WO2016051663A1 - Composition à cristaux liquides, film d'émission de lumière polarisée, élément de conversion de fréquence et procédé de production pour ce dernier, unité de rétroéclairage et dispositif d'affichage à cristaux liquides - Google Patents

Composition à cristaux liquides, film d'émission de lumière polarisée, élément de conversion de fréquence et procédé de production pour ce dernier, unité de rétroéclairage et dispositif d'affichage à cristaux liquides Download PDF

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WO2016051663A1
WO2016051663A1 PCT/JP2015/004417 JP2015004417W WO2016051663A1 WO 2016051663 A1 WO2016051663 A1 WO 2016051663A1 JP 2015004417 W JP2015004417 W JP 2015004417W WO 2016051663 A1 WO2016051663 A1 WO 2016051663A1
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liquid crystal
polarized light
film
group
quantum rod
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PCT/JP2015/004417
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English (en)
Japanese (ja)
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石川　博之
森嶌　慎一
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S2/00—Systems of lighting devices, not provided for in main groups F21S4/00 - F21S10/00 or F21S19/00, e.g. of modular construction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
    • F21V9/14—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters for producing polarised light
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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

Definitions

  • the present invention relates to a liquid crystal composition, a polarized light emitting film, a wavelength conversion member and a manufacturing method thereof, a backlight unit, and a liquid crystal display device.
  • Quantum rods are fine particles (semiconductor nanocrystals) of a rod-like (rod-like) semiconductor compound that emits polarized light because of its rod-like shape and directivity.
  • Patent Document 1 discloses an aspect in which polarized light is obtained by irradiating an optically active structure including quantum rods oriented in one direction with pumping light, and is useful as a backlight system for a display device. Is marked.
  • the quantum rod is oriented by mechanically stretching a polymer film in which the quantum rod is dispersed.
  • Patent Document 2 includes a nematic liquid crystal and a zinc sulfide or zinc oxide quantum rod having a domain-like structure, and each quantum rod in the domain includes a quantum rod arranged in a substantially parallel state.
  • Quantum rod formulations for liquid crystal displays are disclosed. In this blend, the orientation of the quantum rod is controlled by the characteristics of the nematic liquid crystal.
  • a quantum rod with an extremely small size having an inner diameter of 1.2 nm and a length of 4.0 nm is specifically used.
  • the quantum rods cannot be sufficiently oriented. Therefore, the polarized light emission property of the polymer film that has been subjected to the stretching treatment does not necessarily satisfy the level required recently.
  • polarized light emission means a property of emitting predetermined polarized light, and when the polarized light emission property is excellent, the intensity of a specific polarization becomes high. Moreover, productivity is not necessarily good in the above stretching treatment, and it is difficult to reduce the thickness of the resulting film.
  • the polarized light emission does not necessarily satisfy the level required recently. Further, in Patent Document 2, since the liquid crystal compound is aligned using an external electric field, the orientation of the quantum rod is easily lost when the application of the external electric field is stopped. In particular, in a high-temperature and high-humidity environment, the orientation of the liquid crystal compound is likely to be lost, and as a result, the polarized light emission is reduced.
  • the present invention provides a liquid crystal composition that can easily produce a polarized light-emitting film that is excellent in polarized light-emitting properties and that suppresses the decrease in polarized light-emitting properties even in a high-temperature and high-humidity environment.
  • Another object of the present invention is to provide a polarized light-emitting film, a wavelength conversion member and a method for producing the same, a backlight unit, and a liquid crystal display device.
  • the liquid crystal composition of the present invention includes a quantum rod that is excited by incident excitation light and emits fluorescence, and a side chain polymer liquid crystal compound having a crosslinkable group.
  • a preferred molecular weight for the side chain polymer liquid crystal compound is a weight average molecular weight of 5,000 to 1,000,000, more preferably 7,000 to 500,000, and particularly preferably 7,000 to 100,000. If the molecular weight is too high, the viscosity becomes high and the orientation is deteriorated. If the molecular weight is too low, the liquid stability is lowered.
  • a weight average molecular weight is defined as a polystyrene conversion value by gel permeation chromatography (GPC) measurement.
  • the weight average molecular weight is, for example, HLC-8220 (manufactured by Tosoh Corporation), TSKgel (registered trademark) Super AWM-H (manufactured by Tosoh Corporation), 6.0 mm ID ⁇ 15. It can be determined by using 0 cm and a column temperature of 40 ° C. Unless otherwise stated, the eluent was measured using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution.
  • the length of the major axis of the quantum rod is preferably 20 to 100 nm, and the ratio of the major axis length to the minor axis length of the quantum rod is preferably 4 to 20.
  • the side chain type polymer liquid crystal compound has a group adsorbing to the quantum rod.
  • the group adsorbing to the quantum rod is any one of a phosphate group, an amino group, and a carboxyl group.
  • Quantum rods CdS, CdSe, CdTe, ZnS , ZnSe, ZnSeS, ZnTe, ZnO, GaP, GaAs, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, AlSb, CuS, Cu 2 S, It is preferable to include at least one component selected from the group consisting of Cu 2 Se, CuInS, CuInS 2 , CuInSe 2 , Cu 2 (ZnSn) S 4 , and Cu 2 (InGa) S 4 .
  • the polarized light-emitting film of the present invention is formed from the liquid crystal composition of the present invention.
  • the polarized light-emitting film of the present invention is formed from the liquid crystal composition of the present invention, and includes a polymer matrix having a crosslinked structure, and a plurality of quantum rods dispersed in the polymer matrix,
  • the polymer matrix has a repeating unit including a liquid crystal structure as a partial structure, and the liquid crystal structure is fixed in an aligned state,
  • the plurality of quantum rods are oriented so that the long axes of the quantum rods are parallel to each other,
  • the length of the long axis of the quantum rod is 20 to 100 nm,
  • the ratio of the major axis length to the minor axis length of the quantum rod is preferably 4 to 20.
  • the wavelength-changing member of the present invention is a support that is disposed on at least one surface of the polarized light-emitting film of the present invention and the polarized light-emitting film and has an oxygen permeability of 50 cm 3 / (m 2 ⁇ day ⁇ atm) or less. Including the body.
  • the wavelength changing member of the present invention preferably includes an alignment film subjected to an alignment treatment between the polarized light-emitting film and the support.
  • the backlight unit of the present invention includes at least the wavelength conversion member of the present invention and a blue light emitting diode or an ultraviolet light emitting diode.
  • the liquid crystal display device of the present invention includes at least the backlight unit and a liquid crystal cell.
  • the method for producing a wavelength conversion member of the present invention includes a step of rubbing one side of a support, a step of applying the liquid crystal composition of the present invention to one side subjected to rubbing, and a liquid crystal composition Forming a polarized light-emitting film by crosslinking the side-chain polymer liquid crystal compound having a crosslinkable group.
  • Another method for producing a wavelength conversion member of the present invention includes a step of forming an alignment film subjected to an alignment treatment on a support, a step of applying the liquid crystal composition of the present invention on the alignment film, and a liquid crystal And a step of forming a polarized light-emitting film by crosslinking the side chain type polymer liquid crystal compound having a crosslinkable group in the composition.
  • liquid crystal composition of the present invention it is possible to easily produce a polarized light-emitting film that is excellent in polarized light-emitting properties and that suppresses a decrease in polarized light-emitting properties even in a high temperature and high humidity environment.
  • FIG. 1 is a schematic diagram illustrating a configuration of a liquid crystal display device according to an embodiment of the present invention.
  • 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.
  • the liquid crystal composition of the present invention includes at least a plurality of quantum rods and a side chain type polymer liquid crystal compound having a crosslinkable group.
  • the liquid crystal composition of the present invention is suitable as a film-forming composition for a film in which a plurality of quantum rods are dispersed with a major axis orientation in a polymer matrix, which is suitable for a polarized light-emitting film or the like. Can be used.
  • the side chain liquid crystal structure is fixed in an aligned state. For example, it is aligned in the alignment direction of the side chain liquid crystal structure. The movement of the quantum rod is suppressed, and its orientation state can be fixed.
  • an optically anisotropic film such as a polarized light-emitting film formed using the liquid crystal composition of the present invention has a quantum rod mobility limited by the polymer matrix even in a high temperature and high humidity environment. Is easily maintained, and as a result, a decrease in polarized light emission is suppressed.
  • the liquid crystal composition of the present invention includes at least a quantum rod that is excited by incident excitation light to emit fluorescence and a side-chain polymer liquid crystal compound having a crosslinkable group.
  • composition includes at least a quantum rod that is excited by incident excitation light to emit fluorescence and a side-chain polymer liquid crystal compound having a crosslinkable group.
  • each component contained in the composition will be described in detail, and then a polarized light-emitting film formed using the composition, a wavelength conversion member including the polarized light-emitting film, a backlight unit, a liquid crystal display device, and the like will be described in detail. To do.
  • Quantum rods also called semiconductor nanorods, are rod-shaped (rod-shaped) semiconductor nanocrystals (nanoparticles) that are rod-shaped and have directivity, so that light emitted from a light source emits polarized light. . That is, the quantum rod is a material that is excited by incident excitation light and emits fluorescence.
  • the length of the long axis of the quantum rod (length in the long axis direction) is 20 to 100 nm, and the polarization emission property of the polarized light-emitting film is more excellent, and the polarization emission property is further reduced even in a high-temperature and high-humidity environment. In order to satisfy at least one of the points to be suppressed, 20 to 60 nm is preferable, and 20 to 50 nm is more preferable. If the length of the long axis is 20 nm or more, the shape anisotropy of the quantum rod is sufficient, and the polarized light emission property of the quantum rod itself can be obtained. Moreover, if the length of a long axis is 100 nm or less, it is easy to disperse
  • the length of the short axis of the quantum rod is not particularly limited, but is preferably 2 to 10 nm, more preferably 2 to 7 nm in terms of better orientation of the quantum rod in the polarized light-emitting film. preferable.
  • the long axis of a quantum rod means the line segment in which the line segment which crosses a quantum rod becomes the longest in the two-dimensional image of the quantum rod obtained by observing with a microscope (for example, transmission electron microscope).
  • the short axis is a line segment that is orthogonal to the long axis and has the longest line segment that crosses the quantum rod.
  • the length of the long axis is an average value, and the length of the long axis of 20 or more arbitrarily selected quantum rods is measured with a microscope (for example, a transmission electron microscope), and they are arithmetically averaged. It is the value.
  • the length of the short axis is an average value, and the length of the short axis of 20 or more arbitrarily selected quantum rods is measured with a microscope (for example, a transmission electron microscope), and they are arithmetically averaged. It is the value.
  • the aspect ratio of the quantum rod (the length of the long axis of the quantum rod / the length of the short axis of the quantum rod) is 4 to 20, and is preferably 4 to 15 in terms of more excellent effects of the present invention. Is more preferable.
  • the aspect ratio is 4 or more, the shape anisotropy of the quantum rod is sufficient, the polarization property of the quantum rod itself is obtained, and the effect of aligning with the liquid crystal is obtained.
  • the aspect ratio is 20 or less, the dispersibility in the liquid crystal compound is good, and it is possible to suppress the occurrence of phase separation due to inability to disperse and white turbidity.
  • the aspect ratio is an average value, and is an arithmetic average value obtained by measuring the aspect ratio of 20 or more arbitrarily selected quantum rods with a microscope (for example, a transmission electron microscope).
  • the shape of the quantum rod may be a shape extending in one direction (rod shape), and may be a so-called columnar shape, quadrangular prism shape (preferably a rectangular parallelepiped shape), a triangular prism shape, a hexagonal prism shape, or the like.
  • the material constituting the quantum rod is not particularly limited, and is usually composed of a semiconductor, such as II-VI semiconductor, III-V semiconductor, IV-VI semiconductor, or a combination thereof. More specifically, CdS, CdSe, CdTe, ZnS, ZnSe, ZnSeS, ZnTe, ZnO, GaP, GaAs, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, AlSb, CuS, Cu 2 It can be selected from S, Cu 2 Se, CuInS, CuInS 2 , CuInSe 2 , Cu 2 (ZnSn) S 4 , Cu 2 (InGa) S 4 , these TiO 2 alloys, and mixtures thereof.
  • a semiconductor such as II-VI semiconductor, III-V semiconductor, IV-VI semiconductor, or a combination thereof. More specifically, CdS, CdSe, CdTe, ZnS, ZnSe,
  • Quantum rods CdS, CdSe, CdTe, ZnS , ZnSe, ZnSeS, ZnTe, ZnO, GaP, GaAs, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, AlSb, CuS, Cu 2 S, It is preferable to include at least one component selected from the group consisting of Cu 2 Se, CuInS, CuInS 2 , CuInSe 2 , Cu 2 (ZnSn) S 4 , and Cu 2 (InGa) S 4 .
  • the quantum rod of the present invention is preferably CdS, CdSe, ZnS, ZnSe, InP, CuS, or CuInS.
  • the quantum rod may be a single-component quantum rod or a core / shell type quantum rod including a first semiconductor core and a second semiconductor shell. Further, a core / multi-shell type quantum rod may be used, and a quantum rod having a core / shell structure with a stepwise composition of the shell can also be used.
  • a ligand may be coordinated on the surface of the quantum rod as necessary.
  • the ligand include phosphines and phosphine oxides such as trioctylphosphine oxide (TOPO, Trioctylphosphineoxide), trioctylphosphine (TOP), tributylphosphine (TBP), and tributylphosphine; acid), tridecylphosphonic acid (TDPA, Tridecylphosphonic acid), hexylphosphonic acid (HPA, Hexylphosphonic acid), etc .; dodecylamine (DDA, Dodecylylamine), tetradecylamine (TDA, Tetradedecylamine) Examples include amines such as HDA, Hexadecylamine, and octadecylamine; thiols such as hexadecanethiol and hexanethiol; mercaptocarboxy
  • the quantum rod include, for example, a quantum rod R having a light emission center wavelength in a wavelength band of 600 nm to 680 nm and a half width of 60 nm or less, and a light emission center in a wavelength band of 500 nm to 600 nm.
  • a quantum rod G having a wavelength and a half width of 60 nm or less
  • a quantum rod B having an emission center wavelength in a wavelength band of 430 nm to 480 nm and a half width of 60 nm or less.
  • the “half-value width” means a wavelength difference between both ends of a wavelength at which the emission intensity is 0.5 when the emission peak of the emission spectrum is 1.
  • the quantum rod R is excited by excitation light to emit red light
  • the quantum rod G emits green light
  • the quantum rod B emits blue light.
  • red light emitted by the quantum rod R, green light emitted by the quantum rod G, and a polarized light emitting film White light can be realized by the transmitted blue light.
  • ultraviolet light incident as polarized light on a polarizing light-emitting film including quantum rods R, G, and B red light emitted by quantum rod R, green light emitted by quantum rod G, and quantum rod White light can be realized by the blue light emitted by B.
  • the emission wavelength of the quantum rod can be adjusted by the composition and size.
  • light having an emission center wavelength in the wavelength band of 430 to 480 nm is referred to as blue light
  • light having an emission center wavelength in the wavelength band of 500 to 600 nm is referred to as green light
  • wavelength of 600 to 680 nm is called red light.
  • the content of the quantum rod in the composition of the present invention is not particularly limited, but is 0.001 with respect to the total mass of the composition in terms of the orientation of the quantum rod in the polarized light-emitting film and the handleability of the composition. ⁇ 10% by mass is preferable, and 0.01 to 1% by mass is more preferable.
  • a quantum rod may use only 1 type and may use 2 or more types together. When using 2 or more types together, you may use 2 or more types of quantum rods from which the light emission wavelength differs. In addition, when using multiple types of quantum rods, it is preferable that the total amount is the said range.
  • the side chain polymer liquid crystal compound is a polymer liquid crystal compound having a liquid crystal structure in the side chain, and the side chain polymer liquid crystal compound having a crosslinkable group is a main chain in the side chain polymer liquid crystal compound. And / or a compound having a crosslinkable group in a side chain and exhibiting a liquid crystal state (for example, a liquid crystal state of a smectic liquid crystal phase) under a specific temperature condition.
  • a liquid crystal state for example, a liquid crystal state of a smectic liquid crystal phase
  • an optically anisotropic film formed using a liquid crystal composition containing a quantum rod and such a polymer liquid crystal compound as a film-forming composition has a high alignment property along the alignment direction of the side-chain liquid crystal structure.
  • the arranged quantum rods are fixed in a state in which the orientation is maintained in a polymer matrix formed by crosslinking the side chain type polymer liquid crystal compound.
  • the side chain polymer liquid crystal compound having a crosslinkable group has a structure in which a crosslinkable group is introduced into a side chain polymer liquid crystal compound having a liquid crystal structure in the side chain.
  • the side chain type polymer liquid crystal compound is a polymer compound having at least one liquid crystal structure in the side chain, and a liquid crystal having a polymerizable group so as to be polymerized in a state having the liquid crystal structure in the side chain. It is a compound obtained by polymerizing at least one monomer containing at least a compound (hereinafter referred to as a side chain type raw material liquid crystal compound).
  • the kind of the polymerizable group of the side chain type raw material liquid crystal compound is not particularly limited, and a functional group capable of addition polymerization reaction is preferable, and a polymerizable ethylenically unsaturated group or a ring polymerizable group is preferable. More specifically, a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, etc. are mentioned preferably, and a (meth) acryloyl group is more preferable.
  • the (meth) acryloyl group is a concept including both a methacryloyl group and an acryloyl group.
  • the number of polymerizable groups in the side chain raw material liquid crystal compound is not particularly limited, but may be one or two or more, and the orientation of the quantum rod in a high temperature and high humidity environment is further maintained. Two or more are preferable, 2 to 10 are preferable, and 2 to 6 are more preferable.
  • the liquid crystal structure of the side chain may be a rod-like liquid crystal structure or a disk-like liquid crystal structure (discotic liquid crystal structure).
  • rod-like liquid crystal compounds can be used as the rod-like liquid crystal structure.
  • rod-like liquid crystal structures composed of substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, alkenylcyclohexylbenzonitriles, and the like.
  • discotic (discotic) liquid crystal structure a known discotic (discotic) liquid crystal structure (compound) can be used.
  • the discotic liquid crystal structure there are also compounds having liquid crystallinity in which a linear alkyl group, an alkoxy group, and a substituted benzoyloxy group are radially substituted as a side chain of the mother nucleus with respect to the mother nucleus at the center of the molecule. included.
  • the discotic liquid crystal structure having a polymerizable group has a polymerizable group bonded as a substituent to the discotic core of the discotic liquid crystal structure, and the discotic core and the polymerizable group are bonded via a linking group. be able to.
  • the length (molecular length) of the molecular long axis of the liquid crystal structure in the side chain type raw material liquid crystal compound is not particularly limited, but the orientation property of the side chain type polymer liquid crystal compound is more excellent, and the polarized light emitting property of the polarized light emitting film is From the viewpoint of superiority, 2 to 10 nm is preferable, and 3 to 6 nm is more preferable.
  • the length (Lp) of the molecular long axis of the liquid crystal structure is 2 nm or more, alignment anchoring to the quantum rod is easy to function, and if the length of the molecular long axis (Lp) of the liquid crystal structure is 10 nm or less, the side The chain type polymer liquid crystal compound tends to have a viscosity that facilitates alignment.
  • the length (Lp) of the molecular long axis in the discotic liquid crystal structure is the diameter of the discotic core.
  • the length of the molecular long axis of the liquid crystal structure in the side-chain polymer liquid crystal compound can be calculated by density functional calculation using a computer.
  • an optimized structure of a molecule is obtained by density functional calculation, and an axis connecting two atoms with the longest distance among arbitrary two interatomic distances in the obtained molecular structure is defined as a molecular major axis.
  • GausView 3.0 (trade name, manufactured by Gaussain Inc.) is used.
  • Gaussian 03 Rev. is used.
  • D. 02 (trade name, manufactured by Gaussain Inc.)
  • B3LYP / 6-31G (d) is used as the basis function, and the convergence condition is a default value.
  • the liquid crystal structure in the side chain polymer liquid crystal compound the length of the molecular long axis of the liquid crystal structure in the side chain polymer liquid crystal compound and the length of the long axis of the quantum rod in terms of more excellent effects of the present invention.
  • the following formula (1) (preferably, formula (2)) is preferably satisfied.
  • two or more kinds of liquid crystal structures may be used together.
  • Lq represents the length of the long axis of the quantum rod
  • Lp represents the length of the molecular long axis of the rod-like liquid crystal structure.
  • the side chain type polymer liquid crystal compound preferably contains a group that adsorbs to the quantum rod (hereinafter referred to as an adsorbing group).
  • the side chain polymer liquid crystal compound having an adsorbing group also functions as a ligand for the quantum rod.
  • the adsorptive group is preferably selected from the group consisting of a phosphate group, a phosphine oxide group, a phosphine group, a phosphonic acid group, an amino group, a mercapto group, and a carboxyl group.
  • the phosphate group, amino group, carboxyl group It is particularly preferred to be selected from the group consisting of The adsorbing group may be contained in the main chain of the side chain type polymer liquid crystal compound or may be contained in the side chain. Moreover, when it is contained in the side chain, it may be contained in the liquid crystal structure of the side chain or may be contained in other side chains. Adsorption groups may be introduced into the side chain polymer liquid crystal compound at the time of polymerization of the side chain polymer liquid crystal compound, or after the side chain polymer liquid crystal compound is obtained, the treatment for introducing the adsorption group is performed. You may give it.
  • the method for introducing the adsorbing group is not particularly limited, but the following monomers can be preferably used when introducing the adsorbing group during the polymerization of the side chain type polymer liquid crystal compound.
  • a monomer that is polymerized so as to have an adsorptive group such as a phosphine oxide group, phosphine group, phosphonic acid group, amine group, mercapto group, or carboxyl group in the side chain is preferable.
  • Preferred examples of such a monomer include acrylic acid monomer, dimethylaminoethyl methacrylate, 2-methacryloxyethyl acid phosphate and the like.
  • the crosslinkable group is preferably a functional group capable of addition polymerization reaction, and is preferably a polymerizable ethylenically unsaturated group or a ring polymerizable group, like the polymerizable group described above. More specifically, a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, etc. are mentioned preferably, and a (meth) acryloyl group is more preferable.
  • the method for introducing a crosslinkable group into the side chain polymer liquid crystal compound is not particularly limited. For example, a method obtained by condensing a compound having a crosslinkable group and a carboxyl group and a polymer having an alcohol group, And a method of loading a polymer having a group, a crosslinkable group, and a compound having an epoxy.
  • the crosslinkable group may be bonded to the main chain or may be bonded to the side chain.
  • the side chain may have a crosslinkable group or not.
  • the content of the side chain type polymer liquid crystal compound having a crosslinkable group in the composition of the present invention is not particularly limited, but in terms of the orientation of the quantum rod in the polarized light emitting film and the handleability of the composition.
  • the amount is preferably 5 to 50% by weight, more preferably 10 to 50% by weight, based on the total weight of the composition.
  • the mass ratio of the quantum rod in the composition to the side chain type polymer liquid crystal compound having a crosslinkable group is not particularly limited, but the quantum rod is contained in the composition in that the effect of the present invention is more excellent.
  • the amount is preferably 0.005 to 10 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the side chain polymer liquid crystal compound.
  • composition of the present invention may contain components other than the quantum rod and the side chain type polymer liquid crystal compound described above.
  • a monomer, a polymerization initiator, a solvent, a surfactant and the like can be mentioned.
  • optional components that may be added to the composition will be described in detail.
  • the composition of the present invention may contain a monomer (monomer) having no liquid crystal structure. By using a monomer, the viscosity is lowered, the coating suitability is improved, and the curability is increased.
  • the monomer may be a monofunctional monomer having one polymerizable group or a polyfunctional monomer having two or more polymerizable groups.
  • the monomer may contain various functional groups other than the polymerizable group (for example, a boronic acid group).
  • a preferable monomer is a monomer having a long-chain alkyl group having 4 to 30 carbon atoms from the viewpoint of more excellent effects of the present invention.
  • the long-chain alkyl group preferably has 12 to 22 carbon atoms.
  • the monomer is preferably a monofunctional (meth) acrylate monomer or a monofunctional (meth) acrylamide monomer having a long-chain alkyl group having 4 to 30 carbon atoms, specifically, butyl (meth) acrylate, octyl (meth) ) Acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, butyl (meth) acrylamide, octyl (meth) acrylamide, lauryl (meth) acrylamide, oleyl (meth) acrylamide , Stearyl (meth) acrylamide, and behenyl (meth) acrylamide.
  • lauryl (meth) acrylate, oleyl (meth) acrylate, and stearyl (meth) acrylate are particularly preferable.
  • the content of the monomer in the liquid crystal composition of the present invention is not particularly limited, but is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the side chain polymer liquid crystal compound in terms of more excellent effects of the present invention. 5 to 30 parts by mass is more preferable.
  • the composition of the present invention may contain a polymerization initiator.
  • the polymerization initiator used is selected according to the type of the polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.
  • examples of photopolymerization initiators include ⁇ -carbonyl compounds, acyloin ethers, ⁇ -hydrocarbon substituted aromatic acyloin compounds, polynuclear quinone compounds, or combinations of triarylimidazole dimers and p-aminophenyl ketones. Is mentioned.
  • the content of the polymerization initiator in the composition of the present invention is not particularly limited, but with respect to 100 parts by mass of the total amount of the side chain type polymer liquid crystal compound and the polymerizable monomer in terms of more excellent effects of the present invention. 0.1 to 10 parts by mass is preferable, and 0.2 to 8 parts by mass is more preferable.
  • the composition may contain a solvent, and 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, ethyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane).
  • amides eg N, N-dimethylformamide
  • sulfoxides eg dimethyl sulfoxide
  • heterocyclic compounds eg pyridine
  • hydrocarbons eg benzene, hexane
  • alkyl halides e
  • the composition may contain a surfactant from the viewpoint of the uniformity of the coating film and the strength of the film.
  • the surfactant include conventionally known compounds, and fluorine compounds are particularly preferable. Specifically, for example, compounds described in paragraphs [0028] to [0056] of JP-A No. 2001-330725, and compounds described in paragraphs [0069] to [0126] of Japanese Patent Application No. 2003-295212 are listed. It is done.
  • the composition may contain an orientation agent, an adhesion improver, a plasticizer, a polymer, and the like.
  • the polarized light-emitting film of the present invention can be produced.
  • mode of the polarizing light-emitting film manufacturing method using the said liquid-crystal composition is explained in full detail first, and the structure of a polarizing light-emitting film is explained in full detail after that.
  • the first embodiment of the method for producing a polarized light-emitting film using the above composition comprises a step of rubbing the surface of the support, a step of applying the composition on the support, and a side chain type having a crosslinkable group. Cross-linking the polymer liquid crystal compound to form a polarized light-emitting film.
  • the method of rubbing treatment is not particularly limited, and a known method can be adopted. For example, a method of obtaining orientation by rubbing the surface of the support in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. Generally, it is carried out by rubbing several times using a cloth or the like in which fibers having a uniform length and thickness are planted on average.
  • a general method for rubbing is described in, for example, “Liquid Crystal Handbook” (issued by Maruzen, October 30, 2000).
  • the description in JP-A-2003-329833 can be referred to.
  • the type of the support used in this step is not particularly limited as long as it is a substrate that can support the above composition.
  • a resin substrate cellulose, cyclic olefin, acrylic, polycarbonate, polyester, polyvinyl alcohol, etc.
  • Transparent support cellulose, cyclic olefin, acrylic, polycarbonate, polyester, polyvinyl alcohol, etc.
  • a barrier film it is preferable to perform a rubbing process on the organic layer contained in the barrier film.
  • This step is a step of applying the liquid crystal composition described above to the surface of the support subjected to the rubbing treatment.
  • the coating film (precursor film) used as the precursor of a polarization light emitting film is arrange
  • Composition coating methods include curtain coating, dip coating, spin coating, print coating, spray coating, slot coating, roll coating, slide coating, blade coating, gravure coating, wire bar Known coating methods such as a method are listed.
  • coating you may give a drying process for solvent removal as needed.
  • This step is a step of forming a polarized light-emitting film by orienting the side chain type polymer liquid crystal compound in the liquid crystal composition coated on the support and then fixing it by crosslinking the alignment state.
  • the method for aligning the side-chain polymer liquid crystal compound in the liquid crystal composition (the coating film of the liquid crystal composition) on the support is not particularly limited, and examples thereof include heat treatment. Particularly preferred is a method of heating to a phase transition temperature or higher of the side chain polymer liquid crystal compound. Moreover, after implementing the said heat processing, in order to maintain an orientation state, you may implement a cooling process as needed.
  • the quantum rods dispersed in the side-chain polymer liquid crystal compound are also aligned, resulting in a plurality of quantum rods in the composition (coating film). Are aligned in one direction. In order to fix this state, the side chain polymer liquid crystal compound is crosslinked.
  • a rod-like liquid crystal structure is used as the liquid crystal structure of the side chain of the side chain type raw material liquid crystal compound, it is preferable to horizontally align the rod-like liquid crystal structure.
  • horizontal alignment means that the molecular major axis direction of the rod-like liquid crystal structure and the coating surface (layer surface) are parallel.
  • Parallel does not require strictly parallel, but means an orientation in which the inclination angle formed by the molecular major axis direction of the rod-like liquid crystal structure and the coating surface (layer surface) is 20 ° or less. To do.
  • the inclination angle is preferably 0 to 5 °, more preferably 0 to 3 °, still more preferably 0 to 2 °, and most preferably 0 to 1 °.
  • the polymerizable rod-like liquid crystal structure may be a nematic liquid crystal structure or a smectic liquid crystal structure. However, since a high degree of alignment is obtained, it may be a smectic liquid crystal structure. preferable.
  • the coating surface is the surface of the coating film, and the layer surface is the surface on the support side on which the coating film is applied.
  • the quantum rod is also horizontally aligned with the rod-like liquid crystal structure.
  • the quantum rods are horizontally oriented” means that the major axis direction of the quantum rods and the coating surface (layer surface) are parallel.
  • Parallel does not require strictly parallel, but means an orientation with an inclination angle of 20 ° or less between the major axis direction of the quantum rod and the coating surface (layer surface).
  • the inclination angle is preferably 0 to 5 °, more preferably 0 to 3 °, still more preferably 0 to 2 °, and most preferably 0 to 1 °.
  • the discotic liquid crystal structure is vertically aligned.
  • vertical alignment means that the disc surface of the discotic liquid crystal structure and the coating surface (layer surface) are vertical.
  • “Vertical” does not require strictly vertical, but means an orientation in which the inclination angle formed by the disc surface of the discotic liquid crystal structure and the coating surface (layer surface) is 70 ° or more.
  • the inclination angle is preferably 85 to 90 °, more preferably 87 to 90 °, still more preferably 88 to 90 °, and most preferably 89 to 90 °.
  • the discotic liquid crystal structure When the discotic liquid crystal structure is vertically aligned as described above, it is preferable to horizontally align the quantum rods inserted between the columns formed by the disc portions of the vertically aligned discotic liquid crystal structure.
  • the discotic liquid crystal structure may be a nematic liquid crystal structure or a columnar liquid crystal structure, but a columnar liquid crystal structure is particularly preferable from the viewpoint of easily forming a column.
  • one surface of the optically anisotropic layer having the molecular long axis of the rod-like liquid crystal structure, the disc surface of the discotic liquid crystal structure or the long axis of the quantum rod (here, the coating It is difficult to directly and accurately measure the inclination angle ⁇ 1 with respect to the surface) and the inclination angle ⁇ 2 with respect to the other surface (here, the layer surface).
  • the coating film surface of the optically anisotropic layer of the molecular long axis of the rod-like liquid crystal structure, the disc surface of the discotic liquid crystal structure or the long axis of the quantum rod (hereinafter collectively referred to as the symmetric axis) and
  • the inclination angles ⁇ 1 and ⁇ 2 with respect to the layer surface are calculated by the following method.
  • the optically anisotropic layer is assumed to be a multilayer body composed of layers containing a side chain type polymer liquid crystal compound. Further, the minimum unit layer constituting the same is assumed to be optically uniaxial (the inclination angles ⁇ 1 and ⁇ 2 of the symmetry axis are assumed to be uniform in the minimum unit layer). 2. It is assumed that the inclination angle in each layer changes monotonically with a linear function along the thickness direction of the optically anisotropic layer.
  • a specific method for calculating the inclination angles ⁇ 1 and ⁇ 2 is as follows. (1) The angle of incidence of the measurement light on the optically anisotropic layer is changed within a plane in which the inclination angle in each layer changes monotonically with a linear function along the thickness direction of the optically anisotropic layer. The retardation value is measured at the measurement angle. 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 °.
  • 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 inclination angle ⁇ 1 with respect to the coated surface of the anisotropic layer and the inclination angle ⁇ 2 with respect to the layer 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 procedure for proceeding with the crosslinking is not particularly limited, and includes heat treatment or light irradiation treatment (ultraviolet irradiation, electron beam irradiation, etc.), and light irradiation treatment is preferable.
  • heat treatment it is preferable to perform the heat treatment at 90 to 150 ° C. for 10 to 120 minutes.
  • ultraviolet rays for light irradiation.
  • the irradiation energy is preferably 10 mJ / cm 2 to 50 J / cm 2 .
  • light irradiation may be performed under heating conditions.
  • the second embodiment of the method for producing a polarized light-emitting film using the composition includes a step of forming an alignment film subjected to an alignment treatment on a support, and a step of applying the composition on the alignment film. And a step of polymerizing the side chain polymer liquid crystal compound in an aligned state to form a polarized light emitting film.
  • the second embodiment is compared with the first embodiment described above, the same procedure is performed except that the alignment film is used in the second embodiment. Therefore, the composition application step and the polymerization step in the second embodiment are the same as those in the first embodiment. Therefore, in the following, the process of forming the alignment film will be mainly described in detail.
  • This step is a step of forming an alignment film that has been subjected to an alignment treatment on a support. By carrying out this step, an alignment film to which the side chain type polymer liquid crystal compound having a crosslinkable group is applied is formed.
  • the type of the alignment film subjected to the alignment treatment is not particularly limited, and examples thereof include an alignment film subjected to rubbing treatment and a photo alignment film subjected to photo alignment treatment.
  • the alignment film that has been subjected to the rubbing treatment is a film that has been treated so as to have the orientation of the liquid crystal structure by the rubbing treatment.
  • a rubbing treatment method the same method as the rubbing treatment applied to the support surface in the first embodiment can be used.
  • a material constituting the alignment film a known material can be used.
  • polyvinyl alcohol or polyimide, and derivatives thereof are preferable.
  • modified or unmodified polyvinyl alcohol is preferred.
  • Polyvinyl alcohols having various saponification degrees exist.
  • the photo-alignment film subjected to the photo-alignment process is a film processed so as to have the alignment ability of the liquid crystal structure by the photo-alignment process.
  • the photo-alignment film is a film having liquid crystal alignment ability, containing a compound having a group (photo-alignment group) that generates liquid crystal alignment ability by absorbing light.
  • the photo-alignment treatment is a treatment for irradiating the photo-alignment group contained in the photo-alignment film with light and arranging it in a certain direction to impart liquid crystal alignment ability.
  • One method of the photo-alignment treatment includes a method of irradiating the photo-alignment film with polarized light.
  • a polarized light-emitting film exhibiting predetermined characteristics can be obtained.
  • the quantum rods are fixed in a state of being oriented in a predetermined direction, exhibiting excellent polarized light-emitting properties, and excellent after performing a durability test that is left in a high-temperature and high-humidity environment. Shows polarized light emission.
  • the polarized light-emitting film can be suitably used as a constituent member of a backlight unit of a liquid crystal display device.
  • a repeating unit comprising a polymer matrix having a crosslinked structure and a plurality of quantum rods dispersed in the polymer matrix, wherein the polymer matrix includes a liquid crystal structure as a partial structure And a liquid crystal structure is fixed in an aligned state, and a plurality of quantum rods are polarized light-emitting films that are aligned so that their long axes are parallel to each other.
  • FIG. 1A is a diagram schematically showing a cross section of the polarized light-emitting film 1.
  • a configuration in the case of using a rod-like liquid crystal structure as a liquid crystal structure serving as a side chain is shown as an example.
  • the polarized light-emitting film 1 is arranged in a polymer matrix 5 with the quantum rods 4 oriented so that their long axes are parallel to each other.
  • the polarized light-emitting film is applied and formed on a support (not shown) as described above.
  • the surface 1a is referred to as an application surface
  • the surface 1b on the support side is referred to as a layer surface
  • the quantum rod 4 is oriented so that the major axis is substantially parallel to these surfaces.
  • the rod-like liquid crystal structure is not shown in FIG. 1A, the long axis of the quantum rod 4 and the molecular long axis of the rod-like liquid crystal structure are aligned substantially in parallel.
  • FIG. 1B is a diagram schematically showing a structure in which the liquid crystal structure (side chain of the liquid crystal compound) 3 and the quantum rod 4 are aligned in the polarized light-emitting film 1 shown in FIG. 1A.
  • the polymer matrix 5 of the polarized light-emitting film 1 shown in FIG. 1A has a three-dimensional structure in which a liquid crystal structure is arranged as a side chain 3 with respect to a main chain 2 of a liquid crystal compound, and crosslinkable groups imparted to the side chain are cross-linked.
  • the crosslinked structure 6 is formed.
  • An adsorbing group L is bonded to a part of the main chain 2, and the adsorbing group L is coordinated to the quantum rod 4.
  • Quantum rod so that the length direction of the side chain 3 is aligned along the rubbing direction in the rubbing process described above and the length direction of the side chain 3 coincides with the major axis direction so as to be sandwiched between the side chains 3 4 is also oriented.
  • the side chains 3 are fixed in an aligned state by the cross-linked structure 6, and the quantum rod 4 is taken into the cross-linked structure 6 and fixed.
  • the polymer matrix is a matrix obtained by crosslinking the above-mentioned side chain type polymer liquid crystal compound having a crosslinkable group.
  • the polymer matrix has a crosslinkable group in the side chain and is formed by crosslinking the side chains. And a three-dimensional matrix having a crosslinked structure.
  • the polymer matrix includes a liquid crystal structure derived from a polymer liquid crystal compound. That is, a repeating unit having a liquid crystal structure as a partial structure is included in the polymer matrix. Further, as described above, since the side chain polymer liquid crystal compound is cross-linked in an aligned state, the liquid crystal structure is fixed in a state of being aligned in a predetermined direction.
  • the liquid crystal structure (liquid crystal molecular structure) intends a structural portion exhibiting liquid crystallinity, and includes a partial structure exhibiting liquid crystallinity contained in the side chain polymer liquid crystal compound contained in the above-described composition. .
  • the polarized light-emitting film can be used as a wavelength conversion member by laminating with other members.
  • a wavelength conversion member provided with a polarized light-emitting film and a support disposed on at least one surface of the polarized light-emitting film can be mentioned.
  • the support body may be arrange
  • a polarized light emission film may be called a wavelength conversion film.
  • FIG. 2 is a schematic cross-sectional view showing the layer configuration of an embodiment of the wavelength conversion member 40.
  • the wavelength conversion member 40 shown in FIG. 2 is formed by sequentially forming an alignment layer 42, a polarized light emitting film 43, and a support 41B on a support 41A.
  • the wavelength conversion member 40 having this configuration can be obtained by the method for manufacturing a wavelength conversion member according to the second embodiment described above.
  • the supports 41A and 41B may be the same film or different.
  • a resin substrate is mentioned.
  • a support having an oxygen permeability of 50 cm 3 / (m 2 ⁇ day ⁇ atm) or less is preferable in that oxygen inhibition of light emission characteristics of the polarized light-emitting film can be further suppressed.
  • the oxygen permeability of the support is preferably 10 cm 3 / (m 2 ⁇ day ⁇ atm) or less, and more preferably 1 cm 3 / (m 2 ⁇ day ⁇ atm) or less.
  • the oxygen permeability is measured by a method according to JIS K 7126 (differential pressure method). Specifically, it is a value measured using an oxygen gas permeability measuring device (manufactured by MOCON, OX-TRAN 2/20: trade name) under the conditions of a measurement temperature of 23 ° C. and a relative humidity of 90%.
  • a so-called barrier film can be suitably used as the supports 41A and 41B.
  • the barrier film is a layer having a gas barrier function of blocking oxygen. It is also preferable that the barrier film has a function of blocking water vapor.
  • the barrier film is preferably included in the wavelength conversion member as a layer adjacent to or in direct contact with the polarized light-emitting film.
  • One or more barrier films may be included in the wavelength conversion member, and the wavelength conversion member has a structure in which a barrier film, a polarized light emitting film, and a barrier film are laminated in this order. Preferably it is.
  • the barrier film may be any known barrier film, for example, a barrier film described below.
  • the barrier film preferably includes at least an inorganic layer, and may be a film including a base film and an inorganic layer.
  • the barrier film may include a barrier laminate including at least one inorganic layer and at least one organic layer on the base film. It is preferable to stack a plurality of layers in this manner because the barrier property can be further improved. On the other hand, as the number of layers to be stacked increases, the light transmittance of the wavelength conversion member tends to decrease. Therefore, it is desirable to increase the number of layers within a range in which good light transmittance can be maintained.
  • the barrier film preferably has a total light transmittance of 80% or more in the visible light region and an oxygen permeability of 1.00 cm 3 / (m 2 ⁇ day ⁇ atm) or less.
  • Oxygen permeability of the barrier film more preferably 0.50cm 3 / (m 2 ⁇ day ⁇ atm) or less, more preferably 0.10cm 3 / (m 2 ⁇ day ⁇ atm) or less, more preferably 0.01cm 3 / (m 2 ⁇ day ⁇ atm) or less.
  • the measuring method of oxygen permeability is as above-mentioned.
  • the visible light region is a wavelength region of 380 to 780 nm
  • the total light transmittance is an average value of light transmittance over the visible light region.
  • the “inorganic layer” is a layer mainly composed of an inorganic material, and is preferably a layer formed only from an inorganic material.
  • the organic layer is a layer containing an organic material as a main component and intended for a layer having an organic material content of 50% by mass or more, preferably 80% by mass or more, and 90% by mass or more. More preferred.
  • the inorganic material constituting the inorganic layer is not particularly limited, and is a metal oxide, metal nitride, metal carbide, metal oxynitride, or metal oxycarbide, Si, Al, In, Sn, Zn, An oxide, nitride, carbide, oxynitride, oxycarbide, or the like containing one or more metals selected from Ti, Cu, Ce, Ta, or the like can be preferably used.
  • metal oxides, nitrides, oxynitrides or carbides selected from Si, Al, In, Sn, Zn, Ti are preferable, and in particular, metal oxides, nitrides, oxynitrides or Si or Al Carbides are more preferable, including one of silicon oxide, silicon nitride, silicon carbide, and aluminum oxide, particularly preferably silicon nitride.
  • a method for forming the inorganic layer is not particularly limited, and various film formation methods that can evaporate or scatter the film formation material and deposit it on the deposition surface can be used.
  • the thickness of the inorganic layer is preferably 1 to 500 nm, more preferably 5 to 300 nm, and even more preferably 10 to 150 nm.
  • the organic layer preferably contains a cardo polymer. Thereby, the adhesiveness between the organic layer and the adjacent layer, particularly the adhesiveness with the inorganic layer is improved, and a further excellent gas barrier property can be realized.
  • the thickness of the organic layer is preferably 0.05 to 10 ⁇ m, more preferably 0.5 to 10 ⁇ m.
  • FIG. 3 is a schematic diagram showing the configuration of the liquid crystal display device 10 according to an embodiment of the present invention.
  • the liquid crystal display device 10 includes a pair of polarizing plates (an upper polarizing plate 11 and a lower polarizing plate 18), a liquid crystal cell 20 sandwiched between them, and a liquid crystal cell of the lower polarizing plate 18.
  • the backlight unit 30 includes a polarized light-emitting film, the lower polarizing plate 18 can be omitted.
  • the upper polarizing plate 11 is a front side (viewing side) polarizing plate and the lower polarizing plate 18 is a rear side (backlight side) polarizing plate, which is not shown in the figure.
  • the color filter is provided between the layer 15 and the front polarizing plate 11.
  • 12 and 19 indicate the directions of the absorption axes of the polarizing plates substantially orthogonal to each other, and 14 and 17 indicate the orientation control directions of the electrode substrates.
  • the backlight unit 30 includes the wavelength conversion member 40 of the present invention.
  • the backlight unit 30 has an edge light type configuration including a light source 36 and a light guide plate 37 together with the wavelength conversion member 40.
  • the light source 36 one that emits blue light having an emission center wavelength in a wavelength band of 430 nm to 480 nm, for example, a blue light emitting diode that emits blue light can be used.
  • the polarized light-emitting film preferably includes at least a quantum rod R that is excited by excitation light and emits red light, and a quantum rod G that emits green light.
  • white light can be embodied by blue light emitted from the light source and transmitted through the wavelength conversion member, and red light and green light emitted from the wavelength conversion member.
  • a light source that emits ultraviolet light having an emission center wavelength in a wavelength band of 300 nm to 430 nm, for example, an ultraviolet light emitting diode can be used.
  • the polarized light-emitting film preferably includes quantum rods R and G, and quantum rods B that are excited by excitation light and emit blue light.
  • white light can be embodied by red light, green light, and blue light emitted from the wavelength conversion member.
  • a laser light source can be used instead of the light emitting diode.
  • the wavelength conversion member 40 is disposed on the path of light emitted from the light guide plate 37.
  • the backlight unit can also include a reflecting member at the rear of the light source. There is no restriction
  • the backlight unit preferably includes a known diffusion plate, diffusion sheet, prism sheet (for example, BEF series manufactured by Sumitomo 3M Limited), and a light guide. Other members are also described in Japanese Patent No. 3416302, Japanese Patent No. 3363565, Japanese Patent No. 4091978, Japanese Patent No. 3448626, and the contents of these publications are incorporated in the present invention.
  • the driving mode of the liquid crystal cell is not particularly limited, and twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), and in-plane switching.
  • Various modes such as (IPS) and optically compensated bend cell (OCB) can be used.
  • the liquid crystal cell is preferably VA mode, OCB mode, IPS mode, or TN mode, but is not limited thereto.
  • the configuration shown in FIG. 2 of Japanese Patent Application Laid-Open No. 2008-262161 is given as an example.
  • the specific configuration of the liquid crystal display device is not particularly limited, and a known configuration can be adopted.
  • a white side-chain polymer liquid crystal compound (A-1) represented by the following chemical formula.
  • Acrylic acid is formulated to impart an adsorption group composed of a carboxyl group to the side chain polymer liquid crystal compound, and the side chain polymer liquid crystal compound (A-1) has an adsorption group composed of a carboxyl group.
  • the obtained reaction solution was filtered, and the filtrate was dropped into hexane and stirred for 10 minutes, and then the polymer was taken out. Furthermore, this polymer was dissolved in tetrahydrofuran, and the obtained solution was dropped into methanol to perform reprecipitation purification of the polymer. Thereafter, the polymer was dried in a vacuum dryer at room temperature for 2 hours, and 3.2 g of a white-chain polymer liquid crystal compound having a crosslinkable group represented by the following chemical formula (hereinafter referred to as a crosslinkable polymer liquid crystal compound). ) (B-1) was obtained.
  • the crosslinkable polymer liquid crystal compound (B-1) is obtained by adding a crosslinkable group to the terminal of the liquid crystal monomer (P6BCOH) which is the raw material liquid crystal compound of the side chain type polymer liquid crystal compound (A-1). Yes.
  • Some liquid crystal monomers (P6BCOH), which are raw material liquid crystal compounds in the crosslinkable polymer liquid crystal compound (B-1), are not provided with a crosslinkable group.
  • the number average molecular weight (Mn) of the crosslinkable polymer liquid crystal compound (B-1) obtained in Synthesis Example 1 was 12000.
  • a crosslinkable polymer liquid crystal compound (B-2) was synthesized in the same manner as in Synthesis Example 1, except that acrylic acid was changed to dimethylaminoethyl methacrylate (Light Ester DM (manufactured by Kyoeisha Chemical Co., Ltd.)). By adding the light ester DM, the crosslinkable polymer liquid crystal compound (B-2) is provided with an amino group instead of a carboxyl group as an adsorbing group.
  • the number average molecular weight (Mn) of the crosslinkable polymer liquid crystal compound (B-2) obtained in Synthesis Example 2 was 13000.
  • a crosslinkable polymer liquid crystal compound (B-3) was prepared in the same manner as in Synthesis Example 1 except that acrylic acid was changed to 2-methacryloxyethyl acid phosphate (Light Ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.)). ) was synthesized. By adding the light ester P-1M, the crosslinkable polymer liquid crystal compound (B-3) is provided with a phosphate group instead of a carboxyl group as an adsorbing group.
  • the number average molecular weight (Mn) of the crosslinkable polymer liquid crystal compound (B-3) obtained in Synthesis Example 3 was 13500.
  • a crosslinkable polymer liquid crystal compound (B-4) was synthesized in the same manner as in Synthesis Example 1, except that 120 mg of 1-dodecanethiol (chain transfer agent) was changed to 60 mg of thioglycolic acid.
  • the number average molecular weight (Mn) of the crosslinkable polymer liquid crystal compound (B-4) obtained in Synthesis Example 4 was 11500.
  • a crosslinkable polymer liquid crystal compound (B-6) was synthesized in the same manner as in Synthesis Example 1 except that acrylic acid was not added.
  • the number average molecular weight (Mn) of the crosslinkable polymer liquid crystal compound (B-6) obtained in Synthesis Example 6 was 12500.
  • a barrier laminate was formed on one side of a polyethylene terephthalate film (PET film, manufactured by Toyobo Co., Ltd., trade name: Cosmo Shine A4300, thickness 50 ⁇ m) by the following procedure.
  • PET film manufactured by Toyobo Co., Ltd., trade name: Cosmo Shine A4300, thickness 50 ⁇ m
  • TMPTA manufactured by Daicel Cytec Co., Ltd.
  • a photopolymerization initiator manufactured by Lamberti Co., Ltd., ESACURE KTO46
  • This coating solution was applied onto the PET film with a roll toe roll using a die coater, and passed through a drying zone at 50 ° C. for 3 minutes. Thereafter, ultraviolet rays were irradiated in a nitrogen atmosphere (accumulated dose: about 600 mJ / cm 2 ), cured by UV curing, and wound up.
  • the thickness of the first organic layer formed on the PET film was 1 ⁇ m.
  • an inorganic layer (silicon nitride layer) was formed on the surface of the first organic layer using a roll-to-roll CVD apparatus.
  • Silane gas (flow rate 160 sccm), ammonia gas (flow rate 370 sccm), hydrogen gas (flow rate 590 sccm), and nitrogen gas (flow rate 240 sccm) were used as source gases.
  • a high frequency power supply having a frequency of 13.56 MHz was used as the power supply.
  • the film forming pressure was 40 Pa, and the reached film thickness was 50 nm.
  • stacked on the surface of the 1st organic layer was produced.
  • Example 1 (Preparation of liquid crystal composition of Example 1) The following liquid crystal composition was prepared and filtered through a polypropylene filter having a pore size of 0.2 ⁇ m, and then used as a coating solution.
  • Example 1- 100 parts by mass of toluene dispersion of quantum rod 1 (emission center wavelength: 520 nm, half-value width: 25 nm) 100 parts by mass of toluene dispersion of quantum rod 2 (emission center wavelength: 630 nm, half-value width: 30 nm)
  • Crosslinkable polymer liquid crystal compound (B-1) 100 parts by mass photopolymerization initiator (Irgacure 907, manufactured by Ciba Japan) 3 parts by mass sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass Fluoropolymer (FP4) represented by the following chemical formula 0.3 parts by mass Methyl ethyl ketone (MEK) 193 parts by mass Cyclohexanone 50 parts by mass
  • MEK Methyl ethyl ketone
  • the quantum rod 1 in the “toluene dispersion of the quantum rod 1” is a core / shell type quantum rod having a core made of CdSe and a shell made of CdS (long axis: 36 nm, short axis: 7 nm, aspect ratio Ratio (major axis / minor axis): 5.1), and the concentration of the quantum rod 1 with respect to the total amount of the toluene dispersion was 1% by mass.
  • the quantum rod 2 in the “toluene dispersion of the quantum rod 2” is a core / shell type quantum rod having a core made of CdSe and a shell made of CdS (long axis: 25 nm, short axis: 3 nm, aspect ratio (Major axis / minor axis): 8.3), and the concentration of the quantum rod 2 with respect to the total amount of the toluene dispersion was 1% by mass.
  • the barrier film produced as described above was prepared, and an alignment film forming coating solution having the following composition was continuously applied onto the inorganic layer surface with a # 8 wire bar.
  • the alignment film was formed by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 100 ° C. for 120 seconds.
  • the thickness of the alignment film was 0.5 ⁇ m.
  • liquid crystal composition 1 was applied to the surface of a slide glass and observed with a polarizing microscope while heating. As a result, it was confirmed to have nematic liquid crystal properties.
  • a rubbing treatment was performed on the surface of the alignment film disposed on the barrier film.
  • the liquid crystal composition was applied on the rubbing surface using a bar coater.
  • the film was aged by heating at a film surface temperature of 110 ° C. for 180 seconds and oriented in a nematic phase to obtain an unexposed film.
  • the obtained unexposed film was cooled to 70 ° C. and irradiated with 1000 mJ / cm 2 of ultraviolet rays using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 70 mW / cm 2 in the air, thereby being crosslinkable.
  • a polarized light-emitting film was formed by crosslinking the polymer liquid crystal compound to fix the alignment state.
  • the thickness of the polarized light emitting film was 7.0 ⁇ m.
  • the barrier film 10 on which the polarized light emitting film is formed is wound around a backup roller, and the barrier film is laminated on the polarized light emitting film so that the inorganic layer surface is in contact with the polarized light emitting film, and the polarized light emitting film is sandwiched between the barrier films.
  • the obtained wavelength conversion member was formed.
  • Examples 2 to 5, 8 In the same manner as in Example 1, except that the crosslinkable polymer liquid crystal compound (B-1) was changed to the crosslinkable polymer liquid crystal compounds shown in Table 1, the wavelength conversion members of Examples 2 to 5 and 8 were used. Formed.
  • Example 6 Implementation was carried out except that the toluene dispersion of quantum rod 1 and the toluene dispersion of quantum rod 2 were not used, but 100 parts by mass of the following toluene dispersion of quantum rod 3 (emission center wavelength: 500 nm, half-value width: 80 nm) was used. According to the same procedure as in Example 1, the wavelength conversion member of Example 6 in which the polarized light-emitting film was sandwiched between the barrier films was formed.
  • the quantum rod of the toluene dispersion of the quantum rod 3 is a ZnS rod (long axis: 4.0 nm, short axis: 1.2 nm, aspect ratio (long axis / short axis): 3.3),
  • concentration with respect to the toluene dispersion liquid whole quantity of the quantum rod 5 was 1 mass%.
  • Example 7 The wavelength conversion member of Example 7 was formed in the same manner as Example 1 except that 5 parts by mass of trimethylolpropane triacrylate was added to the liquid crystal composition of Example 1.
  • the wavelength conversion member 7 was formed in the same manner as in Example 1 except that the crosslinkable polymer liquid crystal compound (B-1) was changed to the side chain polymer liquid crystal compound (A-1). That is, this example uses a polymer liquid crystal having no crosslinking group as a liquid crystal composition.
  • the liquid crystal composition of Comparative Example 2 uses two kinds of low-molecular liquid crystal compounds in place of the crosslinkable polymer liquid crystal compound. Since it has a crosslinkable group, it is polymerized during the polymerization process to form a polymer matrix.
  • the liquid crystal composition of Comparative Example 2 was applied to the surface of a slide glass and observed with a polarizing microscope while heating. As a result, it was confirmed to have nematic liquid crystal properties.
  • the rubbing treatment was performed on the surface of the alignment film disposed on the barrier film described in Example 1.
  • the liquid crystal composition of Comparative Example 2 was applied on the rubbing surface using a bar coater.
  • the film surface temperature was 100 ° C. for 60 seconds and the film was aged and oriented in the nematic phase, then cooled to 70 ° C., and an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) of 70 mW / cm 2 was used under air.
  • a polarized light-emitting film was formed by fixing the alignment state by irradiating with 1000 mJ / cm 2 of ultraviolet rays.
  • the thickness of the polarized light emitting film was 7.0 ⁇ m.
  • the barrier film on which the polarized light-emitting film is formed is wound around a backup roller, and the barrier film is laminated on the polarized light-emitting film so that the inorganic layer surface is in contact with the polarized light-emitting film, and the polarized light-emitting film is sandwiched between the barrier films.
  • the wavelength conversion member of Comparative Example 2 was formed.
  • the polarized light emitting properties of the polarized light emitting films prepared in Examples 1 to 8 and Comparative Examples 1 and 2 were measured by the following method. Irradiate blue LED to unexposed film and wavelength conversion member prepared in each example and comparative example, remove blue light from converted green light and red light through filter, and then measure emission intensity with CCD did. At this time, the intensity in two polarization directions, that is, the rubbing direction and the direction orthogonal to the rubbing direction was measured with a polarizer. Table 1 collectively shows the measured polarization emission ratio (intensity in the direction orthogonal to the rubbing: intensity in the rubbing direction).
  • the unexposed film (“before exposure” in Table 1) has a polarization emission ratio of 9: 1
  • the wavelength conversion member (“after exposure” in Table 1) has a polarization emission ratio of 9: 1.
  • a polarized light emission ratio of 8: 1 or more was obtained both before and after exposure.
  • the unexposed film is a film in a state in which a liquid crystal composition is applied onto a barrier film and then heated and aged at a predetermined temperature and oriented, and the wavelength conversion member exposes the unexposed film. Further, the wavelength conversion member is completed by laminating with a barrier film.
  • the wavelength conversion member showed excellent polarized light emission, and after the endurance test, there was little decrease in polarized light emission and haze was small.
  • the wavelength conversion member of Comparative Example 1 using the side chain type polymer liquid crystal compound having no crosslinkability and the wavelength conversion member of Comparative Example 2 using the low molecular liquid crystal compound have desired effects. I could't. Further, in terms of liquid stability, the liquid crystal compositions of the examples obtained better results than the liquid crystal compositions of the comparative examples.

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Abstract

Le problème décrit par la présente invention est de fournir un composé à cristaux liquides qui a d'excellentes propriétés d'émission de lumière polarisée et qui peut être utilisé pour produire commodément un film d'émission de lumière polarisée qui supprime des réductions de propriétés d'émission de lumière polarisée même dans des environnements à haute température/humidité élevée. L'invention a également pour objet un film d'émission de lumière polarisée qui est produit à l'aide de la composition à cristaux liquides, un élément de conversion de fréquence et un procédé de production pour l'élément de conversion de fréquence. La solution selon l'invention porte sur la composition à cristaux liquides, qui comprend : une pluralité de bâtonnets quantiques qui sont excités par de la lumière d'excitation incidente et émettent de la fluorescence ; et un composé à cristaux liquides de type polymère à chaîne latérale qui a un groupe de réticulation.
PCT/JP2015/004417 2014-09-29 2015-08-31 Composition à cristaux liquides, film d'émission de lumière polarisée, élément de conversion de fréquence et procédé de production pour ce dernier, unité de rétroéclairage et dispositif d'affichage à cristaux liquides WO2016051663A1 (fr)

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CN110383154A (zh) * 2018-08-29 2019-10-25 昆山龙腾光电有限公司 显示面板和显示装置
CN110412793A (zh) * 2019-07-05 2019-11-05 昆山龙腾光电有限公司 显示面板及显示装置
WO2021152720A1 (fr) * 2020-01-29 2021-08-05 シャープ株式会社 Élément électroluminescent et procédé de production d'élément électroluminescent

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JP6846756B2 (ja) * 2016-09-27 2021-03-24 エルジー ディスプレイ カンパニー リミテッド 光源装置および表示装置
JP6699759B2 (ja) * 2016-12-12 2020-05-27 Dic株式会社 偏光発光フィルム
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WO2020184424A1 (fr) * 2019-03-08 2020-09-17 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides

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CN110383154B (zh) * 2018-08-29 2022-03-25 昆山龙腾光电股份有限公司 显示面板和显示装置
CN110412793A (zh) * 2019-07-05 2019-11-05 昆山龙腾光电有限公司 显示面板及显示装置
CN110412793B (zh) * 2019-07-05 2021-07-23 昆山龙腾光电股份有限公司 显示面板及显示装置
WO2021152720A1 (fr) * 2020-01-29 2021-08-05 シャープ株式会社 Élément électroluminescent et procédé de production d'élément électroluminescent

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