WO2012014964A1 - 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 - Google Patents
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 Download PDFInfo
- Publication number
- WO2012014964A1 WO2012014964A1 PCT/JP2011/067225 JP2011067225W WO2012014964A1 WO 2012014964 A1 WO2012014964 A1 WO 2012014964A1 JP 2011067225 W JP2011067225 W JP 2011067225W WO 2012014964 A1 WO2012014964 A1 WO 2012014964A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- control region
- alignment
- region
- film
- Prior art date
Links
- 0 CCC(*(C)C)[n]1c(cccc2)c2c2c1cccc2 Chemical compound CCC(*(C)C)[n]1c(cccc2)c2c2c1cccc2 0.000 description 2
- ZMZIBQZQLQJWJU-UHFFFAOYSA-N CCC(C)C(Nc1cc(C(O)=O)ccc1)O Chemical compound CCC(C)C(Nc1cc(C(O)=O)ccc1)O ZMZIBQZQLQJWJU-UHFFFAOYSA-N 0.000 description 1
- YXPUKDVFMAHVIW-UHFFFAOYSA-N CCC(C)C(Oc1cc(C(O)=O)ccc1)=O Chemical compound CCC(C)C(Oc1cc(C(O)=O)ccc1)=O YXPUKDVFMAHVIW-UHFFFAOYSA-N 0.000 description 1
- OMLFPTCJQSCRSU-UHFFFAOYSA-N CCC(C)C1OC1NCCO Chemical compound CCC(C)C1OC1NCCO OMLFPTCJQSCRSU-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
-
- 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
- G02B5/3025—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
-
- 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
- G02F1/133753—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle
-
- 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
-
- 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
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/02—Alignment layer characterised by chemical composition
-
- 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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133753—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle
- G02F1/133757—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle with different alignment orientations
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
Definitions
- the present invention relates to a laminate useful as a support for a patterned optical film, a method for producing the same, an optical film using the same, a polarizing plate, and an image display device, particularly a stereoscopic image display device.
- an optically anisotropic layer patterned in liquid crystal domains having slow axes orthogonal to each other has been provided.
- a method for producing an optical film having such a patterned optically anisotropic layer regions having different orientation control ability are alternately formed by irradiating light from two directions using a photomask or the like.
- a method using a photo-alignment film that has been subjected to alignment treatment see Patent Document 1 and Non-Patent Document 1).
- a method using a rubbing alignment film has also been proposed.
- Patent Document 2 discloses a method of forming a pattern retardation layer using an alignment layer having patterns composed of portions aligned in different directions, and is aligned in different directions by mask rubbing treatment. A method of forming an alignment layer composed of the formed portions is disclosed.
- the photo-alignment film using the photomask and the method for manufacturing the alignment film by mask rubbing require expensive manufacturing equipment and high-precision alignment with the mask film. Dissatisfaction remained in the patterning accuracy of the two alignment control regions.
- the method for performing mask rubbing requires a change in the rubbing direction with respect to the film conveying direction, and therefore has a large problem from the viewpoint of ease of manufacture.
- Patent Document 3 a photolithographic technique is used instead of a photo-alignment film using a photomask or a method for producing an alignment film by mask rubbing, and a photosensitive vertical alignment film and a horizontal alignment film forming material are applied.
- this document manufactures a patterned alignment film for controlling the alignment of the liquid crystal in the liquid crystal cell of the liquid crystal display device, and controls the alignment of the liquid crystal in the vertical and horizontal directions with respect to the obtained patterned alignment film. Therefore, only a patterning alignment film has been disclosed.
- the rubbing alignment film a parallel alignment film capable of aligning rod-like liquid crystal molecules in the same direction as the rubbing treatment is generally used, but by using a predetermined polymer, the rod-like liquid crystal molecules are rubbed in the rubbing direction.
- An orthogonal alignment film that can be aligned in a direction orthogonal to the above is also known (see Patent Document 5).
- various proposals have been made as materials for the rubbing alignment film (see Patent Documents 6 and 7). However, it does not disclose the use for forming the patterned optically anisotropic layer.
- a patterned optically anisotropic layer is manufactured differently, such as 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.
- the general idea is that an alignment film that is oriented in the direction is necessary.
- the first object of the present invention is that two or more types of alignment control layers are formed on the transparent support, and the alignment of the major axes of the liquid crystals can be controlled in directions orthogonal to each other in a plane parallel to the alignment control surface. It is to provide a certain laminate and an optical film using the laminate. The second object is to provide a simple method for producing such a laminate and an optical film. A third object is to provide a polarizing plate using the optical film, a low-cost and highly visible image display device, and a stereoscopic image display system.
- the present inventors tried to form an orientation control layer on a transparent support by using two or more kinds of materials having different compositions and patterning them in a specific lamination mode. As a result, it has been found that a well-patterned optically anisotropic layer can be produced, and a laminate and an optical film that can solve the above problems can be provided.
- the present invention has the following configuration.
- [1] comprising a first orientation control region and a second orientation control region having a transparent support, and an orientation control surface having different orientation controllability on the transparent support, the composition being different from each other;
- Each of the alignment control surfaces has a pattern alignment control layer in which the alignment control surfaces are alternately arranged, and the alignment control surfaces of the first alignment control region and the second alignment control region are parallel to the alignment control surface.
- a laminate in which the orientation of the major axes of the liquid crystals can be controlled in directions orthogonal to each other.
- [2] The laminate according to [1], wherein the first alignment control region and the second alignment control region are processed in the same direction.
- the first alignment control region and the second alignment control region each contain a modified or non-modified polyvinyl alcohol as a main component; a modified or non-modified polyacrylic acid as a main component.
- a film a film containing as a main component a (meth) acrylic acid copolymer containing a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II) or (III); or Any one of the following: a film mainly composed of a polymer having at least one structural unit represented by any one of the following general formula (I-TH), general formula (II-TH) and general formula (III-TH)
- the laminate according to any one of [1] to [3], wherein (In the general formulas (I) to (III): R 1 and R 2 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; M is a proton, an alkali metal ion; Or L 0 is a divalent linking group selected from the group consisting of —O—, —CO—, —NH—, —SO 2 —, an alkylene group, an alkenylene group, an ary
- R 0 is a hydrocarbon group having 10 to 100 carbon atoms or a fluorine atom-substituted hydrocarbon group having 1 to 100 carbon atoms; Cy is an aliphatic ring group, aromatic group or heterocyclic ring M is from 10 to 99 mol%; and n is from 1 to 90 mol%.
- General formula (I-TH) (Wherein R 1 represents a hydrogen atom, a methyl group, a halogen atom or a cyano group, P 1 represents an oxygen atom, —CO— or —NR 12 —, and R 12 represents a hydrogen atom or a substituted or unsubstituted carbon.
- L 1 represents a substituted or unsubstituted alkylene group, divalent cycloaliphatic group, divalent aromatic group, divalent heterocycle group, and combinations thereof
- General formula (II-TH) (In the formula, R 2 represents a hydrogen atom, a methyl group, a halogen atom or a cyano group, L 21 represents a substituted or unsubstituted divalent aromatic group or divalent heterocyclic group, and P 21 represents a single atom.
- L 32 represents a substituted or unsubstituted divalent linkage selected from the group consisting of an alkylene group, a divalent cycloaliphatic group, a divalent aromatic group, a divalent heterocyclic group, and combinations thereof.
- X 3 represents a hydrogen bonding group, and n3 is an integer of 0 to 3.
- the first alignment control region and the second alignment control region both have the same resin as a main component, and at least one region contains at least one of a pyridinium compound and an imidazolium compound.
- [8] The laminate according to [6] or [7], wherein the pyridinium compound or imidazolium compound is liquid crystalline.
- the first alignment control region and the second alignment control region are mainly composed of a non-developable resin. Laminated body.
- Any of [1] to [9], wherein the first alignment control region and the second alignment control region are any one of the following (1) and (2): The laminate according to claim 1.
- Aspect (1) The first alignment control region is formed on the transparent support, and the second alignment control region is formed on a partial region of the first alignment control region.
- An optically anisotropic layer In the optically anisotropic layer, the first retardation region and the second retardation region having different in-plane slow axes are alternately patterned. [15] In the optically anisotropic layer, the first retardation region and the second retardation region are alternately patterned in a strip shape having a long side parallel to one side of the optically anisotropic layer, and The optical film according to [14], wherein a slow axis in the plane of the first retardation region and a slow axis in the plane of the second retardation region are substantially orthogonal.
- the optical film according to one item. [20] The optical film as described in any one of [14] to [19], wherein a black matrix is provided between the first retardation region and the second retardation region. [21] The optical film according to any one of [14] to [20] and a polarizing film, each of the first retardation region and the second retardation region of the optically anisotropic layer.
- the in-plane slow axis direction and the absorption axis direction of the polarizing film are both 45 °.
- a liquid crystal cell including a pair of substrates disposed between the first and second polarizing films, each having an electrode on at least one side thereof, and a liquid crystal layer between the pair of substrates; and the first polarizing film;
- the optical film according to any one of [14] to [23],
- An image display device having at least The absorption axis direction of the first polarizing film and the in-plane slow axis of the first phase difference region and the in-plane slow axis of the second retardation region of the optical film both form an angle of ⁇ 45 °.
- An image display device characterized by that.
- a stereoscopic image display system including at least the image display device according to [24] and a third polarizing plate disposed outside the optical film, and allowing a stereoscopic image to be visually recognized through the third polarizing plate.
- An alignment control layer comprising the first alignment control region and the second alignment control region in the plane on the transparent support is represented by the following (IA), (IB) and (II-A) [26]
- the second alignment control region is formed by flexographic printing.
- the first composition used for printing the first alignment control region is a parallel alignment film composition or an orthogonal alignment film composition.
- the second composition used for printing the second alignment control region contains the other compound and the second alignment solvent
- the first composition used for printing the first alignment control region contains an alignment film compound and a first solvent, and the second alignment control region.
- At least one of the first alignment control region and the second alignment control region in the laminate includes at least one of a pyridinium compound and an imidazolium compound, the liquid crystal is a discotic liquid crystal, and the laminate The first retardation region and the second retardation region are formed by controlling the orientation of the discotic liquid crystal by performing heat treatment after disposing the composition containing the discotic liquid crystal on the body.
- the method according to [34] The method according to [34].
- the laminate and the optical film of the present invention can provide an optically anisotropic layer patterned using an existing alignment film manufacturing equipment without using an expensive photomask, and can perform an alignment process such as rubbing. Therefore, the production cost is very high and the ease of manufacturing is excellent.
- the optical film of the present invention has an optically anisotropic layer having a high-definition orientation pattern and is excellent in practicality.
- the laminate and the optical film of the present invention can be provided simply and inexpensively.
- ADVANTAGE OF THE INVENTION According to this invention, the polarizing plate using the optical film of this invention, an image display apparatus, and a three-dimensional image display system can be provided simply and cheaply.
- 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.
- 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.
- the parallel alignment means that the major axis of the liquid crystal molecule is aligned substantially parallel to the processing direction of the alignment control region, and the orthogonal alignment is the length of the liquid crystal molecule relative to the processing direction of the alignment control region. It indicates that the axes are oriented substantially orthogonally.
- compositions differ from each other” in a composition not only means that the main component and / or one or more additives in the composition are different from each other, It is used to mean that the content ratio is different.
- the long axis direction of a molecule means the direction of the longest axis in the molecule in the case of a rod-like liquid crystal molecule, and the direction in which the disk surfaces are aligned (in the case of a discotic liquid crystal molecule) Azimuth).
- the laminate of the present invention has a first orientation control region and a second orientation control having a transparent support and an orientation control surface having different composition controllability and different orientation control ability on the transparent support.
- Each of the first alignment control region and the second alignment control region has an alignment control surface.
- the alignment of the major axes of the liquid crystals can be controlled in a direction perpendicular to each other in a plane parallel to.
- the laminate of the present invention has an alignment control layer in which alignment control surfaces having different control capabilities are alternately arranged, and when the same liquid crystal is aligned thereon, the first and second alignment control regions are formed.
- the liquid crystal molecules are aligned with their major axes orthogonal to each other.
- the laminate of the present invention when an optically anisotropic layer made of a liquid crystal composition is formed using the laminate of the present invention as a support, the first and second retardation layers whose in-plane slow axis directions are orthogonal to each other are alternated. It is possible to easily form the patterned optically anisotropic layer disposed on the substrate. That is, by providing the laminate of the present invention with such a configuration, an optically anisotropic layer in which a good pattern is formed using an existing alignment film manufacturing facility without using an expensive photomask is provided. it can.
- the alignment control surfaces of the first alignment control region and the second alignment control region can be controlled in a direction perpendicular to each other in the major axis of the liquid crystal in a plane parallel to the alignment control surface.
- the alignment control ability of each alignment control surface of the first alignment control region and the second alignment control region satisfies the following (A), and in another example, satisfies the following (B): To do.
- A) It is possible to control horizontal alignment in a direction in which the long axes of the rod-like liquid crystals are orthogonal to each other.
- B It is possible to control the orientation of the disc surface of the discotic liquid crystal in the direction perpendicular to the orientation control layer film surface and in the direction perpendicular to the major axes.
- the alignment control surfaces that exhibit different alignment control capabilities do not have to be on the same plane.
- one of the first and second alignment control regions may be uniformly formed, and the other alignment region control may be formed in a pattern on the alignment control region.
- the orientation control surfaces showing different orientation control abilities may be alternately arranged on the same plane, that is, the orientation control regions may be alternately arranged on the same plane.
- the first orientation control is performed when the surface of the orientation control layer opposite to the transparent support is orthogonally projected onto a virtual plane parallel to the transparent support. It means that the region and the second alignment control region are alternately patterned.
- the cross section has the configuration shown in FIG.
- a first alignment control region 22a is formed on the transparent support 21, and one of the first alignment control regions 22a is formed.
- a second alignment control region 22b is formed on the part region. Since the alignment film can maintain the alignment regulating force of the liquid crystal molecules stacked in the direction perpendicular to the film surface even if it has a certain thickness, it may be an alignment control layer having unevenness on the film surface as described above. . At this time, even if the first alignment control region 22a and the second alignment control region 22b are both processed in one direction, the alignment control region 22b is not subjected to physical alignment processing such as rubbing processing.
- the second alignment control region 22b is stacked on the first alignment control region 22a, and the alignment processing of the lower alignment control region 2a is performed.
- the liquid crystal molecules stacked on the alignment control region 22b can be aligned in a direction different from the direction. In this case, since the surface of the orientation control layer opposite to the transparent support is the second orientation control region 22b of the upper layer, the orientation control layer of the laminate is opposite to the transparent support.
- the first orientation control region derived from the portion where the lower first orientation control region 22a is the surface, and the upper layer The second alignment control regions derived from the portion where the second alignment control region 22b is the surface are alternately patterned.
- the thickness of the orientation control region is preferably 0.01 to 10 ⁇ m. More preferably, the thickness is 01 to 1 ⁇ m. With such a thickness, even if the film surface is uneven, the alignment regulating force of the liquid crystal molecules stacked in the direction perpendicular to the film surface can be sufficiently maintained.
- the cross section has the configuration shown in FIG. In FIG. 5, the first orientation control region 21a is formed on a part of the transparent support 21 and the second orientation control region 22a of the transparent support 21 is not formed on the second region.
- An orientation control region 22c is formed. It is preferable that both the first alignment control region 22a and the second alignment control region 22c are processed in one direction.
- the surface of the orientation control layer on the side opposite to the transparent support is the first orientation control region 22a and the second orientation control region 22c.
- the first orientation control region and the second orientation control region are processed in the same orientation. More preferably, the first alignment control region and the second alignment control region are rubbing alignment films that are rubbed in the same direction.
- the “alignment film” means a film treated so as to have an alignment regulating ability of liquid crystal molecules.
- the alignment film can be divided into a rubbing alignment film, a photo-alignment film, and other films provided with liquid crystal alignment by applying an electric field or a magnetic field, from the viewpoint of a method for providing alignment.
- the alignment film can be roughly divided into a parallel alignment film and an orthogonal alignment film.
- the rubbing alignment film has an alignment axis that regulates the alignment of liquid crystal molecules.
- the liquid crystal molecules are aligned according to the alignment axis of the rubbing alignment film.
- the conceptual description of the parallel alignment film and the orthogonal alignment film here is as follows.
- Control of the liquid crystal orientation by the molecularly oriented monomolecular film or polymer thin film is also determined by a partial atomic group forming a molecular level or a molecular skeleton.
- the rubbing alignment film exhibits an alignment control ability by rubbing treatment, and has a property that the alignment axis is determined according to the rubbing treatment direction and heating conditions in the manufacturing method. Normally, when liquid crystal is aligned on an alignment film that has been rubbed in one direction, the liquid crystal is aligned with its major axis parallel or orthogonal to the rubbing direction.
- One example is given below.
- This anisotropic optical axis is parallel to the rubbing direction for polyimide and orthogonal to polystyrene.
- the rubbing treatment has the same effect as stretching the polymer chain of the surface layer, and in both cases, the polymer main chain is rearranged in the rubbing direction.
- the hydroxyl group which is a side chain of polyvinyl alcohol is perpendicular to the rubbing direction, and in the case of a polystyrene film, the phenyl group of the side chain is also perpendicular to the main chain.
- the orientation direction of the liquid crystal molecules by the polymer film subjected to the rubbing treatment is considered to be determined by either the uniaxially oriented polymer main chain and / or the substituents extending in the direction perpendicular to the main chain.
- liquid crystal alignment using a polyimide film which is an orthogonal alignment film that is in practical use
- very fine grooves by rubbing play an important role in alignment control, and polymers aligned in the rubbing direction
- the main chain effect is also considered to be involved.
- a physical surface shape change that is, a fine groove is generated even in the polystyrene film, as a result, the interaction between the side chain phenyl group and the liquid crystal molecule is dominant.
- the “alignment control layer” means a film processed so as to have an alignment regulating ability of liquid crystal molecules.
- the orientation control layer may be a single layer or may be composed of two or more layers.
- the alignment control layer is roughly classified into an alignment film such as a rubbing alignment film and a photo alignment film, and a film mainly composed of an alignment control agent capable of regulating the alignment of liquid crystal molecules at the interface.
- the alignment state of the liquid crystal molecules stacked on the alignment film is determined by the conditions in the manufacturing method described later, the alignment film material, the type of liquid crystal molecules, the type of alignment control agent, and the like. Each will be described in detail below.
- the alignment control region is preferably an alignment film.
- the alignment film generally contains a polymer as a main component.
- polymer materials for alignment films there are many literatures, and many commercially available products can be obtained. Among these, as the rubbing alignment film, the following materials can be preferably used as the alignment film.
- the first alignment control region and the second alignment control region each contain a modified or non-modified polyvinyl alcohol as a main component; a modified or non-modified polyacrylic acid as a main component
- R 1 and R 2 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; M is a proton, an alkali metal ion; Or L 0 is a divalent linking group selected from the group consisting of —O—, —CO—, —NH—, —SO 2 —, an alkylene group, an alkenylene group, an arylene group, and combinations thereof.
- R 0 is a hydrocarbon group having 10 to 100 carbon atoms or a fluorine atom-substituted hydrocarbon group having 1 to 100 carbon atoms; Cy is an aliphatic ring group, aromatic group or heterocyclic ring M is from 10 to 99 mol%; and n is from 1 to 90 mol%.
- General formula (I-TH) (Wherein R 1 represents a hydrogen atom, a methyl group, a halogen atom or a cyano group, P 1 represents an oxygen atom, —CO— or —NR 12 —, and R 12 represents a hydrogen atom or a substituted or unsubstituted carbon.
- L 1 represents a substituted or unsubstituted alkylene group, divalent cycloaliphatic group, divalent aromatic group, divalent heterocycle group, and combinations thereof
- General formula (II-TH) (In the formula, R 2 represents a hydrogen atom, a methyl group, a halogen atom or a cyano group, L 21 represents a substituted or unsubstituted divalent aromatic group or divalent heterocyclic group, and P 21 represents a single atom.
- L 32 represents a substituted or unsubstituted divalent linkage selected from the group consisting of an alkylene group, a divalent cycloaliphatic group, a divalent aromatic group, a divalent heterocyclic group, and combinations thereof.
- X 3 represents a hydrogen bonding group, and n3 is an integer of 0 to 3.
- the alignment film mainly composed of the alignment film material can be an orthogonal alignment film or a parallel alignment film depending on the type of liquid crystal to be combined, the presence or absence of addition of a predetermined additive, and the like. Selection can be made according to the type of liquid crystal compound to be combined so as to satisfy the conditions of the alignment control region.
- the orthogonal alignment film examples include a copolymer composed of a repeating unit necessary for the orthogonal alignment and a repeating unit necessary for solubility in a solvent for preparation as a coating solution or the like.
- the molar ratio of repeating units necessary for the orthogonal orientation is preferably 1 to 90%, more preferably 5 to 70%, and particularly preferably 10 to 50%.
- the molar ratio of repeating units necessary for solubility is preferably 99% to 1%, more preferably 95% to 10%, and most preferably 90% to 5%. It is preferable to satisfy these numerical ranges simultaneously. However, when the component necessary for the orthogonal orientation and the component necessary for the solubility are included in the same structure, there is a preferable example in which the above numerical range does not apply.
- the component necessary for orthogonal orientation is a component having a repeat number of a, and the component necessary for solubility in an alcohol solvent has a repeat number of b. It is a component that is an individual.
- the components necessary for orthogonal orientation are a component having a repetition number of c and a component having c repetitions, and a component necessary for solubility in an alcohol solvent has a repetition number of b. It is an ingredient.
- the skeletons described in Compound Nos. 30 to 42 in Tables 15 to 20 are the same as the components requiring orientation and the solubility-imparting component having a repeat number of a.
- the polymer for alignment films shown in the above table can be prepared by synthesis.
- it can be synthesized according to the methods described in JP-A-2006-276203 and JP-A-2005-99228.
- An example is shown below. (Method for synthesizing Compound No. 5 described in Table 1 above)
- NEP N-ethylpyrrolidone
- a solution prepared by dissolving 9.62 g of 9-vinylcarbazole, 5.38 g of acrylic acid and 409 mg of AIBN in 10.08 g of NEP was filtered with pyrene, and a solution washed with 2.75 g of NEP was added dropwise over 2 hours with a syringe pump. The mixture was stirred and polymerized at 75 ° C. with a nitrogen flow (10 ml / min) at 350 rpm. Further, after completion of the dropping, the inside of the syringe pump was washed with 3.3 g of NEP.
- Both the first alignment control region and the second alignment control region preferably include a non-developable resin as a main component.
- the non-developable resin means a resin that can solidify and leave only the exposed portion and easily remove the remaining portion by exposure, development processing, and possibly a subsequent curing step.
- Specific examples include resins that are not known developable resins used in photolithography.
- known developable resins such as photosensitive polyimide films are not included in the non-developable resins.
- a photomask for the exposure location is required. Similar to the case of film formation, the problem of alignment occurs.
- the first alignment control region and the second alignment control region are formed without using a photomask, these regions are mainly composed of a non-developable resin. It is preferable.
- the first alignment control region and the second alignment control region may have different resins as main components.
- the first alignment control region and the second alignment control region may both have the same resin as a main component.
- they may interact strongly with each other, and the alignment behavior of the liquid crystal molecules may be different in the presence and absence of the additive. An embodiment using this phenomenon may be used.
- examples of the additive used in the first alignment control region and the second alignment control region include a pyridinium compound and an imidazolium compound. It is also preferable in some cases that at least one of the first alignment control region and the second alignment control region includes at least one of a pyridinium compound and an imidazolium compound.
- both the first alignment control region and the second alignment control region are mainly composed of the same resin (for example, polyacrylic acid)
- at least one of a pyridinium compound and an imidazolium compound is included in at least one region. It is preferable to include one.
- the pyridinium compound or imidazolium compound that can be used as an alignment control agent in the present invention may be liquid crystalline or non-liquid crystalline, and in any case interacts with a predetermined alignment film material, The orientation direction of the molecules of the discotic liquid crystal contained in the optically anisotropic layer can be controlled.
- the pyridinium compound or the imidazolium compound is preferably liquid crystalline from the viewpoint of further improving the alignment control ability to the discotic liquid crystal, and among them, the pyridinium compound represented by the following general formula (2a) or the following The imidazolium compound represented by the general formula (2b) is particularly preferable.
- the pyridinium compound and imidazolium compound represented by the following general formulas (2a) and (2b) interact with a predetermined alignment film material to control the alignment of liquid crystal molecules and determine the major axis direction thereof.
- a predetermined alignment film material to control the alignment of liquid crystal molecules and determine the major axis direction thereof.
- there is an action of controlling the alignment at the interface of the alignment film more specifically, It has the 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 heterocyclic rings 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, 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 is 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.
- the pyridinium derivative of the formula (2a) is generally obtained by alkylating the pyridine ring (Menstokin reaction).
- the addition amount of the pyridinium compound and the imidazolium compound is preferably 0.01 to 20% by mass, and preferably about 0.1 to 2% by mass with respect to the main component resin of the orientation control layer. .
- pyridinium compound and imidazolium compound represented by the general formulas (2a) and (2b) can be considered as follows, however, it is not limited to the mode of action as follows. Absent.
- the pyridinium compound and the imidazolium compound represented by the general formulas (2a) and (2b) are unevenly distributed on the surface of the hydrophilic polyvinyl alcohol alignment film 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
- the amino group is substituted, intermolecular hydrogen bonds are generated with the polyvinyl alcohol, and it is unevenly distributed on the surface of the alignment film at a higher density, and due to the effect of the hydrogen bonds, the pyridinium derivative is a main chain of the polyvinyl alcohol. Alignment in a direction orthogonal to the direction of the liquid crystal promotes orthogonal alignment of the liquid crystal with respect to the rubbing direction.
- the pyridinium derivative Since 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 heated in excess of a certain temperature so that the major axis is parallel to the rubbing direction. It is possible to promote parallel alignment. This is because the hydrogen bond with polyvinyl alcohol is broken by the heat energy by heating, the pyridinium compound and imidazolium compound are uniformly dispersed in the alignment film, the density on the alignment film surface is lowered, and the liquid crystal is controlled by the regulating force of the rubbing alignment film itself. This is because of orientation.
- one aspect of the laminate of the present invention is an aspect having first and second alignment control towns in which the rod-like liquid crystal can be horizontally aligned in the direction perpendicular to each other.
- An example of this embodiment is an example in which a parallel alignment film is used for one of the first alignment control region and the second alignment control region, and an orthogonal alignment film is used for the other region.
- the alignment film described below has a function of aligning the long axis of rod-like liquid crystal molecules in parallel with the alignment axis (generally a rubbing axis).
- the polymer material used as the parallel alignment film is an alignment film made of polyvinyl alcohol, polyacrylic acid or polyimide and derivatives thereof.
- the parallel alignment film is more preferably a film containing modified or unmodified polyvinyl alcohol or modified or unmodified polyacrylic acid as a main component.
- 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.
- PVA103”, “PVA203” (manufactured by Kuraray Co., Ltd.) and the like are PVA having the above saponification degree.
- rubbing alignment film reference can be made to the modified polyvinyl alcohol described in WO01 / 88574A1, page 43, line 24 to page 49, line 8, and paragraph Nos. [0071] to [0095] of Japanese Patent No.
- the modified or unmodified polyacrylic acid means a poly (meth) acrylic acid copolymer, and may contain acrylic acid or methacrylic acid.
- the content of acrylic acid or methacrylic acid in the polymer chain is 1% to 100%, preferably 10% to 100%, and more preferably 30% to 100% in molar ratio.
- the weight average molecular weight is 1,000 to 1,000,000, preferably 3000 to 100,000, more preferably 5000 to 50,000.
- the alignment film listed below has a function of aligning the long axis of rod-like liquid crystal molecules so as to be orthogonal to the alignment axis (generally the rubbing axis).
- Examples of the orthogonal alignment film include polymers reported in JP-A Nos. 2002-268068 and 2002-62427, and the above-mentioned polystyrene.
- a polymer having at least one repeating unit represented by any one of the general formula (II-TH) and the general formula (III-TH) can also be preferably used. It can be used more preferably.
- the laminate of the present invention has a resin in which the first alignment control region and the second alignment control region are different from each other in the alignment control layer, and parallel alignment with respect to each of the rod-like liquid crystals.
- the parallel alignment film and the orthogonal alignment film are processed in one position.
- the parallel alignment film and the orthogonal alignment film are preferably rubbing alignment films subjected to a rubbing treatment. For example, in FIG.
- first alignment control region 22a when the first alignment control region 22a is a parallel alignment film and the second alignment control region 22b is an orthogonal alignment film, both are aligned in one direction,
- the liquid crystal molecules stacked on the first alignment control region 22a and the second alignment control region 22b can be aligned in directions orthogonal to each other, and the pattern optical anisotropy of the present invention described later is formed.
- An optical film can be manufactured, which is preferable.
- the first and second alignment control regions that can orient the discotic liquid crystal in the direction perpendicular to each other with the disk surface vertical. It is the aspect which has.
- An example of this embodiment is preferably a film in which at least one of the first alignment control region and the second alignment control region contains a modified or non-modified polyacrylic acid as a main component.
- unmodified PAA polyacrylic acid
- unmodified PAA can align a discotic liquid crystal compound in parallel and vertical alignment. Therefore, unmodified PAA can be used as a material for an alignment control region for aligning a discotic liquid crystal compound in parallel and vertical alignment.
- At least one of the first alignment control region and the second alignment control region is represented by the repeating unit represented by the following general formula (I) and the following general formula (II) or (III).
- a film containing a (meth) acrylic acid copolymer containing as a main component; or any one of the following general formula (I-TH), general formula (II-TH) and general formula (III-TH) It is preferable that it is a film
- PSt (polystyrene) -PAA can be used as a material for an alignment control region for orthogonally aligning a discotic liquid crystal compound.
- Another example of this aspect is an example in which at least one of the first alignment control region and the second alignment control region contains at least one of a pyridinium compound and an imidazolium compound.
- the pyridinium compound and the imidazolium compound also contribute to the alignment control of the liquid crystal molecules, there are various methods for combining the resins that are the main components of the alignment film, and various methods can be employed.
- the main component resins of the alignment film are different from each other or added in different amounts)
- the amount of pyridinium compound and imidazolium compound is small.
- first and second alignment control regions one of which is a region in which the discotic liquid crystal compound is orthogonally aligned vertically, and the other is a region in which the discotic liquid crystal compound is aligned in parallel and vertical alignment. What is necessary is just to comprise.
- the alignment film includes a film having a function of vertically orthogonally aligning with a discotic liquid crystal at a certain normal alignment temperature in the presence of a pyridinium compound or an imidazolium compound.
- a film having a function of vertically orthogonally aligning with a discotic liquid crystal at a certain normal alignment temperature in the presence of a pyridinium compound or an imidazolium compound.
- an alignment film containing modified and non-modified polyvinyl alcohol as a main component and PSt-PAA as a main component is an example of such behavior.
- some of the above-mentioned alignment films include a film that exhibits a function of performing vertical parallel alignment with a discotic liquid crystal at a certain normal alignment temperature in the presence of a pyridinium compound or an imidazolium compound.
- a film that exhibits a function of performing vertical parallel alignment with a discotic liquid crystal at a certain normal alignment temperature in the presence of a pyridinium compound or an imidazolium compound there are those that turn into an alignment film that exhibits the function of vertically orthogonal alignment.
- an alignment film containing polyacrylic acid as a main component is an example that exhibits such behavior. Whether these alignment films have the function of vertically orthogonal alignment or the function of vertically parallel alignment depends on whether the liquid crystal is aligned at a temperature below the isotropic phase, or the liquid crystal is once at or above the isotropic phase.
- the temperature is determined depending on whether the temperature is lowered to the orientation temperature or the orientation is performed under any temperature condition.
- the function may be switched by alignment control under other temperature conditions, and is not limited to the alignment control under this temperature condition.
- each may contain the same resin as a main component.
- the first alignment control region and the second alignment control region are both mainly composed of the same resin, and only one of the regions includes at least one of a pyridinium compound and an imidazolium compound. From the viewpoint of production suitability, it is preferable.
- both of the alignment control regions are added with a pyridinium compound or an imidazolium compound as an additive. It is possible to change the alignment regulating ability of the obtained discotic liquid crystal compound only by slightly changing the composition.
- the first alignment control region and the second alignment control region each contain a modified or non-modified polyvinyl alcohol as a main component;
- Any of the membranes can be used.
- the timing for adding the pyridinium compound or the imidazolium compound at this time may be that each orientation control region is formed after being added to the composition for forming each orientation control region to form a laminate. After forming the alignment control region, it may be added (for example, coating or printing) onto a part of the region, and the other alignment control region may be formed to form a laminate.
- Transparent support As the transparent support used in the laminate of the present invention, a known transparent support for alignment films can be used without particular limitation. Among these, as the transparent support, it is also desirable to use a film having almost no in-plane and thickness direction retardation.
- the Re (550) of the transparent support is 0 to 10 nm and is included in the optical film of the present invention described later without being affected by the optical characteristics of the support. It is preferable from the viewpoint that Re of all the first retardation regions and the second retardation regions can be adjusted to a preferable range.
- Re (550) is a front retardation value (unit: nm) at a wavelength of 550 nm.
- the transparent support Preferably satisfies ⁇ 150 ⁇ Rth (630) ⁇ 100.
- Re ( ⁇ ) is the front retardation value (unit: nm) at the wavelength ⁇ nm
- Rth ( ⁇ ) is the retardation value (unit: nm) in the film thickness direction at the wavelength ⁇ nm.
- the material for forming the transparent support is preferably a polymer excellent in optical performance transparency, mechanical strength, thermal stability, moisture shielding property, isotropy, etc., and the above-mentioned Re and Rth are represented by the above formula (I Any material may be used as long as it satisfies the requirements.
- 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 represented by triacetyl cellulose (hereinafter referred to as cellulose acylate), which has been conventionally used as a transparent protective film of a polarizing plate, is preferably used. I can do it.
- cellulose acylate will be mainly described in detail as an example of the transparent support of the present invention, but it is obvious that the technical matters can be applied to other polymer films as well.
- Cellulose acylate film examples of cellulose as the cellulose acylate raw material include cotton linter and wood pulp (hardwood pulp, conifer pulp). Cellulose acylate obtained from any raw material cellulose can be used, and may be used in some cases. . 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.
- the cellulose acylate produced from the above-mentioned cellulose is obtained by acylating a hydroxyl group of cellulose, and the substituent can be any from an acetyl group having 2 carbon atoms to an acyl group having 22 carbon atoms.
- the degree of substitution of cellulose with a hydroxyl group is not particularly limited, but the degree of substitution of acetic acid and / or a fatty acid having 3 to 22 carbon atoms substituted with a hydroxyl group of cellulose is measured, and the degree of substitution is calculated. Obtainable. As a measuring method, it can be carried out according to ASTM D-817-91.
- the degree of substitution of cellulose with a hydroxyl group is not particularly limited, but the degree of acyl substitution with a 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 degree of substitution is 2 It was found that the optical anisotropy of the cellulose acylate film can be reduced in the case of .50 to 3.00.
- a more preferable degree of acyl substitution is 2.60 to 3.00, and more preferably 2.65 to 3.00.
- the acyl substituent substituted for the hydroxyl group of cellulose consists only of acetyl groups, in addition to being able to reduce the optical anisotropy of the film, it is further compatible with additives and solubility in organic solvents used.
- the degree of substitution is preferably 2.80 to 2.99, more preferably 2.85 to 2.95.
- the degree of polymerization of cellulose acylate preferably used in the present invention is 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. .
- 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 Society, Vol. 18, No. 1, pp.
- Mw mass average molecular weight
- Mn number average molecular weight
- 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 obtained. 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). .
- the cellulose acylate may be used in the form of a substituent, a substitution degree, a polymerization degree, a molecular weight distribution, or the like as described above, and a single or a mixture of two or more different cellulose acylates may be used.
- the thickness of the transparent support 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 Re ( ⁇ ), with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (if there is no slow axis, any in-plane film
- the light of wavelength ⁇ nm is incident from each of the inclined directions in steps of 10 degrees 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 ( ⁇ ) being the in-plane slow axis (determined by KOBRA 21ADH or WR) and the tilt axis (rotating axis).
- the light of wavelength ⁇ nm is incident from each inclined direction in 10 degree steps and measured at 11 points, and KOBRA 21ADH or WR is calculated.
- the assumed value of the average refractive index may be a value in a polymer handbook (John Wiley & Sons, Inc.) or a catalog of various optical films. 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).
- a preferred example of the polymer film used as the 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 laminate of the present invention is preferably used as a support for the patterned optically anisotropic layer. More specifically, it is preferably used for an alignment film for a patterned optical anisotropic layer disposed further on the front side of the front polarizing plate of the liquid crystal display device.
- a patterning phase difference plate for a 3D image display device can be easily manufactured.
- the black matrix is disposed between the first alignment control region and the second alignment control region. It is preferable from the viewpoint of reducing crosstalk when used as an alignment film for a phase difference plate.
- the black matrix is disposed between the first alignment control region and the second alignment control region so as to separate the first alignment control region and the second alignment control region.
- positioned as a partition also includes the aspect arrange
- the first alignment control region forming step of forming the first alignment control region comprising the first composition on the transparent support, and the first composition and the composition are It includes at least a second alignment control region forming step of printing a second alignment control region made of a different second composition in a pattern.
- the laminate of the present invention can be manufactured.
- the manufacturing method of the laminated body of this invention is demonstrated in order of the film forming of a transparent support body, and the lamination
- the transparent support preferably cellulose acylate
- has various additives for example, a compound that reduces optical anisotropy, a wavelength dispersion adjusting agent, fine particles, a plasticizer, an ultraviolet ray inhibitor, an anti-degradation agent, a release agent). 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.
- the compound that reduces the optical anisotropy of the cellulose acylate film will be described.
- the present inventors have sufficiently reduced the optical anisotropy using a compound that suppresses the in-plane and film thickness orientation of cellulose acylate in the film, and Re and Rth are It was close to zero.
- the compound that lowers the optical anisotropy is sufficiently compatible with cellulose acylate, and the compound itself does not have a rod-like structure or a planar structure.
- planar functional groups such as aromatic groups
- octanol- A compound having a 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 more preferable range for the log P 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. Chem.-Chim.
- Theor., 19, 71 (1984).) And the like are preferably used, but the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987).
- the Crippen's fragmentation method J. Chem. Inf. Comput. Sci., 27, 21 (1987).
- the log P value of a certain compound varies depending on the measurement method or calculation method, it is preferable to determine whether or not the compound is within the scope of the present invention by the Crippen's fragmentation method.
- the value of logP described in this specification is determined by the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)).
- 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 addition amount of the compound that decreases the 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 the 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.
- Specific examples of the compound that lowers the optical anisotropy of the cellulose acylate film preferably used in the present invention include compounds described in JP-A 2006-199855, [0035] to [0058].
- the present invention is not limited to these compounds.
- the laminate of the present invention and the optical film of the present invention described later are applied to an image display device, when used for a general liquid crystal display device, it is used on the viewing side than the polarizing plate, It is particularly susceptible to ultraviolet rays. Therefore, it is desirable to contain a UV absorber in any member constituting the laminate or optical film of the present invention, and it is also preferable to contain a UV absorber in the transparent support.
- 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 used in the present invention as described above 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 the 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.
- 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. In addition, 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 while maintaining low turbidity of the optical film, friction This is particularly preferable because the effect of reducing the coefficient is great.
- 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) and There is a way to mix.
- This method is a preferable 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%. Mass% is 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, Japanese Patent Application Laid-Open No. 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 it may be performed at room temperature or further by a cooling dissolution method or a high temperature dissolution method, or a combination thereof.
- the Technical Report of the Society of Invention Public Technical Number 2001-1745, published on March 15, 2001, Invention Association
- the production process described in detail on pages 22 to 25 is 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 sent 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 first orientation control region is formed on the transparent support formed by the above method by any one of the following methods (I) or (II). It is preferable to include an alignment control region forming step.
- an alignment control layer comprising a first alignment control region and a second alignment control region in a plane on a transparent support is represented by the following (IA) and (IB): ) And (II-A) are preferably included in the printing step.
- the printing method used in the printing step is not particularly limited, and a known method can be used.
- the method for printing the alignment film in a pattern on the support is not particularly limited, and gravure printing, screen printing, spray coating, spin coating, comma coating, bar coating, knife coating, offset printing, flexographic printing, inkjet printing, A method such as dispenser printing can be used.
- flexographic printing and inkjet printing are preferred from the viewpoint that fine patterning can be performed.
- flexographic printing In flexographic printing, as shown in FIG. 1, it is preferable to use a flexographic plate 1 in which irregularities having a width corresponding to a pattern of a pattern optical anisotropic layer preferably used in a stereoscopic image display system are used. Is not limited to the embodiment of FIG.
- the flexographic printing method is shown in FIG.
- the printing process using the flexographic printing apparatus 10 used for the manufacturing method of the laminated body of this invention is shown based on FIG. First, a layer in which a parallel alignment film (or orthogonal alignment film) is laminated on the entire surface of a transparent support by coating or the like is prepared in advance.
- the flexographic plate 1 on which a target pattern is formed is mounted on a pressure drum 11 provided at a position facing the printing pressure roller 12.
- an orthogonal alignment film liquid for pattern printing (or a parallel alignment film liquid for pattern printing) is supplied to the doctor blade 14, and the convex portion of the flexographic plate 1 attached to the impression cylinder 11 through the anix roller 13.
- the orthogonally oriented film liquid 3 for pattern printing is transferred.
- the pattern printing orthogonal alignment film liquid 3 transferred to the convex portions of the flexographic plate 1 is then transferred only to a partial region of the parallel alignment film 2 mounted on the pressure roller 12.
- the coating liquid can be directly printed on the transparent support in correspondence with the desired pattern optical anisotropic layer pattern required for each stereoscopic image display system. Compared with the conventional photo-alignment method and the lithography method using a photoresist, productivity can be improved remarkably.
- a first alignment control region is printed on a transparent support
- a second alignment control region is printed on a partial region of the first alignment control region
- the first alignment control region and the second alignment control region are simultaneously processed in one direction.
- the method for producing a laminate of the present invention is used for printing the first orientation control region when producing a laminate for controlling the orientation of a rod-like compound in the case of using the printing step (IA).
- the first alignment control region printing liquid contains either one of the parallel alignment film composition and the orthogonal alignment film composition and the first alignment control region solvent, and prints the second alignment control region. It is preferable that the second orientation control region printing liquid used in the step comprises the other compound and the second orientation control region solvent.
- the first alignment control region printing liquid used for printing the first alignment control region comprises a composition for a parallel vertical alignment film and One of the compositions for orthogonal vertical alignment films and the first alignment control region solvent
- the second alignment control region printing liquid used for printing the second alignment control region is the other compound. It is preferable to include a second alignment control region solvent.
- the parallel vertical alignment and the orthogonal vertical alignment change depending on the presence or absence of additives (pyridinium compound and imidazolium compound) and the manufacturing temperature in addition to the resin material used as the main component. Therefore, the manufacturing method of this invention is not limited to the aspect which uses these compositions for parallel vertical alignment films, and the composition for orthogonal vertical alignment films properly.
- the film 1) is prepared as a coating solution and coated on the entire surface of the support, and the composition containing the modified or unmodified polyvinyl alcohol as the main component (alignment film 2) is applied by pattern printing and dried. After that, it is rubbed in one direction. Through such a process, the laminate of the present invention shown in FIG. 4 can be obtained.
- Printing process (IB) Printing step (IB): printing a first orientation control region on a transparent support, treating the first orientation control region in one orientation, and then treating the treated surface of the first orientation control region A second alignment control region is printed on a part of the region.
- the laminate manufacturing method of the present invention when manufacturing a laminate for controlling the orientation of a discotic liquid crystal, for example, printing the first alignment control region
- the first alignment control region printing liquid used in the step includes a composition for a parallel vertical alignment film and a first alignment control region solvent, and is used for printing the second alignment control region. It is preferable that the printing liquid contains at least one of a pyridinium compound and an imidazolium compound and a second alignment control region solvent.
- the first alignment control region printing liquid contains the composition for the orthogonal vertical alignment film and the first alignment control region solvent, and is used for printing the second alignment control region.
- the printing liquid for printing contains at least one of a pyridinium compound and an imidazolium compound and a second solvent for the orientation control region.
- the second orientation control region printing liquid is preferably ink-jet printed from the viewpoint of increasing the pattern accuracy.
- the ink jet printing that can be preferably used in the present invention include those described in JP-A-2008-26391, JP-A-2010-150409, and JP-A-2010-046822.
- the embodiment described in JP2008-26391 can be preferably used in the present invention.
- the second orientation control region may be printed and raised on the first orientation control region as shown in FIG.
- the film surface of the laminate of the present invention may be flat. Even when the pyridinium compound and the imidazolium compound are placed on the first alignment control region or penetrated into the first alignment control region, the orientation of the first orientation control region in the permeated portion
- the second orientation control region can be formed by changing the control direction. However, when the pyridinium compound and the imidazolium compound are installed on the first alignment control region, they may be rubbed after the second alignment control region is installed even if the first alignment control region is rubbed in advance. May be.
- the second alignment control region when the pyridinium compound and the imidazolium compound are formed so as to rise is treated in one position depending on the degree of penetration of the compound.
- the processing direction of the second orientation control region represents the processing direction of the first (lower layer) orientation control region. This is the same when the upper layer is not processed in one position in other modes.
- the second alignment control region printing liquid may contain a resin for the second alignment control region.
- the combination with the resin as the main component in the alignment film composition contained in the first alignment control region printing liquid is as described in the description of the laminate of the present invention.
- the component resins may be different or the same.
- either one and / or both of the first alignment control region printing liquid and the second alignment control region printing liquid may be a pyridinium compound. And an imidazolium compound.
- the first alignment control region printing liquid used for printing the first alignment control region is a composition for a parallel alignment film.
- the second alignment control region printing solution used for printing the second alignment control region is the other compound. And a second solvent for the orientation control region.
- a composition (alignment film 2) containing modified or unmodified polyvinyl alcohol as a main component is applied by pattern printing so as to be repeatedly arranged, dried, and then rubbed in one direction. Through such steps, the laminate of the present invention shown in FIG. 5 can be obtained.
- the second alignment control region solvent does not substantially dissolve the compound contained in the first alignment control region printing liquid.
- the manufacturing method of the laminated body of this invention includes the process of orientating the said 1st orientation control area
- the rubbing treatment can be generally carried out by rubbing the surface of a film mainly composed of a polymer 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).
- the rubbing density (L) is quantified by the following formula (A).
- Formula (A) L 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 rubbing density and 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.
- the rubbing treatment direction coincides with the longitudinal direction of the polymer film from the viewpoint of production suitability. Is preferred.
- the optical film of the present invention includes the laminate of the present invention and an optically anisotropic layer formed from a composition containing a liquid crystal having a polymerizable group as a main component on the alignment control region on the laminate.
- the optically anisotropic layer is characterized in that first retardation regions and second retardation regions having different in-plane slow axes are alternately patterned.
- the first retardation region and the second retardation region are orthogonally projected in the direction perpendicular to the film surface of the first orientation control region and the second orientation control region on the surface of the orientation control layer, respectively. It is formed in the area
- the optical film having such a configuration can form a good stereoscopic image when incorporated in a stereoscopic image display system.
- the optically anisotropic layer of the present invention preferably has a function of converting ⁇ / 4 plate, that is, linearly polarized light into circularly polarized light.
- a rod-like liquid crystal compound having a polymerizable group or a discotic liquid crystal is horizontally or vertically aligned. It is preferable to form in a state polymerized and fixed.
- the optical anisotropic layer has at least one parallel alignment region and orthogonal alignment region as the first retardation region and the second retardation region.
- the parallel alignment region and the orthogonal alignment region referred to here are such that the major axis of the rod-like liquid crystal compound is horizontal to the layer surface in the optically anisotropic layer surface.
- a region parallel to the alignment processing direction for example, a rubbing processing direction
- a region horizontal to the layer surface and orthogonal to the alignment processing direction for example, a rubbing processing direction
- the optical film of the present invention is such that the liquid crystal having a polymerizable group is a discotic liquid crystal, and the discotic liquid crystal is in the optically anisotropic layer.
- a vertically aligned state in which the disk surface is aligned perpendicular to the layer surface, and the major axis (direction in which the disk surfaces are continuous) is parallel to the alignment processing direction (for example, the rubbing processing direction).
- a region means a region which is in a vertical alignment state and whose major axis is perpendicular to the alignment treatment direction.
- the optical film of the present invention is alternately patterned in a strip shape in which the first retardation region and the second retardation region have long sides parallel to one side of the optical anisotropic layer in the optical anisotropic layer. It is preferable that the in-plane slow axis of the first retardation region and the in-plane slow axis of the second retardation region are substantially orthogonal.
- the first region and the second region have a strip shape in which the lengths of the short sides are substantially equal, and are alternately and repeatedly patterned. It is preferable from the viewpoint of use for a system.
- 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.
- liquid crystal compound having a polymerizable group that can be used as the main raw material of the optically anisotropic layer of the present invention
- liquid crystal compound having a polymerizable group that can be used as the main raw material of the optically anisotropic layer of the present invention
- examples of the liquid crystal compound having a polymerizable group that can be used as the main raw material of the optically anisotropic layer of the present invention include a rod-like liquid crystal having a polymerizable group and a discotic liquid crystal having a polymerizable group.
- a discotic liquid crystal having is preferred.
- the rod-like liquid crystal include Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. Nos. 4,683,327, 5,622,648 and 5,770,107, World Patents (WO) 95/22586, 95/24455. No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, No.
- a compound represented by the following general formula (X) is preferable.
- 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.
- the liquid crystal having the polymerizable group is a rod-like liquid crystal, and that the rod-like liquid crystal is fixed in a horizontal alignment state in the optically anisotropic layer when the rod-like liquid crystal is used. It is preferable to achieve fixing the rod-like liquid crystal in a horizontal alignment state by a compound that promotes horizontal alignment, which will be described later.
- the discotic liquid crystal that can be used as the main raw material of the optically anisotropic layer of the optical film of the present invention is a compound having a polymerizable group as described above.
- the discotic liquid crystal having a polymerizable group is preferably a compound represented by the following general formula (I).
- 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 between the pyridinium compound or the imidazolium compound used as a vertical alignment, vertical alignment can be realized. Particularly, for example, in the general formula (II), when L is a divalent linking group containing at least one of * —CH ⁇ CH— or * —C ⁇ C—, and In (III), when a plurality of aromatic rings and heterocycles are linked by a single bond, the free rotation of the bond is strongly constrained by the linking group, thereby maintaining the linearity of the molecule. As well as stronger intermolecular ⁇ - ⁇ interactions occur and stable 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, in view of the ease of synthesis of the compound and the 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 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 a 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 It is preferably a divalent linking group selected more.
- 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 is preferably a cyclic group having a 5-membered ring, a 6-membered ring, or a 7-membered ring, more preferably a cyclic group having a 5-membered ring or a 6-membered ring, and a cyclic group having a 6-membered ring being Further preferred.
- 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 halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups, alkyl groups having 1 to 16 carbon atoms, alkenyl groups 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.
- 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.
- 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— and —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.
- 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.
- 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 represent 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.
- substituents include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups, alkyl groups having 1 to 16 carbon atoms, alkenyl groups 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 atoms fluorine atoms, chlorine atoms, bromine
- 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.
- 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 the horizontal alignment of the liquid crystal may be added to the composition. Examples of the additive are described in [0055] to [0063] of JP-A No. 2009-22001. 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, in order to facilitate calculation, the following two points are assumed and the tilt angle at the two interfaces of the optically anisotropic layer is used. 1.
- the optically anisotropic layer is assumed to be a multilayer body composed of a layer containing a liquid crystalline compound. Further, 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 type 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 isotropic 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.
- the optically anisotropic layer of the optical film of the present invention may contain a pyridinium compound and an imidazolium compound as an alignment film side alignment control agent.
- a pyridinium compound and an imidazolium compound in the optically anisotropic layer, particularly when a discotic liquid crystal compound is used, the vertical alignment of the discotic liquid crystal compound at the interface on the alignment film side, that is, the laminate side of the present invention Can be controlled to be more perpendicular to the film surface of the laminate of the present invention.
- the preferred ranges of the pyridinium compound and imidazolium compound that can be used in the optically anisotropic layer of the optical film of the present invention are the preferred ranges of the pyridinium compound and imidazolium compound when used as an additive in the laminate of the present invention. It is the same.
- the addition amount of the pyridinium compound and the imidazolium compound does not exceed 5 mass% with respect to the liquid crystal compound, and is preferably about 0.1 to 2 mass%.
- the fluoroaliphatic group-containing copolymer is added mainly for the purpose of controlling the orientation at the air interface of the discotic liquid crystal represented by the general formula (I), and is near the air interface of the molecules of the discotic liquid crystal. Has the effect of increasing the tilt angle. Furthermore, applicability such as unevenness and repellency is also improved.
- Examples of the fluoroaliphatic group-containing copolymer that can be used in the optically anisotropic layer of the present invention include JP-A Nos.
- the addition amount of the fluoroaliphatic group-containing copolymer does not exceed 2% by mass with respect to the liquid crystal compound, and is preferably about 0.1 to 1% by 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.
- at least one hydrophilic group selected from the group consisting of a carboxyl group (—COOH), a sulfo group (—SO 3 H), a phosphonoxy ⁇ —OP ( ⁇ O) (OH) 2 ⁇ and a salt thereof.
- the optical film of the present invention has a black matrix between the first retardation region and the second retardation region when the optical film of the present invention is used as a patterning retardation plate of a 3D image display device.
- the black matrix is disposed between the first alignment control region and the second alignment control region so as to separate the first alignment control region and the second alignment control region.
- positioned as a partition also includes the aspect arrange
- the optical film of the present invention has an overall Re (550) of 100 to 190 nm, preferably 100 to 175 nm, and more preferably 110 to 165 nm.
- the total of Rth of the transparent support of the laminate and Rth of the optically anisotropic layer is preferably
- Re and Rth are retardation values in the film thickness direction (unit: nm) at a wavelength of 550 nm.
- the thermal expansion coefficient in the present invention can be measured in accordance with ISO11359-2. From the gradient of the film length when the sample is heated from room temperature to 80 ° C. and then cooled from 60 ° C. to 50 ° C. Calculated.
- Humidity expansion coefficient [/% RH] ⁇ (L 1 ⁇ L 0 ) / L 0 ⁇ / (R 1 ⁇ R 0 )
- the humidity expansion coefficient of the optical film of the present invention 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.
- RH means relative humidity.
- the direction in which the speed of sound (sound 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) is used. It was used as a direction in which the propagation speed of the longitudinal wave vibration of the ultrasonic pulse was maximized.
- the elastic modulus in the present invention was prepared by preparing a film sample having a length of 150 mm and a width of 10 mm, adjusting the humidity for 24 hours at 25 ° C. and a relative humidity of 60%, and following an ISO 527-3: 1995 standard, an initial sample length of 100 mm, This is the tensile modulus measured from the initial slope of the stress-strain curve measured at a tensile 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, in the present invention, 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 ratio (E1 / E2) is a dimension while maintaining the flexibility of the film. From the viewpoint of reducing the change, it is preferably 1.1 to 5.0, more preferably 1.5 to 3.0.
- the elastic modulus of the film of the present invention 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.
- the total light transmittance of the optical film of the present invention is preferably as high as possible from the viewpoint of efficiently using light from the light source and reducing the power consumption of the panel. Specifically, it is preferably 85% or more. 90% or more, more preferably 92% or more. Further, the haze of the optical film of the present invention is preferably 5% or less, more preferably 3% or less, still more preferably 2% or less, and still more preferably 1% or less. Is particularly preferably 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 optical film of the present invention is preferably 3 to 50 g, more preferably 5 to 40 g, and still more preferably 10 to 30 g from the viewpoint of the brittleness of the film.
- the thickness of the optical film of the present invention 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.
- an optically anisotropic layer is formed by arranging a composition containing a liquid crystal having a polymerizable group on a laminate produced by the method for producing a laminate of the present invention. Forming a patterned optical anisotropic layer including a first retardation region whose orientation is controlled on the first orientation control region and a second retardation region whose orientation is controlled on the second orientation control region.
- the optically anisotropic layer is formed by applying a composition containing a liquid crystal having a polymerizable group (for example, a coating solution) onto the surface of a rubbing alignment film described later to obtain an alignment state exhibiting a desired liquid crystal phase.
- the layer is preferably a layer prepared by fixing the alignment state by irradiation with heat or ionizing radiation.
- the manufacturing method of the optical film of this invention includes the process of apply
- Application methods include curtain coating, dip coating, spin coating, print coating, spray coating, slot coating, roll coating, slide coating, blade coating, gravure coating, wire bar method, etc. A well-known coating method is mentioned.
- the coating liquid contains at least one of a pyridinium compound and an imidazolium compound. From the viewpoint of increasing the vertical alignment, it is preferable.
- the liquid crystal having a polymerizable group is preferably a discotic liquid crystal.
- organic solvent As a solvent used for preparing the coating solution, an organic solvent is preferably used.
- 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.
- the solvent contained in the coating liquid containing the solvent and the liquid crystal having a polymerizable group is contained in the first alignment control region printing liquid, and the first It is preferable that substantially none of the compounds contained in the orientation control region printing liquid is dissolved.
- 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 the horizontal alignment of the liquid crystal may be added to the composition. Examples of the additive are described in [0055] to [0063] of JP-A No. 2009-22001. 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 length of the liquid crystal on one of the first alignment control region and the second alignment control region is increased. Aligning the axis perpendicular to the rubbing treatment direction to form an orthogonal alignment region, and aligning the major axis of the liquid crystal on the other alignment control region parallel to the rubbing treatment direction to form a parallel alignment region It is preferable to contain.
- at least one of the first composition used for printing the first alignment control region and the second composition used for printing the second alignment control region is at least one of a pyridinium compound and an imidazolium compound.
- the alignment direction of the discotic liquid crystal compound can be changed with respect to the alignment control region including at least one of the pyridinium compound and the imidazolium compound, and a desired alignment state is obtained. be able to.
- the aligned liquid crystal compound is preferably fixed while maintaining the alignment state.
- the immobilization is preferably performed by a polymerization reaction of a reactive group introduced into the liquid crystal compound.
- the polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, and a photopolymerization reaction is more preferable.
- the production method of the present invention preferably includes a step of fixing the alignment state of the liquid crystal in the coating film by light 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. 4,212,970).
- 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 may be used in addition to the polymerization initiator.
- 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 in addition to the polymerizable liquid crystal compound.
- 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% by mass with respect to the liquid crystal compound, and is preferably about 0 to 20% by mass.
- X-rays, electron beams, ultraviolet rays, visible rays, or infrared rays (heat rays) can be used as the irradiation light.
- ultraviolet rays for light irradiation for polymerization of the liquid crystal compound.
- 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 (super-high pressure mercury lamp, xenon lamp, mercury xenon lamp). Used.
- Exposure is preferably 50 ⁇ 1000mJ / cm 2 or so, more preferably from 50 ⁇ 200mJ / cm 2 approximately.
- 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 laminate of the present invention is used for the formation of the patterned optically anisotropic layer.
- the laminate of the present invention including at least a rubbing alignment film.
- the rubbing alignment film of the present invention has the property that the alignment control ability is expressed by rubbing treatment, and the alignment axis is determined according to the rubbing direction and heating conditions. Therefore, by applying a pattern to the alignment film and the liquid crystal composition using a printing method and heating, a domain in which the alignment axes are orthogonal to each other can be formed, and then the rod-like liquid crystal is horizontally aligned, or By vertically aligning the discotic liquid crystal, it is possible to form a quarter wavelength layer composed of domains whose slow axes are orthogonal to each other.
- the discotic liquid crystal prepared as a coating liquid, a pyridinium compound, a fluoroaliphatic group-containing copolymer, a polymerization initiator, an increase in the surface on the orientation control region side (preferably a rubbing surface) of the laminate of the present invention.
- a composition for forming an optically anisotropic layer containing a sensitizer and the like is applied.
- the coating film of the composition is dried and then heated to bring it into a vertically aligned state so that the major axis of the discotic liquid crystal is parallel or orthogonal to the rubbing direction and the pattern.
- the molecules of the discotic liquid crystal are brought into this desired alignment state, they are cured by polymerization, the alignment state is fixed, and a pattern is formed.
- the coating film of the composition is dried and then heated so that the major axis of the rod-like liquid crystals is parallel and orthogonal to the rubbing direction according to the pattern.
- the rod-like liquid crystal molecules are brought into this desired alignment state and then cured by polymerization, and the alignment state is fixed to form a pattern.
- the method for producing an optical film of the present invention may include a step of forming a black matrix between the first retardation region and the second retardation region before or after the formation of the optically anisotropic layer.
- Good there is no restriction
- the present invention includes a step of forming a black matrix on the laminate so as to separate the first retardation region and the second retardation region, and the coating liquid containing the rod-like liquid crystal or the discotic liquid crystal is It is preferably applied during black matrix.
- a step of forming a black matrix on at least a boundary line between the adjacent first retardation region and the second retardation region is also preferable to include.
- the polarizing plate of the present invention includes at least one optical film of the present invention and a polarizing film, and the in-plane retardation of each of the first retardation region and the second retardation region of the optical anisotropic layer. Both the phase axis direction and the absorption axis direction of the polarizing film form approximately 45 °.
- Examples of the polarizing plate include a conventionally known polarizing plate having a general configuration. The specific configuration of the polarizing plate is not particularly limited, and a known configuration can be employed. The configuration described in FIG. 6 of Japanese Patent No. 262161 can be employed.
- the optical film of the present invention can be laminated on one surface of a general polarizing plate to form a patterning retardation film that can be used in a polarized glasses 3D stereoscopic image display system.
- the mode of the polarizing plate 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, in a long shape by continuous production.
- 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 method for producing a polarizing plate of the present invention comprises a step of rubbing the whole film in which a cellulose acylate as a transparent support and a patterned alignment film are laminated, and a composition mainly comprising a rod-like liquid crystal or a discotic liquid crystal.
- the manufacturing method of the polarizing plate of this invention has a manufacturing cost lower than the conventional manufacturing method from a viewpoint which can be manufactured continuously.
- the optical film and the polarizing film are laminated via an adhesive layer.
- the polarizing plate of the present invention preferably further has one or more antireflection films laminated on the outermost surface.
- Antireflection layer It is preferable to provide a functional film such as an antireflection layer on the protective film disposed on the opposite side of the polarizing plate from the liquid crystal cell.
- a functional film such as an antireflection layer
- the light scattering layer and the low refractive index layer are laminated in this order on the transparent protective film, or the medium refractive index layer, the high refractive index layer, and the 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.
- the light scattering layer of the present invention has mat particles dispersed therein, and the refractive index of the material other than the mat particles in the light scattering layer is preferably in the range of 1.50 to 2.00.
- the refractive index is preferably in the range of 1.35 to 1.49.
- the light scattering layer has both an antiglare property and a hard coat property, 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, since 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 present invention is reduced, which is preferable.
- the optical properties of the antireflection layer of the present invention are such that the specular reflectance is 2.5% or less, the transmittance is 90% or more, and the 60 ° glossiness is 70% or less. Is preferable.
- the specular reflectance is more preferably 1% or less, and most preferably 0.5% or less.
- the refractive index of the low refractive index layer of the antireflection film of the present invention is from 1.20 to 1.49, preferably from 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 of the present invention contains a fluorine-containing polymer as a low refractive index binder.
- the fluorine polymer is preferably a fluorine-containing polymer that is crosslinked by heat or ionizing radiation with 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 performed 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 isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and 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 above 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 from the viewpoint 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%.
- a filler since such a filler has a particle size sufficiently smaller than the wavelength of light, scattering does not occur, 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 film having a layer structure of at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer) on the substrate is designed to have a refractive index satisfying the following relationship.
- a hard coat layer is provided between the transparent support and the medium refractive index layer.
- it may comprise a medium refractive index hard coat layer, a high refractive index layer and a low refractive index layer (for example, JP-A-8-122504, JP-A-8-110401, JP-A-10-300902, JP 2002-243906, JP-A 2000-11706, etc.).
- Other functions 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 JP 2001-310432 A, etc., a core-shell structure with high refractive index particles as a core (JP 2001-166104 2001-310432 A, 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 ⁇ , more preferably 10 nm to 1 ⁇ m.
- the low refractive index layer is formed by sequentially laminating 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, it is effective to impart slipperiness to the surface, 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 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, a protective layer, and the like may be provided.
- the liquid crystal display device of the present invention includes a first and second polarizing films; a pair of substrates disposed between the first and second polarizing films, each having an electrode on at least one side, and the pair of substrates.
- a liquid crystal cell comprising: a liquid crystal layer between the substrates; and an optical film of the present invention on the outside of the first polarizing film, the absorption axis direction of the first polarizing film, and the optical film
- Each of the in-plane slow axis of the first phase difference region and the in-plane slow axis of the second phase difference region has an angle of ⁇ 45 °.
- the liquid crystal display device of the present invention can be used for liquid crystal cells and liquid crystal display devices in various display modes.
- TN Transmission Nematic
- IPS In-Plane Switching
- FLC Fluoroelectric Liquid Crystal
- AFLC Anti-Ferroelectric Liquid Crystal
- OCB OpticallySyPB
- HAN Hybrid Aligned Nematic
- the stereoscopic image display system of the present invention includes at least the image display device of the present invention and a third polarizing plate disposed outside the optical film of the present invention, and allows a stereoscopic image to be visually recognized through the third polarizing plate. It is characterized by that. In the present invention, it is preferable to recognize an image through a glasses-shaped polarizing plate as the third polarizing plate in order to make the viewer recognize a stereoscopic image called a 3D image.
- the video display system of the present invention includes polarized glasses in which the slow axes of the right glasses and the left glasses are orthogonal, and the right eye emitted from either the first region or the second region of the patterning retardation film.
- Image light for the left eye is transmitted through the right spectacles and shielded by the left spectacles, and the image light for the left eye emitted from the remaining one of the first region or the second region of the patterning phase difference film It is preferable to be configured to transmit light and be shielded from light by the right glasses.
- the polarizing glasses form a polarizing glasses by including a retardation functional layer and a linear polarizer in an arrangement corresponding to the patterning phase difference described in detail in the present invention.
- the patterning retardation film is formed on a plurality of first lines and a plurality of second lines that are alternately repeated on the image display panel (for example, on odd-numbered lines and even-numbered lines in the horizontal direction if the lines are in the horizontal direction).
- the first region and the second region having different polarization conversion functions are provided on the odd-numbered lines and the even-numbered lines in the vertical direction if the line is in the vertical direction.
- the phase difference between the first region and the second region is preferably ⁇ / 4, and the first region and the second region have a slow axis. More preferably, they are orthogonal.
- both the phase difference values of the first area and the second area are set to ⁇ / 4, the right-eye image is displayed on the odd lines of the video display panel, and the phase of the odd line phase difference area is delayed.
- the axis is a 45 degree direction, it is preferable to arrange ⁇ / 4 plates on both the right and left glasses of the polarized glasses, and the slow axis of the ⁇ / 4 plate of the right glasses of the polarized glasses is specifically What is necessary is just to fix to about 45 degree
- 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 once emitting image light as circularly polarized light 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 closer to the horizontal 135 degrees (or -45 degrees) accurately.
- 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-numbered phase retardation region and even-numbered phase retardation region of the patterning retardation film are 45 degrees in terms of polarization conversion efficiency. 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.
- the image display device includes a panel for displaying pixels,
- the pixels form a group of pixels that are repeatedly arranged in a line with the height of each pixel aligned, It is preferable that the first retardation region and the second retardation region of the optical film are alternately patterned corresponding to one line of the line-shaped pixel group.
- liquid crystal composition 1 0.35 ml was taken on a glass substrate with an alignment film, spin-coated (2500 rpm, 10 seconds), After curing by UV irradiation (10 seconds) while heating at 90 ° C., the arrangement was confirmed with a microscope.
- Reference Example 2 In Reference Example 1, an optical film was prepared in the same manner except that the following rod-shaped liquid crystal composition 2 was used instead of the liquid crystal composition 1, and the optical film obtained with a microscope was confirmed.
- Reference Example 3 In Reference Example 1, the following discotic liquid crystal composition 1 was used in place of the liquid crystal composition 1, and the coating film of the discotic liquid crystal composition 1 was heated to 140 ° C. and then cooled to 90 ° C. and irradiated with UV. In the same manner, an optical film of Reference Example 3 was prepared, and the arrangement of the optical film obtained with a microscope was confirmed.
- Reference Example 4 In Reference Example 1, the following discotic liquid crystal composition 2 was used in place of the liquid crystal composition 1, and the coating film of the discotic liquid crystal composition 1 was heated to 140 ° C. and then cooled to 90 ° C. and irradiated with UV. In the same manner, an optical film of Reference Example 4 was prepared, and the arrangement of the optical film obtained with a microscope was confirmed.
- Discotic liquid crystal composition 2 The following polymerizable liquid crystal 4 / the polymerization initiator 2 / the sensitizer 1 / the pyridinium compound 1 / the air interface alignment agent 2 / the air interface alignment agent 3 (100: 3: 1: 2: 0.3: 0) .5) 20% solid content MEK solution
- Example 1 [Preparation of pattern retardation film] (1) Application of parallel alignment film (first alignment film) A 4% water / methanol solution (PVA-103 (4.0 g)) of polyvinyl alcohol “PVA103” manufactured by Kuraray Co., Ltd. on the surface of the TAC film was 72 g and methanol. 24 g dissolved in a viscosity of 4.35 cp and a surface tension of 44.8 dyne) was applied with a No. 12 bar and dried at 80 ° C. for 5 minutes (film A).
- PVA-103 4% water / methanol solution
- PVA103 polyvinyl alcohol “PVA103” manufactured by Kuraray Co., Ltd.
- a synthetic rubber-like flexo plate having irregularities with dimensions shown in FIG. 1 was prepared.
- a flexiproof 100 (RK Print Coat Instruments Ltd. UK) was used.
- anilox roller 13 a cell of 400 lines / cm (volume: 3 cm 3 / m 2 ) was used.
- the flexographic plate 1 was bonded to the pressure drum 11 of the flexoproof 100 with a pressure sensitive tape (not shown).
- the pattern printing orthogonal alignment film liquid 1 (reference numeral 3 in FIG. 2) is put into a doctor blade 14, and the printing speed is 30 m / min (anilox roller pressure 40, printing pressure).
- An orthogonal alignment film was pattern-printed on the parallel alignment film with a roller pressure of 42 (no unit) (film B).
- the rod-like liquid crystal composition 1 was spin-coated on the film C1 (2500 rpm, 10 seconds), and UV irradiation was performed while heating at 90 ° C. ( After curing for 10 seconds, the arrangement was confirmed with a microscope (pattern retardation film 1). In the pattern retardation film 1, the parallel alignment film region is aligned in the direction in which the slow axis is parallel to the rubbing direction, and the orthogonal alignment film region is aligned in the direction in which the slow axis is orthogonal. confirmed.
- Example 2 A patterned retardation film 2 was obtained in the same manner as in Example 1 except that the liquid crystal composition to be applied was changed from the rod-shaped liquid crystal composition 1 to the rod-shaped liquid crystal composition 2.
- the parallel alignment film region is aligned in the direction in which the slow axis is parallel to the rubbing direction
- the orthogonal alignment film region is aligned in the direction in which the slow axis is orthogonal. confirmed.
- Example 3 The liquid crystal composition to be applied is changed from the rod-shaped liquid crystal composition 1 to the discotic liquid crystal composition 1, and the temperature is raised to 140 ° C. at the time of heating, and then the temperature is lowered to 90 ° C. and UV irradiation is performed in the same manner as in Example 1. Pattern retardation film 3 was obtained. In the pattern retardation film 3, the parallel alignment film region is aligned in the direction in which the slow axis is parallel and perpendicular to the rubbing direction, and the orthogonal alignment film region is aligned in the direction in which the slow axis is orthogonal and perpendicular. It was confirmed.
- the patterned optically anisotropic layer is formed by either one of the two polarizing plates in which the slow axes of either the first retardation region or the second retardation region are combined in the 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. 3A).
- FIG. 3B the state where the optically anisotropic layer was rotated by + 45 °
- FIG. 3B the state where the optically anisotropic layer was rotated by ⁇ 45 °
- Example 4 The liquid crystal composition to be applied was changed from the rod-shaped liquid crystal composition 1 to the discotic liquid crystal composition 2, and the temperature was raised to 140 ° C. during heating, and then the temperature was lowered to 90 ° C. and UV irradiation was performed in the same manner as in Example 1. Pattern retardation film 4 was obtained. In the pattern retardation film 4, the parallel alignment film region is aligned in the direction in which the slow axis is parallel and perpendicular to the rubbing direction, and the orthogonal alignment film region is aligned in the direction in which the slow axis is orthogonal and perpendicular. It was confirmed.
- Example 5 The pattern orientation was changed in the same manner as in Example 1 except that the pattern printing orthogonal alignment film liquid 1 was changed from the pattern printing orthogonal alignment film liquid 1 to the pattern printing orthogonal alignment film liquid 2 using (Compound No. 31). A phase difference film 5 was obtained. In the pattern retardation film 5, the parallel alignment film region is aligned in the direction in which the slow axis is parallel to the rubbing direction, and the orthogonal alignment film region is aligned in the direction in which the slow axis is orthogonal. confirmed.
- Example 6 The pattern orientation was changed in the same manner as in Example 1 except that the pattern printing orthogonal alignment film liquid 1 was changed from the pattern printing orthogonal alignment film liquid 1 to the pattern printing orthogonal alignment film liquid 2 using (Compound No. 46). A phase difference film 5 was obtained. In the pattern retardation film 5, the parallel alignment film region is aligned in the direction in which the slow axis is parallel to the rubbing direction, and the orthogonal alignment film region is aligned in the direction in which the slow axis is orthogonal. confirmed.
- the parallel alignment film region is aligned in the direction in which the slow axis is parallel and perpendicular to the rubbing direction
- the orthogonal alignment film region is aligned in the direction in which the slow axis is orthogonal and perpendicular. It was confirmed.
- Example 8 An aqueous solution of propanol (polyacrylic acid 2.0 g / water) obtained by dissociating 90% of polyacrylic acid (Mw 25000, manufactured by Wako Pure Chemical Industries, Ltd.) from the orthogonal alignment film liquid 1 for pattern printing using triethylamine. 1.12 g / propanol 5.09 g / 3-methoxy-1-butanol 5.09 g / triethylamine 2.52 g), except that the liquid crystal composition to be applied was replaced with the discotic liquid crystal composition 2. 3 to obtain a pattern retardation film 8.
- propanol polyacrylic acid 2.0 g / water
- the region above the PVA103 portion with respect to the rubbing direction is oriented in a direction in which the slow axis is parallel and perpendicular, and the region above the polyacrylic acid portion that is originally oriented in parallel is a pyridinium additive.
- the slow axis was oriented in the perpendicular direction. That is, when a discotic liquid crystalline compound containing a pyridinium compound is applied to the region above the PVA 103 portion and once reaches T Iso , the temperature drops and the discotic liquid crystalline compound is in a direction perpendicular to the rubbing direction. It was found to be oriented.
- Example 9 (1) Application of parallel alignment film (first alignment film) A 4% water / methanol / triethylamine solution of polyacrylic acid manufactured by Wako Pure Chemical Industries, Ltd. was applied to the surface of the TAC film with a No. 12 bar at 80 ° C. It was dried for 5 minutes (film A2). (2) Pattern application of alignment control region containing pyridinium compound As an orthogonal alignment film solution for pattern printing, 10 g of the pyridinium compound was dissolved in 100 g of methyl ethyl ketone to prepare a pyridinium solution 1 for pattern printing. The pyridinium solution 1 was printed on the film A2 by an inkjet method to form a pattern.
- an ink jet head is used as the discharge unit.
- DMC2831 head DMC-11610 (product model number) manufactured by FUJIFILM DIMATIX was used for this inkjet head.
- the pyridinium solution remained on the first alignment film and did not dry, but had penetrated into the first alignment film directly below the printed portion. It was.
- the optically anisotropic layer of the pattern retardation film 9 is oriented in the direction in which the slow axis is parallel to the orientation film region above the portion not containing the pyridinium compound with respect to the rubbing direction. It was confirmed that the region above the portion printed with was oriented in the direction in which the slow axis was orthogonal due to the influence of the pyridinium additive.
- a discotic liquid crystalline compound (not containing a pyridinium compound) is applied to a region above a polyacrylic acid portion not containing a pyridinium compound, and the temperature is lowered after reaching T Iso once, the discotic liquid crystalline compound Were oriented in a direction perpendicular to the rubbing direction.
- Pattern retardation film 10 was obtained.
- the region above the PVA-103 portion with respect to the rubbing direction is oriented in the direction in which the slow axis is orthogonally perpendicular, and the region above the polyacrylic acid portion is influenced by the pyridinium additive. It was confirmed that the slow axis was oriented in the direction perpendicular to the parallel.
- the discotic liquid crystalline compound containing a pyridinium compound when a discotic liquid crystalline compound containing a pyridinium compound is applied to the region above the PVA-103 portion and heated to 100 to 120 ° C. without reaching T Iso even once, the discotic liquid crystalline compound is in the rubbing direction. It was found to be oriented in a direction perpendicular to the direction perpendicular to the direction. Also, when a discotic liquid crystalline compound containing a pyridinium compound is applied to the region above the polyacrylic acid portion and heated to 100 to 120 ° C. without reaching T Iso , the discotic liquid crystalline compound is rubbed in the rubbing direction. It was found that the film was oriented in the direction perpendicular to the direction.
- Example 11 Polystyrene (55% by mass) -polyacrylic acid (45% by mass) copolymer (BASF, Jonkrill 690, Mw16500, acid value instead of 4% water / methanol / triethylamine solution of Wako Pure Chemicals polyacrylic acid 240) Dissolving 50% of the acrylic acid moiety and dissolving in propanol, the temperature was raised to 140 ° C. instead of heating at 100 ° C. to less than 140 ° C. (T Iso ) during heating, and then dropped to 90 ° C. A pattern retardation film 11 was obtained in the same manner as in Example 9 except that.
- the alignment film region above the portion not containing the pyridinium compound with respect to the rubbing direction is oriented in a direction in which the slow axis is orthogonal, and above the portion where the pyridinium compound is printed by ink jet printing.
- This region was confirmed to be oriented in the direction in which the slow axis was parallel due to the influence of the pyridinium additive. That is, a discotic liquid crystalline compound (not containing a pyridinium compound) is applied to the region above the polystyrene-polyacrylic acid copolymer portion not containing a pyridinium compound, and 100 ° C or higher without reaching T Iso even once.
- the discotic liquid crystalline compound when heated below 140 ° C., the discotic liquid crystalline compound is aligned in a direction perpendicular to the rubbing direction.
- a discotic liquid crystalline compound (not containing a pyridinium compound) is applied to a region above a polystyrene-polyacrylic acid copolymer portion containing a pyridinium compound, and 100 ° C. or more 140 ° C. without reaching T Iso even once. It was found that the discotic liquid crystalline compound was aligned in a direction perpendicular to the rubbing direction when heated to less than ° C.
- Example 12 The pattern phase difference of the pattern alignment film obtained in Example 8 was flexographically printed with black ink (manufactured by Dainippon Seika Co., Ltd., Hydrick FCG) over a width of 30 ⁇ m in the boundary region between the printed portion and the non-printed portion. 12 was obtained. Thereafter, liquid crystal was applied in the same manner as in Example 8 to obtain a patterned retardation film 12 containing a black matrix.
- black ink manufactured by Dainippon Seika Co., Ltd., Hydrick FCG
- Example 2 In the same manner as in Example 1, except that 2.646 g of the alignment film compound was dissolved in 0.658 g of triethylamine and 12 g of tetrafluoropropanol to obtain an orthogonal alignment film solution for pattern printing, the film A was subjected to flexographic printing. An orthogonal orientation film was applied in a pattern. As a result, all regions showed parallel alignment, and the orthogonally aligned portion could not be confirmed.
- the orthogonal alignment film solution for pattern printing of the orthogonal alignment film (Comparative Example 3) is applied with a 12 bar, dried at 120 ° C. for 2 minutes, and then reciprocated once in one direction at 1000 rpm. Then, a rubbing treatment was performed to produce a glass support with a rubbing alignment film.
- the rod-shaped liquid crystal composition 1 was spin-coated on the alignment film. The solvent was evaporated, and the coating film of the liquid crystal composition was heated and fixed by UV irradiation over the entire surface. As a result, all regions showed parallel alignment, and the orthogonally aligned portion could not be confirmed.
- the alignment film compound 2.646 g was dissolved in triethylamine 0.658 g and tetrafluoropropanol 12 g to obtain an orthogonal alignment film solution for pattern printing.
- the orthogonal orientation film was applied in a pattern by a printing method. As a result, all regions showed parallel alignment, and the orthogonally aligned portion could not be confirmed.
- the orthogonal alignment film solution for pattern printing of the orthogonal alignment film (Comparative Example 3) is applied with a 12 bar, dried at 120 ° C. for 2 minutes, and then reciprocated once in one direction at 1000 rpm. Then, a rubbing treatment was performed to produce a glass support with a rubbing alignment film.
- the rod-like liquid crystal composition 1 was spin-coated on the alignment film. The solvent was evaporated, and the coating film of the liquid crystal composition was heated and fixed by UV irradiation over the entire surface. As a result, all regions showed parallel alignment, and the orthogonally aligned portion could not be confirmed.
- Example 101 ⁇ Preparation of antireflection film> The hard coat layer was applied to the upper part of the pattern retardation film 1 of Example 1.
- the following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.
- 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.
- 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.
- 50:50 represents a molar ratio
- 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.
- 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 Examples of the pamphlet of International Publication No. 2003/022906: 5% by mass
- the hard coat layer coating solution 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 .
- ⁇ Preparation of polarizing plate> The film prepared above was coated with 20 ml / m 2 of the following pressure-sensitive adhesive coating liquid and upper layer coating liquid B on the transparent support side, and dried at 100 ° C. for 5 minutes to obtain a film sample with pressure-sensitive adhesive.
- 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.
- Re (550) is 3 nm and
- an adhesive layer is applied and bonded to prepare a polarizing plate.
- Example 201 ⁇ Creation of transparent film for stereoscopic images> A right-eye image and a left-eye image were created using a digital camera (FinePix Real 3D W1 manufactured by FUJIFILM Corporation) equipped with two left and right photographing lenses. Next, an image in which the right-eye image and the left-eye image were alternately replaced every 200 ⁇ m was created using 3D image creation software (striper). Finally, the image data was printed out on an OHP sheet (manufactured by KOKUYO, VF-1300) using an electrophotographic printer (manufactured by Fuji Xerox, Docupurint C3540) to obtain a transparent image 1 for three-dimensional stereoscopic photography. .
- OHP sheet manufactured by KOKUYO, VF-1300
- an electrophotographic printer manufactured by Fuji Xerox, Docupurint C3540
- Example 202 ⁇ Creation of transparent film for stereoscopic images>
- the digital image 1 data was printed on an IJ transparent film (Mitsubishi Paper Co., Ltd., IJ-FilmFT100) using an inkjet (EPSON Co., PM-A820) and used for 3D stereoscopic photography.
- Transparent image 2 was obtained.
- ⁇ Creation of pattern polarizing film> Using the adhesive of the pattern retardation film 1 of Example 1, it was bonded to the polarizing plate. Furthermore, it is possible to observe a clear three-dimensional image without crosstalk when bonded to the transparent image 2 for 3D stereoscopic photography using an adhesive and observed through circular polarizing glasses for the right eye / left eye. It was.
- Example 203 ⁇ Creation of transparent film for stereoscopic images> (Production of photographic paper for stereoscopic images) ⁇ Preparation of transparent dye image-receiving layer>
- the surface of the cellulose acetate protective film was subjected to corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided.
- an intermediate layer A having the following composition was applied by a bar coater and dried, and subsequently, a receiving layer A having the following composition was applied by a bar coater and dried. Bar coater coating was performed at 40 ° C., and drying was performed at 50 ° C. for 16 hours for each layer. Coating was performed such that the coating amount at the time of drying was intermediate layer A: 1.0 g / m 2 and receiving layer A 1: 3.0 g / m 2 .
- Polyester resin (Byron 200, trade name, manufactured by Toyobo Co., Ltd.) 10 parts by weight
- Optical brightener 1 part by weight (Uvitex OB, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) Titanium oxide 30 parts by mass Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts by mass
- ⁇ Receptive layer A 100 parts by mass of polyester resin (Resin described in Example 1 of JP-A-2-265789) Amino-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-3050C) Epoxy-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-300E) Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass
- a polyester film having a thickness of 6.0 ⁇ m (Lumirror, trade name, manufactured by Toray Industries, Inc.) was used as a base film.
- a heat-resistant slip layer (thickness 1 ⁇ m) was formed on the back side of the film, and yellow, magenta and cyan compositions having the following compositions were applied to the surface side in a single color (coating amount 1 g / m 2 during dry film formation).
- the polarizing glasses are composed of a circular polarizing filter for the left eye and a circular polarizing filter for the right eye, and each circular polarizing filter includes a linear polarizing filter and a 1 / 4 ⁇ phase difference film, and its polarization axis and slow phase.
- the layers are stacked so that the axes form an angle of 45 °, and for the left eye and the right eye, the polarization axes of the linear polarizing filters are orthogonal.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Multimedia (AREA)
- Signal Processing (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
Description
また、ラビング配向膜を利用する方法も提案されている。例えば、特許文献2には、異なる方向に配向された部分からなるパターンを有する配向層を利用して、パターン位相差層を形成する方法が開示され、マスクラビング処理することにより、異なる方向に配向された部分からなる配向層を形成する方法が開示されている。しかしながら、フォトマスクを用いた光配向膜や、マスクラビングによる配向膜の製造方法は、製造設備が高価な上、マスクのフィルムへの高精度な位置合わせが必要であり、得られる配向膜の2つの配向制御領域のパターニング精度に不満が残るものであった。さらに、マスクラビングを行う方法は、フィルム搬送方向に対するラビング方向を変える必要があるため、製造の容易さの観点からの問題が大きい。
これに対し、特許文献3では、フォトマスクを用いた光配向膜やマスクラビングによる配向膜の製造方法の代わりにフォトリソグラフィ技術を用い、感光性の垂直配向膜と水平配向膜形成材料を塗布し、露光し、一方の一部を現像処理した後で、一括してラビング処理して垂直配向膜と水平配向膜とがパターニングされた配向膜を製造する方法が開示されている。しかしながら、同文献は、液晶表示装置の液晶セルの液晶の配向を制御するためのパターニング配向膜を製造しており、得られたパターニング配向膜に対して垂直方向と水平方向に液晶の配向を制御するためにパターニング配向膜が開示されているのみであった。
特に、3D画像表示装置用のパターニング位相差板のように、位相差板面に平行な面内において2つの位相差領域が直交するように液晶化合物を制御できるような、2種の配向制御領域がパターニングされた配向膜は知られていなかった。
本発明の第一の目的は、透明支持体上に2種類以上の配向制御層が形成されており、配向制御面に平行な面内において液晶の長軸を互いに直交する方向に配向制御可能である積層体と、該積層体を用いた光学フィルムを提供することである。第二の目的は、かかる積層体および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、前記光学フィルムを用いた偏光板、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] 透明支持体と、該透明支持体上に、組成が互いに異なり、且つ互いに異なる配向制御能を示す配向制御表面を有する、第一の配向制御領域及び第二の配向制御領域を含み、それぞれの配向制御表面が交互に配置されたパターン配向制御層を有し、前記第一の配向制御領域及び前記第二の配向制御領域のそれぞれの配向制御面が、該配向制御面に平行な面内において液晶の長軸を互いに直交する方向に配向制御可能であることを特徴とする積層体。
[2] 前記第一の配向制御領域と前記第二の配向制御領域が同じ方位に処理されていることを特徴とする[1]に記載の積層体。
[3] 前記第一の配向制御領域と前記第二の配向制御領域が、同じ方位にラビング処理されたラビング配向膜であることを特徴とする[1]に記載の積層体。
[4] 前記第一の配向制御領域と前記第二の配向制御領域が、それぞれ変性または無変性のポリビニルアルコールを主成分として含有する膜;変性または無変性のポリアクリル酸を主成分として含有する膜;下記一般式(I)で表される繰り返し単位と、下記一般式(II)もしくは(III)で表される繰り返し単位とを含む(メタ)アクリル酸コポリマーを主成分として含有する膜;または、下記一般式(I-TH)、一般式(II-TH)及び一般式(III-TH)のいずれかで表される構造単位を少なくとも1種有する重合体を主成分とする膜;のいずれかであることを特徴とする[1]~[3]のいずれか一項に記載の積層体。
:R1およびR2は、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数が1乃至6のアルキル基であり
;Mは、プロトン、アルカリ金属イオンまたはアンモニウムイオンであり;L0は、-O-、-CO-、-NH-、-SO2-、アルキレン基、アルケニレン基、アリーレン基およびそ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り
;R0は、炭素原子数が10乃至100の炭化水素基または炭素原子数が1乃至100のフッ素原子置換炭化水素基であり
;Cyは、脂肪族環基、芳香族基または複素環基であり
;mは、10乃至99モル%であり;そして、nは、1乃至90モル%である。)
一般式(I-TH)
一般式(II-TH)
一般式(III-TH)
[5] 前記第一の配向制御領域と前記第二の配向制御領域が、それぞれ異なる樹脂を主成分とする[1]~[4]のいずれか一項に記載の積層体。
[6] 前記第一の配向制御領域と前記第二の配向制御領域の少なくとも一方の領域が、ピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方を含むことを特徴とする[1]~[5]のいずれか一項に記載の積層体。
[7] 前記第一の配向制御領域と前記第二の配向制御領域が、共に同じ樹脂を主成分とし、かつ、少なくとも一方の領域にピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方を含むことを特徴とする[1]~[4]のいずれか一項に記載の積層体。
[8] 前記ピリジニウム化合物またはイミダゾリウム化合物が、液晶性であることを特徴とする[6]又は[7]に記載の積層体。
[9] 前記第一の配向制御領域と前記第二の配向制御領域が、共に非現像性樹脂を主成分とすることを特徴とする[1]~[8]のいずれか一項に記載の積層体。
[10] 前記第一の配向制御領域と前記第二の配向制御領域が、下記(1)または(2)のいずれか1つの態様であることを特徴とする[1]~[9]のいずれか一項に記載の積層体。
態様(1):透明支持体上に第一の配向制御領域が形成され、該第一の配向制御領域の一部の領域上に第二の配向制御領域が形成されている。
態様(2):透明支持体の一部の領域上に第一の配向制御領域が形成され、前記透明支持体の第一の配向制御領域が形成されていない領域上に第二の配向制御領域が形成されている。
[11] 前記第一の配向制御領域と前記第二の配向制御領域との間に、ブラックマトリックスが配置されていることを特徴とする[1]~[10]のいずれか一項に記載の積層体。
[12] 前記透明支持体のRe(550)が、0~10nmであることを特徴とする[1]~[11]のいずれか一項に記載の積層体:
但し、Re(550)は波長550nmにおける正面レターデーション値(単位:nm)である。
[13] パターン光学異方性層の支持体として用いられることを特徴とする[1]~[12]のいずれか一項に記載の積層体。
[14] [1]~[13]のいずれか一項に記載の積層体と、該積層体上の前記配向制御領域上に、重合性基を有する液晶を主成分とする組成物から形成された光学異方性層を有し、
該光学異方性層は、面内遅相軸が互いに異なる第一位相差領域と第二位相差領域とが交互にパターニングされていることを特徴とする光学フィルム。
[15] 前記光学異方性層中、前記第一位相差領域と前記第二位相差領域が前記光学異方性層の一辺に平行な長辺を有する帯状に交互にパターニングされており、且つ、前記第一位相差領域の面内の遅相軸と前記第二位相差領域の面内の遅相軸が略直交していることを特徴とする[14]に記載の光学フィルム。
[16] 全体のRe(550)が100~190nmであることを特徴とする[14]又は[15]に記載の光学フィルム:ただし、前記Re(550)は波長550nmにおける正面レターデーション値(単位:nm)である。
[17] 前記重合性基を有する液晶がディスコティック液晶であり、前記光学異方性層中、ディスコティック液晶が垂直配向状態に固定されていることを特徴とする[14]~[16]のいずれか一項に記載の光学フィルム。
[18] 前記光学異方性層が、ピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方を含有していることを特徴とする[17]に記載の光学フィルム。
[19] 前記重合性基を有する液晶が棒状液晶であり、前記光学異方性層中、棒状液晶が水平配向状態に固定されていることを特徴とする[14]~[16]のいずれか一項に記載の光学フィルム。
[20] 前記第一位相差領域と前記第二位相差領域との間にブラックマトリックスを有することを特徴とする[14]~[19]のいずれか一項に記載の光学フィルム。
[21] [14]~[20]のいずれか一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前記第一位相差領域と前記第二位相差領域のそれぞれの面内遅相軸方位と、偏光膜の吸収軸方位とがいずれも45°をなすことを特徴とする偏光板。
[22] 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ことを特徴とする[21]に記載の偏光板。
[23] 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ことを特徴とする[21]または[22]に記載の偏光板。
[24] 第一及び第二の偏光膜;
第一及び第二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
第一偏光膜の外側に[14]~[23]のいずれか一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、
前記第一偏光膜の吸収軸方向と、前記光学フィルムの第一相差領域の面内遅相軸及び第二位相差領域のそれぞれの面内遅相軸が、いずれも±45°の角度をなすことを特徴とする画像表示装置。
[25] [24]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三の偏光板とを少なくとも備え、第三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。
[26] 第一の組成物からなる第一の配向制御領域を透明支持体上に形成する第一の配向制御領域形成工程と、及び
第一の組成物と組成が異なる第二の組成物からなる第二の配向制御領域をパターン状に印刷する第二の配向制御領域形成工程を、少なくとも含むことを特徴とする[1]~[13]のいずれか1項に記載の積層体の製造方法。
[27] 前記第一の配向制御領域を下記(I)または(II)のいずれかの方法で透明支持体上に形成する第一の配向制御領域形成工程を特徴とする[26]に記載の積層体の製造方法。
方法(I):前記第一の配向制御領域を前記透明支持体の全面上に形成する工程。
方法(II):前記第一の配向制御領域を前記透明支持体の一部の領域上に形成する工程。
[28] 前記第一の配向制御領域と前記第二の配向制御領域を1つの方位に配向処理する工程を含むことを特徴とする[26]または[27]に記載の積層体の製造方法。
[29] 透明支持体上に、第一の配向制御領域と第二の配向制御領域とを面内に含む配向制御層を下記(I-A)、(I-B)および(II-A)のいずれか1つの印刷工程で形成する工程を含むことを特徴とする[26]~[28]のいずれか一項に記載の方法。
印刷工程(I-A):透明支持体上に第一の配向制御領域を印刷し、該第一の配向制御領域の一部の領域上に第二の配向制御領域を印刷し、該第一の配向制御領域および該第二の配向制御領域を同時に1つの方位に処理する工程。
印刷工程(I-B):透明支持体上に第一の配向制御領域を印刷し、該第一の配向制御領域を1つの方位に処理した後、該第一の配向制御領域の処理面の一部の領域上に第二の配向制御領域を印刷する工程。
印刷工程(II-A):透明支持体の一部の領域上に第一の配向制御領域を印刷し、前記透明支持体の第一の配向制御領域が印刷されていない領域上に第二の配向制御領域を印刷し、該第一の配向制御領域および該第二の配向制御領域を同時に1つの方位に処理する工程。
[30] 前記1つの方位に処理する工程が、一方位へのラビング処理工程であることを特徴とする[28]または[29]に記載の方法。
[31] 前記第二の配向制御領域を、フレキソ印刷により形成することを特徴とする[26]~[30]のいずれか一項に記載の方法。
[32] 前記印刷工程(I-A)または(II-A)において、前記第一の配向制御領域の印刷に用いる第一の組成物が、平行配向膜用組成物および直交配向膜用組成物のうちいずれか一方と第一の溶媒を含み、前記第二の配向制御領域の印刷に用いる第二の組成物がもう一方の化合物と第二の配向溶媒を含むことを特徴とする[29]~[31]のいずれか一項に記載の方法。
[33] 前記印刷工程(I-B)において、前記第一の配向制御領域の印刷に用いる第一の組成物が、配向膜用化合物と第一の溶媒を含み、前記第二の配向制御領域の印刷に用いる第二の組成物が、ピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方と第二の溶媒を含むことを特徴とする[29]~[32]のいずれか一項に記載の方法。
[34] [1]~[13]のいずれか一項に記載の積層体上に、重合性基を有する液晶を含有する組成物を配置し、光学異方性層を形成し、第一の配向制御領域上で配向制御された第一位相差領域及び第二の配向制御領域上で配向制御された第二位相差領域を含むパターン光学異方性層を形成することを特徴とする光学フィルムの製造方法。
[35] 前記積層体中の第一の配向制御領域および前記第二の配向制御領域の少なくとも一方が、ピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方を含み、前記液晶がディスコティック液晶であり、前記積層体上に、前記ディスコティック液晶を含有する組成物を配置した後で加熱処理することにより、前記ディスコティック液晶の配向を制御して前記第一の位相差領域および第二の位相差領域を形成することを特徴とする[34]に記載の方法。
[36] 前記光学異方性層の形成前又は後に、前記第一位相差領域及び前記第二位相差領域との間にブラックマトリックスを形成することを含む[34]または[35]に記載の方法。
本発明の積層体の製造方法および光学フィルムの製造方法によれば、本発明の積層体および光学フィルムを簡便、且つ、安価に提供することができる。
本発明によれば、本発明の光学フィルムを用いた偏光板、画像表示装置、および立体画像表示システムを、簡便、且つ、安価に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。
本明細書では、平行配向とは配向制御領域の処理方向に対して液晶分子の長軸が略平行に配向することを示し、直交配向とは配向制御領域の処理方向に対して液晶分子の長軸が略直交に配向することを示す。
本明細書では、組成物の「組成が互いに異なる」とは、組成物中の主成分及び/又は1以上の添加剤が互いに異なることを意味するだけではなく、成分が同一であっても、含有割合が異なることも含む意味で用いる。
本明細書では、分子の長軸方向とは、棒状液晶分子の場合は分子内で最も長い軸の方位のことを言い、ディスコティック液晶分子の場合は円盤面が並ぶ方位(円盤面の垂線の方位)のことを言う。
本発明の積層体は、透明支持体と、該透明支持体上に、組成が互いに異なり、且つ互いに異なる配向制御能を示す配向制御表面を有する、第一の配向制御領域及び第二の配向制御領域を含み、それぞれの配向制御表面が交互に配置されたパターン配向制御層を有し、前記第一の配向制御領域及び前記第二の配向制御領域のそれぞれの配向制御面が、該配向制御面に平行な面内において液晶の長軸を互いに直交する方向に配向制御可能であることを特徴とする。
本発明の積層体は、制御能が互いに異なる配向制御表面が交互に配置された配向制御層を有し、その上で同一の液晶を配向させると、第一及び第二の配向制御領域上の液晶分子はそれぞれ、長軸を互いに直交にして配向する。よって、本発明の積層体を支持体として用いて液晶組成物からなる光学異方性層を形成すると、面内遅相軸方向が互いに直交している第一及び第二の位相差層が交互に配置されたパターン光学異方性層を容易に形成できる。即ち、本発明の積層体をこのような構成を有することで、高価なフォトマスクを用いずに、既存の配向膜製造設備を使用して良好なパターンが形成された光学異方性層を提供できる。
(A)棒状液晶の長軸を互いに直交する方向に水平配向制御できる。
(B)ディスコティック液晶の円盤面を、配向制御層膜面に対して垂直方向かつ長軸を互いに直交する方向に配向制御できる。
この場合、前記配向制御層の前記透明支持体とは反対側の表面は、前記上層の第二の配向制御領域22bであるため、積層体の前記配向制御層の前記透明支持体とは反対側の表面を、前記透明支持体と平行な仮想平面上に正射影したとき、下層の第一の配向制御領域22aが表面となっている部分に由来する前記第一の配向制御領域と、上層の第二の配向制御領域22bが表面となっている部分に由来する前記第二の配向制御領域が交互にパターニングされていることとなる。
なお、本発明の積層体は、前記配向制御層が前記(I)の態様で製造された場合であるとき、配向制御領域の厚さは、0.01~10μmであることが好ましく、0.01~1μmであることがさらに好ましい。この程度の厚さであれば、膜面に凹凸があってもその膜面に垂直な方向に積層された液晶分子の配向規制力を十分に維持できる。
この場合、前記配向制御層の前記透明支持体とは反対側の表面は、前記第一の配向制御領域22aおよび第二の配向制御領域22cであるため、積層体の前記配向制御層の前記透明支持体とは反対側の表面を、前記透明支持体と平行な仮想平面上に正射影したとき、前記第一の配向制御領域と、前記第二の配向制御領域が交互にパターニングされていることとなる。
ここで、本明細書中、「配向膜」とは、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。配向膜は、配向性を付与する方法の観点から、ラビング配向膜、光配向膜、その他電場の付与や磁場の付与により液晶配向性を付与した膜に分けることができる。本発明の積層体では、ラビング配向膜を用いることが、製造速度向上による生産性の観点から好ましい。そこで、以下、ラビング配向膜について主として説明するが、本発明は以下のラビング配向膜の態様に限定されるものではない。
ここでいう、平行配向膜、直交配向膜について概念的な説明は以下のとおりである。
ラビングにより、高分子の表面に特定の深さまでの領域に加工層が生じる。そこで生じるのはラビング方向に発生する溝と屈折率の異方性である。この異方性の光軸はポリイミドではラビング方向に平行、ポリスチレンでは直交している。ラビングによる液晶分子の一方向性の配向の機構として、溝にそって棒状分子が並ぶという説と異方的分散力による説明とがある。具体的には、ラビング処理は、表面層の高分子鎖を延伸するのと同様な効果があり、両者とも高分子の主鎖はラビングした方向に並び代えが起こる。そうするとポリビニルアルコールの側鎖である水酸基はラビング方向に垂直になるし、ポリスチレン膜の場合には主鎖ではなく、側鎖のフェニル基も垂直になる。つまりラビング処理を施した高分子フィルムによる液晶分子の配向方向は、1軸配向したポリマー主鎖、及び/またはその主鎖に対して垂直方向に張り出した置換基のいずれかによっても決まると考えてよい。
実用に供されている直交配向膜であるポリイミド膜による液晶配向では、ラビング処理による非常に細かな溝が配向制御に重要な役割を果たしていることが示唆されており、ラビング方向に並んだ高分子主鎖の効果も同時に関与していると考えられている。ポリスチレン膜でも物理的な表面形状の変化、つまり細かな溝が発生していると考えられるが、結果的には側鎖のフェニル基と液晶分子の相互作用が支配的となっている。すなわち、ポリイミドでは両者は平行に協力して作用し,ポリスチレンでは異方的分散力による機構の方が優勢となり、平行配向膜と直交配向膜に分かれる。
ここで、本明細書中、「配向制御層」とは、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。前記配向制御層は、単層であっても、2層以上から構成されていてもよい。前記配向制御層は、ラビング配向膜や光配向膜のような配向膜と、液晶分子のその界面における配向を規制することができる配向制御剤を主成分とする膜に大別される。
(配向制御領域を構成する材料)
前記配向制御領域は配向膜であることが好ましい。前記配向膜は、一般的にはポリマーを主成分とする。配向膜用ポリマー材料としては、多数の文献に記載があり、多数の市販品を入手することができる。この中でもラビング配向膜としては、以下の材料を配向膜として好ましく用いることができる。
:R1およびR2は、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数が1乃至6のアルキル基であり
;Mは、プロトン、アルカリ金属イオンまたはアンモニウムイオンであり;L0は、-O-、-CO-、-NH-、-SO2-、アルキレン基、アルケニレン基、アリーレン基およびそ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り
;R0は、炭素原子数が10乃至100の炭化水素基または炭素原子数が1乃至100のフッ素原子置換炭化水素基であり
;Cyは、脂肪族環基、芳香族基または複素環基であり
;mは、10乃至99モル%であり;そして、nは、1乃至90モル%である。)
一般式(I-TH)
一般式(II-TH)
一般式(III-TH)
下記表1~27に、本発明に利用可能な直交配向膜の例を示すが、本発明はこれらの態様に限定されるものではない。
下記表1~6、9~12、14、21~27において直交配向に必要な成分は、繰り返し数がa個である成分であり、アルコール溶媒への溶解性に必要な成は繰り返し数がb個である成分である。表7、8、13において直交配向に必要な成分は、繰り返し数がa個である成分とc個である成分であり、アルコール溶媒への溶解性に必要な成分は繰り返し数がb個である成分である。表15~20の化合物番号30~42に記載の骨格は、配向必要成分と溶解性付与成分がともに繰り返し数がa個である成分であり同一である。
(上記表1に記載の化合物番号5の合成方法)
三口フラスコに溶媒としてNEP(N-エチルピロリドン)1.83gを入れた。9-ビニルカルバゾール9.62g、アクリル酸5.38g及びAIBN409mgをNEP10.08gに溶解した溶液をパイレンで濾過して、NEP2.75gで洗浄した溶液をシリンジポンプで2時間かけて滴下し、内温75℃、窒素フロー(10ml/min)で攪拌回数350rpm攪拌・重合した。さらに滴下終了後NEP3.3gでシリンジポンプ内を洗浄した。さらにAIBN163mgをNEP367mgに溶解した溶液を滴下して、内温75℃、窒素フロー(10ml/min)、攪拌回数350rpmで3時間攪拌し・重合した。内温を室温まで低下させて、THF30mlを添加した。反応液をメタノール:水(=9:1)600mlに入れ再沈殿させ、デカントして溶媒を除いた。さらにメタノール:水(=9:1)300mlを30分攪拌し、さらにデカントして溶媒を除いた。最後にメタノール:水(=1:1)400mlを30分攪拌して、固体を吸引濾過した。その後真空乾燥(40℃)した後に、白色固体を15.79g得た。
本発明に配向制御剤として利用可能な前記ピリジニウム化合物またはイミダゾリウム化合物は、液晶性であっても、非液晶性であってもよく、いずれの場合も所定の配向膜材料と相互作用して、光学異方性層に含まれるディスコティック液晶の分子の配向方向を制御することができる。その中でも、前記ピリジニウム化合物またはイミダゾリウム化合物は液晶性であることがディスコティック液晶への配向制御能をより改善する観点から好ましく、その中でも、下記一般式(2a)で表されるピリジニウム化合物又は下記一般式(2b)で表されるイミダゾリウム化合物であることが特に好ましい。下記一般式(2a)及び(2b)で表されるピリジニウム化合物およびイミダゾリウム化合物は、所定の配向膜材料と相互作用して、液晶分子の配向を制御して、その長軸方向を決定する作用があるとともに、特にディスコティック液晶(特に後述の一般式(I)~(IV)で表される液晶)に対しては、配向膜界面における配向を制御する作用があり、より具体的には、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。
前記ピリジニウム化合物およびイミダゾリウム化合物は、その添加量が、配向制御層の主成分樹脂に対して0.01~20質量%であることが好ましく、0.1~2質量%程度であるのが好ましい。
前記一般式(2a)及び(2b)で表されるピリジニウム化合物およびイミダゾリウム化合物は、ピリジニウム基又はイミダリウム基が親水的であるため親水的なポリビニルアルコール配向膜表面に偏在する。特に、ピリジニウム基に、さらに、水素原子のアクセプターの置換基であるアミノ基(一般式(2a)及び(2a’)において、R22が無置換のアミノ基又は炭素原子数が1~20の置換アミノ基)が置換されていると、ポリビニルアルコールとの間に分子間水素結合が発生し、より高密度に配向膜表面に偏在すると共に、水素結合の効果により、ピリジニウム誘導体がポリビニルアルコールの主鎖と直交する方向に配向するため、ラビング方向に対して液晶の直交配向を促進する。前記ピリジニウム誘導体は、分子内に複数個の芳香環を有しているため、前述した、液晶、特にディスコティック液晶との間に強い分子間π-π相互作用が起こり、ディスコティック液晶の配向膜界面近傍における直交配向を誘起する。特に、一般式(2a’)で表されるように、親水的なピリジニウム基に疎水的な芳香環が連結されていると、その疎水性の効果により垂直配向を誘起する効果も有する。
上記した通り、本発明の積層体の一態様は、棒状液晶を、その長軸を互いに直交する方向に水平配向させ得る第一及び第二の配向制御町域を有する態様である。
本態様の一例は、前記前記第一の配向制御領域と前記第二の配向制御領域の一方に、平行配向膜を用い、他方の領域に直交配向膜を用いる例である。
下記の配向膜は、棒状液晶分子の長軸を当該配向軸(一般的にはラビング軸)に対して平行にして配向させる機能を有する。平行配向膜として利用されるポリマー材料は、ポリビニルアルコール、ポリアクリル酸又はポリイミド及びその誘導体からなる配向膜である。前記平行配向膜は、特に変性もしくは未変性のポリビニルアルコールまたは変性もしくは無変性のポリアクリル酸を主成分として含有する膜であることがより好ましい。ここで、ポリビニルアルコールは、種々の鹸化度のものが存在する。本発明では、鹸化度85~99程度のものを用いるのが好ましい。市販品を用いてもよく、例えば、「PVA103」、「PVA203」(クラレ社製)等は、上記鹸化度のPVAである。ラビング配向膜については、WO01/88574A1号公報の43頁24行~49頁8行、特許第3907735号公報の段落番号[0071]~[0095]に記載の変性ポリビニルアルコールを参照することができる。前記変性もしくは未変性ポリアクリル酸とは、ポリ(メタ)アクリル酸共重合体を意味し、アクリル酸もしくはメタクリル酸を含有していればよい。アクリル酸もしくはメタクリル酸の高分子鎖中への含有率はモル比で1%~100%、好ましくは10%~100%、さらに好ましくは30%~100%である。重量平均分子量としては1000~1000000、好ましくは3000~100000、より好ましくは5000~50000を用いることができる。
上記した通り、本発明の積層体の他の態様は、ディスコティック液晶を、その円盤面を垂直にして、その長軸を互いに直交する方向に配向させ得る第一及び第二の配向制御領域を有する態様である。
本発明の積層体に用いられる透明支持体としては、特に制限なく公知の配向膜用透明支持体を用いることができる。その中でも、前記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フィルムを用いることも望ましい態様である。
但し、Re(550)は波長550nmにおける正面レターデーション値(単位:nm)である。
後述する透明支持体への添加剤の添加量を調整することにより、前記透明支持体の好ましいRe(550)の範囲に制御することができる。
なお、ここに、Re(λ)は波長λnmにおける正面レターデーション値(単位:nm)、Rth(λ)は波長λnmにおける膜厚方向のレターデーション値(単位:nm)である。
前記透明支持体を形成する材料としては、光学性能透明性、機械的強度、熱安定性、水分遮蔽性、等方性などに優れるポリマーが好ましく、上述のRe、Rthが、上述した式(I)を満たす範囲であればどのような材料を用いてもよい。例えば、ポリカーボネート系ポリマー、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル系ポリマー、ポリメチルメタクリレート等のアクリル系ポリマー、ポリスチレンやアクリロニトリル・スチレン共重合体(AS樹脂)等のスチレン系ポリマーなどがあげられる。また、ポリエチレン、ポリプロピレン等のポリオレフィン、エチレン・プロピレン共重合体の如きポリオレフィン系ポリマー、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミド等のアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、塩化ビニリデン系ポリマー、ビニルアルコール系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー、又は前記ポリマーを混合したポリマーも例としてあげられる。また本発明の高分子フィルムは、アクリル系、ウレタン系、アクリルウレタン系、エポキシ系、シリコーン系等の紫外線硬化型、熱硬化型の樹脂の硬化層として形成することもできる。
前記セルロースアシレート原料のセルロースとしては、綿花リンタや木材パルプ(広葉樹パルプ,針葉樹パルプ)などがあり、何れの原料セルロースから得られるセルロースアシレートでも使用でき、場合により混合して使用してもよい。これらの原料セルロースについての詳細は、例えばプラスチック材料講座(17)繊維素系樹脂(丸澤、宇田著、日刊工業新聞社、1970年発行)や発明協会公開技報2001-1745(7頁~8頁)に記載されているが、本発明は、該記載に制限されるものではない。
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。
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。
本発明の積層体は、パターン光学異方性層の支持体として用いられることが好ましい。より詳しくは、液晶表示装置のフロント側偏光板のさらにフロント側に配置されるパターン光学異方性層用の配向膜に用いられることが好ましい。このような積層体を用いることで、3D画像表示装置用のパターニング位相差板を容易に製造することができる。
本発明の積層体は、前記第一の配向制御領域と前記第二の配向制御領域との間に、ブラックマトリックスが配置されていることが、本発明の積層体を3D画像表示装置のパターニング位相差板の配向膜として用いたときに、クロストークを低減させる観点から、好ましい。ここで、ブラックマトリックスが前記第一の配向制御領域と前記第二の配向制御領域との間に配置されるとは、前記第一の配向制御領域と前記第二の配向制御領域を隔てるように仕切りとして配置されている態様も、前記第一の配向制御領域と前記第二の配向制御領域の境界線上に積層されて配置されている態様も含む。
本発明の積層体の製造方法は、第一の組成物からなる第一の配向制御領域を透明支持体上に形成する第一の配向制御領域形成工程と、及び第一の組成物と組成が異なる第二の組成物からなる第二の配向制御領域をパターン状に印刷する第二の配向制御領域形成工程を、少なくとも含むことを特徴とする。
このような構成により、本発明の積層体を製造することができる。
以下、本発明の積層体の製造方法を、透明支持体の製膜、配向制御層の積層の順に説明する。
前記透明支持体の製造方法としては特に制限はなく、公知の方法を用いることができる。
前記透明支持体(好ましくはセルロースアシレート)には、種々の添加剤(例えば、光学的異方性を低下する化合物、波長分散調整剤、微粒子、可塑剤、紫外線防止剤、劣化防止剤、剥離剤、光学特性調整剤など)を加えることができ、これらについて以下に説明する。またその添加する時期はドープ作製工程(セルロースアシレート溶液の作製工程)における何れでもよいが、ドープ作製工程の最後に添加剤を添加し調製する工程を行ってもよい。
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、該化合物が本発明の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ないし30質量%であることが好ましく、1ないし25質量%であることがより好ましく、5ないし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。
本発明の積層体の製造方法は、前記第一の配向制御領域を下記(I)または(II)のいずれかの方法で上記の方法で製膜された透明支持体上に形成する第一の配向制御領域形成工程を含むことが好ましい。
方法(I):前記第一の配向制御領域を前記透明支持体の全面上に形成する工程。
方法(II):前記第一の配向制御領域を前記透明支持体の一部の領域上に形成する工程。
これらの方法で前記第一の配向制御領域を透明支持体上に形成することで、図4または図5に記載の本発明の積層体を得ることができる。
本発明の積層体の製造方法は、透明支持体上に、第一の配向制御領域と第二の配向制御領域とを面内に含む配向制御層を下記(I-A)、(I-B)および(II-A)のいずれか1つの印刷工程で形成する工程を含むことが好ましい。
印刷工程(I-A):透明支持体上に第一の配向制御領域を印刷し、該第一の配向制御領域の一部の領域上に第二の配向制御領域を印刷し、該第一の配向制御領域および該第二の配向制御領域を同時に1つの方位に処理する工程。
印刷工程(I-B):透明支持体上に第一の配向制御領域を印刷し、該第一の配向制御領域を1つの方位に処理した後、該第一の配向制御領域の処理面の一部の領域上に第二の配向制御領域を印刷する工程。
印刷工程(II-A):透明支持体の一部の領域上に第一の配向制御領域を印刷し、前記透明支持体の第一の配向制御領域が印刷されていない領域上に第二の配向制御領域を印刷し、該第一の配向制御領域および該第二の配向制御領域を同時に1つの方位に処理する工程。
以下、これらの印刷工程について、順に説明する。
フレキソ印刷では、図1に示すような、立体画像表示システムに好ましく用いられるパターン光学異方性層のパターンに対応した幅の凹凸が形成されているフレキソ版1を用いることが好ましいが、本発明は図1の態様に限定されるものではない。
フレキソ印刷の方法を図2に示した。図2をもとに、本発明の積層体の製造方法に用いられるフレキソ印刷装置10を用いた印刷工程を示す。まず、あらかじめ透明支持体の全面上に平行配向膜(または直交配向膜)を塗布等により積層したものを準備しておく。そして、印圧ローラ12に、その平行配向膜(または直交配向膜)が表面側となるように装着する。次に、目的とするパターンが形成されているフレキソ版1を、前記印圧ローラ12に対向する位置に設けられている圧胴11に装着する。次に、パターン印刷用直交配向膜液(またはパターン印刷用平行配向膜液)をドクターブレート14に供給し、アニックスローラ13を介して、圧胴11に装着されているフレキソ版1の凸部に、パターン印刷用直交配向膜液3を転写する。フレキソ版1の凸部に転写されたパターン印刷用直交配向膜液3は、その後、印圧ローラ12に装着された平行配向膜2の一部の領域にのみ転写される。
前記印刷工程(I-A)では、透明支持体上に第一の配向制御領域を印刷し、該第一の配向制御領域の一部の領域上に第二の配向制御領域を印刷し、該第一の配向制御領域および該第二の配向制御領域を同時に1つの方位に処理することを特徴とする。
また、ディスコティック液晶化合物を配向制御するための積層体を製造するときは、前記第一の配向制御領域の印刷に用いる第一の配向制御領域用印刷液が、平行垂直配向膜用組成物および直交垂直配向膜用組成物のうちいずれか一方と第一の配向制御領域用溶媒を含み、前記第二の配向制御領域の印刷に用いる第二の配向制御領域用印刷液がもう一方の化合物と第二の配向制御領域用溶媒を含むことが好ましい。但し、前述のとおり、平行垂直配向と直交垂直配向は、主成分として用いる樹脂材料の他、添加剤(ピリジニウム化合物およびイミダゾリウム化合物)の有無、製造温度によっても変化する。そのため、本発明の製造方法は、これらの平行垂直配向膜用組成物および直交垂直配向膜用組成物の使い分けをする態様に限定されるものではない。
まず、配向膜として一般式(I)で表される繰り返し単位と、下記一般式(II)又は(III)で表される繰り返し単位とを含むアクリル酸コポリマー又はメタクリル酸コポリマーを主成分とする組成物もしくは一般式(I-TH)、一般式(II-TH)及び一般式(III-TH)のいずれかで表される構造単位を少なくとも1種有する重合体を主成分とする組成物(配向膜1)を塗布液として調製して支持体の全面上に塗布し、その上に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組成物(配向膜2)をパターン印刷塗布して、乾燥させた後に一方向にラビング処理する。このような工程により、図4に記載の本発明の積層体を得ることができる。
印刷工程(I-B):透明支持体上に第一の配向制御領域を印刷し、該第一の配向制御領域を1つの方位に処理した後、該第一の配向制御領域の処理面の一部の領域上に第二の配向制御領域を印刷することを特徴とする。
また、前記第一の配向制御領域用印刷液が、直交垂直配向膜用組成物と第一の配向制御領域用溶媒を含み、前記第二の配向制御領域の印刷に用いる第二の配向制御領域用印刷液が、ピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方と第二の配向制御領域用溶媒を含むことも好ましい。
このとき、第二の配向制御領域用印刷液は、場合によりインクジェット印刷されることもパターン精度を高める観点から好ましい。本発明に好ましく用いることができるインクジェット印刷の態様としては、例えば、特開2008-26391、特開2010-150409号公報、特開2010-046822号公報に記載の態様を挙げることができる。その中でも、特開2008-26391に記載の態様を本発明では好ましく用いることができる。
これらの態様の場合、得られる本発明の積層体は、前記第二の配向制御領域は、図4のように前記第一の配向制御領域の上に印刷されて盛り上がっていてもよい。また、図5の態様のように前記第一の配向制御領域中に浸透して、本発明の積層体の膜面が平面となっていてもよい。ピリジニウム化合物およびイミダゾリウム化合物は、前記第一の配向制御領域上に設置された場合も、前記第一の配向制御領域中に浸透した場合も、浸透した部分の前記第一の配向制御領域の配向制御方向を変化させて第二の配向制御領域を形成することができる。但し、ピリジニウム化合物およびイミダゾリウム化合物が前記第一の配向制御領域上に設置する場合、あらかじめ第一の配向制御領域をラビングした後で設置しても、第二の配向制御領域を設置後にラビングしてもよい。あらかじめ第一の配向制御領域をラビングする場合、ピリジニウム化合物およびイミダゾリウム化合物が盛り上がるように形成されたときの第二の配向制御領域(上層)は、該化合物の浸透の度合いによっては一方位に処理されていないこととなり得るが、その場合における第二の配向制御領域の処理方向とは、第1の(下層の)配向制御領域の処理方向を表す。これは、その他の態様で上層が一方位に処理されていないときも同様である。
印刷工程(II-A):透明支持体の一部の領域上に第一の配向制御領域を印刷し、前記透明支持体の第一の配向制御領域が印刷されていない領域上に第二の配向制御領域を印刷し、該第一の配向制御領域および該第二の配向制御領域を同時に1つの方位に処理することを特徴とする。
本発明の積層体の製造方法は、前記印刷工程(II-A)を用いる場合において、前記第一の配向制御領域の印刷に用いる第一の配向制御領域用印刷液が、平行配向膜用組成物および直交配向膜用組成物のうちいずれか一方と第一の配向制御領域用溶媒を含み、前記第二の配向制御領域の印刷に用いる第二の配向制御領域用印刷液がもう一方の化合物と第二の配向制御領域用溶媒を含むことが好ましい。
本発明の積層体の製造方法では、前記第二の配向制御領域用溶媒が、前記第一の配向制御領域用印刷液中に含まれる化合物を実質的に溶解しないことが好ましい。
このような溶媒を用いることで、本発明の積層体の第一配向領域と、第二配向領域の境界を互いに侵すことがなく、より高精度なパターニングを得ることができる。
また、本発明の積層体の製造方法は、前記第一の配向制御領域と前記第二の配向制御領域を1つの方位に配向処理する工程を含むことが好ましい。前記1つの方位に処理する工程が、一方位へのラビング処理工程であることがより好ましい。このように1つの方位に配向処理することで、マスクラビングを行ったときの位置合わせの困難さに起因する位置ずれを解消することができる。
ラビング処理は、一般にはポリマーを主成分とする膜の表面を、紙や布で一定方向に数回擦ることにより実施することができる。ラビング処理の一般的な方法については、例えば、「液晶便覧」(丸善社発行、平成12年10月30日)に記載されている。
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。
長尺状のポリマーフィルムからなる支持体上に連続的に配向膜を形成する態様では、製造適性の観点では、ラビング処理の方向(ラビング方向)は、ポリマーフィルムの長手方向と一致しているのが好ましい。
本発明の光学フィルムは、本発明の積層体と、該積層体上の前記配向制御領域上に、重合性基を有する液晶を主成分とする組成物から形成された光学異方性層を有し、該光学異方性層は、面内遅相軸が互いに異なる第一位相差領域と第二位相差領域とが交互にパターニングされていることを特徴とする。
言い換えれば、前記第一位相差領域と前記第二位相差領域が、それぞれ前記配向制御層の表面における前記第一の配向制御領域と前記第二の配向制御領域の膜面垂直方向の正射影に対応した前記光学異方性層内の領域に形成されていることを特徴とする。
このような構成の光学フィルムは、立体画像表示システムに組み込んだときに良好な立体画像を形成させることができる。
本発明の光学異方性層は、λ/4板即ち直線偏光を円偏光に変換する機能を有することが好ましい。λ/4板としての機能を有する光学異方性層の形成には種々の方法があるが、特に本発明では、重合性基を有する棒状液晶化合物又はディスコティック液晶を水平配向又は垂直配向させた状態で重合させ、固定化して形成することが好ましい。
一方、前記重合性基を有する液晶が円盤状液晶である場合、本発明の光学フィルムは、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、円盤状液晶が層面に対して円盤面を垂直にして配向した垂直配向状態であって、且つその長軸(円盤面が連なっている方向)が配向処理方向(例えば、ラビンク゛処理方向)に対して平行方向となる領域と、垂直配向状態であって、且つその長軸が配向処理方向に対して直交方向となる領域のことを意味する。
(棒状液晶)
本発明の光学異方性層の主原料として使用可能な重合性基を有する液晶化合物としては、重合性基を有する棒状液晶及び重合性基を有するディスコティック液晶を挙げることができ、重合性基を有するディスコティック液晶が好ましい。
前記棒状液晶としては、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。
本発明の光学フィルムの前記光学異方性層の主原料として使用可能なディスコティック液晶は、前記のとおり重合性基を有する化合物である。
前記重合性基を有する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することができる。
本発明の光学フィルムの前記光学異方性層は、配向膜側配向制御剤として、ピリジニウム化合物およびイミダゾリウム化合物を含んでいてもよい。光学異方性層中にピリジニウム化合物およびイミダゾリウム化合物が含まれていることで、特にディスコティック液晶化合物を用いる場合、配向膜側、すなわち本発明の積層体側の界面におけるディスコティック液晶化合物の垂直配向を、本発明の積層体の膜面に対してより垂直となるように制御することができる。
本発明の光学フィルムの前記光学異方性層に用いることができるピリジニウム化合物およびイミダゾリウム化合物の好ましい範囲は、本発明の積層体に添加剤として用いる場合のピリジニウム化合物およびイミダゾリウム化合物の好ましい範囲と同様である。
前記ピリジニウム化合物およびイミダゾリウム化合物は、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、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、ディスコティック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。
本発明の光学異方性層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。
本発明の光学フィルムは、前記第一位相差領域と前記第二位相差領域との間にブラックマトリックスを有することが、本発明の光学フィルムを3D画像表示装置のパターニング位相差板として用いたときに、クロストークを低減させる観点から、好ましい。ここで、ブラックマトリックスが前記第一の配向制御領域と前記第二の配向制御領域との間に配置されるとは、前記第一の配向制御領域と前記第二の配向制御領域を隔てるように仕切りとして配置されている態様も、前記第一の配向制御領域と前記第二の配向制御領域の境界線上に積層されて配置されている態様も含む。
(Re、Rth)
本発明の光学フィルムは、全体のRe(550)が100~190nmであり、100~175nmであることが好ましく、110~165nmであることがより好ましい。
本発明の光学フィルムは、前記積層体の透明支持体のRthと、前記光学異方性層のRthの合計が|Rth|≦20nmであることが好ましい。
ただし、前記ReおよびRth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。
本発明における熱膨張係数は、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した。
本発明における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)
本発明の光学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、RHは、相対湿度を意味する。
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。
本発明における弾性率は、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、前述で求めた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。
本発明の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。
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。
本発明の光学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、本発明の光学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。
本発明の光学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。
(膜厚)
本発明の光学フィルムの厚さは、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。
本発明の光学フィルムの製造方法は、本発明の積層体の製造方法で製造された積層体の上に、重合性基を有する液晶を含有する組成物を配置し、光学異方性層を形成し、第一の配向制御領域上で配向制御された第一位相差領域及び第二の配向制御領域上で配向制御された第二位相差領域を含むパターン光学異方性層を形成することを特徴とする。
パターン化された光学異方性層の形成方法について述べる。
本発明の光学フィルムの製造方法は、重合性基を有する液晶を含有する組成物を配置する工程として、溶媒と重合性基を有する液晶とを含む塗布液を塗布する工程を含むことが好ましい。
塗布方法としては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。
また、本発明の光学フィルムの製造方法は、前記重合性基を有する液晶が円盤状液晶であることが好ましい。
本発明の光学フィルムの製造方法は、前記溶媒と重合性基を有する液晶とを含む塗布液に含まれる溶媒が、前記第一の配向制御領域用印刷液中に含まれる化合物と、前記第一の配向制御領域用印刷液中に含まれる化合物のいずれも実質的に溶解しないことが好ましい。このような溶媒を用いて溶媒と重合性基を有する液晶とを含む塗布液を塗布することで、本発明の積層体の配向制御領域の配向規制能を乱さないようにすることができ、良好なパターン化された光学異方性層を得ることができる。
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としてピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方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。
パターン光学異方性層の配向制御の方法としては、前記塗布膜を加熱することで、第一の配向制御領域または第二の配向制御領域のうちいずれか一方の配向制御領域上の液晶の長軸を前記ラビング処理方向に対して直交に配向させて直交配向領域とし、もう一方の配向制御領域上の液晶の長軸を前記ラビング処理方向に対して平行に配向させて平行配向領域とする工程を含むことが好ましい。
特に、前記第一の配向制御領域の印刷に用いる第一の組成物と、前記第二の配向制御領域の印刷に用いる第二の組成物の少なくとも一方が、ピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方を含み、前記第一の組成物と前記第二の組成物の加熱配向処理を行う工程を含むことが好ましい。上述したとおり、配向温度を制御することによりピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方を含む配向制御領域に対して、ディスコティック液晶化合物が配向する方向を変化させることができ、所望の配向状態を得ることができる。
次に、配向させた液晶化合物は、配向状態を維持して固定することが好ましい。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。重合反応には、熱重合開始剤を用いる熱重合反応と光重合開始剤を用いる光重合反応とが含まれるが、光重合反応がより好ましい。本発明の製造方法は、光照射して前記塗布膜中の液晶の配向状態を固定化する工程を含むことが好ましい。
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。
本発明の積層体の前記配向制御領域側の表面(好ましくはラビング処理面)に、塗布液として調製された前記ディスコティック液晶、ピリジニウム化合物、フルオロ脂肪族基含有共重合体、重合開始剤、増感剤等を含有する光学異方性層形成用組成物を塗布する。
ディスコティック液晶を用いる場合、前記組成物の塗膜を乾燥したのち加熱して、ディスコティック液晶の長軸がラビング方向とパターンに合わせて平行・直交するように垂直配向状態にする。ディスコティック液晶の分子をこの所望の配向状態とした後、重合により硬化させ、その配向状態を固定して、パターンを形成する。
一方、棒状液晶を用いる場合、前記組成物の塗膜を乾燥したのち加熱して、棒状液晶の長軸がラビング方向とパターンに合わせて平行・直交するように水平配向状態にする。棒状液晶の分子をこの所望の配向状態とした後、重合により硬化させ、その配向状態を固定して、パターンを形成する。
本発明の光学フィルムの製造方法は、前記光学異方性層の形成前又は後に、前記第一位相差領域及び前記第二位相差領域との間にブラックマトリックスを形成する工程を含んでいてもよい。
具体的な形成方法としては、特に制限はないが、例えば以下の例を挙げることができる。
本発明では、前記積層体の上に、前記第一位相差領域と前記第二位相差領域を隔てるようにブラックマトリックスを形成する工程を含み、前記棒状液晶またはディスコティック液晶を含む塗布液を前記ブラックマトッリクスの間に塗布することが好ましい。
また、本発明では、前記棒状液晶またはディスコティック液晶を含む塗布液を塗布する工程の後に、隣接する第一位相差領域と前記第二位相差領域の少なくとも境界線上にブラックマトリックスを形成する工程を含むことも好ましい。
本発明の偏光板は、少なくとも1枚の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前記第一位相差領域と前記第二位相差領域のそれぞれの面内遅相軸方位と、偏光膜の吸収軸方位とがいずれも略45°をなすことを特徴とする。
前記偏光板は、従来公知の一般的な構成の偏光板を挙げることができ、前記偏光板の具体的な構成については、特に制限はなく公知の構成を採用できるが、例えば、特開2008-262161号公報の図6に記載の構成を採用することができる。本発明の光学フィルムは、一般的な偏光板の一方の面上に積層させ、偏光眼鏡方式の3D立体映像表示システムに用いることができるパターニング位相差フィルムとすることができる。前記偏光板の態様は、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は、透明支持体であるセルロースアシレートとパターン形成された配向膜が積層されたフィルム全体をラビングする工程と、棒状液晶もしくはディスコティック液晶を主成分とする組成物を配向状態にする工程と、全面露光して第一位相差領域と第二位相差領域を形成する工程と、得られた光学異方性フィルムを透過軸が45°方向にある偏光板とをロール・トゥ・ロールで積層する工程を含むことを特徴とする。
このような態様により、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。
本発明の偏光板は、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ことが好ましい。
本発明において、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。
本発明の偏光板は、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ことが好ましい。
偏光板の、液晶セルと反対側に配置される保護膜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。
本発明の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。本発明において光散乱層は、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、面光源上と本発明の反射防止フィルムの間に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。
本発明の反射防止フィルムの低屈折率層の屈折率は、1.20~1.49であり、好ましくは1.30~1.44の範囲にある。更に、低屈折率層は下記数式(IX)を満たすことが低反射率化の点で好ましい。
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。
本発明の低屈折率層には、低屈折率バインダーとして、含フッ素ポリマーを含む。フッ素ポリマーとしては動摩擦係数0.03~0.20、水に対する接触角90°~120°、純水の滑落角が70°以下の熱又は電離放射線により架橋する含フッ素ポリマーが好ましい。本発明の反射防止フィルムを画像表示装置に装着した時、市販の接着テープとの剥離力が低いほどシールやメモを貼り付けた後に剥がれ易くなり好ましく、500gf以下が好ましく、300gf以下がより好ましく、100gf以下が最も好ましい。また、微小硬度計で測定した表面硬度が高いほど、傷がつき難く、0.3GPa以上が好ましく、0.5GPa以上がより好ましい。
光散乱層は、表面散乱及び/又は内部散乱による光拡散性と、フィルムの耐擦傷性を向上するためのハードコート性をフィルムに寄与する目的で形成される。従って、ハードコート性を付与するためのバインダー、光拡散性を付与するためのマット粒子、及び必要に応じて高屈折率化、架橋収縮防止、高強度化のための無機フィラーを含んで形成される。
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。
基体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、透明支持体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~10mμであることが好ましく、10nm~1μmであることが更に好ましい。
低屈折率層は、高屈折率層の上に順次積層して成る。低屈折率層の屈折率は1.20~1.55である。好ましくは1.30~1.50である。
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よい。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。
更に、ハードコート層、前方散乱層、プライマー層、帯電防止層、下塗り層や保護層等を設けてもよい。
本発明の液晶表示装置は、第一及び第二の偏光膜;第一及び第二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;及び第一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、前記第一偏光膜の吸収軸方向と、前記光学フィルムの第一相差領域の面内遅相軸及び第二位相差領域のそれぞれの面内遅相軸が、いずれも±45°の角度をなすことを特徴とする。
本発明の立体画像表示システムは、本発明の画像表示装置と、前記本発明の光学フィルムの外側に配置される第三の偏光板とを少なくとも備え、第三の偏光板を通じて立体画像を視認させることを特徴とする。
本発明は、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、前記第三の偏光板として眼鏡形状の偏光板を通して画像を認識することが好ましい。
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、前記パターニング位相差フィルムの前記第一領域又は前記第二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、かつ、左眼鏡で遮光され、前記パターニング位相差フィルムの前記第一領域又は前記第二領域の残りの一方から出射された左眼用画像光が左眼鏡を透過し、かつ、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。
当然ではあるが、前記偏光眼鏡は、本発明において詳細説明がなされている前記パターニング位相差に対応する配置の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。
前記画像表示装置が画素を表示するパネルを含み、
前記画素が、各画素の高さを揃えたライン状に繰り返し配置された画素群を形成しており、
前記光学フィルムの第一位相差領域と第二位相差領域が、前記ライン状の画素群の1ラインに対応して交互にパターニングされていることが好ましい。
(1)ラビング配向膜付きの透明支持体(配向膜A~C)の作製
(配向膜Aの作成)
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/メタノール溶液(PVA-103(4.0g)を、水72g及びメタノール24gに溶解させた、粘度4.35cp、表面張力44.8dyne)を、12番バーで塗布を行い、120℃で2分間乾燥させた。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。その後に、1000rpmで一方向に1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(配向膜A)。本配向膜は一般に平行配向膜として作用する。
上記と同様に透明ガラス支持体の表面に、直交配向膜(化合物番号5)の溶液(配向膜1.323gを、トリエチルアミン0.329gとメタノール38.35gに溶解させた、粘度0.84cp、表面張力22.7dyne)を12番バーで塗布を行い、120℃で2分間乾燥させた。配向膜の膜厚は、0.9μmであった。その後に、1000rpmで一方向に1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(配向膜B)。本配向膜は一般に直交配向膜として作用する。
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/メタノール溶液(PVA-103(4.0g)を、水72g及びメタノール24gに溶解させた、粘度4.35cp、表面張力44.8dyne)を、12番バーで塗布を行い、120℃で2分間乾燥させた。なお、ガラス支持体のRe(550)は0nmであり、Rthは0nmであり、PVA配向膜の膜厚は、0.9μmであった。この平行配向膜上に、直交配向膜(化合物番号5)の溶液(配向膜1.323gをトリエチルアミン0.329gとメタノール38.35gに溶解させた、粘度0.84cp、表面張力22.7dyne)を12番バーで塗布を行い、120℃で2分間乾燥させた。配向膜全体の膜厚は、1.8μmであった。その後に、1000rpmで一方向に1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(配向膜C)。
下記液晶組成物1を用いて配向膜付ガラス基板上に0.35mlを取り、スピンコート塗布し(2500rpm、10秒間)、90℃で加熱しながらUV照射(10秒間)して硬化させた後に、顕微鏡で配列を確認した。
下記重合性液晶1:下記重合開始剤1:下記空気界面配向剤1(=100:3:0.3、以下比率は重量%で記載)の固形分26%メチルエチルケトン(MEK)溶液
参考例1において、前記液晶組成物1の代わりに、下記棒状液晶組成物2を用いた以外は同様にして光学フィルムを作成し、顕微鏡で得られた光学フィルムを確認した。
参考例1において、前記液晶組成物1の代わりに下記ディスコティック液晶組成物1を用い、また、ディスコティック液晶組成物1の塗布膜を140℃まで加熱した後に90℃まで降温してUV照射した以外は同様にして参考例3の光学フィルムを作成し、顕微鏡で得られた光学フィルムの配列を確認した。
下記重合性液晶3/下記重合開始剤2/下記増感剤1/下記ピリジニウム化合物1/下記空気界面配向剤2/下記空気界面配向剤3(=100:3:1:2:0.3:0.5)の固形分20%MEK溶液
セルロースアシレートブチレート(イーストマンケミカル社製CAB551-0.2)
参考例1において、前記液晶組成物1の代わりに下記ディスコティック液晶組成物2を用い、また、ディスコティック液晶組成物1の塗布膜を140℃まで加熱した後に90℃まで降温してUV照射した以外は同様にして参考例4の光学フィルムを作成し、顕微鏡で得られた光学フィルムの配列を確認した。
下記重合性液晶4/前記重合開始剤2/前記増感剤1/前記ピリジニウム化合物1/前記空気界面配向剤2/前記空気界面配向剤3(100:3:1:2:0.3:0.5)の固形分20%MEK溶液
[パターン位相差フィルムの作製]
(1)平行配向膜(第一の配向膜)の塗布
TACフィルムの表面に、クラレ社製ポリビニルアルコール「PVA103」の4%水/メタノール溶液(PVA-103(4.0g)を水72g及びメタノール24gに溶解させた、粘度4.35cp、表面張力44.8dyne)を、12番バーで塗布を行い、80℃で5分間乾燥させた(フィルムA)。
前記直交配向膜用の化合物(化合物番号5)2.646gをトリエチルアミン0.658gとテトラフルオロプロパノール12gに溶解させ、パターン印刷用直交配向膜液1を調整した。
フィルムBを80℃で5分間乾燥させた後に、1000rpmで一方向に1往復、ラビング処理を行い、ラビング配向膜付きTACフィルムを作製した(フィルムC1)。
フィルムC1に前記棒状液晶組成物1をスピンコート塗布し(2500rpm、10秒間)、90℃で加熱しながらUV照射(10秒間)して硬化させた後に、顕微鏡で配列を確認した(パターン位相差フィルム1)。パターン位相差フィルム1は、ラビング方向に対して平行配向膜領域は遅相軸が平行になる方向に配向しており、直交配向膜領域は遅相軸が直交する方向に配向していることを確認した。
塗布する液晶組成物を棒状液晶組成物1から前記棒状液晶組成物2に代えた以外は、実施例1と同様にしてパターン位相差フィルム2を得た。パターン位相差フィルム2は、ラビング方向に対して平行配向膜領域は遅相軸が平行になる方向に配向しており、直交配向膜領域は遅相軸が直交する方向に配向していることを確認した。
塗布する液晶組成物を棒状液晶組成物1から前記ディスコティック液晶組成物1に代え、加熱時に140℃まで昇温した後に90℃まで降温してUV照射した以外は、実施例1と同様にしてパターン位相差フィルム3を得た。パターン位相差フィルム3は、ラビング方向に対して平行配向膜領域は遅相軸が平行垂直になる方向に配向しており、直交配向膜領域は遅相軸が直交垂直する方向に配向していることを確認した。
塗布する液晶組成物を棒状液晶組成物1から前記ディスコティック液晶組成物2に代え、加熱時に140℃まで昇温した後に90℃まで降温してUV照射した以外は、実施例1と同様にしてパターン位相差フィルム4を得た。パターン位相差フィルム4は、ラビング方向に対して平行配向膜領域は遅相軸が平行垂直になる方向に配向しており、直交配向膜領域は遅相軸が直交垂直する方向に配向していることを確認した。
塗布するパターン印刷用直交配向膜液をパターン印刷用直交配向膜液1から(化合物番号31)を用いたパターン印刷用直交配向膜液2に代えた以外は、実施例1と同様にしてパターン位相差フィルム5を得た。パターン位相差フィルム5は、ラビング方向に対して平行配向膜領域は遅相軸が平行になる方向に配向しており、直交配向膜領域は遅相軸が直交する方向に配向していることを確認した。
塗布するパターン印刷用直交配向膜液をパターン印刷用直交配向膜液1から(化合物番号46)を用いたパターン印刷用直交配向膜液2に代えた以外は、実施例1と同様にしてパターン位相差フィルム5を得た。パターン位相差フィルム5は、ラビング方向に対して平行配向膜領域は遅相軸が平行になる方向に配向しており、直交配向膜領域は遅相軸が直交する方向に配向していることを確認した。
〔ディスコティック液晶組成物3〕
まず、前記重合性液晶4/前記重合開始剤2/前記増感剤1/前記空気界面配向剤2/前記空気界面配向剤3(=100:3:1:0.3:0.5)の固形分20%MEK溶液を調製した。
TACフィルムの表面に、和光純薬製ポリアクリル酸の4%水/メタノール/トリエチルアミン溶液を、12番バーで塗布を行い、80℃で5分間乾燥させた(フィルムA2)。この上にポリスチレン(55質量%)-ポリアクリル酸(45質量%)共重合体(BASF社製、ジョンクリル690、Mw16500、酸価240)のアクリル酸部分を50%解離させ、プロパノールに溶解させた溶液をフレキソ印刷して乾燥してから同様にラビングし、さらに塗布する液晶組成物を前記棒状液晶組成物1から上記にて調製したディスコティック液晶組成物3に替え、110℃で加熱した以外は、実施例1と同様にしてパターン位相差フィルム7を得た。パターン位相差フィルム7は、ラビング方向に対して平行配向膜領域は遅相軸が平行垂直になる方向に配向しており、直交配向膜領域は遅相軸が直交垂直する方向に配向していることを確認した。
パターン印刷用直交配向膜液をパターン印刷用直交配向膜液1からポリアクリル酸(Mw25000、和光純薬製)を、トリエチルアミンを用いて90%解離させたプロパノール水溶液(ポリアクリル酸2.0g/水1.12g/プロパノール5.09g/3-メトキシ-1-ブタノール5.09g/トリエチルアミン2.52g)に代え、さらに塗布する液晶組成物を前記ディスコティック液晶組成物2に代えた以外は、実施例3と同様にしてパターン位相差フィルム8を得た。パターン位相差フィルム8は、ラビング方向に対してPVA103部分の上方の領域は遅相軸が平行垂直になる方向に配向しており、本来平行配向するポリアクリル酸部分の上方の領域はピリジニウム添加剤の影響で遅相軸が直交垂直する方向に配向していることを確認した。すなわち、PVA103部分の上方の領域にピリジニウム化合物を含むディスコティック液晶性化合物を塗布して一度TIsoに到達させてから降温した場合はディスコティック液晶性化合物がラビング方向に対して平行垂直の方向に配向することがわかった。また、ポリアクリル酸部分の上方の領域にピリジニウム化合物を含むディスコティック液晶性化合物を塗布して一度TIsoに到達させてから降温した場合はディスコティック液晶性化合物がラビング方向に対して直交垂直の方向に配向することがわかった。
(1)平行配向膜(第一の配向膜)の塗布
TACフィルムの表面に、和光純薬製ポリアクリル酸の4%水/メタノール/トリエチルアミン溶液を、12番バーで塗布を行い、80℃で5分間乾燥させた(フィルムA2)。
(2)ピリジニウム化合物を含有する配向制御領域のパターン塗布
パターン印刷用直交配向膜液として、前記ピリジニウム化合物10gをメチルエチルケトン100gに溶解させ、パターン印刷用ピリジニウム溶液1を調整した。
インクジェット方式により前記ピリジニウム溶液1をフィルムA2上に印字してパターンを形成させた。本実施例においては、インクジェットヘッドを吐出部として用いた。このインクジェットヘッドには、FUJIFILM DIMATIX製 DMP2831用ヘッド DMC-11610(製品型番)を用いた。なお、このとき前記ピリジニウム溶液は、第一の配向膜上に留まったまま乾燥せず、印字した部分の真下に向けて第一の配向膜の内部まで浸透していたことが目視にて確認された。
(3)ラビング配向膜の形成
その後塗布する液晶組成物として前記ディスコティック液晶組成物1を用いて、さらに100℃以上140℃(Tiso)未満に加熱温度を変更した以外は、実施例3と同様にしてパターン位相差フィルム9を得た。パターン位相差フィルム9の光学異方性層は、ラビング方向に対してピリジニウム化合物を含まない部分の上方の配向膜領域は遅相軸が平行になる方向に配向しており、インクジェット印刷によりピリジニウム化合物を印字した部分の上方の領域はピリジニウム添加剤の影響で遅相軸が直交する方向に配向していることを確認した。すなわち、ピリジニウム化合物を含まないポリアクリル酸部分の上方の領域に、(ピリジニウム化合物を含まない)ディスコティック液晶性化合物を塗布して一度TIsoに到達させてから降温した場合はディスコティック液晶性化合物がラビング方向に対して平行垂直の方向に配向することがわかった。また、ピリジニウム化合物を含むポリアクリル酸部分の上方の領域に、(ピリジニウム化合物を含まない)ディスコティック液晶性化合物を塗布して一度TIsoに到達させてから降温した場合はディスコティック液晶性化合物がラビング方向に対して直交垂直の方向に配向することがわかった。
加熱時に140℃まで昇温した後に90℃まで降温する代わりに、一度も140℃(TIso)まで到達せずに100~120℃での加熱に代えた以外は、実施例8と同様にしてパターン位相差フィルム10を得た。パターン位相差フィルム10は、ラビング方向に対してPVA-103部分の上方の領域は遅相軸が直交垂直になる方向に配向しており、ポリアクリル酸部分の上方の領域はピリジニウム添加剤の影響で遅相軸が平行垂直する方向に配向していることを確認した。すなわち、PVA-103部分の上方の領域にピリジニウム化合物を含むディスコティック液晶性化合物を塗布して一度もTIsoに到達させずに100~120℃に加熱した場合はディスコティック液晶性化合物がラビング方向に対して直交垂直の方向に配向することがわかった。また、ポリアクリル酸部分の上方の領域にピリジニウム化合物を含むディスコティック液晶性化合物を塗布して一度もTIsoに到達させずに100~120℃に加熱した場合はディスコティック液晶性化合物がラビング方向に対して平行垂直の方向に配向することがわかった。
和光純薬製ポリアクリル酸の4%水/メタノール/トリエチルアミン溶液の代わりにポリスチレン(55質量%)-ポリアクリル酸(45質量%)共重合体(BASF社製、ジョンクリル690、Mw16500、酸価240)のアクリル酸部分を50%解離させ、プロパノールに溶解させた溶液を用い、加熱時に100℃以上140℃(TIso)未満での加熱の代わりに140℃まで昇温した後に90℃まで降温する以外は、実施例9と同様にしてパターン位相差フィルム11を得た。パターン位相差フィルム11は、ラビング方向に対してピリジニウム化合物を含まない部分の上方の配向膜領域は遅相軸が直交になる方向に配向しており、インクジェット印刷によりピリジニウム化合物を印字した部分の上方の領域はピリジニウム添加剤の影響で遅相軸が平行する方向に配向していることを確認した。すなわち、ピリジニウム化合物を含まないポリスチレン-ポリアクリル酸共重合体部分の上方の領域に、(ピリジニウム化合物を含まない)ディスコティック液晶性化合物を塗布して一度もTIsoに到達させずに100℃以上140℃未満に加熱した場合はディスコティック液晶性化合物がラビング方向に対して直交垂直の方向に配向することがわかった。また、ピリジニウム化合物を含むポリスチレン-ポリアクリル酸共重合体部分の上方の領域に、(ピリジニウム化合物を含まない)ディスコティック液晶性化合物を塗布して一度もTIsoに到達させずに100℃以上140℃未満に加熱した場合はディスコティック液晶性化合物がラビング方向に対して平行垂直の方向に配向することがわかった。
実施例8で得たパターン配向膜フィルムの、印刷部分と非印刷部分の境界領域に幅30μmに渡って、黒色インキ(大日本精化社製、ハイドリックFCG)をフレキソ印刷してパターン位相差12を得た。その後に実施例8と同様に液晶を塗布してブラックマトリックスが入ったパターン位相差フィルム12を得た。
一般に公知の直交配向膜であるポリスチレン(液晶の光配向、米田出版、市村國宏著、p83)をトルエン溶媒に溶解して、実施例1に使用した直交配向膜の代わりにパターン印刷用直交配向膜液として用い、パターン印刷した。その後実施例1と同様に棒状液晶組成物1をスピンコート塗布した後、加熱し、室温で全面UV照射した。しかし直交配向を確認できず部分的に平行配向しているのみであることがわかった。これは直交配向膜のポリスチレンが棒状液晶組成物1の溶剤であるMEKに可溶であるために、パターン配向膜が溶解してしまったことに起因する。以上のことから配向膜の印刷の際には、液晶組成物の塗布溶剤が平行配向膜及び直交配向膜を侵さない必要があることがわかった。
実施例1に使用した化合物5と同様の合成法で下記組成の配向膜化合物を合成した(Mn13421、Mw31543、Mw/Mn=2.350)。
実施例1に使用した化合物5と同様の合成法で下記組成の配向膜化合物を合成した(Mn5053、Mw24501、Mw/Mn=4.848)。
実施例1に使用した化合物5と同様の合成法で下記組成の配向膜化合物を合成した。
実施例1に使用した化合物5と同様の合成法で下記組成の化合物を合成した。
<反射防止膜の作製>
実施例1のパターン位相差フィルム1の上部へのハードコート層の塗布を行った。
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。
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。
また、実施例12で作成したブラックマトリックスを第一位相差領域と第二操作領域の間に設けた以外は同様にして実装したところ、よりクロストークの少ない鮮明な立体画像を観察することができた。
<立体画像用透明フィルムの作成>
左右二系統の撮影レンズを備えたデジタルカメラ(富士フイルム(株)社製FinePix Real 3D W1)を用いて、右目用画像と左目用画像を作成した。ついで3D画像作成用ソフト(ストライパー)を用いて右目用画像と左目用画像を200μmごとに交互に入れ代えた画像を作成した。最後にOHPシート(コクヨ社製、VF-1300)に該画像データを、電子写真印刷機(富士ゼロックス社製、Docupurint C3540)を用いてプリント出力して3次元立体写真用透明画像1を得た。
<パターン偏光フィルムの作成>
実施例1のパターン位相差フィルム1の粘着剤を用いて、偏光板と貼り合わせた。さらに粘着剤を用いて上記3次元立体写真用透明画像1と貼り合わせて、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。
<立体画像用透明フィルムの作成>
実施例201と同様にIJ用透明フィルム(三菱製紙社製、IJ-FilmFT100)に該デジタル画像1データを、インクジェット(EPSON社製、PM-A820)を用いてプリント出力して3次元立体写真用透明画像2を得た。
<パターン偏光フィルムの作成>
実施例1のパターン位相差フィルム1の粘着剤を用いて、偏光板と貼り合わせた。さらに粘着剤を用いて上記3次元立体写真用透明画像2と貼り合わせて、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。
<立体画像用透明フィルムの作成>
(立体画像用印画紙の作製)
<透明色素受像層の作製>
セルロースアセテート保護フィルム表面に、コロナ放電処理を施した後、ドデシルベンゼンスルホン酸ナトリウムを含むゼラチン下塗層を設けた。さらに下記組成の中間層Aをバーコーターにより塗布し乾燥した後、引き続いて下記組成の受容層Aをバーコーターにより塗布し乾燥させた。バーコーター塗布は40℃で行い、乾燥は各層50℃で16時間行った。それぞれの乾燥時の塗布量が中間層A:1.0g/m2、受容層A1:3.0g/m2となるように塗布を行った。
ポリエステル樹脂(バイロン200、商品名、東洋紡(株)製)10質量部
蛍光増白剤 1質量部
(Uvitex OB、商品名、チバ・スペシャルティ・ケミカルズ(株)製)
酸化チタン 30質量部
メチルエチルケトン/トルエン(質量比1/1) 90質量部
ポリエステル樹脂 100質量部
(特開平2-265789号公報の実施例1に記載の樹脂)
アミノ変性シリコーン 5質量部
(信越化学工業(株)社製、商品名、X-22-3050C)
エポキシ変性シリコーン 5質量部
(信越化学工業(株)社製、商品名、X-22-300E)
メチルエチルケトン/トルエン(質量比1/1) 400質量部
この様にして、透明立体画像用印画紙を製造した。
厚さ6.0μmのポリエステルフィルム(ルミラー、商品名、(株)東レ製)を基材フィルムとして用いた。そのフィルム背面側に耐熱スリップ層(厚み1μm)を形成し、かつ表面側に下記組成のイエロー、マゼンタ、シアン組成物を、それぞれ単色に塗布(乾膜時の塗布量1g/m2)した。
イエロー組成物
染料(マクロレックスイエロー6G、商品名、バイエル社製)5.5質量部
ポリビニルブチラール樹脂 4.5質量部
(エスレックBX-1、商品名、積水化学工業(株)製)
メチルエチルケトン/トルエン(質量比1/1) 90質量部
マゼンタ組成物
マゼンタ染料(ディスパーズレッド60) 5.5質量部
ポリビニルブチラール樹脂 4.5質量部
(エスレックBX-1、商品名、積水化学工業(株)製)
メチルエチルケトン/トルエン(質量比1/1) 90質量部
シアン組成物
シアン染料(ソルベントブルー63) 5.5質量部
ポリビニルブチラール樹脂 4.5質量部
(エスレックBX-1、商品名、積水化学工業(株)製)
メチルエチルケトン/トルエン(質量比1/1) 90質量部
(右眼用及び左眼用画像形成)
前記インクシート及び前記印画紙を、日本電産コパル社製昇華型プリンターDPB1500(商品名)に装填可能なように加工し、高速プリントモードで3次元立体写真用透明画像3を得た。
観察者が円偏光メガネを介して前記立体画像印刷物を観察したところ、クロストークやゴースト像のない鮮明な立体画像を観察することができた。なお、偏光メガネは、左眼用円偏光フィルタ及び右眼用円偏光フィルタから構成されており、各々の円偏光フィルタは、直線偏光フィルタと1/4λ位相差フィルムが、その偏光軸と遅相軸が45°の角度をなすように積層されており、且つ、左眼用と右眼用で、直線偏光フィルタの偏光軸が直交しているものを使用した。
実施例1のパターン位相差フィルム1の粘着剤を用いて、偏光板と貼り合わせた。さらに粘着剤を用いて上記3次元立体写真用透明画像3と貼り合わせて、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。
2 平行配向膜(または直交配向膜)
3 パターン印刷用直交配向膜液(またはパターン印刷用平行配向膜液)
10 フレキソ印刷装置
11 圧胴
12 印圧ローラ
13 アニックスローラ
14 ドクターブレード
21 透明支持体
22a 第一の配向制御領域
22b、22c 第二の配向制御領域
Claims (36)
- 透明支持体と、
該透明支持体上に、組成が互いに異なり、且つ互いに異なる配向制御能を示す配向制御表面を有する、第一の配向制御領域及び第二の配向制御領域を含み、それぞれの配向制御表面が交互に配置されたパターン配向制御層を有し、
前記第一の配向制御領域及び前記第二の配向制御領域のそれぞれの配向制御面が、該配向制御面に平行な面内において液晶の長軸を互いに直交する方向に配向制御可能であることを特徴とする積層体。 - 前記第一の配向制御領域と前記第二の配向制御領域が同じ方位に処理されていることを特徴とする請求項1に記載の積層体。
- 前記第一の配向制御領域と前記第二の配向制御領域が、同じ方位にラビング処理されたラビング配向膜であることを特徴とする請求項1に記載の積層体。
- 前記第一の配向制御領域と前記第二の配向制御領域が、それぞれ
変性または無変性のポリビニルアルコールを主成分として含有する膜;
変性または無変性のポリアクリル酸を主成分として含有する膜;
下記一般式(I)で表される繰り返し単位と、下記一般式(II)もしくは(III)で表される繰り返し単位とを含む(メタ)アクリル酸コポリマーを主成分として含有する膜;または、
下記一般式(I-TH)、一般式(II-TH)及び一般式(III-TH)のいずれかで表される構造単位を少なくとも1種有する重合体を主成分とする膜;
のいずれかであることを特徴とする請求項1~3のいずれか一項に記載の積層体。
:R1およびR2は、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数が1乃至6のアルキル基であり
;Mは、プロトン、アルカリ金属イオンまたはアンモニウムイオンであり;L0は、-O-、-CO-、-NH-、-SO2-、アルキレン基、アルケニレン基、アリーレン基およびそ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り
;R0は、炭素原子数が10乃至100の炭化水素基または炭素原子数が1乃至100のフッ素原子置換炭化水素基であり
;Cyは、脂肪族環基、芳香族基または複素環基であり
;mは、10乃至99モル%であり;そして、nは、1乃至90モル%である。)
一般式(I-TH)
一般式(II-TH)
一般式(III-TH)
- 前記第一の配向制御領域と前記第二の配向制御領域が、それぞれ異なる樹脂を主成分とする請求項1~4のいずれか一項に記載の積層体。
- 前記第一の配向制御領域と前記第二の配向制御領域の少なくとも一方の領域が、ピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方を含むことを特徴とする請求項1~5のいずれか一項に記載の積層体。
- 前記第一の配向制御領域と前記第二の配向制御領域が、共に同じ樹脂を主成分とし、
かつ、少なくとも一方の領域にピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方を含むことを特徴とする請求項1~4のいずれか一項に記載の積層体。 - 前記ピリジニウム化合物またはイミダゾリウム化合物が、液晶性であることを特徴とする請求項6又は7に記載の積層体。
- 前記第一の配向制御領域と前記第二の配向制御領域が、共に非現像性樹脂を主成分とすることを特徴とする請求項1~8のいずれか一項に記載の積層体。
- 前記第一の配向制御領域と前記第二の配向制御領域が、下記(1)または(2)のいずれか1つの態様であることを特徴とする請求項1~9のいずれか一項に記載の積層体。
態様(1):透明支持体上に第一の配向制御領域が形成され、該第一の配向制御領域の一部の領域上に第二の配向制御領域が形成されている。
態様(2):透明支持体の一部の領域上に第一の配向制御領域が形成され、前記透明支持体の第一の配向制御領域が形成されていない領域上に第二の配向制御領域が形成されている。 - 前記第一の配向制御領域と前記第二の配向制御領域との間に、ブラックマトリックスが配置されていることを特徴とする請求項1~10のいずれか一項に記載の積層体。
- 前記透明支持体のRe(550)が、0~10nmであることを特徴とする請求項1~11のいずれか一項に記載の積層体:
但し、Re(550)は波長550nmにおける正面レターデーション値(単位:nm)である。 - パターン光学異方性層の支持体として用いられることを特徴とする請求項1~12のいずれか一項に記載の積層体。
- 請求項1~13のいずれか一項に記載の積層体と、
該積層体上の前記配向制御領域上に、重合性基を有する液晶を主成分とする組成物から形成された光学異方性層を有し、
該光学異方性層は、面内遅相軸が互いに異なる第一位相差領域と第二位相差領域とが交互にパターニングされていることを特徴とする光学フィルム。 - 前記光学異方性層中、前記第一位相差領域と前記第二位相差領域が前記光学異方性層の一辺に平行な長辺を有する帯状に交互にパターニングされており、
且つ、前記第一位相差領域の面内の遅相軸と前記第二位相差領域の面内の遅相軸が略直交していることを特徴とする請求項14に記載の光学フィルム。 - 全体のRe(550)が100~190nmであることを特徴とする請求項14又は15に記載の光学フィルム:ただし、前記Re(550)は波長550nmにおける正面レターデーション値(単位:nm)である。
- 前記重合性基を有する液晶がディスコティック液晶であり、前記光学異方性層中、ディスコティック液晶が垂直配向状態に固定されていることを特徴とする請求項14~16のいずれか一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およびイミダゾリウム化合物の少なくとも一方を含有していることを特徴とする請求項17に記載の光学フィルム。
- 前記重合性基を有する液晶が棒状液晶であり、前記光学異方性層中、棒状液晶が水平配向状態に固定されていることを特徴とする請求項14~16のいずれか一項に記載の光学フィルム。
- 前記第一位相差領域と前記第二位相差領域との間にブラックマトリックスを有することを特徴とする請求項14~19のいずれか一項に記載の光学フィルム。
- 請求項14~20のいずれか一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前記第一位相差領域と前記第二位相差領域のそれぞれの面内遅相軸方位と、偏光膜の吸収軸方位とがいずれも45°をなすことを特徴とする偏光板。
- 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ことを特徴とする請求項21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ことを特徴とする請求項21または22に記載の偏光板。
- 第一及び第二の偏光膜;
第一及び第二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
第一偏光膜の外側に請求項14~23のいずれか一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、
前記第一偏光膜の吸収軸方向と、前記光学フィルムの第一相差領域の面内遅相軸及び第二位相差領域のそれぞれの面内遅相軸が、いずれも±45°の角度をなすことを特徴とする画像表示装置。 - 請求項24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三の偏光板とを少なくとも備え、第三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。
- 第一の組成物からなる第一の配向制御領域を透明支持体上に形成する第一の配向制御領域形成工程と、及び
第一の組成物と組成が異なる第二の組成物からなる第二の配向制御領域をパターン状に印刷する第二の配向制御領域形成工程を、少なくとも含むことを特徴とする請求項1~13のいずれか1項に記載の積層体の製造方法。 - 前記第一の配向制御領域を下記(I)または(II)のいずれかの方法で透明支持体上に形成する第一の配向制御領域形成工程を特徴とする請求項26に記載の積層体の製造方法。
方法(I):前記第一の配向制御領域を前記透明支持体の全面上に形成する工程。
方法(II):前記第一の配向制御領域を前記透明支持体の一部の領域上に形成する工程。 - 前記第一の配向制御領域と前記第二の配向制御領域を1つの方位に配向処理する工程を含むことを特徴とする請求項26または27に記載の積層体の製造方法。
- 透明支持体上に、第一の配向制御領域と第二の配向制御領域とを面内に含む配向制御層を下記(I-A)、(I-B)および(II-A)のいずれか1つの印刷工程で形成する工程を含むことを特徴とする請求項26~28のいずれか一項に記載の方法。
印刷工程(I-A):透明支持体上に第一の配向制御領域を印刷し、該第一の配向制御領域の一部の領域上に第二の配向制御領域を印刷し、該第一の配向制御領域および該第二の配向制御領域を同時に1つの方位に処理する工程。
印刷工程(I-B):透明支持体上に第一の配向制御領域を印刷し、該第一の配向制御領域を1つの方位に処理した後、該第一の配向制御領域の処理面の一部の領域上に第二の配向制御領域を印刷する工程。
印刷工程(II-A):透明支持体の一部の領域上に第一の配向制御領域を印刷し、前記透明支持体の第一の配向制御領域が印刷されていない領域上に第二の配向制御領域を印刷し、該第一の配向制御領域および該第二の配向制御領域を同時に1つの方位に処理する工程。 - 前記1つの方位に処理する工程が、一方位へのラビング処理工程であることを特徴とする請求項28または29に記載の方法。
- 前記第二の配向制御領域を、フレキソ印刷により形成することを特徴とする請求項26~30のいずれか一項に記載の方法。
- 前記印刷工程(I-A)または(II-A)において、
前記第一の配向制御領域の印刷に用いる第一の組成物が、平行配向膜用組成物および直交配向膜用組成物のうちいずれか一方と第一の溶媒を含み、
前記第二の配向制御領域の印刷に用いる第二の組成物がもう一方の化合物と第二の配向溶媒を含むことを特徴とする請求項29~31のいずれか一項に記載の方法。 - 前記印刷工程(I-B)において、
前記第一の配向制御領域の印刷に用いる第一の組成物が、配向膜用化合物と第一の溶媒を含み、
前記第二の配向制御領域の印刷に用いる第二の組成物が、ピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方と第二の溶媒を含むことを特徴とする請求項29~32のいずれか一項に記載の方法。 - 請求項1~13のいずれか一項に記載の積層体上に、重合性基を有する液晶を含有する組成物を配置し、光学異方性層を形成し、第一の配向制御領域上で配向制御された第一の位相差領域及び第二の配向制御領域上で配向制御された第二位相差領域を含むパターン光学異方性層を形成することを特徴とする光学フィルムの製造方法。
- 前記積層体中の第一の配向制御領域および前記第二の配向制御領域の少なくとも一方が、ピリジニウム化合物およびイミダゾリウム化合物の少なくとも一方を含み、
前記液晶がディスコティック液晶であり、
前記積層体上に、前記ディスコティック液晶を含有する組成物を配置した後で加熱処理することにより、前記ディスコティック液晶の配向を制御して前記第一の位相差領域および第二の位相差領域を形成することを特徴とする請求項34に記載の方法。 - 前記光学異方性層の形成前又は後に、前記第一位相差領域及び前記第二位相差領域との間にブラックマトリックスを形成することを含む請求項34または35に記載の方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180037258.3A CN103038679B (zh) | 2010-07-30 | 2011-07-28 | 积层体、光学膜及它们的制造方法、偏光板、影像显示装置、立体影像显示系统 |
KR1020137004766A KR101658692B1 (ko) | 2010-07-30 | 2011-07-28 | 적층체, 광학 필름 및 그들의 제조 방법, 편광판, 화상 표시 장치, 입체 화상 표시 시스템 |
US13/752,895 US20130141681A1 (en) | 2010-07-30 | 2013-01-29 | Laminate, optical film and production method for these, polarizing plate, image display device, three-dimensional image display system |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-173077 | 2010-07-30 | ||
JP2010173077A JP5481306B2 (ja) | 2010-07-30 | 2010-07-30 | 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 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/752,895 Continuation US20130141681A1 (en) | 2010-07-30 | 2013-01-29 | Laminate, optical film and production method for these, polarizing plate, image display device, three-dimensional image display system |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012014964A1 true WO2012014964A1 (ja) | 2012-02-02 |
Family
ID=45530164
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/067225 WO2012014964A1 (ja) | 2010-07-30 | 2011-07-28 | 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 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20130141681A1 (ja) |
JP (1) | JP5481306B2 (ja) |
KR (1) | KR101658692B1 (ja) |
CN (1) | CN103038679B (ja) |
TW (1) | TW201222024A (ja) |
WO (1) | WO2012014964A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102591069A (zh) * | 2012-03-27 | 2012-07-18 | 深圳市华星光电技术有限公司 | 立体影像显示装置 |
US20150323824A1 (en) * | 2013-01-18 | 2015-11-12 | Fujifilm Corporation | Optical film, polarizing plate, and image display device |
JPWO2019082746A1 (ja) * | 2017-10-27 | 2020-11-19 | 住友化学株式会社 | 偏光フィルムの製造方法及び偏光フィルム |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012256028A (ja) * | 2011-05-13 | 2012-12-27 | Fujifilm Corp | 光学異方性素子、偏光板、立体画像表示装置、及び立体画像表示システム |
WO2013140811A1 (ja) * | 2012-03-23 | 2013-09-26 | 凸版印刷株式会社 | 反射防止フィルム |
US8873143B2 (en) * | 2012-03-27 | 2014-10-28 | Shenzhen China Star Optoelectronics Technology Co., Ltd | Three-dimensional image display apparatus |
JP5891165B2 (ja) * | 2012-07-20 | 2016-03-22 | 富士フイルム株式会社 | 積層体、偏光板及び液晶表示装置 |
JP6166930B2 (ja) * | 2013-03-29 | 2017-07-19 | リンテック株式会社 | 透明導電性フィルム |
CN103364863B (zh) * | 2013-06-17 | 2016-12-28 | 明基材料有限公司 | 用于调光装置的偏光板 |
KR102177052B1 (ko) * | 2013-08-09 | 2020-11-10 | 스미또모 가가꾸 가부시키가이샤 | 광학 이방성 적층체의 제조 방법 |
WO2016121856A1 (ja) * | 2015-01-30 | 2016-08-04 | 日本ゼオン株式会社 | 複層フィルム、その用途、及び製造方法 |
CN107406312B (zh) | 2015-04-10 | 2021-03-26 | 积水化学工业株式会社 | 夹层玻璃用中间膜、夹层玻璃、压花辊的制造方法和夹层玻璃用中间膜的制造方法 |
CN108603960B (zh) | 2015-10-30 | 2021-11-09 | 光学转变有限公司 | 用喷墨印刷设备制造光学制品的方法 |
EP3379326B1 (en) * | 2015-11-19 | 2021-03-31 | Nippon Kayaku Kabushiki Kaisha | Optical film for eyewear, and functional film for eyewear, optical laminate for eyewear, and eyewear which have same |
CN108780169B (zh) | 2016-03-25 | 2020-06-05 | 东丽株式会社 | 光源单元、层叠构件及使用它们的显示器及照明装置 |
JP6993976B2 (ja) * | 2016-09-14 | 2022-01-14 | 株式会社巴川製紙所 | 反射型表示装置用光拡散フィルム積層体及びこれを用いた反射型表示装置 |
CN107966755B (zh) * | 2016-10-19 | 2019-07-30 | 京东方科技集团股份有限公司 | 位相差膜、其制备方法及显示装置 |
JP7064290B2 (ja) * | 2017-04-06 | 2022-05-10 | Eneos株式会社 | 光学位相差部材、及び光学位相差部材の製造方法 |
JP6992158B2 (ja) | 2018-03-16 | 2022-01-13 | 富士フイルム株式会社 | 光学フィルム、偏光板、画像表示装置 |
CN110927855A (zh) * | 2019-11-15 | 2020-03-27 | 浙江怡诚光电科技有限公司 | 3d显示装置、图样化圆偏光板及制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004126539A (ja) * | 2002-08-07 | 2004-04-22 | Fuji Photo Film Co Ltd | 位相差板およびその製造方法 |
JP2006085098A (ja) * | 2004-09-17 | 2006-03-30 | Fuji Photo Film Co Ltd | 配向膜、光学補償シートおよび液晶表示装置 |
JP2006276203A (ja) * | 2005-03-28 | 2006-10-12 | Fuji Photo Film Co Ltd | 位相差板 |
JP2007304256A (ja) * | 2006-05-10 | 2007-11-22 | Fujifilm Corp | 光学補償フィルム、偏光板及び液晶表示装置 |
JP2008287273A (ja) * | 2008-06-27 | 2008-11-27 | Sony Corp | 分割波長板フィルターの製造方法 |
JP2009086241A (ja) * | 2007-09-28 | 2009-04-23 | Fujifilm Corp | 位相差膜、光学フィルム、偏光板、及び液晶表示装置 |
JP2009229493A (ja) * | 2008-03-19 | 2009-10-08 | Fujifilm Corp | 液晶表示装置の製造方法 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4378023B2 (ja) * | 2000-03-24 | 2009-12-02 | 富士フイルム株式会社 | 円偏光板および反射型液晶表示装置 |
JP4320129B2 (ja) | 2000-03-29 | 2009-08-26 | 富士フイルム株式会社 | 棒状液晶性分子を配向させる方法、光学補償シートおよび偏光板 |
JP2003207641A (ja) | 2001-11-08 | 2003-07-25 | Dainippon Printing Co Ltd | 位相差層積層体およびその製造方法 |
JP4843189B2 (ja) | 2003-09-24 | 2011-12-21 | 富士フイルム株式会社 | 配向膜、位相差板及びその製造方法 |
WO2005096041A1 (ja) * | 2004-03-30 | 2005-10-13 | National Institute Of Advanced Industrial Science And Technology | マイクロパターン位相差素子 |
US20050260334A1 (en) * | 2004-05-24 | 2005-11-24 | The Hong Kong Univerisity Of Science And Technology | Method of achieving high pretilt angles in a lilquid crystal cell |
WO2006038574A1 (ja) * | 2004-10-04 | 2006-04-13 | Sharp Kabushiki Kaisha | 表示装置および電子機器 |
JP2007163722A (ja) | 2005-12-13 | 2007-06-28 | Epson Imaging Devices Corp | 液晶装置とその製造方法、位相差板、及び電子機器 |
KR100736661B1 (ko) * | 2006-01-18 | 2007-07-06 | 한양대학교 산학협력단 | 액정 표시 장치 및 그 제조방법 |
US8080587B2 (en) * | 2006-05-01 | 2011-12-20 | Fujifilm Corporation | Oil-in-water (O/W) emulsion coating compositing, laminate, polarizing plate, image display device and production method of the laminate |
US8574454B2 (en) * | 2006-12-22 | 2013-11-05 | Rolic Ag | Patternable liquid crystal polymer comprising thio-ether units |
JP5227623B2 (ja) * | 2008-03-18 | 2013-07-03 | 富士フイルム株式会社 | 複屈折パターンを有する物品の製造方法 |
US8358391B2 (en) * | 2008-05-06 | 2013-01-22 | The Hong Kong University Of Science And Technology | Method to obtain a controlled pretilt and azimuthal angles in a liquid crystal cell |
JP4547641B2 (ja) * | 2008-09-22 | 2010-09-22 | ソニー株式会社 | 位相差板の製造方法 |
US9618839B2 (en) * | 2009-02-18 | 2017-04-11 | Rolic Ag | Surface relief microstructures, related devices and method of making them |
-
2010
- 2010-07-30 JP JP2010173077A patent/JP5481306B2/ja active Active
-
2011
- 2011-07-28 WO PCT/JP2011/067225 patent/WO2012014964A1/ja active Application Filing
- 2011-07-28 KR KR1020137004766A patent/KR101658692B1/ko active IP Right Grant
- 2011-07-28 CN CN201180037258.3A patent/CN103038679B/zh active Active
- 2011-07-29 TW TW100127026A patent/TW201222024A/zh unknown
-
2013
- 2013-01-29 US US13/752,895 patent/US20130141681A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004126539A (ja) * | 2002-08-07 | 2004-04-22 | Fuji Photo Film Co Ltd | 位相差板およびその製造方法 |
JP2006085098A (ja) * | 2004-09-17 | 2006-03-30 | Fuji Photo Film Co Ltd | 配向膜、光学補償シートおよび液晶表示装置 |
JP2006276203A (ja) * | 2005-03-28 | 2006-10-12 | Fuji Photo Film Co Ltd | 位相差板 |
JP2007304256A (ja) * | 2006-05-10 | 2007-11-22 | Fujifilm Corp | 光学補償フィルム、偏光板及び液晶表示装置 |
JP2009086241A (ja) * | 2007-09-28 | 2009-04-23 | Fujifilm Corp | 位相差膜、光学フィルム、偏光板、及び液晶表示装置 |
JP2009229493A (ja) * | 2008-03-19 | 2009-10-08 | Fujifilm Corp | 液晶表示装置の製造方法 |
JP2008287273A (ja) * | 2008-06-27 | 2008-11-27 | Sony Corp | 分割波長板フィルターの製造方法 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102591069A (zh) * | 2012-03-27 | 2012-07-18 | 深圳市华星光电技术有限公司 | 立体影像显示装置 |
WO2013143124A1 (zh) * | 2012-03-27 | 2013-10-03 | 深圳市华星光电技术有限公司 | 立体影像显示装置 |
US20150323824A1 (en) * | 2013-01-18 | 2015-11-12 | Fujifilm Corporation | Optical film, polarizing plate, and image display device |
US10459290B2 (en) * | 2013-01-18 | 2019-10-29 | Fujifilm Corporation | Optical film, polarizing plate, and image display device |
JPWO2019082746A1 (ja) * | 2017-10-27 | 2020-11-19 | 住友化学株式会社 | 偏光フィルムの製造方法及び偏光フィルム |
JP7272957B2 (ja) | 2017-10-27 | 2023-05-12 | 住友化学株式会社 | 偏光フィルムの製造方法及び偏光フィルム |
Also Published As
Publication number | Publication date |
---|---|
JP2012032661A (ja) | 2012-02-16 |
JP5481306B2 (ja) | 2014-04-23 |
KR20130131304A (ko) | 2013-12-03 |
TW201222024A (en) | 2012-06-01 |
KR101658692B1 (ko) | 2016-09-21 |
CN103038679A (zh) | 2013-04-10 |
CN103038679B (zh) | 2016-01-20 |
US20130141681A1 (en) | 2013-06-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
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 | |
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 | |
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 | |
JP6097619B2 (ja) | 光学フィルム、偏光板及びこれを用いた画像表示装置 | |
JP5380029B2 (ja) | 液晶表示装置 | |
US20130027767A1 (en) | Optical film, security product, and authenticity determination method | |
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 | |
JP5871615B2 (ja) | 立体表示装置 | |
TW200844509A (en) | Transparent protective film, optical compensation film, polarizing plate, and liquid crystal display device | |
KR101296179B1 (ko) | 액정표시장치 및 그 제조방법, 그리고 화상표시장치 | |
JP2013047794A (ja) | 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 | |
JP2014089431A (ja) | 光学フィルム、偏光板および画像表示装置 | |
JP5848557B2 (ja) | 3d表示システム | |
JP5871480B2 (ja) | 画像表示装置及び3d画像表示システム | |
JP2014066931A (ja) | 液晶表示装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180037258.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11812553 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: 20137004766 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11812553 Country of ref document: EP Kind code of ref document: A1 |