WO2021010351A1 - Élément électroluminescent polarisé utilisant un composé émettant de la lumière ou un sel de celui-ci, plaque électroluminescente polarisée et dispositif d'affichage - Google Patents

Élément électroluminescent polarisé utilisant un composé émettant de la lumière ou un sel de celui-ci, plaque électroluminescente polarisée et dispositif d'affichage Download PDF

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WO2021010351A1
WO2021010351A1 PCT/JP2020/027151 JP2020027151W WO2021010351A1 WO 2021010351 A1 WO2021010351 A1 WO 2021010351A1 JP 2020027151 W JP2020027151 W JP 2020027151W WO 2021010351 A1 WO2021010351 A1 WO 2021010351A1
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group
light emitting
polarized light
substituent
film
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PCT/JP2020/027151
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English (en)
Japanese (ja)
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典明 望月
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日本化薬株式会社
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Publication of WO2021010351A1 publication Critical patent/WO2021010351A1/fr

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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
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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

Definitions

  • the present invention relates to a novel polarized light emitting device, a polarized light emitting plate, and a display device using a light emitting compound or a salt thereof.
  • a polarizing plate having a light transmitting / shielding function is a basic component of a display device such as a liquid crystal display (Liquid Crystal Display) together with a liquid crystal having a light switching function.
  • a display device such as a liquid crystal display (Liquid Crystal Display) together with a liquid crystal having a light switching function.
  • the fields of application of LCDs equipped with such polarizing plates are also from small devices such as calculators and watches in the early days to notebook computers, word processors, liquid crystal projectors, liquid crystal televisions, car navigation systems, indoor and outdoor information display devices, and measurement. Equipment and the like can be mentioned.
  • the polarizing plate can be applied to a lens having a polarizing function, and has been applied to sunglasses having improved visibility, and in recent years, polarized glasses compatible with 3D televisions and the like.
  • the applications of the polarizing plate have expanded widely, and since they have come to be used under a wide range of conditions of low temperature to high temperature, low humidity to high humidity, and low light amount to high light amount, the polarization performance is high.
  • a polarizing plate having excellent durability is required.
  • the polarizing film constituting the polarizing plate is a stretch-oriented film of polyvinyl alcohol or a derivative thereof, or a polyene-based film obtained by dehydroxicating a polyvinyl chloride film or dehydrating a polyvinyl alcohol-based film to generate and orient a polyene. It is produced by dyeing or impregnating a polarizing film base material such as a film with iodine or a bicolor dye as a polarizing element. Since the polarizing plate composed of such a conventional polarizing film uses a dichroic dye having absorption in the visible region, the transmittance is lowered. For example, the transmittance of a general polarizing plate on the market is 35 to 45%.
  • Patent Document 1 describes a technique for a polarizing plate for ultraviolet rays as a technique for providing a polarizing function while maintaining a certain degree of transmittance in the visible region, in response to the problem of a conventional polarizing plate in which the transmittance in the visible region is lowered. Has been done. However, this technique also uses a yellow pigment that absorbs in the visible region, so that the transmittance is not sufficient and a strong yellow coloring is confirmed.
  • the polarizing plates described in Patent Documents 2 to 4 are expensive because they use special metals, for example, metals having high rare value such as lanthanoids and europium, and are extremely difficult to manufacture and are not suitable for mass production. .. Further, these polarizing plates are difficult to use for a display because the light emission of polarized light is weak, and it is not possible to obtain light emission which is linearly polarized light. Therefore, we have developed a new polarizing plate and materials for it that show polarized light emission action, have high transmittance (transparency) in the visible range, and can be applied to liquid crystal displays that are required to be durable in harsh environments. It is desired to do.
  • Patent Document 5 a dye having a polarization function for ultraviolet light and a film using the same have been published, but the light emission is not disclosed, and the light in the visible region No light emission has been confirmed. Moreover, it was not disclosed to emit polarized light. Therefore, there has been a demand for an element capable of emitting light having high brightness and high degree of polarization in the visible region.
  • the present invention is a novel polarized light emitting element that can be applied to a liquid crystal display or the like that requires high transmittance in the visible range and high durability in a harsh environment, a polarized light emitting plate using the same, and a polarized light emitting plate using the same. It is an object of the present invention to provide a display device.
  • the present inventors have made a film made of a polyvinyl alcohol resin or a derivative thereof, which contains a boron compound having a specific concentration and a specific birefringence.
  • a polarized light emitting element having an angle dependence emits light having a high dichroism, and have reached the present invention.
  • the polarized light emitting element in a preferred embodiment has not been found so far by incorporating a compound having a specific structure or a salt thereof into a film made of a polyvinyl alcohol resin having birefringence thereof or a derivative thereof. It was found that it emits polarized light.
  • the polarized light emitting device of one preferred embodiment has a high dichroic ratio in the ultraviolet region, exhibits high transmittance in the visible region, and exhibits excellent durability in a harsh environment.
  • a polarized light emitting device including a film made of a polyvinyl alcohol resin or a derivative thereof, which is formed by adsorbing and orienting one or more kinds of luminescent compounds capable of emitting light by using absorbed light. Contains 5-30% by weight of boron compound The time when the birefringence is measured from the vertical direction of the film plane is 0 °, and the angle dependence of the birefringence obtained when the film is tilted 50 ° with respect to the slow axis of the film is 0 °.
  • a luminescent compound having a stilbene skeleton exhibits a polarization action (light absorption anisotropy) at a wavelength at which light is absorbed, and at a wavelength showing the highest polarization action, an order parameter (OPD: Order) given by the following formula (i) is given.
  • OPD Order
  • OPD (log (Kz / 100) / Log (Ky / 100) -1) / ((log (Kz / 100) / log (Ky / 100) +2) Equation (i)
  • Ky in the above formula (i) represents the light transmittance when irradiating light polarized at an orthogonal position to the axis showing the highest absorption in the dye-oriented element
  • Kz represents the light transmittance in the dye-oriented element. Represents the light transmittance when irradiating light polarized parallel to the axis showing the highest absorption.
  • X or Y are independently nitro groups, amino groups which may have a substituent, amide groups which may have a substituent, and aromatics which may have a substituent.
  • the substituent of the amide group may be an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, respectively, and may have a substituent, an aromatic hydrocarbon group or a substituent.
  • the substituents of the heterocyclic group or the polycyclic heterocyclic group which may have a substituent each have a hydrogen atom, a halogen group, a nitro group, a hydroxy group and 1 to 4 carbon atoms, respectively.
  • the polarized light emitting device has an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, an alkoxy group having 1 to 4 carbon atoms having a hydroxy group, or an alkoxy group having 1 to 4 carbon atoms having a carboxy group. It is an alkoxy group, M represents a hydrogen, a metal ion, or an ammonium ion, and m represents an integer of 0 to 2.) [5].
  • the polarized light emitting device according to any one of Items [1] to [4], which is a film made of a polyvinyl alcohol resin having a degree of polymerization of 1000 to 6000 or a derivative thereof. [6].
  • the polarized light emitting device according to any one of Items [1] to [4], which is a film made of a polyvinyl alcohol resin having a saponification degree of 90% or more or a derivative thereof. [7].
  • the polarized light emitting element according to any one of Items [1] to [5], wherein the birefringence index is 0.020 to 0.060 when measured from the vertical direction (0 °) of the film plane. [8].
  • X or Y is an independently nitro group, an amino group which may have a substituent, or a group selected from the group of the following formulas (3) to (7) [4].
  • the polarized light emitting element according to any one of Items [7].
  • A has a hydrogen atom, a halogen group, a nitro group, a hydroxy group, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a sulfo group, each of which has 1 carbon number.
  • An aliphatic hydrocarbon group of 4 to 4 an aliphatic hydrocarbon group having 1 to 4 carbon atoms having a hydroxy group, an aliphatic hydrocarbon group having 1 to 4 carbon atoms having a carboxy group, and 1 to 4 carbon atoms having a sulfo group.
  • the alkoxy group, the hydroxy group having 1 to 4 carbon atoms, or the carboxy group having 1 to 4 carbon atoms, q 1 represents an integer of 0 to 4, and M is hydrogen or metal.
  • the polarized light emitting device according to any one of Items [1] to [8], further comprising one or more kinds of organic dyes or fluorescent dyes other than the luminescent compound. [10].
  • the method for manufacturing a polarized light emitting device according to any one of items [1] to [9].
  • a production method characterized by subjecting a film made of a polyvinyl alcohol resin or a derivative thereof in which the luminescent compound is adsorbed and oriented to a drying treatment or a heat treatment at a temperature equal to or higher than the glass transition temperature (Tg) of the polyvinyl alcohol resin or a derivative thereof. .. [11].
  • a polarized light emitting plate comprising the polarized light emitting device according to any one of items [1] to [9] and a transparent protective layer provided on at least one surface thereof. [12].
  • a display device including the polarized light emitting device according to any one of [1] to [9] or the polarized light emitting plate according to [11].
  • the present inventors have a polarized light emitting element containing a film made of a polyvinyl alcohol resin or a derivative thereof, containing a specific concentration of boron compound, and having a specific birefringence angle dependence, which has high dichroism.
  • the light we have, that is, polarized light is emitted, and we have arrived at the present invention.
  • a preferred embodiment of the polarized light emitting element has not been found so far by incorporating a compound having a specific structure or a salt thereof into a film made of a polyvinyl alcohol resin having birefringence thereof or a derivative thereof. It was found that it emits polarized light.
  • the polarized light emitting device of one preferred embodiment has a high dichroic ratio in the ultraviolet region, exhibits high transmittance in the visible region, and exhibits excellent durability in a harsh environment.
  • an element obtained by using a compound having the structure of the formula (2) or a salt thereof is known to exhibit a high degree of polarization in the ultraviolet region as described in Patent Document 5, but ultraviolet rays. It has not been known that it absorbs light and uses its energy to exhibit a polarized light emitting effect in the visible region.
  • the compound of the formula (2) or a salt thereof is used in the polarized light emitting device according to the present invention, it has a high degree of polarization in the ultraviolet region and exhibits a polarized light emitting action. ..
  • the polarized light emitting device and the polarized light emitting plate according to the present invention show high transmittance in the visible region in a preferable aspect, and further show excellent durability against heat, humidity and the like. Therefore, the polarized light emitting element and the polarized light emitting plate can be applied to a display device such as a liquid crystal display which is required to have high transparency in the visible region and high durability in a harsh environment.
  • the polarized light emitting element of the present invention is a film made of a polyvinyl alcohol resin or a derivative thereof (hereinafter, also abbreviated as PVA film) formed by adsorbing and orienting one or more kinds of luminescent compounds capable of emitting light by utilizing absorbed light.
  • the birefringence is measured from the direction perpendicular to the plane of the film by containing 5 to 30% by mass of a boron compound such as boric acid, and the birefringence is set to 0 °, and the film is placed with respect to the slow axis of the film.
  • a film characterized in that the birefringence of 50 ° is 1.0 to 1.9 times the birefringence of 0 ° in the angle dependence of the birefringence obtained when tilted by 50 °. Including.
  • the polarized light emitting element according to the present invention is a polarized light emitting element composed of a luminescent compound or a salt thereof and a PVA film on which the polarized compound or a salt thereof is adsorbed and oriented.
  • a film or the like obtained by forming a film of a polyvinyl alcohol-based resin or a derivative thereof that can contain a luminescent compound.
  • any derivative of the polyvinyl alcohol-based resin generally known in the art can be used.
  • unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, acrylic sulfonic acid, methacrylic sulfonic acid, p-styrene sulfonic acid, 2-acrylamide-2-
  • unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, acrylic sulfonic acid, methacrylic sulfonic acid, p-styrene sulfonic acid, 2-acrylamide-2-
  • unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, acrylic sulfonic acid, methacrylic sulfonic acid, p-styrene sulfonic acid, 2-acrylamide-2-
  • unsaturated sulfonic acids such as methylpropane sulfonic acid and
  • the shape of the base material is not particularly limited, and can be produced in any shape such as a film shape, a sheet shape, a flat plate shape, a curved plate shape, and a hemispherical shape.
  • the thickness of the base material (before the swelling treatment) is usually 10 ⁇ m to 100 ⁇ m, preferably 20 ⁇ m to 80 ⁇ m.
  • the polarized light emitting device of the present invention contains 5 to 30% by mass of the boron compound, and the emission brightness can be increased by containing the boron compound.
  • polarized light emission is expressed because there is a difference in light emission between the highly oriented axis and the low-oriented or non-oriented axis of the luminescent compound. Therefore, it is preferable to contain a boron compound because it is possible to emit light having high dichroism of light emission, that is, highly polarized light.
  • a water-soluble boron compound such as boric acid, borax or ammonium borate is preferable, boric acid and borax are more preferable, and boric acid is particularly preferable.
  • a film obtained by forming a film of a polyvinyl alcohol-based resin or a derivative thereof is said to be divided into a crystalline portion, an aggregated structure portion with boric acid, and an amorphous portion.
  • a compound having a biphenyl skeleton or a stilbene skeleton for example, a luminescent compound of the above formula (2) is excluded from the crystal part, so that it does not exist in the crystal part, and the aggregated structure part with boric acid or the aggregated structure part or It is considered to be present in the amorphous part. Further, it is considered that such a compound emits strong light and emits polarized light, especially when the abundance is large in the aggregated structure portion with boric acid. Therefore, the concentration of the boron compound, for example, boric acid, is 5 to 30% by mass, and the polarized light can be strongly emitted.
  • the concentration of the boron compound (for example, boric acid) is preferably 10 to 28% by mass, more preferably 12 to 27% by mass, more preferably 13 to 26% by mass, and particularly preferably 14 to 25% by mass.
  • the boric acid content was determined from the boric acid concentration.
  • the boric acid content is determined by the formula (8).
  • F indicates the factor of the aqueous sodium hydroxide solution.
  • luminescent compounds particularly compounds having a formula stilbene structure
  • they are present in the aggregated structure portion with boric acid and the amorphous portion.
  • the degree of polymerization of the polyvinyl alcohol-based resin for that purpose may be 1000 to 10,000, but is not limited.
  • the higher the degree of polymerization of the polyvinyl alcohol-based resin the higher the crystallinity. It is preferable to use a polyvinyl alcohol-based resin having a degree of polymerization of 1500 to 6000, and more preferably a degree of polymerization of 2000 to 6000. When the degree of polymerization is 10,000 or less, the crystallinity can be maintained in an appropriate range and stretched at a sufficient magnification, and the decrease in transparency due to the occurrence of fish eyes and the like can be suppressed.
  • the degree of saponification of the polyvinyl alcohol resin or its derivative is not limited, and a film made of a polyvinyl alcohol resin or its derivative having an arbitrary degree of saponification can be used. If the saponification is 90% or more, an element that emits highly polarized light can be obtained. It is preferable that the luminescent compound, particularly the compound having the structure of the formula (2), further increases the density present in the aggregated structure portion with boric acid and the amorphous portion, and enhances the emission brightness of the polarized light.
  • a polyvinyl alcohol resin having a kenka degree of 98%, more preferably a kenka degree of 99% or more, still more preferably a kenka degree of 99.5% or more, and particularly preferably a kenka degree of 99.9% or more, or a derivative thereof. Is good.
  • a polarized light emitting device having a higher degree of polarization and higher brightness can be obtained.
  • a polarized light emitting element having a birefringence of 50 ° of 1.0 to 1.9 times a birefringence of 0 ° emits highly polarized light with high emission brightness.
  • Birefringence is a phenomenon in which two refracted lights appear due to refraction when light is incident on a medium having anisotropy.
  • the anisotropy referred to here means that the physical properties of a substance or space differ depending on the direction, and birefringence causes anisotropy in light.
  • the two refracted lights are called normal rays and abnormal rays, respectively, and the polarization directions with respect to the optic axis are different.
  • Light emitted from an isotropic substance causes a "phase difference" by the difference in passing speed. ..
  • the digitized value of the phase difference is the phase difference value
  • the birefringence ( ⁇ n) is given by “phase difference value / film thickness of medium”.
  • the phase difference value and the birefringence can be measured by a commercially available device such as KOBRA manufactured by Oji Measuring Instruments Co., Ltd.
  • the time measured from the vertical direction of the film plane is 0 °, and the angle dependence of the birefringence obtained when the slow axis tilt of the film is 50 ° with respect to the birefringence of 0 °.
  • the polarized light emitting element of the present invention can be obtained.
  • the ratio of the birefringence of the slow axis inclination of 50 ° to the birefringence of 0 ° is higher than 1.9 times, that is, the phase advance rather than the orientation of the slow axis when the slow axis is inclined.
  • the ratio of the orientation of the axis is remarkably high, that is, the influence of the orientation of the orthogonal axis on the orientation axis (stretching axis) is remarkably strong.
  • the birefringence of 50 ° needs to be 1.0 times or more and 1.9 times or less with respect to the birefringence of 0 °.
  • the light emitting compound has a high directionality in a specific direction on the film plane.
  • stretching in the width direction is applied by neck-in or the like, and when the stretching in the width direction is applied, the emission brightness is significantly reduced or polarized light is applied. Is difficult to express, or low-polarized light is expressed. That is, it is known that a conventional polarizing plate can obtain a polarizing plate having a high degree of polarization by containing a dichroic dye such as iodine or an azo dichroic dye in the film and applying a high draw ratio to the film. Has been done.
  • Patent Document 5 it is shown that by using a compound having the structure of the formula (2), it irradiates ultraviolet rays and functions as a polarizing plate of ultraviolet rays, but on the other hand, it is a film that emits polarized light. Is not shown at all. This means that controlling the birefringence of 50 ° to 1.0 to 1.9 times the birefringence of 0 ° as defined in the present invention is extremely important for emitting polarized light. Means that it is important to.
  • the fact that the birefringence of 50 ° is higher than 1.9 times the birefringence of 0 ° means that the orientation is high in the slow axis, that is, in a direction other than a specific uniaxial axis. Therefore, it cannot be said that it is a preferable form in the present application.
  • the ratio of the birefringence of 50 ° to the birefringence of 0 ° is higher than 1.9 times, the orientation of the phase-advancing axis is very high, that is, the direction orthogonal to the orientation axis (stretching axis). The ratio of orientation of the light becomes extremely high, and the emission of polarized light becomes invisible.
  • This phenomenon is an extremely important factor because the birefringence in the width direction is exhibited in the polarized light emitting element even if it is uniaxially oriented and stretched as in the conventional polarizing plate.
  • the birefringence at the time of slow axis inclination is determined by the neck-in behavior of the PVA film, the use of a curved roll (expander roll) to prevent wrinkles that occur during the film stretching process, the neck-in of drying after stretching, etc. , It is generated by increasing the orientation other than the stretching axis by giving a dynamic influence in the width direction on the film stretching axis.
  • the dynamic influence in the width direction is reduced as much as possible in each process during processing, and the finally obtained polarized light emitting element has a birefringence of 50 ° of 1.0 to 1. It is extremely important to control the orientation of the PVA film in the manufacturing process so that it is 9 times larger.
  • the birefringence of 50 ° at the time of tilting the slow axis is 1.0 to 1.9 times the birefringence of 0 °, and this ratio is preferably 1. It is 0 to 1.7 times, more preferably 1.0 to 1.5 times, still more preferably 1.0 to 1.3 times, and particularly preferably 1.0 to 1.2 times.
  • the birefringence index measured from the vertical direction (0 °) of the film plane of the polarizing light emitting element is 0.020 to 0.060.
  • a birefringence of 0 ° of 0.020 to 0.060 indicates that the film has high orientation. It is preferably 0.020 to 0.045, more preferably 0.025 to 0.040.
  • the birefringence when measured from the vertical direction (0 °) of the film plane is 0.060 or less, physical defects such as microcracks and voids are suppressed in PVA, and haze (cloudiness) is visually observed. It is preferable because it prevents the occurrence of turbidity.
  • the luminescent compound preferably has a stilbene skeleton or a biphenyl skeleton, whereby an element having high brightness and polarized light emission can be obtained.
  • a luminescent compound having a stilbene skeleton or a biphenyl skeleton is a compound capable of emitting polarized visible light mainly by absorbing light in the ultraviolet region or near ultraviolet visible region and exhibiting orientation or anisotropy.
  • the structure is not particularly limited.
  • the light emitted by a luminescent compound having a stilbene skeleton or a biphenyl skeleton in a PVA film is excellent in that it is linearly polarized light.
  • the element that emits light that is linearly polarized has an advantage that the degree of freedom of a display device such as a liquid crystal display is improved.
  • Linearly polarized light is light that can also be represented as a wave in the direction of a certain axis. By emitting linearly polarized light, that is, uniaxially polarized light, it becomes easier to design a display device such as a liquid crystal display.
  • Most of the commercially available liquid crystal displays and polarized lenses use an iodine-based polarizing plate or a dye-based polarizing plate that can provide light that is linearly polarized light, that is, a polarizing plate that uses a bicolor dye that absorbs light in one axis.
  • linearly polarized light is suitable for industrial use.
  • the design of the orientation of the liquid crystal cell and the liquid crystal used there becomes complicated, or the design of the retardation plate and the like becomes extremely complicated. Industrial use will be difficult. Therefore, the polarized light is preferably linearly polarized. Emission of light that is linearly polarized can be achieved by orienting the luminescent compound in the same direction in the device.
  • the luminescence intensity is increased, and when the luminescent compound is present in a solution (disordered state) at the same concentration and emits light. It is possible to provide stronger light than the emission intensity of.
  • the dye having a stilbene skeleton is preferably a compound represented by the following formula (9) or a salt thereof.
  • K and L may independently have a nitro group, an amino group which may have a substituent, a carbonylamide group which may have a substituent, and a substituent.
  • the dye having a stilbene skeleton represented by the formula (9) has fluorescence emission and can obtain dichroism by orientation. This is mainly derived from the stilbene skeleton, and any substituent may be introduced. However, when the azo group is provided at the L position and the K position of the stilbene skeleton, the fluorescence emission is significantly reduced, which is not suitable.
  • Examples of the amino group which may have the above-mentioned substituent include an unsubstituted amino group, a methylamino group, an ethylamino group, an n-butylamino group, a tertiary butylamino group, an n-hexylamino group and a dodecylamino group.
  • arylamino group methylcarbonylamino group, ethylcarbonylamino group, n-butyl-carbonylamino group and the like which may have a substituent such as an amino group, a naphthylamino group and an N-phenyl-N-naphthylamino group. It may have a substituent such as an alkylcarbonylamino group having 1 to 20 carbon atoms, a phenylcarbonylamino group, a biphenylcarbonylamino group, a naphthylcarbonylamino group and the like, an arylcarbonylamino group and a methylsulfonylamino group.
  • an alkylsulfonylamino group having 1 to 20 carbon atoms such as a group, an ethylsulfonylamino group, a propylsulfonylamino group and an n-butyl-sulfonylamino group, a phenylsulfonylamino group and a naphthylsulfonylamino group.
  • a substituent such as an alkylsulfonylamino group having 1 to 20 carbon atoms such as a group, an ethylsulfonylamino group, a propylsulfonylamino group and an n-butyl-sulfonylamino group, a phenylsulfonylamino group and a naphthylsulfonylamino group.
  • Good arylsulfonylamino and the like can be mentioned.
  • alkylcarbonylamino group having 1 to 20 carbon atoms which may have a substituent an arylcarbonylamino group which may have a substituent, an alkylsulfonylamino group which may have 1 to 20 carbon atoms, or a substituent.
  • a good arylsulfonylamino group is preferred.
  • an alkylamino group having 1 to 20 carbon atoms which may have a substituent, an arylamino group which may have a substituent, and an alkylcarbonylamino having 1 to 20 carbon atoms which may have a substituent may be used.
  • the substituent in the arylcarbonylamino group which may have a group and a substituent, the alkylsulfonylamino group having 1 to 20 carbon atoms, and the arylsulfonylamino group which may have a substituent is not particularly limited.
  • a nitro group, a cyano group, a hydroxyl group, a sulfonic acid group, a phosphoric acid group, a carboxy group, a carboxyalkyl group, a halogen atom, an alkoxy group, an aryloxy group and the like can be mentioned.
  • the carboxyalkyl group include a methyl carboxy group and an ethyl carboxy group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group and the like.
  • aryloxy group examples include a phenoxy group and a naphthoxy group.
  • Examples of the carbonylamide group that may have the above-mentioned substituent include N-methyl-carbonylamide group (-CONHCH 3 ), N-ethyl-carbonylamide group (-CONHC 2 H 5 ), and N-phenyl-carbonyl. Examples thereof include an amide group (-CONHC 6 H 5 ).
  • Examples of the naphthotriazole group which may have the above-mentioned substituent include a benzotriazole group and a naphthotriazole group.
  • alkyl group having 1 to 20 carbon atoms which may have the above-mentioned substituent include direct groups such as methyl group, ethyl group, n-butyl group, n-hexyl group, n-octyl group and n-dodecyl group.
  • Examples thereof include branched chain alkyl groups such as chain alkyl groups, isopropyl groups, sec-butyl groups and tertiary butyl groups, and cyclic alkyl groups such as cyclohexyl groups and cyclopentyl groups.
  • Examples of the vinyl group which may have the above-mentioned substituent include a vinyl group, a methyl vinyl group, an ethyl vinyl group, a divinyl group, a pentadiene group and the like.
  • Examples of the amide group which may have the above-mentioned substituent include an acetamide group (-NHCOCH 3 ), a benzamide group (-NHCOC 6 H 5 ) and the like.
  • Examples of the aryl group which may have the above-mentioned substituent include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group and the like.
  • Examples of the carbonyl group which may have the above-mentioned substituent include a methylcarbonyl group, an ethylcarbonyl group, an n-butyl-carbonyl group, a phenylcarbonyl group and the like. It may have a carbonylamide group which may have the above-mentioned substituent, a naphthotriazole group which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a substituent.
  • an amide group which may have a substituent As a substituent in a vinyl group, an amide group which may have a substituent, a ureido group which may have a substituent, an aryl group which may have a substituent, and a carbonyl group which may have a substituent. Is not particularly limited, but may be the same as the substituent described in the section of amino group which may have the above-mentioned substituent.
  • the luminescent compound having a stilbene skeleton represented by the above formula (9) or a salt thereof is a compound represented by the following formula (10) or a salt thereof, or a luminescent compound represented by the following formula (11) or a salt thereof. Is particularly preferable.
  • the dyes of these luminescent compounds it is possible to obtain a polarized light emitting device that emits clearer white light with higher brightness.
  • the substituent R is a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent.
  • the halogen atom may be the same as above.
  • the alkyl group which may have a substituent may be the same as that described in the section of the alkyl group having 1 to 20 carbon atoms which may have a substituent.
  • the alkoxy group which may have a substituent may be preferably a methoxy group, an ethoxy group or the like, and the substituent is not particularly limited, but the term of an amino group which may have the above-mentioned substituent. It may be the same as the substituent described in.
  • the amino group which may have a substituent may be the same as above, and is preferably a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a phenylamino group or the like.
  • the substituent R may be bonded to any carbon of the naphthalene ring in the naphthotriazole ring, but when the carbon condensed with the triazole ring is at the 1-position and the 2-position, the 3-position, 5-position, or It is preferably bonded to the 8-position.
  • n is an integer of 0 to 3, preferably 1 or 2.
  • - (SO 3 H) groups may be attached to any carbon of the naphthalene ring in naphthotriazole ring.
  • n 1, when the carbon that is condensed with the triazole ring position 1 and position 2 and 4-position, 6-position, or 7
  • R is a hydrogen atom and n is 1.
  • G represents an amino group which may have a nitro group or a substituent, and is preferably a nitro group.
  • the amino group which may have a substituent may be the same as above, an alkylcarbonylamino group having 1 to 20 carbon atoms which may have a substituent, and an arylcarbonylamino group which may have a substituent.
  • An alkylsulfonylamino group having 1 to 20 carbon atoms, or an arylsulfonylamino group which may have a substituent is preferable.
  • T in the above formula (11) is an alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, or an aryl group which may have a substituent. .. It is preferably an aryl group which may have a substituent, more preferably a naphthyl group which may have a substituent, and a naphthyl group in which an amino group and a sulfo group are substituted as a substituent. Especially preferable.
  • H represents the same substituent as described for G in the above formula (10), and is preferably a nitro group.
  • the substituent here is not particularly limited, but may be the same as the substituent described in the section of the amino group which may have the above-mentioned substituent.
  • Examples of the compound represented by the above formula (9) include the Kayaphor series (manufactured by Nippon Kayaku Co., Ltd.), the Whitex series (manufactured by Sumitomo Chemical Co., Ltd.) such as Whitex RP, and the like. Further, the compounds shown in Compound Examples 9-1 to 9-6 are exemplified below, but the compounds are not limited thereto.
  • the dye having a biphenyl skeleton is preferably a compound represented by the following formula (11) or a salt thereof.
  • P and Q may independently have a nitro group, an amino group which may have a substituent, a carbonylamide group which may have a substituent, and a substituent.
  • An amino group which may have a substituent a carbonylamide group which may have a substituent, a naphthotriazole group which may have a substituent, and an alkyl having 1 to 20 carbon atoms which may have a substituent. It has a group, a vinyl group which may have a substituent, an amide group which may have a substituent, a ureido group which may have a substituent, an aryl group which may have a substituent and a substituent.
  • the carbonyl groups may be the same as above. However, when the biphenyl skeleton in the above formula (11) has an azo group at the P position and / or the Q position, fluorescence emission is significantly reduced, which is not suitable.
  • the compound represented by the above formula (11) is preferably a compound represented by the following formula (12).
  • j represents an integer of 0 to 2.
  • - preferred substitution position of (SO 3 H) group is not particularly limited, preferably, when the 1-position of the bonded carbon with a vinyl group, 2-position, preferably 4-position, particularly preferably 2-position.
  • R 1 , R 2 , R 3 , and R 4 are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, aralkyl groups, and alkenyloxy. It is a group selected from the group consisting of a group, an alkylsulfonyl group having 1 to 4 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, a carboxylic amide group, a sulfonamide group, and a carboxyalkyl group.
  • the carboxyalkyl group may be the same as above.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a tertiary butyl group, a cyclobutyl group and the like.
  • Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, a sec-butoxy group, a tert-butyloxy group, a cyclobutoxy group and the like.
  • Examples of the aralkyloxy group include an aralkyloxy group having 7 to 18 carbon atoms.
  • alkeniroxy group examples include an alkeniroxy group having 1 to 18 carbon atoms.
  • alkylsulfonyl group having 1 to 4 carbon atoms include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an n-butylsulfonyl group, a sec-butylsulfonyl group, a tertiary butylsulfonyl group, a cyclobutylsulfonyl group and the like. Be done.
  • Examples of the arylsulfonyl group having 6 to 20 carbon atoms include a phenylsulfonyl group, a naphthylsulfonyl group, and a biphenylsulfonyl group.
  • the preferred substitution positions of R 1 to R 4 are preferably 2-positions and 4-positions, preferably when the carbon bonded to the vinyl group is the 1-position.
  • the compound represented by the above formula (12) can be prepared by a known method, and is obtained, for example, by condensing 4-nitrobenzaldehyde-2-sulfonic acid with phosphonate and then reducing the nitro group.
  • the compound represented by the formula (12) is not limited to this, and a compound or the like described in JP-A-4-226162 can be used. Specifically, the following compounds and the like are exemplified.
  • the salts of the compounds represented by the above formulas (9) to (12) are salts formed together with inorganic cations or organic cations.
  • the inorganic cations include alkali metals such as lithium, sodium, and cations such as potassium, and, ammonium ions (NH 4 +) and the like.
  • Examples of the organic cation include organic ammonium represented by the following formula (D).
  • Z 1 to Z 4 independently represent a hydrogen atom, an alkyl, a hydroxyalkyl, or a hydroxyalkoxyalkyl, respectively.
  • Z 1 to Z 4 include C 1- C 6 alkyl such as methyl, ethyl, butyl, pentyl, and hexyl, preferably C 1- C 4 alkyl; hydroxymethyl, 2-hydroxyethyl, 3-hydroxy.
  • Hydroxy C 1- C 6 alkyl preferably hydroxy C 1- C 4 alkyl, such as propyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, and 2-hydroxybutyl; and hydroxyethoxymethyl, 2-hydroxy.
  • Hydroxy C 1- C 6 alkoxy C 1- C 6 alkyl preferably hydroxy C 1- C 4 alkoxy C 1 -C, such as ethoxyethyl, 3-hydroxyethoxypropyl, 3-hydroxyethoxybutyl, and 2-hydroxyethoxybutyl. Examples thereof include 4- alkyl.
  • examples thereof include isopropanol ammonium ion and cations such as ammonium ion.
  • lithium ion, ammonium ion, and sodium ion are more preferable.
  • luminescent compound examples include, for example. C. I. Fluorescent Fluorescent 5, C. I. Fluorescent Fluorescent 8, C. I. Fluorescent Fluorescent 12, C. I. Fluorescent Fluorescent 28, C. I. Fluorescent Fluorescent 30, C. I. Fluorescent Fluorescent 33, C. I. Fluorescent Fluorescent 350, C. I. Fluorescent Fluorescent 360, C. I. Fluorescent Fluorescent 365, And so on.
  • These luminescent compounds may be free acids, alkali metal salts (eg Na salt, K salt, Li salt), or ammonium salts.
  • At least one kind of the luminescent compound has a structure shown in (2) having a stillben skeleton, and the luminescent compound exhibits a polarizing action at a wavelength at which light is absorbed, which is the highest.
  • the value of the order parameter (OPD: Older compounder of day) given by the following formula (i) is 0.75 to 1.00 at the wavelength exhibiting the polarization action. This value is more preferably 0.75 to 0.96.
  • OPD Older compounder of day
  • X or Y each independently represents a nitro group, an amino group which may have a substituent, or an amide group which may have a substituent, and may have a substituent.
  • the substituent of a good amino group or an amide group which may have a substituent may independently have an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an aromatic group which may have a substituent.
  • OPD (log (Kz / 100) / Log (Ky / 100) -1) / ((log (Kz / 100) / log (Ky / 100) +2) Equation (i)
  • Ky represents the light transmittance when the light polarized at an orthogonal position to the axis showing the highest absorption in the dye-oriented element is irradiated
  • Kz is the most in the dye-oriented element. It represents the light transmittance when irradiating light polarized in a position parallel to the axis showing high absorption.
  • the compound of the formula (2) has absorption mainly in the ultraviolet region and the near-ultraviolet visible region, and the preferable polarized light emitting device of the present invention can be obtained by having the OPD of 0.75 to 1.00 at that wavelength. it can. It is preferably 0.88 or more, more preferably 0.90 or more, still more preferably 0.92 or more, and particularly preferably 0.93 or more. Further, the value of OPD is more preferably 0.96 or less.
  • each of X and Y independently has a nitro group, an amino group which may have a substituent, an amide group which may have a substituent, and an aromatic carbide which may have a substituent.
  • the substituent of the amide group may be an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, respectively, and may have a substituent, an aromatic hydrocarbon group or a substituent.
  • the substituents of the heterocyclic group which may have a substituent or the substituent of the polycyclic heterocyclic group which may have a substituent are independently a hydrogen atom, a halogen group, a nitro group, a hydroxy group, and a fat having 1 to 4 carbon atoms. It has a group hydrocarbon group, an alkoxy group having 1 to 4 carbon atoms, an aliphatic hydrocarbon group having 1 to 4 carbon atoms having a sulfo group, an aliphatic hydrocarbon group having 1 to 4 carbon atoms having a hydroxy group, and a carboxy group.
  • X or Y is not limited to these options.
  • X or Y is a heterocyclic group which may have a substituent or a polycyclic heterocyclic group which may have a substituent
  • this is, for example, a nitrogen atom or sulfur which may have a substituent.
  • It may be a heterocyclic group containing an atom or a polycyclic heterocyclic group containing a nitrogen atom or a sulfur atom which may have a substituent.
  • Preferred heterocyclic or polycyclic heterocyclic groups include azole, diazole, triazole, benzotriazole, naphthotriazole, thiazole, benzothiazole and naphthozol as preferred structures. It is more preferable that X or Y has a structure represented by the following formulas (3) to (7).
  • each formula represents the bonding position with the phenyl group.
  • each of A has a hydrogen atom, a halogen group, a nitro group, a hydroxy group, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a sulfo group having 1 to 1 to carbon atoms.
  • An aliphatic hydrocarbon group of 4 an aliphatic hydrocarbon group having 1 to 4 carbon atoms having a hydroxy group, an aliphatic hydrocarbon group having 1 to 4 carbon atoms having a carboxy group, and 1 to 4 carbon atoms having a sulfo group.
  • q 1 represents an integer of 0 to 4
  • M is hydrogen or a metal ion.
  • M in the formulas (3) to (7) and M in the formula (2) may be the same, and n 1 and n 2 represent integers of 0 to 3, respectively.
  • M represents hydrogen, a metal ion, and an ammonium ion.
  • the metal ion include alkali metal ions such as lithium ion, sodium ion and potassium ion, and alkaline earth metal ions such as calcium ion and magnesium ion.
  • ammonium ions include ammonium ion, methylammonium ion, dimethylammonium ion, triethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion, monoethanolammonium ion, and diethanolammonium ion.
  • Triethanolammonium ion monoisopropanolammonium ion, diisopropanolammonium ion, triisopropanolammonium ion, triethanolammonium ion and the like. More specifically, for example, when M is hydrogen, it is sulfonic acid (-SO 3 H), when M is sodium ion, it is sodium sulfonate (-SO 3 Na), and when M is ammonium ion, it is sulfone. Represents ammonium acid (-SO 3 NH 4 ). Among these, particularly preferable ones include lithium ion, ammonium ion, and sodium ion.
  • a preferable example of the method for synthesizing the compound represented by the formula (2) will be described below.
  • the method for synthesizing this compound is not limited to the following examples.
  • the method disclosed in Patent Document 5 can be used. Put 1 equivalent of each of the compound (14) and the compound (15) in a beaker, add water and heat to 60 ° C., and add 25% caustic soda to dissolve.
  • One equivalent of terephthalic acid dichloride represented by the formula (13), which is commercially available, is added thereto little by little over about 1 hour. After adding all, stir at 60 ° C. for 1 hour.
  • the desired product can be obtained by allowing to cool to room temperature, or by adding salt, salting out, filtering and drying.
  • the equivalent ratio of the compound of the formula (14), the compound of the formula (15) and the terephthalic acid dichloride may be appropriately adjusted according to the individual reactivity.
  • the sulfo group and the like in the formula are represented in the form of a free acid. These compounds can take the form of salts.
  • the content of the compound of the formula (2) in the polarized light emitting device is not particularly limited, and an arbitrary content can be designed.
  • the blending amount may be determined according to the required transmittance.
  • the polarization performance of the polarized light emitting element is not only the compounding ratio of the compound of the formula (2) contained in the polarized light emitting element, but also the degree of swelling of the substrate to adsorb the compound, the stretching ratio, the dyeing time, the dyeing temperature, and the time of dyeing. It changes due to various factors such as the influence of pH and salt.
  • the blending ratio of the compound of the formula (2) contained in the polarizing light emitting element depends on the degree of swelling of the base material, the temperature at the time of dyeing, the time, the pH, the type of salt, the concentration of salt, and the stretching ratio. Can be decided. Such adjustment of the blending ratio can be appropriately performed.
  • a film (PVA film) made of a polyvinyl alcohol resin or a derivative thereof for adsorbing and orienting a luminescent compound such as the compound represented by (2) or a salt thereof is prepared.
  • PVA film for example, a commercially available film made of a polyvinyl alcohol-based resin or a derivative thereof may be used, or may be produced by forming a film of the polyvinyl alcohol-based resin.
  • the film-forming method of the polyvinyl alcohol-based resin is not particularly limited, and for example, a method of melt-extruding a hydrous polyvinyl alcohol, a casting film-forming method, a wet film-forming method, and a gel film-forming method (the polyvinyl alcohol aqueous solution is once cooled).
  • a known film-forming method can be adopted, such as a method of extracting and removing the solvent after gelation), a cast film-forming method (flowing a polyvinyl alcohol aqueous solution on a substrate and drying), and a method using a combination thereof.
  • the swelling treatment is preferably carried out by immersing the base material in a swelling solution at 20 to 50 ° C. for 30 seconds to 10 minutes.
  • the swelling liquid is preferably water.
  • the draw ratio of the base material with the swelling liquid is preferably adjusted to 1.00 to 1.50 times, more preferably 1.10 to 1.35 times.
  • the substrate obtained by performing the swelling treatment as described above is adsorbed and impregnated with a dye which is at least one kind of luminescent compound or a salt thereof.
  • the dyeing step is not particularly limited as long as it is a method of adsorbing and impregnating the base material with the luminescent compound or a salt thereof, but for example, the base material is a dyeing solution containing the luminescent compound or a salt thereof (generally). It is preferable to immerse it in an aqueous solution), and it can also be adsorbed by applying a dyeing solution to a substrate.
  • the concentration of the luminescent compound or its salt in the dyeing solution is not particularly limited as long as the luminescent compound or its salt is sufficiently adsorbed in the substrate, but for example, 0.0001 in the dyeing solution. It is preferably ⁇ 1% by mass, and more preferably 0.001 to 0.5% by mass.
  • the temperature of the dyeing solution in the dyeing step is preferably 5 to 80 ° C, more preferably 20 to 50 ° C, and particularly preferably 40 to 50 ° C.
  • the time for immersing the substrate in the dyeing solution can be appropriately adjusted, and is preferably between 30 seconds and 20 minutes, more preferably between 1 and 10 minutes.
  • the luminescent compound contained in the dyeing solution may be used alone or in combination of two or more. Since the emission color of such a luminescent compound differs depending on the structure, the resulting emission color can be appropriately adjusted to a desired color by containing one or more of the above dyes in the substrate. .. Further, if necessary, the dyeing solution may further contain one or more of the above organic dyes or fluorescent dyes.
  • the dyeing solution may further contain a dyeing aid, if necessary, in addition to the above dyes (luminescent compounds and other optional dyes).
  • the dyeing aid include sodium carbonate, sodium hydrogencarbonate, sodium chloride, sodium sulfate (Glauber's salt), anhydrous sodium sulfate, sodium tripolyphosphate and the like, and sodium sulfate is preferable.
  • the content of the dyeing aid can be arbitrarily adjusted by the time of immersion and the temperature of the dyeing solution based on the dyeability of the dye used.
  • the content of the dyeing aid is preferably 0.05 to 10% by mass, more preferably 0.05 to 2% by mass in the dyeing solution (when used).
  • a pre-cleaning step can be optionally performed in order to remove excess dyeing solution adhering to the surface of the base material in the dyeing step.
  • a pre-cleaning step By carrying out the pre-cleaning step, it is possible to suppress the transfer of the dye remaining on the surface of the base material into the liquid to be treated next.
  • water is generally used as the cleaning liquid.
  • cleaning method it is preferable to immerse the dyed base material in the cleaning liquid, and on the other hand, cleaning can also be performed by applying the cleaning liquid to the base material.
  • the washing time is not particularly limited, but is preferably 1 to 300 seconds, and more preferably 1 to 60 seconds.
  • the temperature of the cleaning liquid in the pre-cleaning step needs to be a temperature at which the material constituting the base material does not dissolve, and generally may be 5 to 40 ° C. Even if there is no pre-cleaning step, the pre-cleaning step can be omitted because it does not have a particularly large effect on the performance of the polarized light emitting element.
  • the substrate may contain a boron compound as a cross-linking agent, or a cross-linking agent which is not a boron compound together with the boron compound.
  • a boron compound as a cross-linking agent or a cross-linking agent that is not a boron compound together with the boron compound in the base material it is preferable to immerse the base material in a treatment solution containing the cross-linking agent, while the treatment solution is used as the base material. May be coated or coated. It is particularly preferable to use a solution containing boric acid as the treatment solution in this step.
  • the solvent in the treatment solution is not particularly limited, but water is preferable.
  • the concentration of the boron compound such as boric acid in the treatment solution is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass, and preferably 1 to 5% by mass. Even more preferable.
  • the temperature of the treatment solution is preferably 30 to 80 ° C, more preferably 40 to 75 ° C.
  • the treatment time of this cross-linking step is preferably 30 seconds to 10 minutes, more preferably 1 to 6 minutes.
  • a fixing treatment may be further performed with an aqueous solution containing a cationic polymer compound. The fixing process makes it possible to immobilize the dye.
  • cationic polymer compound for example, dicyanamide and formalin polymerization condensate as dicyan, dicyandiamide / diethylenetriamine polycondensate as polyamine, epichlorohydrin / dimethylamine addition polymer as polycation, dimethyldialylammonium Chloride-ion dioxide copolymers, diallylamine salt polymers, dimethyldiallylammonium chloride polymers, allylamine salt polymers, and dialkylaminoethyl acrylate quaternary salt polymers can be used.
  • the stretching step is carried out.
  • the stretching step is performed by uniaxially stretching the base material in a certain direction.
  • the stretching method may be either a wet stretching method or a dry stretching method.
  • the draw ratio is preferably 3 to 9 times, more preferably 4 to 8 times, and even more preferably 5 to 8 times.
  • the time when the birefringence is measured from the vertical direction of the film plane is set to 0 °, and the angle dependence of the birefringence obtained when the film is tilted with respect to the slow axis of the film is 0 °.
  • the stretching in the width direction with respect to the stretching axis should be as small as possible. Is preferable. That is, while adjusting the bending angle of the curved roll (expander roll) for preventing wrinkles generated during the stretching process and adjusting the neck-in ratio in PVA, the requirement of the angle dependence of the birefringence of the present invention is satisfied. A satisfying polarized light emitting element can be obtained.
  • the stretching heating medium when the stretching heating medium is an air medium, it is preferable to stretch the base material at a temperature of the air medium of room temperature to 180 ° C. Further, the humidity is preferably in an atmosphere of 20 to 95% RH.
  • the method for heating the base material include, but are not limited to, an inter-roll zone stretching method, a roll heating stretching method, a hot pressure stretching method, and an infrared heating stretching method.
  • the dry stretching step may be carried out by one-step stretching or by two or more steps of multi-step stretching.
  • the boron compound-containing method may be contained before stretching or may be contained by treating after stretching.
  • the stretching treatment is performed while immersing the base material in a solution containing at least one cross-linking agent (that is, the boron compound-containing or cross-linking step and the stretching step can be carried out at the same time).
  • a cross-linking agent for example, boric acid in the above-mentioned cross-linking agent step can be used, and preferably, the stretching treatment can be performed in the treatment solution used in the cross-linking step.
  • the stretching temperature is preferably 40 to 70 ° C, more preferably 45 to 65 ° C, but is not limited.
  • the stretching time is usually 30 seconds to 20 minutes, preferably 2 to 7 minutes.
  • the wet stretching step may be carried out by one-step stretching or by two or more steps of multi-step stretching.
  • the stretching treatment may be optionally performed before the dyeing step, and in this case, the dye orientation can also be performed at the time of dyeing.
  • the cross-linking agent may precipitate or foreign matter may adhere to the surface of the base material, so that the cleaning step of cleaning the surface of the base material can be performed.
  • the washing time is preferably 1 second to 5 minutes.
  • a cleaning method it is preferable to immerse the base material in the cleaning liquid, and on the other hand, the base material can be cleaned by applying or applying the cleaning liquid to the base material. Water is preferable as the cleaning liquid.
  • the cleaning treatment may be carried out in one step or in two or more steps.
  • the temperature of the washing solution in the washing step is not particularly limited, but is usually 5 to 50 ° C., preferably 10 to 40 ° C., and may be room temperature.
  • the solvent of the solution or treatment liquid used in each of the above-mentioned steps in addition to the above-mentioned water, for example, dimethyl sulfoxide, N-methylpyrrolidone, methanol, ethanol, propanol, isopropyl alcohol, glycerin, ethylene glycol, propylene glycol, diethylene glycol. , Alcohols such as triethylene glycol, tetraethylene glycol or trimethylolpropane, amines such as ethylenediamine and diethylenetriamine and the like.
  • the solvent of the solution or the treatment liquid is not limited to these, but is most preferably water. Further, the solvent of these solutions or the treatment liquid may be used alone or as a mixture of two or more kinds.
  • drying process After the cleaning step, it is preferable to carry out a drying step of the base material.
  • the drying treatment can be carried out by natural drying, it can be carried out by compression with a roll, removal of moisture on the surface with an air knife, a water absorbing roll, or the like in order to further improve the drying efficiency. Furthermore, it is also possible to perform blast drying.
  • the drying treatment can be performed at an arbitrary temperature, but specifically, it may be 10 to 105 ° C, more preferably 45 to 90 ° C, and further preferably 55 to 75 ° C.
  • the polarized light emitting element exhibits higher emission brightness by drying treatment or heat treatment at a glass transition temperature (Tg) or higher of a film made of a polyvinyl alcohol resin or a derivative thereof.
  • Tg glass transition temperature
  • the film obtained by forming a film of a polyvinyl alcohol-based resin or a derivative thereof is divided into a crystalline part, an aggregated structure part with boric acid, and an amorphous part as described in Patent Document 6. As described above.
  • the biphenyl skeleton or the stilbene skeleton is heat-treated at Tg or more to promote the formation of a crystal portion, and the luminescent compound is excluded from the crystal portion to be combined with boric acid.
  • the agglomerated structure portion or the amorphous portion is abundantly present, emits stronger light than when heat-treated at Tg or less, and emits more polarized light.
  • a film made of a polyvinyl alcohol resin or a derivative thereof has a Tg of about 20 to 40 ° C. when measured by a thermomechanical analyzer (TMA) or a dynamic viscoelasticity measurement (DMA) in an unstretched state.
  • the polarized light emitting device is preferably manufactured by heat treatment at a temperature equal to or higher than the obtained Tg.
  • the Tg of the polarized light emitting element can be adjusted in the range of 45 to 100 ° C., whereby the emission brightness can be further increased.
  • the Tg of the polarized light emitting device is preferably 45 to 90 ° C, more preferably 55 to 70 ° C.
  • the drying time or heat treatment time is preferably 30 seconds to 20 minutes, more preferably 2 to 10 minutes.
  • the time when the birefringence is measured from the vertical direction of the film plane in the dry state after stretching is set to 0 °, and the birefringence obtained when the film is tilted with respect to the slow axis of the film.
  • the extension axis is not particularly limited.
  • the drying step of the stretched film since the film necks in, it is stretched in the width direction, but at that time, it is better than maintaining the stretched width direction (constant length width). It is preferable to apply the drying step so that free behavior is allowed in order to obtain the polarized light emitting element of the present application.
  • the polarized light emitting device according to the present invention can be manufactured.
  • the polarized light emitting device of the present application can be used together with a generally known dichroic dye to produce a polarized light emitting device having various colors or neutral gray.
  • the polarized light emitting element may further contain one or more other dichroic dyes such as iodine and organic dyes as long as it does not impair the polarization performance or for the purpose of color adjustment.
  • the organic dye used in combination is not particularly limited, but a dye having a high dichroism is preferable, and a dye having little influence on the polarization performance in the ultraviolet region of the luminescent compound is preferable. Examples of the organic dye that may be used in combination include C.I. Ai. direct. Yellow 12, Sea. Ai. direct. Yellow 28, Sea. Ai. direct. Yellow 44, Sea. Ai. direct. Orange 26, Sea. Ai. direct. Orange 39, Sea. Ai. direct. Orange 71, Sea. Ai. direct. Orange 107, Sea.
  • the content thereof is not particularly limited, but generally, the total of at least one or more organic dyes used in combination is 0.01 to 10 parts by mass based on the mass of the polarizing compound or a salt thereof. It is preferably in the range of.
  • the luminescent compound or a salt thereof is contained in a film as a base material, polyvinyl alcohol or a derivative thereof, by a known method in combination with a general fluorescent dye or a dichroic dye, if necessary.
  • the polarized light emitting element of the present invention can be manufactured by the method of directing and orienting.
  • the obtained polarized light emitting element may be provided with a transparent protective layer to form a polarized light emitting plate, and the polarized light emitting plate may be further provided with a protective layer or an AR (antireflection) layer, a support, or the like, if necessary.
  • Such polarized light emitting elements and polarized light emitting plates include liquid crystal projectors, calculators, watches, laptop computers, word processors, liquid crystal televisions, car navigation systems, security displays, anti-counterfeiting devices, indoor and outdoor measuring instruments and indicators, etc. Suitable for lenses and glasses.
  • the polarized light emitting plate according to the present invention may usually have a transparent protective layer on at least one surface of the above polarized light emitting element.
  • the transparent protective layer is used to improve the water resistance and handleability of the polarized light emitting element. Therefore, such a transparent protective layer does not affect the polarization action exhibited by the polarized light emitting device according to the present invention.
  • the transparent protective layer is preferably a transparent protective layer having excellent optical transparency and mechanical strength. Further, the transparent protective layer is preferably a film having a layer shape capable of maintaining the shape of the polarizing light emitting element.
  • the transparent protective layer is preferably a plastic film having excellent thermal stability, moisture shielding property, etc. in addition to transparency and mechanical strength.
  • the material for forming such a protective layer include a cellulose acetate film, an acrylic film, a fluorofilm such as an ethylene tetrafluoride / propylene hexafluoride copolymer, a polyester resin, and a polyolefin resin.
  • a film made of a polyamide resin or the like can be mentioned.
  • a triacetyl cellulose (TAC) film or a cycloolefin-based film is preferably used.
  • the thickness of the transparent protective layer is preferably in the range of 1 ⁇ m to 200 ⁇ m, more preferably in the range of 10 ⁇ m to 150 ⁇ m, and particularly preferably in the range of 40 ⁇ m to 100 ⁇ m.
  • the method for producing the polarized light emitting plate according to the present invention is not particularly limited, but for example, the polarized light emitting plate is produced by superimposing a transparent protective layer on the polarized light emitting element and laminating with a known formulation. be able to.
  • Such a polarized light emitting plate may further include an adhesive layer for adhering the transparent protective layer to the polarized light emitting element between the transparent protective layer and the polarized light emitting element.
  • the adhesive constituting the adhesive layer is not particularly limited, and examples thereof include polyvinyl alcohol-based adhesives, urethane emulsion-based adhesives, acrylic-based adhesives, polyester-isocyanate-based adhesives, and the like.
  • a polyvinyl alcohol-based adhesive is preferably used.
  • a polarized light emitting plate can be produced by adhering the transparent protective layer and the polarized light emitting element with an adhesive and then drying or heat-treating at an appropriate temperature.
  • the polarized light emitting plate according to the present invention may appropriately have various known functional layers such as an antireflection layer, an antiglare layer, and a further transparent protective layer on the exposed surface of the transparent protective layer.
  • a method of applying a material having various functions to the exposed surface of the transparent protective layer is preferable.
  • the above-mentioned further transparent protective layer examples include an acrylic-based and polysiloxane-based hard coat layer, a urethane-based protective layer, and the like.
  • an antireflection layer can be provided on the exposed surface of the transparent protective layer.
  • the antireflection layer can be formed, for example, by depositing or sputtering a substance such as silicon dioxide or titanium oxide on the transparent protective layer, or by applying a thin layer of a fluorine-based substance on the transparent protective layer. ..
  • the polarized light emitting plate according to the present invention may be further provided with a transparent support such as glass, crystal, or sapphire, if necessary.
  • a transparent support such as glass, crystal, or sapphire
  • Such a support is not particularly limited, but preferably has a flat portion because a polarizing light emitting plate is attached to the support.
  • the support is preferably a transparent support from the viewpoint of optical use.
  • the transparent support is divided into an inorganic support and an organic support.
  • examples of the inorganic support include a support composed of soda glass, borosilicate glass, quartz, sapphire, spinel and the like.
  • the organic support include a support composed of acrylic, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer and the like.
  • the thickness and size of the transparent support are not particularly limited and can be appropriately determined. Further, in a polarized light emitting plate having such a transparent support, it is preferable to provide an antireflection layer on one or both surfaces of the support surface or the polarized light emitting plate surface in order to further improve the single transmittance. In order to bond the polarized light emitting plate and the support, a transparent adhesive (adhesive) agent may be applied to the support, and then the polarized light emitting plate according to the present invention may be attached to the coated surface.
  • the adhesive or pressure-sensitive adhesive to be used is not particularly limited, and commercially available ones can be used, and an acrylic ester-based adhesive or pressure-sensitive adhesive is preferable.
  • the polarized light emitting plate according to the present invention can also be used as a polarized light emitting plate capable of emitting circularly polarized light or an polarized light emitting plate capable of emitting elliptically polarized light to which a retardation plate is attached.
  • the support may be on the retardation plate side or the polarized light emitting plate side.
  • various functional layers, supports and the like can be further provided on the polarizing light emitting plate.
  • Such polarized light emitting plates can be used in various products such as liquid crystal projectors, calculators, watches, notebook computers, word processors, liquid crystal televisions, car navigation systems, indoor and outdoor measuring instruments and displays, lenses, and glasses. ..
  • the polarized light emitting element and the polarized light emitting plate according to the present invention produced in this manner exhibit a high degree of polarization in the ultraviolet region, and further exhibit a polarized light emitting action and a high transmittance in the visible region. Further, since the polarized light emitting element and the polarized light emitting plate according to the present invention show excellent durability against heat, humidity, light and the like, their performance can be maintained even in a harsh environment, and the performance thereof has been conventionally maintained. It has higher durability than the iodine-based polarizing plate of.
  • the polarized light emitting element and the polarized light emitting plate according to the present invention are liquid crystal displays that are required to have high transparency in the visible range and high durability in a harsh environment, for example, a television, a wearable terminal, a tablet terminal, a smartphone, and the like. It can be applied to various display devices such as in-vehicle monitors, digital signage used outdoors or indoors, and smart windows.
  • the display device has the above-mentioned polarized light emitting element and polarized light emitting plate.
  • a display having a polarized light emitting element containing a luminescent compound and a polarized light emitting plate exhibits a polarized light emitting action even when irradiated with light of 400 nm or less, for example, ultraviolet light, and the display can be performed by utilizing this action. Since the display device according to the present invention has a high transmittance in the visible region, there is no decrease in the transmittance in the visible region like a conventional polarizing plate, or even if there is a decrease in the transmittance, the conventional one.
  • the decrease in transmittance is significantly smaller than the transmittance of the polarizing plate.
  • iodine-based polarizing plates which are conventional polarizing plates, and dye-based polarizing plates using other dye compounds require a luminosity factor correction of 35 to 43 in the visible range in order to achieve a degree of polarization of almost 100%. It is about%.
  • the conventional polarizing plate has both the vertical axis and the horizontal axis as the light absorption axis, but one of the vertical axis and the horizontal axis is incident in order to obtain a degree of polarization of almost 100%.
  • Polarization is produced by absorbing light, that is, by absorbing light on one axis and transmitting light on the other axis.
  • the transmittance is inevitably 50% or less.
  • a dichroic dye is oriented in a stretched film to produce a polarizing plate.
  • the dichroic dye is not necessarily 100% oriented and has a slight absorption component with respect to the light transmission axis, the transmittance is about 43% or less due to the surface reflection of the substance. Otherwise, a degree of polarization of almost 100% cannot be achieved, that is, a high degree of polarization cannot be achieved unless the transmittance is lowered.
  • the polarized light emitting element and the polarized light emitting plate according to the present invention have a light absorbing axis near about 400 nm, that is, have a light absorbing action in the ultraviolet region and emit polarized light in the visible region. Although it exhibits a light emitting effect, it hardly absorbs light in the visible region, so that the transmittance in the visible region becomes very high. Further, in the visible region, since it exhibits a polarized light emitting action, there is no light loss as compared with the case of using a conventional polarizing plate, that is, the decrease in transmittance as in the conventional polarizing plate is very small.
  • a display device using the polarized light emitting element and the polarized light emitting plate according to the present invention can obtain higher brightness than a liquid crystal display using a conventional polarizing plate. Further, since the display device using the polarized light emitting element and the polarized light emitting plate according to the present invention has high transparency, a substantially transparent display can be obtained even though it is a liquid crystal display. Further, since it can be designed so that polarized light is transmitted when displaying characters and images, it is possible to obtain a display that can be displayed even though it is a transparent liquid crystal display, that is, a display capable of displaying characters and the like on a transparent display. can get. Therefore, as the display device according to the present invention, a transparent liquid crystal display having no light loss, particularly a see-through display can be obtained.
  • the display device can polarize ultraviolet light that is invisible to the human eye, it can be applied to a liquid crystal display that can display by ultraviolet light.
  • a liquid crystal display that can display by ultraviolet light.
  • the display device exhibits a polarized light emitting action by irradiating ultraviolet light, and a liquid crystal display using the polarized light emission can be manufactured. Therefore, a normal liquid crystal display using visible light can be used. It is also possible to realize a liquid crystal display using ultraviolet light. That is, even in a dark space without light, if it is a space that can be irradiated with ultraviolet light, it is possible to manufacture a light emitting liquid crystal display on which displayed characters, images, and the like are displayed.
  • the visible region has a liquid crystal display portion that can be displayed by light in the visible region and a liquid crystal display portion that can be displayed by the polarized light emission effect of ultraviolet light. It is also possible to produce a display capable of displaying two different displays in which Although there have been two displays capable of different displays, there is no display capable of displaying differently by different light sources in the ultraviolet region and the visible region even though they have the same liquid crystal panel. From this, the display device according to the present invention can manufacture a new display by having the above-mentioned polarized light emitting element and polarized light emitting plate.
  • the liquid crystal cell used in the in-vehicle or outdoor display liquid crystal display using the polarized light emitting element and the polarized light emitting plate according to the present invention is not limited to, for example, TN liquid crystal, STN liquid crystal, VA liquid crystal, IPS liquid crystal and the like. ..
  • the polarized light emitting element and the polarized light emitting plate can be used in any liquid crystal display mode.
  • An in-vehicle display device or an outdoor display device using such a polarized light emitting element or a polarized light emitting plate has high display brightness, excellent display contrast, and particularly a liquid crystal having a higher transmittance than a conventional liquid crystal display device. It has a feature that a display device can be obtained. Further, the device has a feature that it does not cause discoloration or deterioration of polarization performance even in a high temperature and high humidity state inside or outdoors.
  • Example 1 (Synthesis Example 1) 136.4 parts of the compound of the formula (16) was added to 1000 parts of water and heated to 60 ° C., and 25% caustic soda was added to dissolve the compound. 20.2 parts of terephthalic acid dichloride was added little by little over about 1 hour. After adding all, the mixture was stirred at 60 ° C. for 1 hour. After completion of the reaction, the mixture was allowed to cool to room temperature, salted out, filtered, and dried at 70 ° C. to obtain 104.5 parts of the compound of the above example (2-1).
  • a polyvinyl alcohol film (VF-PS # 7500 manufactured by Kuraray Co., Ltd.) having a thickness of 75 ⁇ m and a width of 12.0 cm and a degree of polymerization of 2400 and a complete saponification (a degree of saponification of 99% or more) was immersed in water at 40 ° C. for 3 minutes. The film was swollen.
  • the film obtained by swelling contains 0.2 parts by mass of the compound of the above example (2-1) obtained in Synthesis Example 1, 1.0 part by mass of sardine, and 1000 parts by mass of water at 45 ° C.
  • the film was immersed in an aqueous solution for 4 minutes to contain the compound of the above example (2-1).
  • the film containing the compound of the above example (2-1) was set so that the length in the stretching direction was 3.0 cm, and the film was quadrupled in a 3% 50 ° C. boric acid aqueous solution over 5 minutes. Stretched to.
  • the film obtained by stretching was washed with water at room temperature for 2 seconds while maintaining a tense state to obtain a polarized light emitting device of the present invention.
  • a triacetyl cellulose film (ZRD manufactured by Fuji Film Co., Ltd.) containing no ultraviolet absorber with a thickness of 60 ⁇ m, in which both sides of the polarized light emitting element obtained by washing with water were immediately saponified with a 1.5 specified aqueous solution of sodium hydroxide.
  • an aqueous polyvinyl alcohol solution (an aqueous solution containing 4% NH-26 manufactured by Japan Vam & Poval) was laminated as an adhesive and dried at 70 ° C. for 9 minutes to obtain a polarized light emitting plate of the present invention.
  • Example 2 In Example 1, the stretching ratio applied over 5 minutes in a 3% 50 ° C. boric acid aqueous solution was changed from 4 times to 5 times, and the stretched film was kept in a tense state.
  • the polarized light emitting device and the polarized light emitting plate of the present invention were obtained in the same manner except that they were immersed in water at room temperature for 25 seconds.
  • Example 3 (Synthesis Example 2) 80 parts of the compound of the formula (17) was added to 1000 parts of water and heated to 60 ° C., and 25% caustic soda was added to dissolve the compound. 20.2 parts of terephthalic acid dichloride was added little by little over about 1 hour. After adding all, the mixture was stirred at 60 ° C. for 1 hour. After completion of the reaction, the mixture was allowed to cool to room temperature, salted out, filtered, and dried at 70 ° C. to obtain 65 parts of the compound of the above example (2-6).
  • the compound of the above example (2-6) was used instead of the compound of the above example (2-1), and the compound of the above example (2-6) was contained.
  • the film was set so that the length in the stretching direction was 4.5 cm, stretched 5 times in a 3% aqueous solution of boric acid at 50 ° C. over 5 minutes, and the film obtained by stretching was obtained.
  • the polarized light emitting element and the polarized light emitting plate of the present invention were obtained in the same manner except that they were immersed in water at room temperature for 30 seconds while maintaining a tense state.
  • Example 4 In Example 3, the film containing the compound of the above example (2-6) was set so that the length in the stretching direction was 3.0 cm, and was placed in a 3% 50 ° C. boric acid aqueous solution for 5 minutes. After stretching the film 5 times, the film obtained by stretching was washed with water at room temperature for 5 seconds while maintaining a tense state, without fixing the length in the width direction (the width can be freely increased). A polarized light emitting element was obtained by drying at 70 ° C. for 9 minutes (in a state where it could behave).
  • Both sides of the obtained polarized light emitting element are treated with a triacetyl cellulose film (ZRD-60 manufactured by Fuji Film Co., Ltd.) containing no ultraviolet absorber with a thickness of 60 ⁇ m whose surface is saponified with a 1.5 specified aqueous solution of sodium hydroxide.
  • An aqueous solution of polyvinyl alcohol (an aqueous solution containing 4% NH-26 manufactured by Japan Vam & Poval) was laminated as an adhesive and dried at 70 ° C. for 9 minutes to obtain a polarized light emitting plate of the present invention.
  • Example 5 In Example 3, the film containing the compound of the above example (2-6) was set so that the length in the stretching direction was 4.5 cm, and was placed in a 3% 50 ° C. boric acid aqueous solution for 5 minutes. After stretching the film 5 times over, the film obtained by stretching was washed with water at room temperature for 25 seconds while maintaining a tense state, without fixing the length in the width direction (the width can be freely increased). A polarized light emitting element was obtained by drying at 70 ° C. for 9 minutes (in a state where it could behave).
  • Both sides of the obtained polarized light emitting element are treated with a triacetyl cellulose film (ZRD-60 manufactured by Fuji Film Co., Ltd.) containing no ultraviolet absorber with a thickness of 60 ⁇ m whose surface is saponified with a 1.5 specified aqueous solution of sodium hydroxide.
  • An aqueous solution of polyvinyl alcohol (an aqueous solution containing 4% NH-26 manufactured by Japan Vam & Poval) was laminated as an adhesive and dried at 70 ° C. for 9 minutes to obtain a polarized light emitting plate of the present invention.
  • Example 6 In Example 5, the film containing the compound of the above example (2-6) was set so that the length in the stretching direction was 13.3 cm, and was placed in a 3% 50 ° C. boric acid aqueous solution for 5 minutes. The film obtained by stretching the film was washed with water at room temperature for 20 seconds while maintaining a tense state, without fixing the length in the width direction (the width can be freely increased). A polarized light emitting element was obtained by drying at 70 ° C. for 9 minutes (in a state where it could behave).
  • Both sides of the obtained polarized light emitting element are treated with a triacetyl cellulose film (ZRD-60 manufactured by Fuji Film Co., Ltd.) containing no ultraviolet absorber with a thickness of 60 ⁇ m whose surface is saponified with a 1.5 specified aqueous solution of sodium hydroxide.
  • An aqueous solution of polyvinyl alcohol (an aqueous solution containing 4% NH-26 manufactured by Japan Vam & Poval) was laminated as an adhesive and dried at 70 ° C. for 9 minutes to obtain a polarized light emitting plate of the present invention.
  • Example 7 A polyvinyl alcohol film (VF-PS # 7500 manufactured by Kuraray Co., Ltd.) having a thickness of 75 ⁇ m and a width of 12.0 cm was immersed in water at 40 ° C. for 3 minutes to swell the film.
  • the film obtained by swelling contains 0.2 parts by mass of the compound of the above example (2-1) obtained in Synthesis Example 1, 1.0 part by mass of sardine, and 1000 parts by mass of water at 45 ° C.
  • the film was immersed in an aqueous solution for 4 minutes to contain the compound of the above example (2-1).
  • the film containing the compound of the above example (2-1) was set so that the length in the stretching direction was 13.3 cm, and the film was quintupled in a 1% 50 ° C. boric acid aqueous solution over 5 minutes. It was stretched. The film obtained by stretching was washed with water at room temperature for 20 seconds while maintaining a tense state to obtain a polarized light emitting device.
  • a triacetyl cellulose film (ZRD-manufactured by Fuji Film Co., Ltd.) containing no ultraviolet absorber with a thickness of 60 ⁇ m, in which both sides of the polarized light emitting element obtained by washing with water are saponified with a 1.5-specified aqueous solution of sodium hydroxide.
  • an aqueous polyvinyl alcohol solution (an aqueous solution containing 4% NH-26 manufactured by Japan Vam & Poval) was laminated as an adhesive and dried at 70 ° C. for 9 minutes to obtain a polarized light emitting plate of the present invention.
  • Example 8 In Example 7, the above example (2-1) was immersed in an aqueous solution at 45 ° C. containing 0.2 parts by mass of the compound, 1.0 part by mass of sardine, and 1000 parts by mass of water for 4 minutes. Instead of containing the compound of 2-1) in the film, it contains 0.8 parts by mass of the compound of the above example (2-1), 1.0 part by mass of sardine, and 1000 parts by mass of water at 45 ° C.
  • the polarized light emitting element and the polarized light emitting plate of the present invention were obtained in the same manner except that the compound of the above example (2-1) was contained in the film by immersing in an aqueous solution for 7 minutes.
  • Example 9 The polyvinyl alcohol film (VF-PS # 7500 manufactured by Kuraray Co., Ltd.) used in Example 7 is completely saponified (sakenization degree of polymerization 98 to 99%) and a polyvinyl alcohol resin having a degree of polymerization of 1700 (PVA-117 manufactured by Kuraray Co., Ltd.). ) was converted into an aqueous solution and cast into a 75 ⁇ m polyvinyl alcohol film, and the same was used to obtain the polarized light emitting element and the polarized light emitting plate of the present invention.
  • VF-PS # 7500 manufactured by Kuraray Co., Ltd. The polyvinyl alcohol film (VF-PS # 7500 manufactured by Kuraray Co., Ltd.) used in Example 7 is completely saponified (sakenization degree of polymerization 98 to 99%) and a polyvinyl alcohol resin having a degree of polymerization of 1700 (PVA-117 manufactured by Kuraray Co., Ltd.). ) was converted into
  • Example 10 The polyvinyl alcohol film (VF-PS # 7500 manufactured by Kuraray Co., Ltd.) used in Example 7 is cast into an aqueous solution using a polyvinyl alcohol resin (PVA-617 manufactured by Kuraray Co., Ltd.) having a saponification degree of 95% and a degree of polymerization of 1700.
  • the polarized light emitting element and the polarized light emitting plate of the present invention were obtained in the same manner except that the film was changed to the obtained polyvinyl alcohol film having a thickness of 75 ⁇ m.
  • Example 11 A polyvinyl alcohol film (VF-PS # 7500 manufactured by Kuraray Co., Ltd.) having a thickness of 75 ⁇ m and a width of 12.0 cm was immersed in water at 40 ° C. for 3 minutes to swell the film.
  • the film obtained by swelling contains 0.2 parts by mass of the compound of the above example (2-1) obtained in Synthesis Example 1, 1.0 part by mass of sardine, and 1000 parts by mass of water at 45 ° C.
  • the film was immersed in an aqueous solution for 4 minutes to contain the compound of the above example (2-1).
  • the film containing the compound of the above example (2-1) was set so that the length in the stretching direction was 13.3 cm, and 5 times over 5 minutes in a 3% 50 ° C.
  • Example 11 the polarized light emitting device and the polarized light emitting plate of the present invention were obtained in the same manner except that the compound of the above example (2-5) was used instead of the compound of the above example (2-1).
  • Example 11 the polarized light emitting device and the polarized light emitting plate of the present invention were obtained in the same manner except that the compound of the above example (2-7) was used instead of the compound of the above example (2-1).
  • Example 14 (Synthesis Example 5) 114.0 parts of the compound of the formula (18) was added to 800 parts of water and heated to 60 ° C., and 25% caustic soda was added to dissolve the compound. 20.2 parts of terephthalic acid dichloride was added little by little over about 1 hour. After adding all, the mixture was stirred at 60 ° C. for 1 hour. After completion of the reaction, the mixture was allowed to cool to room temperature, filtered, and dried at 70 ° C. to obtain 84.5 parts of the compound of the above example (2-3).
  • Example 11 the polarized light emitting device and the polarized light emitting plate of the present invention were obtained in the same manner except that the compound of the above example (2-3) was used instead of the compound of the above example (2-1).
  • Example 15 (Synthesis Example 6) 114.0 parts of the compound of the formula (19) was added to 800 parts of water and heated to 60 ° C., and 25% caustic soda was added to dissolve the compound. 20.2 parts of terephthalic acid dichloride was added little by little over about 1 hour. After adding all, the mixture was stirred at 60 ° C. for 1 hour. After completion of the reaction, the mixture was allowed to cool to room temperature, filtered, and dried at 70 ° C. to obtain 88.8 parts of the compound of the above example (2-4).
  • Example 11 the polarized light emitting device and the polarized light emitting plate of the present invention were obtained in the same manner except that the compound of the above example (2-4) was used instead of the compound of the above example (2-1).
  • Example 16 (Synthesis Example 7) 40 parts of 4-nitroaminostilbene-2,2'-disulfonic acid and 60.2 parts of the compound of the formula (20) were added to 500 parts of water and heated to 60 ° C., and 25% caustic soda was added to dissolve them. 20.2 parts of terephthalic acid dichloride was added little by little over about 1 hour. After adding all, the mixture was stirred at 60 ° C. for 1 hour. After completion of the reaction, the mixture was allowed to cool to room temperature, filtered, and dried at 70 ° C. to obtain 84.1 parts of the compound of the formula (21).
  • Example 11 the polarized light emitting device and the polarized light emitting plate of the present invention were obtained in the same manner except that the compound of the formula (21) was used instead of the compound of the above example (2-1).
  • Example 11 the polarized light emitting device and the polarized light emitting plate of the present invention were obtained in the same manner except that the compound of the formula (22) was used instead of the compound of the above example (2-1).
  • a polyvinyl alcohol resin (PVA-124 manufactured by Kuraray Co., Ltd.) having a degree of polymerization of 98 to 99% and a degree of polymerization of 2400 is made into an aqueous solution, and the compound of the above example (2-1) is added to 100 parts of PVA.
  • a vinyl alcohol film having a thickness of 75 ⁇ m and a width of 5 cm obtained by adding .55 parts and forming a cast film was fixed to a tensile tester so as to have a length of 2 cm in the stretching direction, and 4 in an environment of 150 ° C. In the same manner except that the film was stretched twice, a polarized light emitting element and a polarized light emitting plate of Comparative Example 1 containing no boric acid were obtained.
  • a polyvinyl alcohol resin (PVA-124 manufactured by Kuraray Co., Ltd.) having a degree of polymerization of 98 to 99% and a degree of polymerization of 2400 is made into an aqueous solution, and the compound of the above example (2-1) is added to 100 parts of PVA.
  • a vinyl alcohol film having a thickness of 75 ⁇ m and a width of 5 cm obtained by adding .55 parts and forming a cast film was fixed to a tensile tester so as to have a length of 2 cm in the stretching direction, and was 7 in an environment of 150 ° C. In the same manner except that the film was stretched twice, a polarized light emitting element and a polarized light emitting plate of Comparative Example 2 containing no boric acid were obtained.
  • Example 11 a film containing the compound of Compound Example (2-1) was stretched 5 times in a 0.5% aqueous boric acid solution at 50 ° C. over 5 minutes in the same manner as in Comparative Example. 3 polarized light emitting elements and polarized light emitting plates were obtained.
  • Example 4 In Example 1, instead of the polyvinyl alcohol film (VF-PS # 7500 manufactured by Kuraray Co., Ltd.), a polyvinyl alcohol resin having a partially saponified (sakenization degree of polymerization 87 to 89%) and a degree of polymerization of 2400 (PVA-made by Kuraray Co., Ltd.) A polarized light emitting element and a polarized light emitting plate of Comparative Example 4 were obtained in the same manner except that 224) was made into an aqueous solution and a vinyl alcohol film having a thickness of 75 ⁇ m obtained by casting a film was used.
  • VF-PS # 7500 manufactured by Kuraray Co., Ltd.
  • Example 5 In Example 1, in the stretching step of stretching 4 times in a 3% boric acid aqueous solution at 50 ° C. over 5 minutes, the boric acid concentration of the boric acid aqueous solution used was 2% and the stretching ratio was doubled. The polarized light emitting element and the polarized light emitting plate of Comparative Example 5 were obtained in the same manner except for the change to.
  • Orthogonal transmittance Tc (%) is a spectral transmittance measured by superimposing two measurement samples so that their absorption axes are orthogonal to each other. Measurements of each transmittance were performed over wavelengths of 220 to 780 nm.
  • Luminosity-corrected single transmittance Ys and luminosity-corrected polarization degree ⁇ y The single transmittance Ys (%) of each measurement sample is determined in the wavelength region of 380 to 780 nm in the visible region at predetermined wavelength intervals d ⁇ (here, 5 nm), and the single transmittance Ts is determined according to JIS Z 8722: 2009. It is the transmittance corrected to the visual sensitivity. Specifically, it was calculated by substituting the simple substance transmittance Ts into the equation (II).
  • the birefringence index of the polarized light emitting element or the polarized light emitting plate was measured using KOBRA-21ADH (manufactured by Oji Measuring Instruments Co., Ltd.). The phase difference value was measured by KOBRA-21ADH. The retardation value from the vertical direction (0 °) of the film plane and the retardation value when the film is tilted 50 ° with respect to the slow axis of the film are measured, and the film thickness of the polarizing light emitting element is used. The divided value was taken as the birefringence index of each angle.
  • a polarizing plate having polarized light in the visible region and the ultraviolet region (“SKN-18043P” manufactured by Polar Techno Co., Ltd., thickness 180 ⁇ m). , Ys is 43%) to obtain polarized light, and the light is incident on a polarized light emitting element or a polarized light emitting plate.
  • the polarized light emitted by the measurement sample was measured using a spectroscopic irradiance meter (“USR-40” manufactured by Usio Electric Co., Ltd.). That is, the light from the light source is arranged so as to pass through the ultraviolet transmission / visible light cut filter, the polarizing plate having polarization in the visible region and the ultraviolet region, and the measurement sample in this order and enter the spectroirradiance meter. Polarized light emission was measured. At that time, the absorption axis that maximizes the absorption of ultraviolet rays of the measurement sample and the absorption axis direction of the polarizing plate having polarization in the visible region and the ultraviolet region (“SKN-18043P” manufactured by Polar Techno Co., Ltd.) are parallel to each other.
  • the spectral emission amount of each wavelength measured by superimposition is defined as Lw (weak emission axis), and the absorption axis that maximizes the absorption of ultraviolet rays of the measurement sample and the polarizing plate having polarization in the visible region and the ultraviolet region (manufactured by Polar Techno Co., Ltd. Lw and Ls were measured with the spectral emission amount of each wavelength measured by superimposing them so as to be orthogonal to the absorption axis direction of SKN-18043P) as Ls (strong emission axis).
  • Table 1 shows the 0 ° double-reflectance ( ⁇ n (0 °)) and 50 ° double-reflectance ( ⁇ n (50 °)) of the measurement samples obtained in Examples 1 to 17 and Comparative Examples 1 to 5.
  • Ts,%) parallel transmittance
  • Tc,%) orthogonal transmittance
  • ⁇ ,%) degree of polarization
  • Rd dichroic ratio
  • the corrected single transmittance (Ys,%) and the degree of polarization corrected to the visual sensitivity ( ⁇ y,%) are shown.
  • Table 2 shows the birefringence of 0 ° ( ⁇ n (0 °)) and the birefringence of 50 ° ( ⁇ n (50 °)) of the measurement samples shown in Table 1 of Examples 1 to 17 and Comparative Examples 1 to 5.
  • Ls and Lw of each wavelength, and the degree of polarization ( ⁇ L,%) at the time of light emission thereof are shown.
  • the birefringence of 0 ° is in the range of 0.020 to 0.060, so that the medium is specific. It is shown that they are oriented in the axial direction, and the ratio of the birefringence of 0 ° to the birefringence of 50 ° ( ⁇ n ratio (0 ° / 50 °)) is 1.0 to 1.
  • the absorption wavelength is obtained by containing a boron compound having a specific concentration and having an angle dependence of a specific birefringence. It is possible to obtain a polarized light emitting element and a polarized light emitting plate that not only have a high degree of polarization but also exhibit a polarized light emitting action. Therefore, the polarized light emitting element and the polarized light emitting plate using the luminescent compound according to the present invention can function as a polarizing plate at an absorption wavelength and can be further applied as a self-luminous polarizing element capable of emitting polarized light.
  • the display device using the polarized light emitting element and the polarized light emitting plate according to the present invention has high transparency in the visible range and can display an image by polarized light emission for a long period of time. Therefore, it is transparent to a television, a personal computer, a tablet terminal, and further. It can be applied to a wide range of applications such as displays (see-through displays).
  • a polarized light emitting device or a polarized light emitting plate of a preferred embodiment made by using a stilbene compound can emit light by ultraviolet light, and therefore can be applied to a display or a medium that requires high security.

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  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Polarising Elements (AREA)

Abstract

La présente invention concerne un élément électroluminescent polarisé, comprenant un film qui est constitué d'une résine d'alcool polyvinylique ou d'un dérivé de celle-ci, la résine étant formée par adsorption et alignement d'au moins un type de composé électroluminescent qui peut émettre de la lumière à l'aide d'une lumière absorbée, l'élément électroluminescent polarisé étant caractérisé en ce que : de 5 à 30 % en masse d'un composé de bore est inclus ; et, la dépendance angulaire du taux de biréfringence du film est telle que la vitesse obtenue lorsque le film est incliné de 50° par rapport à l'axe lent du film est de 1,0 à 1,9 fois la vitesse à 0° lorsqu'elle est mesurée à partir d'une direction perpendiculaire au plan de film. Le composé de bore peut être de l'acide borique ou du borax. Le composé électroluminescent peut avoir une structure biphényle ou une structure stilbène. Un composé électroluminescent avec une structure stilbène présente une action de polarisation à des longueurs d'onde d'absorption de lumière, et la valeur de paramètre d'ordre (OPD) peut être de 0,75 à 1,00 à des longueurs d'onde auxquelles ladite action de polarisation est la plus grande.
PCT/JP2020/027151 2019-07-12 2020-07-10 Élément électroluminescent polarisé utilisant un composé émettant de la lumière ou un sel de celui-ci, plaque électroluminescente polarisée et dispositif d'affichage WO2021010351A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06347641A (ja) * 1993-06-07 1994-12-22 Kuraray Co Ltd 新規な偏光フィルム
JP2003240944A (ja) * 2002-02-14 2003-08-27 Nitto Denko Corp 偏光子の製造方法、偏光子、偏光板および画像表示装置
JP2008033275A (ja) * 2006-06-16 2008-02-14 Mitsubishi Chemicals Corp 異方性膜用材料
JP2017090903A (ja) * 2015-11-06 2017-05-25 日本化薬株式会社 無彩色な偏光素子、並びにこれを用いた無彩色偏光板および液晶表示装置
US20180355179A1 (en) * 2017-06-08 2018-12-13 Samsung Display Co. Ltd. Dye compound, composition comprising dye compound, and display device using dye compound
WO2019022211A1 (fr) * 2017-07-28 2019-01-31 日本化薬株式会社 Composé stilbène ou son sel, film polarisant, plaque polarisante et écran
WO2019022212A1 (fr) * 2017-07-28 2019-01-31 日本化薬株式会社 Élément d'émission de lumière polarisée, plaque d'émission de lumière polarisée, dispositif d'affichage et procédé de fabrication d'élément d'émission de lumière polarisée
JP2019056904A (ja) * 2017-09-20 2019-04-11 日本化薬株式会社 面状偏光発光素子
WO2019117131A1 (fr) * 2017-12-11 2019-06-20 日本化薬株式会社 Élément polarisant achromatique, et plaque polarisante achromatique et dispositif d'affichage l'utilisant

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06347641A (ja) * 1993-06-07 1994-12-22 Kuraray Co Ltd 新規な偏光フィルム
JP2003240944A (ja) * 2002-02-14 2003-08-27 Nitto Denko Corp 偏光子の製造方法、偏光子、偏光板および画像表示装置
JP2008033275A (ja) * 2006-06-16 2008-02-14 Mitsubishi Chemicals Corp 異方性膜用材料
JP2017090903A (ja) * 2015-11-06 2017-05-25 日本化薬株式会社 無彩色な偏光素子、並びにこれを用いた無彩色偏光板および液晶表示装置
US20180355179A1 (en) * 2017-06-08 2018-12-13 Samsung Display Co. Ltd. Dye compound, composition comprising dye compound, and display device using dye compound
WO2019022211A1 (fr) * 2017-07-28 2019-01-31 日本化薬株式会社 Composé stilbène ou son sel, film polarisant, plaque polarisante et écran
WO2019022212A1 (fr) * 2017-07-28 2019-01-31 日本化薬株式会社 Élément d'émission de lumière polarisée, plaque d'émission de lumière polarisée, dispositif d'affichage et procédé de fabrication d'élément d'émission de lumière polarisée
JP2019056904A (ja) * 2017-09-20 2019-04-11 日本化薬株式会社 面状偏光発光素子
WO2019117131A1 (fr) * 2017-12-11 2019-06-20 日本化薬株式会社 Élément polarisant achromatique, et plaque polarisante achromatique et dispositif d'affichage l'utilisant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YAMASHITA, YOSHIO: "Fluorescence and Photostability of Aqueous Solution of Asymmetricallysubstituted Derivatives of Sodium 4, 4'-diaminostilbene-2, 2'-disulfonate", JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY, vol. 30, no. 9, 12 February 1972 (1972-02-12), Japan, pages 818 - 822, XP009518576, DOI: 10.5059/yukigoseikyokaishi.30.818 *

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