WO2011162204A1 - 光学フィルム、その製造方法、並びにそれを用いた偏光板、画像表示装置及び立体画像表示システム - Google Patents
光学フィルム、その製造方法、並びにそれを用いた偏光板、画像表示装置及び立体画像表示システム Download PDFInfo
- Publication number
- WO2011162204A1 WO2011162204A1 PCT/JP2011/064049 JP2011064049W WO2011162204A1 WO 2011162204 A1 WO2011162204 A1 WO 2011162204A1 JP 2011064049 W JP2011064049 W JP 2011064049W WO 2011162204 A1 WO2011162204 A1 WO 2011162204A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- film
- optical film
- carbon atoms
- liquid crystal
- Prior art date
Links
- 0 **(C=C1)C=*1[N+]([O-])=O Chemical compound **(C=C1)C=*1[N+]([O-])=O 0.000 description 2
- GPWHFPWZAPOYNO-UHFFFAOYSA-N CC(C)(C)CCN Chemical compound CC(C)(C)CCN GPWHFPWZAPOYNO-UHFFFAOYSA-N 0.000 description 2
Images
Classifications
-
- 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
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00634—Production of filters
- B29D11/00644—Production of filters polarizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
- B29D11/00788—Producing optical films
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- 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
- G02F1/1313—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 specially adapted for a particular application
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0425—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a specific unit that results in a functional effect
- C09K2019/0429—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a specific unit that results in a functional effect the specific unit being a carbocyclic or heterocyclic discotic unit
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
- C09K2019/328—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems containing a triphenylene ring system
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
- G02B2207/113—Fluorescence
-
- 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
- G02F1/133502—Antiglare, refractive index matching layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
- G02F1/133538—Polarisers with spatial distribution of the polarisation direction
-
- 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
- G02F1/13363—Birefringent elements, e.g. for optical compensation
- G02F1/133631—Birefringent elements, e.g. for optical compensation with a spatial distribution of the retardation value
-
- 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
- G02F1/13363—Birefringent elements, e.g. for optical compensation
- G02F1/133638—Waveplates, i.e. plates with a retardation value of lambda/n
-
- 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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133784—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by rubbing
-
- 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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N13/00—Stereoscopic video systems; Multi-view video systems; Details thereof
- H04N13/30—Image reproducers
- H04N13/332—Displays for viewing with the aid of special glasses or head-mounted displays [HMD]
- H04N13/337—Displays for viewing with the aid of special glasses or head-mounted displays [HMD] using polarisation multiplexing
Definitions
- the present invention has an optically anisotropic layer having a high-definition orientation pattern, is easy to manufacture and has excellent practicality, a manufacturing method thereof, a polarizing plate using the optical film, and a stereoscopic image
- the present invention also relates to an image display device and a stereoscopic image display system capable of displaying the above.
- the 3D image display device that displays a stereoscopic image requires an optical member for converting the right-eye image and the left-eye image into, for example, circularly polarized images in opposite directions.
- a pattern technique is required in which regions where the absorption axis of the polarizing film and the slow axis of the retardation film are different from each other are regularly arranged.
- Patent Document 1 discloses a method of manufacturing an optical rotatory optical element that is patterned into an optical rotatory region and a non-optical rotatory region using a photoresist material.
- Patent Document 2 discloses a phase difference sheet having first and second regions each having a different fast axis or slow axis using a photoisomerized substance.
- due to material constraints it may be difficult to achieve optimal properties for various applications.
- Patent Documents 3 and 4 disclose a patterned elliptically polarizing plate and an optically anisotropic material that can be produced by using a photo-alignment film, respectively.
- a technique using the photo-alignment film it is necessary to perform the alignment process by irradiating the photo-alignment film with light from different directions, which is complicated.
- a technique for forming a patterned optically anisotropic layer using a rubbing alignment film is also known, but it is necessary to perform rubbing processing in a plurality of directions by mask rubbing, and the processing is complicated. is there.
- a patterned optically anisotropic layer is differently produced by using a photo-alignment film irradiated with light from different directions or a rubbing alignment film subjected to rubbing treatment in different directions by mask rubbing. It is a general idea that an alignment film that is oriented in one direction is necessary, and a patterned optically anisotropic layer is formed using only an orientation film that is oriented in one direction. It can be said that there was no idea that it could be produced.
- the first object of the present invention is to provide an optical film having an optically anisotropic layer having a high-definition orientation pattern, easy to manufacture and excellent in practicality.
- the second object is to provide a simple method for producing such an optical film.
- a third object is to provide an image display device and a stereoscopic image display system that are low in cost and high in visibility.
- An optical film having, on a transparent support, at least an alignment film treated in one direction and an optically anisotropic layer formed of a kind of composition mainly composed of a liquid crystal having a polymerizable group.
- the optically anisotropic layer includes a first phase difference region and a second phase difference region having in-plane slow axes orthogonal to each other, and the first and second phase difference regions are alternately arranged in a plane.
- the alignment film is a film containing a modified or unmodified polyvinyl alcohol as a main component.
- the liquid crystal having a polymerizable group is a disk-like liquid crystal.
- the optically anisotropic layer further contains at least one of a pyridinium compound or an imidazolium compound.
- L 23 and L 24 each represent a divalent linking group (including a single bond);
- R 22 represents a hydrogen atom, an unsubstituted amino group, or a substituted amino group having 1 to 20 carbon atoms;
- R 22 is a dialkyl-substituted amino group, two alkyl groups may be bonded to each other to form a nitrogen-containing heterocycle;
- X represents an anion;
- Y 22 and Y 23 are each 5 or 6-membered A divalent linking group having a ring as a partial structure;
- m is 1 or 2, and when m is 2, a plurality of Y 23 and L 24 may be the same or different;
- 21 is halogen-substituted phenyl, nitro-substituted phenyl, cyano-substituted phenyl, phenyl substituted with an alkyl group having 1 to 10 carbon atoms, phenyl substituted with an alkoxy group having 2 to 10
- the liquid crystal having a polymerizable group is a disc-like liquid crystal, and the disc-like liquid crystal is fixed in a vertically aligned state in the optically anisotropic layer.
- a liquid crystal cell which is disposed between the first and second polarizing films, and includes a pair of substrates having electrodes disposed on at least one side thereof and facing each other; and a liquid crystal layer between the pair of substrates; and the first polarizing film On the outside of the optical film of any one of [1] to [11];
- An image display device having at least An image display device in which the absorption axis direction of the first polarizing film and the in-plane slow axes of the first and second retardation regions of the optical film form an angle of ⁇ 45 °, respectively.
- a stereoscopic image display system including at least the image display device according to [15] and a third polarizing plate disposed outside the optical film, and allowing a stereoscopic image to be visually recognized through the third polarizing plate.
- the optical film which has the optically anisotropic layer of a high-definition orientation pattern, is easy to manufacture, and was excellent in practical use.
- the simple manufacturing method of the said optical film can be provided.
- a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- visible light means 380 nm to 780 nm.
- a measurement wavelength is 550 nm.
- the angle for example, an angle such as “90 °”
- the relationship for example, “orthogonal”, “parallel”, “crossing at 45 °”, etc.
- the range of allowable error is included. For example, it means that the angle is within the range of strict angle ⁇ 10 °, and the error from the strict angle is preferably 5 ° or less, and more preferably 3 ° or less.
- Optical film has at least an alignment film processed in one direction and an optically anisotropic layer formed from a kind of composition mainly composed of a liquid crystal having a polymerizable group on a transparent support.
- the optical film of the present invention is disposed further outside the viewing-side polarizer of the image display device for stereoscopic image display, and the polarized image that has passed through each of the first and second retardation regions of the optical film is polarized. It is recognized as an image for the right eye or the left eye through glasses or the like. Therefore, it is preferable that the first and second retardation regions have the same shape so that the left and right images do not become non-uniform, and that the respective arrangements are preferably uniform and symmetrical.
- FIG. 1 shows a schematic cross-sectional view of an example of the optical film of the present invention
- FIG. 2 shows a top view thereof.
- the optical film 10 shown in FIGS. 1 and 2 includes a transparent support 16, an alignment film 14, and an optically anisotropic layer 12.
- the optically anisotropic layer 12 is provided in the image display device with a first and a first film.
- the two retardation regions 12a and 12b are patterned optically anisotropic layers arranged uniformly and symmetrically.
- the first and second retardation regions 12a and 12b have in-plane slow axes a and b that are orthogonal to each other.
- the Re of the optical film 10 is preferably ⁇ / 4, specifically, 110 to 165 nm. Re is more preferably 120 to 145 nm, and particularly preferably 130 to 145 nm.
- the transparent support 16 is a retardation film, it is preferable that Re is in the above range as a whole of the optical film including Re of the transparent support 16.
- the smaller Rth is, the more preferable from the viewpoint of reducing crosstalk.
- the absolute value of Rth is preferably 20 nm or less for the entire optical film.
- the alignment film 14 of the optical film 10 is a rubbing alignment film, and C1 coincides with the in-plane slow axis a of the first retardation region 12a or the in-plane slow axis b of the second retardation region 12b.
- the alignment film is rubbed in the C2 direction.
- the rubbing alignment film can maintain the alignment regulating force even if it has a certain thickness. Therefore, even if the surface of the transparent support 16 has irregularities, it is possible to form an alignment film having a thickness that compensates for the unevenness. Can be flattened.
- the photo-alignment film needs to be thin in order to sufficiently exert the alignment regulating force, and the thickness may be insufficient to flatten the unevenness of the transparent support. From the viewpoint of flattening the unevenness of the transparent support and stably producing the patterned optically anisotropic layer, this embodiment using a rubbing alignment film is preferred.
- Step of forming a rubbing alignment film on a transparent support 2) Step of rubbing the rubbing alignment film in one direction 3) A kind of composition mainly comprising a liquid crystal having a polymerizable group on the rubbing alignment film 4) Step of heating at a temperature T 1 ° C.
- a rubbing alignment film that has been rubbed in one direction is used to form the patterned optically anisotropic layer.
- the rubbing alignment film exhibits alignment control ability by rubbing treatment, and has a property that an alignment axis is determined according to the rubbing treatment direction and heating conditions. Normally, when liquid crystal is aligned on an alignment film that has been rubbed in one direction, the liquid crystal is aligned with its slow axis parallel or orthogonal to the rubbing direction.
- the alignment state is determined by one or more kinds of alignment film material, liquid crystal, and alignment control agent.
- the slow axis of the liquid crystal is orthogonal to the rubbing direction by changing the affinity between any two or three of the alignment film material, the liquid crystal, and the alignment control agent according to the temperature change.
- the alignment state and the alignment state in which the slow axis of the liquid crystal is aligned parallel to the rubbing direction are realized.
- the alignment state is fixed in a predetermined pattern by ultraviolet irradiation under a photomask, and then non-irradiation at a temperature T 2 (where T 1 ⁇ T 2 ) ° C.
- T 2 where T 1 ⁇ T 2
- the first and second phase difference regions are in a strip shape in which the lengths of the short sides of each other are substantially equal, and are alternately and repeatedly patterned. preferable.
- the transition from the orthogonal orientation state to the parallel orientation state is enabled by increasing the temperature from T 1 ° C to T 2 ° C.
- T 1 ° C. the interaction between any two or three of the alignment film material, the liquid crystal, and the alignment controller dominates the alignment state, and aligns the liquid crystal in the direction perpendicular to the rubbing direction.
- T 2 ° C. the interaction between the rubbing direction of the rubbing alignment film dominates the alignment state, and the liquid crystal is aligned in parallel with its slow axis parallel to the rubbing direction.
- the preferable ranges of the temperatures T 1 ° C and T 2 ° C for achieving these states vary depending on the materials used and cannot be determined in general.
- T 1 ° C is preferably 60 to 90 ° C.
- T 2 ° C. may be equal to or higher than the isotropic phase transition temperature of the liquid crystal compound as long as the alignment regulating force of the alignment film can be secured and the polymer film used as the support is not deteriorated.
- T 2 ° C is more than 90 ° and 180 ° C or less.
- you may heat between the 3) process and the 4) process in order to evaporate the solvent in a composition.
- the heating temperature may be higher or lower than T 1 ° C., or may be a T 1 ° C. and the same temperature.
- ultraviolet rays are irradiated to advance the polymerization reaction of the liquid crystal compound.
- the irradiation energy is preferably 10 mJ / cm 2 to 10 J / cm 2 , and more preferably 25 to 800 mJ / cm 2 .
- the illuminance is preferably 10 ⁇ 1000mW / cm 2, more preferably 20 ⁇ 500mW / cm 2, further preferably 40 ⁇ 350mW / cm 2.
- the irradiation wavelength preferably has a peak at 250 to 450 nm, and more preferably has a peak at 300 to 410 nm.
- light irradiation may be performed under an inert gas atmosphere such as nitrogen or under heating conditions.
- the light source is preferably a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp) or short arc discharge lamp (ultra-high pressure mercury lamp, xenon lamp, mercury xenon lamp). Used.
- the liquid crystal molecules are brought into an orthogonal alignment state, and then irradiated with ultraviolet rays under a photomask to advance the polymerization, fix the alignment state, and form a first retardation region.
- the UV irradiation under a photomask, exposure is preferably 50 ⁇ 1000mJ / cm 2 or so, more preferably from 50 ⁇ 200mJ / cm 2 approximately. In order to improve the pattern resolution, it is preferable to perform exposure at room temperature.
- the exposure dose in the step is preferably about 200 to 2000 mJ / cm 2 , more preferably about 500 to 1000 mJ / cm 2 .
- the step 5) may be performed at a temperature T 1 ° C, or may be performed after the temperature is lowered to about room temperature.
- the step 7) may be performed at a temperature T 2 ° C or after a temperature lower than T 2 ° C.
- the exposure temperatures in steps 5) and 7) are equal.
- Rubbing alignment film A rubbing alignment film is formed by the steps 1) and 2).
- the “rubbing alignment film” that can be used in the present invention means a film that has been processed by rubbing so as to have alignment ability of liquid crystal molecules.
- the rubbing alignment film has an alignment axis that regulates alignment of liquid crystal molecules, and the liquid crystal molecules are aligned according to the alignment axis.
- the liquid crystal molecules are aligned so that the slow axis of the liquid crystal is orthogonal to the rubbing direction at a temperature T 1 ° C, and then the liquid crystal molecules are delayed at a temperature T 2 (where T 1 ⁇ T 2 ) ° C.
- the material of the alignment film, the liquid crystal, and the alignment control agent are selected so that the alignment transition occurs so that the phase axis is parallel to the rubbing direction.
- the rubbing alignment film generally contains a polymer as a main component.
- the polymer material for alignment film is described in many documents, and many commercially available products can be obtained.
- the polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. In particular, modified or unmodified polyvinyl alcohol is preferred.
- Polyvinyl alcohols having various saponification degrees exist. In the present invention, those having a saponification degree of about 85 to 99 are preferably used.
- Commercial products may be used. For example, “PVA103”, “PVA203” (manufactured by Kuraray Co., Ltd.) and the like are PVA having the above saponification degree.
- the thickness of the rubbing alignment film is preferably 0.01 to 10 ⁇ m, and more preferably 0.01 to 1 ⁇ m.
- the rubbing treatment can be generally performed by rubbing the surface of a film containing a polymer as a main component several times in a certain direction with paper or cloth.
- a general method of rubbing is described in, for example, “Liquid Crystal Handbook” (issued by Maruzen, October 30, 2000).
- As a method for changing the rubbing density a method described in “Liquid Crystal Handbook” (published by Maruzen) can be used.
- the rubbing density (L) is quantified by the following formula (A).
- N Nl (1 + 2 ⁇ rn / 60v)
- N is the number of rubbing
- l is the contact length of the rubbing roller
- r is the radius of the roller
- n is the number of rotations (rpm) of the roller
- v is the stage moving speed (second speed).
- the rubbing frequency should be increased, the contact length of the rubbing roller should be increased, the radius of the roller should be increased, the rotation speed of the roller should be increased, and the stage moving speed should be decreased, while the rubbing density should be decreased.
- the pretilt angle of the alignment film there is a relationship in which the pretilt angle decreases as the rubbing density increases and the pretilt angle increases as the rubbing density decreases.
- an alignment film is formed on a support made of a long polymer film, and the direction is 45 ° to the longitudinal direction. It is preferable that a rubbing alignment film is formed by continuous rubbing treatment.
- Optically anisotropic layer In the step 3), a kind of composition containing as a main component a liquid crystal having a polymerizable group prepared as a coating solution is applied to the rubbing-treated surface of the alignment film.
- the coating method is not particularly limited, curtain coating method, dip coating method, spin coating method, printing coating method, spray coating method, slot coating method, roll coating method, slide coating method, blade coating method, gravure coating method, A known coating method such as a wire bar method may be used.
- the slow axis of the liquid crystal is aligned perpendicularly and parallel to the rubbing direction, respectively.
- the directions of the first and second in-plane slow axes are determined, and the first and second phase difference regions having the in-plane slow axes perpendicular to each other are formed.
- the optical properties (Re and Rth) of the optically anisotropic layer are determined by the alignment state of the liquid crystal in these steps.
- the optically anisotropic layer is preferably a ⁇ / 4 plate, that is, an optically anisotropic layer having a function of converting linearly polarized light into circularly polarized light.
- an optically anisotropic layer having a function as a ⁇ / 4 plate there are various methods for forming an optically anisotropic layer having a function as a ⁇ / 4 plate.
- One example is a method of fixing the slow axis of a rod-like liquid crystal compound having a polymerizable group to a state where it is horizontally aligned on the layer surface, or a state where the disc surface of the discotic liquid crystal is aligned vertically to the layer surface. It is a method of immobilization. More preferred is a method of fixing the discotic liquid crystal in a vertically aligned state.
- composition used for forming the optically anisotropic layer is a liquid crystal composition containing at least one liquid crystal compound having a polymerizable group and at least one alignment control agent.
- a polymerization initiator and a sensitizer may be contained.
- liquid crystal compound having a polymerizable group examples include rod-like liquid crystals and discotic liquid crystals. Discotic liquid crystals are preferred, and discotic liquid crystals having a polymerizable group as described above. More preferred.
- rod-like liquid crystal examples include Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Pat. No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, No. 6-16616, No. 7-110469, No. 11-80081, No. 11-513019 And compounds described in each publication and specification such as Japanese Patent Application No. 2001-64627.
- the low molecular rod-like liquid crystal compound is preferably a compound represented by the following general formula (X).
- Formula (X) Q 1 -L 1 -Cy 1 -L 2- (Cy 2 -L 3 ) n -Cy 3 -L 4 -Q 2
- Q 1 and Q 2 each independently represent a polymerizable group
- L 1 and L 4 each independently represent a divalent linking group
- L 2 and L 3 each independently represent a single bond or a divalent group.
- Cy 1 , Cy 2 and Cy 3 each independently represent a divalent cyclic group
- n is 0, 1 or 2.
- Q 1 and Q 2 are each independently a polymerizable group.
- the polymerization reaction of the polymerizable group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization.
- the polymerizable group is preferably a functional group capable of an addition polymerization reaction or a condensation polymerization reaction.
- a compound having a polymerizable group is preferable as described above.
- a compound represented by the following general formula (I) is preferable.
- D is a discotic core
- L is a divalent linking group
- H is a divalent aromatic ring or heterocyclic ring
- Q is a polymerizable group
- n is an integer of 3 to 12 Represents.
- the discotic core (D) is preferably a benzene ring, naphthalene ring, triphenylene ring, anthraquinone ring, truxene ring, pyridine ring, pyrimidine ring, or triazine ring, and particularly a benzene ring, triphenylene ring, pyridine ring, pyrimidine ring, or triazine ring. preferable.
- L is preferably a divalent linking group selected from the group consisting of * —O—CO—, * —CO—O—, * —CH ⁇ CH—, * —C ⁇ C—, and combinations thereof.
- a divalent linking group containing at least one of CH ⁇ CH— and * —C ⁇ C— is particularly preferable.
- * represents a position bonded to D in the general formula (I).
- H is preferably an aromatic ring such as a benzene ring and a naphthalene ring, particularly preferably a benzene ring.
- a pyridine ring and a pyrimidine ring are preferable, and a pyridine ring is particularly preferable.
- H is particularly preferably an aromatic ring.
- the polymerization reaction of the polymerizable group Q is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization.
- the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction.
- (meth) acrylate groups and epoxy groups are preferred.
- the discotic liquid crystal represented by the general formula (I) is particularly preferably a discotic liquid crystal represented by the following general formula (II) or (III).
- L, H and Q have the same meanings as L, H and Q in the general formula (I), respectively, and preferred ranges thereof are also the same.
- Y 1 , Y 2 , and Y 3 are synonymous with Y 11 , Y 12 , and Y 13 in the general formula (IV) described later, and their preferred ranges are also the same.
- L 1 , L 2 , L 3 , H 1 , H 2 , H 3 , R 1 , R 2 , and R 3 are also L 1 , L 2 , L 3 , H 1 in the general formula (IV) described later.
- H 2 , H 3 , R 1 , R 2 , R 3 and their preferred ranges are also the same.
- the discotic liquid crystal having a plurality of aromatic rings in the molecule is an alignment control agent. Since an intermolecular ⁇ - ⁇ interaction occurs with an onium salt such as a pyridinium compound or an imidazolium compound used as a vertical alignment, vertical alignment can be realized.
- Y 11 , Y 12 and Y 13 each independently represent a methine group or a nitrogen atom which may be substituted.
- the hydrogen atom of methine may be replaced by a substituent.
- substituent that methine may have include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, a halogen atom, and A cyano group can be mentioned as a preferred example.
- an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon number A 2-12 alkoxycarbonyl group, an acyloxy group having 2-12 carbon atoms, a halogen atom and a cyano group are more preferred.
- Y 11 , Y 12 and Y 13 are all preferably methine, and more preferably unsubstituted, from the viewpoint of ease of synthesis of the compound and cost.
- L 1 , L 2 and L 3 each independently represents a single bond or a divalent linking group.
- L 1 , L 2 and L 3 are divalent linking groups, each independently represents —O—, —S—, —C ( ⁇ O) —, —NR 7 —, —CH ⁇ CH—, —C
- R 7 is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group, or a hydrogen atom.
- it is a hydrogen atom.
- the divalent cyclic group in L 1 , L 2 and L 3 is a divalent linking group having at least one kind of cyclic structure (hereinafter sometimes referred to as a cyclic group).
- the cyclic group is preferably a 5-membered ring, a 6-membered ring, or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring.
- the ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring.
- the ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring.
- Preferred examples of the aromatic ring include a benzene ring and a naphthalene ring.
- a preferable example of the aliphatic ring is a cyclohexane ring.
- Preferred examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.
- the cyclic group is more preferably an aromatic ring or a heterocyclic ring.
- the divalent cyclic group in the present invention is more preferably a divalent linking group consisting of only a cyclic structure (including a substituent) (hereinafter the same).
- the cyclic group having a benzene ring is preferably a 1,4-phenylene group.
- a naphthalene ring a naphthalene-1,5-diyl group and a naphthalene-2,6-diyl group are preferable.
- the cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group.
- the cyclic group having a pyridine ring is preferably a pyridine-2,5-diyl group.
- the cyclic group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group.
- the divalent cyclic group represented by L 1 , L 2 and L 3 may have a substituent.
- substituents include a halogen atom (preferably a fluorine atom and a chlorine atom), a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, and 2 to 2 carbon atoms.
- alkynyl group halogen-substituted alkyl group having 1 to 16 carbon atoms, alkoxy group having 1 to 16 carbon atoms, acyl group having 2 to 16 carbon atoms, alkylthio group having 1 to 16 carbon atoms, 2 carbon atoms And an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, a carbamoyl group substituted with an alkyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms.
- * represents the position bonded to the 6-membered ring side including Y 11 , Y 12 and Y 13 in the general formula (IV).
- H 1 , H 2 and H 3 each independently represent a group of general formula (IV-A) or (IV-B).
- YA 1 and YA 2 each independently represents a methine group or a nitrogen atom;
- XA represents an oxygen atom, a sulfur atom, methylene or imino;
- * Represents a position bonded to the L 1 to L 3 side in the general formula (IV); ** represents a position bonded to the R 1 to R 3 side in the general formula (IV).
- YB 1 and YB 2 each independently represent a methine or a nitrogen atom;
- XB represents an oxygen atom, a sulfur atom, methylene or imino;
- * Represents a position bonded to the L 1 to L 3 side in the general formula (IV); ** represents a position bonded to the R 1 to R 3 side in the general formula (IV).
- R 1 , R 2 and R 3 each independently represents the following general formula (IV-R).
- L 21 represents a single bond or a divalent linking group.
- L 21 is a divalent linking group, the group consisting of —O—, —S—, —C ( ⁇ O) —, —NR 7 —, —CH ⁇ CH—, —C ⁇ C—, and combinations thereof A divalent linking group selected more preferably.
- R 7 is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group, or a hydrogen atom. Preferably, it is a hydrogen atom.
- Q 2 represents a divalent group (cyclic group) having at least one kind of cyclic structure.
- a cyclic group having a 5-membered ring, a 6-membered ring, or a 7-membered ring is preferable, a cyclic group having a 5-membered ring or a 6-membered ring is more preferable, and a cyclic group having a 6-membered ring is preferable.
- the cyclic structure contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring.
- the ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring.
- the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.
- a preferable example of the aliphatic ring is a cyclohexane ring.
- Preferred examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.
- the cyclic group having a benzene ring is preferably a 1,4-phenylene group.
- the cyclic group having a naphthalene ring include naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-2,5-diyl group, naphthalene-2,6.
- a diylnaphthalene-2,7-diyl group is preferred.
- the cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group.
- the cyclic group having a pyridine ring is preferably a pyridine-2,5-diyl group.
- the cyclic group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group.
- 1,4-phenylene group, naphthalene-2,6-diyl group and 1,4-cyclohexylene group are particularly preferable.
- Q 2 may have a substituent.
- substituents include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 16 carbon atoms An alkylthio group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms.
- halogen atom fluorine atom, chlorine
- a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, and a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
- N1 represents an integer of 0-4.
- n1 is preferably an integer of 1 to 3, and more preferably 1 or 2.
- L 22 is **-O-, **-O-CO-, **-CO-O-, **-O-CO-O-, **-S-, **-NH-, ** —SO 2 —, ** — CH 2 —, ** — CH ⁇ CH— or ** — C ⁇ C— is represented, and ** represents a position bonded to the Q 2 side.
- L 22 is preferably ** — O—, ** — O—CO—, ** — CO—O—, ** — O—CO—O—, ** — CH 2 —, ** — CH. ⁇ CH—, ** — C ⁇ C—, more preferably ** — O—, ** — O—CO—, ** — O—CO—O—, ** — CH 2 —. .
- L 22 is a group containing a hydrogen atom
- the hydrogen atom may be substituted with a substituent.
- substituents include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.
- An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.
- L 23 represents —O—, —S—, —C ( ⁇ O) —, —SO 2 —, —NH—, —CH 2 —, —CH ⁇ CH—, —C ⁇ C— and combinations thereof.
- the hydrogen atom of —NH—, —CH 2 —, —CH ⁇ CH— may be substituted with a substituent.
- substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.
- An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.
- L 23 is preferably selected from the group consisting of —O—, —C ( ⁇ O) —, —CH 2 —, —CH ⁇ CH—, —C ⁇ C—, and combinations thereof.
- L 23 preferably contains 1 to 20 carbon atoms, more preferably 2 to 14 carbon atoms.
- L 23 is, -CH 2 - preferably contains 1 to 16 pieces of, -CH 2 - is more preferable that 2 to be 12 contains.
- Q 1 represents a polymerizable group or a hydrogen atom.
- Q 1 is preferably a polymerizable group.
- the polymerization reaction is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. That is, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.
- the polymerizable group is particularly preferably a functional group that can undergo an addition polymerization reaction.
- a polymerizable group is preferably a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group.
- Examples of the polymerizable ethylenically unsaturated group include the following formulas (M-1) to (M-6).
- R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.
- (M-1) to (M-6) (M-1) or (M-2) is preferable, and (M-1) is more preferable.
- the ring-opening polymerizable group is preferably a cyclic ether group, more preferably an epoxy group or an oxetanyl group.
- Y 11 , Y 12 and Y 13 each independently represent methine or a nitrogen atom, methine is preferred, and methine is preferably unsubstituted.
- R 11 , R 12 and R 13 each independently represents the following general formula (IV′-A), the following general formula (IV′-B) or the following general formula (IV′-C).
- general formula (IV′-A) or general formula (IV′-C) is preferable, and general formula (IV′-A) is more preferable.
- a 11 , A 12 , A 13 , A 14 , A 15 and A 16 each independently represents a methine or nitrogen atom. At least one of A 11 and A 12 is preferably a nitrogen atom, and more preferably both are nitrogen atoms. Of A 13 , A 14 , A 15 and A 16 , at least three of them are preferably methine, and more preferably all methine. Furthermore, methine is preferably unsubstituted.
- substituents when A 11 , A 12 , A 13 , A 14 , A 15 or A 16 is methine include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups
- a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, and a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
- X 1 represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.
- a 21 , A 22 , A 23 , A 24 , A 25 and A 26 each independently represents a methine or nitrogen atom. At least one of A 21 and A 22 is preferably a nitrogen atom, and more preferably both are nitrogen atoms. Of A 23 , A 24 , A 25 and A 26 , at least three of them are preferably methine, more preferably all methine.
- substituents when A 21 , A 22 , A 23 , A 24 , A 25 or A 26 is methine include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups
- a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, and a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
- X 2 represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.
- a 31 , A 32 , A 33 , A 34 , A 35 and A 36 each independently represents a methine or nitrogen atom. At least one of A 31 and A 32 is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A 33 , A 34 , A 35 and A 36 are preferably methine, more preferably methine. When A 31 , A 32 , A 33 , A 34 , A 35 or A 36 is methine, the methine may have a substituent.
- substituents examples include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 16 carbon atoms An alkylthio group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms.
- halogen atom fluorine atom, chlorine atom, bromine atom, i
- a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, and a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
- X 3 represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.
- L 11 in the general formula (IV′-A), L 21 in the general formula (IV′-B), and L 31 in the general formula (IV′-C) are each independently —O—, —C ( ⁇ O) —, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO 2 —, —CH 2 —, —CH ⁇ CH— or —C ⁇ C— is represented.
- L 11 in the general formula (DI-A) that can be expected to have small intrinsic birefringence wavelength dispersibility is particularly preferably —O—, —CO—O—, —C ⁇ C—, and among them, —CO— -O- is preferable because it can exhibit a discotic nematic phase at a higher temperature.
- the hydrogen atom may be replaced with a substituent.
- substituents include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.
- An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.
- L 12 in the general formula (IV′-A), L 22 in the general formula (IV′-B), and L 32 in the general formula (IV′-C) are each independently —O—, —S A divalent linking group selected from the group consisting of —, —C ( ⁇ O) —, —SO 2 —, —NH—, —CH 2 —, —CH ⁇ CH—, —C ⁇ C—, and combinations thereof.
- —S A divalent linking group selected from the group consisting of —, —C ( ⁇ O) —, —SO 2 —, —NH—, —CH 2 —, —CH ⁇ CH—, —C ⁇ C—, and combinations thereof.
- the hydrogen atom of —NH—, —CH 2 —, —CH ⁇ CH— may be substituted with a substituent.
- Examples of such a substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and 1 carbon atom.
- Preferred examples include a carbamoyl group substituted with an alkyl having 2 to 6 carbon atoms and an acylamino group having 2 to 6 carbon atoms, and a halogen atom, a hydroxyl group, and an alkyl group having 1 to 6 carbon atoms are more preferable, A halogen atom, a methyl group, and an ethyl group are preferable.
- L 12 , L 22 , and L 32 are each independently selected from the group consisting of —O—, —C ( ⁇ O) —, —CH 2 —, —CH ⁇ CH—, —C ⁇ C—, and combinations thereof. It is preferable to be selected.
- L 12 , L 22 , and L 32 each independently preferably have 1 to 20 carbon atoms, and more preferably 2 to 14 carbon atoms.
- the number of carbon atoms is preferably 2 to 14, more preferably 1 to 16 —CH 2 —, and still more preferably 2 to 12 —CH 2 —.
- the number of carbon atoms constituting L 12 , L 22 , and L 32 affects the phase transition temperature of the liquid crystal and the solubility of the compound in the solvent. Generally the more increased the number of carbon atoms, transition temperature of the discotic nematic phase from (N D phase) to the isotropic liquid tends to decrease. Further, the solubility in a solvent generally tends to improve as the number of carbon atoms increases.
- Q 11 in the general formula (IV′-A), Q 21 in the general formula (IV′-B), and Q 31 in the general formula (IV′-C) each independently represent a polymerizable group or a hydrogen atom.
- Q 11 , Q 21 and Q 31 are preferably a polymerizable group.
- the polymerization reaction is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. That is, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction.
- examples of the polymerizable group are the same as described above, and preferable examples are also the same as described above.
- Specific examples of the compound represented by the general formula (IV) include the exemplified compounds described in [Chemical Formula 13] to [Chemical Formula 43] of [0052] of JP-A-2006-76992, and JP-A-2007-2220.
- the exemplified compounds described in [Chemical Formula 13] of [Chemical Formula 13] to [0063] of [0040] are included. However, it is not limited to these compounds.
- the above compounds can be synthesized by various methods, for example, by the methods described in JP-A 2007-2220, [0064] to [0070].
- the discotic liquid crystal compound a liquid crystal phase, it is preferred to exhibit a columnar phase and a discotic nematic phase (N D phase), among these liquid crystal phases, a discotic nematic phase having a good monodomain property (N D phase) is preferred.
- the liquid crystal phase is expressed in the range of 20 ° C. to 300 ° C. More preferably, it is 40 ° C to 280 ° C, and further preferably 60 ° C to 250 ° C.
- the expression of the liquid crystal phase at 20 ° C. to 300 ° C. means that the liquid crystal temperature range extends over 20 ° C. (for example, 10 ° C. to 22 ° C.) or the case where it crosses 300 ° C. (for example, 298 ° C. to 310 ° C.) Including. The same applies to 40 ° C to 280 ° C and 60 ° C to 250 ° C.
- the discotic liquid crystal represented by the general formula (IV) Since the discotic liquid crystal represented by the general formula (IV) has a plurality of aromatic rings in the molecule, a strong intermolecular ⁇ - ⁇ mutual bond is formed between the pyridinium compound or the imidazolium compound described later. As a result, the tilt angle near the interface of the alignment film of the discotic liquid crystal is increased.
- the discotic liquid crystal represented by the general formula (IV ′) has a highly linear molecular structure in which the rotational degrees of freedom of the molecules are constrained because a plurality of aromatic rings are connected by a single bond. Therefore, a stronger intermolecular ⁇ - ⁇ interaction occurs between the pyridinium compound or the imidazolium compound, and the tilt angle near the alignment film interface of the discotic liquid crystal can be increased to realize a vertical alignment state.
- horizontal alignment means that the child major axis of the rod-like liquid crystal is parallel to the layer surface. It is not required to be strictly parallel, and in this specification, it means an orientation with an inclination angle of less than 10 degrees with the horizontal plane.
- the inclination angle is preferably 0 to 5 degrees, more preferably 0 to 3 degrees, further preferably 0 to 2 degrees, and most preferably 0 to 1 degree.
- An additive for promoting horizontal alignment of liquid crystals may be added to the composition. Examples of the additive are described in JP-A-2009-222001 [0055] to [0063]. These compounds are included.
- vertical alignment means that the disc surface and the layer surface of the discotic liquid crystal are vertical. It is not required to be strictly perpendicular, and in this specification, it means an orientation having an inclination angle of 70 degrees or more with a horizontal plane.
- the inclination angle is preferably 85 to 90 degrees, more preferably 87 to 90 degrees, further preferably 88 to 90 degrees, and most preferably 89 to 90 degrees.
- the tilt angle on one surface of the optically anisotropic layer (the angle formed by the physical target axis in the liquid crystalline compound and the interface of the optically anisotropic layer) It is difficult to directly and accurately measure the tilt angle ⁇ 1 and the tilt angle ⁇ 2 of the other surface. Therefore, in this specification, ⁇ 1 and ⁇ 2 are calculated by the following method. Although this method does not accurately represent the actual orientation state of the present invention, it is effective as a means for expressing the relative relationship of some optical properties of the optical film. In this method, the following two points are assumed and the tilt angle at the two interfaces of the optically anisotropic layer is assumed to facilitate calculation. 1.
- the optically anisotropic layer is assumed to be a multilayer body composed of a layer containing a liquid crystalline compound. Furthermore, the minimum unit layer (assuming that the tilt angle of the liquid crystal compound is uniform in the layer) is assumed to be optically uniaxial. 2. It is assumed that the tilt angle of each layer changes monotonically with a linear function along the thickness direction of the optically anisotropic layer.
- the specific calculation method is as follows. (1) In a plane in which the tilt angle of each layer changes monotonically with a linear function along the thickness direction of the optically anisotropic layer, the incident angle of the measurement light to the optically anisotropic layer is changed, and three or more The retardation value is measured at the measurement angle.
- the retardation value In order to simplify measurement and calculation, it is preferable to measure the retardation value at three measurement angles of ⁇ 40 °, 0 °, and + 40 °, with the normal direction to the optically anisotropic layer being 0 °.
- Such measurements include KOBRA-21ADH and KOBRA-WR (manufactured by Oji Scientific Instruments), transmission ellipsometer AEP-100 (manufactured by Shimadzu Corporation), M150 and M520 (manufactured by JASCO Corporation). , ABR10A (manufactured by UNIOPT Co., Ltd.).
- the refractive index of ordinary light in each layer is no
- the refractive index of extraordinary light is ne (ne is the same value in all layers, and no is the same)
- the thickness of the entire multilayer body is d.
- the calculation of the angular dependence of the retardation value of the optically anisotropic layer agrees with the measured value. Fitting is performed using the tilt angle ⁇ 1 on one surface of the anisotropic layer and the tilt angle ⁇ 2 on the other surface as variables, and ⁇ 1 and ⁇ 2 are calculated.
- known values such as literature values and catalog values can be used for no and ne. If the value is unknown, it can also be measured using an Abbe refractometer.
- the thickness of the optically anisotropic layer can be measured by an optical interference film thickness meter, a cross-sectional photograph of a scanning electron microscope, or the like.
- an onium salt is preferably added in order to realize vertical alignment of a liquid crystal compound having a polymerizable group, particularly a discotic liquid crystal having a polymerizable group.
- the onium salt is unevenly distributed at the alignment film interface and acts to increase the tilt angle in the vicinity of the alignment film interface of the liquid crystal molecules.
- the onium salt is preferably a compound represented by the following general formula (1).
- General formula (1) Z- (YL-) n Cy + ⁇ X-
- Cy is a 5- or 6-membered onium group
- L, Y, Z, and X are L 23 , L 24 , Y 22 , Y 23 , Z in the general formulas (2a) and (2b) described later.
- 21 and X have the same meaning, and the preferred ranges thereof are also the same, and n represents an integer of 2 or more.
- the 5- or 6-membered onium group (Cy) is preferably a pyrazolium ring, an imidazolium ring, a triazolium ring, a tetrazolium ring, a pyridinium ring, a pyrazinium ring, a pyrimidinium ring, or a triazinium ring, and particularly preferably an imidazolium ring or a pyridinium ring.
- the 5- or 6-membered onium group (Cy) preferably has a group having an affinity for the alignment film material.
- the onium salt compound preferably has a high affinity with the alignment film material at a temperature T 1 ° C., while the affinity is decreased at a temperature T 2 ° C. Since the hydrogen bond can be in a bonded state or a state in which the bond disappears within the actual temperature range (room temperature to 150 ° C.) for aligning the liquid crystal, it is preferable to use the affinity due to the hydrogen bond. . However, it is not limited to this example.
- polyvinyl alcohol in an embodiment in which polyvinyl alcohol is used as the alignment film material, it preferably has a hydrogen bonding group in order to form a hydrogen bond with the hydroxyl group of polyvinyl alcohol.
- hydrogen bonding for example, H.H. Unneyama and K.M.
- Specific examples of hydrogen bonding include J.I. N. Examples include KArs Ativiri, Yasuo Kondo, Hiroyuki Oshima, Intermolecular Force and Surface Force, McGraw Hill, 1991, page 98, FIG.
- Specific examples of hydrogen bonding include, for example, G.I. R. Examples include those described in Desiraju, Angewent Chemistry International Edition England, Vol. 34, p. 2311, 1995.
- the 5- or 6-membered onium group having a hydrogen bonding group enhances the surface unevenness of the alignment film interface by hydrogen bonding to the polyvinyl alcohol, and the polyvinyl alcohol main chain Promotes the function of imparting orthogonal orientation to the.
- Preferred hydrogen bonding groups include amino groups, carbonamido groups, sulfonamido groups, acid amide groups, ureido groups, carbamoyl groups, carboxyl groups, sulfo groups, nitrogen-containing heterocyclic groups (for example, imidazolyl groups, benzimidazolyl groups, Pyrazolyl group, pyridyl group, 1,3,5-triazyl group, pyrimidyl group, pyridazyl group, quinolyl group, benzimidazolyl group, benzthiazolyl group, succinimide group, phthalimide group, maleimide group, uracil group, thiouracil group, barbituric acid group And hydantoin group, maleic hydrazide group, isatin group, uramil group and the like.
- heterocyclic groups for example, imidazolyl groups, benzimidazolyl groups, Pyrazolyl group, pyridy
- More preferred hydrogen bonding groups include amino groups and pyridyl groups.
- a 5- or 6-membered onium ring contains an atom having a hydrogen bonding group, such as a nitrogen atom of an imidazolium ring.
- N is preferably an integer of 2 to 5, more preferably 3 or 4, and particularly preferably 3.
- a plurality of L and Y may be the same as or different from each other.
- the onium salt represented by the general formula (1) has three or more 5- or 6-membered rings, so that the discotic liquid crystal and the strong intermolecular ⁇ - ⁇ interaction Therefore, the vertical alignment of the discotic liquid crystal, particularly the orthogonal vertical alignment with respect to the polyvinyl alcohol main chain can be realized on the polyvinyl alcohol alignment film.
- the onium salt represented by the general formula (1) is particularly preferably a pyridinium compound represented by the following general formula (2a) or an imidazolium compound represented by the following general formula (2b).
- the compounds represented by the general formulas (2a) and (2b) are added mainly for the purpose of controlling the alignment at the alignment film interface of the discotic liquid crystal represented by the general formulas (I) to (IV). In addition, there is an effect of increasing the tilt angle in the vicinity of the alignment film interface of the molecules of the discotic liquid crystal.
- L 23 and L 24 each represent a divalent linking group.
- L 23 represents a single bond, —O—, —O—CO—, —CO—O—, —C ⁇ C—, —CH ⁇ CH—, —CH ⁇ N—, —N ⁇ CH—, —N ⁇ .
- L 23 represents a single bond, —O—, —O—AL—O—, —O—AL—O—CO—, —O—AL—CO—O—, —CO—O—AL—O—, — CO-O-AL-O-CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO- or -O-CO- AL-CO-O- is preferred, a single bond or -O- is more preferred, and -O- is most preferred.
- L 24 represents a single bond, —O—, —O—CO—, —CO—O—, —C ⁇ C—, —CH ⁇ CH—, —CH ⁇ N—, —N ⁇ CH— or —N ⁇ .
- N- is preferable, and —O—CO— or —CO—O— is more preferable. More preferably, when m is 2 or more, the plurality of L 24 are alternately —O—CO— and —CO—O—.
- R 22 is a hydrogen atom, an unsubstituted amino group, or a substituted amino group having 1 to 20 carbon atoms.
- R 22 is a dialkyl-substituted amino group
- two alkyl groups may be bonded to each other to form a nitrogen-containing heterocycle.
- the nitrogen-containing heterocycle formed at this time is preferably a 5-membered ring or a 6-membered ring.
- R 23 is more preferably a hydrogen atom, an unsubstituted amino group, or a dialkyl-substituted amino group having 2 to 12 carbon atoms, and a hydrogen atom, an unsubstituted amino group, or a dialkyl-substituted group having 2 to 8 carbon atoms. Even more preferred is an amino group.
- R 23 is an unsubstituted amino group or a substituted amino group
- the 4-position of the pyridinium ring is preferably substituted.
- X is an anion.
- X is preferably a monovalent anion.
- examples of anions include halide ions (fluorine ions, chlorine ions, bromine ions, iodine ions) and sulfonate ions (eg, methanesulfonate ions, p-toluenesulfonate ions, benzenesulfonate ions).
- Y 22 and Y 23 are each a divalent linking group having a 5- or 6-membered ring as a partial structure.
- the 5- or 6-membered ring may have a substituent.
- at least one of Y 22 and Y 23 is a divalent linking group having a 5- or 6-membered ring having a substituent as a partial structure.
- Y 22 and Y 23 are preferably each independently a divalent linking group having a 6-membered ring which may have a substituent as a partial structure.
- the 6-membered ring includes an aliphatic ring, an aromatic ring (benzene ring) and a heterocyclic ring.
- 6-membered aliphatic ring examples include a cyclohexane ring, a cyclohexene ring, and a cyclohexadiene ring.
- 6-membered heterocycles include pyran ring, dioxane ring, dithiane ring, thiin ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring. Including.
- Another 6-membered ring or 5-membered ring may be condensed to the 6-membered ring.
- the substituent include a halogen atom, cyano, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.
- the alkyl group and alkoxy group may be substituted with an acyl group having 2 to 12 carbon atoms or an acyloxy group having 2 to 12 carbon atoms.
- the substituent is preferably an alkyl group having 1 to 12 carbon atoms (more preferably 1 to 6 and even more preferably 1 to 3).
- the number of substituents may be 2 or more.
- the number of carbon atoms of 1 to 4 is 1 to 12 (more preferably 1 to 6, more preferably 1 to The alkyl group of 3) may be substituted.
- n 1 or 2, and is preferably 2.
- the plurality of Y 23 and L 24 may be the same as or different from each other.
- Z 21 is halogen-substituted phenyl, nitro-substituted phenyl, cyano-substituted phenyl, phenyl substituted with an alkyl group having 1 to 10 carbon atoms, phenyl substituted with an alkoxy group having 2 to 10 carbon atoms, carbon atom
- Z 21 is preferably cyano, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and is an alkoxy group having 4 to 10 carbon atoms. Is more preferable.
- Z 21 is an alkyl group having 7 to 12 carbon atoms, an alkoxy group having 7 to 12 carbon atoms, an acyl-substituted alkyl group having 7 to 12 carbon atoms, or 7 carbon atoms.
- An acyl-substituted alkoxy group having ⁇ 12, an acyloxy-substituted alkyl group having 7 to 12 carbon atoms, or an acyloxy-substituted alkoxy group having 7 to 12 carbon atoms is preferable.
- the acyl group is represented by —CO—R
- the acyloxy group is represented by —O—CO—R
- R is an aliphatic group (alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group) or aromatic Group (aryl group, substituted aryl group).
- R is preferably an aliphatic group, and more preferably an alkyl group or an alkenyl group.
- C p H 2p means a chain alkylene group which may have a branched structure.
- C p H 2p is preferably a linear alkylene group (— (CH 2 ) p —).
- R 30 is a hydrogen atom or an alkyl group having 1 to 12 (more preferably 1 to 6, more preferably 1 to 3) carbon atoms.
- L 25 has the same meaning as L 24 , and the preferred range is also the same.
- L 24 and L 25 are preferably —O—CO— or —CO—O—, preferably L 24 is —O—CO— and L 25 is —CO—O—.
- R 23 , R 24 and R 25 are each an alkyl group having 1 to 12 (more preferably 1 to 6, more preferably 1 to 3) carbon atoms.
- n 23 represents 0 to 4
- n 24 represents 1 to 4
- n 25 represents 0 to 4. It is preferable that n 23 and n 25 are 0 and n 24 is 1 to 4 (more preferably 1 to 3).
- R 30 is preferably an alkyl group having 1 to 12 carbon atoms (more preferably 1 to 6 and even more preferably 1 to 3).
- Specific examples of the compound represented by the general formula (2) include compounds described in [0058] to [0061] in JP-A-2006-113500.
- the compounds of the formulas (2a) and (2b) can be produced by a general method.
- a pyridinium derivative of the formula (2a) is generally obtained by alkylating a pyridine ring (Menstokin reaction).
- the addition amount of the onium salt does not exceed 5% by mass relative to the liquid crystal compound, and is preferably about 0.1 to 2% by mass.
- the onium salts represented by the general formulas (2a) and (2b) are unevenly distributed on the hydrophilic polyvinyl alcohol alignment film surface because the pyridinium group or the imidazolium group is hydrophilic.
- a pyridinium group is further substituted with an amino group which is a substituent of an acceptor of a hydrogen atom (in the general formulas (2a) and (2a ′), R 22 is an unsubstituted amino group or a carbon atom having 1 to 20 carbon atoms)
- R 22 is an unsubstituted amino group or a carbon atom having 1 to 20 carbon atoms
- Alignment in a direction orthogonal to the direction of the liquid crystal promotes the orthogonal alignment of the liquid crystal with respect to the rubbing direction.
- the pyridinium derivative has a plurality of aromatic rings in the molecule, a strong intermolecular ⁇ - ⁇ interaction occurs between the liquid crystal, particularly the discotic liquid crystal, and the alignment film of the discotic liquid crystal. Induces orthogonal orientation near the interface.
- the general formula (2a ′) when a hydrophobic aromatic ring is connected to a hydrophilic pyridinium group, it also has an effect of inducing vertical alignment due to the hydrophobic effect.
- the liquid crystal is aligned with its slow axis parallel to the rubbing direction by heating above a certain temperature.
- the parallel orientation can be promoted. This is because the thermal bond caused by heating breaks hydrogen bonds with polyvinyl alcohol, the onium salt is uniformly dispersed in the alignment film, the density on the alignment film surface is reduced, and the liquid crystal is aligned by the regulating force of the rubbing alignment film itself. It is.
- fluoroaliphatic group-containing copolymer air interface orientation control agent
- the fluoroaliphatic group-containing copolymer is added for the purpose of controlling the orientation of the liquid crystal, mainly the discotic liquid crystal represented by the general formula (I), at the air interface. There is an effect of increasing the tilt angle in the vicinity. Furthermore, applicability such as unevenness and repellency is also improved.
- Examples of the fluoroaliphatic group-containing copolymer that can be used in the present invention include JP-A Nos. 2004-333852, 2004-333863, 2005-134848, 2005-179636, and 2005-181977. It can be used by selecting from the compounds described in each publication and specification.
- the addition amount of the fluoroaliphatic group-containing copolymer does not exceed 2 mass% with respect to the liquid crystal compound, and is preferably about 0.1 to 1 mass%.
- the fluoroaliphatic group-containing copolymer increases the uneven distribution at the air interface due to the hydrophobic effect of the fluoroaliphatic group, and provides a low surface energy field on the air interface side, and tilts liquid crystals, particularly discotic liquid crystals.
- the corner can be increased.
- one or more hydrophilic groups selected from the group consisting of a carboxyl group (—COOH), a sulfo group (—SO 3 H), phosphonoxy ⁇ —OP ( ⁇ O) (OH) 2 ⁇ , and salts thereof, When having a copolymer component contained in the side chain, vertical alignment of the liquid crystal compound can be realized by charge repulsion between these anions and ⁇ electrons of the liquid crystal.
- the composition used for forming the optically anisotropic layer is preferably prepared as a coating solution.
- an organic solvent is preferably used as a solvent used for preparing the coating solution.
- organic solvents include amides (eg N, N-dimethylformamide), sulfoxides (eg dimethyl sulfoxide), heterocyclic compounds (eg pyridine), hydrocarbons (eg benzene, hexane), alkyl halides (eg , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.
- a composition containing a liquid crystal compound having a polymerizable group (for example, a coating solution) is brought into an alignment state showing a desired liquid crystal phase, and then the alignment state is fixed by ultraviolet irradiation (5 of the above method) and 7 ) Process).
- the immobilization is preferably performed by a polymerization reaction of a reactive group introduced into the liquid crystal compound. It is preferable to fix by a photopolymerization reaction by ultraviolet irradiation.
- the photopolymerization reaction may be either radical polymerization or cationic polymerization. Examples of radical photopolymerization initiators include ⁇ -carbonyl compounds (described in US Pat. Nos.
- acyloin ether described in US Pat. No. 2,448,828,, ⁇ -hydrocarbon-substituted aromatics.
- An acyloin compound (described in US Pat. No. 2,722,512), a polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No.
- Examples of the cationic photopolymerization initiator include organic sulfonium salt systems, iodonium salt systems, phosphonium salt systems, and the like. Organic sulfonium salt systems are preferable, and triphenylsulfonium salts are particularly preferable. As counter ions of these compounds, hexafluoroantimonate, hexafluorophosphate, and the like are preferably used.
- the amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution.
- a sensitizer In addition to a polymerization initiator, a sensitizer may be used for the purpose of increasing sensitivity.
- the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone and the like.
- a plurality of photopolymerization initiators may be combined, and the amount used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution.
- the light irradiation for the polymerization of the liquid crystal compound preferably uses ultraviolet rays.
- the composition may contain a non-liquid crystalline polymerizable monomer.
- a non-liquid crystalline polymerizable monomer a compound having a vinyl group, a vinyloxy group, an acryloyl group or a methacryloyl group is preferable.
- a polyfunctional monomer having two or more polymerizable reactive functional groups for example, ethylene oxide-modified trimethylolpropane acrylate because durability is improved.
- the non-liquid crystalline polymerizable monomer is a non-liquid crystalline component, the addition amount thereof does not exceed 40 mass% with respect to the liquid crystal compound, and is preferably about 0 to 20 mass%.
- the thickness of the optically anisotropic layer thus formed is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
- the optical film of the present invention has a transparent support.
- As the transparent support it is preferable to use a member having little in-plane and thickness direction retardation.
- a polymer excellent in optical performance transparency, mechanical strength, thermal stability, moisture shielding property, isotropy and the like is preferable, and Re and Rth are as described above. Any material may be used within the range. Examples include polycarbonate polymers, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, acrylic polymers such as polymethyl methacrylate, and styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin).
- Polyolefins such as polyethylene and polypropylene, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers, polyethersulfone polymers , Polyether ether ketone polymers, polyphenylene sulfide polymers, vinylidene chloride polymers, vinyl alcohol polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers, or polymers mixed with the above polymers Take an example.
- the polymer film of the present invention can also be formed as a cured layer of an ultraviolet-curable or thermosetting resin such as acrylic, urethane, acrylic urethane, epoxy, or silicone.
- thermoplastic norbornene resin can be preferably used as a material for forming the transparent support.
- thermoplastic norbornene-based resin examples include ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., and ARTON manufactured by JSR Corporation.
- a cellulose polymer (hereinafter referred to as cellulose acylate) represented by triacetyl cellulose, which has been conventionally used as a transparent protective film of a polarizing plate, is preferably used. I can do it.
- the transparent support the cellulose acylate will be mainly described in detail. However, it is obvious that the technical matters can be applied to other polymer films as well.
- Cellulose acylate raw material cellulose includes cotton linter and wood pulp (hardwood pulp, softwood pulp) and the like. Any cellulose acylate obtained from any raw material cellulose can be used, or a mixture thereof may be used. Details of these raw material celluloses can be found in, for example, the course of plastic materials (17) Fibrous resin (Maruzawa, Uda, Nikkan Kogyo Shimbun, published in 1970) and Invention Association Open Technical Report 2001-1745 (pages 7-8). However, the present invention is not limited to the description.
- Cellulose acylate is obtained by acylating the hydroxyl group of cellulose, and the substituent can be any acetyl group having 2 carbon atoms in the acyl group to those having 22 carbon atoms.
- the degree of substitution of the hydroxyl group of cellulose is not particularly limited, but the degree of binding of acetic acid and / or fatty acid having 3 to 22 carbon atoms substituted for the hydroxyl group of cellulose is measured and substituted by calculation. You can get a degree. As a measuring method, it can be carried out according to ASTM D-817-91.
- the degree of substitution of the cellulose with a hydroxyl group is not particularly limited, but the degree of acyl substitution with the hydroxyl group of cellulose is preferably 2.50 to 3.00. Further, the degree of substitution is preferably 2.75 to 3.00, and more preferably 2.85 to 3.00.
- the acyl group having 2 to 22 carbon atoms may be an aliphatic group or an aromatic group, and is not particularly limited. It may be a mixture of more than one type. These are, for example, cellulose alkylcarbonyl esters, alkenylcarbonyl esters, aromatic carbonyl esters, aromatic alkylcarbonyl esters, and the like, each of which may further have a substituted group.
- acyl groups include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl, t-butanoyl, cyclohexanecarbonyl, Examples include oleoyl, benzoyl, naphthylcarbonyl, and cinnamoyl groups.
- acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like are preferable, and acetyl, propionyl and butanoyl are more preferable.
- the substitution degree is 2.50 to 3.00.
- the optical anisotropy of the cellulose acylate film can be reduced.
- a more preferable degree of acyl substitution is 2.60 to 3.00, and more desirably 2.65 to 3.00.
- the degree of substitution is preferably 2.80 to 2.99, and more preferably 2.85 to 2.95.
- the degree of polymerization of cellulose acylate is preferably 180 to 700 in terms of viscosity average degree of polymerization. In cellulose acetate, 180 to 550 is more preferred, 180 to 400 is still more preferred, and 180 to 350 is particularly preferred. If the degree of polymerization is too high, the viscosity of the cellulose acylate dope solution becomes high, and film production becomes difficult due to casting. If the degree of polymerization is too low, the strength of the produced film will decrease.
- the average degree of polymerization can be measured by the intrinsic viscosity method of Uda et al. (Kazuo Uda, Hideo Saito, Journal of Textile Science, Vol. 18, No. 1, pp. 105-120, 1962).
- the molecular weight distribution of cellulose acylate preferably used in the present invention is evaluated by gel permeation chromatography, and its polydispersity index Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) is small, and the molecular weight distribution. Is preferably narrow.
- Mw / Mn is preferably 1.0 to 3.0, more preferably 1.0 to 2.0, and most preferably 1.0 to 1.6. preferable.
- the average molecular weight (polymerization degree) increases, but the viscosity is lower than that of normal cellulose acylate, which is useful.
- Cellulose acylate having a small amount of low molecular components can be obtained by removing low molecular components from cellulose acylate synthesized by a usual method. The removal of the low molecular component can be carried out by washing the cellulose acylate with an appropriate organic solvent.
- the amount of sulfuric acid catalyst in the acetylation reaction is preferably adjusted to 0.5 to 25 parts by mass with respect to 100 parts by mass of cellulose.
- cellulose acylate that is preferable in terms of molecular weight distribution (uniform molecular weight distribution) can be synthesized.
- the water content is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly 0.7% by mass or less.
- cellulose acylate contains water and is known to have a water content of 2.5 to 5% by mass.
- the method is not particularly limited as long as the desired moisture content is achieved. The method for synthesizing these cellulose acylates of the present invention is described in detail on pages 7 to 12 in the Japan Institute of Invention Disclosure Technical Bulletin (Technical No. 2001-1745, published on March 15, 2001, Japan Institute of Invention). .
- Cellulose acylate can be used as a single group or a mixture of two or more different types of cellulose acylate as long as the substituent, substitution degree, polymerization degree, molecular weight distribution and the like are within the above-mentioned ranges.
- various additives for example, compounds that reduce optical anisotropy, wavelength dispersion adjusting agents, fine particles, plasticizers, ultraviolet inhibitors, deterioration inhibitors, together with cellulose acylate, Release agents, optical property modifiers, etc.
- the addition time may be any in the dope preparation step (the preparation step of the cellulose acylate solution), but a step of adding and preparing an additive may be performed at the end of the dope preparation step.
- a cellulose acylate film satisfying 0 ⁇ Re (550) ⁇ 10 can be produced.
- the optical properties of the support can be improved.
- the Re of all the first and second retardation regions contained in the optical film of the present invention can be set in the range of 110 nm ⁇ Re (550) ⁇ 165 nm with little influence.
- the Re value is preferably 120 ⁇ Re (550) ⁇ 145, and particularly preferably 130 ⁇ Re (550) ⁇ 145.
- the transparent support Preferably satisfies ⁇ 150 nm ⁇ Rth (630) ⁇ 100 nm.
- the compound that reduces the optical anisotropy of the cellulose acylate film will be described.
- Optical anisotropy can be reduced by using a compound that suppresses the orientation of cellulose acylate in the film in the plane and in the film thickness direction.
- the compound that lowers the optical anisotropy is sufficiently compatible with cellulose acylate, and it is advantageous that the compound itself does not have a rod-like structure or a planar structure. Specifically, when a plurality of planar functional groups such as aromatic groups are provided, a structure having these functional groups in a non-planar rather than the same plane is advantageous.
- a compound having an octanol-water partition coefficient (log P value) of 0 to 7 is preferred.
- a compound having a log P value of more than 7 is poor in compatibility with cellulose acylate, and tends to cause film turbidity or powder blowing.
- a compound having a log P value smaller than 0 has high hydrophilicity, the water resistance of the cellulose acetate film may be deteriorated.
- a more preferable range for the logP value is 1 to 6, and a particularly preferable range is 1.5 to 5.
- the octanol-water partition coefficient (log P value) can be measured by a flask immersion method described in JIS Japanese Industrial Standard Z7260-107 (2000). Further, the octanol-water partition coefficient (log P value) can be estimated by a computational chemical method or an empirical method instead of the actual measurement. As a calculation method, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29,). 163 (1989).), Broto's fragmentation method (Eur. J. Med.
- the compound that reduces optical anisotropy may or may not contain an aromatic group.
- the compound that reduces the optical anisotropy preferably has a molecular weight of 150 or more and 3000 or less, more preferably 170 or more and 2000 or less, and particularly preferably 200 or more and 1000 or less.
- a specific monomer structure may be used as long as these molecular weights are within the range, and an oligomer structure or a polymer structure in which a plurality of the monomer units are bonded may be used.
- the compound that reduces the optical anisotropy is preferably a liquid at 25 ° C. or a solid having a melting point of 25 to 250 ° C., more preferably a liquid at 25 ° C. or a melting point of 25 to 200.
- the compound which reduces optical anisotropy does not volatilize in the process of dope casting and drying of cellulose acylate film production.
- the amount of the compound that reduces optical anisotropy is preferably 0.01 to 30% by mass, more preferably 1 to 25% by mass, and more preferably 5 to 20% by mass with respect to cellulose acylate. It is particularly preferred.
- the compound that decreases the optical anisotropy may be used alone, or two or more compounds may be mixed and used in an arbitrary ratio.
- the timing for adding the compound for reducing the optical anisotropy may be any time during the dope preparation process, or may be performed at the end of the dope preparation process.
- the compound that reduces the optical anisotropy is such that the average content of the compound in the portion from the surface on at least one side to 10% of the total film thickness is the average content of the compound in the center of the cellulose acylate film. 80-99% of the rate.
- the abundance of the compound can be determined by measuring the amount of the compound at the surface and in the center by, for example, a method using an infrared absorption spectrum described in JP-A-8-57879.
- the compound that reduces the optical anisotropy of the cellulose acylate film include, for example, compounds described in [0035] to [0058] of JP-A-2006-199855, but the compounds are not limited thereto. Is not to be done.
- the optical film of the present invention is arranged on the viewing side, it is susceptible to the influence of external light, particularly ultraviolet rays. Therefore, it is desirable to add an ultraviolet (UV) absorber to a polymer film or the like used as a transparent support.
- UV ultraviolet
- UV absorbers there is a compound that absorbs in the ultraviolet region of 200 to 400 nm and decreases both
- 0.01 to 30% by mass based on the solid content of cellulose acylate is used.
- a cellulose acylate film is a compound having absorption in the ultraviolet region of 200 to 400 nm and reducing
- the spectral transmittance at a wavelength of 380 nm is preferably 45% to 95%, and the spectral transmittance at a wavelength of 350 nm is preferably 10% or less.
- the UV absorber preferably has a molecular weight of 250 to 1000 from the viewpoint of volatility. More preferably, it is 260 to 800, still more preferably 270 to 800, and particularly preferably 300 to 800.
- a specific monomer structure may be used as long as these molecular weights are within the range, and an oligomer structure or a polymer structure in which a plurality of monomer units are bonded may be used.
- the UV absorber does not evaporate during the dope casting and drying process for producing the cellulose acylate film.
- UV absorber for the cellulose acylate film examples include compounds described in [0059] to [0135] of JP-A-2006-199855.
- fine particles as a matting agent to the cellulose acylate film.
- the fine particles used in the present invention include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, silica Mention may be made of magnesium and calcium phosphates. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.
- the silicon dioxide fine particles preferably have a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more.
- the apparent specific gravity is preferably 90 to 200 g / liter or more, and more preferably 100 to 200 g / liter or more. A larger apparent specific gravity is preferable because a high-concentration dispersion can be produced, and haze and aggregates are improved.
- These fine particles usually form secondary particles having an average particle diameter of 0.1 to 3.0 ⁇ m, and these fine particles are present in the film as aggregates of primary particles, and 0.1 to 3.0 ⁇ m on the film surface. An unevenness of 3.0 ⁇ m is formed.
- the secondary average particle size is preferably from 0.2 to 1.5 ⁇ m, more preferably from 0.4 to 1.2 ⁇ m, and most preferably from 0.6 to 1.1 ⁇ m.
- the primary and secondary particle sizes were determined by observing the particles in the film with a scanning electron microscope and determining the diameter of a circle circumscribing the particles as the particle size. Also, 200 particles were observed at different locations, and the average value was taken as the average particle size.
- silicon dioxide fine particles for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) can be used.
- Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.
- Aerosil 200V and Aerosil R972V are fine particles of silicon dioxide having a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more, and the coefficient of friction is maintained while keeping the turbidity of the optical film low. This is particularly preferable because it has a great effect of lowering.
- a fine particle dispersion prepared by stirring and mixing a solvent and fine particles is prepared in advance, and this fine particle dispersion is added to a separately prepared small amount of cellulose acylate solution and dissolved by stirring. Further, a main cellulose acylate solution (dope solution) There is a way to mix.
- This method is a preferred preparation method in that the dispersibility of the silicon dioxide fine particles is good and the silicon dioxide fine particles are more difficult to reaggregate.
- the concentration of silicon dioxide when the silicon dioxide fine particles are mixed and dispersed with a solvent or the like is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and 15 to 20% by mass. Most preferred. A higher dispersion concentration is preferable because the liquid turbidity with respect to the added amount is lowered, and haze and aggregates are improved.
- the addition amount of the matting agent fine particles in the final cellulose acylate dope solution is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, more preferably 0.08 to 0.16 g per m 3. Is most preferred.
- the solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.
- a plasticizer for example, a plasticizer, an ultraviolet ray inhibitor, a deterioration inhibitor, and a release agent
- various additives for example, a plasticizer, an ultraviolet ray inhibitor, a deterioration inhibitor, and a release agent
- Infrared absorbers, etc. which may be solid or oily. That is, the melting point and boiling point are not particularly limited.
- mixing of an ultraviolet absorbing material of 20 ° C. or lower and 20 ° C. or higher, and similarly, mixing of a plasticizer is described in, for example, JP-A-2001-151901.
- infrared absorbers are described in, for example, JP-A-2001-194522.
- the addition time may be any time in the dope production process, but it is preferable to add an additive at the end of the dope production process.
- the amount of each additive added is not particularly limited as long as the function is exhibited.
- the kind and addition amount of the additive of each layer may differ. For example, it is described in Japanese Patent Application Laid-Open No. 2001-151902, and these are conventionally known techniques. For these details, materials described in detail on pages 16 to 22 in the Japan Institute of Invention Disclosure Technical Bulletin (Public Technical Number 2001-1745, published on March 15, 2001, Japan Institute of Invention) are preferably used.
- plasticizer some of the examples described later do not have a plasticizer added, but compounds that optically reduce anisotropy are compounds that exert an effect as a plasticizer. It goes without saying that in some cases it is not necessary to add a plasticizer.
- the cellulose acylate film is preferably produced by a solution casting method using a cellulose acylate solution.
- the method for dissolving the cellulose acylate solution (dope) is not particularly limited, and may be room temperature, and further, a cooling dissolution method or a high temperature dissolution method, and further a combination thereof.
- 22 of the Japan Society for Invention and Technology Public Technical No. 2001-1745, published on March 15, 2001, Japan Institute of Invention
- Production processes described in detail on pages 25 to 25 are preferably used.
- the dope transparency of the cellulose acylate solution is preferably 85% or more. More preferably, it is 88% or more, and more preferably 90% or more. In the present invention, it was confirmed that various additives were sufficiently dissolved in the cellulose acylate dope solution. Specifically, the dope transparency was calculated by injecting the dope solution into a 1 cm square glass cell and measuring the absorbance at 550 nm with a spectrophotometer (UV-3150, Shimadzu Corporation). Only the solvent was measured in advance as a blank, and the transparency of the cellulose acylate solution was calculated from the ratio with the absorbance of the blank.
- a spectrophotometer UV-3150, Shimadzu Corporation
- a solution casting film forming method and a solution casting film forming apparatus used for producing a conventional cellulose triacetate film are used.
- the dope (cellulose acylate solution) prepared from the dissolving machine (kettle) is temporarily stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation.
- the dope is fed from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the number of rotations, and the dope is run endlessly from the die (slit) of the pressure die.
- the dry-dried dope film (also referred to as web) is peeled off from the metal support at a peeling point that is uniformly cast on the metal support and substantially rounds the metal support.
- the both ends of the obtained web are sandwiched between clips, transported by a tenter while holding the width and dried, and then the obtained film is mechanically transported by a roll group of a drying device, dried, and then rolled by a winder. Wind up to a predetermined length.
- the combination of the tenter and the roll group dryer varies depending on the purpose.
- the undercoat layer In many cases, a coating apparatus is added for surface processing of a film such as an antistatic layer, an antihalation layer, or a protective layer. These are described in detail in pages 25 to 30 of the Invention Association's public technical report (public technical number 2001-1745, issued March 15, 2001, Invention Association). Including), metal support, drying, peeling and the like, and can be preferably used in the present invention.
- the thickness of the cellulose acylate film is preferably 10 to 120 ⁇ m, more preferably 20 to 100 ⁇ m, and still more preferably 30 to 90 ⁇ m.
- Re ( ⁇ ) and Rth ( ⁇ ) represent in-plane retardation and retardation in the thickness direction at a wavelength ⁇ , respectively.
- Re ( ⁇ ) is measured by making light having a wavelength of ⁇ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments). In selecting the measurement wavelength ⁇ nm, the wavelength selection filter can be exchanged manually, or the measurement value can be converted by a program or the like.
- Rth ( ⁇ ) is calculated by the following method.
- Rth ( ⁇ ) is the Re ( ⁇ )
- the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotation axis).
- the light is incident at a wavelength of ⁇ nm in 10 degree steps from the normal direction to 50 degrees on one side with respect to the film normal direction (with the direction of the rotation axis as the rotation axis).
- KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value.
- Re ( ⁇ ) represents a retardation value in a direction inclined by an angle ⁇ from the normal direction.
- nx represents the refractive index in the slow axis direction in the plane
- ny represents the refractive index in the direction orthogonal to nx in the plane
- nz represents the refractive index in the direction orthogonal to nx and ny.
- d is the film thickness.
- Formula (12): Rth ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ d
- nx represents the refractive index in the slow axis direction in the plane
- ny represents the refractive index in the direction perpendicular to nx in the plane
- nz represents the refractive index in the direction perpendicular to nx and ny.
- d is the film thickness.
- Rth ( ⁇ ) is calculated by the following method.
- Rth ( ⁇ ) is from ⁇ 50 degrees to +50 degrees with respect to the normal direction of the film, with Re ( ⁇ ) as the slow axis (indicated by KOBRA 21ADH or WR) in the plane and the tilt axis (rotation axis).
- the light of wavelength ⁇ nm is incident from each inclined direction in 10 degree steps and measured at 11 points. Based on the measured retardation value, the assumed average refractive index, and the input film thickness value, KOBRA 21ADH or WR is calculated.
- the assumed value of the average refractive index values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer.
- the average refractive index values of main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59).
- An example of a polymer film used as a transparent support is a low retardation film having Re of 0 to 10 nm and an absolute value of Rth of 20 nm or less.
- the humidity expansion coefficient of the polymer film can be appropriately set depending on the combination with the thermal expansion coefficient, but is preferably 3.0 ⁇ 10 ⁇ 6 to 500 ⁇ 10 ⁇ 6 /% RH, and 4.0 ⁇ 10. ⁇ 6 to 100 ⁇ 10 ⁇ 6 /% RH is more preferable, 5.0 ⁇ 10 ⁇ 6 to 50 ⁇ 10 ⁇ 6 /% RH is more preferable, and 5.0 ⁇ 10 ⁇ 6 to 40 ⁇ 10 ⁇ 6 /%. RH is most preferred.
- the thermal expansion coefficient can be measured according to ISO11359-2, and is calculated from the slope of the film length when the sample is heated from room temperature to 80 ° C. and then cooled from 60 ° C. to 50 ° C.
- the elastic modulus of the polymer film is not particularly limited, but is preferably 1 to 50 GPa, more preferably 5 to 50 GPa, and further preferably 7 to 20 GPa.
- the elastic modulus can be controlled by the type of polymer, the type and amount of additives, and stretching. Note that a film sample having a length of 150 mm and a width of 10 mm was prepared, and after adjusting the humidity for 24 hours at 25 ° C. and a relative humidity of 60%, the initial sample length was 100 mm according to the standard of ISO527-3: 1995. It is the tensile modulus measured from the initial slope of the stress-strain curve measured at a speed of 10 mm / min.
- the elastic modulus generally differs depending on how the film sample is taken in the length direction and the width direction
- a value obtained by preparing a film sample in the direction in which the elastic modulus is maximum is expressed as the elastic modulus of the present invention.
- the elastic modulus in the direction where the sound velocity is maximum is E1
- the elastic modulus in the direction orthogonal to the elastic modulus is E2
- the ratio (E1 / E2) reduces the dimensional change while maintaining the flexibility of the film.
- 1.1 to 5.0 is preferable, and 1.5 to 3.0 is more preferable.
- the direction in which the speed of sound (sonic wave propagation speed) is maximized is that the film is conditioned at 25 ° C. and a relative humidity of 60% for 24 hours, and then an orientation measuring machine (SST-2500: manufactured by Nomura Corporation). ) Was used to determine the direction in which the propagation speed of the longitudinal vibration of the ultrasonic pulse was maximized.
- Total light transmittance, haze In the present invention, the sample was conditioned at 25 ° C. and a relative humidity of 60% for 24 hours, and then the values measured using a haze meter (NDH 2000: manufactured by Nippon Denshoku Industries Co., Ltd.) were used as the total light transmittance and haze. It was.
- the total light transmittance of the polymer film is preferably higher from the viewpoint of efficiently using the light from the light source and reducing the power consumption of the panel, specifically, it is preferably 85% or more. % Or more is more preferable, and it is still more preferable that it is 92% or more.
- the haze of the film of the present invention is preferably 5% or less, more preferably 3% or less, further preferably 2% or less, still more preferably 1% or less, It is especially preferable that it is 0.5% or less.
- the tear strength (Elmendorf tear method) is determined by cutting out a sample of 64 mm ⁇ 50 mm, with the direction parallel to the slow axis of the film and the direction perpendicular thereto as the longitudinal direction, respectively, at 25 ° C. and 60% relative humidity. After adjusting the humidity for 2 hours, it was measured using a light load tear strength tester, and the smaller value was taken as the tear strength of the film.
- the tear strength of the polymer film is preferably 3 to 50 g, more preferably 5 to 40 g, and still more preferably 10 to 30 g from the viewpoint of film brittleness.
- the thickness of the polymer film is preferably 10 to 1000 ⁇ m, more preferably 40 to 500 ⁇ m, and particularly preferably 40 to 200 ⁇ m from the viewpoint of reducing the manufacturing cost.
- Polarizing plate also relates to a polarizing plate having the optical film of the present invention.
- One aspect of the polarizing plate of the present invention includes the optical film of the present invention and a polarizing film, and the in-plane slow axis directions of the first and second retardation regions of the optically anisotropic layer,
- the polarizing plate is characterized in that the absorption axis direction of the polarizing film is 45 °.
- the polarizing plate of the present invention is disposed with the optical film facing the viewing side as the viewing-side polarizing plate of the image display device for displaying a stereoscopic image.
- the polarizing plate of the present invention is not only a polarizing plate in the form of a film piece cut into a size that can be incorporated into a liquid crystal display device as it is, but also is produced in a strip shape, that is, a long shape by continuous production, and a roll
- the polarizing plate of the aspect wound up in the shape (for example, roll length 2500m or more, 3900m or more aspect) is also contained.
- the width of the polarizing plate is preferably 1470 mm or more as described above.
- the layer structure of the polarizing plate of the present invention is not particularly limited. Although it may be the same as the layer structure of the polarizing plate of a general structure, it is characterized by including the optical film of this invention.
- FIG. 4 shows a schematic cross-sectional view of an example.
- the polarizing plate 20 shown in FIG. 4 has the optical film of the present invention on one surface of the polarizing film 22 and the protective film 24 on the other surface.
- Examples of the polymer film that can be used as the protective film 24 are the same as those of the polymer film that can be used as the transparent support of the optical film 10.
- Manufacturing method of polarizing plate is as follows: Forming a rubbing alignment film continuously on a long polymer film such as a cellulose acylate film that is a transparent support, Rubbing the rubbing alignment film continuously in a direction about 45 degrees oblique to the film conveying direction; Applying a composition containing at least a liquid crystal compound having a polymerizable group to the rubbing-treated surface; Heating at a temperature T 1 ° C.
- a striped photomask is arranged so that the boundary between the light shielding part / transmission part is parallel to the film transport direction, and exposed to ultraviolet light under the mask, the orthogonal orientation state is fixed, and the first retardation region is formed. Forming, and Heating at a temperature T 2 ° C.
- the manufacturing method of the polarizing plate of the present invention is lower in manufacturing cost than the conventional manufacturing method from the viewpoint of continuous production. Further, when the rubbing direction is at an angle of about 45 degrees with respect to the film conveying direction, it is not necessary to smoothly punch the obtained roll-shaped polarizing plate, and the manufacturing cost for manufacturing the polarizing plate can be reduced.
- Polarizing film As the polarizing film, a general polarizing film can be used. For example, a polarizer film made of a polyvinyl alcohol film dyed with iodine or a dichroic dye can be used.
- Adhesive layer In the polarizing plate of the present invention, an adhesive layer may be disposed between the optical film and the polarizing film.
- limiting in particular about an adhesive For example, a polyvinyl alcohol-type adhesive can be used.
- a functional film such as an antireflection layer is preferably provided on the surface of the polarizing plate on the side opposite to the liquid crystal cell.
- at least a light scattering layer and a low refractive index layer are laminated in this order on the transparent protective film, or a medium refractive index layer, a high refractive index layer, and a low refractive index layer are formed on the transparent protective film.
- An antireflection layer laminated in order is preferably used. This is because flickering due to external light reflection can be effectively prevented, particularly when a 3D image is displayed. Preferred examples thereof are described below.
- a preferred example of an antireflection layer in which a light scattering layer and a low refractive index layer are provided on a transparent protective film will be described.
- the matting particles are dispersed in the light scattering layer, and the refractive index of the material other than the matting particles in the light scattering layer is preferably in the range of 1.50 to 2.00, and the refractive index of the low refractive index layer Is preferably in the range of 1.35 to 1.49.
- the light scattering layer has both antiglare properties and hard coat properties, and may be a single layer or a plurality of layers, for example, 2 to 4 layers.
- the antireflection layer has an uneven surface shape with a center line average roughness Ra of 0.08 ⁇ m to 0.40 ⁇ m, a 10-point average roughness Rz of 10 times or less of Ra, an average mountain valley distance Sm of 1 ⁇ m to 100 ⁇ m, and an uneven deepest depth.
- the standard deviation of the height of the convex part from the part is 0.5 ⁇ m or less
- the standard deviation of the average mountain valley distance Sm with respect to the center line is 20 ⁇ m or less
- the surface with the inclination angle of 0 to 5 degrees is 10% or more.
- the ratio between the minimum value and the maximum value of the reflectance when the color of the reflected light under the C light source is in the range of a * value ⁇ 2 to 2, b * value ⁇ 3 to 3, 380 nm to 780 nm is 0.5.
- the color of the reflected light becomes neutral, which is preferable.
- the b * value of the transmitted light under the C light source is 0 to 3 because the yellow color of white display when applied to a display device is reduced.
- the standard deviation of the luminance distribution is 20 or less. The glare when applying the film of the invention is reduced, which is preferable.
- the optical properties of the antireflection layer are as follows: specular reflectance of 2.5% or less, transmittance of 90% or more, and 60 ° gloss of 70% or less, thereby suppressing reflection of external light and improving visibility. Therefore, it is preferable.
- specular reflectance is more preferably 1% or less, and most preferably 0.5% or less.
- Haze 20% to 50%, internal haze / total haze value (ratio) of 0.3 to 1, haze value after formation of low refractive index layer from haze value up to light scattering layer within 15%, comb width Prevents glare on a high-definition LCD panel by setting the transmitted image sharpness at 0.5mm to 20% to 50% and the transmittance ratio of vertical transmitted light / 2 ° tilted from vertical to 1.5 to 5.0 Reduction of blurring of characters and the like is achieved, which is preferable.
- the refractive index of the low refractive index layer is 1.20 to 1.49, preferably 1.30 to 1.44. Further, the low refractive index layer preferably satisfies the following formula (IX) from the viewpoint of reducing the reflectance.
- m is a positive odd number
- n1 is the refractive index of the low refractive index layer
- d1 is the film thickness (nm) of the low refractive index layer.
- ⁇ is a wavelength, which is a value in the range of 500 to 550 nm.
- the low refractive index layer contains a fluorine-containing polymer as a low refractive index binder.
- the fluorine polymer is preferably a fluorine-containing polymer which is crosslinked by heat or ionizing radiation having a coefficient of dynamic friction of 0.03 to 0.20, a contact angle with water of 90 ° to 120 °, and a sliding angle of pure water of 70 ° or less.
- fluorine-containing polymer used in the low refractive index layer examples include hydrolysis and dehydration condensates of perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane). And a fluorine-containing copolymer having a fluorine-containing monomer unit and a structural unit for imparting crosslinking reactivity as structural components.
- fluorine-containing monomer examples include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc. ), Partially (meth) acrylic acid or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, and the like.
- Perfluoroolefins are preferred, and hexafluoropropylene is particularly preferred from the viewpoints of refractive index, solubility, transparency, availability, and the like.
- structural units for imparting crosslinking reactivity structural units obtained by polymerization of monomers having a self-crosslinkable functional group in advance in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxyl groups, hydroxy groups, amino groups Obtained by polymerization of a monomer having a sulfo group or the like (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.) And a structural unit in which a crosslinkable reactive group such as a (meth) acryloyl group is introduced into these structural units by a polymer reaction (for example, an acrylic acid chloride is allowed to act on a hydroxy group). And the like.
- monomers that do not contain fluorine atoms can be copolymerized as appropriate from the viewpoints of solubility in solvents and film transparency. There are no particular limitations on the monomer units that can be used in combination.
- olefins ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.
- acrylic esters methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl
- methacrylates methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.
- styrene derivatives styrene, divinylbenzene, vinyl toluene, ⁇ -methylstyrene, etc.
- vinyl ethers (methyl) Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.)
- acrylamides N-tert-butylacrylamide, N- Black hexyl acrylamide
- methacrylamides
- a curing agent may be appropriately used in combination with the above polymer.
- the light scattering layer is formed for the purpose of contributing to the film light diffusibility due to surface scattering and / or internal scattering and hard coat properties for improving the scratch resistance of the film. Therefore, it is formed including a binder for imparting hard coat properties, matte particles for imparting light diffusibility, and inorganic fillers for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength as necessary.
- the film thickness of the light scattering layer is preferably from 1 ⁇ m to 10 ⁇ m, more preferably from 1.2 ⁇ m to 6 ⁇ m, from the viewpoint of imparting hard coat properties and from the viewpoint of curling and suppressing deterioration of brittleness.
- the binder of the scattering layer is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as the main chain, and more preferably a polymer having a saturated hydrocarbon chain as the main chain.
- the binder polymer preferably has a crosslinked structure.
- a polymer of an ethylenically unsaturated monomer is preferable.
- a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
- the monomer structure contains an aromatic ring, at least one atom selected from halogen atoms other than fluorine, sulfur atoms, phosphorus atoms, and nitrogen atoms. You can also choose.
- Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di ( (Meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,
- high refractive index monomer examples include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4'-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.
- Polymerization of the monomer having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator. Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then ionizing radiation or heat is applied.
- the antireflection film can be formed by curing by the polymerization reaction.
- these photo radical initiators known ones can be used.
- the polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound.
- the ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator. Therefore, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, matte particles and an inorganic filler is prepared, and the coating liquid is applied onto a transparent support and then subjected to a polymerization reaction by ionizing radiation or heat. Curing can form an antireflection film.
- a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
- the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxyl group, a methylol group, and an active methylene group.
- Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure.
- a functional group that exhibits crosslinkability as a result of the decomposition reaction such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
- These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.
- the light scattering layer contains matte particles having an average particle size of 1 ⁇ m to 10 ⁇ m, preferably 1.5 ⁇ m to 7.0 ⁇ m, such as inorganic compound particles or resin particles, for the purpose of imparting antiglare properties.
- inorganic particles such as silica particles and TiO 2 particles
- resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable.
- crosslinked styrene particles, crosslinked acrylic particles, crosslinked acrylic styrene particles, and silica particles are preferable.
- the shape of the mat particles can be either spherical or irregular.
- mat particles having different particle diameters may be used in combination. It is possible to impart anti-glare properties with mat particles having a larger particle size and to impart other optical characteristics with mat particles having a smaller particle size.
- the particle size distribution of the mat particles is most preferably monodisperse, and the particle sizes of the particles are preferably closer to each other.
- the proportion of the coarse particle is preferably 1% or less, more preferably 0.1% of the total number of particles. Or less, more preferably 0.01% or less. Matt particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and a matting agent having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.
- the mat particles are contained in the light scattering layer so that the amount of mat particles in the formed light scattering layer is preferably 10 mg / m 2 to 1000 mg / m 2 , more preferably 100 mg / m 2 to 700 mg / m 2.
- the particle size distribution of the mat particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.
- the light scattering layer is made of an oxide of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony, in addition to the matte particles, in order to increase the refractive index of the layer.
- an inorganic filler having an average particle diameter of 0.2 ⁇ m or less, preferably 0.1 ⁇ m or less, more preferably 0.06 ⁇ m or less is contained.
- a silicon oxide in order to keep the refractive index of the layer low in the light scattering layer using the high refractive index mat particles.
- the preferred particle size is the same as that of the aforementioned inorganic filler.
- the inorganic filler to be used in the light scattering layer TiO 2, ZrO 2, Al 2 O 3, In 2 O 3, ZnO, SnO 2, Sb 2 O 3, ITO and SiO 2 and the like. TiO 2 and ZrO 2 are particularly preferable in terms of increasing the refractive index.
- the surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
- the amount of these inorganic fillers added is preferably 10% to 90% of the total mass of the light scattering layer, more preferably 20% to 80%, and particularly preferably 30% to 75%. Such a filler does not scatter because the particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.
- the bulk refractive index of the mixture of binder and inorganic filler in the light scattering layer is preferably 1.48 to 2.00, more preferably 1.50 to 1.80.
- the kind and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.
- the light scattering layer should be coated with either a fluorine-based surfactant or a silicone-based surfactant, or both for forming an antiglare layer. Contained in the composition.
- a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antireflection film of the present invention appears in a smaller addition amount. The purpose is to increase productivity by giving high-speed coating suitability while improving surface uniformity.
- An antireflection layer in which a medium refractive index layer, a high refractive index layer, and a low refractive index layer are laminated in this order on the transparent protective film will be described.
- An anti-reflection film comprising at least a middle refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer) in order on the transparent protective film is designed to have a refractive index satisfying the following relationship.
- each layer may be imparted to each layer, for example, an antifouling low refractive index layer or an antistatic high refractive index layer (eg, JP-A-10-206603, JP-A-2002). No. -243906) and the like.
- the strength of the antireflection film is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400.
- the layer having a high refractive index of the antireflection film is composed of a curable film containing at least an ultrafine particle of an inorganic compound having a high refractive index having an average particle size of 100 nm or less and a matrix binder.
- the high refractive index inorganic compound fine particles include inorganic compounds having a refractive index of 1.65 or more, preferably those having a refractive index of 1.9 or more. Examples thereof include oxides such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, and In, and composite oxides containing these metal atoms.
- the surface of the particles is treated with a surface treatment agent (for example, silane coupling agents, etc .: JP-A-11-295503, JP-A-11-153703, JP-A-2000-9908).
- a surface treatment agent for example, silane coupling agents, etc .: JP-A-11-295503, JP-A-11-153703, JP-A-2000-9908).
- Anionic compounds or organometallic coupling agents Japanese Patent Laid-Open No. 2001-310432, etc., core-shell structure with high refractive index particles as a core (Japanese Patent Laid-Open No. 2001-166104 2001-310432, etc.), specific (For example, JP-A-11-153703, US Pat. No. 6,210,858, JP-A-2002-27776069, etc.).
- Examples of the material forming the matrix include conventionally known thermoplastic resins and curable resin films. Furthermore, a polyfunctional compound-containing composition having at least two radically polymerizable and / or cationically polymerizable groups, and a composition containing an organometallic compound having a hydrolyzable group and a partial condensate thereof. At least one composition selected is preferred. Examples thereof include the compositions described in JP-A Nos. 2000-47004, 2001-315242, 2001-31871, and 2001-296401. A curable film obtained from a colloidal metal oxide obtained from a hydrolyzed condensate of metal alkoxide and a metal alkoxide composition is also preferred. For example, it is described in JP-A-2001-293818.
- the refractive index of the high refractive index layer is generally 1.70 to 2.20.
- the thickness of the high refractive index layer is preferably 5 nm to 10 ⁇ m, and more preferably 10 nm to 1 ⁇ m.
- the refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer.
- the refractive index of the middle refractive index layer is preferably 1.50 to 1.70.
- the thickness is preferably 5 nm to 10 m ⁇ m, and more preferably 10 nm to 1 ⁇ m.
- the low refractive index layer is sequentially stacked on the high refractive index layer.
- the refractive index of the low refractive index layer is 1.20 to 1.55. It is preferably 1.30 to 1.50. It is preferable to construct as the outermost layer having scratch resistance and antifouling property. As means for greatly improving the scratch resistance, imparting slipperiness to the surface is effective, and conventionally known thin film layer means such as introduction of silicone or introduction of fluorine can be applied.
- the refractive index of the fluorine-containing compound is preferably 1.35 to 1.50. More preferably, it is 1.36 to 1.47.
- the fluorine-containing compound is preferably a compound containing a crosslinkable or polymerizable functional group containing a fluorine atom in the range of 35% by mass to 80% by mass.
- the silicone compound is a compound having a polysiloxane structure, preferably containing a curable functional group or a polymerizable functional group in the polymer chain and having a crosslinked structure in the film.
- reactive silicone eg., Silaplane (manufactured by Chisso Corporation), silanol group-containing polysiloxane (Japanese Patent Application Laid-Open No. 11-258403, etc.) and the like can be mentioned.
- the crosslinking or polymerization reaction of the fluorine-containing and / or siloxane polymer having a crosslinking or polymerizable group is performed simultaneously with or after the application of the coating composition for forming the outermost layer containing a polymerization initiator, a sensitizer and the like. It is preferable to carry out by light irradiation or heating. Also preferred is a sol-gel cured film in which an organometallic compound such as a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent are cured by a condensation reaction in the presence of a catalyst.
- an organometallic compound such as a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent are cured by a condensation reaction in the presence of a catalyst.
- a polyfluoroalkyl group-containing silane compound or a partially hydrolyzed condensate thereof Japanese Patent Laid-Open Nos. 58-142958, 58-147483, 58-147484, Japanese Patent Laid-Open Nos. 9-157582, 11) -106704
- silyl compounds containing a poly "perfluoroalkyl ether" group which is a fluorine-containing long chain group Japanese Patent Application Laid-Open Nos. 2000-117902, 2001-48590, 2002
- the low refractive index layer has an average primary particle diameter of 1 nm to 150 nm such as fillers (for example, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)) as additives other than the above.
- fillers for example, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)
- silane coupling agents silane coupling agents
- slip agents ion plating method
- surfactants surfactants, and the like
- the low refractive index layer may be formed by a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.).
- the coating method is preferable because it can be manufactured at a low cost.
- the film thickness of the low refractive index layer is preferably 30 nm to 200 nm, more preferably 50 nm to 150 nm, and most preferably 60 nm to 120 nm.
- a hard coat layer a forward scattering layer, a primer layer, an antistatic layer, an undercoat layer or a protective layer may be provided.
- the present invention also relates to an image display device and a stereoscopic image display system having the optical film of the present invention.
- An example of the image display device of the present invention is: First and second polarizing films; A liquid crystal cell, which is disposed between the first and second polarizing films, and includes a pair of substrates having electrodes disposed on at least one side thereof and facing each other; and a liquid crystal layer between the pair of substrates; and the first polarizing film
- An image display device having at least the optical film of the present invention on the outside of The image display device is characterized in that the absorption axis direction of the first polarizing film and the in-plane slow axes of the first and second retardation regions of the optical film form an angle of ⁇ 45 °, respectively.
- an example of the stereoscopic image display system of the present invention includes at least the image display device and a third polarizing plate disposed outside the optical film, and allows a stereoscopic image to be visually recognized through the third polarizing plate.
- An image display system includes at least the image display device and a third polarizing plate disposed outside the optical film, and allows a stereoscopic image to be visually recognized through the third polarizing plate.
- the image display apparatus of the present invention includes TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (Supper Twed). ), VA (Vertically Aligned), and HAN (Hybrid Aligned Nematic).
- the video display system of the present invention includes a pair of polarizing glasses that have right and left glasses whose slow axes are orthogonal to each other, and are used for the right eye emitted from one of the first and second retardation regions of the optical film.
- the image light is transmitted through the right glasses and is blocked by the left glasses; the image light for the left eye emitted from the other of the first and second phase difference regions is transmitted through the left glasses and is blocked by the right glasses. It is preferable that it is comprised so that.
- the polarizing glasses form polarizing glasses by including a retardation functional layer and a linear polarizer. In addition, you may use the other member which has a function equivalent to a linear polarizer.
- the optical film of the present invention is provided on a plurality of first lines and a plurality of second lines that are alternately repeated on the video display panel (for example, on the odd-numbered lines in the horizontal direction and even-numbered if the lines are in the horizontal direction).
- the first phase difference region and the second phase difference region having different polarization conversion functions are provided on the line, and if the line is in the vertical direction, it may be on the odd-numbered line and the even-numbered line in the vertical direction.
- the phase difference between the first phase difference region and the second phase difference region is preferably ⁇ / 4, and the first phase difference region is More preferably, the slow axis of the second phase difference region is orthogonal.
- the phase difference values of the first phase difference region and the second phase difference region are both set to ⁇ / 4, an image for the right eye is displayed on the odd line of the video display panel, and the odd line
- the slow axis of the phase difference region is 45 degrees
- the shaft may be fixed at approximately 45 degrees.
- the left eye image is displayed on the even line of the video display panel, and if the slow axis of the even line phase difference region is in the direction of 135 degrees, the left eyeglass of the polarizing glasses Specifically, the slow axis may be fixed at approximately 135 degrees. Furthermore, from the viewpoint of emitting image light as circularly polarized light once in the patterning retardation film and returning the polarization state to the original state by the polarized glasses, the angle of the slow axis fixed by the right glasses in the above example is exactly The closer to 45 degrees in the horizontal direction, the better. Further, it is preferable that the angle of the slow axis fixed by the left spectacles is exactly close to 135 degrees (or -45 degrees) horizontally.
- the absorption axis direction of the front-side polarizing plate of the liquid crystal display panel is usually a horizontal direction
- the absorption axis of the linear polarizer of the polarizing glasses is the front-side polarization
- the direction perpendicular to the absorption axis direction of the plate is preferable, and the absorption axis of the linear polarizer of the polarizing glasses is more preferably the vertical direction.
- the absorption axis direction of the front-side polarizing plate of the liquid crystal display panel and the slow axis of the odd line retardation region and the even line retardation region of the patterning retardation film are 45 degrees on the efficiency of polarization conversion. It is preferable to make it.
- a preferable arrangement of such polarizing glasses, a patterning retardation film, and a liquid crystal display device is disclosed in, for example, Japanese Patent Application Laid-Open No. 2004-170693.
- Examples of polarized glasses include those described in Japanese Patent Application Laid-Open No. 2004-170693, and examples of commercially available products include accessories from Zalman and ZM-M220W.
- Example 1 [Preparation of transparent support with rubbing alignment film] A 4% aqueous solution of polyvinyl alcohol “PVA103” manufactured by Kuraray Co., Ltd. was applied to the surface of the transparent glass support with a No. 12 bar and dried at 80 ° C. for 5 minutes. Thereafter, rubbing treatment was performed three times in one direction at 400 rpm to produce a glass support with a rubbing alignment film.
- Re (550) of the glass support was 0 nm
- Rth was 0 nm
- the thickness of the alignment film was 0.9 ⁇ m.
- the first retardation region was formed by irradiating ultraviolet rays for 5 seconds to fix the alignment state. Subsequently, the film surface temperature was raised to 140 ° C., and after making it isotropic phase, the temperature was lowered to 100 ° C. and heated at that temperature for 1 minute for uniform orientation. After cooling to room temperature, the entire surface was irradiated at 20 mW / cm 2 for 20 seconds to fix the orientation state, thereby forming a second retardation region. The slow axes of the first retardation region and the second retardation region were orthogonal to each other, and the film thickness was 0.8 ⁇ m.
- Discotic liquid crystal E-1 100 parts by weight alignment film interface aligner (II-1) 1.0 part by weight air interface aligner (P-1) 0.4 part by weight photopolymerization initiator 3.0 parts by weight (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.) Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by weight Methyl ethyl ketone 300 parts by weight
- the patterned optically anisotropic layer is formed by either one of the two polarizing plates in which the slow axis of either the first retardation region or the second retardation region is combined in an orthogonal position.
- An optically anisotropic layer is placed between the polarizing plates so as to be parallel to the polarizing axis, and a sensitive color plate having a phase difference of 530 nm is formed so that the slow axis forms an angle of 45 ° with the polarizing axis of the polarizing plate. (Fig. 5).
- Fig. 5 Next, the state where the optically anisotropic layer was rotated by + 45 ° (FIG. 6) and the state where the optically anisotropic layer was rotated by ⁇ 45 ° (FIG.
- the discotic liquid crystal is aligned on a PVA rubbing alignment film rubbed in one direction in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, and the heating temperature is changed. It can be understood that the patterned optically anisotropic layer having the first retardation region and the second retardation region having the vertical alignment and the slow axis orthogonal to each other can be obtained by performing the exposure. .
- Example 2 An attempt was made to produce an optical film with an optically anisotropic layer patterned by the same operation as in Example 1, except that the coating liquid for the optically anisotropic layer was changed to the following composition.
- the film thickness of the optically anisotropic layer was 0.8 ⁇ m.
- Discotic liquid crystal E-2 100 parts by mass alignment film interface alignment agent (II-1) 1.0 part by mass air interface alignment agent (P-2) 0.3 part by mass photopolymerization initiator 3.0 parts by mass (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.) Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by weight Methyl ethyl ketone 300 parts by weight
- Example 3 [Preparation of transparent support with rubbing alignment film] (Preparation of transparent support)
- the following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acylate solution A.
- ⁇ Composition of cellulose acylate solution A> Cellulose acetate having a substitution degree of 2.86 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 300 parts by weight Methanol (second solvent) 54 parts by weight 1-butanol 11 parts by weight
- additive solution B composition The following composition was charged into another mixing tank, stirred while heating to dissolve each component, and an additive solution B was prepared.
- additive solution B composition The following compound B1 (Re reducing agent) 40 parts by mass
- a dope was prepared by adding 40 parts by mass of the additive solution B to 477 parts by mass of the cellulose acylate solution A and stirring sufficiently.
- the dope was cast from a casting port onto a drum cooled to 0 ° C.
- the film is peeled off at a solvent content of 70% by mass, and both ends in the width direction of the film are fixed with a pin tenter (a pin tenter described in FIG. 3 of JP-A-4-1009), and the solvent content is 3 to 5% by mass.
- a pin tenter a pin tenter described in FIG. 3 of JP-A-4-1009
- the solvent content is 3 to 5% by mass.
- it was dried while maintaining an interval at which the stretching ratio in the transverse direction (direction perpendicular to the machine direction) was 3%.
- it dried further by conveying between the rolls of a heat processing apparatus, and produced the 60-micrometer-thick cellulose acetate protective film.
- Re (550) of the transparent support was 2.0 nm, and
- the cellulose acetate transparent support is passed through a dielectric heating roll having a temperature of 60 ° C., and the film surface temperature is raised to 40 ° C., and then an alkali solution having the composition shown below is applied to one side of the film using a bar coater.
- the coating was carried out for 10 seconds under a steam far-infrared heater manufactured by Noritake Company Limited, which was applied at an amount of 14 ml / m 2 and heated to 110 ° C. Subsequently, 3 ml / m 2 of pure water was applied using the same bar coater. Next, washing with a fountain coater and draining with an air knife were repeated three times, followed by transporting to a drying zone at 70 ° C. for 10 seconds and drying to prepare an alkali saponified cellulose acetate transparent support.
- Alkaline solution composition Alkaline solution composition (parts by mass) ⁇ Potassium hydroxide 4.7 parts by weight Water 15.8 parts by weight Isopropanol 63.7 parts by weight
- Surfactant SF-1 C 14 H 29 O (CH 2 CH 2 O) 20 H 1.0 part by weight Propylene glycol 14. 8 parts by mass ⁇
- a rubbing alignment film coating solution having the following composition was continuously applied to the saponified surface of the prepared support with a # 14 wire bar.
- the alignment film was formed by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 100 ° C. for 120 seconds.
- the thickness of the alignment film was 0.9 ⁇ m.
- ⁇ Composition of coating liquid for forming alignment film> The following modified polyvinyl alcohol PVA-1 10 parts by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde 0.5 parts by weight
- the surface of the formed rubbing alignment film was rubbed along the longitudinal direction of the film.
- a coating solution for optically anisotropic layer having the following composition was coated at a coating amount of 4 ml / m 2 using a bar coater. After drying at a film surface temperature of 80 ° C. for 1 minute to obtain a liquid crystal phase and uniform alignment, it was cooled to room temperature. Next, a stripe mask is placed on the substrate coated with the coating liquid for the optically anisotropic layer, and 5 ultraviolet rays are applied using an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) of 20 mW / cm 2 under air. The first retardation region was formed by fixing the alignment state by irradiation for 2 seconds.
- the film surface temperature was raised to 115 ° C., and after making it isotropic phase, the temperature was lowered to 100 ° C. and heated at that temperature for 1 minute for uniform orientation. After cooling to room temperature, the entire surface was irradiated at 20 mW / cm 2 for 20 seconds to fix the orientation state, thereby forming a second retardation region. Finally, it was wound up into a cylindrical shape to obtain a roll-shaped optical film.
- the slow axes of the first retardation region and the second retardation region were orthogonal to each other, and the film thickness was 0.9 ⁇ m.
- composition for optically anisotropic layer ⁇
- Optically anisotropic layer coating solution composition ⁇ 100.0 parts by mass of the discotic liquid crystal E-1 1.0 part by mass of the alignment film interface aligner (II-1) 0.4 parts by mass of the following air interface aligner (P-2) Ethylene oxide-modified trimethylolpropane tri Acrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 10.0 parts by mass Photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 3.0 parts by mass Sensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) (Product made) 1.0 part by weight Methyl ethyl ketone 300.0 parts by weight ⁇
- the patterned optically anisotropic layer is formed by either one of the two polarizing plates in which the slow axis of either the first retardation region or the second retardation region is combined in an orthogonal position.
- An optically anisotropic layer is placed between the polarizing plates so as to be parallel to the polarizing axis, and a sensitive color plate having a phase difference of 530 nm is formed so that the slow axis forms an angle of 45 ° with the polarizing axis of the polarizing plate. (Fig. 8).
- the discotic liquid crystal is aligned on a PVA rubbing alignment film rubbed in one direction in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, and the heating temperature is changed. It can be understood that the patterned optically anisotropic layer having the first retardation region and the second retardation region having the vertical alignment and the slow axis orthogonal to each other can be obtained by performing the exposure. .
- Example 4 [Production of optical film] An optical film with an optically anisotropic layer patterned by the same operation as in Example 3 was prepared except that a stripe mask with a period of 100 ⁇ m was used.
- [Preparation of antireflection film] (Preparation of coating solution for hard coat layer) The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution. 100 parts by weight of cyclohexanone, 750 parts by weight of partially caprolactone-modified polyfunctional acrylate (DPCA-20, manufactured by Nippon Kayaku Co., Ltd.), silica sol (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.) with respect to 900 parts by weight of methyl ethyl ketone ) 200 parts by mass and 50 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 ⁇ m to prepare a coating solution for a hard coat layer.
- DPCA-20 partially caprolactone-modified polyfunctional acrylate
- MIBK-ST silica sol
- a medium refractive index coating liquid was prepared by mixing an appropriate amount of medium refractive index coating liquid A and medium refractive index coating liquid B so that the refractive index was 1.36 and the film thickness was 90 ⁇ m.
- the reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 0.31 MPa (3.2 kg / cm 2 ), the heating was stopped and the mixture was allowed to cool.
- the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out.
- the obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 g of polymer was obtained.
- hollow silica particle dispersion A To 500 parts by mass of hollow silica particle fine particle sol (isopropyl alcohol silica sol, CS60-IPA manufactured by Catalyst Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20 mass%, silica particle refractive index 1.31) After 30 parts by mass of acryloyloxypropyltrimethoxysilane and 1.51 parts by mass of diisopropoxyaluminum ethyl acetate were added and mixed, 9 parts by mass of ion-exchanged water was added.
- dispersion liquid After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 mass parts of acetylacetone, and obtained the dispersion liquid. Then, while adding cyclohexanone so that the silica content was substantially constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 30 Torr, and finally a dispersion A having a solid content concentration of 18.2% by mass was obtained by concentration adjustment. . The amount of IPA remaining in the obtained dispersion A was analyzed by gas chromatography and found to be 0.5% by mass or less.
- each component was mixed as described below and dissolved in methyl ethyl ketone to prepare a coating solution Ln6 for a low refractive index layer having a solid content concentration of 5% by mass.
- the mass% of each component below is the ratio of the solid content of each component to the total solid content of the coating solution.
- P-1 Perfluoroolefin copolymer (1): 15% by mass
- DPHA Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.): 7% by mass
- -MF1 The following fluorine-containing unsaturated compound (weight average molecular weight 1600) described in the examples of WO2003 / 022906: 5% by mass
- the coating liquid for hard coat layer having the above composition was applied using a gravure coater. After drying at 100 ° C., an irradiance of 400 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. 2. The coating layer was cured by irradiating with an irradiation amount of 150 mJ / cm 2 to form a hard coat layer A having a thickness of 12 ⁇ m. Further, a medium refractive index layer coating solution, a high refractive index layer coating solution, and a low refractive index layer coating solution were applied using a gravure coater.
- the medium refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 180 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 1.0% by volume or less. ), And the irradiation dose was 300 mW / cm 2 and the irradiation dose was 240 mJ / cm 2 .
- the drying condition of the high refractive index layer is 90 ° C. for 30 seconds, and the ultraviolet curing condition is a 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less.
- the irradiation dose was 300 mW / cm 2 and the irradiation dose was 240 mJ / cm 2 .
- the low refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. ), And the irradiation amount was 600 mW / cm 2 and the irradiation amount was 600 mJ / cm 2 .
- a rolled polyvinyl alcohol film having a thickness of 80 ⁇ m was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a polarizing film having a thickness of 30 ⁇ m.
- a commercially available cellulose acetate film (Fujitac TD80UF, Fuji Photo Film Co., Ltd.) Manufactured, Re (550) 3 nm,
- Example 5 An optical film was prepared in the same manner as in Example 4 except that additive B1 (Re reducing agent) and additive B2 (wavelength dispersion controlling agent) were removed from additive solution B when the cellulose acetate transparent support was prepared.
- the thickness of the cellulose acetate transparent support at this time was 200 ⁇ m, Re at 550 nm was 15 nm, and Rth was 102 nm.
- a polarizing plate was prepared in the same manner as in Example 4, and the pattern retardation plate and front polarizing plate used in a circularly polarized glasses 3D monitor (manufactured by ZALMAN) were peeled off, and the polarizing plate was bonded.
- the stereoscopic image was projected on the produced 3D monitor and observed through the circular polarizing glasses for the right eye / left eye, it could be observed as a stereoscopic image, but some crosstalk was recognized.
- Example 6 An attempt was made to produce an optical film with an optically anisotropic layer patterned by the same operation as in Example 1, except that the coating liquid for the optically anisotropic layer was changed to the following composition.
- the film thickness of the optically anisotropic layer was 0.8 ⁇ m.
- Discotic liquid crystal E-3 100 parts by mass alignment film interface alignment agent (II-1) 1.0 part by mass air interface alignment agent (P-2) 0.3 part by mass photopolymerization initiator 3.0 parts by mass (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.) Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by mass Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 9.9 parts by mass Methyl ethyl ketone 300 parts by mass Part
- Example 7 An attempt was made to produce an optical film with an optically anisotropic layer patterned by the same operation as in Example 1, except that the coating liquid for the optically anisotropic layer was changed to the following composition.
- the film thickness of the optically anisotropic layer was 0.8 ⁇ m.
- Discotic liquid crystal E-2 100 parts by mass alignment film interface alignment agent (II-2) 1.0 part by mass air interface alignment agent (P-2) 0.3 part by mass photopolymerization initiator 3.0 parts by mass (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.) Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by weight Methyl ethyl ketone 300 parts by weight
- the coating solution for the optically anisotropic layer of Example 3 was applied at a coating amount of 4 ml / m 2 using a bar coater. After drying at a film surface temperature of 80 ° C. for 1 minute to obtain a liquid crystal phase and uniform alignment, it was cooled to room temperature. An optically anisotropic layer was formed by fixing the alignment state by irradiating the entire surface with ultraviolet rays for 25 seconds using an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) of 20 mW / cm 2 under air. .
- the coating solution for the optically anisotropic layer of Example 3 was applied at a coating amount of 4 ml / m 2 using a bar coater. After raising the film surface temperature to 115 ° C. and making it isotropic phase once, the temperature was lowered to 100 ° C. and heated at that temperature for 1 minute for uniform orientation. After cooling to room temperature, the entire surface was irradiated at 20 mW / cm 2 for 25 seconds to fix the alignment state, thereby forming an optically anisotropic layer.
- Comparative Example 3 (Mounting evaluation on liquid crystal display devices) A 3D monitor was produced in the same manner as in Example 4 except that the polarizing plate produced in Comparative Example 1 was used. When a stereoscopic image was projected on the produced 3D monitor and observed through circular polarizing glasses for the right eye / left eye, the crosstalk was large and the stereoscopic image could not be recognized.
- Comparative Example 4 (Mounting evaluation on liquid crystal display devices) A 3D monitor was produced in the same manner as in Example 4 except that the polarizing plate produced in Comparative Example 2 was used. When a stereoscopic image was projected on the produced 3D monitor and observed through circular polarizing glasses for the right eye / left eye, the crosstalk was large and the stereoscopic image could not be recognized.
- Discotic liquid crystal E-4 100 parts by mass alignment film interface alignment agent (II-1) 1.0 part by mass air interface alignment agent (P-2) 0.3 part by mass photopolymerization initiator 3.0 parts by mass (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.) Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by mass Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 9.9 parts by mass Methyl ethyl ketone 300 parts by mass Part
- Discotic liquid crystal E-1 100 parts by mass alignment film interface aligner (II-3) 1.0 part by mass air interface aligner (P-2) 0.3 part by mass photopolymerization initiator 3.0 parts by mass (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.) Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by weight Methyl ethyl ketone 300 parts by weight
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ophthalmology & Optometry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Mathematical Physics (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Laminated Bodies (AREA)
Abstract
Description
例えば、特許文献1には、フォトレジスト材料を用いて、旋光領域と非旋光領域とにパターニングされた旋光光学素子の作製方法が開示されている。しかし、工程数が多く、工業的に連続生産するのは困難な場合もある。
また、特許文献2には、光異性化物質を利用した進相軸または遅相軸がそれぞれ異なる第1及び第2の領域を有する位相差シートが開示されている。しかし、材料の制約があるので、種々の用途に応じて、最適な特性を達成するのは困難な場合もある。
本発明の第一の目的は、高精細な配向パターンの光学異方性層を有し、かつ製造が容易で実用性に優れた光学フィルムを提供することである。第二の目的は、かかる光学フィルムの簡易な製造方法を提供することである。第三の目的は、低コストで視認性の高い画像表示装置及び立体画像表示システムを提供することである。
[1] 透明支持体上に、一方向に処理された配向膜と、重合性基を有する液晶を主成分とする一種の組成物から形成された光学異方性層とを少なくとも有する光学フィルムであって、
前記光学異方性層が、互いに直交する面内遅相軸を有する第1相差領域及び第2位相差領域を含み、前記第1及び第2位相差領域が、面内において交互に配置されているパターン光学異方性層である光学フィルム。
[2] 前記配向膜が、一方向にラビング処理されたラビング配向膜である[1]の光学フィルム。
[3] Re(550)が、110~165nmである[1]又は[2]の光学フィルム:
但し、Re(550)は波長550nmにおける面内レターデーション値(単位:nm)である。
[4] 前記透明支持体のRe(550)が、0~10nmである[1]~[3]のいずれかの光学フィルム。
[5] Rth(550)が、|Rth(550)|≦20を満足する[1]~[4]のいずれかの光学フィルム:
但し、Rth(550)は、波長550nmにおける膜厚方向のレターデーション値(単位:nm)である。
[6] 前記配向膜が、変性又は未変性ポリビニルアルコールを主成分として含有する膜である[1]~[5]のいずれかの光学フィルム。
[7] 前記重合性基を有する液晶が、円盤状液晶である[1]~[6]のいずれかの光学フィルム。
[8] 前記光学異方性層が、ピリジニウム化合物又はイミダゾリウム化合物の少なくとも1種をさらに含有する[1]~[7]のいずれかの光学フィルム。
[11] 前記重合性基を有する液晶が円盤状液晶であり、前記光学異方性層中、円盤状液晶が垂直配向状態に固定されている[1]~[10]のいずれかの光学フィルム。
[12] [1]~[11]のいずれかの光学フィルムと、偏光膜とを含み、前記光学異方性層の第1及び第2の位相差領域のそれぞれの面内遅相軸方向と、偏光膜の吸収軸方向とが45°である偏光板。
[13] 前記光学フィルムと、前記偏光膜とが粘着層を介して積層されている[12]の偏光板。
[14] さらに最表面に一層以上の反射防止フィルムが積層されている[12]又は[13]の偏光板。
第1及び第2の偏光膜の間に配置される、少なくとも一方に電極を有し対向配置された一対の基板と、該一対の基板間の液晶層とを含む液晶セル;及び
第1偏光膜の外側に[1]~[11]のいずれかの光学フィルム;
を少なくとも有する画像表示装置であって、
前記第1偏光膜の吸収軸方向と、前記光学フィルムの第1及び第2位相差領域の面内遅相軸がそれぞれ±45°の角度をなす画像表示装置。
[16] [15]の画像表示装置と、前記光学フィルムの外側に配置される第3の偏光板とを少なくとも備え、第3の偏光板を通じて立体画像を視認させる立体画像表示システム。
[17] [1]~[11]のいずれかの光学フィルムの製造方法であって、
1)透明支持体上にラビング配向膜を形成する工程
2)ラビング配向膜を一方向にラビング処理する工程
3)ラビング配向膜上に、重合性基を有する液晶を主成分とする一種の組成物を塗布する工程
4)温度T1℃で加熱してラビング方向に対して、液晶の遅相軸を直交配向させる工程
5)フォトマスク下、紫外線照射して照射領域を直交配向状態で固定化する工程
6)温度T2(但し、T1<T2)℃で加熱して、ラビング方向に対して未照射領域の液晶の遅相軸を平行配向させる工程
7)紫外線照射して平行配向状態で固定化する工程
をこの順で含む光学フィルムの製造方法。
また、本発明によれば、前記光学フィルムの簡易な製造方法を提供することができる。
また、本発明によれば、低コストで視認性の高い画像表示装置及び立体画像表示システムを提供することができる。
なお、本明細書では、「可視光」とは、380nm~780nmのことをいう。また、本明細書では、測定波長について特に付記がない場合は、測定波長は550nmである。
また、本明細書において、角度(例えば「90°」等の角度)、及びその関係(例えば「直交」、「平行」、及び「45°で交差」等)については、本発明が属する技術分野において許容される誤差の範囲を含むものとする。例えば、厳密な角度±10°未満の範囲内であることなどを意味し、厳密な角度との誤差は、5°以下であることが好ましく、3°以下であることがより好ましい。
本発明は、透明支持体上に、一方向に処理された配向膜と、重合性基を有する液晶を主成分とする一種の組成物から形成された光学異方性層とを少なくとも有する光学フィルムであって、前記光学異方性層が、互いに直交する面内遅相軸を有する第1位相差領域及び第2位相差領域を含み、前記第1及び第2位相差領域が、面内において交互に配置されているパターン光学異方性層であることを特徴とする光学フィルムに関する。本発明の光学フィルムは、立体画像表示用の画像表示装置の視認側偏光子のさらに外側に配置され、当該光学フィルムの第1及び第2の位相差領域のそれぞれを通過した偏光画像が、偏光メガネ等を介して右眼用又は左眼用の画像として、認識される。従って、左右画像が不均一とならないように、第1及び第2の位相差領域は、互いに等しい形状であるのが好ましく、またそれぞれの配置は、均等且つ対称的であるのが好ましい。
(1)光学フィルムの製造方法
本発明の光学フィルムの製造方法の一例は、
1)透明支持体上にラビング配向膜を形成する工程
2)ラビング配向膜を一方向にラビング処理する工程
3)ラビング配向膜上に、重合性基を有する液晶を主成分とする一種の組成物を塗布する工程
4)温度T1℃で加熱してラビング方向に対して液晶の遅相軸を直交配向させる工程
5)フォトマスク下、紫外線照射して照射領域を直交配向状態で固定化する工程
6)温度T2(但し、T1<T2)℃で加熱して、ラビング方向に対して未照射領域の液晶の遅相軸を平行配向させる工程
7)紫外線照射して平行配向状態で固定化する工程
をこの順で含む製造方法である。
なお、3)工程と4)工程との間に、組成物中の溶剤を蒸発されるために、加熱してもよい。加熱温度は、T1℃より高くても低くてもよく、またT1℃と同一の温度であってもよい。
上記1)及び2)工程により、ラビング配向膜を形成する。本発明に利用可能な「ラビング配向膜」とは、ラビングによって、液晶分子の配向規制能を有するように処理された膜を意味する。ラビング配向膜には、液晶分子を配向規制する配向軸があり、当該配向軸に従って、液晶分子は配向する。本発明では、液晶分子は、温度T1℃でラビング方向に対して液晶の遅相軸が直交するように配向したのち、温度T2(但し、T1<T2)℃で液晶分子の遅相軸がラビング方向に対して平行になるように配向転移するように、配向膜の材料、液晶、及び配向制御剤を選択する。
ラビング密度を変える方法としては、「液晶便覧」(丸善社発行)に記載されている方法を用いることができる。ラビング密度(L)は、下記式(A)で定量化されている。
式(A) L=Nl(1+2πrn/60v)
式(A)中、Nはラビング回数、lはラビングローラーの接触長、rはローラーの半径、nはローラーの回転数(rpm)、vはステージ移動速度(秒速)である。
ラビング密度と配向膜のプレチルト角との間には、ラビング密度を高くするとプレチルト角は小さくなり、ラビング密度を低くするとプレチルト角は大きくなる関係がある。
長尺状の偏光膜であって、吸収軸が長手方向の偏光膜と貼り合わせるには、長尺のポリマーフィルムからなる支持体上に配向膜を形成し、長手方向に対して45°の方向に連続的にラビング処理して、ラビング配向膜を形成するのが好ましい。
上記3)工程で、配向膜のラビング処理面に、塗布液として調製された重合性基を有する液晶を主成分とする一種の組成物を塗布する。塗布方法としては特に制限はく、カーテンコーティング法、ディップコーティング法、スピンコーティング法、印刷コーティング法、スプレーコーティング法、スロットコーティング法、ロールコーティング法、スライドコーテティング法、ブレードコーティング法、グラビアコーティング法、ワイヤーバー法等の公知の塗布方法が挙げられる。
以下、各材料について詳細に説明する。
本発明の光学異方性層の主原料として使用可能な液晶化合物としては、棒状液晶及びディスコティック液晶を挙げることができ、ディスコティック液晶が好ましく、前記のとおり重合性基を有するディスコティック液晶がより好ましい。
棒状液晶としては、例えば、Makromol. Chem., 190巻、2255頁(1989年)、Advanced Materials 5巻、107頁(1993年)、米国特許4683327号、同5622648号、同5770107号、世界特許(WO)95/22586号、同95/24455号、同97/00600号、同98/23580号、同98/52905号、特開平1-272551号、同6-16616号、同7-110469号、同11-80081号、同11-513019号及び特願2001-64627号などの各公報及び明細書に記載の化合物の中から選んで用いることができる。
一般式(X)
Q1-L1-Cy1-L2-(Cy2-L3)n-Cy3-L4-Q2
式中、Q1及びQ2はそれぞれ独立に重合性基を表し、L1及びL4はそれぞれ独立に二価の連結基を表し、L2及びL3はそれぞれ独立に単結合又は二価の連結基を表し、Cy1、Cy2及びCy3はそれぞれ独立に二価の環状基を表し、nは0、1又は2である。
前記ディスコティック液晶としては、下記一般式(I)で表される化合物が好ましい。
一般式(I): D(-L-H-Q)n
式中、Dは円盤状コアであり、Lは二価の連結基であり、Hは二価の芳香族環又は複素環であり、Qは重合性基であり、nは3~12の整数を表す。
Y11、Y12およびY13は、化合物の合成の容易さおよびコストの点において、いずれもメチンであることがより好ましく、メチンは無置換であることがさらに好ましい。
L1、L2およびL3が二価の連結基の場合、それぞれ独立に、-O-,-S-、-C(=O)-、-NR7-、-CH=CH-、-C≡C-、二価の環状基およびこれらの組み合わせからなる群より選ばれる二価の連結基であることが好ましい。上記R7は炭素原子数1~7のアルキル基または水素原子であり、炭素原子数1~4のアルキル基または水素原子であることが好ましく、メチル基、エチル基または水素原子であることがさらに好ましく、水素原子であることが最も好ましい。
XAは、酸素原子、硫黄原子、メチレン又はイミノを表し;
*は上記一般式(IV)におけるL1~L3側と結合する位置を表し;
**は上記一般式(IV)におけるR1~R3側と結合する位置を表す。
XBは、酸素原子、硫黄原子、メチレン又はイミノを表し;
*は上記一般式(IV)におけるL1~L3側と結合する位置を表し;
**は上記一般式(IV)におけるR1~R3側と結合する位置を表す。
*-(-L21-Q2)n1-L22-L23-Q1
一般式(IV-R)中、*は、一般式(IV)におけるH1~H3側と結合する位置を表す。
L21は単結合又は二価の連結基を表す。L21が二価の連結基の場合、-O-、-S-、-C(=O)-、-NR7-、-CH=CH-および-C≡C-ならびにこれらの組み合わせからなる群より選ばれる二価の連結基であることが好ましい。上記R7は炭素原子数1~7のアルキル基または水素原子であり、炭素原子数1~4のアルキル基または水素原子であることが好ましく、メチル基、エチル基または水素原子であることがさらに好ましく、水素原子であることが最も好ましい。
L22は、好ましくは、**-O-、**-O-CO-、**-CO-O-、**-O-CO-O-、**-CH2-、**-CH=CH-、**-C≡C-であり、より好ましくは、**-O-、**-O-CO-、**-O-CO-O-、**-CH2-である。L22が水素原子を含む基であるときは、該水素原子は置換基で置換されていてもよい。このような置換基として、ハロゲン原子、シアノ基、ニトロ基、炭素原子数1~6のアルキル基、炭素原子数1~6のハロゲンで置換されたアルキル基、炭素原子数1~6のアルコキシ基、炭素原子数2~6のアシル基、炭素原子数1~6のアルキルチオ基、炭素原子数2~6のアシルオキシ基、炭素原子数2~6のアルコキシカルボニル基、カルバモイル基、炭素原子数2~6のアルキルで置換されたカルバモイル基および炭素原子数2~6のアシルアミノ基が好ましい例として挙げられ、ハロゲン原子、炭素原子数1~6のアルキル基がより好ましい。
上記式(M-1)~(M-6)の中、(M-1)または(M-2)が好ましく、(M-1)がより好ましい。
A11およびA12は、少なくとも一方が窒素原子であることが好ましく、両方が窒素原子であることがより好ましい。
A13、A14、A15およびA16は、それらのうち、少なくとも3つがメチンであることが好ましく、すべてメチンであることがより好ましい。さらに、メチンは無置換であることが好ましい。
A11、A12、A13、A14、A15またはA16がメチンの場合の置換基の例には、ハロゲン原子(フッ素原子、塩素原子、臭素原子、ヨウ素原子)、シアノ基、ニトロ基、炭素原子数1~16のアルキル基、炭素原子数2~16のアルケニル基、炭素原子数2~16のアルキニル基、炭素原子数1~16のハロゲンで置換されたアルキル基、炭素原子数1~16のアルコキシ基、炭素原子数2~16のアシル基、炭素原子数1~16のアルキルチオ基、炭素原子数2~16のアシルオキシ基、炭素原子数2~16のアルコキシカルボニル基、カルバモイル基、炭素原子数2~16のアルキル置換カルバモイル基および炭素原子数2~16のアシルアミノ基が含まれる。これらの中でも、ハロゲン原子、シアノ基、炭素原子数1~6のアルキル基、炭素原子数1~6のハロゲンで置換されたアルキル基が好ましく、ハロゲン原子、炭素原子数1~4のアルキル基、炭素原子数1~4のハロゲンで置換されたアルキル基がより好ましく、ハロゲン原子、炭素原子数が1~3のアルキル基、トリフルオロメチル基がさらに好ましい。
X1は、酸素原子、硫黄原子、メチレンまたはイミノを表し、酸素原子が好ましい。
A21およびA22は、少なくとも一方が窒素原子であることが好ましく、両方が窒素原子であることがより好ましい。
A23、A24、A25およびA26は、それらのうち、少なくとも3つがメチンであることが好ましく、すべてメチンであることがより好ましい。
A21、A22、A23、A24、A25またはA26がメチンの場合の置換基の例には、ハロゲン原子(フッ素原子、塩素原子、臭素原子、ヨウ素原子)、シアノ基、ニトロ基、炭素原子数1~16のアルキル基、炭素原子数2~16のアルケニル基、炭素原子数2~16のアルキニル基、炭素原子数1~16のハロゲンで置換されたアルキル基、炭素原子数1~16のアルコキシ基、炭素原子数2~16のアシル基、炭素原子数1~16のアルキルチオ基、炭素原子数2~16のアシルオキシ基、炭素原子数2~16のアルコキシカルボニル基、カルバモイル基、炭素原子数2~16のアルキル置換カルバモイル基および炭素原子数2~16のアシルアミノ基が含まれる。これらの中でも、ハロゲン原子、シアノ基、炭素原子数1~6のアルキル基、炭素原子数1~6のハロゲンで置換されたアルキル基が好ましく、ハロゲン原子、炭素原子数1~4のアルキル基、炭素原子数1~4のハロゲンで置換されたアルキル基がより好ましく、ハロゲン原子、炭素原子数が1~3のアルキル基、トリフルオロメチル基がさらに好ましい。
X2は、酸素原子、硫黄原子、メチレンまたはイミノを表し、酸素原子が好ましい。
A31およびA32は、少なくとも一方が窒素原子であることが好ましく、両方が窒素原子であることがより好ましい。
A33、A34、A35およびA36は、少なくとも3つがメチンであることが好ましく、すべてメチンであることがより好ましい。
A31、A32、A33、A34、A35またはA36がメチンの場合、メチンは置換基を有していてもよい。置換基の例には、ハロゲン原子(フッ素原子、塩素原子、臭素原子、ヨウ素原子)、シアノ基、ニトロ基、炭素原子数1~16のアルキル基、炭素原子数2~16のアルケニル基、炭素原子数2~16のアルキニル基、炭素原子数1~16のハロゲンで置換されたアルキル基、炭素原子数1~16のアルコキシ基、炭素原子数2~16のアシル基、炭素原子数1~16のアルキルチオ基、炭素原子数2~16のアシルオキシ基、炭素原子数2~16のアルコキシカルボニル基、カルバモイル基、炭素原子数2~16のアルキル置換カルバモイル基および炭素原子数2~16のアシルアミノ基が含まれる。これらの中でも、ハロゲン原子、シアノ基、炭素原子数1~6のアルキル基、炭素原子数1~6のハロゲンで置換されたアルキル基が好ましく、ハロゲン原子、炭素原子数1~4のアルキル基、炭素原子数1~4のハロゲンで置換されたアルキル基がより好ましく、ハロゲン原子、炭素原子数が1~3のアルキル基、トリフルオロメチル基がさらに好ましい。
X3は、酸素原子、硫黄原子、メチレンまたはイミノを表し、酸素原子が好ましい。
なお、前記組成物中には、液晶の水平配向を促進する添加剤を添加してもよく、該添加剤の例には、特開2009-223001号公報の[0055]~[0063]に記載の化合物が含まれる。
なお、前記組成物中には、液晶の垂直配向を促進する添加剤を添加していることが好ましく、該添加剤の例は、前記の通りである。
本手法では算出を容易にすべく、下記の2点を仮定し、光学異方性層の2つの界面におけるチルト角とする。
1.光学異方性層は液晶性化合物を含む層で構成された多層体と仮定する。さらに、それを構成する最小単位の層(液晶性化合物のチルト角は該層内において一様と仮定)は光学的に一軸と仮定する。
2.各層のチルト角は光学異方性層の厚み方向に沿って一次関数で単調に変化すると仮定する。
具体的な算出法は下記のとおりである。
(1)各層のチルト角が光学異方性層の厚み方向に沿って一次関数で単調に変化する面内で、光学異方性層への測定光の入射角を変化させ、3つ以上の測定角でレターデーション値を測定する。測定及び計算を簡便にするためには、光学異方性層に対する法線方向を0°とし、-40°、0°、+40°の3つの測定角でレターデーション値を測定することが好ましい。このような測定は、KOBRA-21ADH及びKOBRA-WR(王子計測器(株)製)、透過型のエリプソメータAEP-100((株)島津製作所製)、M150及びM520(日本分光(株)製)、ABR10A(ユニオプト(株)製)で行うことができる。
(2)上記のモデルにおいて、各層の常光の屈折率をno、異常光の屈折率をne(neは各々すべての層において同じ値、noも同様とする)、及び多層体全体の厚みをdとする。さらに各層におけるチルト方向とその層の一軸の光軸方向とは一致するとの仮定の元に、光学異方性層のレターデーション値の角度依存性の計算が測定値に一致するように、光学異方性層の一方の面におけるチルト角θ1及び他方の面のチルト角θ2を変数としてフィッティングを行い、θ1及びθ2を算出する。
ここで、no及びneは文献値、カタログ値等の既知の値を用いることができる。値が未知の場合はアッベ屈折計を用いて測定することもできる。光学異方性層の厚みは、光学干渉膜厚計、走査型電子顕微鏡の断面写真等により測定数することができる。
本発明では、前述のように、重合性基を有する液晶化合物、特に、重合性基を有するディスコティック液晶の垂直配向を実現するために、オニウム塩を添加することが好ましい。オニウム塩は配向膜界面に偏在し、液晶分子の配向膜界面近傍におけるチルト角を増加させる作用をする。
一般式(1)
Z-(Y-L-)nCy+・X‐
式中、Cyは5又は6員環のオニウム基であり、L、Y、Z、Xは、後述する一般式(2a)及び(2b)におけるL23、L24、Y22、Y23、Z21、Xに同義であり、その好ましい範囲も同一であり、nは2以上の整数を表す。
例えば、配向膜材料としてポリビニルアルコールを利用する態様では、ポリビニルアルコールの水酸基と水素結合を形成するために、水素結合性基を有しているのが好ましい。水素結合の理論的な解釈としては、例えば、H.Uneyama and K.Morokuma、Journal of American Chemical Society、第99巻、第1316~1332頁、1977年に報告がある。具体的な水素結合の様式としては、例えば、J.N.イスラエスアチヴィリ著、近藤保、大島広行訳、分子間力と表面力、マグロウヒル社、1991年の第98頁、図17に記載の様式が挙げられる。具体的な水素結合の例としては、例えば、G.R.Desiraju、Angewante Chemistry International Edition English、第34巻、第2311頁、1995年に記載のものが挙げられる。
例えば、イミダゾリウム環の窒素原子ように、5又は6員環のオニウム環に、水素結合性基を有する原子を含有していることも好ましい。
一般式(2a)及び(2b)で表される化合物は、主に、前記一般式(I)~(IV)で表されるディスコティック液晶の配向膜界面における配向を制御することを目的として添加され、ディスコティック液晶の分子の配向膜界面近傍におけるチルト角を増加させる作用がある。
L23は、単結合、-O-、-O-CO-、-CO-O-、-C≡C-、-CH=CH-、-CH=N-、-N=CH-、-N=N-、-O-AL-O-、-O-AL-O-CO-、-O-AL-CO-O-、-CO-O-AL-O-、-CO-O-AL-O-CO-、-CO-O-AL-CO-O-、-O-CO-AL-O-、-O-CO-AL-O-CO-又は-O-CO-AL-CO-O-であるのが好ましく、ALは、炭素原子数が1~10のアルキレン基である。L23は、単結合、-O-、-O-AL-O-、-O-AL-O-CO-、-O-AL-CO-O-、-CO-O-AL-O-、-CO-O-AL-O-CO-、-CO-O-AL-CO-O-、-O-CO-AL-O-、-O-CO-AL-O-CO-または-O-CO-AL-CO-O-が好ましく、単結合または-O-がさらに好ましく、-O-が最も好ましい。
R22が、ジアルキル置換アミノ基である場合、2つのアルキル基が互いに結合して含窒素複素環を形成してもよい。このとき形成される含窒素複素環は、5員環または6員環が好ましい。R23は水素原子、無置換アミノ基、または炭素原子数が2~12のジアルキル置換アミノ基であるのがさらに好ましく、水素原子、無置換アミノ基、または炭素原子数が2~8のジアルキル置換アミノ基であるのがよりさらに好ましい。R23が無置換アミノ基及び置換アミノ基である場合、ピリジニウム環の4位が置換されていることが好ましい。
Xは、一価のアニオンであることが好ましい。アニオンの例には、ハライドイオン(フッ素イオン、塩素イオン、臭素イオン、ヨウ素イオン)およびスルホン酸イオン(例、メタンスルホネートイオン、p-トルエンスルホネートイオン、ベンゼンスルホネートイオン)が含まれる。
前記5又は6員環が置換基を有していてもよい。好ましくは、Y22及びY23のうち少なくとも1つは、置換基を有する5又は6員環を部分構造として有する2価の連結基である。Y22およびY23は、それぞれ独立に、置換基を有していてもよい6員環を部分構造として有する2価の連結基であるのが好ましい。6員環は、脂肪族環、芳香族環(ベンゼン環)および複素環を含む。6員脂肪族環の例は、シクロヘキサン環、シクロヘキセン環およびシクロヘキサジエン環を含む。6員複素環の例は、ピラン環、ジオキサン環、ジチアン環、チイン環、ピリジン環、ピペリジン環、オキサジン環、モルホリン環、チアジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペラジン環およびトリアジン環を含む。6員環に、他の6員環または5員環が縮合していてもよい。
置換基の例は、ハロゲン原子、シアノ、炭素原子数が1~12のアルキル基および炭素原子数が1~12のアルコキシ基を含む。アルキル基およびアルコキシ基は、炭素原子数が2~12のアシル基または炭素原子数が2~12のアシルオキシ基で置換されていてもよい。置換基は、炭素原子数が1~12(より好ましくは1~6、さらに好ましくは1~3)のアルキル基であるのが好ましい。置換基は2以上であってもよく、例えば、Y22及びY23がフェニレン基である場合は、1~4の炭素原子数が1~12(より好ましくは1~6、さらに好ましくは1~3)のアルキル基で置換されていてもよい。
mが2の場合、Z21は、シアノ、炭素原子数が1~10のアルキル基または炭素原子数が1~10のアルコキシ基であることが好ましく、炭素原子数4~10のアルコキシ基であるのがさらに好ましい。
mが1の場合、Z21は、炭素原子数が7~12のアルキル基、炭素原子数が7~12のアルコキシ基、炭素原子数が7~12のアシル置換アルキル基、炭素原子数が7~12のアシル置換アルコキシ基、炭素原子数が7~12のアシルオキシ置換アルキル基または炭素原子数が7~12のアシルオキシ置換アルコキシ基であることが好ましい。
R30は、炭素原子数が1~12(より好ましくは1~6、さらに好ましくは1~3)のアルキル基であるのが好ましい。
オニウム塩は、その添加量が、液晶化合物に対して5質量%を超えることはなく、0.1~2質量%程度であるのが好ましい。
フルオロ脂肪族基含有共重合体は、液晶、主に、前記一般式(I)で表されるディスコティック液晶、の空気界面における配向を制御することを目的として添加され、液晶の分子の空気界面近傍におけるチルト角を増加させる作用がある。さらに、ムラ、ハジキなどの塗布性も改善される。
本発明に使用可能なフルオロ脂肪族基含有共重合体としては、特開2004-333852号、同2004-333861号、同2005-134884号、同2005-179636号、及び同2005-181977号などの各公報及び明細書に記載の化合物の中から選んで用いることができる。特に好ましくは、特開2005-179636号、及び同2005-181977号の各公報及び明細書に記載の、フルオロ脂肪族基と、カルボキシル基(-COOH)、スルホ基(-SO3H)、ホスホノキシ{-OP(=O)(OH)2}}及びそれらの塩からなる群より選ばれる1種以上の親水性基とを側鎖に含むポリマーである。
フルオロ脂肪族基含有共重合体は、その添加量が、液晶化合物に対して2質量%を超えることはなく、0.1~1質量%程度であるのが好ましい。
光学異方性層の形成に利用する、前記組成物は塗布液として調製するのが好ましい。塗布液の調製に使用する溶媒としては、有機溶媒が好ましく用いられる。有機溶媒の例には、アミド(例、N,N-ジメチルホルムアミド)、スルホキシド(例、ジメチルスルホキシド)、ヘテロ環化合物(例、ピリジン)、炭化水素(例、ベンゼン、ヘキサン)、アルキルハライド(例、クロロホルム、ジクロロメタン)、エステル(例、酢酸メチル、酢酸ブチル)、ケトン(例、アセトン、メチルエチルケトン)、エーテル(例、テトラヒドロフラン、1,2-ジメトキシエタン)が含まれる。アルキルハライドおよびケトンが好ましい。二種類以上の有機溶媒を併用してもよい。
前記の重合性基を有する液晶化合物を含有する組成物(例えば塗布液)を、所望の液晶相を示す配向状態とした後、該配向状態を紫外線照射により固定する(上記方法の5)及び7)工程)。固定化は、液晶化合物に導入した反応性基の重合反応により実施することが好ましい。紫外線照射による、光重合反応により固定化するのが好ましい。光重合反応としては、ラジカル重合、カチオン重合のいずれでも構わない。ラジカル光重合開始剤の例には、α-カルボニル化合物(米国特許2367661号、同2367670号の各明細書記載)、アシロインエーテル(米国特許2448828号明細書記載)、α-炭化水素置換芳香族アシロイン化合物(米国特許2722512号明細書記載)、多核キノン化合物(米国特許3046127号、同2951758号の各明細書記載)、トリアリールイミダゾールダイマーとp-アミノフェニルケトンとの組み合わせ(米国特許3549367号明細書記載)、アクリジンおよびフェナジン化合物(特開昭60-105667号公報、米国特許4239850号明細書記載)およびオキサジアゾール化合物(米国特許4212970号明細書記載)が含まれる。カチオン光重合開始剤の例には、有機スルフォニウム塩系、ヨードニウム塩系、フォスフォニウム塩系等を例示する事ができ、有機スルフォニウム塩系、が好ましく、トリフェニルスルフォニウム塩が特に好ましい。これら化合物の対イオンとしては、ヘキサフルオロアンチモネート、ヘキサフルオロフォスフェートなどが好ましく用いられる。
光重合開始剤の使用量は、塗布液の固形分の0.01~20質量%であることが好ましく、0.5~5質量%であることがさらに好ましい。
また、感度を高める目的で重合開始剤に加えて、増感剤を用いてもよい。増感剤の例には、n-ブチルアミン、トリエチルアミン、トリ-n-ブチルホスフィン、及びチオキサントン等が含まれる。光重合開始剤は複数種を組み合わせてもよく、使用量は、塗布液の固形分の0.01~20質量%であることが好ましく、0.5~5質量%であることがより好ましい。液晶化合物の重合のための光照射は紫外線を用いることが好ましい。
前記組成物は、重合性液晶化合物とは別に、非液晶性の重合性モノマーを含有していてもよい。重合性モノマーとしては、ビニル基、ビニルオキシ基、アクリロイル基又はメタクリロイル基を有する化合物が好ましい。なお、重合性の反応性官能基数が2以上の多官能モノマー、例えば、エチレンオキサイド変性トリメチロールプロパンアクリレートを用いると、耐久性が改善されるので好ましい。前記非液晶性の重合性モノマーは、非液晶性成分であるので、その添加量が、液晶化合物に対して40質量%を超えることはなく、0~20質量%程度であるのが好ましい。
本発明の光学フィルムは、透明支持体を有する。透明支持体としては、面内及び厚み方向の位相差がほとんどない部材を用いることが好ましい。
以下に、前記透明支持体の例として、主にセルロースアシレートについて詳細を説明するが、その技術的事項は、他の高分子フィルムについても同様に適用できることは明らかである。
また、本発明で好ましく用いられるセルロースアシレートの分子量分布はゲルパーミエーションクロマトグラフィーによって評価され、その多分散性指数Mw/Mn(Mwは質量平均分子量、Mnは数平均分子量)が小さく、分子量分布が狭いことが好ましい。具体的なMw/Mnの値としては、1.0~3.0であることが好ましく、1.0~2.0であることが更に好ましく、1.0~1.6であることが最も好ましい。
これらの添加剤の添加量を調整することにより、0≦Re(550)≦10を満たすセルロースアシレートフィルムを作製することができ、当該フィルムを支持体として用いることで、支持体の光学特性の影響をほとんど受けずに、本発明の光学フィルム中に含まれる全ての前記第1及び第2の位相差領域のReを、110nm≦Re(550)≦165nmの範囲にすることができる。Re値は、120≦Re(550)≦145であることが好ましく、130≦Re(550)≦145であることが特に好ましい。
セルロースアシレートフィルムの光学的異方性を低下させる化合物について説明する。フィルム中のセルロースアシレートが面内及び膜厚方向に配向するのを抑制する化合物を利用することで、光学的異方性を低下させることができる。光学的異方性を低下させる化合物はセルロースアシレートに十分に相溶し、化合物自身が棒状の構造や平面性の構造を持たないことが有利である。具体的には芳香族基のような平面性の官能基を複数持っている場合、それらの官能基を同一平面ではなく、非平面に持つような構造が有利である。
オクタノール-水分配係数(logP値)の測定は、JIS日本工業規格Z7260-107(2000)に記載のフラスコ浸とう法により実施することができる。また、オクタノール-水分配係数(logP値)は実測に代わって、計算化学的手法あるいは経験的方法により見積もることも可能である。計算方法としては、Crippen’s fragmentation法(J.Chem.Inf.Comput.Sci.,27,21(1987).)、Viswanadhan’s fragmentation法(J.Chem.Inf.Comput.Sci.,29,163(1989).)、Broto’s fragmentation法(Eur.J.Med.Chem.- Chim.Theor.,19,71(1984).)などが好ましく用いられるが、Crippen’s fragmentation法(J.Chem.Inf.Comput.Sci.,27,21(1987).)がより好ましい。ある化合物のlogPの値が測定方法あるいは計算方法により異なる場合に、該化合物が範囲内であるかどうかは、Crippen’s fragmentation法により判断することが好ましい。なお本明細書に記載のlogPの値は、Crippen’s fragmentation法(J.Chem.Inf.Comput.Sci.,27,21(1987).)により求めたものである。
光学的異方性を低下させる化合物は、好ましくは、25℃で液体であるか、融点が25~250℃の固体であり、更に好ましくは、25℃で液体であるか、融点が25~200℃の固体である。また光学的異方性を低下させる化合物は、セルロースアシレートフィルム作製のドープ流延、乾燥の過程で揮散しないことが好ましい。
光学的異方性を低下させる化合物の添加量は、セルロースアシレートに対し0.01~30質量%であることが好ましく、1~25質量%であることがより好ましく、5~20質量%であることが特に好ましい。
光学的異方性を低下させる化合物は、単独で用いても、2種以上化合物を任意の比で混合して用いてもよい。
光学的異方性を低下させる化合物を添加する時期はドープ作製工程中の何れであってもよく、ドープ作製工程の最後に行ってもよい。
また、セルロースアシレートフィルムの厚さは10~120μmが好ましく、20~100μmがより好ましく、30~90μmが更に好ましい。
以下に、本発明において透明支持体として用いられるポリマーフィルムの好ましい性質について説明する。
本明細書において、Re(λ)、Rth(λ)は各々、波長λにおける面内のリターデーション及び厚さ方向のリターデーションを表す。Re(λ)はKOBRA 21ADH又はWR(王子計測機器(株)製)において波長λnmの光をフィルム法線方向に入射させて測定される。測定波長λnmの選択にあたっては、波長選択フィルターをマニュアルで交換するか、又は測定値をプログラム等で変換して測定することができる。
測定されるフィルムが1軸又は2軸の屈折率楕円体で表されるものである場合には、以下の方法によりRth(λ)は算出される。
Rth(λ)は前記Re(λ)を、面内の遅相軸(KOBRA 21ADH又はWRにより判断される)を傾斜軸(回転軸)として(遅相軸がない場合にはフィルム面内の任意の方向を回転軸とする)のフィルム法線方向に対して法線方向から片側50度まで10度ステップで各々その傾斜した方向から波長λnmの光を入射させて全部で6点測定し、その測定されたレターデーション値と平均屈折率の仮定値及び入力された膜厚値を基にKOBRA 21ADH又はWRが算出する。
上記において、法線方向から面内の遅相軸を回転軸として、ある傾斜角度にレターデーションの値がゼロとなる方向をもつフィルムの場合には、その傾斜角度より大きい傾斜角度でのレターデーション値はその符号を負に変更した後、KOBRA 21ADH又はWRが算出する。
なお、遅相軸を傾斜軸(回転軸)として(遅相軸がない場合にはフィルム面内の任意の方向を回転軸とする)、任意の傾斜した2方向からレターデーション値を測定し、その値と平均屈折率の仮定値及び入力された膜厚値を基に、以下の式(11)及び式(12)よりRthを算出することもできる。
式(11)
式(11)におけるnxは面内における遅相軸方向の屈折率を表し、nyは面内においてnxに直交する方向の屈折率を表し、nzはnx及びnyに直交する方向の屈折率を表す。dは膜厚である。
式(12)におけるnxは面内における遅相軸方向の屈折率を表し、nyは面内においてnxに直交する方向の屈折率を表し、nzはnx及びnyに直交する方向の屈折率を表す。dは膜厚である。
Rth(λ)は前記Re(λ)を、面内の遅相軸(KOBRA 21ADH又はWRにより判断される)を傾斜軸(回転軸)としてフィルム法線方向に対して-50度から+50度まで10度ステップで各々その傾斜した方向から波長λnmの光を入射させて11点測定し、その測定されたレターデーション値と平均屈折率の仮定値及び入力された膜厚値を基にKOBRA 21ADH又はWRが算出する。
上記の測定において、平均屈折率の仮定値は ポリマーハンドブック(JOHN WILEY&SONS,INC)、各種光学フィルムのカタログの値を使用することができる。平均屈折率の値が既知でないものについてはアッベ屈折計で測定することができる。主な光学フィルムの平均屈折率の値を以下に例示する: セルロースアシレート(1.48)、シクロオレフィンポリマー(1.52)、ポリカーボネート(1.59)、ポリメチルメタクリレート(1.49)、ポリスチレン(1.59)である。これら平均屈折率の仮定値と膜厚を入力することで、KOBRA 21ADH又はWRはnx、ny、nzを算出する。この算出されたnx,ny,nzよりNz=(nx-nz)/(nx-ny)が更に算出される。
前記ポリマーフィルムの湿度膨張係数は、熱膨張係数との組合せにより、適宜、設定することができるが、3.0×10-6~500×10-6/%RHが好ましく、4.0×10-6~100×10-6/%RHがより好ましく、5.0×10-6~50×10-6/%RHが更に好ましく、5.0×10-6~40×10-6/%RHが最も好ましい。
なお、熱膨張係数は、ISO11359-2に準じて測定することができ、サンプルを室温から80℃まで昇温させた後、60℃から50℃に降温するときのフィルムの長さの傾きから算出することができる。
また、湿度膨張係数を測定する際には、弾性率が最大となる方向を長手方向として切り出した長さ25cm(測定方向)、幅5cmのフィルム試料を用意し、該試料に20cmの間隔でピン孔を空け、25℃、相対湿度10%にて24時間調湿後、ピン孔の間隔をピンゲージで測長する(測定値をL0とする)。次いで、試料を25℃、相対湿度80%にて24時間調湿後、ピン孔の間隔をピンゲージで測長する(測定値をL1とする)。これらの測定値を用いて下記式により湿度膨張係数を算出する。
湿度膨張係数[/%RH]={(L1-L0)/L0}/(R1-R0)
前記ポリマーフィルムの弾性率は特に限定されないが、1~50GPaが好ましく、5~50GPaがより好ましく、7~20GPaが更に好ましい。弾性率はポリマーの種類、添加剤の種類及び量、延伸によって制御することができる。
なお、弾性率は、長さ150mm、巾10mmのフィルム試料を用意し、25℃、相対湿度60%にて24時間調湿後、ISO527-3:1995の規格に準じ、初期試料長100mm、引張速度10mm/minにて測定し、応力-歪み曲線の初期の傾きから求めた引張り弾性率である。フィルム試料の長さ方向と幅方向の取り方によって一般に弾性率は異なるが、本発明では弾性率が最大となる方向でフィルム試料を用意して測定した値を本発明の弾性率として表記する。なお、音速が最大となる方向における弾性率をE1、それと直交する方向における弾性率をE2としたとき、それらの比(E1/E2)は、フィルムのしなやかさを保ちつつも寸法変化を小さくする観点から、1.1~5.0であることが好ましく、1.5~3.0であることがより好ましい。
なお、本発明において音速(音波伝播速度)が最大となる方向は、フィルムを25℃、相対湿度60%にて24時間調湿後、配向性測定機(SST-2500:野村商事(株)製)を用いて、超音波パルスの縦波振動の伝搬速度が最大となる方向として求めた。
本発明において、サンプルを25℃、相対湿度60%にて24時間調湿後、ヘイズメーター(NDH 2000:日本電色工業(株)製)を用いて測定した値を全光透過率、及びヘイズとした。
前記ポリマーフィルムの全光透過率は、光源からの光を効率的に使用して、パネルの消費電力を低減する観点から、高いほうが好ましく、具体的には85%以上であることが好ましく、90%以上であることがより好ましく、92%以上であることが更に好ましい。また、本発明のフィルムのヘイズは、5%以下であることが好ましく、3%以下であることがより好ましく、2%以下であることが更に好ましく、1%以下であることが更にまた好ましく、0.5%以下であることが特に好ましい。
本発明において、引裂き強度(エルメンドルフ引裂き法)は、フィルムの遅相軸と平行な方向、及び直交する方向を長手方向として、それぞれ64mm×50mmの試料を切り出し、25℃、相対湿度60%にて2時間調湿後、軽荷重引裂き強度試験機を用いて測定し、小さい方の値をフィルムの引裂き強度とした。
前記ポリマーフィルムの引裂き強度は、フィルムの脆さの観点から、3~50gであることが好ましく、5~40gであることがより好ましく、10~30gであることが更に好ましい。
前記ポリマーフィルムの厚さは、製造コストを下げる観点から、10~1000μmであることが好ましく、40~500μmであることがより好ましく、40~200μmであることが特に好ましい。
本発明は、本発明の光学フィルムを有する偏光板にも関する。本発明の偏光板の一態様は、本発明の光学フィルムと、偏光膜とを含み、前記光学異方性層の第1及び第2の位相差領域のそれぞれの面内遅相軸方向と、偏光膜の吸収軸方向とが45°であることを特徴とする偏光板である。本発明の偏光板は、立体画像表示用の画像表示装置の視認側偏光板として、光学フィルムを視認側に向けて配置される。
本発明の偏光板は、液晶表示装置にそのまま組み込むことが可能な大きさに切断されたフィルム片の態様の偏光板のみならず、帯状、すなわち、連続生産により、長尺状に作製され、ロール状に巻き上げられた態様(例えば、ロール長2500m以上や3900m以上の態様)の偏光板も含まれる。大画面液晶表示装置用とするためには、上記した通り、偏光板の幅は1470mm以上とすることが好ましい。
本発明の偏光板の製造方法の一例は、
透明支持体であるセルロースアシレートフィルム等の長尺のポリマーフィルムを搬送しつつ、その上に、ラビング配向膜を連続的に形成すること、
ラビング配向膜を、フィルム搬送方向に対して約斜め45度方向に連続的にラビング処理すること、
少なくとも重合性基を有する液晶化合物を含有する組成物を、ラビング処理面に塗布すること、
温度T1℃で加熱して、液晶の遅相軸がラビング方向と直交した直交配向状態にすること、
ストライプ状のフォトマスクを遮光部/透過部の境界線がフィルム搬送方向と平行になるように配置してマスク下で紫外線露光して、直交配向状態を固定して、第1の位相差領域を形成する工程と、
温度T2℃(但しT1<T2)で加熱して、液晶の遅相軸がラビング方向と平行になる平行配向状態にすること、
全面露光して、平行配向状態を固定し、第2の位相差領域を形成すること、
透過軸が幅方向にある長尺の偏光膜と、ロール・トゥ・ロールで積層すること、
を含む方法により製造することができる。
この本発明の偏光板の製造方法は、連続生産できる観点から、従来の製造方法よりも製造コストが低い。また、ラビング方向がフィルム搬送方向に対して約斜め45度方向であると、得られたロール状の偏光板をななめに打ち抜く必要がなく、偏光板製造時の製造コストも低下させることができる。
偏光膜は、一般的な偏光膜を用いることができる。例えば、ヨウ素や二色性色素によって染色されたポリビニルアルコールフィルム等からなる偏光子膜を用いることができる。
本発明の偏光板は、光学フィルムと偏光膜との間には、粘着層が配置されていてもよい。光学フィルムと偏光膜との積層のために用いられる粘着層とは、例えば、動的粘弾性測定装置で測定したG’とG”との比(tanδ=G”/G’)が0.001~1.5である物質のことを表し、いわゆる、粘着剤やクリープしやすい物質等が含まれる。粘着剤については特に制限はなく、例えば、ポリビニルアルコール系粘着剤を用いることができる。
偏光板の、液晶セルと反対側に配置される側の表面には、反射防止層などの機能性膜を設けることが好ましい。特に、本発明では透明保護膜上に少なくとも光散乱層と低屈折率層がこの順で積層した反射防止層又は透明保護膜上に中屈折率層、高屈折率層、低屈折率層がこの順で積層した反射防止層が好適に用いられる。これは、特に3D画像を表示する場合に、外光反射によるフリッカが発生してしまうのを効果的に防ぐことができるからである。
以下にそれらの好ましい例を記載する。
光散乱層にはマット粒子が分散しており、光散乱層のマット粒子以外の部分の素材の屈折率は1.50~2.00の範囲にあることが好ましく、低屈折率層の屈折率は1.35~1.49の範囲にあることが好ましい。光散乱層は、防眩性とハードコート性を兼ね備えており、1層でもよいし、複数層、例えば2層~4層で構成されていてもよい。
また、C光源下での反射光の色味がa*値-2~2、b*値-3~3、380nm~780nmの範囲内での反射率の最小値と最大値の比0.5~0.99であることで、反射光の色味がニュートラルとなり、好ましい。またC光源下での透過光のb*値が0~3とすることで、表示装置に適用した際の白表示の黄色味が低減され、好ましい。
また、面光源上と反射防止層との間に120μm×40μmの格子を挿入して、フィルム上で輝度分布を測定した際の輝度分布の標準偏差が20以下であると、高精細パネルに本発明のフィルムを適用したときのギラツキが低減され、好ましい。
数式(IX):(mλ/4)×0.7<n1d1<(mλ/4)×1.3
式中、mは正の奇数であり、n1は低屈折率層の屈折率であり、そして、d1は低屈折率層の膜厚(nm)である。また、λは波長であり、500~550nmの範囲の値である。
従って、エチレン性不飽和基を有するモノマー、光ラジカル開始剤あるいは熱ラジカル開始剤、マット粒子及び無機フィラーを含有する塗液を調製し、該塗液を透明支持体上に塗布後電離放射線又は熱による重合反応により硬化して反射防止膜を形成することができる。これらの光ラジカル開始剤等は公知のものを使用することができる。
従って、多官能エポシキシ化合物、光酸発生剤あるいは熱酸発生剤、マット粒子及び無機フィラーを含有する塗液を調製し、該塗液を透明支持体上に塗布後電離放射線又は熱による重合反応により硬化して反射防止膜を形成することができる。
架橋性官能基の例には、イソシアナート基、エポキシ基、アジリジン基、オキサゾリン基、アルデヒド基、カルボニル基、ヒドラジン基、カルボキシル基、メチロール基及び活性メチレン基が含まれる。ビニルスルホン酸、酸無水物、シアノアクリレート誘導体、メラミン、エーテル化メチロール、エステル及びウレタン、テトラメトキシシランのような金属アルコキシドも、架橋構造を導入するためのモノマーとして利用できる。ブロックイソシアナート基のように、分解反応の結果として架橋性を示す官能基を用いてもよい。すなわち、本発明において架橋性官能基は、すぐには反応を示すものではなくとも、分解した結果反応性を示すものであってもよい。
これら架橋性官能基を有するバインダーポリマーは塗布後、加熱することによって架橋構造を形成することができる。
上記マット粒子の具体例としては、例えばシリカ粒子、TiO2粒子等の無機化合物の粒子;アクリル粒子、架橋アクリル粒子、ポリスチレン粒子、架橋スチレン粒子、メラミン樹脂粒子、ベンゾグアナミン樹脂粒子等の樹脂粒子が好ましく挙げられる。なかでも架橋スチレン粒子、架橋アクリル粒子、架橋アクリルスチレン粒子、シリカ粒子が好ましい。マット粒子の形状は、球状あるいは不定形のいずれも使用できる。
マット粒子の粒度分布はコールターカウンター法により測定し、測定された分布を粒子数分布に換算する。
また逆に、マット粒子との屈折率差を大きくするために、高屈折率マット粒子を用いた光散乱層では層の屈折率を低目に保つためにケイ素の酸化物を用いることも好ましい。好ましい粒径は前述の無機フィラーと同じである。
光散乱層に用いられる無機フィラーの具体例としては、TiO2、ZrO2、Al2O3、In2O3、ZnO、SnO2、Sb2O3、ITOとSiO2等が挙げられる。TiO2及びZrO2が高屈折率化の点で特に好ましい。該無機フィラーは表面をシランカップリング処理又はチタンカップリング処理されることも好ましく、フィラー表面にバインダー種と反応できる官能基を有する表面処理剤が好ましく用いられる。
これらの無機フィラーの添加量は、光散乱層の全質量の10%~90%であることが好ましく、より好ましくは20%~80%であり、特に好ましくは30%~75%である。
なお、このようなフィラーは、粒径が光の波長よりも十分小さいために散乱が生じず、バインダーポリマーに該フィラーが分散した分散体は光学的に均一な物質として振舞う。
透明保護膜上に少なくとも中屈折率層、高屈折率層、低屈折率層(最外層)の順序の層構成から成る反射防止膜は、以下の関係を満足する屈折率を有する様に設計される。
高屈折率層の屈折率>中屈折率層の屈折率>透明支持体の屈折率>低屈折率層の屈折率
また、透明保護膜と中屈折率層の間に、ハードコート層を設けてもよい。更には、中屈折率ハードコート層、高屈折率層及び低屈折率層からなってもよい(例えば、特開平8-122504号公報、同8-110401号公報、同10-300902号公報、特開2002-243906号公報、特開2000-111706号公報等参照)。また、各層に他の機能を付与させてもよく、例えば、防汚性の低屈折率層、帯電防止性の高屈折率層としたもの(例、特開平10-206603号公報、特開2002-243906号公報等)等が挙げられる。
反射防止膜の強度は、JIS K5400に従う鉛筆硬度試験でH以上であることが好ましく、2H以上であることが更に好ましく、3H以上であることが最も好ましい。
反射防止膜の高い屈折率を有する層は、平均粒径100nm以下の高屈折率の無機化合物超微粒子及びマトリックスバインダーを少なくとも含有する硬化性膜から成る。
高屈折率の無機化合物微粒子としては、屈折率1.65以上の無機化合物が挙げられ、好ましくは屈折率1.9以上のものが挙げられる。例えば、Ti、Zn、Sb、Sn、Zr、Ce、Ta、La、In等の酸化物、これらの金属原子を含む複合酸化物等が挙げられる。
このような超微粒子とするには、粒子表面が表面処理剤で処理されること(例えば、シランカップリング剤等:特開平11-295503号公報、同11-153703号公報、特開2000-9908、アニオン性化合物或は有機金属カップリング剤:特開2001-310432号公報等)、高屈折率粒子をコアとしたコアシェル構造とすること(:特開2001-1661042001-310432号公報等)、特定の分散剤併用(例、特開平11-153703号公報、米国特許第6210858号明細書、特開2002-2776069号公報等)等挙げられる。
更に、ラジカル重合性及び/又はカチオン重合性の重合性基を少なくとも2個有する多官能性化合物含有組成物と、加水分解性基を有する有機金属化合物及びその部分縮合体を含有する組成物とから選ばれる少なくとも1種の組成物が好ましい。例えば、特開2000-47004号公報、同2001-315242号公報、同2001-31871号公報、同2001-296401号公報等に記載の組成物が挙げられる。また、金属アルコキドの加水分解縮合物から得られるコロイド状金属酸化物と金属アルコキシド組成物から得られる硬化性膜も好ましい。例えば、特開2001-293818号公報等に記載されている。
中屈折率層の屈折率は、低屈折率層の屈折率と高屈折率層の屈折率との間の値となるように調整する。中屈折率層の屈折率は、1.50~1.70であることが好ましい。また、厚さは5nm~10mμmであることが好ましく、10nm~1μmであることが更に好ましい。
耐擦傷性、防汚性を有する最外層として構築することが好ましい。耐擦傷性を大きく向上させる手段として表面への滑り性付与が有効で、従来公知のシリコーンの導入、フッ素の導入等から成る薄膜層の手段を適用できる。
含フッ素化合物の屈折率は1.35~1.50であることが好ましい。より好ましくは1.36~1.47である。また、含フッ素化合物はフッ素原子を35質量%~80質量%の範囲で含む架橋性若しくは重合性の官能基を含む化合物が好ましい。
例えば、特開平9-222503号公報明細書段落番号[0018]~[0026]、同11-38202号公報明細書段落番号[0019]~[0030]、特開2001-40284号公報明細書段落番号[0027]~[0028]、特開2000-284102号公報等に記載の化合物が挙げられる。
シリコーン化合物としてはポリシロキサン構造を有する化合物であり、高分子鎖中に硬化性官能基あるいは重合性官能基を含有して、膜中で橋かけ構造を有するものが好ましい。例えば、反応性シリコーン(例、サイラプレーン(チッソ(株)製等)、両末端にシラノール基含有のポリシロキサン(特開平11-258403号公報等)等が挙げられる。
また、シランカップリング剤等の有機金属化合物と特定のフッ素含有炭化水素基含有のシランカップリング剤とを触媒共存下に縮合反応で硬化するゾルゲル硬化膜も好ましい。
例えば、ポリフルオロアルキル基含有シラン化合物又はその部分加水分解縮合物(特開昭58-142958号公報、同58-147483号公報、同58-147484号公報、特開平9-157582号公報、同11-106704号公報記載等記載の化合物)、フッ素含有長鎖基であるポリ「パーフルオロアルキルエーテル」基を含有するシリル化合物(特開2000-117902号公報、同2001-48590号公報、同2002-53804号公報記載の化合物等)等が挙げられる。
低屈折率層が最外層の下層に位置する場合、低屈折率層は気相法(真空蒸着法、スパッタリング法、イオンプレーティング法、プラズマCVD法等)により形成されても良い。安価に製造できる点で、塗布法が好ましい。
低屈折率層の膜厚は、30nm~200nmであることが好ましく、50nm~150nmであることが更に好ましく、60nm~120nmであることが最も好ましい。
本発明は、本発明の光学フィルムを有する画像表示装置及び立体画像表示システムにも関する。本発明の画像表示装置の一例は、
第1及び第2の偏光膜;
第1及び第2の偏光膜の間に配置される、少なくとも一方に電極を有し対向配置された一対の基板と、該一対の基板間の液晶層とを含む液晶セル;及び
第1偏光膜の外側に本発明の光学フィルム;を少なくとも有する画像表示装置であって、
前記第1偏光膜の吸収軸方向と、前記光学フィルムの第1及び第2位相差領域の面内遅相軸がそれぞれ±45°の角度をなすことを特徴とする画像表示装置である。
また、本発明の立体画像表示システムの一例は、前記画像表示装置と、前記光学フィルムの外側に配置される第3の偏光板とを少なくとも備え、第3の偏光板を通じて立体画像を視認させる立体画像表示システムである。
本発明の立体画像表示システムでは、特に3D映像とよばれる立体画像を視認者に認識させるため、眼鏡形状の偏光板(第3の偏光板)を通して画像を認識する。
[偏光眼鏡]
本発明の映像表示システムは、右眼鏡と左眼鏡の遅相軸が直交する偏光眼鏡を含み、前記光学フィルムの前記第1及び第2の位相差領域のいずれか一方から出射された右眼用画像光が右眼鏡を透過し、且つ左眼鏡で遮光され;前記第1及び第2の位相差領域の他方から出射された左眼用画像光が左眼鏡を透過し、且つ右眼鏡で遮光されるように構成されていることが好ましい。
前記偏光眼鏡は、位相差機能層と直線偏光子を含むことで偏光眼鏡を形成している。なお、直線偏光子と同等の機能を有するその他の部材を用いてもよい。
更に、一度前記パターニング位相差フィルムにおいて円偏光として画像光を出射し、偏光眼鏡により偏光状態を元に戻す観点からは、上記の例の場合の右眼鏡の固定する遅相軸の角度は正確に水平方向45度に近いほど好ましい。また、左眼鏡の固定する遅相軸の角度は正確に水平135度(又は-45度)に近いほど好ましい。
また、前記液晶表示パネルのフロント側偏光板の吸収軸方向と、前記パターニング位相差フィルムの奇数ライン位相差領域と偶数ライン位相差領域の各遅相軸は、偏光変換の効率上、45度をなすことが好ましい。
なお、このような偏光眼鏡と、パターニング位相差フィルム及び液晶表示装置の好ましい配置については、例えば特開2004-170693号公報に開示がある。
[ラビング配向膜付透明支持体の作製]
透明ガラス支持体の表面に、クラレ社製ポリビニルアルコール「PVA103」の4%水溶液を、12番バーで塗布を行い、80℃で5分間乾燥させた。その後に、400rpmで一方向に3往復、ラビング処理を行い、ラビング配向膜付ガラス支持体を作製した。なお、ガラス支持体のRe(550)は0nmであり、Rthは0nmであり、配向膜の膜厚は、0.9μmであった。
下記の光学異方性層用組成物を調製後、孔径0.2μmのポリプロピレン製フィルタでろ過して、光学異方性層用塗布液として用いる。該塗布液を塗布、膜面温度80℃で1分間乾燥して液晶相状態とし均一配向させた後、室温まで冷却した。次に、100μm角の格子マスクを光学異方性層用塗布液を塗布した基板上に配置し、空気下にて20mW/cm2の空冷メタルハライドランプ(アイグラフィックス(株)製)を用いて紫外線を5秒間照射して、その配向状態を固定化することにより第1の位相差領域を形成した。続いて、膜面温度140℃まで昇温し、一旦等方相にした後、100℃まで降温し、その温度で1分間加熱して均一配向させた。室温まで冷却した後、20mW/cm2で20秒間全面照射して、その配向状態を固定化することにより第2の位相差領域を形成した。第1の位相差領域と第2の位相差領域の遅相軸は直交しており、膜厚は、0.8μmであった。
ディスコティック液晶E-1 100質量部
配向膜界面配向剤(II-1) 1.0質量部
空気界面配向剤(P-1) 0.4質量部
光重合開始剤 3.0質量部
(イルガキュア907、チバ・スペシャルティ・ケミカルズ(株)製)
増感剤(カヤキュア-DETX、日本化薬(株)製) 1.0質量部
メチルエチルケトン 300質量部
作製した光学フィルムについて、KOBRA-21ADH(王子計測器(株)製)を用いて前記方法に従って、配向膜界面のディスコティック液晶のチルト角、空気界面のディスコティック液晶のチルト角、及びRe、Rthをそれぞれ測定した。結果を表1に示す。下記表中、垂直とは、チルト角70°~90°を表す。また、光学フィルムについて、KOBRA-21ADH(王子計測器(株)製)を用いて、前記方法に従って、光学異方性層の遅相軸の方向を決定した。表1に、光学異方性層の遅相軸と配向膜のラビング方向の方向との関係を示す。
光学異方性層塗布液を下記組成に変更した以外、実施例1と同様の操作にてパターン化された光学異方性層付光学フィルムの作製を試みた。光学異方性層の膜厚は、0.8μmであった。
<光学異方性層用組成>
ディスコティック液晶E-2 100質量部
配向膜界面配向剤(II-1) 1.0質量部
空気界面配向剤(P-2) 0.3質量部
光重合開始剤 3.0質量部
(イルガキュア907、チバ・スペシャルティ・ケミカルズ(株)製)
増感剤(カヤキュア-DETX、日本化薬(株)製) 1.0質量部
メチルエチルケトン 300質量部
作製した光学フィルムについて、実施例1と同様にして、光学異方性層の遅相軸の方向を決定した。表1に、光学異方性層の遅相軸と配向膜のラビング方向の方向との関係を示す。表1に示す結果から、ディスコティック液晶を、ピリジニウム塩化合物、及びフルオロ脂肪族基含有共重合体の存在下で、一方向にラビング処理したPVA系ラビング配向膜上で配向させ、加熱温度を変化させて露光することによって、垂直配向であるとともに、遅相軸が直交した第1の位相差領域と第2の位相差領域を有するパターン化された光学異方性層が得られることが理解できる。
[ラビング配向膜付透明支持体の作製]
(透明支持体の作製)
下記の組成物をミキシングタンクに投入し、加熱しながら攪拌して、各成分を溶解し、セルロースアシレート溶液Aを調製した。
<セルロースアシレート溶液A組成>
置換度2.86のセルロースアセテート 100質量部
トリフェニルホスフェート(可塑剤) 7.8質量部
ビフェニルジフェニルホスフェート(可塑剤) 3.9質量部
メチレンクロライド(第1溶媒) 300質量部
メタノール(第2溶媒) 54質量部
1-ブタノール 11質量部
<添加剤溶液B組成>
下記化合物B1(Re低下剤) 40質量部
下記化合物B2(波長分散制御剤) 4質量部
メチレンクロライド(第1溶媒) 80質量部
メタノール(第2溶媒) 20質量部
セルロースアシレート溶液Aを477質量部に、添加剤溶液Bの40質量部を添加し、充分に攪拌して、ドープを調製した。ドープを流延口から0℃に冷却したドラム上に流延した。溶媒含有率70質量%の場外で剥ぎ取り、フィルムの巾方向の両端をピンテンター(特開平4-1009号の図3に記載のピンテンター)で固定し、溶媒含有率が3乃至5質量%の状態で、横方向(機械方向に垂直な方向)の延伸率が3%となる間隔を保ちつつ乾燥した。その後、熱処理装置のロール間を搬送することにより、さらに乾燥し、厚み60μmのセルロースアセテート保護フィルムを作製した。透明支持体のRe(550)は2.0nmであり、Rthは12.3nmであった。
セルロースアセテート透明支持体を、温度60℃の誘電式加熱ロールを通過させ、フィルム表面温度を40℃に昇温した後に、フィルムの片面に下記に示す組成のアルカリ溶液を、バーコーターを用いて塗布量14ml/m2で塗布し、110℃に加熱した(株)ノリタケカンパニーリミテド製のスチーム式遠赤外ヒーターの下に、10秒間搬送した。続いて、同じくバーコーターを用いて、純水を3ml/m2塗布した。次いで、ファウンテンコーターによる水洗とエアナイフによる水切りを3回繰り返した後に、70℃の乾燥ゾーンに10秒間搬送して乾燥し、アルカリ鹸化処理したセルロースアセテート透明支持体を作製した。
─────────────────────────────────
アルカリ溶液組成(質量部)
─────────────────────────────────
水酸化カリウム 4.7質量部
水 15.8質量部
イソプロパノール 63.7質量部
界面活性剤
SF-1:C14H29O(CH2CH2O)20H 1.0質量部
プロピレングリコール 14.8質量部
─────────────────────────────────
上記作製した支持体の、鹸化処理を施した面に、下記の組成のラビング配向膜塗布液を#14のワイヤーバーで連続的に塗布した。60℃の温風で60秒、さらに100℃の温風で120秒乾燥し、配向膜を形成した。配向膜の膜厚は0.9μmであった。
<配向膜形成用塗布液の組成>
下記の変性ポリビニルアルコールPVA-1 10質量部
水 371質量部
メタノール 119質量部
グルタルアルデヒド 0.5質量部
下記組成の光学異方性層用塗布液を、バーコーターを用いて塗布量4ml/m2で塗布した。膜面温度80℃で1分間乾燥して液晶相状態とし均一配向させた後、室温まで冷却した。次に、ストライプマスクを光学異方性層用塗布液を塗布した基板上に配置し、空気下にて20mW/cm2の空冷メタルハライドランプ(アイグラフィックス(株)製)を用いて紫外線を5秒間照射して、その配向状態を固定化することにより第1の位相差領域を形成した。続いて、膜面温度115℃まで昇温し、一旦等方相にした後、100℃まで降温し、その温度で1分間加熱して均一配向させた。室温まで冷却した後、20mW/cm2で20秒間全面照射して、その配向状態を固定化することにより第2の位相差領域を形成した。最後に、円筒状に巻き取ってロール状の光学フィルムを得た。第1の位相差領域と第2の位相差領域の遅相軸は直交しており、膜厚は、0.9μmであった。
──────────────────────────────────
光学異方性層塗布液組成(質量部)
──────────────────────────────────
前記ディスコティック液晶E-1 100.0質量部
前記配向膜界面配向剤(II-1) 1.0質量部
下記空気界面配向剤(P-2) 0.4質量部
エチレンオキサイド変性トリメチロールプロパントリアクリレート
(V#360、大阪有機化学(株)製) 10.0質量部
光重合開始剤(イルガキュアー907、チバガイギー社製)3.0質量部
増感剤(カヤキュアDETX、日本化薬(株)製) 1.0質量部
メチルエチルケトン 300.0質量部
──────────────────────────────────
作製した光学フィルムについて、KOBRA-21ADH(王子計測器(株)製)を用いて前記方法に従って、配向膜界面のディスコティック液晶のチルト角、空気界面のディスコティック液晶のチルト角、及びRe、Rthをそれぞれ測定した。結果を表1に示す。下記表中、垂直とは、チルト角70°~90°を表す。また、光学フィルムについて、KOBRA-21ADH(王子計測器(株)製)を用いて、前記方法に従って、光学異方性層の遅相軸の方向を決定した。表1に、光学異方性層の遅相軸と配向膜のラビング方向の方向との関係を示す。
[光学フィルムの作製]
100μm周期のストライプマスクを用いる以外、実施例3と同様の操作にてパターン化された光学異方性層付光学フィルムを作製した。
(ハードコート層用塗布液の調製)
下記組成物をミキシングタンクに投入し、攪拌してハードコート層塗布液とした。
メチルエチルケトン900質量部に対して、シクロヘキサノン100質量部、部分カプロラクトン変性の多官能アクリレート(DPCA-20、日本化薬(株)製)750質量部、シリカゾル(MIBK-ST、日産化学工業(株)製)200質量部、光重合開始剤(イルガキュア184、チバ・スペシャルティ・ケミカルズ(株)製)50質量部、を添加して攪拌した。孔径0.4μmのポリプロピレン製フィルターで濾過してハードコート層用の塗布液を調製した。
ZrO2微粒子含有ハードコート剤(デソライトZ7404[屈折率1.72、固形分濃度:60質量%、酸化ジルコニウム微粒子含量:70質量%(対固形分)、酸化ジルコニウム微粒子の平均粒子径:約20nm、溶剤組成:メチルイソブチルケトン/メチルエチルケトン=9/1、JSR(株)製])5.1質量部に、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物(DPHA)1.5質量部、光重合開始剤(イルガキュア907、チバ・スペシャルティ・ケミカルズ(株)製)0.05質量部、メチルエチルケトン66.6質量部、メチルイソブチルケトン7.7質量部及びシクロヘキサノン19.1質量部を添加して攪拌した。充分に攪拌の後、孔径0.4μmのポリプロピレン製フィルターで濾過して中屈折率層用塗布液Aを調製した。
ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物(DPHA)4.5質量部、光重合開始剤(イルガキュア907、チバ・スペシャルティ・ケミカルズ(株)製)0.14質量部、メチルエチルケトン66.5質量部、メチルイソブチルケトン9.5質量部及びシクロヘキサノン19.0質量部を添加して攪拌した。十分に攪拌ののち、孔径0.4μmのポリプロピレン製フィルターで濾過して中屈折率層用塗布液Bを調製した。
ZrO2微粒子含有ハードコート剤(デソライトZ7404[屈折率1.72、固形分濃度:60質量%、酸化ジルコニウム微粒子含量:70質量%(対固形分)、酸化ジルコニウム微粒子の平均粒子径:約20nm、光重合開始剤含有、溶剤組成:メチルイソブチルケトン/メチルエチルケトン=9/1、JSR(株)製])14.4質量部に、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物(DPHA)0.75質量部、メチルエチルケトン62.0質量部、メチルイソブチルケトン3.4質量部、シクロヘキサノン1.1質量部を添加して攪拌した。充分に攪拌の後、孔径0.4μmのポリプロピレン製フィルターで濾過して高屈折率層用塗布液Cを調製した。
(パーフルオロオレフィン共重合体(1)の合成)
中空シリカ粒子微粒子ゾル(イソプロピルアルコールシリカゾル、触媒化成工業(株)製CS60-IPA、平均粒子径60nm、シエル厚み10nm、シリカ濃度20質量%、シリカ粒子の屈折率1.31)500質量部に、アクリロイルオキシプロピルトリメトキシシラン30質量部、及びジイソプロポキシアルミニウムエチルアセテート1.51質量部加え混合した後に、イオン交換水9質量部を加えた。60℃で8時間反応させた後に室温まで冷却し、アセチルアセトン1.8質量部を添加し、分散液を得た。その後、シリカの含率がほぼ一定になるようにシクロヘキサノンを添加しながら、圧力30Torrで減圧蒸留による溶媒置換を行い、最後に濃度調整により固形分濃度18.2質量%の分散液Aを得た。得られた分散液AのIPA残存量をガスクロマトグラフィーで分析したところ0.5質量%以下であった。
各成分を下記のように混合し、メチルエチルケトンに溶解して固形分濃度5質量%の低屈折率層用塗布液Ln6を作製した。下記各成分の質量%は、塗布液の全固形分に対する、各成分の固形分の比率である。
・DPHA:ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物(日本化薬(株)製):7質量%
・MF1:国際公開第2003/022906号パンフレットの実施例記載の下記含フッ素不飽和化合物(重量平均分子量1600):5質量%
・分散液A:前記中空シリカ粒子分散液A(アクリロイルオキシプロピルトリメトキシシランで表面修飾した中空シリカ粒子ゾル、固形分濃度18.2%):50質量%
・Irg127:光重合開始剤イルガキュア127(チバ・スペシャルティ・ケミカルズ(株)製):3質量%
更に中屈折率層用塗布液、高屈折率層用塗布液、低屈折率層用塗布液をグラビアコーターを用いて塗布した。 中屈折率層の乾燥条件は90℃、30秒とし、紫外線硬化条件は酸素濃度が1.0体積%以下の雰囲気になるように窒素パージしながら180W/cmの空冷メタルハライドランプ(アイグラフィックス(株)製)を用いて、照度300mW/cm2、照射量240mJ/cm2の照射量とした。
高屈折率層の乾燥条件は90℃、30秒とし、紫外線硬化条件は酸素濃度が1.0体積%以下の雰囲気になるように窒素パージしながら240W/cmの空冷メタルハライドランプ(アイグラフィックス(株)製)を用いて、照度300mW/cm2、照射量240mJ/cm2の照射量とした。
低屈折率層の乾燥条件は90℃、30秒とし、紫外線硬化条件は酸素濃度が0.1体積%以下の雰囲気になるように窒素パージしながら240W/cmの空冷メタルハライドランプ(アイグラフィックス(株)製)を用いて、照度600mW/cm2、照射量600mJ/cm2の照射量とした。
上記にて作製したフィルムに、下記の粘着剤塗布液及び上層塗布液Bを、透明支持体側にそれぞれ20ml/m2塗布し、100℃で5分乾燥して粘着剤付きフィルム試料とした。
(粘着剤塗布液)
下記水溶性ポリマー(m) 0.5g
アセトン 40ml
酢酸エチル 55ml
イソプロパノール 5ml
ポリビニルアルコール(日本合成化学工業株式会社製ゴーセノールNH-26) 0.3g
サポニン(メルク社製界面活性剤) 0.03g
純水 57ml
メタノール 40ml
メチルプロピレングリコール 3ml
円偏光眼鏡方式の3Dモニター(ZALMAN製)に使用されているパターン位相差板とフロント偏光板をはがし、上記で作製した偏光板を貼合した。
作製した3Dモニターに立体視用画像を映し、右眼用/左眼用の円偏光メガネを通して観察したところ、クロストークのない鮮明な立体画像を観察することができた。
[光学フィルムの作製]
セルロースアセテート透明支持体作製時の添加剤溶液Bから添加剤B1(Re低下剤)及び添加剤B2(波長分散制御剤)を除いた以外は、実施例4と同様に光学フィルムを作製した。このときのセルロースアセテート透明支持体の厚みは200μmであり、550nmにおけるReは15nmであり、Rthは102nmであった。
実施例4と同様の方法にて偏光板を作製し、円偏光眼鏡方式の3Dモニター(ZALMAN製)に使用されているパターン位相差板とフロント偏光板をはがし、前記偏光板を貼合した。
作製した3Dモニターに立体視用画像を映し、右眼用/左眼用の円偏光メガネを通して観察したところ、立体画像として観察することはできたが、若干のクロストークが認識された。
光学異方性層塗布液を下記組成に変更した以外、実施例1と同様の操作にてパターン化された光学異方性層付光学フィルムの作製を試みた。光学異方性層の膜厚は、0.8μmであった。
<光学異方性層用組成>
ディスコティック液晶E-3 100質量部
配向膜界面配向剤(II-1) 1.0質量部
空気界面配向剤(P-2) 0.3質量部
光重合開始剤 3.0質量部
(イルガキュア907、チバ・スペシャルティ・ケミカルズ(株)製)
増感剤(カヤキュア-DETX、日本化薬(株)製) 1.0質量部
エチレンオキサイド変性トリメチロールプロパントリアクリレート
(V#360、大阪有機化学(株)製) 9.9質量部
メチルエチルケトン 300質量部
作製した光学フィルムについて、実施例1と同様にして、光学異方性層の遅相軸の方向を決定した。表1に、光学異方性層の遅相軸と配向膜のラビング方向の方向との関係を示す。表1に示す結果から、ディスコティック液晶を、ピリジニウム塩化合物、及びフルオロ脂肪族基含有共重合体の存在下で、一方向にラビング処理したPVA系ラビング配向膜上で配向させ、加熱温度を変化させて露光することによって、垂直配向であるとともに、遅相軸が直交した第1の位相差領域と第2の位相差領域を有するパターン化された光学異方性層が得られることが理解できる。
光学異方性層塗布液を下記組成に変更した以外、実施例1と同様の操作にてパターン化された光学異方性層付光学フィルムの作製を試みた。光学異方性層の膜厚は、0.8μmであった。
<光学異方性層用組成>
ディスコティック液晶E-2 100質量部
配向膜界面配向剤(II-2) 1.0質量部
空気界面配向剤(P-2) 0.3質量部
光重合開始剤 3.0質量部
(イルガキュア907、チバ・スペシャルティ・ケミカルズ(株)製)
増感剤(カヤキュア-DETX、日本化薬(株)製) 1.0質量部
メチルエチルケトン 300質量部
作製した光学フィルムについて、実施例1と同様にして、光学異方性層の遅相軸の方向を決定した。表1に、光学異方性層の遅相軸と配向膜のラビング方向の方向との関係を示す。表1に示す結果から、ディスコティック液晶を、イミダゾリウム塩化合物、及びフルオロ脂肪族基含有共重合体の存在下で、一方向にラビング処理したPVA系ラビング配向膜上で配向させ、加熱温度を変化させて露光することによって、垂直配向であるとともに、遅相軸が直交した第1の位相差領域と第2の位相差領域を有するパターン化された光学異方性層が得られることが理解できる。
[光学フィルムの作製]
光学異方性層の作製方法を下記作製方法に変更した以外、実施例3と同様の操作にて光学フィルムを作製した。配向膜の膜厚は、0.9μmであり、光学異方性層の膜厚は、0.9μmであった。
実施例3の光学異方性層用塗布液を、バーコーターを用いて塗布量4ml/m2で塗布した。膜面温度80℃で1分間乾燥して液晶相状態とし均一配向させた後、室温まで冷却した。空気下にて20mW/cm2の空冷メタルハライドランプ(アイグラフィックス(株)製)を用いて紫外線を25秒間全面照射して、その配向状態を固定化することにより光学異方性層を形成した。
作製した光学フィルムについて、KOBRA-21ADH(王子計測器(株)製)を用いて前記方法に従って、配向膜界面のディスコティック液晶のチルト角、空気界面のディスコティック液晶のチルト角、及びRe、Rthをそれぞれ測定した。結果を表1に示す。下記表中、垂直とは、チルト角70°~90°を表す。また、光学フィルムについて、KOBRA-21ADH(王子計測器(株)製)を用いて、前記方法に従って、光学異方性層の遅相軸の方向を決定した。表1に、光学異方性層の遅相軸と配向膜のラビング方向の方向との関係を示す。
[光学フィルムの作製]
光学異方性層の作製方法を下記作製方法に変更した以外、実施例3と同様の操作にて光学フィルムを作製した。配向膜の膜厚は、0.9μmであり、光学異方性層の膜厚は、0.9μmであった。
実施例3の光学異方性層用塗布液を、バーコーターを用いて塗布量4ml/m2で塗布した。膜面温度115℃まで昇温し、一旦等方相にした後、100℃まで降温し、その温度で1分間加熱して均一配向させた。室温まで冷却した後、20mW/cm2で25秒間全面照射して、その配向状態を固定化することにより光学異方性層を形成した。
作製した光学フィルムについて、KOBRA-21ADH(王子計測器(株)製)を用いて前記方法に従って、配向膜界面のディスコティック液晶のチルト角、空気界面のディスコティック液晶のチルト角、及びRe、Rthをそれぞれ測定した。結果を表1に示す。下記表中、垂直とは、チルト角70°~90°を表す。また、光学フィルムについて、KOBRA-21ADH(王子計測器(株)製)を用いて、前記方法に従って、光学異方性層の遅相軸の方向を決定した。表1に、光学異方性層の遅相軸と配向膜のラビング方向の方向との関係を示す。
(液晶表示装置への実装評価)
比較例1で作製した偏光板に変更した以外は、実施例4と同様の方法にて3Dモニターを作製した。
作製した3Dモニターに立体視用画像を映し、右眼用/左眼用の円偏光メガネを通して観察したところ、クロストークが大きく立体画像として認識できなかった。
(液晶表示装置への実装評価)
比較例2で作製した偏光板に変更した以外は、実施例4と同様の方法にて3Dモニターを作製した。
作製した3Dモニターに立体視用画像を映し、右眼用/左眼用の円偏光メガネを通して観察したところ、クロストークが大きく立体画像として認識できなかった。
光学異方性層塗布液を下記組成に変更した以外、実施例1と同様の操作にてパターン化された光学異方性層付光学フィルムの作製を試みた。光学異方性層の膜厚は、0.8μmであった。
<光学異方性層用組成>
ディスコティック液晶E-4 100質量部
配向膜界面配向剤(II-1) 1.0質量部
空気界面配向剤(P-2) 0.3質量部
光重合開始剤 3.0質量部
(イルガキュア907、チバ・スペシャルティ・ケミカルズ(株)製)
増感剤(カヤキュア-DETX、日本化薬(株)製) 1.0質量部
エチレンオキサイド変性トリメチロールプロパントリアクリレート
(V#360、大阪有機化学(株)製) 9.9質量部
メチルエチルケトン 300質量部
作製した光学フィルムについて、実施例1と同様にして、光学異方性層の遅相軸の方向を決定した。側鎖円盤状コアとの間の連結基に-C=C-を含まないトリフェニレン系ディスコティック液晶E-4を用いると、直交配向状態になり難く、得られた光学フィルムは、実施例の光学フィルムと比較して、パターン形成性について劣っていた。
光学異方性層塗布液を下記組成に変更した以外、実施例1と同様の操作にてパターン化された光学異方性層付光学フィルムの作製を試みた。光学異方性層の膜厚は、0.8μmであった。
<光学異方性層用組成>
ディスコティック液晶E-1 100質量部
配向膜界面配向剤(II-3) 1.0質量部
空気界面配向剤(P-2) 0.3質量部
光重合開始剤 3.0質量部
(イルガキュア907、チバ・スペシャルティ・ケミカルズ(株)製)
増感剤(カヤキュア-DETX、日本化薬(株)製) 1.0質量部
メチルエチルケトン 300質量部
作製した光学フィルムについて、実施例1と同様にして、光学異方性層の遅相軸の方向を決定した。式(2)の範囲外のピリジニウム塩を用いると、直交配向状態になり難く、得られた光学フィルムは、実施例の光学フィルムと比較して、パターン形成性について劣っていた。
12 パターン光学異方性層
14 配向膜
16 透明支持体
20 偏光板
22 偏光膜
24 保護フィルム
Claims (17)
- 透明支持体上に、一方向に処理された配向膜と、重合性基を有する液晶を主成分とする一種の組成物から形成された光学異方性層とを少なくとも有する光学フィルムであって、
前記光学異方性層が、互いに直交する面内遅相軸を有する第1相差領域及び第2位相差領域を含み、前記第1及び第2位相差領域が、面内において交互に配置されているパターン光学異方性層である光学フィルム。 - 前記配向膜が、一方向にラビング処理されたラビング配向膜である請求項1に記載の光学フィルム。
- Re(550)が、110~165nmである請求項1又は2に記載の光学フィルム:
但し、Re(550)は波長550nmにおける面内レターデーション値(単位:nm)である。 - 前記透明支持体のRe(550)が、0~10nmである請求項1~3のいずれか1項に記載の光学フィルム。
- Rth(550)が、|Rth(550)|≦20を満足する請求項1~4のいずれか1項に記載の光学フィルム:
但し、Rth(550)は、波長550nmにおける膜厚方向のレターデーション値(単位:nm)である。 - 前記配向膜が、変性又は未変性ポリビニルアルコールを主成分として含有する膜である請求項1~5のいずれか1項に記載の光学フィルム。
- 前記重合性基を有する液晶が、円盤状液晶である請求項1~6のいずれか1項に記載の光学フィルム。
- 前記光学異方性層が、ピリジニウム化合物又はイミダゾリウム化合物の少なくとも1種をさらに含有する請求項1~7のいずれか1項に記載の光学フィルム。
- 前記光学異方性層が、下記一般式(2a)のピリジニウム化合物又は下記一般式(2b)のイミダゾリウム化合物をさらに含有する請求項1~8のいずれか1項に記載の光学フィルム:
- 前記光学異方性層が、フルオロ脂肪族基含有共重合体の少なくとも1種をさらに含有する請求項1~9のいずれか1項に記載の光学フィルム。
- 前記重合性基を有する液晶が円盤状液晶であり、前記光学異方性層中、円盤状液晶が垂直配向状態に固定されている請求項1~10のいずれか1項に記載の光学フィルム。
- 請求項1~11のいずれか1項に記載の光学フィルムと、偏光膜とを含み、前記光学異方性層の第1及び第2の位相差領域のそれぞれの面内遅相軸方向と、偏光膜の吸収軸方向とが45°である偏光板。
- 前記光学フィルムと、前記偏光膜とが粘着層を介して積層されている請求項12に記載の偏光板。
- さらに最表面に一層以上の反射防止フィルムが積層されている請求項12又は13に記載の偏光板。
- 第1及び第2の偏光膜;
第1及び第2の偏光膜の間に配置される、少なくとも一方に電極を有し対向配置された一対の基板と、該一対の基板間の液晶層とを含む液晶セル;及び
第1偏光膜の外側に請求項1~11のいずれか1項に記載の光学フィルム;
を少なくとも有する画像表示装置であって、
前記第1偏光膜の吸収軸方向と、前記光学フィルムの第1及び第2位相差領域の面内遅相軸がそれぞれ±45°の角度をなす画像表示装置。 - 請求項15に記載の画像表示装置と、前記光学フィルムの外側に配置される第3の偏光板とを少なくとも備え、第3の偏光板を通じて立体画像を視認させる立体画像表示システム。
- 請求項1~11のいずれか1項に記載の光学フィルムの製造方法であって、
1)透明支持体上にラビング配向膜を形成する工程
2)ラビング配向膜を一方向にラビング処理する工程
3)ラビング配向膜上に、重合性基を有する液晶を主成分とする一種の組成物を塗布する工程
4)温度T1℃で加熱してラビング方向に対して、液晶の遅相軸を直交配向させる工程
5)フォトマスク下、紫外線照射して照射領域を直交配向状態で固定化する工程
6)温度T2(但し、T1<T2)℃で加熱して、ラビング方向に対して未照射領域の液晶の遅相軸を平行配向させる工程
7)紫外線照射して平行配向状態で固定化する工程
をこの順で含む光学フィルムの製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180031153.7A CN103097928B (zh) | 2010-06-22 | 2011-06-20 | 光学膜、其制备方法、和包括该光学膜的偏振片、图像显示设备和立体图像显示系统 |
KR20137001076A KR20130128356A (ko) | 2010-06-22 | 2011-06-20 | 광학 필름, 그 제조 방법, 그리고 그것을 사용한 편광판, 화상 표시 장치 및 입체 화상 표시 시스템 |
US13/714,075 US20130100367A1 (en) | 2010-06-22 | 2012-12-13 | Optical film, method for manufacturing the same, and polarizing plate, image display device, and stereo picture display system including the optical film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010141346A JP4963732B2 (ja) | 2010-06-22 | 2010-06-22 | 光学フィルム、その製造方法、並びにそれを用いた偏光板、画像表示装置及び立体画像表示システム |
JP2010-141346 | 2010-06-22 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/714,075 Continuation US20130100367A1 (en) | 2010-06-22 | 2012-12-13 | Optical film, method for manufacturing the same, and polarizing plate, image display device, and stereo picture display system including the optical film |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011162204A1 true WO2011162204A1 (ja) | 2011-12-29 |
Family
ID=45371387
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/064049 WO2011162204A1 (ja) | 2010-06-22 | 2011-06-20 | 光学フィルム、その製造方法、並びにそれを用いた偏光板、画像表示装置及び立体画像表示システム |
Country Status (5)
Country | Link |
---|---|
US (1) | US20130100367A1 (ja) |
JP (1) | JP4963732B2 (ja) |
KR (1) | KR20130128356A (ja) |
CN (1) | CN103097928B (ja) |
WO (1) | WO2011162204A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104185802A (zh) * | 2012-01-25 | 2014-12-03 | 柯尼卡美能达株式会社 | 光学膜 |
CN104813222A (zh) * | 2012-11-29 | 2015-07-29 | Lg化学株式会社 | 光学膜 |
US9885907B2 (en) | 2013-03-08 | 2018-02-06 | Fujifilm Corporation | Optical film, polarizing plate and liquid crystal display device |
CN110297286A (zh) * | 2019-06-26 | 2019-10-01 | 昆山工研院新型平板显示技术中心有限公司 | 一种偏光片、显示面板及显示面板的制备方法 |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013114960A1 (ja) * | 2012-01-31 | 2013-08-08 | 富士フイルム株式会社 | 積層体、並びにそれを有する偏光板、立体画像表示装置、及び立体画像表示システム |
JP5827906B2 (ja) * | 2012-02-13 | 2015-12-02 | 富士フイルム株式会社 | 積層体、及びその用途 |
WO2013137093A1 (ja) * | 2012-03-14 | 2013-09-19 | 日本ゼオン株式会社 | 光学積層体及びその製造方法、並びに立体画像表示装置 |
WO2013151030A1 (ja) * | 2012-04-06 | 2013-10-10 | 富士フイルム株式会社 | 立体画像表示装置及び立体画像表示システム |
JP5899032B2 (ja) * | 2012-04-06 | 2016-04-06 | 富士フイルム株式会社 | 光学フィルム、光学フィルムの製造方法、偏光板、立体画像表示装置、及び立体画像表示システム |
JP2013246302A (ja) * | 2012-05-25 | 2013-12-09 | Dainippon Printing Co Ltd | 光学フィルム、画像表示装置及び光学フィルムの製造方法 |
JPWO2014050387A1 (ja) * | 2012-09-28 | 2016-08-22 | 富士フイルム株式会社 | 光学積層体 |
EP2910986B1 (en) * | 2012-10-22 | 2019-03-13 | Zeon Corporation | Retarder, circularly polarising plate, and image display device |
KR101565321B1 (ko) | 2012-12-13 | 2015-11-03 | 동우 화인켐 주식회사 | 편광판 및 이를 포함하는 화상 표시 장치 |
CN103267994B (zh) * | 2013-05-22 | 2015-06-17 | 深圳市华星光电技术有限公司 | 一种偏光器件、液晶显示装置及其制造方法 |
JP2015225206A (ja) * | 2014-05-28 | 2015-12-14 | 大日本印刷株式会社 | 光学フィルム、光学フィルム積層体及び画像表示装置 |
KR102225931B1 (ko) * | 2014-11-21 | 2021-03-10 | 엘지디스플레이 주식회사 | 유기전계발광표시장치 |
US10533137B2 (en) * | 2015-03-19 | 2020-01-14 | Zeon Corporation | Liquid crystal composition, method for producing retardation layer, and circularly polarizing plate |
US10626329B2 (en) | 2015-04-21 | 2020-04-21 | United States Of America As Represented By The Secretary Of The Air Force | Methods of making voxelated liquid crystal elastomers |
US10281630B2 (en) * | 2016-09-19 | 2019-05-07 | Apple Inc. | Optical films for electronic device displays |
KR102655726B1 (ko) * | 2016-09-30 | 2024-04-05 | 엘지디스플레이 주식회사 | 편광판 및 이를 구비한 액정표시장치 |
KR101988548B1 (ko) | 2016-12-12 | 2019-06-12 | 주식회사 엘지화학 | 광학 필름 및 이를 포함하는 화상 표시 장치 |
KR102008185B1 (ko) | 2017-01-13 | 2019-08-07 | 삼성에스디아이 주식회사 | 발광표시장치용 편광판 및 이를 포함하는 발광표시장치 |
EP3614183B1 (en) * | 2017-04-20 | 2022-09-14 | LG Chem, Ltd. | Anti-reflection optical filter and organic light-emitting device |
US11976214B2 (en) | 2017-08-04 | 2024-05-07 | Daicel Corporation | Antiglare film |
WO2020090522A1 (ja) * | 2018-10-30 | 2020-05-07 | 富士フイルム株式会社 | フィルムロール、光学フィルム、3d画像表示装置及び3d画像表示システム |
JP2022541609A (ja) * | 2019-07-24 | 2022-09-26 | ロリク・テクノロジーズ・アーゲー | 光配向性ポジティブc-プレートリターダ |
JP7324851B2 (ja) * | 2019-08-23 | 2023-08-10 | 富士フイルム株式会社 | 光学積層体、パターン光学異方性層の製造方法、3d画像表示装置および3d画像表示システム |
US11029908B2 (en) * | 2019-08-28 | 2021-06-08 | Himax Display, Inc. | Head mounted display apparatus |
CN114167649A (zh) * | 2021-11-05 | 2022-03-11 | 珠海市科弥光电有限公司 | 一种具有个性化信息的液晶光学薄膜的制造方法 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0277015A (ja) * | 1988-09-13 | 1990-03-16 | Matsushita Electric Ind Co Ltd | 液晶の配向制御方法 |
JPH10161108A (ja) * | 1996-12-02 | 1998-06-19 | Sharp Corp | 位相差素子およびその製造方法並びにそれを備えた立体表示装置 |
JPH10253824A (ja) * | 1997-03-13 | 1998-09-25 | Sharp Corp | 光学素子及びその製造方法と、それを用いた画像表示装置 |
JP2005208416A (ja) * | 2004-01-23 | 2005-08-04 | Nitto Denko Corp | 逆波長分散位相差フィルム、それを用いた偏光板及びディスプレイ装置 |
JP2006113500A (ja) * | 2004-09-17 | 2006-04-27 | Fuji Photo Film Co Ltd | 光学補償シートおよび液晶表示装置 |
JP2006317736A (ja) * | 2005-05-13 | 2006-11-24 | Fuji Photo Film Co Ltd | 光学フィルムおよび液晶表示装置 |
JP2007079337A (ja) * | 2005-09-16 | 2007-03-29 | Fujifilm Corp | 光学異方性体、偏光板及び液晶表示装置 |
JP2007178679A (ja) * | 2005-12-27 | 2007-07-12 | Fujifilm Corp | 光学補償フィルム、偏光板及び液晶表示装置 |
JP2009139593A (ja) * | 2007-12-05 | 2009-06-25 | Arisawa Mfg Co Ltd | 立体画像表示装置および位相差板 |
WO2010032540A1 (ja) * | 2008-09-22 | 2010-03-25 | ソニー株式会社 | 位相差板およびその製造方法並びに表示装置 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20060003340A (ko) * | 2003-04-08 | 2006-01-10 | 메르크 파텐트 게엠베하 | 지연 또는 배향 패턴을 지닌 중합된 액정 필름 |
JP2007206661A (ja) * | 2005-04-25 | 2007-08-16 | Nitto Denko Corp | 液晶パネルおよび液晶表示装置 |
JP2007206207A (ja) * | 2006-01-31 | 2007-08-16 | Fujifilm Corp | 光学フィルム、偏光板及び液晶表示装置 |
JP4887072B2 (ja) * | 2006-05-02 | 2012-02-29 | 富士フイルム株式会社 | セルロース体フィルム、光学補償シート、偏光板、液晶表示装置 |
KR101493082B1 (ko) * | 2007-10-24 | 2015-02-13 | 엘지디스플레이 주식회사 | 표시장치 |
US20100033557A1 (en) * | 2008-07-28 | 2010-02-11 | Sony Corporation | Stereoscopic image display and method for producing the same |
-
2010
- 2010-06-22 JP JP2010141346A patent/JP4963732B2/ja active Active
-
2011
- 2011-06-20 WO PCT/JP2011/064049 patent/WO2011162204A1/ja active Application Filing
- 2011-06-20 KR KR20137001076A patent/KR20130128356A/ko not_active Application Discontinuation
- 2011-06-20 CN CN201180031153.7A patent/CN103097928B/zh active Active
-
2012
- 2012-12-13 US US13/714,075 patent/US20130100367A1/en not_active Abandoned
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0277015A (ja) * | 1988-09-13 | 1990-03-16 | Matsushita Electric Ind Co Ltd | 液晶の配向制御方法 |
JPH10161108A (ja) * | 1996-12-02 | 1998-06-19 | Sharp Corp | 位相差素子およびその製造方法並びにそれを備えた立体表示装置 |
JPH10253824A (ja) * | 1997-03-13 | 1998-09-25 | Sharp Corp | 光学素子及びその製造方法と、それを用いた画像表示装置 |
JP2005208416A (ja) * | 2004-01-23 | 2005-08-04 | Nitto Denko Corp | 逆波長分散位相差フィルム、それを用いた偏光板及びディスプレイ装置 |
JP2006113500A (ja) * | 2004-09-17 | 2006-04-27 | Fuji Photo Film Co Ltd | 光学補償シートおよび液晶表示装置 |
JP2006317736A (ja) * | 2005-05-13 | 2006-11-24 | Fuji Photo Film Co Ltd | 光学フィルムおよび液晶表示装置 |
JP2007079337A (ja) * | 2005-09-16 | 2007-03-29 | Fujifilm Corp | 光学異方性体、偏光板及び液晶表示装置 |
JP2007178679A (ja) * | 2005-12-27 | 2007-07-12 | Fujifilm Corp | 光学補償フィルム、偏光板及び液晶表示装置 |
JP2009139593A (ja) * | 2007-12-05 | 2009-06-25 | Arisawa Mfg Co Ltd | 立体画像表示装置および位相差板 |
WO2010032540A1 (ja) * | 2008-09-22 | 2010-03-25 | ソニー株式会社 | 位相差板およびその製造方法並びに表示装置 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104185802A (zh) * | 2012-01-25 | 2014-12-03 | 柯尼卡美能达株式会社 | 光学膜 |
CN104813222A (zh) * | 2012-11-29 | 2015-07-29 | Lg化学株式会社 | 光学膜 |
CN104813222B (zh) * | 2012-11-29 | 2017-07-18 | Lg化学株式会社 | 光学膜 |
US9891360B2 (en) | 2012-11-29 | 2018-02-13 | Lg Chem, Ltd. | Optical film |
US9885907B2 (en) | 2013-03-08 | 2018-02-06 | Fujifilm Corporation | Optical film, polarizing plate and liquid crystal display device |
CN110297286A (zh) * | 2019-06-26 | 2019-10-01 | 昆山工研院新型平板显示技术中心有限公司 | 一种偏光片、显示面板及显示面板的制备方法 |
CN110297286B (zh) * | 2019-06-26 | 2021-09-07 | 昆山工研院新型平板显示技术中心有限公司 | 一种偏光片、显示面板及显示面板的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2012008170A (ja) | 2012-01-12 |
US20130100367A1 (en) | 2013-04-25 |
KR20130128356A (ko) | 2013-11-26 |
CN103097928A (zh) | 2013-05-08 |
CN103097928B (zh) | 2015-07-08 |
JP4963732B2 (ja) | 2012-06-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4963732B2 (ja) | 光学フィルム、その製造方法、並びにそれを用いた偏光板、画像表示装置及び立体画像表示システム | |
JP5481306B2 (ja) | 積層体、光学フィルムおよびそれらの製造方法、偏光板、画像晶表示装置、立体画像表示システム | |
JP5695532B2 (ja) | 光学フィルム、その製造方法、並びにそれを用いた偏光板、画像表示装置及び立体画像表示システム | |
JP5518628B2 (ja) | 長尺状光学フィルムの製造方法、及び長尺状円偏光板の製造方法 | |
JP5544269B2 (ja) | 光学フィルム、偏光板及び液晶表示装置 | |
JP5038745B2 (ja) | 透明保護フィルム、光学補償フィルム、偏光板、及び液晶表示装置 | |
JP5783846B2 (ja) | 3d画像表示用光学フィルム、3d画像表示装置及び3d画像表示システム | |
JP5380029B2 (ja) | 液晶表示装置 | |
JP5697634B2 (ja) | 光学フィルム、セキュリティ製品、および真贋判定方法 | |
KR20070052243A (ko) | 편광판 및 액정 표시 장치 | |
KR101296179B1 (ko) | 액정표시장치 및 그 제조방법, 그리고 화상표시장치 | |
TWI400282B (zh) | 醯化纖維素薄膜之製法、偏光板及液晶顯示器 | |
JP5016834B2 (ja) | 光学フィルム、これを用いた偏光板および液晶表示装置 | |
JP2013061372A (ja) | フィルム・パターンド・リターダーの製造方法、並びにフィルム・パターンド・リターダー、及びそれを有する偏光板及び画像表示装置 | |
JP2013029552A (ja) | 光学フィルムおよび立体画像表示装置 | |
JP2006201502A (ja) | 位相差フィルム、偏光板、および液晶表示装置 | |
JP2005134863A (ja) | 光学補償シート、偏光板および液晶表示装置 | |
JP5871480B2 (ja) | 画像表示装置及び3d画像表示システム |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180031153.7 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11798088 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137001076 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11798088 Country of ref document: EP Kind code of ref document: A1 |