WO2011138869A1 - Elément optique et procédé permettant d'améliorer l'angle de vue d'un film polarisant l'utilisant - Google Patents

Elément optique et procédé permettant d'améliorer l'angle de vue d'un film polarisant l'utilisant Download PDF

Info

Publication number
WO2011138869A1
WO2011138869A1 PCT/JP2011/002541 JP2011002541W WO2011138869A1 WO 2011138869 A1 WO2011138869 A1 WO 2011138869A1 JP 2011002541 W JP2011002541 W JP 2011002541W WO 2011138869 A1 WO2011138869 A1 WO 2011138869A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
optical element
film
optical
retardation film
Prior art date
Application number
PCT/JP2011/002541
Other languages
English (en)
Japanese (ja)
Inventor
悦幸 矢作
隼也 野口
良崇 大橋
雄一 貞光
義彦 平良
真由 亀田
興一 田中
Original Assignee
日本化薬株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本化薬株式会社 filed Critical 日本化薬株式会社
Priority to KR1020127029753A priority Critical patent/KR20130080789A/ko
Priority to JP2012513771A priority patent/JP5973911B2/ja
Priority to CN201180022769.8A priority patent/CN102884456B/zh
Publication of WO2011138869A1 publication Critical patent/WO2011138869A1/fr

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133634—Birefringent elements, e.g. for optical compensation the refractive index Nz perpendicular to the element surface being different from in-plane refractive indices Nx and Ny, e.g. biaxial or with normal optical axis
    • 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
    • G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
    • G02F2413/12—Biaxial compensators

Definitions

  • the present invention relates to an optical element useful for an image display device such as a liquid crystal display device and a method for improving the viewing angle of a polarizing film using the same.
  • the polarizing film which is an essential member in the liquid crystal display device can be obtained, for example, as follows. First, a polyvinyl alcohol film impregnated with a water-soluble dichroic dye or a dichroic dye such as polyiodine ion is uniaxially stretched in a boric acid warm aqueous solution, or the polyvinyl alcohol film is uniaxially stretched and then dehydrated. A polarizing element is obtained by forming a polyene structure by reaction. Next, the target polarizing plate can be obtained by sandwiching the polarizing element with an adhesive using a protective film such as a triacetyl cellulose film whose surface layer has been subjected to alkali treatment or a cycloolefin polymer.
  • a protective film such as a triacetyl cellulose film whose surface layer has been subjected to alkali treatment or a cycloolefin polymer.
  • Patent Document 1 discloses a method of reducing the viewing angle dependency of a polarizing film using two retardation plates.
  • Patent Document 1 cannot sufficiently improve the viewing angle dependency.
  • colored light leaks because the wavelength dependency of the retardation film to be used can improve the viewing angle dependency of a specific wavelength but other wavelengths are insufficient.
  • the wavelength dependency of the viewing angle improvement effect of the polarizing film can be effectively improved by the method as described in Patent Document 2 or Non-Patent Document 2, it is complicated that a plurality of films must be laminated. There is.
  • JP 2008-310064 A Japanese Patent No. 4137438
  • an object of the present invention is to provide an optical element that improves the viewing angle dependency of the polarizing element or the polarizing film and also reduces the wavelength dependency without using a plurality of films.
  • the inventors of the present invention are optically anisotropic in which a three-dimensional refractive index containing at least two kinds of dichroic dyes is nx>nz> ny and an Nz coefficient is 0.2 to 0.7. It has been found that an optical element comprising a layer (retardation element) or a retardation film having the optical element on a transparent substrate is very useful for solving the above problems.
  • the Nz coefficient means a value of (nx ⁇ nz) / (nx ⁇ ny).
  • the present invention relates to the following inventions.
  • An optical element comprising a colored and oriented optically anisotropic layer having a refractive index of nx>nz> ny and (nx ⁇ nz) / (nx ⁇ ny) of 0.2 to 0.7.
  • the maximum absorption wavelength of at least one organic dye of the organic dye is 380 nm or more and less than 550 nm, and the maximum absorption wavelength of the other at least one organic dye is 550 nm or more and 780 nm or less (1) ) Optical element.
  • the optically anisotropic layer includes at least one of an organic dye having a maximum absorption wavelength of 380 nm to less than 550 nm and an organic dye having a maximum absorption wavelength of 550 nm to 780 nm, an oligophenyl compound, and the following general formula:
  • the optical element according to the above (1) which is a layer formed from a composition comprising the compound represented by (A),
  • X represents —O—CH 2 —ph—CH 2 —O—, —O—CO—ph—CO—O— or —NH—CO—ph—CO—NH—
  • ph has sulfo substitution.
  • n represents the number of repetitions.
  • a naphthylene group (these groups have one or two substituents selected from the group consisting of a C1-C4 alkyl group, a C1-C4 alkoxy group, a hydroxyl group and a sulfonic acid group as a substituent.
  • R 21 is a hydrogen atom, a C1-C4 alkyl group, an acetyl group, a benzoyl group or a substituted or unsubstituted phenyl group
  • R 23 and R 24 are each independently a hydrogen atom, a hydroxyl group, a sulfonic acid group, A C4 alkyl group or a C1-C4 alkoxy group, q represents 0 or 1, and r represents 1 or 2.
  • the optical element of the present invention has a function of causing a phase difference and is useful as a phase difference element, and can be used as a phase difference film by providing the optical element on a transparent substrate film.
  • the optical film having the optical element or the retardation film having the optical element on the polarizing film (hereinafter, also referred to as a polarizing film with an optical element) prevents light from leaking due to the inclination of the observation position in the liquid crystal display device.
  • a polarizing film with an optical element prevents light from leaking due to the inclination of the observation position in the liquid crystal display device.
  • the polarizing film with an optical element and a normal polarizing film are arranged with their absorption axes orthogonal to each other so that the optical elements are arranged between the polarizing elements, the respective absorption axis directions from the front direction Even if the observation position is tilted in a different direction, the omission of light is reduced, and even the slight leaked light is not colored, and the viewing angle dependence of the polarizing film and the wavelength dependence of the viewing angle improvement effect are also improved. It can be greatly reduced. Moreover, the viewing angle characteristic of a liquid crystal display can also be improved by using the polarizing film provided with this optical element for a liquid crystal display.
  • the optical element of the present invention comprises a biaxial layer defined below containing at least two kinds of organic dyes.
  • the biaxiality referred to in the present invention means that the three-dimensional refractive index satisfies the relationship of nx>nz> ny and the Nz coefficient is 0.2 to 0.7, preferably 0.3 to 0.5.
  • nx is the maximum refractive index in the plane
  • ny is the refractive index orthogonal to nx in the plane
  • nz represents the refractive index in the vertical direction with respect to the plane.
  • the Nz coefficient represents a value composed of (nx ⁇ nz) / (nx ⁇ ny).
  • a method of stretching a film and a method of applying a liquid crystal composition so as to be oriented and drying to form a coating film or a coating film layer (hereinafter referred to as an orientation coating film forming method) Say).
  • the method for stretching the film include the methods described in JP-A-2006-291192, WO2006 / 117981, and the like.
  • Examples of the method for applying and aligning the liquid crystalline composition include the methods described in JP-T-2009-540345, W02010 / 020928, JP-A-2006-48078, JP-A-2006-316138, and the like. Is mentioned.
  • the latter method for forming an oriented coating film is preferred.
  • a super-compound comprising at least one polycyclic organic compound having a conjugated ⁇ system and a functional group capable of forming a non-covalent bond between supramolecules. It is preferable to use a liquid crystalline composition exhibiting lyotropic liquid crystallinity composed of supuramolecule. Examples of such polycyclic organic compounds having lyotropic liquid crystallinity include oligophenyl compounds, bibenzimidazole compounds, acetonaphthoquinosaline compounds, and triazine compounds.
  • oligophenyl compounds examples are shown in Table 1, and examples of bibenzimidazole compounds are shown in Table 2, respectively. Examples of acetonaphthoquinosaline compounds are shown in Table 3. Examples of triazine compounds are shown in Table 4.
  • an oligophenyl compound is preferable.
  • preferred compounds are a benzene ring, a biphenyl ring and a naphthalene ring via a 5- or 6-membered heterocyclic ring containing at least one hetero atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom. It is preferable that at least two rings selected from the group consisting of are bonded to each other, and the benzene ring, biphenyl ring or naphthalene ring preferably has one sulfo group.
  • a compound represented by the following general formula (D) can be given as one preferred compound.
  • Y 1 represents —O—, —NH— or —SO 2 —
  • Y 2 represents a single bond, —O— or —NH—
  • A1 and A2 independently represent a benzene ring, a naphthalene ring or a biphenyl ring
  • the sulfo group (HSO 3 ) is substituted on those rings.
  • a liquid crystal composition containing the above-mentioned liquid crystalline compound and an organic dye described later is formed on a substrate such as a film by forming a dry coating layer of the aligned liquid crystal composition on a substrate such as a film.
  • a substrate having an optical element composed of an optically anisotropic layer is formed on a substrate such as a film.
  • a polymer exhibiting liquid crystal properties may be added to the composition exhibiting lyotropic liquid crystal properties.
  • rod-shaped liquid crystal polymers represented by WO2010 / 020928 (pages 16-17), and specific examples are shown in Table 5. It is preferable to add such a polymer exhibiting liquid crystallinity because the relationship between nx, ny, and nz of the obtained optical element can be adjusted and the durability can be improved.
  • X is —O—CH 2 —ph—CH 2 —O—, —O—CO—ph—CO—O— or —NH—CO—ph—CO—NH—, and ph has sulfo-substitution.
  • N represents a repeating number.
  • the weight average molecular number of the liquid crystalline polymer is about 1,000 to 200,000, and preferably about 2,000 to 100,000. In some cases, the weight average molecular number may be about 3,000 to 70,000, or about 4,000 to 70,000.
  • the above-mentioned two or more organic dyes, a polycyclic organic compound having lyotropic liquid crystallinity, and preferably, the liquid crystalline composition containing the above liquid crystalline polymer usually contains a solvent for forming a coating solution.
  • the solvent used is not particularly limited as long as it has excellent solubility and exhibits lyotropic properties in a state where the solvent is dissolved in the composition.
  • water, alcohols, ethers, cellosolves, carboxylic acids And dimethyl sulfoxide In the present invention, water is preferable from the viewpoint of handling. These can be used alone or as a mixture.
  • a water-soluble solvent such as dimethylformamide, glycerin, or ethylene glycol may be added.
  • the amount of the solvent is not particularly limited as long as it is a concentration at which the liquid crystalline composition can be applied.
  • the solid concentration is usually 5 to 50% by weight, preferably 8 to 30% by weight, based on the total amount of the composition.
  • the viscosity of the liquid crystalline composition is 200 to 1000 mPa ⁇ s when measured with an E-type viscometer at 25 ° C., it is suitable for producing a lyotropic liquid crystal. It is preferable to apply or apply a shearing force to the liquid crystal because the liquid crystal is aligned in a direction perpendicular to the MD direction.
  • Examples of at least two kinds of organic dyes used in the optical element of the present invention include azo compounds, anthraquinone compounds, perylene compounds, quinophthalone compounds, naphthoquinone compounds, merocyanine compounds, and the like. Even different types of dyes will not cause any problems. Usually, the same kind of compound is preferred. More preferably, it is an azo compound showing dichroism. For example, an azo compound described in “Application of Functional Dye” (supervised by Masahiro Irie, CMC Publishing) pages 98-100, C.I. I. Direct. Yellow 28, C.I. I. Direct. Yellow 44, C.I. I. Direct. Orange 26, C.I. I. Direct. Orange 107, C.I. I. Direct.
  • the at least two organic dyes used for forming the optical element or the retardation film of the present invention preferably have at least one organic dye having a maximum absorption wavelength of 380 nm or more and less than 550 nm, and the other at least one organic dye.
  • the maximum absorption wavelength is 550 nm or more and 780 nm or less. More preferably, the maximum absorption wavelength of at least one organic dye (first dye) of the organic dye is 430 nm or more and 470 nm or less, and the maximum absorption wavelength of the other at least one organic dye (second dye) is 570 nm or more. It is 630 nm or less.
  • the first dye include C.I. I. Direct. Orange 39, C.I. I. Direct.
  • Orange 71 C.I. I. Direct. Orange 26, C.I. I. Direct.
  • examples thereof include organic dyes described in Orange 107 and WO 2007/138980.
  • an azo compound represented by the following general formula (B) or a salt thereof is preferable.
  • X represents a sulfo group or a carboxy group
  • R 1 and R 2 each independently represent a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 alkoxyl group
  • n represents 1 or 2.
  • Examples of the second dye include C.I. I. Direct. Blue 202, C.I. I. Direct. Black 17, C.I. I. Direct. Blue 83, Direct.
  • Examples thereof include organic dyes described in Green 51, Japanese Patent Application Laid-Open No. 2001-33627, and Japanese Patent No. 3963979 (0022-0027).
  • Preferred examples of the dye include a compound represented by the following general formula (C) or a salt thereof.
  • Q 21 represents one or two sulfonic acid groups, and further represents a naphthyl group optionally having a hydroxyl group or a C1-C4 alkoxy group
  • Q 22 and Q 23 are each independently a phenylene group or A naphthylene group (these groups have one or two substituents selected from a C1 to C4 alkyl group, a C1 to C4 alkoxy group, a hydroxyl group and a sulfonic acid group as a substituent)
  • R 21 is a hydrogen atom, a C1-C4 alkyl group, an acetyl group, a benzoyl group or a substituted or unsubstituted phenyl group
  • R 23 and R 24 are each independently a hydrogen atom, a hydroxyl group, a sulfonic acid group, a C1-C4 alkyl group, or A C1-C4 alkoxy group
  • q represents 0 or 1
  • r represents
  • the optical element of the present invention exhibits a remarkably excellent effect.
  • a polarizing film provided with the optical element of the present invention and a normal polarizing film are arranged with their absorption axes orthogonal to each other so that the optical element is arranged between the polarizing elements, each from the front direction
  • the observation position is tilted in a direction different from the absorption axis direction
  • the light omission is reduced and the viewing angle dependency of the polarizing film and the effect of improving the viewing angle are reduced without coloring the slight leaked light.
  • Wavelength dependence can also be greatly reduced.
  • the total concentration of the above organic dyes is added to such an extent that the transmittance is not significantly reduced.
  • the content is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight, based on the total amount of the solid content of the coating liquid.
  • the ratio of the first dye and the second dye can be selected as appropriate.
  • the amount of the second dye is 0.1 to 10 parts by weight, preferably 0.
  • the ratio is 2 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, and most preferably 0.7 to 1.5 parts by weight.
  • a liquid crystalline composition comprising the polycyclic organic compound having lyotropic liquid crystallinity and an organic dye, preferably a liquid crystalline composition further comprising the liquid crystalline polymer.
  • a phase difference film can be obtained by applying an object to a transparent substrate and orienting it to form an optically anisotropic layer on the substrate.
  • a liquid crystal composition may be directly applied to a polarizing film to directly form an optically anisotropic layer oriented on the polarizing film, and a polarizing film including the optical element of the present invention may be used.
  • the oriented optical anisotropic layer may be first formed on a transfer substrate (releasing substrate), and the optical anisotropic layer may be transferred onto a polarizing film.
  • the optically anisotropic layer is formed by being oriented in a direction perpendicular to the MD direction (Machine Direction) of the polarizing plate.
  • the application method is not particularly limited as long as it can be uniformly applied and oriented. Applying to equipment using an appropriate coater such as slide coater, slot die coater, bar coater, rod coater, roll coater, curtain coater, spray coater, lip die coater, vacuum die coater, gravure coater, reverse gravure coater, micro gravure coater, etc. There is a method of spreading on a metal drum.
  • a drying means for drying die coaters or gravure coaters, and in the case of gravure coaters, the use of a smoothing roll is also effective.
  • the drying means There is no particular limitation on the drying means, and natural drying, vacuum drying, heat drying, vacuum heat drying and the like are used.
  • the heating and drying means a drying method using an arbitrary drying apparatus such as an air circulation type drying oven or a hot roll is used.
  • a preferable drying method is a method of drying at a low temperature of 0 ° C. to 40 ° C. and a relative humidity of 60% or less.
  • a transparent plastic substrate or glass is usually used, and a plastic substrate is preferable.
  • the plastic substrate used in the present invention include acrylic resin, polycarbonate resin, epoxy resin, and cellulose resin.
  • acrylic resin polycarbonate resin
  • epoxy resin epoxy resin
  • cellulose resin e.g., polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and syndiotactic.
  • TAC triacetyl cellulose
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • SPS polystyrene
  • PPS polyphenylene sulfide
  • PC polycarbonate
  • PAr polyacrylate
  • the thickness of the substrate is not particularly limited except for the application, but is generally in the range of 1 ⁇ m to 1000 ⁇ m.
  • the surface of each film is preferably subjected to surface treatment such as corona treatment, plasma treatment, alkali treatment, and primer treatment in order to adjust the wettability of the composition used in the present invention.
  • the optically anisotropic layer or retardation film of the present invention has an in-plane retardation value of 130 to 300 nm at a measurement wavelength of 550 nm.
  • the thickness is preferably 150 to 270 nm, more preferably 180 to 250 nm.
  • the thickness of the optically anisotropic layer depends on various optical parameters such as the type of the liquid crystal cell and the in-plane retardation value, but cannot generally be said, but is usually 0.1 to 10 ⁇ m. Further, it is preferably 0.1 to 2 ⁇ m.
  • the optically anisotropic layer can be subjected to a treatment for improving water resistance after film formation.
  • a method of substituting with a group insoluble or hardly soluble in water using a lake agent for example, a method of substituting with a group insoluble or hardly soluble in water using a lake agent.
  • the rake agent metal ions such as Ni 2+ , Ca 2+ , Fe 3+ , Cu 2+ , Zn 2+ , Al 3+ , Pd 2+ , Cd 2+ , Pb 2+ , Sn 2+ , Co 2+ , Mn 2+ , Ba 2+ , and Ce 3+ Or a salt of an organic amine.
  • These rake agents may be used alone or in combination of two or more in any ratio and combination.
  • Another method is to provide a protective layer on the optically anisotropic layer.
  • the material used for the protective layer is not particularly limited, and examples thereof include a urethane resin, an epoxy resin, and an acrylic resin, and these may be used alone or in combination of two or more.
  • a hydrophobic material is preferred, and a polyurethane resin is more preferred.
  • a polyurethane resin excellent in flexibility can be laminated on the optical anisotropic layer without disturbing the orientation state of the optical anisotropic layer.
  • the method of using the chelating agent and the method of providing a protective layer can be performed in combination.
  • an optical anisotropic layer can be laminated on a substrate in order to obtain a desired characteristic value.
  • the water resistance treatment using a chelating agent and / or the water resistance treatment for providing a protective layer may be performed for each layer or after all the optical anisotropic layers are laminated.
  • the optical element or retardation film of the present invention is used in combination with a polarizing film or other retardation film.
  • the optical element or the retardation film 2 is laminated so that the slow axis 4 of the retardation film 2 and the absorption axis 3 of the polarizing film 1 are orthogonal to each other.
  • the optically anisotropic layer 2 is formed by directly applying to the polarizing film 1 as shown in FIG.
  • the optical anisotropic layer side of the retardation film in which the optical anisotropic layer 2 is formed on the substrate is laminated with the polarizing film 1 or another retardation film via the acrylic adhesive 5.
  • the optically anisotropic layer 2 formed on the base material 7 as shown in FIG. 3 is bonded to the polarizing film 1 or another retardation film via an acrylic adhesive, and the base material 7 is peeled off, so that the optically anisotropic layer 2
  • the side layer 2 may be transferred to the polarizing film 1 or another retardation film.
  • the retardation film of the present invention can be used by being laminated with other retardation films, and for example, it can be used in combination with a negative C plate or a positive C plate.
  • any polarizing film that is usually used can be used as the polarizing film used in the production of the polarizing film with an optical element of the present invention.
  • the polarizing element (polarizer) used in the polarizing film is not particularly limited as long as it is an element having a function of polarizing light from a light source and absorbs light in a specific direction to be polarized. Any reflective polarizing element that reflects light in a specific direction to be polarized can be used.
  • an absorptive polarizing element for example, a polarizing element obtained by uniaxially stretching a hydrophilic polymer film such as a polyvinyl alcohol film containing a dichroic dye such as a dye or polyvalent iodine ion, a polyvinyl alcohol film A polarizing element obtained by dehydrating with an acid before and after uniaxial stretching to form a polyene structure, and a solution of a dichroic dye that develops a lyotropic liquid crystal state on an alignment film that has been processed to align in a certain direction Examples thereof include a polarizing element obtained by applying and then removing the solvent.
  • a reflective polarizing element for example, a polarizing element composed of a large number of laminated bodies having different birefringence, a polarizing element formed by combining a cholesteric liquid crystal having a selective reflection region and a quarter wavelength plate, and a substrate
  • a polarizing element provided with a fine wire grid.
  • a hydrophilic polymer such as a polyvinyl alcohol film containing a dichroic dye such as a dye or polyvalent iodine ion, which is excellent in polarization characteristics as a polarizing element.
  • a polarizing element obtained by uniaxially stretching a film or a polarizing element obtained by forming a polyene structure by dehydration with an acid before and after uniaxial stretching of a polyvinyl alcohol film.
  • the polarizing element can be manufactured by a conventional method.
  • a polarizing element comprising a polyvinyl alcohol film containing a dichroic dye such as a dye and polyvalent iodine ions
  • the polyvinyl alcohol film was first swollen with warm water and then the dichroic dye was dissolved.
  • the polarizing element can be obtained by immersing in a dyeing tank, dyeing the film, then stretching in a uniaxial direction in a tank containing a crosslinking agent such as boric acid or borax and drying.
  • Examples of the dye used for dyeing include iodine-potassium iodide aqueous solution, “Application of functional dye” (supervised by Masahiro Irie, CMC Publishing Co., Ltd.), pages 98-100, C.I. I. Direct. Yellow 12, C.I. I. Direct. Yellow 28, C.I. I. Direct. Yellow 44, C.I. I. Direct. Orange 26, C.I. I. Direct. Orange 39, C.I. I. Direct. Orange 107, C.I. I. Direct. Red2, C.I. I. Direct. Red31, C.I. I. Direct. Red 79, C.I. I. Direct. Red 81, C.I. I. Direct. Red247, C.I. I. Direct.
  • Green 80 C.I. I. Direct. Green 59, and JP 2001-33627, JP 2002-296417, JP 2003-215338, WO 2004/092822, JP 2001-0564112, JP 2001-027708, JP 11-218611, JP 11-218610, Examples thereof include organic dyes described in JP-A-60-156759, JP-A-2001-33627, and JP-A-2622748. These dichroic dyes are free acids, alkali metal salts (for example, Na salts, K salts and Li salts), ammonium salts, salts of amines, or complex salts (for example, Cu complexes, Ni complexes and Co complexes). Etc.
  • the performance of the polarizing element can be adjusted by the dichroism of the dichroic dye, the stretch ratio during stretching, and the like.
  • the image display device of the present invention for example, a liquid crystal display device can be obtained by disposing it in combination with a polarizing plate in the light path of the image display device, for example, at least one side of the liquid crystal cell of the liquid crystal display device.
  • the liquid crystal display device has various modes depending on the type of the liquid crystal cell to be used. In any case, a polarizing film provided with the optical anisotropic layer (optical element) of the present invention can be used.
  • the retardation film of the present invention can be used in the apparatus. What is necessary is just to adjust the NZ coefficient and retardation value of an optically anisotropic layer (optical element) or each retardation film according to each viewing angle characteristic.
  • Formulation Example 1 13.6 parts of the following compound described in JP-T-2009-540345, 2.4 parts of the following compound described in WO2010 / 020928, 84 parts of water, and 0.08 part of organic dye (CI Direct. Orange 39) described in WO2007 / 138980 and 0.08 part of organic dye described in Japanese Patent No. 3963979, Were mixed and dissolved to prepare a solution having a solid content of about 16%.
  • the viscosity of the solution was 330 mPa ⁇ s as measured by an E-type viscometer at 25 ° C.
  • Formulation Example 2 In the above Formulation Example 1, in place of 0.08 part of the organic dye described in Japanese Patent No. 3963799, C.I. I. Direct. A solution having a solid content of about 16% was prepared in the same manner as in Formulation Example 1 except that 0.08 part of Blue67 was used. The viscosity of the solution was 330 mPa ⁇ s as measured by an E-type viscometer at 25 ° C.
  • Formulation Example 3 In the above Formulation Example 1, the organic dye C.I. I. Direct. A solution having a solid content of about 16% was prepared in the same manner as in Formulation Example 1 except that the blending of both of the organic dyes described in Orange 39 and Japanese Patent No. 3963379 was stopped. The viscosity of the solution was 330 mPa ⁇ s as measured by an E-type viscometer at 25 ° C.
  • Formulation Example 4 In the above Formulation Example 1, C.I. I. Direct. A solution having a solid content of about 16% was prepared in the same manner as in Formulation Example 1 except that the blending of Orange 39 was stopped. The viscosity of the solution was 330 mPa ⁇ s as measured by an E-type viscometer at 25 ° C.
  • Example 1 The solution obtained in Formulation Example 1 was applied onto iodine-based polarizing plate 1a (trade name: SKN, manufactured by Polatechno Co., Ltd.) so that the thickness after drying was 1.0 ⁇ m, and a wire bar (# 10) was used. A shear stress was applied in the MD direction, and the compressor air was sprayed and dried. Further, a 10% barium nitrate aqueous solution was sprayed onto the coated surface by spraying, and compressed air was sprayed again to form an optically anisotropic layer, thereby producing a polarizing film with an optical element (optical film) of the present invention.
  • iodine-based polarizing plate 1a (trade name: SKN, manufactured by Polatechno Co., Ltd.) so that the thickness after drying was 1.0 ⁇ m, and a wire bar (# 10) was used. A shear stress was applied in the MD direction, and the compressor air was sprayed and dried. Further, a 10%
  • Example 2 Using the solution prepared in Formulation Example 2 instead of the solution prepared in Formulation Example 1, a polarizing film with an optical element (optical film) of the present invention was produced in the same manner as in Example 1.
  • Example 3 The solution prepared in Formulation Example 1 was applied onto a triacetylcellulose (TAC) film whose surface was alkali-treated so that the thickness after drying was 1.0 ⁇ m, and the wire bar (# 10) was used in the MD direction. Shear stress was applied, and compressor air was sprayed to dry. Further, a 10% barium nitrate aqueous solution was sprayed onto the coated surface by spraying, and compressed air was sprayed again to dry, thereby producing a retardation film having an optically anisotropic layer on the film.
  • the TAC film surface of the retardation film and the iodine-based polarizing plate 1a (trade name: SKN, manufactured by Polatechno Co., Ltd.) are used.
  • the acrylic adhesive 5 (product) Name: PTR-2500, manufactured by Nippon Kayaku Co., Ltd.).
  • Comparative Example 1 The iodine type polarizing plate 1a (trade name: SKN, manufactured by Polatechno Co., Ltd.) having no optically anisotropic layer used in Example 1 was used as it was.
  • Comparative Example 2 Using the solution prepared in Formulation Example 3 instead of the solution prepared in Formulation Example 1, the same operation as in Example 1 was performed to obtain a polarizing film having a comparative optically anisotropic layer.
  • Comparative Example 3 Using the solution prepared in Formulation Example 4 instead of the solution prepared in Formulation Example 1, the same operation as in Example 1 was performed to obtain a polarizing film having a comparative optically anisotropic layer.
  • nx ny nz NZ factor Example 1 1.81 1.60 1.73 0.38
  • Example 2 1.80 1.60 1.73 0.35
  • Example 3 1.81 1.60 1.73 0.38 Comparative Example 1 (no optical anisotropic layer) Comparative Example 2 1.80 1.59 1.73 0.33 Comparative Example 3 1.80 1.60 1.73 0.35
  • the in-plane retardation value at the measurement wavelength of 550 nm in the optically anisotropic layer was as follows.
  • Example 1 205nm
  • Example 2 205 nm
  • Example 3 215 nm Comparative Example 1 (no optical anisotropic layer) Comparative Example 2 195 nm Comparative Example 3 200nm
  • the optical anisotropic layer side 2 of the optical film (polarizing film with an optical element of the present invention) on which the optical anisotropic layer obtained in Examples 1 and 2 and Example 3 is formed is an acrylic adhesive.
  • 5 (trade name: PTR-2500, manufactured by Nippon Kayaku Co., Ltd.) was attached to one side of the glass plate 8.
  • An iodine polarizing plate 1a (trade name: SKN, manufactured by Polatechno Co., Ltd.) is also applied to the opposite side of the glass plate 8 via an acrylic adhesive 5 (trade name: PTR-2500, manufactured by Nippon Kayaku Co., Ltd.).
  • a laminated sample (optical system) for optical property test was prepared by arranging the plates 1a (trade name: SKN, manufactured by Polatechno Co., Ltd.) so that their absorption axes are orthogonal to each other. In the same manner for Comparative Examples 1 to 3, laminated samples (optical systems) for optical property tests were prepared.
  • the laminated sample having the above configuration is measured from a polar angle of 0 °, an azimuth angle of 0 °, a polar angle of 50 °, and an azimuth angle of 45 °, and the visibility corrected orthogonal transmittances Yc (0,0) and Yc (50 45).
  • the transmittance was measured using a spectrophotometer (U-4100, manufactured by Hitachi Spectroscopic Co., Ltd.). The black luminance in the oblique direction is better as the Yc value is smaller.
  • FIG. 7 shows orthogonal transmittance waveforms for Example 1 and Comparative Examples 1 and 2. The results for Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 6.
  • the orthogonal transmittance is uniformly low at a wavelength of about 450 to 700 nm regardless of the wavelength, and as can be seen from Table 6. Further, it can be seen that the black luminance Yc value in the oblique direction is low, and there is no or very little coloration in the oblique direction.
  • the slow axis of the optically anisotropic layer and the retardation film and the long side direction of the panel were made parallel.
  • the absorption axis of the polarizing plate (trade name: SKN, manufactured by Polatechno Co., Ltd.) of the film formed with the optical anisotropic layer obtained in Example 1 and Example 2 bonded to the backlight side,
  • the absorption axis of the surface-side polarizing plate of the cell is orthogonal.
  • the obtained liquid crystal panel was used for the test.
  • test liquid crystal panels were prepared.
  • the obtained test liquid crystal panel was placed on a backlight to obtain a liquid crystal display device. After the black screen was displayed on the liquid crystal display device and the backlight was turned on in the dark room, after 30 minutes had elapsed, the degree of coloring was observed visually from an oblique direction (azimuth angle 45 °, polar angle 50 °). The observation results for Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 6.
  • the orthogonal transmittance can be kept low uniformly regardless of the wavelength in a wavelength range of about 450 to 700 nm without using a large number of retardation films. I can do it. Further, the black luminance in the oblique direction can be suppressed to a low level, and coloring in the oblique direction can be eliminated or significantly reduced, so that it is extremely useful as an optical element.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

La présente invention concerne un élément optique qui est formé d'une couche optiquement anisotrope qui contient des colorants organiques et possède des indices de réfraction tridimensionnels qui satisfont nx > nz > ny, (nx - nz) / (nx - ny) allant de 0,2 à 0.7. L'élément optique est caractérisé en ce qu'au moins un colorant organique possède une longueur d'onde d'absorption maximale supérieure ou égale à 380 nm, mais inférieure ou égale à 550 nm, et qu'au moins un autre colorant organique possède une longueur d'onde d'absorption maximale de 550 à 780 nm (inclus). L'élément optique fonctionne comme un élément de retard. Dans les exemples où un élément polarisant comprenant l'élément optique est utilisé, la luminosité des noirs peut être supprimée uniformément indépendamment de la longueur d'onde dans la plage de longueur d'onde de 450 à 700 nm, la fuite des blancs dans une direction oblique est réduite et la lumière de fuite n'est pas colorée, ou très peu.
PCT/JP2011/002541 2010-05-07 2011-05-02 Elément optique et procédé permettant d'améliorer l'angle de vue d'un film polarisant l'utilisant WO2011138869A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020127029753A KR20130080789A (ko) 2010-05-07 2011-05-02 광학소자 및 이것을 사용한 편광필름의 시야각 개량방법
JP2012513771A JP5973911B2 (ja) 2010-05-07 2011-05-02 光学素子、並びに、該光学素子を有する位相差フィルム、光学フィルムおよび画像表示装置
CN201180022769.8A CN102884456B (zh) 2010-05-07 2011-05-02 光学元件和使用该光学元件改良偏光薄膜的视角的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-107066 2010-05-07
JP2010107066 2010-05-07

Publications (1)

Publication Number Publication Date
WO2011138869A1 true WO2011138869A1 (fr) 2011-11-10

Family

ID=44903722

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/002541 WO2011138869A1 (fr) 2010-05-07 2011-05-02 Elément optique et procédé permettant d'améliorer l'angle de vue d'un film polarisant l'utilisant

Country Status (5)

Country Link
JP (1) JP5973911B2 (fr)
KR (1) KR20130080789A (fr)
CN (1) CN102884456B (fr)
TW (1) TWI541529B (fr)
WO (1) WO2011138869A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016190406A1 (fr) * 2015-05-28 2016-12-01 富士フイルム株式会社 Dispositif d'affichage à cristaux liquides alignés horizontalement
KR20190141124A (ko) 2017-04-28 2019-12-23 닛토덴코 가부시키가이샤 액정 배향 필름 및 그의 제조 방법

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09230142A (ja) * 1995-05-17 1997-09-05 Nippon Kayaku Co Ltd 偏光素子又は偏光板
JPH11218610A (ja) * 1998-01-30 1999-08-10 Nippon Kayaku Co Ltd 新規偏光膜
JP2002071950A (ja) * 2000-09-01 2002-03-12 Nippon Kayaku Co Ltd 光学フィルムおよびこれを用いた偏光板の視野角改良方法
JP2002357720A (ja) * 2001-03-15 2002-12-13 Nippon Kayaku Co Ltd 新規なマイクロパターン偏光素子の製造方法及びこれを用いる立体表示液晶表示装置
JP2006215142A (ja) * 2005-02-02 2006-08-17 Nitto Denko Corp 位相差フィルムおよびその製造方法、ならびに該位相差フィルムを用いた画像表示装置
WO2007138980A1 (fr) * 2006-06-01 2007-12-06 Nippon Kayaku Kabushiki Kaisha Composé azo, sel et film polarisant contenant un colorant comprenant le composé ou son sel
WO2008117347A1 (fr) * 2007-03-22 2008-10-02 Nitto Denko Corporation Panneau à cristaux liquides, dispositif d'affichage à cristaux liquides utilisant le panneau à cristaux liquides et procédé de fabrication d'un panneau à cristaux liquides
WO2009130676A2 (fr) * 2008-04-25 2009-10-29 Crysoptix Kk Écran à cristaux liquides couleur et panneau de compensation
JP2009251443A (ja) * 2008-04-09 2009-10-29 Nitto Denko Corp 積層光学フィルム、積層光学フィルムを用いた液晶パネルおよび液晶表示装置
WO2010020928A2 (fr) * 2008-08-19 2010-02-25 Crysoptix Kk Composition de composés organiques, film optique et son procédé de production

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4137438B2 (ja) * 2000-12-18 2008-08-20 日本化薬株式会社 光学フィルムおよびこれを用いた偏光フィルム、および偏光フィルムの視野角改良方法
JP4236098B2 (ja) * 2003-08-01 2009-03-11 日東電工株式会社 複屈折性光学フィルム
JP4479928B2 (ja) * 2007-06-15 2010-06-09 株式会社 日立ディスプレイズ 液晶表示装置

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09230142A (ja) * 1995-05-17 1997-09-05 Nippon Kayaku Co Ltd 偏光素子又は偏光板
JPH11218610A (ja) * 1998-01-30 1999-08-10 Nippon Kayaku Co Ltd 新規偏光膜
JP2002071950A (ja) * 2000-09-01 2002-03-12 Nippon Kayaku Co Ltd 光学フィルムおよびこれを用いた偏光板の視野角改良方法
JP2002357720A (ja) * 2001-03-15 2002-12-13 Nippon Kayaku Co Ltd 新規なマイクロパターン偏光素子の製造方法及びこれを用いる立体表示液晶表示装置
JP2006215142A (ja) * 2005-02-02 2006-08-17 Nitto Denko Corp 位相差フィルムおよびその製造方法、ならびに該位相差フィルムを用いた画像表示装置
WO2007138980A1 (fr) * 2006-06-01 2007-12-06 Nippon Kayaku Kabushiki Kaisha Composé azo, sel et film polarisant contenant un colorant comprenant le composé ou son sel
WO2008117347A1 (fr) * 2007-03-22 2008-10-02 Nitto Denko Corporation Panneau à cristaux liquides, dispositif d'affichage à cristaux liquides utilisant le panneau à cristaux liquides et procédé de fabrication d'un panneau à cristaux liquides
JP2009251443A (ja) * 2008-04-09 2009-10-29 Nitto Denko Corp 積層光学フィルム、積層光学フィルムを用いた液晶パネルおよび液晶表示装置
WO2009130676A2 (fr) * 2008-04-25 2009-10-29 Crysoptix Kk Écran à cristaux liquides couleur et panneau de compensation
WO2010020928A2 (fr) * 2008-08-19 2010-02-25 Crysoptix Kk Composition de composés organiques, film optique et son procédé de production

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016190406A1 (fr) * 2015-05-28 2016-12-01 富士フイルム株式会社 Dispositif d'affichage à cristaux liquides alignés horizontalement
JPWO2016190406A1 (ja) * 2015-05-28 2018-03-15 富士フイルム株式会社 水平配向型液晶表示装置
US10481435B2 (en) 2015-05-28 2019-11-19 Fujifilm Corporation Horizontal alignment-type liquid crystal display device
KR20190141124A (ko) 2017-04-28 2019-12-23 닛토덴코 가부시키가이샤 액정 배향 필름 및 그의 제조 방법

Also Published As

Publication number Publication date
KR20130080789A (ko) 2013-07-15
TW201200899A (en) 2012-01-01
CN102884456B (zh) 2014-12-31
TWI541529B (zh) 2016-07-11
JP5973911B2 (ja) 2016-08-23
JPWO2011138869A1 (ja) 2013-07-22
CN102884456A (zh) 2013-01-16

Similar Documents

Publication Publication Date Title
US9383493B2 (en) Laminated polarizing plate, method for production thereof and liquid crystal display
WO2014162635A1 (fr) Élément polarisant à base de colorant achromatique possédant une transmittance élevée, et plaque de polarisation
JP5723077B1 (ja) 位相差板、楕円偏光板およびそれを用いた表示装置
US20150293391A1 (en) Brightness enhancement film, polarizing plate and image display device
WO2014162634A1 (fr) Élément polarisant à base de colorant achromatique, et plaque de polarisation
JP2013037222A (ja) 偏光子及びその製造方法
KR100950503B1 (ko) 이색성비가 향상된 편광판 및 이를 구비하는 액정표시장치
CN110908030A (zh) 圆偏光板及其制备方法，显示器
JP5942318B2 (ja) 偏光フィルム、画像表示装置、及び偏光フィルムの製造方法
JP2007121996A (ja) 光学補償シートならびに、これを用いた偏光板および液晶表示装置
JP5973911B2 (ja) 光学素子、並びに、該光学素子を有する位相差フィルム、光学フィルムおよび画像表示装置
US20200292739A1 (en) Image display apparatus and circularly polarizing plate to be used in the image display apparatus
KR102170099B1 (ko) 이방성 색소막용 조성물, 이방성 색소막 및 광학 소자
TWI412843B (zh) 光學補償膜、偏光板及液晶顯示裝置
JP2012203002A (ja) 偏光子及びその製造方法
JP2009258660A (ja) 光学補償フィルム付き偏光板、液晶パネル、及び液晶表示装置
WO2021014685A1 (fr) Procédé de production de plaque de polarisation circulaire mince
JP5978529B2 (ja) 偏光フィルム、画像表示装置、及び偏光フィルムの製造方法
JP4484996B2 (ja) 多軸偏光子の製造方法
KR20070102964A (ko) 광학 보상 시트, 그리고 이것을 사용한 편광판 및 액정표시 장치
WO2023047748A1 (fr) Plaque de polarisation avec couche de différence de phase, dispositif d'affichage d'image l'utilisant, et procédé d'évaluation de plaque de polarisation avec couche de différence de phase
KR102135497B1 (ko) 편광판 및 이를 포함하는 액정 표시 장치
WO2023163119A1 (fr) Film antireflet et dispositif d'affichage électroluminescent organique
CN108885369A (zh) 偏振板组和使用了该偏振板组的ips模式液晶显示装置
JP2004258602A (ja) 液晶表示装置および偏光板

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180022769.8

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11777389

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012513771

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20127029753

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 11777389

Country of ref document: EP

Kind code of ref document: A1