WO2012032919A1 - 複層フィルム及び液晶表示装置 - Google Patents
複層フィルム及び液晶表示装置 Download PDFInfo
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- WO2012032919A1 WO2012032919A1 PCT/JP2011/068799 JP2011068799W WO2012032919A1 WO 2012032919 A1 WO2012032919 A1 WO 2012032919A1 JP 2011068799 W JP2011068799 W JP 2011068799W WO 2012032919 A1 WO2012032919 A1 WO 2012032919A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding 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
- G02F1/133305—Flexible substrates, e.g. plastics, organic film
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/06—Unsaturated polyesters
- C08J2467/07—Unsaturated polyesters having terminal carbon-to-carbon unsaturated bonds
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B30/00—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images
- G02B30/20—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes
- G02B30/22—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the stereoscopic type
- G02B30/25—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the stereoscopic type using polarisation techniques
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
- Y10T428/24975—No layer or component greater than 5 mils thick
Definitions
- the present invention relates to a multilayer film and a liquid crystal display device including the same.
- An optical film provided in a liquid crystal display device or the like may be heated by heat generated from a light source or a change in the usage environment of the liquid crystal display device.
- the heated optical film is usually deformed due to thermal expansion or its optical characteristics are changed. When such deformations or changes in optical characteristics occur, the display quality of the liquid crystal display device tends to deteriorate.
- Patent Documents techniques for suppressing thermal expansion and reducing the linear expansion coefficient have been developed (Patent Documents). 1).
- the passive stereoscopic image display device normally, a right-eye image and a left-eye image are displayed simultaneously on the same screen, and these images are distributed to the left and right eyes using dedicated glasses. . Therefore, in order to display images corresponding to the left and right eyes in different polarization states at different positions, the passive stereoscopic image display device may be provided with a patterned retardation film. In the patterned retardation film, a different phase difference is given for each position in the plane according to the pattern.
- the patterned retardation film is produced, for example, by providing a layer having a desired retardation on the surface of the base film.
- the position of the phase difference film pattern may be shifted.
- a force may be applied to other layers bonded to the base film due to thermal expansion, resulting in deformation.
- the image quality may be deteriorated.
- the thermal expansion occurs in the in-plane direction of the film (that is, the direction orthogonal to the thickness direction of the film)
- the image quality deterioration is more remarkable. Therefore, an optical film that can further suppress thermal expansion than before is desired.
- An object of the present invention is to provide a multilayer film and a liquid crystal display device including the multilayer film.
- the present inventors have provided a resin layer that is cured by irradiation with active energy rays on at least one surface of the substrate, and the ratio of the thickness of the substrate to the resin layer. It was found that the linear expansion coefficient of the substrate can be effectively suppressed by the resin layer by keeping the content in a predetermined range, and the present invention has been completed. That is, according to the present invention, the following [1] to [5] are provided.
- a multilayer film comprising: The ratio of the thickness of the base material to the total thickness of the base material and the resin layer is 0.6 or more and 0.95 or less, A multilayer film in which the linear expansion coefficient of the multilayer film is 5 ppm / ° C. or less smaller than the linear expansion coefficient of the substrate in a temperature range of 30 ° C. or more and 90 ° C. or less.
- a liquid crystal display device comprising the multilayer film as described.
- the multilayer film of the present invention can suppress the thermal expansion coefficient in the in-plane direction in the temperature range during use in the image display device.
- the liquid crystal display device of the present invention can prevent deterioration in image quality due to thermal expansion of the multilayer film during use.
- FIG. 1 is a cross-sectional view schematically showing a multilayer film according to an embodiment of the present invention.
- FIG. 2 is a diagram schematically showing a configuration of a stereoscopic image display device as a first embodiment of the liquid crystal display device of the present invention.
- FIG. 3 is an exploded view of a stereoscopic image display device in order to explain the mechanism of image display in the stereoscopic image display device as the first embodiment of the liquid crystal display device of the present invention, and the liquid crystal panel, the first retardation film, and It is a perspective view which shows a 2nd phase difference film typically.
- FIG. 4 is a diagram schematically showing a configuration of a stereoscopic image display device as a second embodiment of the liquid crystal display device of the present invention.
- FIG. 5 is a schematic view of the liquid crystal panel and the retardation film, which is disassembled in order to explain the mechanism of image display in the stereoscopic image display device as the second embodiment of the liquid crystal display device of the present invention. It is
- (meth) acrylate means “acrylate” and “methacrylate”
- (meth) acryl means “acryl” and “methacryl”.
- FIG. 1 is a cross-sectional view schematically showing a multilayer film according to an embodiment of the present invention.
- the multilayer film 10 of the present invention includes a base material 11 and a resin layer (hereinafter referred to as “cured resin”) which is provided on the surface of the base material 11 and is cured by irradiation with active energy rays. Layer)) 12.
- cured resin a resin layer which is provided on the surface of the base material 11 and is cured by irradiation with active energy rays. Layer
- the cured resin layer 12 suppresses the thermal expansion of the base material 11, the linear expansion coefficient as the whole multilayer film 10 can be made small.
- the base material is a member made of a resin containing a polymer having an alicyclic structure.
- a resin including a polymer having an alicyclic structure is excellent in transparency, low hygroscopicity, dimensional stability, lightness, and the like, and is a material suitable for an optical film.
- the polymer having an alicyclic structure is a polymer having an alicyclic structure in one or both of the main chain and the side chain. Among these, from the viewpoint of mechanical strength and heat resistance, a polymer containing an alicyclic structure in the main chain is preferable.
- alicyclic structure examples include a saturated alicyclic hydrocarbon (cycloalkane) structure and an unsaturated alicyclic hydrocarbon (cycloalkene) structure. From the viewpoint of mechanical strength and heat resistance, the cycloalkane structure is preferable. preferable.
- the number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 or more, preferably 5 or more, usually 30 or less, preferably 20 or less, more preferably 15 or less. At some point, the properties of mechanical strength, heat resistance, and moldability of the substrate are highly balanced and suitable.
- the proportion of the repeating unit having an alicyclic structure in the polymer having an alicyclic structure is preferably 55% by weight or more, more preferably 70% by weight or more, particularly preferably 90% by weight or more, and usually 100% by weight. It is as follows. It is preferable from a viewpoint of transparency and heat resistance that the ratio of the repeating unit which has an alicyclic structure in the polymer which has an alicyclic structure exists in the said range.
- Examples of the polymer having an alicyclic structure include a norbornene polymer, a monocyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and a hydride thereof. Etc. Among these, norbornene-based polymers can be suitably used because of their good transparency and moldability.
- Examples of the norbornene polymer include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening copolymer of a monomer having a norbornene structure and another monomer, or a hydride thereof; norbornene An addition polymer of a monomer having a structure, an addition copolymer of a monomer having a norbornene structure and another monomer, or a hydride thereof.
- a ring-opening (co) polymer hydride of a monomer having a norbornene structure is particularly suitable from the viewpoints of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability, lightness, and the like. Can be used.
- (Co) polymerization” means polymerization and copolymerization.
- Examples of the monomer having a norbornene structure include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 2,5 ] deca-3,7. -Diene (common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4. 0.1 2,5 . 1 7,10 ] dodec-3-ene (common name: tetracyclododecene), and derivatives of these compounds (for example, those having a substituent in the ring).
- the monomer which has a norbornene structure may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- examples of the substituent that the monomer having a norbornene structure has include an alkyl group, an alkylene group, and a polar group. These substituents may be of one type or two or more types. Further, the number of substituents substituted on one monomer may be one or two or more.
- Examples of the polar group include a hetero atom or an atomic group having a hetero atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom.
- the polar group include a carboxyl group, a carbonyloxycarbonyl group, an epoxy group, a hydroxyl group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group.
- the amount of polar groups is small, and it is more preferable not to have polar groups.
- Examples of the monomer capable of ring-opening copolymerization with a monomer having a norbornene structure include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene; Derivatives thereof; and the like. These ring-opening copolymerizable monomers may be used alone or in combination of two or more at any ratio.
- a ring-opening polymer of a monomer having a norbornene structure, and a ring-opening copolymer of a monomer copolymerizable with a monomer having a norbornene structure for example, a known ring-opening polymerization of the monomer It can be obtained by (co) polymerization in the presence of a catalyst.
- Examples of monomers that can be addition copolymerized with a monomer having a norbornene structure include ⁇ -olefins having 2 to 20 carbon atoms such as ethylene, propylene, and 1-butene, and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, and the like. And non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene.
- ⁇ -olefin is preferable, and ethylene is more preferable.
- these addition copolymerizable monomers may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- a polymer having an alicyclic structure for example, a hydride of a ring-opening polymer of a monomer having a norbornene structure, a ring-opening of a monomer having a norbornene structure and a monomer capable of ring-opening copolymerization with this Hydrogenated copolymer, hydride of addition polymer of monomer having norbornene structure, and hydrogen of addition copolymer of monomer having norbornene structure and addition copolymerizable monomer
- a hydride such as a hydride
- the hydrogenation method is not particularly limited and may be performed according to a known method.
- a known hydrogenation catalyst containing a transition metal such as nickel or palladium may be included in the polymer solution, and hydrogen may be contacted.
- the fluidity and heat resistance of the hydride tends to improve, so that the hydrogenation described above hydrogenates 90% or more of the carbon-carbon unsaturated bonds of the polymer. Preferably it is done.
- X bicyclo [3.3.0] octane-2,4-diyl-ethylene structure and Y: tricyclo [4.3.0.1 2,5 ] Having a decane-7,9-diyl-ethylene structure, and the content of these repeating units X and Y is 90% by weight or more with respect to the entire repeating units of the norbornene polymer, and the content of X
- the ratio of the ratio and the content ratio of Y is preferably 100: 0 to 40:60 by weight ratio of X: Y.
- One type of polymer having an alicyclic structure may be used alone, or two or more types may be used in combination at any ratio.
- the molecular weight of a polymer having an alicyclic structure was measured by a gel permeation chromatography using cyclohexane as a solvent (however, toluene may be used when the polymer resin does not dissolve in cyclohexane).
- Isoprene or polystyrene-equivalent weight average molecular weight (Mw) usually 10,000 or more, preferably 15,000 or more, more preferably 20,000 or more, usually 100,000 or less, preferably 80,000 or less, more Preferably it is 50,000 or less.
- Mw weight average molecular weight Mw is in such a range, the mechanical strength and molding processability of the multilayer film are highly balanced and suitable.
- the resin containing a polymer having an alicyclic structure may contain other additional components in addition to the polymer having an alicyclic structure, if necessary.
- additional components are antioxidants, heat stabilizers, light stabilizers, UV absorbers, antistatic agents, dispersants, chlorine scavengers, flame retardants, crystallization nucleating agents, reinforcing agents, antiblocking agents.
- Additives such as antifogging agents, mold release agents, pigments, organic or inorganic fillers, neutralizing agents, lubricants, decomposing agents, metal deactivators, antifouling agents, and antibacterial agents; have no polymer, and the like.
- the amount of the additional component is preferably within a range that does not significantly impair the effects of the present invention. Specifically, it is usually 50 parts by weight or less, preferably 100 parts by weight or less with respect to 100 parts by weight of the polymer having an alicyclic structure. Is 30 parts by weight or less.
- the glass transition temperature of the resin containing a polymer having an alicyclic structure is usually 130 ° C. or higher, preferably 140 ° C. or higher, more preferably 150 ° C. or higher.
- the linear expansion coefficient of the substrate can be reduced in the temperature range of a normal high-temperature environment (30 ° C. or more and 90 ° C. or less) in the image display device.
- the linear expansion coefficient of the multilayer film can also be reduced.
- the upper limit of the glass transition temperature of the resin containing the polymer having an alicyclic structure is usually 200 ° C. or lower, preferably 180 ° C. or lower, more preferably 170 ° C. or lower. By setting the glass transition temperature to such a temperature range, a resin suitable for molding processability can be obtained.
- resins containing a polymer having an alicyclic structure as described above include, as trade names, ZEONOR (manufactured by ZEON CORPORATION), ARTON (manufactured by JSR Corporation), APPEL (manufactured by Mitsui Chemicals), TOPAS (Topas Advanced Polymers). For example).
- the base material is a film-like member.
- the specific thickness range of the substrate is usually 45 ⁇ m or less, preferably 42 ⁇ m or less, more preferably 40 ⁇ m or less.
- the thickness of the substrate is usually 10 ⁇ m or more, preferably 20 ⁇ m or more, more preferably 25 ⁇ m or more.
- the ratio “T11 / T10” of the base material thickness T11 to the total T10 of the base material thickness and the cured resin layer thickness is 0.95 or less.
- the linear expansion coefficient of the multilayer film of this invention can be suppressed effectively in the temperature range of 30 degreeC or more and 90 degrees C or less. That is, in the multilayer film of the present invention, when the thickness ratio T11 / T10 is 0.95 or less, the thickness ratio T11 / T10 is in-plane compared to the case where the thickness ratio T11 / T10 is greater than 0.95. the thermal expansion coefficient of direction can be remarkably suppressed.
- the thickness ratio T11 / T10 is: Usually, it is 0.6 or more, preferably 0.7 or more, more preferably 0.8 or more.
- the thickness of a base material means the thickness of the layer, when the multilayer film of the present invention includes only one layer, and when the multilayer film of the present invention includes two or more layers of the base material. Means the sum of those layers.
- the thickness of the cured resin layer means the thickness of the layer when the multilayer film of the present invention has only one cured resin layer, and the multilayer film of the present invention has two or more cured resin layers. When provided, it means the sum of those layers.
- the substrate is preferably an unstretched film that has not been stretched.
- the substrate is a stretched film
- large expansion or contraction occurs in the direction orthogonal to the stretching direction. is there. Therefore, in the multilayer film of the present invention provided with a stretched film as a base material, when heated, a relatively large deformation may occur in a direction having a large linear expansion coefficient (usually a direction perpendicular to the stretch direction). is there.
- a difference in linear expansion coefficient may occur in the in-plane direction, but the difference is smaller than when a stretched film is used as the base material.
- the substrate is preferably an unstretched film.
- a stretched film may be used as the substrate.
- the base material may have been subjected to surface treatment on one side or both sides.
- the surface treatment include energy ray irradiation treatment and chemical treatment.
- the energy ray irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, and ultraviolet ray irradiation treatment.
- corona discharge treatment and plasma treatment are preferable, and corona discharge treatment is particularly preferable.
- the chemical treatment include a treatment of immersing in an aqueous oxidizing agent solution such as a potassium dichromate solution or concentrated sulfuric acid and then sufficiently washing with water. In addition, it is effective to shake in the soaked state, but if left soaked for a long time, the surface may dissolve or the transparency may be lowered. It is preferable to adjust treatment conditions such as immersion time and temperature according to the above.
- the multilayer film of the present invention usually comprises only one base material, but may comprise two or more base materials as long as the effects of the present invention are not impaired.
- the production method of the substrate there is no limitation on the production method of the substrate, and for example, it can be produced by molding a resin containing a polymer having an alicyclic structure by a known film molding method.
- the film forming method include a cast forming method, an extrusion forming method, and an inflation forming method.
- a melt extrusion method that does not use a solvent can reduce the amount of residual volatile components efficiently, and is preferable from the viewpoints of the global environment and work environment, and excellent manufacturing efficiency.
- the melt extrusion method include an inflation method using a die, but a method using a T die is preferable in terms of excellent productivity and thickness accuracy.
- the cured resin layer is a resin layer that is cured by irradiation with active energy rays. Therefore, an active energy ray curable resin is used as the resin for forming the cured resin layer.
- a cured resin layer is formed by forming a film of an uncured resin composition on the surface of a substrate and irradiating the film with an active energy ray to cure.
- the resin composition in an uncured state includes any one of a monomer, an oligomer, and a polymer that are cured by a polymerization reaction or a crosslinking reaction when irradiated with active energy rays. Any monomer, oligomer, and polymer may be used as long as they are in an uncured state before irradiation with active energy rays, but those containing one or both of the monomer and oligomer are preferred.
- the polymerization reaction or crosslinking reaction proceeds on the surface of the substrate, not only the polymerization reaction or crosslinking reaction between the monomers or oligomers, but also the polymerization reaction between the monomer or oligomer and the reactive functional group present on the substrate surface Or it is because a crosslinking reaction advances and the adhesive strength of a base material and a cured resin layer can be raised. Moreover, by using a monomer or an oligomer, the surface hardness can be remarkably improved and the scratch resistance can be improved.
- the oligomer refers to a component in which two or more monomers are bonded and has a polymerization degree smaller than that of the polymer, and its weight average molecular weight is usually 10,000 or less.
- the monomer, oligomer and polymer contained in the uncured resin composition are preferably those having a polar group, and more preferably those having a large number of polar groups, from the viewpoint of enhancing the adhesion to the substrate.
- the monomer, oligomer and polymer contained in the uncured resin composition are cured with a small refractive index anisotropy. What does not express an in-plane retardation in a resin layer is preferable.
- polyester (meth) acrylate examples include polyester (meth) acrylate.
- the polyester (meth) acrylate is obtained, for example, 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 examples include phthalic acid, adipic acid, maleic acid, itaconic acid, succinic acid, terephthalic acid and the like.
- a polybasic acid may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- polyhydric alcohol examples include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and the like.
- a polyhydric alcohol may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- polyester (meth) acrylate examples include, for example, EBECRYL 851,852,853,884,885 (manufactured by Daicel Cytec); Olester (manufactured by Mitsui Chemicals); Aronix M-6100, M-6400,6200 , 6250, 6500 (manufactured by Toagosei Co., Ltd.).
- Examples of the monomer, oligomer and polymer contained in the uncured resin composition also include epoxy (meth) acrylate.
- Epoxy (meth) acrylate is obtained, for example, as a reaction product obtained by subjecting an epoxy resin to ring-opening addition reaction of (meth) acrylic acid.
- Examples of the epoxy resin include bisphenol A type composed of bisphenol A and epichlorohydrin, novolak type composed of phenol novolac and epichlorohydrin, aliphatic type, and alicyclic type.
- aliphatic epoxy resin examples include ethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Trimethylolpropane 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 resin examples 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.
- an epoxy resin may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- epoxy (meth) acrylate examples include EBECRYL 600, 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 (Harima) (Made by Kasei Co., Ltd.); Miramer PE210, PE230, EA2280 (made by Toyo Chemicals Co., Ltd.) and the like.
- EBECRYL 600, 860, 3105, 3420, 3700, 3701, 3702, 3703, 3708, 6040 manufactured by Daicel
- Examples of the monomer, oligomer and polymer contained in the uncured resin composition also include urethane (meth) acrylate.
- Urethane (meth) acrylate is obtained as a reactant having a urethane skeleton at the center, for example, by reacting a (meth) acrylic monomer having a hydroxyl group, a polyfunctional isocyanate and a polyhydric alcohol.
- Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
- the (meth) acryl monomer which has a hydroxyl group may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylolpropane tolylene diisocyanate, and diphenylmethane triisocyanate. Among these, hexamethylene diisocyanate having good weather resistance is preferably used.
- a polyfunctional isocyanate may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- polyester (meth) acrylate As a polyhydric alcohol, what can be used for polyester (meth) acrylate can be used, for example.
- urethane (meth) acrylate include EBECRYL 204, 210, 220, 230, 270, 4858, 8200, 8201, 8402, 8804, 8807, 9260, 9270, KRM 8098, 7735, 8296 (manufactured by Daicel Cytec); UX2201, 3012, 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, 7640B (Manufactured by Nippon Synthetic Chemical Co., Ltd.); Iupica 8921, 8932, 8940
- monomers, oligomers and polymers contained in the uncured resin composition include acrylic acids such as acrylic acid and methacrylic acid; acrylonitrile; methacrylonitrile; acrylate or methacrylate of ethylene oxide modified phenol, propylene oxide modified Phenol acrylate or methacrylate, ethylene oxide modified nonylphenol acrylate or methacrylate, propylene oxide modified nonylphenol acrylate or methacrylate, 2-ethylhexyl carbitol acrylate, 2-ethylhexyl carbitol methacrylate, isobornyl acrylate, isobornyl methacrylate, tetrahydrofur Furyl acrylate, tetrahydrofurfuryl Tacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate,
- 2,2,6,6-tetramethyl-4-piperidinyl methacrylate having a cyclic hindered amine structure 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, 2 having a benzotriazole ring -(2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole and the like.
- these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
- the uncured resin composition contains (A) at least one oligomeric acrylate selected from the group consisting of urethane acrylate, epoxy acrylate and polyester acrylate.
- A at least one oligomeric acrylate selected from the group consisting of urethane acrylate, epoxy acrylate and polyester acrylate.
- the uncured resin composition may contain components other than the monomers, oligomers and polymers described above.
- the uncured resin composition preferably includes (B) inorganic fine particles having a number average particle diameter of 100 nm or less.
- inorganic fine particles having a number average particle diameter of 100 nm or less.
- oligomer type acrylate selected from the group consisting of urethane acrylate, epoxy acrylate and polyester acrylate
- inorganic fine particles having a number average particle diameter of 100 nm or less.
- the material of the inorganic fine particles examples include oxides such as silicon oxide, magnesium oxide, zirconium oxide, and titanium oxide; fluorides such as magnesium fluoride, lithium fluoride, and sodium fluoride. Of these, oxides are preferable. In particular, silicon oxide (silica) is preferable.
- the inorganic fine particles may be formed of one kind of material or may be formed of two or more kinds of materials. As the inorganic fine particles, one kind of inorganic fine particles may be used, or two or more kinds of inorganic fine particles may be used in combination.
- the number average particle diameter of the inorganic fine particles is usually 100 nm or less, preferably 90 nm or less, and usually 5 nm or more, preferably 15 nm or more.
- the coating of the resin composition becomes easy.
- the particle size distribution of the inorganic fine particles is preferably narrow and monodispersed, but may be polydispersed particles. Therefore, as the inorganic fine particles, two or more kinds of particles having different number average particle diameters may be used in combination.
- the inorganic fine particles may be agglomerated particles as long as a predetermined particle diameter is satisfied.
- the shape of the inorganic fine particles is preferably spherical, but may be indefinite.
- a number average particle diameter can be calculated
- the amount of the inorganic fine particles is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, particularly preferably 100 parts by weight of the total weight of the monomer, oligomer and polymer. It is 15 parts by weight or more, preferably 60 parts by weight or less, more preferably 50 parts by weight or less, and particularly preferably 40 parts by weight or less.
- the uncured resin composition may contain a polymerization initiator.
- the polymerization initiator include aryl ketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethylketals, benzoylbenzoates, ⁇ - And photopolymerization initiators such as sulfur-containing photopolymerization initiators (for example, sulfides and thioxanthones); acylphosphine oxide photopolymerization initiators; and the like.
- aryl ketone photopolymerization initiators for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethylketals, benzoylbenzoates, ⁇ - And photopolymerization initiators such as
- a polymerization initiator may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Moreover, you may use a polymerization initiator in combination with photosensitizers, such as amines, for example.
- the amount of the polymerization initiator is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 20 parts by weight or less, based on 100 parts by weight of the total weight of the monomer, oligomer and polymer. More preferably, it is 10 parts by weight or less.
- the uncured resin composition may contain a solvent.
- the solvent include ethers such as diacetone alcohol, propylene glycol monomethyl ether and ethylene glycol monomethyl ether; alcohols such as isobutyl alcohol, isopropyl alcohol, n-butyl alcohol and n-propyl alcohol; acetone, methyl ethyl ketone and methyl isobutyl. Ketones such as ketone and acetylacetone; ethyl acetate, butyl acetate, xylene, toluene and the like.
- a solvent may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. What is necessary is just to adjust the quantity of a solvent suitably with the coating conditions (for example, appropriate viscosity, appropriate film thickness) of the coating machine to be used.
- the uncured resin composition may contain additives that may be contained in the resin that forms the base material, if necessary.
- the amount of the additive is preferably within a range that does not significantly impair the effects of the present invention.
- the total weight of the monomer, oligomer and polymer is usually 20 parts by weight or less, preferably 100 parts by weight or less. Is 10 parts by weight or less.
- a coating process for forming a film of the uncured resin composition on the surface of the substrate is performed.
- a film of the resin composition is formed on the surface of the substrate by a coating method.
- the coating method include spin coating, dipping, spraying, bar coating, die coating, and micro gravure coating.
- Heating process After the film of the resin composition is formed on the surface of the substrate, a heating step of applying heat to the film is performed as necessary.
- a heating step of applying heat to the film is performed as necessary.
- volatile components such as solvents can be removed quickly, and adhesion between the substrate and the cured resin layer can be improved.
- the thermal expansion of the multilayer film of the present invention can be further improved by increasing it.
- the temperature around the resin composition film is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, preferably 150 ° C. or lower, more preferably 130 ° C. or lower.
- the time to heat is normally 1 minute or more and less than 5 minutes.
- the atmosphere during heating may be an oxidizing atmosphere in which oxygen such as air is present, or may be an inert gas atmosphere in which a nitrogen purge or the like is performed.
- the heating may be performed by a known method such as a hot stove, a near infrared heater, a far infrared heater, a carbon heater, or a hot roll.
- a hot stove When it is performed in a hot air furnace, it is preferable to block the air to the coating film with a baffle plate or a slit so that the blown hot air does not directly hit the resin composition film.
- membrane of a resin composition is irradiated with an active energy ray.
- active energy ray various energy rays may be used according to the type of the resin composition, and examples thereof include ultraviolet rays, visible rays, and other electron beams, among which ultraviolet rays are preferable.
- the active energy ray light source examples include a high-pressure mercury lamp and an electrodeless lamp.
- the illuminance of the active energy ray is preferably 100 mW or more, more preferably 200 mW or more, preferably 600 mW or less, more preferably 500 mW or less.
- the irradiation of active energy rays, as the integrated quantity of light preferably 300 mJ / cm 2 or more, more preferably 400 mJ / cm 2 or more, preferably 700 mJ / cm 2 or less, more preferably at 650 mJ / cm 2 or less .
- the atmosphere of the resin composition film upon irradiation with active energy rays may be an oxidizing atmosphere in which oxygen such as air exists, or an inert gas atmosphere in which a nitrogen purge or the like is performed.
- the resin composition is cured and a cured resin layer is obtained.
- the uncured resin composition is (A) at least one oligomer type acrylate selected from the group consisting of urethane acrylate, epoxy acrylate and polyester acrylate, and (B) inorganic fine particles having a number average particle diameter of 100 nm or less.
- the cured resin layer contains a polymer obtained by polymerizing the oligomer type acrylate and the inorganic fine particles.
- the amount (parts by weight) of the inorganic fine particles relative to the polymer is usually the same as the amount relative to the monomer, oligomer and polymer in the uncured resin composition.
- the thickness of the cured resin layer can be arbitrarily set as long as the ratio T11 / T10 of the thickness T11 of the substrate to the total T10 of the thickness of the substrate and the thickness of the cured resin layer is within the above-described range. Further, when the cured resin layers are provided on both the front surface and the back surface of the substrate, the thicknesses of the two cured resin layers may be different, but are preferably the same. This is for stably preventing warpage or the like of the multilayer film of the present invention.
- the cured resin layer may be provided on at least one side of the base material, but is preferably provided on both sides of the base material as shown in FIG. This is to more effectively suppress the thermal expansion of the multilayer film of the present invention and to stably prevent warping and the like of the multilayer film of the present invention.
- the cured resin layer is preferably provided directly on the surface of the base material, but may be provided indirectly on the surface of the base material via another layer as long as the effects of the present invention are not significantly impaired.
- a cured resin layer may be provided on the surface of the substrate via a thin adhesive layer having a thickness of 0.5 ⁇ m or less.
- the cured resin layer is preferably provided directly on the surface of the substrate.
- the cured resin layer after curing has a small linear expansion coefficient
- the cured resin layer restrains the thermal expansion of the base material in the in-plane direction even when the base material is about to thermally expand due to a change in temperature.
- the linear expansion coefficient can be suppressed.
- the linear expansion coefficient of the multilayer film of the present invention is smaller than the linear expansion coefficient of the substrate. Specifically, when measured in a temperature range from 30 ° C. to 90 ° C., the linear expansion coefficient of the multilayer film of the present invention is usually 5 ppm / ° C. or less smaller than the linear expansion coefficient of the substrate, preferably 8 ppm / ° C. or more, more preferably 10 ppm / ° C. or less.
- the linear expansion coefficient of the multilayer film of the present invention refers to the linear expansion coefficient in the in-plane direction of the multilayer film
- the linear expansion coefficient of the substrate refers to the linear expansion coefficient in the in-plane direction of the substrate.
- the linear expansion coefficient in the in-plane direction is usually not uniform in the multilayer film and the substrate of the present invention, but the linear expansion of the multilayer film of the present invention as described above in at least one of the in-plane directions.
- the coefficient should just be small compared with the linear expansion coefficient of a base material.
- the linear expansion coefficient of the multilayer film of the present invention is smaller than the linear expansion coefficient of the substrate as described above in all the in-plane directions.
- the linear expansion coefficient is determined by cutting a measurement object (multilayer film, base material, etc.) into a sample piece, heating it once from 25 ° C. to 120 ° C. at a heating rate of 20 ° C./min, cooling the sample piece, The measurement is performed while heating from 25 ° C. to 120 ° C. at a heating rate of ° C./min, and otherwise, it is performed according to JIS K7197. From the measurement result, the linear expansion coefficient when heated from 30 ° C. to 90 ° C. may be calculated.
- the moisture permeability of the multilayer film of the present invention is preferably 500 g / m 2 ⁇ 24 h or less, more preferably 100 g / m 2 ⁇ 24 h or less, and particularly preferably 60 g / m 2 ⁇ 24 h or less.
- the lower limit is preferably 20 g / m 2 ⁇ 24 h or more, more preferably 30 g / m 2 ⁇ 24 h or more, and particularly preferably 40 g / m 2 ⁇ 24 h or more.
- the specific value of moisture permeability can be controlled by adjusting the material and thickness of the base material and the cured resin layer, for example. The moisture permeability may be measured under the conditions of 40 ° C. and 90% RH based on JIS K7129B.
- the multilayer film of the present invention is usually used as an optical film, it preferably has high transparency.
- the total light transmittance as the entire multilayer film is preferably 85% or more, more preferably 92% or more.
- the upper limit is ideally 100%.
- the total light transmittance may be measured according to JIS K7361-1997.
- the multilayer film of the present invention may be used as a base film such as a retardation film, it is preferable that the haze is small.
- the haze of the multilayer film as a whole is usually 10% or less, preferably 5% or less, more preferably 1% or less.
- the lower limit value is ideally zero, but is usually 0.1% or more.
- the haze may be measured according to JIS K7361-1997.
- the multilayer film of the present invention preferably has a JIS pencil hardness and a hardness of HB or higher.
- the control of the JIS pencil hardness can be performed, for example, by adjusting the material and thickness of the base material and the cured resin layer.
- JIS pencil hardness is JIS K5600-5-4 in accordance with JIS K5600-5-4.
- the multilayer film of the present invention is excellent in scratch resistance.
- the scratch resistance tends to be particularly excellent.
- the evaluation method of scratch resistance is that the steel wool # 0000 is pressed against the surface of the multilayer film with a load of 0.025 MPa, and the steel wool is rubbed by reciprocating 10 times on the surface of the multilayer film. What is necessary is just to observe the surface state of a layer film visually and to evaluate with the following parameters
- the multilayer film of the present invention may include layers other than the base material and the cured resin layer as long as the effects of the present invention are not significantly impaired.
- a removable protective sheet may be provided on the surface of the multilayer film of the present invention.
- the multi-layer film of the present invention can be protected from scratches when the multi-layer film of the present invention is wound into a roll and stored and transported.
- the coefficient of dynamic friction between the multilayer films decreases, and wrinkles and bands (the film is partially raised and extends in the circumferential direction of the roll).
- a roll free from the occurrence of strip-shaped protrusions can be produced.
- the said protection sheet will be peeled off from the multilayer film of this invention at the time of use.
- the liquid crystal display device of the present invention comprises a liquid crystal cell, a viewing side polarizing plate provided on the viewing side of the liquid crystal cell, and a multilayer film of the invention provided on the viewing side of the viewing side polarizing plate. Prepare.
- embodiments of the liquid crystal display device of the present invention will be described with reference to the drawings. However, the liquid crystal display device of the present invention is not limited to the following embodiments.
- FIG. 2 is a diagram schematically showing a configuration of a stereoscopic image display device as a first embodiment of the liquid crystal display device of the present invention.
- the left side in the drawing is the light source side
- the right side in the drawing is the viewing side.
- the stereoscopic image display apparatus 100 includes a light source 110, a liquid crystal panel 120, and a retardation film stack 130 in this order.
- the light source 110 emits light used for image display.
- the liquid crystal panel 120 includes a light source side polarizing plate 121 that is a linear polarizing plate, a liquid crystal cell 122, and a viewing side polarizing plate 123 that is a linear polarizing plate in the order closer to the light source 110. Accordingly, the light emitted from the light source 110 is transmitted through the liquid crystal panel 120 and is emitted from the viewing side surface of the liquid crystal panel 120 as linearly polarized light.
- the retardation film laminate 130 includes a base film 131, a first retardation film 132, and a second retardation film 133.
- the base film 131 the multilayer film of the present invention is used.
- the base film 131 has no in-plane retardation.
- the first retardation film 132 is a retardation film formed directly or through an alignment film on the surface of the base material 131, and regions having different retardations are patterned in the plane. It is a retardation film.
- patterning means an aspect that is repeated at a certain period.
- a region having different in-plane phase differences is “patterned” in the plane, and two or more types of regions having different in-plane phase differences are observed along a certain direction in the plane. In this case, they are arranged so that they appear repeatedly in the same order.
- the patterned region is preferably in the form of a stripe in which elongated band-like regions are arranged in parallel.
- region which has a different phase difference means the aspect in which the some area
- the first retardation film 132 has an anisotropic region 134 that gives an in-plane retardation of approximately 1 ⁇ 2 wavelength to transmitted light so as to function as a 1 ⁇ 2 wavelength plate; It is assumed that isotropic regions 135 that transmit incident light without substantially changing the polarization state of the incident light are provided as band-like regions that alternately exist along a certain direction.
- giving an in-plane phase difference of approximately 1 ⁇ 2 wavelength to transmitted light means that the in-plane phase difference of the anisotropic region 134 in light having a wavelength of 550 nm is the center value of the wavelength range of transmitted light. From the value of 1/2, it usually means ⁇ 65 nm, preferably ⁇ 30 nm, more preferably ⁇ 10 nm.
- the fact that the polarization state is not substantially changed means that when the incident polarized light is linearly polarized light, it is transmitted as it is as linearly polarized light, and when the incident polarized light is circularly polarized light, it is emitted as it is as circularly polarized light.
- the anisotropic region 134 is indicated by hatching in order to distinguish the anisotropic region 134 from the isotropic region 135.
- the second retardation film 133 is a retardation film formed on the surface of the first retardation film 132 directly or via an alignment film or the like, and has a uniform retardation in the plane. It is a film. Specifically, the in-plane retardation of the second retardation film 133 in the light having a wavelength of 550 nm is in the wavelength range of the transmitted light so that the second retardation film 133 functions as a quarter wavelength plate.
- the range from 1/4 of the central value is usually ⁇ 65 nm, preferably ⁇ 30 nm, more preferably ⁇ 10 nm, or 3/4 of the central value is usually ⁇ 65 nm, preferably ⁇ 30 nm, more The range is preferably ⁇ 10 nm.
- the in-plane retardation Re is (nx ⁇ ny) ⁇ d (where nx represents a refractive index in a direction perpendicular to the thickness direction (in-plane direction) and giving the maximum refractive index).
- Ny represents a refractive index in a direction perpendicular to the thickness direction (in-plane direction) and orthogonal to the nx direction
- d represents a film thickness.
- the thickness direction retardation Rth is ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ d (wherein nx is a direction perpendicular to the thickness direction (in-plane direction) and is a refraction in a direction giving the maximum refractive index.
- Ny is a refractive index in a direction perpendicular to the thickness direction (in-plane direction) and orthogonal to the nx direction
- nz is a refractive index in the thickness direction
- d is a film thickness.
- FIG. 3 is an exploded view of the stereoscopic image display device 100 in order to explain the mechanism of image display in the stereoscopic image display device 100 as the first embodiment of the liquid crystal display device of the present invention. It is a perspective view which shows the phase difference film 132 and the 2nd phase difference film 133 typically. In FIG. 3, the anisotropic region 134 is indicated by hatching in order to distinguish the anisotropic region 134 from the isotropic region 135.
- the stereoscopic image display device 100 is configured as described above, as shown in FIG. 3, the light L emitted from the light source 110 (not shown in FIG. 3) is transmitted through the liquid crystal panel 120, and the arrow A As shown at 120 , it is emitted as linearly polarized light.
- the light L that has become linearly polarized light passes through the base film 131 (not shown in FIG. 3) and enters the first retardation film 132.
- the light L incident on the first retardation film 132 is given a phase difference of approximately 1 ⁇ 2 wavelength when passing through the anisotropic region 134, As indicated by an arrow A 134 , the light is emitted as linearly polarized light whose polarization direction is changed by 90 °.
- the light L incident on the isotropic region 135 is emitted as linearly polarized light having the same polarization direction as the incident light as indicated by an arrow A 135 without changing the polarization state.
- the light L transmitted through the first retardation film 132 is incident on the second retardation film 133.
- the light L incident on the second retardation film 133 is given a phase difference of approximately 1 ⁇ 4 wavelength when passing through the second retardation film 133 and is emitted as circularly polarized light. Since the light L that has passed through the anisotropic region 134 of the first retardation film 132 and the light L that has passed through the isotropic region 135 have orthogonal polarization directions,
- the direction of circular polarization of light L transmitted through the second retardation film 133 and the direction of circular polarization of light L transmitted through the isotropic region 135 and then transmitted through the second retardation film 133 are indicated by arrows. As shown by A 133R and arrow A 133L , the directions are reversed.
- the user of the stereoscopic image display apparatus 100 views the light L emitted from the second retardation film 133 through polarized glasses 140 in which the right eye lens and the left eye lens are crossed Nicols.
- the right-eye lens transmits only one circularly polarized light of right circularly polarized light and left circularly polarized light
- the left eye lens transmits the other of right circularly polarized light and left circularly polarized light. Only circularly polarized light is transmitted.
- Such polarizing glasses 140 are, for example, bonded with a quarter-wave plate on a linear polarizer so that the slow axis of the quarter-wave plate forms an angle of 45 ° with respect to the transmission axis of the linear polarizer. Can be produced.
- the user views one of the light transmitted through the anisotropic region 134 and the isotropic region 135 with the right eye, and the light transmitted through the anisotropic region 134 and the isotropic region 135. You will see the other with your left eye. In this way, by displaying the image for the right eye and the image for the left eye, the user can visually recognize the stereoscopic image.
- the multilayer film of the present invention is provided as the base film 131 of the retardation film laminate 130. Even if the material film 131 is heated, the thermal expansion of the base film 131 is suppressed. For this reason, the positions of the anisotropic region 134 and the isotropic region 135 of the first retardation film 132 are shifted, or stress is applied to the first retardation film 132 to cause a refractive index change and deformation. It can be prevented deteriorating the image quality. In particular, if the positions of the anisotropic region 134 and the isotropic region 135 of the first retardation film 132 are shifted, the visibility of the stereoscopic image may be greatly reduced.
- the ability to suppress the thermal expansion of 131 is a great advantage.
- the first retardation film 132 and the second retardation film 133 may be produced by applying and curing a liquid crystal composition.
- the base film 131 is used as a support for the cured liquid crystal composition layer. Therefore, the thermal expansion of the base film 131 greatly affects the visibility of the stereoscopic image, but if the thermal expansion of the base film 131 can be suppressed, the deterioration of the image quality can be prevented even in that case. preferable.
- the first embodiment of the liquid crystal display device of the present invention has been described above. However, the above embodiment may be further modified.
- the order of the first retardation film 132 and the second retardation film 133 may be changed, and the first retardation film 132 may be provided on the viewer side with respect to the second retardation film 133.
- the anisotropic region 134 in the first retardation film 133 may be a region that rotates 90 ° of linearly polarized light by forming it with a twisted nematic liquid crystal or the like.
- the position of the base film 131 may be on the light source side of the first retardation film 132 and the second retardation film 133 as in the above embodiment, or the first retardation film 132.
- the second retardation film 133 may be closer to the viewing side, or may be between the first retardation film 132 and the second retardation film 133.
- the stereoscopic image display device 100 may be provided with a diffusion film, a brightness enhancement film, an adhesive layer, an adhesive layer, a hard coat layer, an antireflection film, a protective layer, and the like.
- a front plate made of glass or plastic may be provided.
- FIG. 4 is a diagram schematically showing a configuration of a stereoscopic image display device as a second embodiment of the liquid crystal display device of the present invention.
- the left side in the figure is the light source side
- the right side in the figure is the viewing side.
- the stereoscopic image display device 200 includes a light source 110, a liquid crystal panel 120, and a retardation film laminate 230 in this order.
- the light source 110 and the liquid crystal panel 120 are the same as those in the first embodiment.
- the retardation film laminate 230 includes a base film 131 and a retardation film 232.
- the base film 131 is the same as in the first embodiment.
- the retardation film 232 is a retardation film formed on the surface of the base material 131 directly or via an alignment film or the like, and the regions having the same retardation but different slow axis directions are in the plane. It is a retardation film that is patterned. A region where the phase difference is the same but the direction of the slow axis is different means that the phase difference has the same value but the direction of the slow axis of the region is not parallel.
- the retardation film 232 has a first anisotropic region 234 that gives an in-plane retardation of approximately 1 ⁇ 4 wavelength to transmitted light so as to function as a 1 ⁇ 4 wavelength plate;
- a second anisotropic region 235 that gives the same in-plane retardation (ie, approximately 1 ⁇ 4 wavelength) to the transmitted light as the first anisotropic region 234 but has a different slow axis direction is constant. It is assumed that it is provided as a band-like region that exists alternately along the direction.
- the direction of the slow axis of the first anisotropic region 234 differs from the direction of the slow axis of the second anisotropic region 235 by 90 °.
- the direction of the circularly polarized light that is transmitted through the first anisotropic region 234 and converted is changed.
- the direction of circularly polarized light that is transmitted through the second anisotropic region 235 and converted is opposite to that of the circularly polarized light.
- the first anisotropic region 234 is indicated by hatching in order to distinguish the first anisotropic region 234 from the second anisotropic region 235.
- FIG. 5 is an exploded view of the stereoscopic image display device 200 in order to explain the mechanism of image display in the stereoscopic image display device 200 as the second embodiment of the liquid crystal display device of the present invention.
- the first anisotropic region 234 is indicated by hatching in order to distinguish the first anisotropic region 234 and the second anisotropic region 235.
- the stereoscopic image display apparatus 200 is configured as described above, the light L emitted from the light source 110 (not shown in FIG. 5) is transmitted through the liquid crystal panel 120 as shown in FIG. As shown at 120 , it is emitted as linearly polarized light.
- the light L that has become linearly polarized light passes through the base film 131 (not shown in FIG. 5) and enters the retardation film 232.
- the light L incident on the retardation film 232 gives a phase difference of approximately 1 ⁇ 4 wavelength when passing through the first anisotropic region 234. And is emitted as circularly polarized light.
- the light L incident on the second anisotropic region 235 is also given a phase difference of approximately 1 ⁇ 4 wavelength when passing through the second anisotropic region 235, and is emitted as circularly polarized light. .
- the direction of the slow axis of the first anisotropic region 234 and the second anisotropic region 235 is orthogonal, the direction of the circularly polarized light that is transmitted through the first anisotropic region 234 and converted The direction of the circularly polarized light that is transmitted through the second anisotropic region 235 and converted is opposite to the direction of the arrow A 234 and the arrow A 235 .
- the user of the stereoscopic image display apparatus 200 views the light L emitted from the retardation film 232 through the polarizing glasses 140 in which the right eye lens and the left eye lens are crossed Nicols as in the first embodiment.
- the user sees one of the lights transmitted through the first anisotropic region 234 and the second anisotropic region 235 with the right eye, and also uses the first anisotropic region 234 and the second anisotropic region 235.
- the other of the light transmitted through the anisotropic region 235 is viewed with the left eye. In this way, by displaying the image for the right eye and the image for the left eye, the user can visually recognize the stereoscopic image.
- the multilayer film of this invention is provided as the base film 131 of the retardation film laminated body 230, the same advantage as 1st embodiment is acquired.
- the present embodiment may be further modified and implemented, for example, may be modified and implemented in the same manner as the first embodiment.
- the linear expansion coefficient is determined by cutting a measurement object (multilayer film, substrate, etc.) into a sample piece, heating it from 25 ° C. to 120 ° C. at a heating rate of 20 ° C./min, cooling the sample piece, The measurement was performed while heating from 25 ° C. to 120 ° C. at a heating rate of minutes, and the other measurements were performed in accordance with JIS K7197. From the measurement results, the linear expansion coefficient when heated from 30 ° C. to 90 ° C. was calculated. The difference in linear expansion coefficient between the multilayer film and the substrate was calculated by subtracting the linear expansion coefficient of the substrate from the linear expansion coefficient of the multilayer film. In addition, evaluation was performed in the MD direction and TD direction of the film, respectively.
- the MD direction refers to the longitudinal direction of the substrate prepared as a long film
- the TD direction refers to the width direction of the substrate.
- Example 1 100 parts urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., product name “UV7640B”), 30 parts of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., product name “4HBA”), organosilica sol (manufactured by Nissan Chemical Industries, Ltd., product) 10 parts of the name “MEK-ST”, solid content 30%, number average particle diameter 10 nm to 15 nm), 7.5 parts of photopolymerization initiator (product name “Irg184” manufactured by Ciba Specialty Chemicals), and as solvent 412 parts of methyl isobutyl ketone was mixed to prepare a liquid resin composition.
- a ZEONOR film (manufactured by Nippon Zeon Co., Ltd., thickness 40 ⁇ m, glass transition temperature Tg 163 ° C. of the norbornene resin as a material) is prepared as a long film-like substrate, and corona discharge is performed so that both surfaces have a wetting index of 56 dyne / cm. Processed. Thereafter, the prepared liquid resin composition was applied to one side of the substrate with a bar coater # 6. After drying at 70 ° C. for 2 minutes, the resin composition was cured by irradiation with a high-pressure mercury lamp at 200 mJ / cm 2 to form a cured resin layer. Further, a cured resin layer was similarly formed on the other surface of the substrate.
- Example 2 A multilayer film was produced and evaluated in the same manner as in Example 1 except that the thickness of the cured resin layer was changed to 1.5 ⁇ m on both sides. The results are shown in Table 1.
- Example 3 A multilayer film was produced and evaluated in the same manner as in Example 1 except that a ZEONOR film (material was the same as in Example 1) having a thickness of 38 ⁇ m was used as the substrate. The results are shown in Table 1.
- Example 4 A multilayer film was produced and evaluated in the same manner as in Example 1 except that the cured resin layer was provided only on one side of the substrate. The results are shown in Table 1.
- Example 5 A multilayer film was produced and evaluated in the same manner as in Example 1 except that a ZEONOR film having a thickness of 23 ⁇ m (the material is the same as in Example 1) was used. The results are shown in Table 1.
- Example 6 A multilayer film was produced in the same manner as in Example 1 except that a zeonore film (thickness is the same as in Example 1) having a glass transition temperature Tg of 135 ° C. of the norbornene resin as a substrate was used. Evaluation was performed. The results are shown in Table 2.
- Example 7 A multilayer film was produced and evaluated in the same manner as in Example 1 except that epoxy acrylate EBECRYL600 (manufactured by Daicel Cytec) was used instead of urethane acrylate UV7640B. The results are shown in Table 2.
- Example 8 As an organosilica sol, a multilayer was formed in the same manner as in Example 1 except that MEK-ST-L (manufactured by Nissan Chemical Industries, solid content 30%, number average particle size 40 nm to 50 nm) was used instead of MEK-ST. Films were manufactured and evaluated. The results are shown in Table 2.
- MEK-ST-L manufactured by Nissan Chemical Industries, solid content 30%, number average particle size 40 nm to 50 nm
- Example 9 A multilayer film was produced and evaluated in the same manner as in Example 1 except that the ZEONOR film as the substrate was used after being stretched 1.5 times in the MD direction at a temperature of 170 ° C. The results are shown in Table 2. In addition, the thickness of the base material became 38 micrometers by extending
- Example 2 A multilayer film was produced and evaluated in the same manner as in Example 1 except that the conditions for applying the resin composition were changed, thereby changing the thickness of the cured resin layer to 0.8 ⁇ m on both sides. The results are shown in Table 3.
- Example 3 A multilayer film was produced and evaluated in the same manner as in Example 1 except that the conditions for applying the resin composition were changed, and thereby the thickness of the cured resin layer was changed to 0.4 ⁇ m on both sides. The results are shown in Table 3.
- Comparative Example 4 A multilayer film was produced and evaluated in the same manner as in Example 1 except that the conditions for applying the resin composition were changed, thereby changing the thickness of the cured resin layer to 15 ⁇ m on both sides. The results are shown in Table 3. In Comparative Example 4, since the cured resin layer was brittle and damaged, the difference in linear expansion coefficient, pencil hardness, and scratch resistance could not be evaluated.
- Example 10 Manufacturing and Evaluation of Image Display Device (Manufacture of multilayer film) A multilayer film was produced in the same manner as in Example 2.
- An alignment film composition comprising 100 parts of modified polyamide (weight average molecular weight 45000), 0.7 part of p-toluenesulfonic acid, and 3265 parts of 1-propanol was prepared.
- One side of the multilayer film was subjected to a corona discharge treatment so that the wetting index was 56 dyne / cm, and the prepared alignment film composition was applied with a bar coater # 4 and dried at 100 ° C. for 5 minutes to form a film.
- a dry film having a thickness of 0.2 ⁇ m was obtained. The dried film was rubbed to form an alignment film.
- Formation of first retardation film on alignment film 40 parts of a polymerizable liquid crystal compound (LC242 manufactured by BASF), 2 parts of a polymerization initiator (manufactured by Ciba Specialty Chemicals, product name “Irg907”), and 0% of surfactant 209F (manufactured by Neos) as a surfactant. .04 parts and 60 parts of methyl ethyl ketone as a solvent were mixed to prepare a liquid crystal composition. This liquid crystal composition was applied to the surface of the alignment film with a bar coater # 8 and subjected to an alignment treatment at 75 ° C. for 2 minutes to align the polymerizable liquid crystal compound.
- LC242 manufactured by BASF
- a polymerization initiator manufactured by Ciba Specialty Chemicals, product name “Irg907”
- surfactant 209F manufactured by Neos
- the polymerizable liquid crystal compound was cured in the region irradiated with ultraviolet rays to form a resin region (anisotropic region) having an in-plane retardation of 1 ⁇ 2 wavelength with respect to the transmitted light.
- an isotropic phase region was cured by irradiating 2000 mJ / cm 2 of ultraviolet rays from the coating surface side in a nitrogen atmosphere. Thereby, an anisotropic region having a dry film thickness of 2 ⁇ m and giving an in-plane phase difference of 1 ⁇ 2 wavelength to the transmitted light, and an isotropic region that does not substantially change the polarization state of the transmitted light.
- a first retardation film having the same plane was prepared.
- a stripe pattern consisting of an anisotropic region and an isotropic region is formed in accordance with the stripe shape of the light shielding portion of the mask used, and the position of this pattern is It matches the pixel position of a 3D liquid crystal monitor described later.
- the alignment film was formed on the first retardation film in the same manner as the alignment film was formed on the multilayer film.
- the viewing-side polarizing plate and the first retardation film were bonded together through an adhesive layer.
- the circularly polarizing plate has a configuration in which a quarter wave plate is bonded to a linear polarizing plate.
- the multilayer film of the present invention is preferably used as an optical film, and in particular, from the viewpoint of effectively utilizing the point of low thermal expansion, it can be used as a base film for an optical film used in an environment with temperature changes. Particularly preferred. If a specific example is given, the base film of the retardation film in a stereo image display apparatus will be mentioned.
- the liquid crystal display device of the present invention is suitable for use as a stereoscopic image display device such as a stereoscopic television.
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Abstract
Description
すなわち、本発明によれば以下の〔1〕~〔5〕が提供される。
前記基材の厚みと樹脂層との厚みとの合計に対する、前記基材の厚みの比が、0.6以上0.95以下であり、
30℃以上90℃以下の温度範囲において、前記複層フィルムの線膨張係数が前記基材の線膨張係数に比べて5ppm/℃以上小さい、複層フィルム。
〔2〕 前記脂環式構造を有する重合体を含む樹脂のガラス転移温度が130℃以上である、〔1〕記載の複層フィルム。
〔3〕 前記複層フィルムの透湿度が20g/m2・24h以上500g/m2・24h以下である、〔1〕又は〔2〕に記載の複層フィルム。
〔4〕 前記の活性エネルギー線を照射して硬化してなる樹脂層が、少なくとも下記成分(A)及び成分(B)を含む組成物を硬化させてなる、〔1〕~〔3〕のいずれか一項に記載の複層フィルム。
(A)ウレタンアクリレート、エポキシアクリレート及びポリエステルアクリレートからなる群より選択される少なくとも1種類のオリゴマー型アクリレート。
(B)数平均粒子径が100nm以下の無機微粒子。
〔5〕 液晶セルと、前記液晶セルよりも視認側に設けられた視認側偏光板と、前記視認側偏光板よりも視認側に設けられた〔1〕~〔4〕のいずれか一項に記載の複層フィルムとを備える、液晶表示装置。
本発明の液晶表示装置は、その使用時において複層フィルムの熱膨張による画質の低下を防止できる。
図1は、本発明の一実施形態に係る複層フィルムを模式的に示す断面図である。図1に示すように、本発明の複層フィルム10は、基材11と、基材11の表面に設けられた、活性エネルギー線の照射により硬化してなる樹脂層(以下、適宜「硬化樹脂層」という。)12とを備える。これにより、硬化樹脂層12が基材11の熱膨張を抑制するので、複層フィルム10の全体としての線膨張係数を小さくすることができる。
基材は、脂環式構造を有する重合体を含む樹脂からなる部材である。脂環式構造を有する重合体を含む樹脂は、透明性、低吸湿性、寸法安定性および軽量性などに優れ、光学フィルムに適した材料である。
ノルボルネン構造を有する単量体の開環重合体、および、ノルボルネン構造を有する単量体と共重合可能な単量体との開環共重合体は、例えば、単量体を公知の開環重合触媒の存在下に(共)重合することにより得ることができる。
ノルボルネン構造を有する単量体の付加重合体、および、ノルボルネン構造を有する単量体と共重合可能な単量体との付加共重合体は、例えば、単量体を公知の付加重合触媒の存在下に重合することにより得ることができる。
エネルギー線照射処理としては、例えば、コロナ放電処理、プラズマ処理、電子線照射処理、紫外線照射処理などが挙げられる。中でも、処理効率の点から、コロナ放電処理およびプラズマ処理が好ましく、コロナ放電処理が特に好ましい。
薬品処理としては、例えば、重クロム酸カリウム溶液、濃硫酸などの酸化剤水溶液中に、浸漬し、その後、充分に水で洗浄する処理が挙げられる。なお、浸漬した状態で振盪すると効果的であるが、長期間浸漬したままにしておくと表面が溶解したり、透明性が低下したりすることがあるので、処理に用いる薬品の反応性、濃度などに応じて、浸漬時間、温度などの処理条件を調整することが好ましい。
硬化樹脂層は、活性エネルギー線の照射により硬化してなる樹脂層である。したがって、硬化樹脂層を形成する樹脂としては、活性エネルギー線硬化型樹脂を用いる。通常は、未硬化状態の樹脂組成物の膜を基板の表面に形成し、その膜に活性エネルギー線を照射して硬化させることにより、硬化樹脂層が形成される。
未硬化状態の樹脂組成物は、活性エネルギー線を照射されることにより重合反応又は架橋反応が進行して硬化するモノマー、オリゴマー及びポリマーのうち、いずれかを含む。活性エネルギー線を照射される以前の時点において未硬化状態であれば、モノマー、オリゴマー及びポリマーのうちいずれを用いてもよいが、モノマー及びオリゴマーの一方又は両方を含むものが好ましい。基材の表面において重合反応又は架橋反応が進行することにより、モノマー又はオリゴマー同士の重合反応又は架橋反応だけでなく、モノマー又はオリゴマーと基材表面に存在する反応性官能基との間でも重合反応又は架橋反応が進行し、基材と硬化樹脂層との接着強度を高めることができるからである。また、モノマー又はオリゴマーを使用することで、表面硬度が格段に向上し、耐擦傷性を向上させることができる。なお、ここでオリゴマーとは、2個以上のモノマーが結合した成分であってポリマーよりも重合度が小さい成分のことを指し、その重量平均分子量は通常10000以下である。
多塩基酸としては、例えば、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。なお、多塩基酸は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
多価アルコールとしては、例えば、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。なお、多価アルコールは、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
ポリエステル(メタ)アクリレートの具体例を挙げると、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,M-6400,6200,6250,6500(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、例えば、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、例えば、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、例えば、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。なお、エポキシ樹脂は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
エポキシ(メタ)アクリレートの具体例を挙げると、EBECRYL600,860,3105,3420,3700,3701,3702,3703,3708,6040(ダイセルサイテック社製);ネオポール8101,8250,8260,8270,8355,8351,8335,8414,8190,8195,8316,8317,8318,8319,8371(日本ユピカ社製);デナコールアクリレート DA212,250,314,721,722,DM201(ナガセケムテックス社製);バンビーム(ハリマ化成社製);Miramer PE210,PE230,EA2280(東洋ケミカルズ社製)などを挙げることができる。
水酸基を有する(メタ)アクリルモノマーとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレートなどを挙げることができる。なお、水酸基を有する(メタ)アクリルモノマーは、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
多官能イソシアネートとしては、例えば、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、トリメチロールプロパントリレンジイソシアネート、ジフェニルメタントリイソシアネートなどが挙げられ、中でも耐候性の良好なヘキサメチレンジイソシアネートが好適に用いられる。なお、多官能イソシアネートは、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
多価アルコールとしては、例えば、ポリエステル(メタ)アクリレートに使用できるものを使用することができる。
ウレタン(メタ)アクリレートの具体例を挙げると、EBECRYL204,210,220,230,270,4858,8200,8201,8402,8804,8807,9260,9270,KRM8098,7735,8296(ダイセルサイテック社製);UX2201,2301,3204,3301,4101,6101,7101,8101,0937(日本化薬社製);UV6640B,6100B,3700B,3500BA,3520TL,3200B,3000B,3310B,3210EA,7000B,6630B,7461TE、7640B(日本合成化学社製);ユピカ8921,8932,8940,8936,8937,8980,8975,8976(日本ユピカ社製);Miramer PU240,PU340(東洋ケミカルズ社製)などを挙げることができる。
なお、これらは1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
例えば、未硬化状態の樹脂組成物は、(B)数平均粒子径が100nm以下の無機微粒子を含むことが好ましい。このように小さい無機微粒子を含むことにより、本発明の複層フィルムの透明性を損なうことなく硬化樹脂層の架橋密度を高めることができ、また、基材と硬化樹脂層との密着性を高めることができる。さらに、無機微粒子を含ませることにより表面硬度を向上させることができる。特に、(A)ウレタンアクリレート、エポキシアクリレート及びポリエステルアクリレートからなる群より選択される少なくとも1種類のオリゴマー型アクリレートと、(B)数平均粒子径が100nm以下の無機微粒子とを組み合わせて用いることが好ましい。
未硬化状態の樹脂組成物を用意した後で、未硬化状態の樹脂組成物の膜を基板の表面に形成する塗工工程を行う。通常は、塗布法により、基材の表面に樹脂組成物の膜を形成する。塗布方法としては、例えば、スピンコート法、ディップ法、スプレー法、バーコート法、ダイコート法、マイクログラビアコート法、などが挙げられる。
基材の表面に樹脂組成物の膜を形成した後で、必要に応じて、その膜に熱を加える加熱工程を行う。加熱工程と活性エネルギー線の照射工程の2段階の工程によって樹脂組成物の膜を硬化させることにより、溶剤等の揮発成分を速やかに除去でき、また、基材と硬化樹脂層との密着性を高くして、本発明の複層フィルムの熱膨張を更に向上させることができる。
必要に応じて加熱工程を行った後で、樹脂組成物の膜に活性エネルギー線を照射する。活性エネルギー線としては、樹脂組成物の種類に応じて各種のエネルギー線を用いればよく、例えば、紫外線、可視光線及びその他の電子線等が挙げられるが、中でも紫外線が好ましい。
活性エネルギー線の照度は、好ましくは100mW以上、より好ましくは200mW以上であり、好ましくは600mW以下、より好ましくは500mW以下である。また、活性エネルギー線の照射は、積算光量として、好ましくは300mJ/cm2以上、より好ましくは400mJ/cm2以上であり、好ましくは700mJ/cm2以下、より好ましくは650mJ/cm2以下である。
活性エネルギー線の照射により、樹脂組成物が硬化して、硬化樹脂層が得られる。
硬化樹脂層は上記のように製造されるため、未硬化状態の樹脂組成物に含まれていたモノマー、オリゴマー及びポリマーが重合体した重合体と、必要に応じて含まれる無機微粒子等の追加の成分とを含む。したがって、未硬化状態の樹脂組成物が(A)ウレタンアクリレート、エポキシアクリレート及びポリエステルアクリレートからなる群より選択される少なくとも1種類のオリゴマー型アクリレートと、(B)数平均粒子径が100nm以下の無機微粒子とを含んでいた場合には、硬化樹脂層は、前記のオリゴマー型アクリレートが重合した重合体と前記の無機微粒子とを含む。硬化樹脂層において、重合体に対する無機微粒子の量(重量部)は、通常は、未硬化状態の樹脂組成物におけるモノマー、オリゴマー及びポリマーに対する量と同様となる。
硬化樹脂層によって基材の熱膨張が抑制されるので、本発明の複層フィルムの線膨張係数は基材の線膨張係数に比べて小さくなっている。具体的には、30℃から90℃までの温度範囲において測定した場合、本発明の複層フィルムの線膨張係数は、基材の線膨張係数に比べて、通常5ppm/℃以上小さく、好ましくは8ppm/℃以上小さく、より好ましくは10ppm/℃以上小さい。ここで、本発明の複層フィルムの線膨張係数とは複層フィルムの面内方向の線膨張係数を指し、基材の線膨張係数とは基材の面内方向の線膨張係数を指す。また、通常は本発明の複層フィルム及び基材において面内方向の線膨張係数は均一ではないが、面内方向のうちの少なくとも一方向において前記のように本発明の複層フィルムの線膨張係数が基材の線膨張係数に比べて小さくなっていればよい。ただし、面内方向のうちの全ての方向において前記のように本発明の複層フィルムの線膨張係数が基材の線膨張係数に比べて小さいことが、より好ましい。
なお、線膨張係数は、測定対象(複層フィルム及び基材等)を試料片に切り出し、20℃/分の加熱速度で25℃から120℃まで一度加熱したあと、試料片を冷却し、10℃/分の加熱速度で25℃から120℃まで加熱しながら測定を行い、それ以外は、JIS K7197に準拠して行う。その測定結果から、30℃から90℃へと加熱した場合の線膨張係数を算出すればよい。
「良」:キズが認められない。
「不良」:キズが認められる。
本発明の複層フィルムは、本発明の効果を著しく損なわない限り、基材及び硬化樹脂層以外の層を備えていてもよい。例えば、本発明の複層フィルムの表面に着脱可能な保護シートを備えていてもよい。保護シートを備えることにより、本発明の複層フィルムをロール状に巻き取って保存及び運搬等を行う場合に本発明の複層フィルムを傷等から保護できる。さらに、本発明の複層フィルムをロール状に巻き取る際に、複層フィルム間の動摩擦係数が低下し、シワ、バンド(フィルムが部分的に盛り上がって形成されるロールの周方向に延在する帯状の凸部)の発生のないロールを作製することができる。なお、通常、使用時には前記の保護シートは本発明の複層フィルムから剥がされることになる。
本発明の液晶表示装置は、液晶セルと、この液晶セルよりも視認側に設けられた視認側偏光板と、この視認側偏光板よりも視認側に設けられた本発明の複層フィルムとを備える。以下、本発明の液晶表示装置の実施形態について図面を示して説明するが、本発明の液晶表示装置は以下の実施形態に限定されるものではない。
図2は、本発明の液晶表示装置の第一実施形態としての立体画像表示装置の構成を模式的に示す図である。なお、図2においては、図中左側が光源側であり、図中右側が視認側である。図2に示すように、立体画像表示装置100は、光源110と、液晶パネル120と、位相差フィルム積層体130とを、この順に備える。
例えば、第一の位相差フィルム132と第二の位相差フィルム133との順番を入れ替えて、第一の位相差フィルム132を第二の位相差フィルム133よりも視認側に設けてもよい。
また、例えば、第一の位相差フィルム133における異方性領域134は、ツイステッドネマチック液晶等で形成することにより、直線偏光を90°旋光させる領域にしてもよい。
また、例えば、基材フィルム131の位置は、上記の実施形態のように第一の位相差フィルム132及び第二の位相差フィルム133よりも光源側にしてもよく、第一の位相差フィルム132及び第二の位相差フィルム133よりも視認側にしてもよく、第一の位相差フィルム132と第二の位相差フィルム133との間にしてもよい。
また、例えば、立体画像表示装置100に、拡散フィルム、輝度向上フィルム、接着層、粘着層、ハードコート層、反射防止膜、保護層などを設けてもよく、位相差フィルム積層体130の視認側にさらに例えばガラスやプラスチック製の前面板を設けてもよい。
図4は、本発明の液晶表示装置の第二実施形態としての立体画像表示装置の構成を模式的に示す図である。なお、図4においては、図中左側が光源側であり、図中右側が視認側である。図4に示すように、立体画像表示装置200は、光源110と、液晶パネル120と、位相差フィルム積層体230とを、この順に備える。
立体画像表示装置200において、光源110及び液晶パネル120は、第一実施形態と同様である。
位相差フィルム232は、基材131の表面に、直接又は配向膜等を介して形成された位相差フィルムであって、位相差は同じであるが遅相軸の方向が異なる領域が面内にパターン化されて存在する位相差フィルムである。位相差が同じであるが遅相軸の方向が異なる領域とは、位相差は同じ値であるが、当該領域の遅相軸の方向が平行ではない態様を意味する。
また、本実施形態は更に変更して実施してもよく、例えば、第一実施形態と同様に変更して実施してもよい。
〔厚みの測定方法〕
接触式厚さ計(ミツトヨ社製、コードNo.547-401)を用いて、フィルムの厚みを測定した。次いで、フィルムを切断し、断面を光学顕微鏡で観察して、各層の厚さ比を求めて、その比率より各層の厚みを計算した。以上の操作をフィルムのMD方向及びTD方向において50mm間隔毎に30箇所行い、厚みの平均値を求め、この平均値をフィルム及び層の厚みとした。
線膨張係数は、測定対象(複層フィルム及び基材等)を試料片に切り出し、20℃/分の加熱速度で25℃から120℃まで一度加熱したあと、試料片を冷却し、10℃/分の加熱速度で25℃から120℃まで加熱しながら測定を行い、それ以外は、JIS K7197に準拠して測定を行った。その測定結果から、30℃から90℃へと加熱した場合の線膨張係数を算出した。
複層フィルムの線膨張係数から基材の線膨張係数を減算し、複層フィルムと基材との線膨張係数の差を算出した。
なお、評価は、フィルムのMD方向及びTD方向においてそれぞれ行った。ここでMD方向とは長尺のフィルムとして用意した基材の長手方向のことを指し、TD方向とは基材の幅方向を指す。
JIS K7129Bに基づいて、「PERMATRAN W3/33」(モコン社製)を用いて、40℃/90%RHの条件で測定を行った。
JIS K5600-5-4に準拠して、各種硬度の鉛筆を45°傾けて、上から500g重の荷重をかけてフィルム表面を引っ掻き、傷が付きはじめる鉛筆の硬さを鉛筆硬度とした。
複層フィルムの表面にスチールウール#0000を荷重0.025MPaで押し付けた状態で、該スチールウールを複層フィルムの表面で10往復させて擦る。擦った後の複層フィルムの表面状態を目視で観察し、以下の指標で評価した。
「良」:キズが認められない。
「不良」:キズが認められる。
ウレタンアクリレート(日本合成化学社製、製品名「UV7640B」)100部と、4-ヒドロキシブチルアクリレート(大阪有機化学社製、製品名「4HBA」)30部と、オルガノシリカゾル(日産化学工業製、製品名「MEK-ST」、固形分30%、数平均粒子径10nm~15nm)10部と、光重合開始剤(チバ・スペシャリティケミカルズ社製、製品名「Irg184」)7.5部と、溶剤としてメチルイソブチルケトン412部とを混合し、液状の樹脂組成物を調製した。
その後、基材の片面に、用意した液状の樹脂組成物を、バーコーター#6で塗布した。70℃で2分乾燥した後で、高圧水銀灯で200mJ/cm2で照射して、樹脂組成物を硬化させ、硬化樹脂層を形成した。
さらに、基材のもう一方の面にも、同様にして硬化樹脂層を形成した。
これにより、厚み40μmの未延伸基材の両面に、それぞれ厚み5μmの硬化樹脂層を備える複層フィルムを製造した。
得られた複層フィルムについて、上述した要領で評価を行った。結果を表1に示す。
硬化樹脂層の厚みを両面とも1.5μmに変更したこと以外は実施例1と同様にして、複層フィルムを製造し、評価を行った。結果を表1に示す。
基材として厚み38μmのゼオノアフィルム(材質は実施例1と同じ)を用いたこと以外は実施例1と同様にして、複層フィルムを製造し、評価を行った。結果を表1に示す。
硬化樹脂層を基材の片面にだけ設けるようにしたこと以外は実施例1と同様にして、複層フィルムを製造し、評価を行った。結果を表1に示す。
基材として厚み23μmのゼオノアフィルム(材質は実施例1と同じ)を用いたこと以外は実施例1と同様にして、複層フィルムを製造し、評価を行った。結果を表1に示す。
基材として、材料であるノルボルネン樹脂のガラス転移温度Tgが135℃のゼオノアフィルム(厚みは実施例1と同じ)を用いたこと以外は実施例1と同様にして、複層フィルムを製造し、評価を行った。結果を表2に示す。
ウレタンアクリレートUV7640Bの代わりに、エポキシアクリレートEBECRYL600(ダイセル・サイテック社製)を用いたこと以外は実施例1と同様にして、複層フィルムを製造し、評価を行った。結果を表2に示す。
オルガノシリカゾルとして、MEK-STの代わりにMEK-ST-L(日産化学工業製、固形分30%、数平均粒子径40nm~50nm)を用いたこと以外は実施例1と同様にして、複層フィルムを製造し、評価を行った。結果を表2に示す。
基材であるゼオノアフィルムを、温度170℃でMD方向に1.5倍に延伸してから使用したこと以外は実施例1と同様にして、複層フィルムを製造し、評価を行った。結果を表2に示す。なお、延伸により基材の厚みは38μmとなった。
基材をそのまま試料として用いて、上述した要領で評価を行った。結果を表3に示す。
樹脂組成物の塗布の条件を変更し、それにより硬化樹脂層の厚みを両面とも0.8μmに変更したこと以外は実施例1と同様にして、複層フィルムを製造し、評価を行った。結果を表3に示す。
樹脂組成物の塗布の条件を変更し、それにより硬化樹脂層の厚みを両面とも0.4μmに変更したこと以外は実施例1と同様にして、複層フィルムを製造し、評価を行った。結果を表3に示す。
樹脂組成物の塗布の条件を変更し、それにより硬化樹脂層の厚みを両面とも15μmに変更したこと以外は実施例1と同様にして、複層フィルムを製造し、評価を行った。結果を表3に示す。なお、比較例4では硬化樹脂層が脆く破損したため、線膨張係数の差、鉛筆硬度及び耐擦傷性を評価できなかった。
前記の実施例及び比較例の比較から、基材の少なくとも片面に活性エネルギー線の照射により硬化してなる硬化樹脂層を設けることにより、基材の熱膨張を硬化樹脂層によって抑制できるので、複層フィルムの線膨張係数を小さくできることが確認された。また、この際、下記の表4に示すように、基材の厚みと硬化樹脂層との厚みとの合計に対する基材の厚み比「0.95」を境にして、複層フィルムと基材との線膨張係数の差がMD方向及びTD方向のいずれでも大きく相違していることから、前記の厚み比を0.95以下とすることには臨界的な意義があることが確認された。
(複層フィルムの製造)
実施例2と同様にして複層フィルムを製造した。
変性ポリアミド(重量平均分子量45000)100部、p-トルエンスルホン酸0.7部、および1-プロパノール3265部からなる配向膜用組成物を用意した。前記の複層フィルムの片面に、濡れ指数56dyne/cmとなるようにコロナ放電処理を施し、用意した配向膜用組成物をバーコーター#4で塗布し、100℃で5分間乾燥して、膜厚0.2μmの乾燥膜を得た。この乾燥膜にラビング処理を施して、配向膜を形成した。
重合性液晶化合物(BASF社製 LC242)を40部、重合開始剤(チバ・スペシャリティケミカルズ社製、製品名「Irg907」)を2部、界面活性剤であるフタージェント209F(ネオス社製)を0.04部、溶剤であるメチルエチルケトンを60部混合して、液晶組成物を調製した。この液晶組成物を、前記の配向膜の表面にバーコーター#8で塗布し、75℃で2分配向処理して、重合性液晶化合物を配向させた。
複層フィルム上に配向膜を形成したのと同様にして、第一の位相差フィルム上に配向膜を形成した。
配向膜上に、「(配向膜上への第一の位相差フィルムの形成)」の項で用意したのと同様の液晶組成物をバーコーター#4で塗布し、75℃で2分配向処理した。さらに、窒素雰囲気下で塗膜面側より2000mJ/cm2の紫外線を照射して硬化させ、透過光に対して1/4波長の面内位相差を有する第二の位相差フィルムを形成した。
これにより、複層フィルム、配向膜、第一の位相差フィルム、配向膜及び第二の位相差フィルムをこの順に備える位相差フィルム積層体を得た。
日本ビクター社製 3D液晶モニター「GD463D10」の視認側偏光板に貼り合わせてあるシートを剥離した。他方、前記の位相差フィルム積層体の硬化樹脂層側の表面に、濡れ指数56dyne/cmとなるようにコロナ放電処理を施した。位相差フィルム積層体のコロナ放電処理を施した表面と、シートを剥離した3D液晶モニターの視認側偏光板とを、3D液晶モニターの画素位置と位相差フィルム積層体のストライプ位置が合致するように、円偏光板を介して透過光で観察しながら位置合わせを実施した後に、粘着層を介して、視認側偏光板と第一の位相差フィルムとを貼り合わせた。
ここで円偏光板とは、直線偏光板に1/4波長板を貼り合わせた構成のものである。
また、3D液晶モニターを60℃環境下に24時間放置し、その後室温に戻し観察したところ、液晶セルのたわみの発生もなく、液晶セルの画素位置と第一の位相差フィルムのパターン位置が合った状態で変化していないことを確認した。
本発明の液晶表示装置は、例えば、立体テレビ等の立体画像表示装置として用いて好適である。
11 基材
12 硬化樹脂層(活性エネルギー線の照射により硬化してなる樹脂層)
100 立体画像表示装置(液晶表示装置)
110 光源
120 液晶パネル
121 光源側偏光板
122 液晶セル
123 視認側偏光板
130 位相差フィルム積層体
131 基材フィルム
132 第一の位相差フィルム
133 第二の位相差フィルム
134 異方性領域
135 等方性領域
140 偏光メガネ
Claims (5)
- 脂環式構造を有する重合体を含む樹脂からなる厚みが45μm以下の基材と、前記基材の少なくとも片面に設けられた、活性エネルギー線の照射により硬化してなる樹脂層とを備えた複層フィルムであって、
前記基材の厚みと樹脂層の厚みとの合計に対する、前記基材の厚みの比が、0.6以上0.95以下であり、
30℃以上90℃以下の温度範囲において、前記複層フィルムの線膨張係数が前記基材の線膨張係数に比べて5ppm/℃以上小さい、複層フィルム。 - 前記脂環式構造を有する重合体を含む樹脂のガラス転移温度が130℃以上である、請求項1記載の複層フィルム。
- 前記複層フィルムの透湿度が20g/m2・24h以上500g/m2・24h以下である、請求項1に記載の複層フィルム。
- 前記の活性エネルギー線を照射して硬化してなる樹脂層が、少なくとも下記成分(A)及び成分(B)を含む組成物を硬化させてなる、請求項1に記載の複層フィルム。
(A)ウレタンアクリレート、エポキシアクリレート及びポリエステルアクリレートからなる群より選択される少なくとも1種類のオリゴマー型アクリレート。
(B)数平均粒子径が100nm以下の無機微粒子。 - 液晶セルと、前記液晶セルよりも視認側に設けられた視認側偏光板と、前記視認側偏光板よりも視認側に設けられた請求項1に記載の複層フィルムとを備える、液晶表示装置。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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JP2012532921A JP5742846B2 (ja) | 2010-09-10 | 2011-08-19 | 複層フィルム及び液晶表示装置 |
KR1020137005918A KR20130097179A (ko) | 2010-09-10 | 2011-08-19 | 복층 필름 및 액정 표시 장치 |
US13/821,881 US20130169912A1 (en) | 2010-09-10 | 2011-08-19 | Multilayer film and liquid crystal display device |
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JP2010-203517 | 2010-09-10 | ||
JP2010203517 | 2010-09-10 |
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PCT/JP2011/068799 WO2012032919A1 (ja) | 2010-09-10 | 2011-08-19 | 複層フィルム及び液晶表示装置 |
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US (1) | US20130169912A1 (ja) |
JP (1) | JP5742846B2 (ja) |
KR (1) | KR20130097179A (ja) |
TW (1) | TWI574842B (ja) |
WO (1) | WO2012032919A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2015029666A1 (ja) * | 2013-08-27 | 2015-03-05 | リンテック株式会社 | 耐熱積層シートおよびその製造方法 |
JP2015085221A (ja) * | 2013-10-28 | 2015-05-07 | 日本ゼオン株式会社 | 光学部材の製造方法 |
JPWO2014133147A1 (ja) * | 2013-03-01 | 2017-02-09 | 富士フイルム株式会社 | 光学フィルム、偏光板および画像表示装置 |
JP2017177367A (ja) * | 2016-03-28 | 2017-10-05 | 日本ゼオン株式会社 | 光学積層体、偏光板及び液晶表示装置 |
WO2018008493A1 (ja) * | 2016-07-07 | 2018-01-11 | 日本ゼオン株式会社 | 積層フィルム及び偏光板 |
WO2018070523A1 (ja) * | 2016-10-14 | 2018-04-19 | 大日本印刷株式会社 | 光学フィルムおよび画像表示装置 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP5495458B1 (ja) * | 2013-09-11 | 2014-05-21 | 日東電工株式会社 | 光学フィルム積層体の製造方法 |
WO2016063793A1 (ja) * | 2014-10-23 | 2016-04-28 | 日本ゼオン株式会社 | 帯電防止フィルム及び液晶表示装置 |
WO2017057269A1 (ja) | 2015-09-28 | 2017-04-06 | 日本ゼオン株式会社 | 積層体及びその製造方法、並びにフレキシブルプリント基板 |
US10353123B2 (en) | 2017-08-08 | 2019-07-16 | Apple Inc. | Electronic Devices with glass layer coatings |
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FR2874005A1 (fr) * | 2004-08-07 | 2006-02-10 | Philippe Zapp | Dispositif de dosage |
TW200630226A (en) * | 2004-11-09 | 2006-09-01 | Zeon Corp | Antireflective film, polarizing plate and display |
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JPWO2007119560A1 (ja) * | 2006-03-31 | 2009-08-27 | 日本ゼオン株式会社 | 偏光板,液晶表示装置,および,保護フィルム |
JP5262610B2 (ja) * | 2008-11-17 | 2013-08-14 | 大日本印刷株式会社 | 光学シートの製造方法 |
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- 2011-08-19 JP JP2012532921A patent/JP5742846B2/ja active Active
- 2011-08-19 US US13/821,881 patent/US20130169912A1/en not_active Abandoned
- 2011-08-19 WO PCT/JP2011/068799 patent/WO2012032919A1/ja active Application Filing
- 2011-08-19 KR KR1020137005918A patent/KR20130097179A/ko active Search and Examination
- 2011-08-25 TW TW100130451A patent/TWI574842B/zh active
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JP2005002176A (ja) * | 2003-06-10 | 2005-01-06 | Asahi Denka Kogyo Kk | フィルム、その製造方法、及び該フィルムを使用した偏光板 |
JP2006178123A (ja) * | 2004-12-22 | 2006-07-06 | Nippon Zeon Co Ltd | 反射防止積層体、偏光板及び、液晶表示装置 |
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JPWO2014133147A1 (ja) * | 2013-03-01 | 2017-02-09 | 富士フイルム株式会社 | 光学フィルム、偏光板および画像表示装置 |
WO2015029666A1 (ja) * | 2013-08-27 | 2015-03-05 | リンテック株式会社 | 耐熱積層シートおよびその製造方法 |
JPWO2015029666A1 (ja) * | 2013-08-27 | 2017-03-02 | リンテック株式会社 | 耐熱積層シートおよびその製造方法 |
JP2015085221A (ja) * | 2013-10-28 | 2015-05-07 | 日本ゼオン株式会社 | 光学部材の製造方法 |
JP2017177367A (ja) * | 2016-03-28 | 2017-10-05 | 日本ゼオン株式会社 | 光学積層体、偏光板及び液晶表示装置 |
WO2018008493A1 (ja) * | 2016-07-07 | 2018-01-11 | 日本ゼオン株式会社 | 積層フィルム及び偏光板 |
WO2018070523A1 (ja) * | 2016-10-14 | 2018-04-19 | 大日本印刷株式会社 | 光学フィルムおよび画像表示装置 |
Also Published As
Publication number | Publication date |
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TWI574842B (zh) | 2017-03-21 |
US20130169912A1 (en) | 2013-07-04 |
KR20130097179A (ko) | 2013-09-02 |
TW201221361A (en) | 2012-06-01 |
JP5742846B2 (ja) | 2015-07-01 |
JPWO2012032919A1 (ja) | 2014-01-20 |
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