタクリレートであることが特に好ましい。また、透明保護フィルムの材料である透明材料としては、熱可塑性樹脂であることが好ましい。
ポリメチルメタクリレートとしては、メタクリ酸メチル、メタクリル酸エチルなどのメタクリル酸アルキルエステルの単独重合体;またはメタクリル酸アルキルエステルとスチレン、酢酸ビニル、α,β-モノエチレン性不飽和カルボン酸、ビニルトルエン、α-メチルスチレンなどの不飽和結合を有するビニル系モノマーとの共重合体を挙げることができる。これらのうち1種のみを用いてもよいし、2種以上を組み合わせてもよい。当該ポリメチルメタクリレートは、ガラス転移温度が80~120℃の範囲のものが好ましい。さらに、ポリメチルメタクリレートは、フィルムに成形したときの表面硬度が高いもの、具体的には、鉛筆硬度(試験荷重を500gとした以外は、JIS K5600-5-4に準拠)で2Hを超えるものが好ましい。
(i.接着剤の塗工性)
塗工基材に塗布直後の濡れ広がり方、乾燥後の塗布ハジキの発生、粘性不足に伴う膜面の乱れなどを目視観察し5段階評価をした。
評価5:塗工性に優れるもの
評価4:塗工性にやや優れるもの
評価3:塗工性が普通のもの
評価2:塗工性にやや劣るもの
評価1:塗工性に劣るもの
荷重500g、走査距離30mm、走印速度20mm/minとしたこと以外は、JIS K5600-5-4引っかき硬度試験法に準拠して実施した。輝度向上フィルムのコレステリック樹脂層表面の硬度を測定した。
輝度向上フィルムのコレステリック樹脂層表面にJIS K5600-5-6クロスカット法に準拠して切り込みを入れて評価した。
評価5:カットの交差点における塗膜の小さなはがれ。
評価4:塗膜がカットの縁に沿って、および/または交差点において剥がれている。
評価3:塗膜がカットの縁に沿って、部分的または全面的に大剥がれを生じており、および/または目の色々な部分が、部分的又は全面的に剥がれている。
評価2:塗膜がカットの縁に沿って、部分的または全面的に大はがれを生じており、および/または数箇所の目が部分的または全面的に剥がれている。
評価1:剥がれの程度が評価2を超える場合。
振動式粘度計(エーアンドデイ社製 音叉型振動式粘度計SV-10)にて測定した。
(i.基材-コレステリック樹脂層積層体の製造)
シート状基材(商品名「ゼオノアZF14-100」、日本ゼオン株式会社製)の片面に、濡れ指数が56mN/mになるようにコロナ放電処理を施した。このコロナ放電処理面に、ポリビニルアルコール(商品名「ポバールPVA203」、株式会社クラレ製)を#2バーコーターにて塗布し、120℃で5分間乾燥し、膜厚0.2μmの乾膜を製造した。該乾膜を一方向にラビング処理することで、配向膜を有する基材を得た。
メタクリル酸メチル97.8重量%とアクリル酸メチル2.2重量%とからなるモノマー組成物を、バルク重合法により重合させ、樹脂ペレットを得た。
特公昭55-27576号公報の実施例3に準じて、ゴム粒子を製造した。このゴム粒子は、球形3層構造を有し、芯内層が、メタクリル酸メチル及び少量のメタクリル酸アリルの架橋重合体であり、内層が、主成分としてのアクリル酸ブチルとスチレン及び少量のアクリル酸アリルとを架橋共重合させた軟質の弾性共重合体であり、外層が、メタクリル酸メチル及び少量のアクリル酸エチルの硬質重合体である。また、内層の平均粒子径は0.19μmであり、外層をも含めた粒径は0.22μmであった。
上記メタクリル酸エステル重合体組成物A(b層)、及びスチレン無水マレイン酸共重合体(ガラス転移温度130℃)(a層)を温度280℃で共押出成形することにより、b層-a層-b層の三層構造で、各層が45-70-45(μm)の平均厚みを有する複層フィルムを得た。この複層フィルムを、延伸温度128℃、延伸倍率1.4倍、延伸速度10m/分でテンター一軸延伸し、延伸複層フィルムである1/4波長板を得た。さらにこの1/4波長板の片面を、濡れ指数が56dyne/cmになるようにコロナ放電処理を施した。
得られた1/4波長板の波長550nmにおけるリターデーション値は、厚み方向のリターデーションRthは-118nm、面内方向のリターデーションReは140nmであった。
オリゴマー型多官能(メタ)アクリレートとしてウレタンアクリレート(商品名「UV-7000B」、日本合成化学(株)社製、官能基数2~3)54.5部、(メタ)アクリレートとして2-ヒドロキシ-3-フェノキシプロピルアクリレート36.4部(商品名「DA141」、ナガセケミテック社製、粘度373mPa・s)、他アクリレートとして4-ヒドロキシブチルアクリレート9.1部、メチルエチルケトン17.8部、および光重合開始剤0.9部(商品名「IRGACURE651」、チバ・スペシャリティケミカルズ社製)を混合溶解させた接着剤液を、上記(i.基材-コレステリック樹脂層積層体の製造)で製造したコレステリック樹脂層表面をコロナ放電処理(処理条件:150W・min/m2)を行ったコロナ放電処理面に#6バーを用いて塗布し、65℃にて1分間乾燥し、膜厚3.4μmの接着層を有する基材-コレステリック樹脂層-接着層の積層体を製造した。
上記(ii.1/4波長板の製造)で得た1/4波長板のコロナ放電処理面と、上記(iii.基材-コレステリック樹脂層-接着層積層体の製造)で得た積層体の接着層側の面とを重ねて、速度0.5m/min、狭圧0.3~0.4MPaでラミネーターにて貼り合わせた。この積層体の1/4波長板側からUV照射(日本電池社製大型UV照射装置、メタルハライドランプ、照射時間12s、積層光量1200J/cm2)を行い、接着層を硬化した。
続いて、積層体から、基材を剥離し、1/4波長板-接着層-コレステリック樹脂層の層構成を有する輝度向上フィルム1を得た。輝度向上フィルム1の評価結果を表1に示す。
オリゴマー型多官能(メタ)アクリレートとしてウレタンアクリレート(商品名「UV-7000B」、日本合成化学(株)社製)18.2部、(メタ)アクリレートとして2-ヒドロキシ-3-フェノキシプロピルアクリレート(商品名「DA141」、ナガセケミテック社製、粘度373mPa・s)72.7部と、比率を変えた以外は、実施例1と同様にして、輝度向上フィルム2を得た。輝度向上フィルム2の評価結果を表1に示す。
(メタ)アクリレートを、モノヒドロキシアルキルアクリレート(商品名「PA500」、東邦化学社製、粘度71.8mPa・s)72.7部に変えた以外は、実施例2と同様にして、輝度向上フィルム3を得た。輝度向上フィルム3の評価結果を表1に示す。
オリゴマー型多官能(メタ)アクリレートを、エポキシアクリレート(商品名「エベクリル EB3708」、ダイセル・サイテック社製、官能基数2)54.5部に変えた以外は、実施例1と同様にして、輝度向上フィルム4を得た。輝度向上フィルム4の評価結果を表1に示す。
ウレタンアクリレート(商品名「UV-7000B」、日本合成化学(株)社製、官能基数2~3)18.2部、(メタ)アクリレートとして2-ヒドロキシ-3-フェノキシプロピルアクリレート72.7部(商品名「DA141」、ナガセケミテック社製、粘度373mPa・s)、他アクリレートとして4-ヒドロキシブチルアクリレート9.1部、メチルエチルケトン71.9部、光重合開始剤(商品名「DAROCURE TPO」、チバ・スペシャリティケミカルズ社製)2.7部、不活性重合体としてウレタン樹脂(商品名「ユリアーノ5242」、荒川化学工業社製)332.2部、および架橋ポリスチレン粒子(商品名「SX130H」、綜研化学社製)13.8部を混合溶解および分散させた接着剤液を、上記(i.基材-コレステリック樹脂層積層体の製造)で製造したコレステリック樹脂層表面をコロナ放電処理(処理条件:150W・min/m2)を行ったコロナ放電処理面にブレードを用いて塗布し、65℃にて2分間乾燥し、膜厚10.5μmの接着層を有する基材-コレステリック樹脂層-接着層の積層体を製造した。後の工程は実施例1と同様にして輝度向上フィルム5を得た。輝度向上フィルム5の評価結果を表1に示す。
(v.拡散剤混合粘着層の製造)
ポリエチレンテレフタレートセパレータ(商品名「PET50AL」、リンテック(株)社製)に、ベース樹脂(商品名「SKダイン2094」、綜研化学株式会社製、アクリル酸エステル共重合体、固形分率25%、溶媒:酢酸エチル/2-ブタノン=93/7))400部、多官能エポキシ架橋剤(商品名「E-AX」、綜研化学株式会社製)1.1部及び微粉体(商品名「ケミスノーMX300」、綜研化学株式会社製)4.3部からなる組成を有する粘着性組成物を、ダイコーターを用いて塗布し、100℃にて2分乾燥し、膜厚20μmの粘着層を形成し、セパレータ-拡散粘着層の層構成を有する積層体を得た。
実施例1で製造した輝度向上フィルム1の1/4波長板側に上記(v)で製造したセパレータ-拡散粘着層積層体の拡散粘着層を貼り合せて、セパレータを剥離し、さらにゼオノアフィルム(商品名「ZF14-100」、日本ゼオン(株)社製)を貼り合せ、コレステリック樹脂層側の面に上記(v)で製造したセパレータ-拡散粘着層積層体の拡散粘着層を貼り合せて、セパレータを剥離し、さらにゼオノアフィルム(商品名「ZF14-100」、日本ゼオン(株)社製)を貼り合せて、輝度向上フィルム6を製造した。
(vii.透明粘着層の製造方法)
上記(v)で用いたものと同一のセパレータに、ベース樹脂(商品名「SKダイン2094」)400部と架橋剤(商品名「E-AX」、綜研化学株式会社製、多官能エポキシ架橋剤)1.1部との混合物を、ダイコーターを用いて塗布し、100℃にて2分乾燥し、膜厚20μmの粘着層を形成し、セパレータ-粘着層の層構成を有する積層体を得た。
実施例1で製造した輝度向上フィルム1の1/4波長板側を濡れ指数56dyne/cmとなるようにコロナ処理を施し、(vii)で製造したセパレータ-粘着層積層体の粘着層を貼り合せてセパレータを剥離し、偏光子の両面に保護フィルムが接着された偏光板の片面に貼り合せて、積層体(偏光板積層体1)を製造した。
面内に点欠陥、コレステリック樹脂層の浮きのない、明るさが均一な表示状態であった。
(ix.液晶表示装置の製造)
実施例1で製造した輝度向上フィルム1の1/4波長板側の面を濡れ指数56dyne/cmとなるようにコロナ処理を施し、PVA(商品名「ゴーセファイマーZ200」、日本合成化学社製)3.0部、グリオキサール(商品名「グリオキザール」、日本合成化学社製)0.05部、純水97.0部からなるPVA接着剤液を#8バーで塗布、偏光子の片面に保護フィルムが接着された偏光板のもう片面に貼り合せて、100℃にて2分乾燥し、積層体を得た。
面内に点欠陥、コレステリック樹脂層の浮きのない、明るさが均一な表示状態であった。
(x.輝度向上フィルムの製造)
(ii)で製造した1/4波長板の片面濡れ指数が56dyne/cmとなるようにコロナ処理を施し、(v)で製造した拡散粘着層を貼り合せてセパレータを剥離し、(i)で製造した積層体のコレステリック樹脂層をコロナ処理(処理条件:150W・min/m2)し、拡散粘着層と貼り合せて、基材を剥離した。
コレステリック樹脂層の拡散粘着層と接触している面とは反対側の面にコロナ処理(処理条件:150W・min/m2)し、実施例1で用いた接着剤液を実施例1と同様の方法で塗工、乾燥し、接着層-コレステリック樹脂層-拡散粘着層-1/4波長板積層体を得た。
さらに、1/4波長板側に上記(v)で製造したセパレータ-拡散粘着層積層体の拡散粘着層を貼り合せて、セパレータを剥離し、さらにゼオノアフィルム(商品名「ZF14-100」、日本ゼオン(株)社製)を貼り合せて、ゼオノアフィルム-拡散粘着層-1/4波長板-拡散粘着層-コレステリック樹脂層-接着層-ゼオノアフィルムの輝度向上フィルム7を製造した。
輝度向上フィルム7を、IO DATA社製液晶モニター LCD-DTV191X(シート構成:拡散シート/プリズムシート)のプリズムシート上に設置し、白表示にて観察を行った。
プリズムシート起因のぎらつきは見られず、またバックライト点灯時の熱による輝度向上フィルム2のうねりも見られず、明るさが均一な表示状態であった。
<比較例1>
(メタ)アクリレートを、2-エチルへキシルアクリレート(商品名「NKオリゴ EA5120」、新中村化学工業社製、粘度50.4mPa・s、分子内に水酸基がない)72.7部に変えた以外は、実施例2と同様にして、輝度向上フィルム8を得た。輝度向上フィルム8の評価結果を表1に示す。分子内に水酸基がないモノ(メタ)アクリレートを使用した場合、接着力が低下するのみでなく、コレステリック樹脂層に傷が見られ、コレステリック樹脂層の表面硬度も低下していることが判った。
オリゴマー型多官能(メタ)アクリレートを、ウレタンアクリレート(商品名「UV-7640B」、日本合成化学(株)社製、官能基数6以上)18.2部に変えた以外は、実施例2と同様にして、輝度向上フィルム9を得た。輝度向上フィルム9の評価結果を表1に示す。オリゴマー型多官能(メタ)アクリレートの官能基数が6以上のものを使用すると接着力が低下していることが判った。
(メタ)アクリレートを、HEA(2-ヒドロキシエチルアクリレート、東邦化学社製、粘度9.0mPa・s)72.7部に変えた以外は、実施例2と同様にして、輝度向上フィルム10を得た。(メタ)アクリレートの粘度が低下すると塗工適正が悪化し、輝度向上フィルムの製造において支障があることが判った。
(メタ)アクリレートを、1,6-ヘキサンジオールジグリシジルエーテルのアクリル酸変性物(商品名「DA212」、ナガセケムテックス社製、粘度1400mPa・s)72.7部に変えた以外は、実施例2と同様にして、輝度向上フィルム11を得た。輝度向上フィルム11の評価結果を表1に示す。分子内に水酸基を有するモノ(メタ)アクリレートの粘度が上限以上だと、塗工適正が悪化し、接着性も悪化することが判った。
<比較例5>
輝度向上フィルムを比較例1で製造したものに変更した以外は、実施例6と同様に液晶テレビを準備し、白表示にて観察を行った。
プリズムシート起因のぎらつきは見られないが、コレステリック樹脂層の浮きが見られた。
輝度向上フィルムを比較例1で製造したものに変更した以外は、実施例7と同様に液晶モニターを準備し、白表示にて観察を行った。
面内に点欠陥やキズ、コレステリック樹脂層の浮きが見られた。
輝度向上フィルムを比較例1で製造したものに変更した以外は、実施例8と同様に液晶モニターを準備し、白表示にて観察を行った。
面内に点欠陥やキズ、コレステリック樹脂層の浮きが見られた。
(xiv.比較のための輝度向上フィルムの製造)
(x)での製造方法において、コレステリック樹脂層上に実施例1で用いた接着剤液を実施例1と同様の方法で塗工、乾燥する代わりに、(vii)の透明粘着層を貼り合せて、セパレータを剥離した以外は、実施例9と同様に積層体を準備し、ゼオノアフィルム-拡散粘着層-1/4波長板-拡散粘着層-コレステリック樹脂層-透明粘着層-ゼオノアフィルムの輝度向上フィルム12を製造した。
輝度向上フィルム12を、IO DATA社製液晶モニター LCD-DTV191X(シート構成:拡散シート/プリズムシート)のプリズムシート上に設置し、白表示にて観察を行った。
プリズムシート起因のぎらつきは見られなかったが、バックライト点灯時の熱による輝度向上フィルム3のうねりが見られ、色味の面内分布が見られた。
2.接着層
3.コレステリック樹脂層
4.塗工基材
5.偏光板保護フィルム
6.偏光子
7.粘着層
Claims (10)
- コレステリック規則性を有する樹脂層の少なくとも一方の面に活性エネルギー線硬化型接着層を介して、透明フィルムが設けられた輝度向上フィルムであって、
活性エネルギー線硬化型接着層は、活性エネルギー線硬化型の接着剤組成物を硬化させてなり、
接着剤組成物が未硬化状態で
(A)官能基数が3以下のオリゴマー型多官能(メタ)アクリレート、及び
(B)温度20±1.0℃における粘度が10mPa・s以上500mPa・s未満の分子内に水酸基を少なくともひとつ有するモノ(メタ)アクリレート
を少なくとも含むことを特徴とする輝度向上フィルム。 - 未硬化状態の接着剤組成物に含まれる(メタ)アクリレート100重量部に対して、(B)の含有率が35~85重量部の範囲にある請求項1に記載の輝度向上フィルム。
- (A)がウレタン(メタ)アクリレート、エポキシ(メタ)アクリレート、およびポリエステル(メタ)アクリレートからなる群より選択される少なくとも1種のオリゴマー型(メタ)アクリレートである請求項1に記載の輝度向上フィルム。
- 未硬化状態の接着剤組成物がさらに
(C)ガラス転移温度が-10℃以上80℃以下の不活性重合体
を含むことを特徴とする請求項1に記載の輝度向上フィルム。 - 透明フィルムがλ/4板である請求項1に記載の輝度向上フィルム。
- 偏光子の両面に透明保護フィルムを設け、一方の面に、請求項1に記載の輝度向上フィルムを貼り合せたことを特徴とする偏光板。
- 偏光子の片面に透明保護フィルムを設け、他方の面に請求項1に記載の輝度向上フィルムを貼り合せたことを特徴とする偏光板。
- 請求項1に記載の輝度向上フィルムを備えた液晶表示装置。
- 請求項6に記載の偏光板を液晶セルの照明装置側に貼り合せた液晶表示装置。
- 請求項7に記載の偏光板を液晶セルの照明装置側に貼り合せた液晶表示装置。
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JP2009154648 | 2009-06-30 |
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JP (1) | JPWO2011001836A1 (ja) |
KR (1) | KR20120030445A (ja) |
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WO (1) | WO2011001836A1 (ja) |
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JP2012197426A (ja) * | 2011-03-08 | 2012-10-18 | Dic Corp | 部分的に粘着剤層を有する基材の製造方法及びその製造方法により製造された粘着シート又は粘着フィルム |
JP2013041111A (ja) * | 2011-08-16 | 2013-02-28 | Dainippon Printing Co Ltd | 赤外線反射部材 |
JP2015028138A (ja) * | 2013-06-28 | 2015-02-12 | 日東電工株式会社 | 光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、粘着剤層付き光学フィルム、液晶表示装置、及び、積層体 |
JP2016071378A (ja) * | 2014-09-30 | 2016-05-09 | 住友化学株式会社 | 偏光板及びその製造方法、並びに偏光板のセット、液晶パネル、液晶表示装置 |
JP2016118761A (ja) * | 2014-12-22 | 2016-06-30 | 住友化学株式会社 | 偏光板及びその製造方法、並びに偏光板のセット、液晶パネル、液晶表示装置 |
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Also Published As
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TW201111176A (en) | 2011-04-01 |
JPWO2011001836A1 (ja) | 2012-12-13 |
KR20120030445A (ko) | 2012-03-28 |
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