WO2015122387A1 - Retardation plate, laminated polarizing plate using retardation plate, and display device using retardation plate - Google Patents
Retardation plate, laminated polarizing plate using retardation plate, and display device using retardation plate Download PDFInfo
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- WO2015122387A1 WO2015122387A1 PCT/JP2015/053538 JP2015053538W WO2015122387A1 WO 2015122387 A1 WO2015122387 A1 WO 2015122387A1 JP 2015053538 W JP2015053538 W JP 2015053538W WO 2015122387 A1 WO2015122387 A1 WO 2015122387A1
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- liquid crystal
- film
- retardation
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Images
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
- G02F1/133633—Birefringent elements, e.g. for optical compensation using mesogenic materials
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
- G02F1/133637—Birefringent elements, e.g. for optical compensation characterised by the wavelength dispersion
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
-
- 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
- G02F2202/00—Materials and properties
- G02F2202/04—Materials and properties dye
- G02F2202/043—Materials and properties dye pleochroic
Definitions
- the present invention relates to a retardation plate, a laminated polarizing plate using the retardation plate, and an image display device, a liquid crystal display device, an organic electroluminescence (EL) display device and the like using the retardation plate.
- a retardation plate a laminated polarizing plate using the retardation plate
- an image display device a liquid crystal display device, an organic electroluminescence (EL) display device and the like using the retardation plate.
- EL organic electroluminescence
- the phase difference plate is an optical element used to obtain polarized light (linearly polarized light, circularly polarized light, elliptically polarized light), and is used for color compensation and viewing angle improving films for liquid crystal display devices, linear polarizers and 1/4 wavelength.
- polarized light linearly polarized light, circularly polarized light, elliptically polarized light
- the phase difference plate is an optical element used to obtain polarized light (linearly polarized light, circularly polarized light, elliptically polarized light), and is used for color compensation and viewing angle improving films for liquid crystal display devices, linear polarizers and 1/4 wavelength.
- Retardation plates are thin films of inorganic materials (calcite, mica, quartz), films obtained by stretching polymer films with high intrinsic birefringence, and films in which a rod-shaped or disk-shaped liquid crystal composition is oriented and fixed in the liquid crystal state. Is used.
- a 1 ⁇ 4 wavelength plate having a retardation corresponding to 1 ⁇ 4 of a wavelength and a 1 ⁇ 2 wavelength plate having a retardation corresponding to 1 ⁇ 2 of a wavelength are typical.
- the quarter wavelength plate has an optical function of converting linearly polarized light into circularly polarized light.
- the half-wave plate has a function of converting the polarization vibration plane of linearly polarized light by 90 degrees.
- the retardation plate is usually designed so as to exhibit a necessary optical function with respect to light of a specific wavelength (monochromatic light).
- a specific wavelength monochromatic light
- the above-described color compensation film for liquid crystal display devices and organic EL displays are used.
- a quarter-wave plate used as an antireflection film for an apparatus has the function of converting linearly polarized light into circularly polarized light and circularly polarized light into linearly polarized light at a measurement wavelength ( ⁇ ) of 400 to 700 nm in the visible light region.
- ⁇ measurement wavelength
- FIG. 1 shows the chromatic dispersion characteristics of birefringence ( ⁇ n ( ⁇ )) at each wavelength in the visible light region normalized by setting the birefringence value ( ⁇ n (550 nm)) at a measurement wavelength of 550 nm to 1.
- ⁇ n ( ⁇ ) birefringence
- the birefringence of a polymer film becomes larger as the measurement wavelength becomes shorter and becomes smaller as the longer wavelength. That is, it has “positive dispersion” characteristics.
- Patent Documents 1 and 2 each disclose a retardation plate obtained by laminating two polymer films having optical anisotropy.
- the retardation plate described in Patent Document 1 includes a quarter-wave plate in which the phase difference of birefringent light is 1 ⁇ 4 wavelength, and a 1 ⁇ 2 wavelength plate in which the phase difference of birefringent light is 1 ⁇ 2 wavelength. , And pasted together with their optical axes crossed.
- the retardation plate described in Patent Document 2 at least two retardation plates having an optical retardation value of 160 to 320 nm are laminated so that their slow axes are not parallel or orthogonal to each other.
- a phase difference plate is disclosed. Specifically, the retardation plate described in any of the publications is composed of a laminate of two birefringent media.
- a quarter wavelength plate can be achieved in a wide wavelength region.
- the optical orientation of the polymer film generally corresponds to the longitudinal or lateral direction of the sheet or roll film. Industrial production of a polymer film having an optical axis or a slow axis in an oblique direction of a sheet or roll is difficult. And in invention of each gazette of patent document 1 and patent document 2, the optical direction of two polymer films is set to the angle which is neither parallel nor orthogonal.
- the cause of birefringence wavelength dispersion of an anisotropic rod-like molecule is the two refractive indices ne and no (ne is an “abnormal refractive index” in a direction parallel to the long molecular axis, and no is “Ordinary ray refractive index” in the direction perpendicular to the long molecular axis.
- FIG. 2 shows the relationship of the refractive index of the rod-like molecule 1 in the polymer film 2) varies at different speeds depending on the wavelength. As shown, due to the fact that ne changes more rapidly than no toward the shorter wavelength side of the visible wavelength spectrum.
- the functional group having a conjugated double bond is oriented in the major axis direction of the molecule, so the refractive index in the major axis direction (abnormal light refractive index ne) is in the visible light region. It has absorption in the near ultraviolet region and changes rapidly toward the short wavelength side of the visible wavelength spectrum, whereas the refractive index in the minor axis direction (ordinary ray refractive index) has a comparatively gentle curve. To do.
- Patent Document 4 discloses a retardation plate capable of arbitrarily controlling wavelength dispersion characteristics by mixing an additive that affects the wavelength dispersion characteristics of retardation with a polymer.
- Patent Document 5 discloses a retardation obtained by uniaxially stretching a mixture or copolymer film of at least two kinds of organic polymers composed of an organic polymer having positive birefringence and an organic polymer having negative birefringence.
- a retardation plate having a “negative dispersion” characteristic with a single film is disclosed.
- the retardation film described in Patent Document 5 will be described with a schematic diagram as shown in FIG. 5 and a birefringence wavelength dispersion characteristic graph as shown in FIG.
- an organic polymer having “positive birefringence” denoted by rod-like molecule 1 in FIG.
- the wavelength dispersion characteristic D2 of the birefringence ⁇ n2 of the organic polymer having “negative birefringence”, D2 ⁇ n2 (450) / ⁇ n2 ( 650) (where ⁇ n2 (450) and ⁇ n2 (650) are the birefringence of the polymer film at the measurement wavelengths of 450 nm and 650 nm, respectively), as shown in FIG.
- wavelength dispersion characteristic D2 of the organic polymer having “birefringence” is designed to be larger than the wavelength dispersion characteristic D1 of the organic polymer having “positive birefringence” (that is, D2> 1), as the mixture, a phase difference plate having a "positive birefringence” and "negative dispersion” characteristics.
- a retardation film formed by uniaxially stretching a copolymer film has a very small birefringence ⁇ n, and therefore it is necessary to increase the thickness to 50 to 200 ⁇ m in order to provide quarter-wave plate characteristics.
- a retardation layer used for a liquid crystal display device or an organic EL display device is required to be thinned, and a polymer stretched film having a small birefringence ⁇ n is desired to be improved from the viewpoint of film thickness.
- Patent Document 6 discloses a liquid crystal film made of a rod-like liquid crystal compound as a retardation plate which is a thin film and becomes larger as the measurement wavelength becomes longer.
- the retardation plate described in Patent Document 6 homogenously aligns a liquid crystal composition containing a compound having two or more kinds of mesogenic groups and a rod-like liquid crystal compound, and at least one kind of mesogen group is in the optical axis direction of the rod-like liquid crystal compound. , Making use of orientation in a substantially orthogonal direction.
- the rod-like liquid crystal compound has a relatively large birefringence ⁇ n compared to the copolymer resin, and therefore has a thickness of several ⁇ m, which is advantageous in terms of thinning the retardation plate.
- the technique of combining a compound composed of a positive birefringent material and a negative birefringent material having different birefringence wavelength dispersion characteristics described in Patent Document 5 and Patent Document 6 is a broadband with a measurement wavelength of 400 to 700 nm in the visible light region. In such a region, it is difficult to obtain a characteristic in which the phase difference becomes a quarter wavelength of the measurement wavelength. Generally, as shown in FIG. 7, the long wavelength side tends to deviate from the ideal straight line. This is because, as can be seen from the birefringence wavelength dispersion curve shown in FIG. 1, the slopes of the curve on the shorter wavelength side and the curve on the longer wavelength side than the center wavelength of visible light 550 nm are different.
- the circularly polarizing plate described above achieves a quarter wavelength plate in a wide wavelength region, so that near-ideal circularly polarized light can be obtained in light incident from the normal direction of the circularly polarizing plate.
- Patent Document 7 discloses a circularly polarizing plate in which a birefringent material of NZ ⁇ 0 is provided between a polarizer and a quarter wavelength plate.
- Patent Document 7 It represents the main refractive index in the thickness direction for light of 550 nm.
- the circularly polarizing plate described in Patent Document 7 compensates for the viewing angle dependency of the phase difference by providing a birefringent body with NZ ⁇ 0, and improves the viewing angle characteristics of the circularly polarizing plate. There are adverse effects such as cost increase and thickness increase by using a special material of 0.
- Patent Documents 8 and 9 disclose a circularly polarizing plate made of a liquid crystal film in which a polarizing plate and a nematic hybrid alignment structure having a phase difference of approximately a quarter wavelength are fixed.
- Japanese Patent Laid-Open No. 10-68816 Japanese Patent Laid-Open No. 10-90521 Japanese Patent Laid-Open No. 11-52131 JP 2000-314885 A JP 2002-48919 A JP 2002-267838 A JP 2005-326818 A JP 2002-31717 A JP 2000-321576 A
- the object of the present invention has been made in view of the above-described present situation, while minimizing a decrease in transmittance, a retardation plate having desired birefringence wavelength dispersion characteristics, a laminated polarizing plate using the retardation plate, And a wide viewing angle display device using a retardation plate.
- a retardation plate comprising a polymerizable liquid crystal composition and at least one dichroic dye, and comprising a liquid crystal film in which a liquid crystal compound is nematic hybrid aligned.
- a retardation film comprising a polymerizable liquid crystal composition and at least one dichroic dye, and comprising a liquid crystal film in which a liquid crystal compound is nematic hybrid aligned.
- Retardation in the normal direction of the retardation plate is ⁇ na ⁇ da
- Retardation in the normal direction of a retardation film composed of a liquid crystal film obtained by removing the dichroic dye from the liquid crystal film is ⁇ nb ⁇ db
- ⁇ na ⁇ da 580
- ⁇ na ⁇ da 580
- ⁇ nb ⁇ db 580
- ⁇ nb ⁇ db 0
- the retardation is represented by the product of birefringence ⁇ n and the thickness d of the retardation plate
- ⁇ na ⁇ da (580) and ⁇ na ⁇ da (580) are retardations of each retardation plate at a wavelength of 580 nm).
- ⁇ na ⁇ da (550) and ⁇ na ⁇ da (550) are retardations of each phase difference plate at a wavelength of 550 nm.
- the liquid crystal film has a twisted nematic hybrid alignment in a liquid crystal state of a mixture containing a polymerizable liquid crystal composition and at least one dichroic dye, and the alignment is fixed by a crosslinking reaction by light or heat.
- the retardation plate according to [3], wherein [6] The retardation ratio in the normal direction of the retardation plate at a specific wavelength is expressed by the following mathematical formulas (2) and (3): 0.80 ⁇ n ⁇ d (500) / ⁇ n ⁇ d (550) ⁇ 1.00 (1) 1.00 ⁇ n ⁇ d (600) / ⁇ n ⁇ d (550) ⁇ 1.15 (2) (Here, retardation is represented by the product of birefringence ⁇ n and the film thickness d of the retardation plate, and ⁇ n ⁇ d (500), ⁇ n ⁇ d (550), and ⁇ n ⁇ d (600) are respectively wavelengths.
- the polymerizable liquid crystal composition in the retardation plate having a “negative dispersion” characteristic in which the birefringence ⁇ n is increased as the measurement wavelength is longer in at least a part of the wavelength region of the visible light region, the polymerizable liquid crystal composition,
- a phase difference plate comprising a liquid crystal film comprising at least one kind of dichroic dye and having a liquid crystal compound nematic hybrid aligned.
- a retardation plate having such a liquid crystal alignment structure and birefringence wavelength dispersibility and having a phase difference of 1/4 wavelength at a measurement wavelength of 550 nm makes circularly polarized light linearly polarized in a wide wavelength region in the front and oblique directions.
- birefringence expresses a "negative dispersion" characteristic by the polymer film which consists of an organic polymer which has positive birefringence, and an organic polymer which has negative birefringence. It is a figure which shows the comparison with the phase difference plate which has a "negative dispersion
- FIG. 1 It is a figure of the emission spectrum when three colors of the organic electroluminescence display device are lit simultaneously and three colors are lit simultaneously to display white. It is a conceptual diagram of the orientation structure of a nematic hybrid liquid crystal film. It is a conceptual diagram for demonstrating the tilt angle and twist angle of a liquid crystal molecule. It is a figure which shows the wavelength dispersion characteristic of birefringence (DELTA) n of the liquid crystal film produced in Example 1, Example 2, Example 3, the comparative example 1, and the comparative example 3.
- DELTA birefringence
- FIG. It is a measurement result of the apparent retardation value measured by inclining the liquid crystal film produced in Example 1 along the alignment direction of a liquid crystal.
- FIG. 2 is a diagram illustrating a layer configuration of circularly polarizing plates manufactured in Example 1, Comparative Example 2, and Comparative Example 3.
- FIG. It is the figure which measured the viewing angle characteristic of the reflectance when it sees from all directions when the circularly-polarizing plate produced in Example 1 is mounted in an organic electroluminescence display.
- 6 is a diagram showing a layer structure of a circularly polarizing plate produced in Example 2.
- FIG. It is the figure which measured the viewing angle characteristic of the reflectance when it sees from all directions when the circularly-polarizing plate produced in Example 2 is mounted in an organic electroluminescence display. It is a measurement result of the apparent retardation value measured by inclining the liquid crystal film produced in Example 3 along the alignment direction of a liquid crystal.
- FIG. 6 is a diagram showing a layer structure of a circularly polarizing plate produced in Example 2.
- FIG. It is the figure which measured the viewing angle characteristic of the reflectance when it sees from all directions when the circularly-polarizing plate produced in Example 2 is mounted in an organic electroluminescence display.
- 4 is a diagram illustrating a layer configuration of a circularly polarizing plate manufactured in Example 3.
- FIG. It is the figure which measured the viewing angle characteristic of the reflectance when it sees from all directions when the circularly-polarizing plate produced in Example 3 is mounted in an organic electroluminescence display.
- 6 is a diagram showing a layer configuration of a circularly polarizing plate manufactured in Comparative Example 1.
- FIG. 1 It is the figure which measured the viewing angle characteristic of the reflectance when it sees from all directions when the circularly-polarizing plate produced in the comparative example 1 is mounted in an organic electroluminescence display. It is a figure which shows the wavelength dispersion characteristic of birefringence (DELTA) n of the liquid crystal film produced in the comparative example 1.
- FIG. 2 It is the figure which measured the viewing angle characteristic of the reflectance when it sees from all the directions when the circularly-polarizing plate produced in the comparative example 2 is mounted in an organic EL display apparatus.
- DELTA wavelength dispersion characteristic of birefringence
- the retardation plate of the present invention is a retardation plate having a “negative dispersion” characteristic in which the birefringence ⁇ n becomes larger as the measurement wavelength is longer in at least a part of the wavelength region of the visible light region. It comprises a liquid crystal film comprising a composition and at least one dichroic dye and having a liquid crystal compound nematic hybrid aligned.
- the refractive index wavelength dispersion characteristic of the organic polymer will be described with reference to FIG.
- n is a real part of N and is equal to what is usually called “refractive index”.
- k imaging part of N
- k ⁇ / (4 ⁇ ) as a function of wavelength ⁇ ( ⁇ ) and is related to the absorption coefficient.
- the refractive index n in a region away from the intrinsic absorption wavelength (regions a1, a2, and a3 in FIG. 8) monotonously decreases as the wavelength increases.
- the refractive index n in the wavelength region including intrinsic absorption regions b1, b2, and b3 in FIG. 8) increases rapidly as the wavelength increases.
- Such dispersion is called “anomalous dispersion”.
- “normal dispersion” is expressed as “positive dispersion” and “abnormal dispersion” is expressed as “negative dispersion”.
- the curves of the extraordinary ray refractive index ne and the ordinary ray refractive index no both have a “positive dispersion” characteristic in the visible light region. Therefore, the prior art proposed as a method for obtaining the “negative dispersion” characteristic in which the birefringence increases as the wavelength increases, and the organic polymer having the “positive birefringence” and the organic high-power having the “negative birefringence”. Both the molecular copolymer and the mixture are made of a material having an extraordinary ray refractive index ne and an ordinary ray refractive index no having “positive dispersion” characteristics.
- the design philosophy is fundamental in that the extraordinary ray refractive index ne has a “negative dispersion” characteristic and, accordingly, the birefringence ⁇ n becomes a phase difference plate having a “negative dispersion” characteristic in the visible light region. Different.
- the retardation plate of the present invention is a retardation plate in which birefringence ⁇ n has a “negative dispersion” characteristic in at least a part of the wavelength region of the visible light region.
- a method for designing birefringence ⁇ n having “negative dispersion” characteristics, which is a feature of the retardation plate of the present invention, will be described. It is formed by uniaxially stretching a mixture or copolymer film of at least two kinds of organic polymers composed of an organic polymer having positive birefringence and an organic polymer having negative birefringence exemplified in Patent Document 5 described above.
- FIG. 9 shows an enlarged view of the “abnormal dispersion region” curve in FIG.
- the contribution of anomalous dispersion is approximately zero at the maximum absorption value in the “abnormal dispersion region”, and the local maximum value of the refractive index is the absorption wavelength of the long wavelength side. It appears just before the half-wave peak value, and the local minimum value of the refractive index appears just after the half-wave peak value on the short wavelength side.
- These positions are shown in FIG. 9 as ⁇ max, ⁇ +, and ⁇ . That is, there is a so-called “negative dispersion” characteristic in which the refractive index increases as the wavelength increases from ⁇ to ⁇ +.
- the design concept of the present invention will be described with reference to FIGS.
- the type of dipole differs depending on the axial direction.
- the rate no indicates a different “positive dispersion” curve.
- this organic polymer by adding a dye having high dichroism having an absorption spectrum having a maximum absorption wavelength at 580 nm as shown in FIG. 11, in the wavelength region of 550 to 650 nm that is near the absorption wavelength, A retardation plate having the characteristic that the light refractive index ne is “negative dispersion” is obtained.
- FIG. 12 shows the birefringence wavelength dispersion characteristics of a retardation plate composed of an organic polymer before and after the addition of the dichroic dye.
- a functional dye By adding a functional dye, a long wavelength region can be improved, and a film having a “negative dispersion” characteristic in which birefringence is closer to ideal in the entire wavelength region of visible light, which is also an object of the present invention, can be obtained.
- the retardation plate of the present invention has a “negative dispersion” characteristic in which the extraordinary ray refractive index ne becomes larger as the measurement wavelength is longer in at least a part of the wavelength region of the visible light region.
- the retardation plate In the visible light region, the retardation plate has a “negative dispersion” characteristic that increases as the measurement wavelength increases.
- the visible light region generally represents a region of 380 nm to 780 nm, but the region where the refractive index ne exhibits “negative dispersion” characteristics is preferably a region including a visible light center wavelength of around 550 nm. This is because the sensitivity of brightness perceived by human eyes for each wavelength (hereinafter referred to as specific visual sensitivity) is maximum near 555 nm, and maximum near 507 nm in dark places.
- ne is preferably as long as possible over the entire wavelength of visible light. However, as described later, it is necessary to increase the addition amount of the dye material, which is not preferable in terms of coloring of the retardation plate. In consideration of human specific visibility characteristics, if a “negative dispersion” characteristic can be obtained within a wavelength range of 550 to 600 nm, a sufficiently desired characteristic can be obtained.
- the retardation plate of the present invention is a retardation plate characterized in that the birefringence ⁇ n has a “negative dispersion” characteristic that increases as the measurement wavelength increases in the visible light region.
- the retardation ratio at a predetermined wavelength in the normal direction of the retardation film made of a liquid crystal film containing a dichroic dye is the normal direction of the retardation film made of a liquid crystal film containing no dichroic dye.
- the retardation at a predetermined wavelength in the normal direction of the retardation plate made of a liquid crystal film containing a dichroic dye is ⁇ na ⁇ da, and the liquid crystal film is obtained by removing the dichroic dye from the liquid crystal film.
- the retardation plate is a retardation plate characterized in that the birefringence ⁇ n has a “negative dispersion” characteristic that increases in the visible light region as the measurement wavelength is longer. More specifically, when the retardation of the liquid crystal film at 500 nm, 550 nm, and 600 nm is ⁇ n ⁇ d (500), ⁇ n ⁇ d (550), and ⁇ n ⁇ d (600), the following formulas (2) and (3 ): 0.80 ⁇ n ⁇ d (500) / ⁇ n ⁇ d (550) ⁇ 1.00 (2) and 1.00 ⁇ n ⁇ d (600) / ⁇ n ⁇ d (550) ⁇ 1.15 (3) Preferably there is.
- the retardation is represented by the product ( ⁇ n ⁇ d) of birefringence ⁇ n and the thickness d of the retardation plate. More preferably 0.90 ⁇ n ⁇ d (500) / ⁇ n ⁇ d (550) ⁇ 0.98 (2-1) And 1.02 ⁇ n ⁇ d (600) / ⁇ n ⁇ d (550) ⁇ 1.10 (3-1) It is. Within the range of these values, for example, in the case of using as a quarter wave plate, when linearly polarized light of 400 to 700 nm is incident on this film, the polarization state is completely circularly polarized.
- the phase difference plate may be required to have a specific phase difference value as well as a film thickness depending on its application.
- the retardation value ( ⁇ n ⁇ d) of the retardation plate is preferably 20 nm to 500 nm (more preferably 50 nm to 300 nm).
- the retardation value ( ⁇ n ⁇ d) referred to here is an in-plane apparent retardation value with respect to light having a wavelength of 550 nm when viewed from the normal direction of the liquid crystal film.
- the retardation value is given as the product of the birefringence and the absolute film thickness.
- an apparatus capable of measuring birefringence for example, trade name “Axoscan” manufactured by Axometrix, product name “KOBRA-21ADH” manufactured by Oji Scientific Instruments), etc. Values can be adopted.
- the liquid crystal film includes a polymerizable liquid crystal composition and at least one dichroic dye, and has an alignment structure in which a liquid crystal compound is nematic hybrid aligned.
- a liquid crystal film is a film obtained by aligning and fixing a liquid crystal compound in a liquid crystal state.
- the orientation of the liquid crystal film indicates a state in which the molecular chains of the liquid crystal compound are arranged in a specific direction, and this state can be measured by measuring the phase difference ( ⁇ n ⁇ d) of the liquid crystal film.
- the orientation refers to, for example, ⁇ n ⁇ d of 20 nm or more at a measurement wavelength of 550 nm.
- ⁇ n ⁇ d is the product of birefringence ⁇ n and film thickness d.
- FIG. 14 shows a cross-sectional structure of the liquid crystal film of the present invention having an alignment structure in which the liquid crystal compound is nematic hybrid aligned.
- the director of the polymerizable liquid crystal compound is oriented at different angles at all positions in the film thickness direction. Accordingly, the retardation plate of the present invention no longer has an optical axis when viewed as a film structure.
- FIG. 15 shows definitions of the tilt angle and twist angle of the liquid crystal molecules.
- the tilt direction (axis) of the liquid crystal film refers to a liquid crystal molecule director and a projection component onto the c plane of the director when the c plane is viewed from the b plane through the liquid crystal film as shown in FIG.
- a direction in which the angle is an acute angle and parallel to the projection component is defined as a tilt direction (axis).
- the angle formed by the director of the liquid crystal molecules and the film plane in the vicinity of one film interface of the liquid crystal film is usually 20 to 90 degrees, preferably 30 degrees as an absolute value. In the vicinity of the film interface opposite to the film surface, the angle is usually 0 to 50 degrees as an absolute value, preferably 0 to 30 degrees.
- the average tilt angle in the alignment structure is usually 5 to 45 degrees as an absolute value, preferably 10 to 40 degrees, and most preferably 15 to 35 degrees. If the average tilt angle is within the above numerical range, the reflective viewing angle characteristics can be improved when the liquid crystal display device or the organic EL display device is provided in combination with a polarizing plate.
- the average tilt angle means the average value of the angle formed by the director of the liquid crystal molecules and the film plane in the film thickness direction of the liquid crystal film.
- the retardation plate of the present invention may be a liquid crystal film in which a twisted nematic hybrid alignment structure is fixed.
- a liquid crystal film in which twisted nematic hybrid alignment is fixed has a structure in which a director of liquid crystal molecules twists an optically anisotropic axis from one surface to the other surface. Therefore, this retardation plate has characteristics equivalent to those obtained by stacking optically anisotropic layers in multiple layers so that the optical anisotropic axis is continuously twisted, and is a normal TN (twisted nematic).
- the liquid crystal film with a fixed twisted nematic hybrid alignment structure is different in the film thickness direction, while the director of the liquid crystal molecules is twisted in the in-plane direction from one side to the other side of the liquid crystal molecule. It is a film inclined at an angle.
- the twist angle in the orientation structure is usually 0 to 70 degrees as an absolute value, preferably 0 to 60 degrees, and most preferably 0 to 59 degrees.
- twist angle deviates more than 70 degrees, such as contrast and antireflection performance when the liquid crystal display device or organic EL display device is combined with a polarizing plate, the display characteristics when viewed from the front, etc. There is a fear.
- the twist angle may be either the right twist or the left twist.
- Such retardation value, twist angle, and tilt angle can be measured by a device capable of measuring birefringence (for example, trade name “Axoscan” manufactured by Axometrix, trade name “KOBRA-21ADH” manufactured by Oji Scientific Instruments), etc. ) Can be calculated from the value measured using birefringence (for example, trade name “Axoscan” manufactured by Axometrix, trade name “KOBRA-21ADH” manufactured by Oji Scientific Instruments), etc. ) Can be calculated from the value measured using birefringence
- a dichroic dye refers to a dye having the property that the absorbance in the major axis direction of a molecule is different from the absorbance in the minor axis direction.
- the dichroic dye is not particularly limited as long as it has such properties, and may be a dye or a pigment. A plurality of these dyes may be used, a plurality of pigments may be used, or a dye and a pigment may be combined. Furthermore, such a dichroic dye may have a polymerizable functional group and may have liquid crystallinity.
- an acrylic group, a methacryl group, a vinyl group, a vinyloxy group, an epoxy group, and an oxetanyl group are preferable, and an acrylic group, an epoxy group, and an oxetanyl group are particularly preferable from the viewpoint of reactivity.
- the liquid crystallinity those having a nematic phase and a smectic phase are preferable.
- the dichroic dye preferably has a maximum absorption wavelength ( ⁇ max) in the range of 380 to 780 nm, more preferably 400 to 750 nm, still more preferably 450 to 700 nm, and most preferably 540 to 620 nm.
- FIG. 13 shows the emission spectrum of the organic electroluminescence display device in three colors of red, blue and green and the emission spectrum when the three colors are turned on simultaneously to display white.
- blue has an emission spectrum having a maximum value at about 460 nm, green at 530 nm, and red at 630 nm.
- absorption by the dichroic dye is inevitable, but in order to minimize the decrease in transmittance due to this absorption, It is preferable to select a dichroic dye having a maximum absorption at a wavelength deviating from the maximum wavelength of the emission spectrum. For example, a dichroic dye having a maximum absorption wavelength near 580 nm as shown in FIG.
- FIG. 11 shows the emission spectrum of the organic electroluminescence display device, but the same applies to other image display devices.
- the decrease in transmittance is reduced by setting the wavelength outside the maximum value of the emission spectrum of the LED using the maximum absorption wavelength of the dichroic dye.
- the difference between the maximum absorption wavelength of the dichroic dye and the maximum wavelength of the emission spectrum of the image display device is 5 nm or more, preferably 10 nm or more, more preferably 20 nm or more. If it is 5 nm or more, the transmittance
- the dichroic ratio of the dichroic dye is defined by the ratio of the absorbance at the maximum absorption wavelength in the major axis direction of the dye molecule to the absorbance in the minor axis direction. It can be determined by measuring the absorbance in the orientation direction of the dye and the absorbance in the direction perpendicular to the orientation direction.
- the dichroic dye that can be used in the present invention has a dichroic ratio of preferably 2 or more and 50 or less, more preferably 5 or more and 30 or less. Such dichroic dyes are not particularly limited.
- acridine dyes for example, acridine dyes, azine dyes, azomethine dyes, oxazine dyes, cyanine dyes, merocyanine dyes, squarylium dyes, naphthalene dyes, azo dyes, anthraquinone dyes, benzotriazole dyes Benzophenone dye, pyrazoline dye, diphenyl polyene dye, binaphthyl polyene dye, stilbene dye, benzothiazole dye, thienothiazole dye, benzimidazole dye, coumarin dye, nitrodiphenylamine dye, polymethine dye, naphthoquinone dye, perylene dye, quinophthalone dye, stilbene dye Examples thereof include dyes and indigo dyes.
- the dichroic dye is preferably an anthraquinone dye or an azo dye.
- the azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbene azo dyes, and preferred examples include bisazo dyes, trisazo dyes, and derivatives of these series of dyes. Any dye that satisfies the above conditions can be used in the present invention.
- An example of a dye that can be used in the present invention is represented by a dye number described in a dye handbook (Shin Okawara, Shinjiro Kitao, Tsuneaki Hirashima, Ken Matsuoka, Kodansha Scientific Co., Ltd .: 1986, 1st edition). It is shown in 1.
- the dichroic dye is particularly preferably one represented by the following formula (1) (hereinafter sometimes referred to as “azo dye (1)”).
- n is an integer of 1 to 4.
- Ar 1 and Ar 3 are each independently selected from the groups shown below.
- Ar 2 is selected from the following groups, and when n in the formula (1) is 2 or more, Ar 2 may be the same as or different from each other.
- a 1 and A 2 are each independently selected from the groups shown below. (M is an integer of 0 to 10, and when there are two m's in the same group, these two m's may be the same or different from each other.)
- the positional isomerism of the azobenzene moiety of the azo dye (1) is preferably trans.
- Examples of the azo dye (1) include compounds represented by formulas (1-1) to (1-58).
- anthraquinone dye a compound represented by the formula (1-59) is preferable.
- R 1 to R 8 each independently represent a hydrogen atom, —Rx, —NH 2 , —NHRx, —NRx 2 , —SRx, —OH, or a halogen atom.
- Rx represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.
- acridine dye a compound represented by the formula (1-60) is preferable.
- R 16 to R 23 each independently represent a hydrogen atom, —Rx, —NH 2 , —NHRx, —NRx 2 , —SRx, or a halogen atom.
- Rx represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.
- a compound represented by the formula (1-61) is preferable.
- R 9 to R 15 each independently represent a hydrogen atom, —Rx, —NH 2 , —NHRx, —NRx 2 , —SRx, —OH, or a halogen atom.
- Rx represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.
- the alkyl group having 1 to 6 carbon atoms of Rx is a methyl group, an ethyl group, a propyl group, a butyl group, or pentyl.
- aryl groups having 6 to 12 carbon atoms include phenyl, toluyl, xylyl, and naphthyl groups.
- cyanine dye a compound represented by the formula (1-62) and a compound represented by the formula (1-63) are preferable.
- D 1 and D 2 each independently represent a group represented by any of the following formulas (1-62a) to (1-62d), and n5 represents 1 to 3 Represents an integer.
- D 3 and D 4 each independently represent a group represented by any of formulas (1-63a) to (1-63h), and n6 is an integer of 1 to 3 Represents.
- the dichroic dye which the said retardation plate contains is an azo dye (1).
- the dichroic dye which this composition for partial retardation plates contains is an azo dye (1).
- at least two kinds of azo dyes (1) having different maximum absorption wavelengths may be contained.
- the content of the dichroic dye in the retardation plate can be adjusted as appropriate according to the type of the dichroic dye, and is, for example, 0.1 part by weight or more and 50 parts by weight with respect to 100 parts by weight of the liquid crystal composition. Parts by weight or less, preferably 0.1 parts by weight or more and 20 parts by weight or less, more preferably 0.1 parts by weight or more and 10 parts by weight or less. When the content of the dichroic dye is within this range, the liquid crystal composition can be formed or polymerized without disturbing the alignment of the liquid crystal compound. If content of a dichroic dye is 50 mass parts or less, the fall of the transmittance
- the content of the dichroic dye is 0.1 parts by mass or more, the refractive index can be controlled and sufficient optical characteristics can be obtained. Therefore, the content of the dichroic dye can be determined within a range in which the liquid crystal compound can maintain the alignment.
- content of a dichroic dye is content of the sum total of the used dichroic dye.
- the polymerizable liquid crystal composition used in the present invention will be described.
- a polymerizable liquid crystal compound is not particularly limited as long as it is a liquid crystalline compound capable of fixing the alignment state by polymerization.
- the polymerizable liquid crystal composition in the present invention includes a liquid crystal compound having one or more polymerizable groups (polymerizable liquid crystal compound), a liquid crystal compound having no polymerizable group, and a polymerizable compound not exhibiting liquid crystallinity.
- a known polymerizable liquid crystal compound can be appropriately used.
- a polymerizable liquid crystal compound it is preferable to use a polymerizable liquid crystal compound that can be nematic hybrid aligned on a substrate to fix the alignment state.
- a polymerizable liquid crystal compound for example, a low molecular weight polymerizable liquid crystal compound (a liquid crystalline monomer having a polymerizable group), a high molecular weight polymerizable liquid crystal compound (a liquid crystalline polymer having a polymerizable group), And mixtures thereof can be used as appropriate.
- a liquid crystal compound having a polymerizable group that reacts with light and / or heat is preferable from the viewpoint that the alignment state can be more efficiently fixed.
- a liquid crystal compound having a polymerizable group that reacts with light or heat can be polymerized with components (liquid crystal compound, etc.) present around it by light and / or heat to fix the alignment.
- the kind is not specifically limited, A liquid crystal compound provided with a well-known polymeric group can be utilized suitably.
- Such a polymerizable group is preferably a vinyl group, a (meth) acryloyl group, a vinyloxy group, an oxiranyl group, an oxetanyl group, an aziridinyl group, or the like.
- other polymerizable groups such as an isocyanate group, a hydroxyl group, an amino group, an acid anhydride group, and a carboxyl group may be used depending on the reaction conditions.
- a liquid crystal compound having a (meth) acryloyl group as a polymerizable group is preferable from the viewpoint of availability, heat resistance, and handleability, and a (meth) acrylate liquid crystal compound ( It is more preferable to use (a liquid crystal compound having a (meth) acrylate group).
- “methacryloyl” and “acryloyl” are sometimes collectively referred to as “(meth) acryloyl”
- “methacrylate” and “acrylate” are sometimes collectively referred to as “( “Meth) acrylate”
- “methacryl” and “acryl” are collectively referred to as “(meth) acryl”.
- the “(meth) acrylate group” refers to a residue ((meth) acryloyloxy group) in which hydrogen is eliminated from the carboxyl group of (meth) acrylic acid.
- W independently represents any one of H and CH 3 .
- n is an integer of 1 to 20 (more preferably 2 to 12, more preferably 3 to 6). If such a value of n is within the above numerical range, the temperature range in which the compound exhibits liquid crystallinity is widened, and the fluidity of the compound derived from the liquid crystal necessary for realizing good nematic hybrid alignment is achieved. As a result, good nematic hybrid alignment can be realized.
- R a is any group selected from an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms.
- Such an alkyl group having 1 to 20 carbon atoms that can be selected as Ra is preferably one having 1 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. If the number of carbon atoms is within the above numerical range, the liquid crystal-derived fluidity necessary to achieve good nematic hybrid alignment is maintained, and as a result, good nematic hybrid alignment can be realized. In addition, the temperature range in which the compound exhibits liquid crystallinity tends to be widened.
- Such an alkyl group may be linear, branched, or cyclic, and is not particularly limited, but it can realize a good nematic hybrid orientation. From a viewpoint, it is more preferable that it is a linear thing.
- the alkoxy group having 1 to 20 carbon atoms that can be selected as Ra is preferably one having 1 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. If such a carbon number is within the above numerical range, the liquidity derived from the liquid crystal of the compound necessary for realizing good nematic hybrid alignment is maintained, and as a result, good nematic hybrid alignment can be realized.
- the temperature range in which the compound exhibits liquid crystallinity tends to be widened.
- the alkoxy group has a structure in which an alkyl group is bonded to an oxygen atom.
- the structure of the alkyl group portion may be linear, branched, or cyclic. Although it may be sufficient and it does not restrict
- Z 1 and Z 2 are each independently any group of —COO— and —OCO—. Such Z 1 and Z 2 are groups in which one of Z 1 and Z 2 is represented by —COO—, and the other group is — A group represented by OCO- is preferred.
- X 1 and X 2 each independently represent any of H and an alkyl group having 1 to 7 carbon atoms.
- the alkyl group having 1 to 7 carbon atoms which can be selected as X 1 and X 2 is more preferably 1 to 3 carbon atoms (the alkyl group is CH 3 ). Is more preferable. If the number of carbon atoms is within the above numerical range, a good nematic hybrid orientation can be realized.
- X 1 and X 2 are each independently one of H and CH 3 .
- examples of the (meth) acrylate liquid crystal compounds represented by the general formulas (10) to (12) include compounds described in the following general formulas (110) to (113). Such (meth) acrylate liquid crystal compounds may be used singly or in combination of two or more.
- the polymerizable liquid crystal compound it is preferable to use a combination of the compounds represented by the general formulas (10) to (12), and a combination of the compounds represented by the general formulas (110) to (113). It is more preferable to use it.
- the content of the compound represented by the general formula (10) It is preferably 20 to 60% by weight, more preferably 30 to 45% by weight, based on the total amount of the compounds represented by formulas (10) to (12).
- the content of the compound represented by the general formula (10) is within the above numerical range, it is possible to suppress the occurrence of alignment defects with respect to nematic hybrid alignment.
- the content of the compound represented by the general formula (11) is represented by the general formulas (10) to (12).
- the amount is preferably 10 to 50% by weight, more preferably 20 to 30% by weight, based on the total amount of the compounds represented. If the content of the compound represented by the general formula (11) is within the above numerical range, it is possible to suppress the occurrence of alignment defects with respect to nematic hybrid alignment.
- the content of the compound represented by the general formula (12) is represented by the general formulas (10) to (12). It is preferably 10 to 70% by weight, more preferably 25 to 45% by weight, based on the total amount of the compounds represented. If the content of the compound represented by the general formula (12) is within the above numerical range, it is possible to suppress the occurrence of alignment defects with respect to nematic hybrid alignment.
- the weight ratio of each compound is ([[ Compound represented by the above general formula (110)]: [Compound represented by the above general formula (111)]: [Compound represented by the above general formula (112)]: [Compound represented by the above general formula (113)] ) Is preferably 45: 40: 15: 0 to 35: 5: 30: 30, more preferably 35: 23: 23: 19 to 38: 25: 25: 12.
- the method for producing such a polymerizable liquid crystal compound is not particularly limited, and a known method can be appropriately used.
- a compound represented by the general formula (110) For example, the method described in British Patent Application Publication No. 2,280,445 may be adopted.
- the compound represented by the above general formula (111) for example, D.I. J. et al.
- the method described in pages 3201 to 3215 of “Makromol. Chem. (Vol. 190, published in 1989)” by Broer et al. May be employed and is represented by the above general formulas (112) to (113).
- a method described in International Publication No. 93/22397 may be employed.
- the polymerizable liquid crystal compound can be produced by appropriately using a known method according to the type of the compound to be used. Moreover, you may utilize a commercial item as such a polymeric liquid crystal compound. Further, such polymerizable liquid crystal compounds may be used singly or in combination of two or more.
- the phase difference ⁇ n ⁇ d is expressed by the following mathematical formulas (2) and (3): 0.80 ⁇ n ⁇ d (500) / ⁇ n ⁇ d (550) ⁇ 1.00 (1) 1.00 ⁇ n ⁇ d (600) / ⁇ n ⁇ d (550) ⁇ 1.15 (2) It is preferable to satisfy.
- the polymerizable liquid crystal compound is a compound having two or more kinds of mesogenic groups, and at least one of them.
- the mesogenic group By aligning the mesogenic group in a direction substantially orthogonal to the slow axis of the homogeneous alignment of the liquid crystal layer, the longer the wavelength, the greater the phase difference, as disclosed in JP-A-2002-267838 and JP-A-2010-31223. It is described in the gazette.
- at least one mesogen group of a liquid crystal compound having two or more kinds of mesogenic groups is aligned in a direction substantially orthogonal to the optical axis direction of the rod-shaped liquid crystal compound, whereby the liquid crystal film contains a polymerizable dichroic dye. Even when not added, it has negative dispersion characteristics.
- liquid crystal phase liquid crystal phase
- the mesogenic group in the rod-like liquid crystal compound is described in various documents (for example, Flussige Kristalle in Tabellen, VEB Deutscher Verlag fur Grundstoffindustrie, Leipzig (1984), Volume 2).
- mesogenic groups include biphenyl, phenylcyclohexyl, cyclohexylphenyl, phenyloxycarbonylphenyl, phenylcarbonyloxyphenyl, phenyloxycarbonylcyclohexyl, cyclohexylcarbonyloxyphenyl, phenylcarbonyloxyphenyloxycarbonylphenyl, phenylcarbonyloxyphenyloxycarbonylphenyl , Phenylcarbonyloxycyclohexyloxycarbonylphenyl, phenyloxycarbonylcyclohexylcarbonyloxyphenyl, phenylcarbonyloxyphenylaminocarbonylphenyl, phenylethenylenephenyl, phenylethynylenephenyl, phenylethynylenephenylethynylenephenyl, phenylethenylenecarbonyloxy Include biphenyl and pheny
- the mesogenic group (the benzene ring or the cyclohexane ring constituting the mesogenic group) may have a substituent.
- the substituent the polymerizable group described above or a derivative thereof is preferable.
- one mesogenic group is biphenyl, phenylcyclohexyl, cyclohexylphenyl, phenyloxycarbonylphenyl, phenylcarbonyloxyphenyl, phenyloxycarbonylcyclohexyl, cyclohexylcarbonyloxyphenyl, phenylcarbonyloxyphenyloxycarbonyl.
- phenyl Selected from the group consisting of phenyl, phenylcarbonyloxyphenyloxycarbonylphenyl, phenylcarbonyloxycyclohexyloxycarbonylphenyl, phenyloxycarbonylcyclohexylcarbonyloxyphenyl and phenylcarbonyloxyphenylaminocarbonylphenyl
- the other mesogenic group is phenylethenylenephenyl Phenylethynylenepheny , Phenyl ethynylene phenyl ethynylene phenyl, particularly preferably selected from the group consisting of phenyl et tennis alkylene carbonyloxy biphenyl and phenyl et tennis alkyleneoxy phenyl ethynylenes phenyl.
- a compound having two or more kinds of mesogenic groups can be synthesized by applying a general synthesis method. For example, 1) a sequential introduction method in which one of two or more kinds of mesogenic groups is first introduced by functional group conversion of the starting material, and then another mesogenic group is continuously introduced by functional group conversion; 2) starting material It is possible to adopt a simultaneous introduction method in which two or more kinds of mesogenic groups are simultaneously introduced by the functional group conversion of 3), or a combined method of 3) sequential introduction method and simultaneous introduction method.
- a method for producing a compound having two or more kinds of mesogenic groups is not particularly limited, and a known method can be appropriately used. For example, a method described in JP-A-2002-267838 May be adopted.
- the polymerizable liquid crystal compound can be produced by appropriately using a known method according to the type of the compound to be used.
- Other methods include: Japanese translations of PCT publication No. 2010-522892, Japanese translation No. 2010-522893, Japanese publication No. 2010-537954, Japanese publication No. 2010-535955, Japanese publication No. 2010-540472, Japanese translation table 2012- No. 532155, JP 2013-509458, JP 2007-2208, JP 2007-2209, JP 2007-2210, JP 2009-173893, JP 2010-30979.
- Specific examples of the compound having two or more kinds of mesogenic groups include the following compounds.
- a chiral agent is added to the liquid crystal composition, or a liquid crystal compound or a non-liquid crystal compound having at least one chiral structural unit is added to the liquid crystal composition. It is particularly desirable to blend.
- the chiral structural unit include optically active 2-methyl-1,4-butanediol, 2,4-pentanediol, 1,2-propanediol, 2-chloro-1,4-butanediol, and 2-fluoro.
- the diols may be either R-form or S-form, and may be a mixture of R-form and S-form.
- polymerizable liquid crystal compound a commercially available product may be used as the polymerizable liquid crystal compound.
- polymerizable liquid crystal compounds may be used alone or in a mixture of two or more.
- a mixture should just show liquid crystallinity.
- a compound having two or more kinds of mesogenic groups may have a liquid crystallinity with a mixture with another liquid crystal compound even if the compound itself does not exhibit liquid crystallinity.
- a mixture of two or more polymerizable liquid crystal compounds it is not necessary that all the liquid crystal compounds have a polymerizable functional group, and at least one liquid crystal compound has a polymerizable functional group. That's fine.
- the polymerizable liquid crystal composition may use a mixture of a liquid crystal compound having a polymerizable group and another polymerizable compound that does not exhibit liquid crystallinity.
- Such other polymerizable compounds are not particularly limited as long as they have compatibility with a liquid crystal compound having a polymerizable group and do not cause significant alignment inhibition when the liquid crystal compound is aligned.
- a known polymerizable compound polymerizable monomer
- a suitable monomer may be selected from known polymerizable monomers according to the design of the target liquid crystal composition.
- Examples of such other polymerizable monomers include compounds having a polymerizable functional group such as an ethylenically unsaturated group (for example, vinyl group, vinyloxy group, (meth) acryloyl group).
- the amount of such other polymerizable monomer added is 0.5 to 50 parts by weight based on 100 parts by weight of the total amount of the liquid crystal compound having a polymerizable group and the other polymerizable monomer not exhibiting liquid crystallinity.
- the amount is preferably 1 to 30 parts by weight.
- the number of polymerizable functional groups of such a polymerizable monomer is preferably 2 or more from the viewpoint of sufficiently increasing the polymerization rate and imparting sufficient heat resistance to the obtained liquid crystal film. .
- the method for producing such a polymerizable monomer is not particularly limited, and a known method can be appropriately used. Moreover, you may utilize a commercial item as such a polymerizable monomer. Even a discotic liquid crystal compound can be used without any problem.
- the liquid crystal polymer those showing optically positive or negative uniaxiality are usually used. These optical characteristics are appropriately selected depending on the function required for the optical anisotropic element, but in the case of a liquid crystal polymer layer with twisted nematic hybrid alignment, a liquid crystal polymer exhibiting positive uniaxiality is preferably used.
- the polymerization initiator for polymerizing the polymerizable liquid crystal composition and the dichroic dye as described above is not particularly limited, and a known polymerization initiator can be appropriately used. As described above, the polymerization initiator can start the polymerization of the polymerizable liquid crystal compound more efficiently according to the type of the polymerizable liquid crystal compound in the composition from among known polymerization initiators. What is necessary is just to select suitably and use.
- a polymerization initiator is a thermal polymerization initiator (an initiator when utilizing a thermal polymerization reaction)
- a photopolymerization initiator an initiator when utilizing light or electron beam irradiation
- a polymerization initiator in the case of using a plastic film or the like as a base material when producing a liquid crystal film, from the viewpoint of preventing the base material and the like from being deformed or altered by heat, It is more preferable to use a photopolymerization initiator.
- photopolymerization initiators include ⁇ -carbonyl compounds, acyloin ethers, ⁇ -hydrocarbon-substituted aromatic acyloin compounds, polynuclear quinone compounds, and triarylimidazole dimers and p-aminophenyl ketones. And acridine and phenazine compounds and oxadiazole compounds.
- ⁇ -carbonyl compounds include ⁇ -carbonyl compounds described in US Pat. No. 2,367,661 and US Pat. No. 2,367,670.
- examples of the acyloin ether include US Pat. The thing etc. which are described in 2448828 specification are mentioned.
- Examples of the ⁇ -hydrocarbon-substituted aromatic acyloin compound include those described in US Pat. No. 2,722,512.
- Examples of the polynuclear quinone compound include US Pat. No. 3,046,127 and US Pat. No. 2,951,758. And the like described in the specification.
- Examples of the combination of triarylimidazole dimer and p-aminophenyl ketone include those described in US Pat. No. 3,549,367.
- Examples of the acridine and phenazine compound include, for example, Examples described in JP-A-60-105667, US Pat. No. 4,239,850 and the like, and examples of the oxadiazole compound include those described in US Pat. No. 4,212,970. .
- a commercially available product may be used as such a photopolymerization initiator.
- a photopolymerization initiator (trade name “Irgacure 907”, trade name “Irgacure 651”, trade name, manufactured by Ciba-Geigy) “Irgacure 184”) or a photopolymerization initiator (trade name “UVI6974”) manufactured by Union Carbide may be used as appropriate.
- photopolymerization initiators include those that generate free radicals and those that generate ions upon irradiation with light or an electron beam, and the type and polymerization of the polymerizable liquid crystal compound in the composition.
- a photopolymerization initiator that generates free radicals for example, “Irgacure 651” manufactured by Ciba-Geigy
- a photopolymerization initiator that generates ions for example, Union Carbide, Inc.
- a suitable photopolymerization initiator (trade name “UVI6974”) may be appropriately selected and used.
- the content of the polymerization initiator in the mixture of the polymerizable liquid crystal compound and the dichroic dye according to the present invention is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the mixture. More preferred are parts by weight. If the content of such a polymerization initiator is within the above numerical range, the resulting retardation plate has sufficient curability and can suppress the occurrence of defects in the alignment of the liquid crystal.
- the manufacturing method of the phase difference plate which consists of a liquid crystal film of this invention is demonstrated.
- the method of producing the retardation plate is not limited to these, but the composition containing the polymerizable liquid crystal compound, the dichroic dye and various compounds added as necessary is in a molten state, or A solution of the composition is applied onto an alignment substrate to form a coating film, and then the coating film is dried, heat-treated (liquid crystal alignment), or, if necessary, light irradiation and / or heat treatment ( By fixing the nematic hybrid alignment using means for fixing the above-described alignment such as polymerization and crosslinking, a liquid crystal film in which the alignment of the liquid crystal and the dichroic dye is fixed is formed.
- the alignment state “fixed in a state of nematic hybrid alignment” means that the liquid crystal film obtained by polymerizing the polymerizable liquid crystal compound to fix the alignment is nematic hybrid alignment (of liquid crystal molecules).
- the director refers to confirming that the director is seen from the film thickness direction (preferably at every location) and is oriented at different angles, and the component derived from the polymerizable liquid crystal compound or the like (preferably Is a component derived from a polymerizable liquid crystal compound: the polymerizable liquid crystal compound itself, a composition formed by decomposing the polymerizable liquid crystal compound, a polymer of the polymerizable liquid crystal compound, or the like).
- the “nematic hybrid structure” refers to an alignment structure in which a liquid crystal compound is nematic hybrid aligned in a liquid crystal film.
- the solvent used for the preparation of the solution is not particularly limited as long as it is a solvent that can dissolve the polymerizable liquid crystal composition of the present invention and the dichroic dye and can be distilled off under appropriate conditions.
- Hydrogens such as tetrahydrofuran and ⁇ -butyrolactone, aromatic hydrocarbons such as benzene, toluene, zylene, methoxybenzene and 1,2-dimethoxybenzene, cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve Etc. or a mixed system thereof is preferably used.
- a drying speed suitable for applying the solution so as to obtain a uniform film thickness, ease of handling (harmful to the environment), and dissolution in the polymerizable liquid crystal compound and the dichroic dye is preferable, and propylene glycol 1-monomethyl ether 2-acetate and ⁇ -butyrolactone are more preferable.
- the content of the solvent used in the present invention is determined by the method of using the composition (for example, when using it to form a liquid crystal film, the method of use including the design of the thickness, the coating method, etc.) It can be adjusted as appropriate.
- the content of the solvent is preferably 30 to 98% by weight, more preferably 50 to 95% by weight, and still more preferably 70 to 90% by weight.
- the content of such a solvent is 30% by mass or more, the amount of the solvent with respect to the mixture of the polymerizable liquid crystal compound and the dichroic dye is ensured, so that the precipitation of the liquid crystal during storage can be suppressed, It is possible to prevent the wettability from being lowered due to an increase in the viscosity of the mixture and to satisfactorily perform coating during the production of the retardation plate.
- the content of the solvent is 95% by mass or less, the removal time (drying time) does not take long when the solvent is removed, and the production efficiency is reduced when the film is manufactured, Since the fluidity of the surface is suppressed when the mixture is coated on a substrate, a uniform retardation plate can be produced.
- the amount of the mixture of components other than the solvent is preferably 5 to 70% by weight, and 10 to 50% by weight. More preferred is 10 to 30% by weight.
- a reaction activator, a sensitizer, a surfactant, an antifoaming agent, a leveling agent, and the like may be added to the solution.
- the alignment substrate As the alignment substrate, a substrate having a smooth plane is preferable, and examples thereof include a film or sheet made of an organic polymer material, a glass plate, and a metal plate. From the viewpoint of cost and continuous productivity, it is preferable to use a material made of an organic polymer.
- organic polymer materials include polyvinyl alcohol, polyimide, polyamide, polyamideimide, polyphenylene sulfide, polyether sulfone, polyphenylene oxide, polyether ketone, polyether ether ketone, polyethylene terephthalate, polyethylene naphthalate, polysulfone, cyclic to thru Examples thereof include cyclopolyolefin having a norbornene structure, diacetyl cellulose, triacetyl cellulose, cellulose acetate, cellulose propionate, cellulose butyrate, epoxy resin, and phenol resin.
- these films exhibit sufficient alignment ability for the liquid crystal substance used in the present invention without performing treatment for expressing the alignment ability again depending on the production method, but the alignment ability is insufficient, or alignment If the film does not show the performance, etc., these films are stretched under appropriate heating if necessary, the film surface is rubbed in one direction with a rayon cloth, etc., so-called rubbing treatment, polyimide, polyvinyl alcohol, silane on the film
- An alignment film made of a known alignment agent such as a coupling agent is provided and subjected to rubbing treatment.
- a photo-alignment film is applied on the film, heated at an appropriate temperature, and then irradiated with linearly polarized ultraviolet rays to form the alignment film.
- a metal plate such as aluminum, iron, or copper having various fine grooves on the surface, various glass plates, or the like can be used as the alignment substrate.
- a peripheral speed ratio This represents the ratio between the movement speed of the cloth and the movement speed of the substrate when the rubbing cloth is wound around a roll and rubbed while the substrate is rubbed.
- the peripheral speed ratio is usually 50 or less, more preferably 25 or less, and particularly preferably 10 or less.
- the application method is not particularly limited as long as the uniformity of the coating film is ensured, and a known method can be adopted. Examples thereof include spin coating, die coating, curtain coating, dip coating, and roll coating.
- Such a coating film differs depending on the content of the solvent in the polymerizable liquid crystal compound of the present invention and the dichroic dye mixture, etc., and cannot generally be said, but the thickness of the coating film before drying.
- the (wet film thickness) is preferably 3 to 50 ⁇ m, more preferably 5 to 20 ⁇ m.
- a thickness (wet film thickness) is 3 ⁇ m or more, in order to obtain desired optical characteristics, precipitation of a solid content (liquid crystal compound or the like) in the polymerizable liquid crystal composition is suppressed, and a uniform liquid crystal film is obtained. Moreover, sufficient smoothness of the liquid crystal film can be obtained by uniform coating. Moreover, since the density
- a drying step for removing the solvent after the application varies depending on the polymerizable liquid crystal compound, dichroic dye, type of solvent, and the like used in the present invention, and is not generally limited, and is not particularly limited.
- the solvent can be removed from the coating film even at room temperature (25 ° C.).
- the temperature condition in such a solvent removal step is preferably 15 to 110 ° C., more preferably 20 to 80 ° C. If such temperature conditions are 15 ° C. or higher, cooling equipment is not required and efficient production is possible.
- it is 110 degrees C or less it can suppress that a base material is distorted with a heat
- the pressure condition in the drying step is not particularly limited, but is preferably 600 to 1400 hPa, and more preferably 900 to 1100 hPa. If such a pressure condition is 600 hPa or more, drying of the solvent is slow and it is possible to suppress the occurrence of drying unevenness. If the pressure condition is 1400 hPa or less, the time required for drying the solvent can be reduced.
- the time for the solvent removal step (drying time) is not particularly limited, but is preferably 10 seconds to 60 minutes, and more preferably 1 minute to 30 minutes. If such a drying time is 10 seconds or more, since the solvent is slowly dried, the smoothness of the liquid crystal film can be maintained. Moreover, if it is 60 minutes or less, a manufacturing speed is quick and sufficient productivity can be maintained.
- the relative moving speed between the coating film and the drying apparatus is controlled so that the relative wind speed is 60 m / min to 1200 m / min.
- Any known method can be employed without particular limitation as long as the uniformity of the coating film is maintained.
- a method such as a heater (furnace) or hot air blowing may be used.
- the thickness of the coated film in the dry state is 0.1 ⁇ m to 50 ⁇ m, preferably 0.2 ⁇ m to 20 ⁇ m. If the film thickness is within the above numerical range, the optical performance of the obtained liquid crystal film can be sufficiently exhibited, and the polymerizable liquid crystal compound and the dichroic dye can be sufficiently aligned.
- a method for fixing the orientation will be described.
- a method for polymerizing the polymerizable liquid crystal compound to fix the alignment state a known method capable of polymerization may be appropriately employed depending on the type of the polymerization initiator used or the type of the polymerizable liquid crystal compound. it can.
- a method for fixing such an alignment state for example, the polymerizable group (reactive property) can be obtained by performing light irradiation and / or heat treatment depending on the kind of the polymerization initiator.
- a method may be employed in which the orientation is fixed in a homogeneous orientation state by reacting a functional group).
- the alignment state of the homogeneous alignment may be fixed by light irradiation.
- the light irradiation method is not particularly limited.
- a light source having a spectrum in the absorption wavelength region of the polymerization initiator used for example, a metal halide lamp, an intermediate pressure or a high pressure mercury lamp having an illuminance of 10 mW / cm 2 or more.
- the integrated irradiation dose of light in such a method of light irradiation of accumulative exposure at a wavelength 365 nm it is preferably 10 ⁇ 2000mJ / cm 2, and more to be 100 ⁇ 1500mJ / cm 2 preferable.
- this is not the case when the absorption region of the polymerization initiator and the spectrum of the light source are significantly different, or when the polymerizable liquid crystal compound itself has the ability to absorb light of the light source wavelength.
- an appropriate photosensitizer and two or more polymerization initiators having different absorption wavelengths are mixed from the viewpoint of fixing (curing) the coating film while maintaining the orientation state more efficiently.
- a method such as use may be employed.
- the temperature condition at the time of such light irradiation is not particularly limited as long as the polymerizable liquid crystal compound can maintain a nematic hybrid alignment state.
- a cold mirror or other cooling device may be provided between the substrate and the light source (such as an ultraviolet lamp) so that the surface temperature of the coating film can maintain the range of the liquid crystal temperature during light irradiation.
- the conditions of the atmosphere at the time of such light irradiation are not particularly limited, and may be an air atmosphere or a nitrogen atmosphere in which oxygen is blocked in order to increase reaction efficiency.
- the oxygen concentration in the atmosphere is related to the degree of polymerization, when the desired degree of polymerization is not reached in the air, it is preferable to perform light irradiation in an atmosphere in which the oxygen concentration is reduced by a method such as nitrogen substitution.
- the oxygen concentration in the atmospheric gas is preferably 10% by volume or less, more preferably 7% by volume or less, and most preferably 3% by volume or less.
- the alignment is fixed in a nematic hybrid alignment state by heat treatment.
- the conditions for such heat treatment are not particularly limited, and the temperature conditions may be selected so that the orientation state is sufficiently maintained according to the type of the polymerization initiator, and known conditions are appropriately employed. be able to. If the base material has low heat resistance, the polymerization initiator that exhibits the function of an initiator by light irradiation is used, and the alignment state of the nematic hybrid alignment is fixed by light irradiation. It is preferable to do.
- the liquid crystal film manufactured by the above process is a sufficiently strong film.
- the mesogens are three-dimensionally bonded by the curing reaction, and not only the heat resistance (the upper limit temperature for maintaining the liquid crystal alignment) is improved as compared to before curing, but also scratch resistance, abrasion resistance, crack resistance.
- the mechanical strength such as property is also greatly improved.
- the solvent is removed from the coating film to align the polymerizable liquid crystal compound and the dichroic dye.
- a liquid crystal film in which the alignment state is fixed in a nematic hybrid alignment state can be formed on the alignment substrate.
- the alignment substrate it is not optically isotropic, or the obtained retardation plate is finally opaque in the intended use wavelength region, or the alignment substrate is too thick, which hinders actual use.
- an optically isotropic substrate a stretched film having a retardation function, or a form directly transferred to a polarizing plate can be used from the form formed on the alignment substrate.
- a transfer method a known method can be adopted. For example, as described in JP-A-4-57017 and JP-A-5-333313, a liquid crystal film is laminated on a substrate different from the alignment substrate via an adhesive or an adhesive, and then, if necessary, an adhesive is used.
- Examples include a method of transferring only the liquid crystal film by performing a surface curing treatment using an agent or an adhesive and peeling the alignment substrate from the liquid crystal film.
- the pressure-sensitive adhesive or adhesive used for transfer is not particularly limited as long as it is of optical grade, and generally used ones such as acrylic, epoxy, and urethane can be used.
- the liquid crystal film alone as the element, but in order to improve the strength and durability of the liquid crystal film, the retardation plate is covered with a transparent protective layer on one or both sides of the liquid crystal film. It can also be configured.
- the transparent protective layer include those obtained by laminating transparent plastic films such as polyester and triacetyl cellulose directly or via an adhesive, resin coating layers, acrylic and epoxy photocurable resin layers, and the like.
- a liquid crystal film can be directly formed on a polarizing plate, and it can also be set as the laminated polarizing plate of this invention as it is.
- a transparent plastic film such as polyester or triacetyl cellulose used for producing the polarizing film
- the polarizing film / transparent plastic film / retardation plate liquid crystal film
- the polarizing film / retardation plate liquid crystal film
- a method for confirming nematic hybrid alignment in the liquid crystal film the following method may be employed.
- a known method can be appropriately employed, and is not particularly limited.
- a pair of orthogonal polarizing plates (a direction in which one deflecting plate is deflected and a direction in which the other deflecting plate is Using a sample in which a liquid crystal film (which may be in the form of a laminate with a base material) is disposed between a pair of polarizing plates whose deflection directions are perpendicular to each other, the transmitted light is confirmed with the naked eye.
- a method of observing the retardation plate with a polarizing microscope may be employed.
- the liquid crystal film is a nematic hybrid alignment liquid crystal film
- the incident angle of light incident on the surface of the liquid crystal film in the sample is tilted
- the tilt direction When light is incident from a certain tilt angle, the light appears to be brightest due to the phase difference of the light.
- the incident angle of light incident on the sample is tilted
- the amount of transmitted light is asymmetric in the vertical direction. The brightness appears to change depending on the direction. Therefore, the presence or absence of nematic hybrid alignment can be confirmed by measuring the brightness of such a sample through the naked eye or a polarizing microscope while shifting the incident angle of light.
- a birefringence measuring apparatus for example, Axo-metrix capable of measuring a phase difference in a vertical direction (perpendicular incident angle) and a phase difference when the incident angle of light is tilted from the vertical incident angle to a specific angle.
- Axo-metrix capable of measuring a phase difference in a vertical direction (perpendicular incident angle) and a phase difference when the incident angle of light is tilted from the vertical incident angle to a specific angle.
- the viewing angle increases from 0 degree (perpendicular to the liquid crystal film).
- the phase difference is measured while appropriately changing the angle to obtain the phase difference of the sample at a plurality of viewing angles, and in a direction perpendicular to the surface of the liquid crystal film.
- the phase difference is confirmed, and the phase difference in the direction in which the viewing angle is larger with respect to the surface of the liquid crystal film is confirmed, and the values of the ⁇ direction and the + direction of the viewing angle show asymmetry with each other. Based on this, a method of confirming the presence or absence of nematic hybrid alignment may be adopted.
- the thickness of the liquid crystal film is preferably 0.1 to 10 ⁇ m, preferably 0.2 to 5 ⁇ m, although it varies depending on the application and required characteristics. Is more preferable. If the thickness of such a liquid crystal film is 0.1 ⁇ m or more, a desired retardation can be expressed, and if it is 10 ⁇ m or less, a decrease in the orientation of the liquid crystal or a decrease in the transmittance due to the dye is suppressed. be able to.
- the birefringence ⁇ n of such a liquid crystal film is preferably 0.005 to 0.5, more preferably 0.01 to 0.3, although it varies depending on the application and required characteristics. If birefringence (DELTA) n is said range, when a film is made into a desired phase difference, thickness can be 10 micrometers or less, Therefore It can use suitably as a phase difference plate and a laminated polarizing plate.
- the laminated polarizing plate used in the present invention is a combination of a retardation plate and a polarizer.
- the linear polarizer one having a protective film on one side or both sides of the polarizer is usually used.
- the polarizer is not particularly limited, and various types can be used. For example, for a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, an ethylene / vinyl acetate copolymer partially saponified film.
- polyene-based oriented films such as those obtained by adsorbing dichroic substances such as iodine and dichroic dyes and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
- dichroic substances such as iodine and dichroic dyes
- uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products are preferably used.
- the thickness of the polarizer is not particularly limited, but is generally about 5 to 80 ⁇ m.
- a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of boric acid or potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there.
- Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching.
- the film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.
- the protective film provided on one side or both sides of the polarizer preferably has excellent transparency, mechanical strength, thermal stability, moisture shielding properties, isotropic properties, and the like.
- the material for the protective film include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, polystyrene, acrylonitrile and styrene copolymer. Examples thereof include styrene polymers such as coalesced (AS resin), polycarbonate polymers, and the like.
- polyolefin polymers such as polyethylene, polypropylene, ethylene / propylene copolymers, polyolefins having cycloolefin or norbornene structures, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfones Polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the protective film include blends of the aforementioned polymers.
- the thickness of the protective film is generally 500 ⁇ m or less, and preferably 1 to 300 ⁇ m. In particular, the thickness is preferably 5 to 200 ⁇ m.
- the protective film is preferably an optically isotropic substrate.
- a triacetyl cellulose (TAC) film such as Fujitac (product of Fujifilm) or Konicatak (product of Konica Minolta Opto), Arton film (product of JSR) And cycloolefin polymers such as ZEONOR film and ZEONEX film (product of ZEON Corporation), acrylic film, TPX film (product of Mitsui Chemicals), and acrylprene film (product of Mitsubishi Rayon Co., Ltd.).
- Triacetyl cellulose, a cycloolefin polymer, and an acrylic polymer are preferable from the viewpoint of planarity, heat resistance, moisture resistance, and the like when a laminated polarizing plate having a function is used.
- the protective film which consists of the same polymer material may be used by the front and back, and the protective film which consists of a different polymer material etc. may be used.
- the polarizer and the protective film are usually in close contact with each other through an aqueous adhesive or the like.
- aqueous adhesives include polyvinyl alcohol adhesives, gelatin adhesives, vinyl latexes, aqueous polyurethanes, aqueous polyesters, and the like.
- substrate used for the phase difference plate which consists of a liquid crystal film of this invention may serve as the protective film of a polarizer.
- a hard coat layer As the protective film, a hard coat layer, an antireflection treatment, an anti-sticking treatment, or a treatment subjected to diffusion or anti-glare treatment can be used.
- the hard coat treatment is applied for the purpose of preventing scratches on the surface of the laminated polarizing plate.
- a hard film with an excellent UV curable resin such as acrylic or silicone is used to protect the cured film with excellent hardness and sliding properties. It can be formed by a method of adding to the surface of the film.
- the antireflection treatment is performed for the purpose of preventing reflection of external light on the surface of the laminated polarizing plate, and can be achieved by forming an antireflection film or the like according to the related art. Further, the anti-sticking treatment is performed for the purpose of preventing adhesion with an adjacent layer.
- the anti-glare treatment is performed for the purpose of preventing external light from being reflected on the surface of the laminated polarizing plate and obstructing the visibility of the light transmitted through the laminated polarizing plate. It can be formed by imparting a fine concavo-convex structure to the surface of the protective film by an appropriate method such as a surface method or a compounding method of transparent fine particles.
- the fine particles to be included in the formation of the fine surface uneven structure include conductive particles made of silica, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide, and the like having an average particle size of 0.5 to 50 ⁇ m.
- transparent fine particles such as inorganic fine particles, organic fine particles composed of a crosslinked or uncrosslinked polymer, and the like are used.
- the amount of fine particles used is generally about 2 to 50 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the transparent resin forming the surface fine uneven structure.
- the antiglare layer may also serve as a diffusion layer (viewing angle expanding function or the like) for diffusing the light transmitted through the polarizing plate to expand the viewing angle.
- the antireflection layer, the antisticking layer, the diffusion layer, the antiglare layer and the like can be provided on the protective film itself, or can be provided separately from the transparent protective layer as an optical layer.
- the laminated polarizing plate can be prepared by laminating a retardation plate and a polarizer to each other via an adhesive layer.
- the retardation plate comprises the liquid crystal film, a polymerizable liquid crystal compound and It can be produced by applying a mixture of dichroic dyes directly or through an alignment film on a polarizer of a polarizing plate and fixing the alignment.
- the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited.
- an acrylic polymer, a silicone-based polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based or rubber-based polymer is appropriately used as a base polymer.
- those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and being excellent in weather resistance, heat resistance and the like can be preferably used.
- the formation of the pressure-sensitive adhesive layer can be performed by an appropriate method.
- a pressure-sensitive adhesive solution of about 10 to 40% by weight in which a base polymer or a composition thereof is dissolved or dispersed in a solvent composed of an appropriate solvent alone or a mixture such as toluene and ethyl acetate is prepared.
- a method in which it is directly attached on the liquid crystal layer by an appropriate development method such as a casting method or a coating method, or an adhesive layer is formed on the separator according to the above and transferred onto the liquid crystal layer Examples include methods.
- the pressure-sensitive adhesive layer includes, for example, natural and synthetic resins, in particular, tackifier resins, glass fibers, glass beads, metal powder, fillers made of other inorganic powders, pigments, colorants, You may contain the additive added to adhesion layers, such as antioxidant. Moreover, the adhesive layer etc. which contain microparticles
- the film surface can be surface-treated to improve adhesion with the adhesive layer.
- the surface treatment means is not particularly limited, and a surface treatment method such as corona discharge treatment, sputtering treatment, low-pressure UV irradiation, or plasma treatment that can maintain the transparency of each liquid crystal film can be suitably employed. Among these surface treatment methods, corona discharge treatment is good.
- the retardation plate of the present invention is a liquid crystal film in which a nematic hybrid alignment structure is fixed, the top and bottom of the liquid crystal film are not optically equivalent. Therefore, as a laminated polarizing plate having the function of elliptically polarized light or circularly polarized light, the display performance varies depending on which film surface of the liquid crystal film is placed on the polarizing plate side and in combination with optical parameters such as a liquid crystal cell.
- the present invention does not limit which film side of the liquid crystal film is on the polarizing plate side, the optical characteristics required for the laminated polarizing plate having the function of elliptically polarized light or circularly polarized light, and the function of the elliptically polarized light or circularly polarized light are also provided.
- the configuration of the laminated polarizing plate having the elliptically polarizing function of the present invention, the liquid crystal display device, and the organic EL display device It is desirable to determine the arrangement conditions and the like.
- the display device of the present invention includes the retardation plate of the present invention and a laminated polarizing plate having a function of elliptically polarized light or circularly polarized light composed of the retardation plate and a polarizer.
- a display device of the present invention only needs to include the retardation plate of the present invention, and the type of the display device is not particularly limited, and is an image display device, a liquid crystal display device, an organic EL display device, a plasma display.
- a known display device such as can be used as appropriate.
- the method of arranging the retardation plate of the present invention on the display device is not particularly limited, and a known method can be appropriately used.
- a liquid crystal display device to which the retardation plate of the present invention is applied will be described.
- the liquid crystal display device of the present invention has at least the retardation plate.
- a liquid crystal display device is generally composed of a polarizer, a liquid crystal cell, and a retardation plate, a reflection layer, a light diffusion layer, a backlight, a front light, a light control film, a light guide plate, a prism sheet, and the like.
- the retardation plate is used.
- the use position of the phase difference plate is not particularly limited, and may be one or a plurality of places. Moreover, it can also be used in combination with another phase difference plate.
- the liquid crystal cell is not particularly limited, and a general liquid crystal cell such as a liquid crystal layer sandwiched between a pair of transparent substrates provided with electrodes can be used.
- the transparent substrate constituting the liquid crystal cell is not particularly limited as long as the liquid crystal material constituting the liquid crystal layer is aligned in a specific alignment direction. Specifically, a transparent substrate having the property of aligning the liquid crystal itself, a substrate itself lacking alignment ability, but a transparent substrate provided with an alignment film having the property of aligning liquid crystal, etc. Can also be used. Moreover, a well-known thing can be used for the electrode of a liquid crystal cell.
- the liquid crystal cell may include various components necessary for forming various types of liquid crystal cells described later.
- TN Transmission Nematic
- STN Super Twisted Nematic
- ECB Electrode Controlled Birefringence
- IPS In-Plane Switching
- VA Vertical Alignment
- OCB Optically Compensated (Birefringence) method
- HAN Hybrid Aligned Nematic
- ASM Analy Symmetric Aligned ⁇ ⁇ ⁇ Microcell
- the driving method of the liquid crystal cell is not particularly limited, and a passive matrix method used for STN-LCD and the like, and an active matrix method using active electrodes such as TFT (Thin Film Transistor) electrodes and TFD (Thin Film Diode) electrodes, Any driving method such as a plasma addressing method may be used.
- the liquid crystal display device of the present invention including the phase plate of the present invention has a desired birefringence wavelength dispersion characteristic because the phase difference plate has a desired birefringence wavelength dispersion characteristic. Thus, it is possible to sufficiently improve the luminance and the like, and thereby the viewing angle and the image quality can be sufficiently improved.
- organic electroluminescence device including the retardation plate of the present invention
- a transparent electrode, an organic light emitting layer, and a metal electrode are sequentially laminated on a transparent substrate to form a light emitter (organic electroluminescent light emitter).
- the organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative and the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Alternatively, a structure having various combinations such as a laminate of such a light emitting layer and an electron injection layer composed of a perylene derivative or the like, or a laminate of these hole injection layer, light emitting layer, and electron injection layer is known. It has been.
- holes and electrons are injected into the organic light-emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by recombination of these holes and electrons excites the fluorescent material. Then, light is emitted on the principle that the excited fluorescent material emits light when returning to the ground state.
- the mechanism of recombination in the middle is the same as that of a general diode, and as can be predicted from this, the current and the emission intensity show strong nonlinearity with rectification with respect to the applied voltage.
- an organic EL display device in order to extract light emitted from the organic light emitting layer, at least one of the electrodes must be transparent, and a transparent electrode usually formed of a transparent conductor such as indium tin oxide (ITO) is used as an anode. It is used as.
- ITO indium tin oxide
- metal electrodes such as Mg—Ag and Al—Li are used.
- the organic light emitting layer is formed of a very thin film having a thickness of about 10 nm. For this reason, the organic light emitting layer transmits light almost completely like the transparent electrode. As a result, light that is incident from the surface of the transparent substrate at the time of non-light emission, passes through the transparent electrode and the organic light emitting layer, and is reflected by the metal electrode is again emitted to the surface side of the transparent substrate.
- the display surface of the organic EL display device looks like a mirror surface.
- an organic EL display device comprising an organic electroluminescent light emitting device comprising a transparent electrode on the surface side of an organic light emitting layer that emits light upon application of a voltage and a metal electrode on the back side of the organic light emitting layer, the surface of the transparent electrode While providing a polarizing plate on the side, a retardation plate can be provided between the transparent electrode and the polarizing plate.
- the retardation plate and the linear polarizer have a function of polarizing light incident from the outside and reflected by the metal electrode, there is an effect that the mirror surface of the metal electrode is not visually recognized by the polarization action.
- the mirror surface of the metal electrode is completely shielded by forming a circularly polarizing plate (laminated polarizing plate) in which the retardation plate is a quarter-wave plate and a linear polarizer and a retardation plate are combined.
- a circularly polarizing plate laminated polarizing plate
- the retardation plate is a quarter-wave plate and a linear polarizer and a retardation plate are combined.
- This linearly polarized light is generally elliptically polarized by the phase difference plate.
- the phase difference plate is a quarter wavelength plate and the angle between the polarization directions of the linear polarizer and the phase difference plate is ⁇ / 4, Become.
- This circularly polarized light is transmitted through the transparent substrate, the transparent electrode, and the organic thin film, reflected by the metal electrode, is again transmitted through the organic thin film, the transparent electrode, and the transparent substrate, and becomes linearly polarized light again on the retardation plate. Since this linearly polarized light is orthogonal to the polarization direction of the linear polarizer, it cannot be transmitted through the polarizing plate. As a result, the mirror surface of the metal electrode can be completely shielded.
- the circular polarizing plate is formed by combining a linear polarizing plate with a quarter-wave plate.
- the retardation plate of the invention When the retardation plate of the invention is in a nematic hybrid orientation, it is usually in the range of 40 to 50 degrees, preferably 42 to 48 degrees, and more preferably about 45 degrees. If it is in the said numerical range, sufficient antireflection effect will be acquired and the fall of an image quality can be suppressed.
- the retardation plate of the present invention When the retardation plate of the present invention is twisted nematic hybrid alignment, it is necessary to change the angle formed by the absorption axis of the polarizing plate and the slow axis of the quarter-wave plate depending on the twist angle. It is difficult to specify the range.
- each analysis method used in the Example is as follows.
- Wavelength region 440-1 A spectrum at 00 nm was measured.
- Example 1 Preparation of mixed solution of polymerizable liquid crystal compound (A) and dichroic dye> A rod-shaped liquid crystal compound (21) represented by the following formula and a compound (22) having two or more kinds of mesogenic groups were prepared. The rod-like liquid crystal compound (21) and the compound (22) having two or more kinds of mesogenic groups were produced by the method described in JP-A No. 2002-267838.
- a first mixture polymerizable liquid crystal compound (A)
- a dichroic dye manufactured by Nagase Sangyo Co., Ltd., G-241, trisazo dye, maximum absorption wavelength 560 nm
- a polymerization initiator (Ciba-Geigy, Irgacure 651, solid at room temperature (25 ° C.)) is added to 100 parts by weight of the total amount of the polymerizable liquid crystal compound (A) and the dichroic dye.
- a polymerization initiator (Ciba-Geigy, Irgacure 651, solid at room temperature (25 ° C.)) is added to 100 parts by weight of the total amount of the polymerizable liquid crystal compound (A) and the dichroic dye.
- a second mixture solid obtained by mixing the polymerizable liquid crystal compound (A), the dichroic dye and the polymerization initiator.
- the second mixture is dissolved in chlorobenzene (solvent), the insoluble matter is filtered through a polytetrafluoroethylene (PTFE) filter having a pore size of 0.45 ⁇ m, and the polymerizable liquid crystal compound (A), A mixed solution (third mixture) containing a dichroic dye, a polymerization initiator, and a solvent was obtained.
- the content of the solvent in the third mixture is 67% by weight, and the polymerizable liquid crystal compound (B), the dichroic dye, the polymerization initiator, The solvent was used so that the total amount of was 33% by weight.
- the alignment substrate was prepared as follows. A 38 ⁇ m thick polyethylene naphthalate film (manufactured by Teijin Limited, PEN) was cut into a 15 cm square, and a 5 wt% solution of alkyl-modified polyvinyl alcohol (PVA: Kuraray Co., Ltd., MP-203) (the solvent was water) And a mixture solvent of isopropyl alcohol in a weight ratio of 1: 1) was applied by spin coating, dried on a hot plate at 50 ° C. for 30 minutes, and then heated in an oven at 120 ° C. for 10 minutes. Subsequently, it was rubbed with a rayon rubbing cloth. The film thickness of the obtained PVA layer was 1.2 ⁇ m. The peripheral speed ratio during rubbing (moving speed of rubbing cloth / moving speed of substrate film) was 4.
- the laminate of the coating film and the alignment substrate was gradually cooled from pressure: 1013 hPa, temperature: 72 ° C. to 62 ° C. over 10 minutes, and the solvent was removed from the coating film by drying (solvent removal step), followed by room temperature. Quenched until.
- the integrated irradiation amount is 200 mJ / cm 2
- ultraviolet light (however, Laminate in which the liquid crystal compound is polymerized (cured) to fix the alignment state, and the alignment state is fixed on the alignment substrate.
- a body laminated body of liquid crystal film and alignment substrate) was obtained.
- the liquid crystal film on the obtained alignment substrate is converted to a triacetyl cellulose (TAC) film (Fuji Film) via an ultraviolet curable adhesive. And Z-TAC, 40 um). That is, after the adhesive is applied on the cured liquid crystal film layer on the PET film so as to have a thickness of 5 ⁇ m, laminated with the TAC film, and the adhesive is cured by irradiating ultraviolet rays from the TAC film side. The alignment substrate was peeled off. When the obtained optical film (liquid crystal film / adhesive layer / TAC) was observed under a polarizing microscope, it was found that there was no disclination (orientation defect) and the monodomain was uniformly oriented.
- TAC triacetyl cellulose
- the wavelength dispersion characteristic of retardation ( ⁇ nd) in the in-plane direction of the laminate of the TAC film and the liquid crystal film and the TAC film alone was measured using a trade name “Axoscan” manufactured by Axometrix, and the liquid crystal film layer was subtracted from both.
- the wavelength dispersion characteristics of the birefringence of was measured.
- FIG. 16 summarizes the birefringence wavelength dispersion characteristics of the liquid crystal film layer
- Table 2 summarizes the optical characteristics results.
- the retardation ( ⁇ nd) when the obtained optical film was tilted in the rubbing direction was measured using “Axoscan”. The measurement results are shown in FIG. As shown in FIG. 17, it has a viewing angle dependency that is asymmetrical to the left and right, and is found to be tilted.
- the obtained optical film was confirmed to be a nematic hybrid alignment film rather than a uniform tilt alignment by the method described in Examples of JP-A-11-194325.
- the average tilt angle was 34 degrees.
- the obtained optical film is made of acrylic resin so that the commercially available polarizing plate 1 (manufactured by Sumitomo Chemical Co., Ltd., SRW062), the absorption axis 2 of the polarizing plate 1 and the tilt direction 5 of the liquid crystal layer 4 in the optical film 3 are 45 degrees.
- the circularly polarizing plate 7 was produced by pasting together via an adhesive. At the time of bonding, the TAC film 6 side was laminated so as to be in contact with the polarizing plate 1.
- FIG. 18 shows a schematic diagram of a cross-sectional structure in the laminated state of the polarizing plate 1 and the liquid crystal layer 4 of the optical film 3. In the liquid crystal layer in the optical film 3, the surface on which the liquid crystal molecules rise more is on the side of the polarizing plate 1, and the surface on which the liquid crystal molecules lie further is on the side opposite to the polarizing plate 1.
- FIG. 19 and Table 2 show the results of measuring the viewing angle characteristics of the reflectance when external light is incident using a reflection viewing angle measuring device EZ-CONTRAST manufactured by ELDIM and the front reflectance.
- the emission spectrum of this organic EL display device is a graph shown in FIG. 13, and even when the produced optical film is bonded, the transmittance is reduced to about 3% as compared with the case of bonding in Comparative Example 2. It was confirmed that
- Example 2 Antireflection performance evaluation of organic EL display>
- the tilt direction 5 of the commercially available polarizing plate 1 manufactured by Sumitomo Chemical Co., SRW062
- the absorption axis 2 of the polarizing plate 1 and the liquid crystal layer 4 in the optical film 3 is 45 degrees.
- the circularly polarizing plate 8 was produced by pasting together through an acrylic adhesive.
- the layers were laminated so that the liquid crystal layer 4 side was in contact with the polarizing plate 1.
- FIG. 20 shows a schematic diagram of a cross-sectional structure in the laminated state of the polarizing plate 1 and the liquid crystal layer 4 of the optical film 3.
- the nematic hybrid structure is the reverse of the case of Example 1, and the liquid crystal layer 4 in the optical film 3 has a surface on which the liquid crystal molecules lie more on the polarizing plate 1 side, and a surface on which the liquid crystal molecules stand more.
- the obtained circularly polarizing plate 8 was attached to a transparent glass substrate of an organic EL element of a commercially available organic EL display in the same manner as in Example 1 via an acrylic pressure-sensitive adhesive, and the organic EL display device of the present invention was attached. Created. As a result, it was found that an organic EL display device that exhibits a significant effect of preventing reflection of external light and has excellent visibility as compared with the case where no circularly polarizing plate is provided.
- FIG. 21 and Table 2 show the results of measuring the viewing angle characteristics of the reflectance when external light is incident by EZ-CONTRAST and the front reflectance.
- Example 3 Provide of liquid crystal film>
- the third mixture prepared in Example 1 was applied by spin coating on an alignment substrate prepared in the same manner as in Example 1, to form a coating film (wet film thickness: 2.5 um). And a laminated body of the alignment substrate was obtained. Since the substrate used on the laminate has a large birefringence with polyethylene naphthalate, the liquid crystal film layer was peeled and transferred to the TAC film in the same manner as in Example 1, and the laminate composed of TAC / adhesive / liquid crystal film. Got the body.
- ⁇ n ⁇ d wavelength dispersion characteristic of retardation ( ⁇ n ⁇ d) in the in-plane direction of the laminate and the average tilt angle by measuring the phase difference in the oblique direction
- ⁇ n ⁇ d at a wavelength of 500 nm was 69 nm
- the average tilt angle was It was 34 degrees
- the wavelength dispersion characteristic of birefringence coincided with the graph (FIG. 16) of the optical film produced in Example 1.
- a second PVA layer was formed on the liquid crystal coating film of the laminate by the same method as in Example 1, and an alignment treatment was performed by rubbing in a direction antiparallel to the first PVA layer.
- the film thickness of the obtained PVA layer was 1.2 ⁇ m.
- the third mixture prepared in Example 1 was applied by the same method by spin coating, solvent removal by drying, and ultraviolet light irradiation were performed to obtain a liquid crystal film / PVA alignment film.
- a laminate comprising: / liquid crystal film / PVA alignment film / PEN substrate was obtained.
- it transferred to the TAC film by the same method as in Example 1 to obtain a laminate composed of TAC / adhesive / liquid crystal film / PVA alignment film / liquid crystal film.
- the wavelength dispersion characteristic of retardation ( ⁇ nd) in the in-plane direction of the obtained liquid crystal film laminate and the TAC film alone was measured using Axoscan, and the birefringence wavelength dispersion characteristic of the liquid crystal film layer was subtracted from both.
- FIG. 22 shows the measurement results of retardation ( ⁇ nd) when the obtained optical film is tilted in the rubbing direction (the alignment direction of liquid crystal molecules). As shown in FIG. 22, since it is bilaterally symmetric and has almost no viewing angle dependency, it is presumed that two liquid crystal layers are laminated in a tilted orientation antiparallel as shown in FIG.
- FIG. 23 shows a schematic diagram of a cross-sectional structure in the laminated state of the polarizing plate 1 and the liquid crystal layer 4 of the optical film 9.
- the nematic hybrid structure is the reverse of the case of Example 1, and the liquid crystal layer 4 in the optical film 9 has a surface on which the liquid crystal molecules lie more on the polarizing plate 1 side and a surface on which the liquid crystal molecules stand more.
- the obtained circularly polarizing plate 10 was attached to a transparent glass substrate of an organic EL element of a commercially available organic EL display in the same manner as in Example 1 via an acrylic pressure-sensitive adhesive, and the organic EL display device of the present invention was attached. Created. As a result, it was found that an organic EL display device that exhibits a significant effect of preventing reflection of external light and has excellent visibility as compared with the case where no circularly polarizing plate is provided. Further, Table 2 and Table 2 show the results of measuring the viewing angle characteristics of the reflectance when external light is incident by EZ-CONTRAST and the front reflectance.
- Example 4 Preparation of mixed solution of polymerizable liquid crystal compound (B) and dichroic dye>
- a first mixture (polymerizable liquid crystal compound (1)) obtained by mixing 17.6 parts by weight of the rod-shaped liquid crystal compound (21) prepared in Example 1 and 2 parts by weight of the compound (22) having two or more kinds of mesogenic groups. A)), except that a fourth mixture (polymerizable liquid crystal compound (B)) in which 0.15% by weight of a polymerizable liquid crystal compound (manufactured by BASF, Palicolor LC756) was used as a twist dopant was used.
- a mixed solution was prepared by various methods.
- the prepared fourth mixture (polymerizable liquid crystal compound (B)) was transferred to a TAC film in the same manner as in Example 1 to obtain an optical film (liquid crystal film / adhesive layer / TAC).
- the wavelength dispersion characteristic of retardation ( ⁇ nd) in the in-plane direction of the obtained liquid crystal film laminate and the TAC film alone was measured using Axoscan, and the birefringence wavelength dispersion characteristic of the liquid crystal film layer was subtracted from both. It was measured.
- ⁇ n ⁇ d at a wavelength of 550 nm was 209 m, and the twist angle was 55 degrees.
- the retardation ( ⁇ nd) when the obtained optical film was tilted in all directions was measured, and it was confirmed that the optical film had an asymmetric viewing angle dependency. It is presumed that the liquid crystal layer is nematic hybrid aligned while being twisted in the film thickness direction. The tilt angle was 25 degrees.
- the optical film produced in Example 4 is obtained by using a commercially available polarizing plate 1 (manufactured by Sumitomo Chemical Co., SRW062), an absorption axis 2 of the polarizing plate 1, and a polarizing plate 1 side alignment direction 11 of the liquid crystal layer 4 in the optical film 13.
- the circularly polarizing plate 14 was produced by pasting together via an acrylic pressure-sensitive adhesive so as to be 5 degrees.
- the alignment direction 12 of the liquid crystal molecules on the side opposite to the polarizing plate 1 of the liquid crystal layer 4 in the optical film 13 is 60 degrees.
- FIG. 25 shows a schematic diagram of a cross-sectional structure of the polarizing plate 1 and the liquid crystal layer of the optical film 13 in the laminated state.
- the nematic hybrid structure is the reverse of the case of Example 1, and the liquid crystal layer 4 in the optical film 13 has a surface on which the liquid crystal molecules lie more on the side of the polarizing plate 1 and a surface on which the liquid crystal molecules stand more.
- the obtained circularly polarizing plate 14 was attached to a transparent glass substrate of an organic EL element of a commercially available organic EL display in the same manner as in Example 1 via an acrylic pressure-sensitive adhesive, and the organic EL display device of the present invention was attached. Created. As a result, it was found that an organic EL display device that exhibits a significant effect of preventing reflection of external light and has excellent visibility as compared with the case where no circularly polarizing plate is provided.
- FIG. 26 and Table 2 show the results of measuring the viewing angle characteristics of the reflectance when external light is incident by EZ-CONTRAST and the front reflectance.
- the optical film (liquid crystal film / adhesive layer / TAC) was the same as in Example 1 except that the drying conditions after coating the coating film were dried at a pressure of 1013 hPa and a temperature of 72 ° C. for 2 minutes, and then rapidly cooled to room temperature. )
- ⁇ n ⁇ d wavelength dispersion characteristic of retardation
- ⁇ n ⁇ d at a wavelength of 550 nm is 138 nm
- the average tilt angle is 0. It was found to be homogeneous and homogeneously oriented.
- FIG. 27 shows a schematic diagram of a cross-sectional structure in the laminated state of the polarizing plate 1 and the liquid crystal layer 4 of the optical film 15.
- the obtained circularly polarizing plate 16 was attached to a transparent glass substrate of an organic EL element of a commercially available organic EL display in the same manner as in Example 1 via an acrylic adhesive, and the organic EL display device of the present invention was attached. Created. As a result, it was found that an organic EL display device that exhibits a significant effect of preventing reflection of external light and has excellent visibility as compared with the case where no circularly polarizing plate is provided.
- FIG. 28 and Table 2 show the results of measuring the viewing angle characteristics of the reflectance when the external light is incident by EZ-CONTRAST and the front reflectance. When comparing Example 1 and Comparative Example 1, it can be seen that Example 1 is superior in viewing angle characteristics of reflectance.
- FIG. 29 summarizes the birefringence wavelength dispersion characteristics of the liquid crystal film layer
- Table 1 summarizes the optical characteristics results.
- the obtained optical film was bonded to a commercially available polarizing plate 1 (manufactured by Sumitomo Chemical Co., Ltd., SRW062) in the same manner as in Example 1.
- the schematic diagram of the cross-sectional structure of the polarizing plate 1 and the liquid crystal layer 4 of the optical film 3 in the laminated state is the same as FIG. 18 as in Example 1, and the liquid crystal layer in the optical film 3 is a surface on which liquid crystal molecules rise more. Becomes the side of the polarizing plate 1, and the surface on which the liquid crystal molecules lie is opposite to the side of the polarizing plate 1.
- the obtained circularly polarizing plate 7 was stuck on a transparent glass substrate of an organic EL element of a commercially available organic EL display via an acrylic pressure-sensitive adhesive to produce the organic EL display device of the present invention.
- an organic EL display device that exhibits a significant effect of preventing external light reflection and has excellent visibility as compared with the case where the circularly polarizing plate 7 is not disposed can be obtained.
- FIG. 30 and Table 2 show the results of measuring the viewing angle characteristics of the reflectance when the external light is incident by EZ-CONTRAST and the front reflectance.
- the antireflection effect could be confirmed as compared with the case where no circularly polarizing plate was arranged, but it was found that the antireflection effect was inferior compared with Example 1 because of being bluish. This is because the birefringence wavelength dispersion characteristic is not ideal as compared with Example 1, and thus the reflectance deteriorates as a whole. From this, it can be seen that the effect of improving the viewing angle characteristics by the nematic hybrid structure can be obtained, but addition of a dichroic dye is essential for improving the front reflectance.
- FIG. 31 summarizes the birefringence wavelength dispersion characteristics of the liquid crystal film layer, and Table 1 summarizes the optical characteristics results.
- ⁇ n ⁇ d (500) / ⁇ n ⁇ d (550) 1.05
- ⁇ n ⁇ d (580) / ⁇ n ⁇ d (550) 0.98
- it was bonded to a polarizing plate and adhered to an organic EL display. When viewed from the front, it was strongly bluish, and the antireflection performance was found to be significantly inferior to that of Example 1. This is considered because the birefringence wavelength dispersion characteristic of the liquid crystal film having a nematic hybrid alignment structure is insufficient.
- FIG. 32 shows the result of measuring the viewing angle characteristic of the reflectance when external light is incident by EZ-CONTRAST.
- the liquid crystal film having a nematic hybrid structure containing a dichroic dye has a significant improvement effect in the front and oblique directions as the antireflection performance of the organic EL display.
- Example 5 The liquid crystal film produced in Example 1 was incorporated into a polarizing plate reflective liquid crystal display device and evaluated. From the observation side, the configuration is polarizing plate / liquid crystal film prepared in Example 1 / glass substrate / ITO transparent electrode / alignment film / twist nematic liquid crystal / alignment film / metal electrode / reflection film / glass substrate. The adhesive layer between each layer is omitted. The color was evaluated visually by setting the bonding angle so as to display white when the voltage was turned off. In particular, it was confirmed that there was little coloration in black display when the voltage was turned on, thereby providing high contrast and excellent visibility.
- Polarizing plate 2 Absorption axes 3, 9, 13, 15 of polarizing plate:
- Optical film 4 Liquid crystal layer 5: Tilt direction 6: TAC films 7, 8, 10, 14, 16: Circularly polarizing plate 11: Liquid crystal alignment Direction (polarizing plate side) 12: Liquid crystal alignment direction (TAC film side)
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Abstract
Description
逆に、複屈折が長波長ほど大きくなる「負の分散」特性を得る方法として、図4とは逆の傾向として、noの正分散が増加され、neの正分散が減少された分子を設計できればよい。 One way to achieve higher dispersion of the “positive dispersion” property of birefringence is to design a molecule in which the positive dispersion of ne is increased and the positive dispersion of no is decreased, as shown in FIG. . This method is possible by designing a rod-like molecular structure having absorption in the ultraviolet region closer to the visible light region, or by mixing a dye having absorption in the ultraviolet region.
On the other hand, as a method of obtaining a “negative dispersion” characteristic in which birefringence increases as the wavelength increases, a molecule in which the positive dispersion of no is increased and the positive dispersion of ne is decreased is designed in the opposite direction to FIG. I can do it.
また、上述の円偏光板は広い波長領域で1/4波長板を達成することにより、円偏光板の法線方向から入射する光においては、理想に近い円偏光を得ることができるが、斜め方向から入射する光においては、円偏光から大きく外れた楕円偏光に変換され、液晶表示装置における表示の視野角を狭くしてしまったり、有機EL表示装置における反射防止板では斜め方向での光漏れを発生させたりするおそれがある。
特許文献7には、偏光子と1/4波長板の間にNZ<0の複屈折体を設けた円偏光板が開示されている。ここで、NZをNZ=(nx-nz)/nx-ny)(式中、nx及びnyは、波長550nmの光に対する面内の主屈折率を表し、nx≧nyを満たす。nzは、波長550nmの光に対する厚さ方向の主屈折率を表す)と定義している。特許文献7に記載の円偏光板は、NZ<0の複屈折体を設けることより位相差の視野角依存性を補償し、円偏光板の視野角特性を向上させるものであるが、NZ<0という特殊な材料を使用することによるコストアップ、厚みアップ等の弊害がある。
特許文献8および9には、偏光板および略4分の1波長の位相差を有するネマチックハイブリッド配向構造を固定化した液晶フィルムからなる円偏光板が開示されている。ネマチックハイブリッド配向構造を有する1/4波長板と偏光板からなる円偏光板により、透過型あるいは反射型液晶表示装置における表示の視野角を広げる方法として提案されているが、広い波長領域で1/4波長板を達成するために、高分子延伸フィルムからなる1/2波長板との組み合わせが必要であり、コストアップ、厚みアップは避けられない。 However, the technique of combining a compound composed of a positive birefringent material and a negative birefringent material having different birefringence wavelength dispersion characteristics described in
In addition, the circularly polarizing plate described above achieves a quarter wavelength plate in a wide wavelength region, so that near-ideal circularly polarized light can be obtained in light incident from the normal direction of the circularly polarizing plate. Light incident from the direction is converted into elliptically polarized light that deviates significantly from circularly polarized light, narrowing the viewing angle of the display in the liquid crystal display device, or light leakage in an oblique direction in the antireflection plate in the organic EL display device May occur.
重合性液晶組成物と、少なくとも1種類以上の二色性色素とを含んでなり、かつ液晶化合物がネマチックハイブリッド配向した液晶フィルムからなる、位相差板。
[2]前記位相差板の法線方向でのリターデーションをΔna・da、
前記液晶フィルムから前記二色性色素を除いた液晶フィルムからなる位相差板の法線方向でのリターデーションをΔnb・db、
とした場合に、下記数式(1):
Δna・da(580)/Δna・da(550)-Δnb・db(580)/Δnb・db(550)>0 (1)
(ここで、リターデーションとは、複屈折Δnと位相差板の膜厚dの積で表され、Δna・da(580)、Δna・da(580)は、波長580nmにおける各位相差板のリターデーションであり、Δna・da(550)、Δna・da(550)は、波長550nmにおける各位相差板のリターデーションである。)
を満たす、前記[1]に記載の位相差板。
[3]前記液晶化合物がツイストネマチックハイブリッド配向した液晶フィルムからなる、前記[1]または[2]に記載の位相差板。
[4]前記液晶フィルムが、重合性液晶組成物と少なくとも1種類以上の二色性色素を含む混合物を液晶状態においてネマチックハイブリッド配向させ、光または熱による架橋反応により該配向を固定化したものである、前記[1]または[2]に記載の位相差板。
[5]前記液晶フィルムが、重合性液晶組成物と少なくとも1種類以上の二色性色素を含む混合物を液晶状態においてツイストネマチックハイブリッド配向させ、光または熱による架橋反応により該配向を固定化したものである、前記[3]に記載の位相差板。
[6]特定波長における位相差板の法線方向でのリターデーションの比が、下記数式(2)および(3):
0.80<Δn・d(500)/Δn・d(550)<1.00 (1)
1.00<Δn・d(600)/Δn・d(550)<1.15 (2)
(ここで、リターデーションとは、複屈折Δnと位相差板の膜厚dの積で表され、Δn・d(500)、Δn・d(550)、Δn・d(600)は、それぞれ波長500nm、550nm、600nmにおける位相差板のリターデーションである。)
を満たす、前記[1]~[5]のいずれかに記載の位相差板。
[7]二色性色素の極大吸収波長が測定波長380~780nmの領域にある、前記[1]~[6]のいずれかに記載の位相差板。
[8]画像表示装置の発光スペクトルの極大波長と二色性色素の極大吸収波長が異なる、前記[1]~[7]のいずれかに記載の位相差板。
[9]前記液晶フィルムの液晶分子の平均チルト角が5~45度である、前記[1]~[8]のいずれかに記載の位相差板。
[10]前記液晶フィルムの液晶分子のフィルム面内のツイスト角が0~70度である、前記[1]~[9]のいずれかに記載の位相差板。
[11]前記[1]~[10]のいずれかに記載の位相差板と偏光子とを備えた、積層偏光板。
[12]前記[1]~[10]のいずれかに記載の位相差板を備えた、表示装置。 [1] A phase difference plate having a “negative dispersion” characteristic in which birefringence Δn becomes larger as the measurement wavelength is longer in at least a part of the wavelength region of the visible light region,
A retardation film comprising a polymerizable liquid crystal composition and at least one dichroic dye, and comprising a liquid crystal film in which a liquid crystal compound is nematic hybrid aligned.
[2] Retardation in the normal direction of the retardation plate is Δna · da,
Retardation in the normal direction of a retardation film composed of a liquid crystal film obtained by removing the dichroic dye from the liquid crystal film is Δnb · db,
When the following formula (1):
Δna · da (580) / Δna · da (550) −Δnb · db (580) / Δnb · db (550)> 0 (1)
(Here, the retardation is represented by the product of birefringence Δn and the thickness d of the retardation plate, and Δna · da (580) and Δna · da (580) are retardations of each retardation plate at a wavelength of 580 nm). Δna · da (550) and Δna · da (550) are retardations of each phase difference plate at a wavelength of 550 nm.)
The retardation plate according to [1], wherein
[3] The retardation plate according to [1] or [2], wherein the liquid crystal compound is formed of a liquid crystal film with twisted nematic hybrid alignment.
[4] In the liquid crystal film, a mixture containing a polymerizable liquid crystal composition and at least one dichroic dye is nematic hybrid aligned in a liquid crystal state, and the alignment is fixed by a crosslinking reaction by light or heat. The retardation plate according to [1] or [2].
[5] The liquid crystal film has a twisted nematic hybrid alignment in a liquid crystal state of a mixture containing a polymerizable liquid crystal composition and at least one dichroic dye, and the alignment is fixed by a crosslinking reaction by light or heat. The retardation plate according to [3], wherein
[6] The retardation ratio in the normal direction of the retardation plate at a specific wavelength is expressed by the following mathematical formulas (2) and (3):
0.80 <Δn · d (500) / Δn · d (550) <1.00 (1)
1.00 <Δn · d (600) / Δn · d (550) <1.15 (2)
(Here, retardation is represented by the product of birefringence Δn and the film thickness d of the retardation plate, and Δn · d (500), Δn · d (550), and Δn · d (600) are respectively wavelengths. Retardation of retardation plate at 500 nm, 550 nm, and 600 nm.)
The retardation plate according to any one of [1] to [5], wherein
[7] The phase difference plate according to any one of [1] to [6], wherein the maximum absorption wavelength of the dichroic dye is in the measurement wavelength region of 380 to 780 nm.
[8] The retardation plate according to any one of [1] to [7], wherein the maximum wavelength of the emission spectrum of the image display device is different from the maximum absorption wavelength of the dichroic dye.
[9] The retardation plate according to any one of [1] to [8], wherein an average tilt angle of liquid crystal molecules of the liquid crystal film is 5 to 45 degrees.
[10] The retardation plate according to any one of [1] to [9], wherein a twist angle in a film plane of liquid crystal molecules of the liquid crystal film is 0 to 70 degrees.
[11] A laminated polarizing plate comprising the retardation plate according to any one of [1] to [10] and a polarizer.
[12] A display device comprising the retardation plate according to any one of [1] to [10].
本発明の位相差板は、複屈折Δnが、可視光領域の少なくとも一部の波長領域において、測定波長が長いほど大きくなる「負の分散」特性を有する位相差板であって、重合性液晶組成物と、少なくとも1種類以上の二色性色素とを含んでなり、かつ液晶化合物がネマチックハイブリッド配向した液晶フィルムからなる。
本発明の位相差板を説明する前に、従来の位相差板と本発明の位相差板の違いを説明する。 <Phase difference plate>
The retardation plate of the present invention is a retardation plate having a “negative dispersion” characteristic in which the birefringence Δn becomes larger as the measurement wavelength is longer in at least a part of the wavelength region of the visible light region. It comprises a liquid crystal film comprising a composition and at least one dichroic dye and having a liquid crystal compound nematic hybrid aligned.
Before describing the retardation plate of the present invention, the difference between the conventional retardation plate and the retardation plate of the present invention will be described.
以下では、屈折率を複素数N=n-ikとして記載する。ここでnはNの実数部であり、通常「屈折率」と呼ばれるものに等しい。k(Nの虚数部)は、波長の関数α(λ)としてk=αλ/(4π)で表され吸収係数に関係している。一般に、有機高分子は、固有吸収波長から離れた領域(図8のa1,a2,a3の領域)における屈折率nは波長が増すと共に単調に減少する。このような分散を「正常分散」と言われ、この分散域ではk=0である。これに対して、固有吸収を含む波長域(図8のb1、b2、b3の領域)における屈折率nは、波長が増すとともに急激に増加する。このような分散を「異常分散」と言われる。なお、本願明細書では、「正常分散」を「正の分散」、「異常分散」を「負の分散」と表記する。 First, the refractive index wavelength dispersion characteristic of the organic polymer will be described with reference to FIG.
Hereinafter, the refractive index is described as a complex number N = n−ik. Here, n is a real part of N and is equal to what is usually called “refractive index”. k (imaginary part of N) is expressed as k = αλ / (4π) as a function of wavelength α (λ) and is related to the absorption coefficient. In general, in an organic polymer, the refractive index n in a region away from the intrinsic absorption wavelength (regions a1, a2, and a3 in FIG. 8) monotonously decreases as the wavelength increases. Such dispersion is called “normal dispersion”, and k = 0 in this dispersion region. On the other hand, the refractive index n in the wavelength region including intrinsic absorption (regions b1, b2, and b3 in FIG. 8) increases rapidly as the wavelength increases. Such dispersion is called “anomalous dispersion”. In the present specification, “normal dispersion” is expressed as “positive dispersion” and “abnormal dispersion” is expressed as “negative dispersion”.
それに対し、本発明では、屈折率が「正の分散」特性を有する有機高分子に、可視光領域内に吸収を持つ二色性色素を添加することで、可視光領域のある波長領域において、異常光線屈折率neが「負の分散」特性を有し、それに伴い、可視光領域において、複屈折Δnが「負の分散」特性を有する位相差板となるという点で設計思想が根本的に異なる。 Since the conventional phase difference plate has no absorption in the visible light region, the curves of the extraordinary ray refractive index ne and the ordinary ray refractive index no both have a “positive dispersion” characteristic in the visible light region. Therefore, the prior art proposed as a method for obtaining the “negative dispersion” characteristic in which the birefringence increases as the wavelength increases, and the organic polymer having the “positive birefringence” and the organic high-power having the “negative birefringence”. Both the molecular copolymer and the mixture are made of a material having an extraordinary ray refractive index ne and an ordinary ray refractive index no having “positive dispersion” characteristics.
On the other hand, in the present invention, by adding a dichroic dye having absorption in the visible light region to an organic polymer having a refractive index “positive dispersion” property, in a wavelength region having a visible light region, The design philosophy is fundamental in that the extraordinary ray refractive index ne has a “negative dispersion” characteristic and, accordingly, the birefringence Δn becomes a phase difference plate having a “negative dispersion” characteristic in the visible light region. Different.
前述の特許文献5で例示した正の複屈折を有する有機高分子と負の複屈折を有する有機高分子からなる少なくとも二種類の有機高分子の混合体あるいは共重合体フィルムを一軸延伸してなる位相差フィルムや、特許文献6で例示した二種類以上のメソゲン基を有する化合物と棒状液晶化合物とを含む液晶組成物からなる液晶性フィルムの場合、図7に示すような「正の複屈折」かつ「負の分散」特性を有する位相差板が得られる。しかしながら、一般的には、図7に示す通り、可視光の中心波長である550nmより短波長側のカーブと長波長側のカーブの傾きが異なることに起因して、長波長側が理想直線から外れる傾向にある。従って、可視光領域である測定波長400~700nmの広帯域な領域で理想的な波長分散カーブに近づけるためには、短波長側のカーブを理想直線に近い状態に維持しながら、別の手法で長波長側のカーブを理想直線に近づける試みが必要となる。上記状況を鑑み、有機高分子の異常分散領域に起因する「負の分散」特性に着目した。
図8のうち、「異常分散領域」のカーブの拡大図を図9に示す。対称な吸収帯を仮定した場合、「異常分散領域」のうち、吸収の最大値では異常分散の寄与が近似的に零になり、屈折率の局部的な最大値が長波長側の吸収帯の半波高値の直前に現れ、屈折率の局部的な最小値が短波長側の半波高値の直後に現れる。これらの位置はλmax、λ+、λ-として図9に示してある。すなわち、λ-からλ+までの範囲内にある長波長になるほど屈折率が大きくなる分散特性、いわゆる「負の分散」特性が存在する。 The retardation plate of the present invention is a retardation plate in which birefringence Δn has a “negative dispersion” characteristic in at least a part of the wavelength region of the visible light region. A method for designing birefringence Δn having “negative dispersion” characteristics, which is a feature of the retardation plate of the present invention, will be described.
It is formed by uniaxially stretching a mixture or copolymer film of at least two kinds of organic polymers composed of an organic polymer having positive birefringence and an organic polymer having negative birefringence exemplified in
FIG. 9 shows an enlarged view of the “abnormal dispersion region” curve in FIG. Assuming a symmetric absorption band, the contribution of anomalous dispersion is approximately zero at the maximum absorption value in the “abnormal dispersion region”, and the local maximum value of the refractive index is the absorption wavelength of the long wavelength side. It appears just before the half-wave peak value, and the local minimum value of the refractive index appears just after the half-wave peak value on the short wavelength side. These positions are shown in FIG. 9 as λmax, λ +, and λ−. That is, there is a so-called “negative dispersion” characteristic in which the refractive index increases as the wavelength increases from λ− to λ +.
以上のことから、複屈折が「正の分散」特性である液晶化合物に、異常分散領域を有する二色性色素を添加することにより、本発明の目的でもある可視光の全波長領域において、複屈折がより理想に近い「負の分散」特性である位相差板が得られている。
また、複屈折が「負の分散」特性を有する有機高分子を用いた場合においては、長波長領域において、複屈折における「負の分散」特性が劣ることがあり、異常分散領域を有する二色性色素を添加することにより、長波長領域を改善でき、本発明の目的でもある可視光の全波長領域において複屈折がより理想に近い「負の分散」特性を有するフィルムが得られる。 The design concept of the present invention will be described with reference to FIGS. As shown by the thin lines in FIG. 10 (the solid line is ne and the dotted line is no), in general, in the case of an organic polymer having anisotropy, the type of dipole differs depending on the axial direction. The rate no indicates a different “positive dispersion” curve. In this organic polymer, by adding a dye having high dichroism having an absorption spectrum having a maximum absorption wavelength at 580 nm as shown in FIG. 11, in the wavelength region of 550 to 650 nm that is near the absorption wavelength, A retardation plate having the characteristic that the light refractive index ne is “negative dispersion” is obtained. Here, high dichroism means that there is a large difference in absorption characteristics between the ne direction and the no direction. FIG. 12 shows the birefringence wavelength dispersion characteristics of a retardation plate composed of an organic polymer before and after the addition of the dichroic dye. By adding a dichroic dye, a retardation plate having birefringence having “negative dispersion” in a wavelength region of 550 to 650 nm can be obtained.
From the above, by adding a dichroic dye having an anomalous dispersion region to a liquid crystal compound whose birefringence has a “positive dispersion” characteristic, in the entire wavelength region of visible light, which is the object of the present invention, A phase difference plate having “negative dispersion” characteristics with refraction closer to ideal is obtained.
In addition, in the case of using an organic polymer whose birefringence has “negative dispersion” characteristics, the “negative dispersion” characteristics in birefringence may be inferior in the long wavelength region, and two colors having anomalous dispersion regions. By adding a functional dye, a long wavelength region can be improved, and a film having a “negative dispersion” characteristic in which birefringence is closer to ideal in the entire wavelength region of visible light, which is also an object of the present invention, can be obtained.
Δna・da(580)/Δna・da(550)-Δnb・db(580)/Δnb・db(550)>0 (1)
(ここで、リターデーションとは、複屈折Δnと位相差板の膜厚dの積で表され、Δna・da(580)、Δna・da(580)は、波長580nmにおける各位相差板のリターデーションであり、Δna・da(550)、Δna・da(550)は、波長550nmにおける各位相差板のリターデーションである。)
を満たすことが好ましい。 In the present invention, the retardation at a predetermined wavelength in the normal direction of the retardation plate made of a liquid crystal film containing a dichroic dye is Δna · da, and the liquid crystal film is obtained by removing the dichroic dye from the liquid crystal film. When the retardation in the normal direction of the phase difference plate is Δnb · db, the following mathematical formula (1):
Δna · da (580) / Δna · da (550) −Δnb · db (580) / Δnb · db (550)> 0 (1)
(Here, the retardation is represented by the product of birefringence Δn and the thickness d of the retardation plate, and Δna · da (580) and Δna · da (580) are retardations of each retardation plate at a wavelength of 580 nm). Δna · da (550) and Δna · da (550) are retardations of each phase difference plate at a wavelength of 550 nm.)
It is preferable to satisfy.
0.80<Δn・d(500)/Δn・d(550)<1.00 (2)かつ
1.00<Δn・d(600)/Δn・d(550)<1.15 (3)であることが好ましい。ここで、リターデーションとは、複屈折Δnと位相差板の膜厚dの積(Δn・d)で表される。より好ましくは
0.90<Δn・d(500)/Δn・d(550)<0.98 (2-1)
かつ
1.02<Δn・d(600)/Δn・d(550)<1.10 (3-1)
である。これらの値の範囲内であれば、例えば、1/4波長板として使用する場合においては、400~700nmの直線偏光をこのフィルムに入射した際、偏光状態は完全な円偏光が得られる。 The retardation plate is a retardation plate characterized in that the birefringence Δn has a “negative dispersion” characteristic that increases in the visible light region as the measurement wavelength is longer. More specifically, when the retardation of the liquid crystal film at 500 nm, 550 nm, and 600 nm is Δn · d (500), Δn · d (550), and Δn · d (600), the following formulas (2) and (3 ):
0.80 <Δn · d (500) / Δn · d (550) <1.00 (2) and 1.00 <Δn · d (600) / Δn · d (550) <1.15 (3) Preferably there is. Here, the retardation is represented by the product (Δn · d) of birefringence Δn and the thickness d of the retardation plate. More preferably 0.90 <Δn · d (500) / Δn · d (550) <0.98 (2-1)
And 1.02 <Δn · d (600) / Δn · d (550) <1.10 (3-1)
It is. Within the range of these values, for example, in the case of using as a quarter wave plate, when linearly polarized light of 400 to 700 nm is incident on this film, the polarization state is completely circularly polarized.
液晶フィルムは、重合性液晶組成物と、少なくとも1種類以上の二色性色素とを含んでなり、かつ液晶化合物がネマチックハイブリッド配向した配向構造を有するものである。液晶フィルムとは、液晶化合物を液晶状態において配向固定化したフィルムである。液晶フィルムの配向とは、液晶化合物の分子鎖が特定の方向に並んだ状態を示しており、この状態は液晶フィルムの位相差(Δn・d)測定により測定できる。なお、配向とは、例えば、測定波長550nmでΔn・dが20nm以上を指す。Δn・dは複屈折Δnと膜厚dの積である。 <Liquid crystal film>
The liquid crystal film includes a polymerizable liquid crystal composition and at least one dichroic dye, and has an alignment structure in which a liquid crystal compound is nematic hybrid aligned. A liquid crystal film is a film obtained by aligning and fixing a liquid crystal compound in a liquid crystal state. The orientation of the liquid crystal film indicates a state in which the molecular chains of the liquid crystal compound are arranged in a specific direction, and this state can be measured by measuring the phase difference (Δn · d) of the liquid crystal film. The orientation refers to, for example, Δn · d of 20 nm or more at a measurement wavelength of 550 nm. Δn · d is the product of birefringence Δn and film thickness d.
このようなリターデーション値、ツイスト角、チルト角は、複屈折を測定することが可能な装置(例えばAxometrix社製の商品名「Axoscan」、王子計測機器社製の商品名「KOBRA-21ADH」等)を用いて測定した値から算出して求めることができる。 The retardation plate of the present invention may be a liquid crystal film in which a twisted nematic hybrid alignment structure is fixed. A liquid crystal film in which twisted nematic hybrid alignment is fixed has a structure in which a director of liquid crystal molecules twists an optically anisotropic axis from one surface to the other surface. Therefore, this retardation plate has characteristics equivalent to those obtained by stacking optically anisotropic layers in multiple layers so that the optical anisotropic axis is continuously twisted, and is a normal TN (twisted nematic). ) Like liquid crystal cells and STN (super twisted nematic) liquid crystal cells, the retardation value (= Δnd: value represented by the product of birefringence Δn and thickness d) and twist when viewed from the normal direction of the film Has horns. Furthermore, the liquid crystal film with a fixed twisted nematic hybrid alignment structure is different in the film thickness direction, while the director of the liquid crystal molecules is twisted in the in-plane direction from one side to the other side of the liquid crystal molecule. It is a film inclined at an angle. The twist angle in the orientation structure is usually 0 to 70 degrees as an absolute value, preferably 0 to 60 degrees, and most preferably 0 to 59 degrees. If the twist angle deviates more than 70 degrees, such as contrast and antireflection performance when the liquid crystal display device or organic EL display device is combined with a polarizing plate, the display characteristics when viewed from the front, etc. There is a fear. Here, although there are two types of twist angles, the twist angle may be either the right twist or the left twist.
Such retardation value, twist angle, and tilt angle can be measured by a device capable of measuring birefringence (for example, trade name “Axoscan” manufactured by Axometrix, trade name “KOBRA-21ADH” manufactured by Oji Scientific Instruments), etc. ) Can be calculated from the value measured using
本発明に使用する二色性色素について説明する。
二色性色素とは、分子の長軸方向における吸光度と、短軸方向における吸光度とが異なる性質を有する色素をいう。このような性質を有するものであれば、二色性色素は特に制限されず、染料であっても顔料であってもよい。この染料は複数種用いてもよく、顔料も複数種用いてもよく、染料と顔料とを組み合わせてもよい。更に、このような二色性色素は、重合性官能基を有していてもよく、液晶性を有していてもよい。重合性官能基としては、アクリル基、メタクリル基、ビニル基、ビニロキシ基、エポキシ基、オキセタニル基が好ましく、反応性の観点からアクリル基、エポキシ基、オキセタニル基が特に好ましい。液晶性については、ネマチック相、スメクチック相を有するものが好ましい。
前記二色性色素は、380~780nmの範囲に極大吸収波長(λmax)を有するものが好ましく、400~750nmがより好ましく、450~700nmがさらに好ましく、540~620nmが最も好ましい。本発明の位相差板を画像表示装置に適用する場合は、画像表示装置の光源の発光スペクトルを考慮して、極大吸収波長を選択するほうが好ましい。 <Dichroic dye>
The dichroic dye used in the present invention will be described.
A dichroic dye refers to a dye having the property that the absorbance in the major axis direction of a molecule is different from the absorbance in the minor axis direction. The dichroic dye is not particularly limited as long as it has such properties, and may be a dye or a pigment. A plurality of these dyes may be used, a plurality of pigments may be used, or a dye and a pigment may be combined. Furthermore, such a dichroic dye may have a polymerizable functional group and may have liquid crystallinity. As the polymerizable functional group, an acrylic group, a methacryl group, a vinyl group, a vinyloxy group, an epoxy group, and an oxetanyl group are preferable, and an acrylic group, an epoxy group, and an oxetanyl group are particularly preferable from the viewpoint of reactivity. As for the liquid crystallinity, those having a nematic phase and a smectic phase are preferable.
The dichroic dye preferably has a maximum absorption wavelength (λmax) in the range of 380 to 780 nm, more preferably 400 to 750 nm, still more preferably 450 to 700 nm, and most preferably 540 to 620 nm. When the retardation film of the present invention is applied to an image display device, it is preferable to select the maximum absorption wavelength in consideration of the emission spectrum of the light source of the image display device.
このような二色性色素としては特に限定はないが、例えば、アクリジン色素、アジン色素、アゾメチン色素、オキサジン色素、シアニン色素、メロシアニン色素、スクアリリウム色素、ナフタレン色素、アゾ色素、アントラキノン色素、ベンゾトリアゾール色素、ベンゾフェノン色素、ピラゾリン色素、ジフェニルポリエン色素、ビナフチルポリエン色素、スチルベン色素、ベンゾチアゾール色素、チエノチアゾール色素、ベンゾイミダゾール色素、クマリン色素、ニトロジフェニルアミン色素、ポリメチン色素、ナフトキノン色素、ペリレン色素、キノフタロン色素、スチルベン色素、インジゴ色素などが挙げられる。中でも、該二色性色素は、アントラキノン色素およびアゾ色素が好ましい。アゾ色素としては、モノアゾ色素、ビスアゾ色素、トリスアゾ色素、テトラキスアゾ色素及びスチルベンアゾ色素などが挙げられ、好ましくはビスアゾ色素、トリスアゾ色素およびこれらの系列の色素の誘導体が例示される。上記の条件を満たす色素であれば本発明で用いることが可能である。本発明で用いることが可能である色素の一例を色素ハンドブック(大河原信、北尾悌次郎、平嶋恒亮、松岡賢 編、講談社サイエンティフィック社:1986年第1版)に記載の色素番号で表1に示す。 The dichroic ratio of the dichroic dye is defined by the ratio of the absorbance at the maximum absorption wavelength in the major axis direction of the dye molecule to the absorbance in the minor axis direction. It can be determined by measuring the absorbance in the orientation direction of the dye and the absorbance in the direction perpendicular to the orientation direction. The dichroic dye that can be used in the present invention has a dichroic ratio of preferably 2 or more and 50 or less, more preferably 5 or more and 30 or less.
Such dichroic dyes are not particularly limited. For example, acridine dyes, azine dyes, azomethine dyes, oxazine dyes, cyanine dyes, merocyanine dyes, squarylium dyes, naphthalene dyes, azo dyes, anthraquinone dyes, benzotriazole dyes Benzophenone dye, pyrazoline dye, diphenyl polyene dye, binaphthyl polyene dye, stilbene dye, benzothiazole dye, thienothiazole dye, benzimidazole dye, coumarin dye, nitrodiphenylamine dye, polymethine dye, naphthoquinone dye, perylene dye, quinophthalone dye, stilbene dye Examples thereof include dyes and indigo dyes. Among these, the dichroic dye is preferably an anthraquinone dye or an azo dye. Examples of the azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbene azo dyes, and preferred examples include bisazo dyes, trisazo dyes, and derivatives of these series of dyes. Any dye that satisfies the above conditions can be used in the present invention. An example of a dye that can be used in the present invention is represented by a dye number described in a dye handbook (Shin Okawara, Shinjiro Kitao, Tsuneaki Hirashima, Ken Matsuoka, Kodansha Scientific Co., Ltd .: 1986, 1st edition). It is shown in 1.
前記アゾ色素(1)としては例えば、式(1-1)~式(1-58)でそれぞれ表される化合物などが挙げられる。 The positional isomerism of the azobenzene moiety of the azo dye (1) is preferably trans.
Examples of the azo dye (1) include compounds represented by formulas (1-1) to (1-58).
本発明に使用する重合性液晶組成物について説明する。
このような重合性液晶化合物としては、重合により配向状態を固定化し得る液晶性の化合物であれば特に制限されない。本発明における重合性液晶組成物は、1種または2種以上の重合性基を有する液晶化合物(重合性液晶化合物)、重合性基を有さない液晶化合物と液晶性を示さない重合性化合物との混合物、重合性基を有する液晶化合物と液晶性を示さない重合性化合物との混合物、および重合性基を有する液晶化合物と重合性基を有さない液晶化合物との混合物のいずれを含むものであってもよい。 <Polymerizable liquid crystal composition>
The polymerizable liquid crystal composition used in the present invention will be described.
Such a polymerizable liquid crystal compound is not particularly limited as long as it is a liquid crystalline compound capable of fixing the alignment state by polymerization. The polymerizable liquid crystal composition in the present invention includes a liquid crystal compound having one or more polymerizable groups (polymerizable liquid crystal compound), a liquid crystal compound having no polymerizable group, and a polymerizable compound not exhibiting liquid crystallinity. A mixture of a liquid crystal compound having a polymerizable group and a polymerizable compound not exhibiting liquid crystallinity, and a mixture of a liquid crystal compound having a polymerizable group and a liquid crystal compound having no polymerizable group. There may be.
また、式(10)~(12)中、nは1~20(より好ましくは2~12、更に好ましくは3~6)の整数である。このようなnの値が上記数値範囲内であれば、化合物が液晶性を発現する温度領域が広くなり、また、良好なネマチックハイブリッド配向を実現するのに必要な、化合物の液晶由来の流動性が保たれる結果、良好なネマチックハイブリッド配向を実現することできる。 In the general formulas (10) to (12), W independently represents any one of H and CH 3 . Depending on the type of W, a group represented by CH 2 = CWCOO in the formula is either an acrylate group or a methacrylate group.
In the formulas (10) to (12), n is an integer of 1 to 20 (more preferably 2 to 12, more preferably 3 to 6). If such a value of n is within the above numerical range, the temperature range in which the compound exhibits liquid crystallinity is widened, and the fluidity of the compound derived from the liquid crystal necessary for realizing good nematic hybrid alignment is achieved. As a result, good nematic hybrid alignment can be realized.
また、前記Raとして選択され得る炭素数が1~20のアルコキシ基は、炭素数が1~12のものがより好ましく、3~6のものが更に好ましい。このような炭素数が上記数値範囲内であれば、良好なネマチックハイブリッド配向を実現するのに必要な、化合物の液晶由来の流動性が保たれる結果、良好なネマチックハイブリッド配向を実現することができ、また、化合物が液晶性を発現する温度領域が広くなる傾向にある。なお、アルコキシ基は、アルキル基が酸素原子に結合した構造を有するが、かかるアルキル基の部分の構造は直鎖状のものであっても、分岐鎖状のものであっても、環状のものであってもよく特に制限されないが、良好なネマチックハイブリッド配向の実現の観点からは、直鎖状のものであることがより好ましい。 In the general formula (10), R a is any group selected from an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms. Such an alkyl group having 1 to 20 carbon atoms that can be selected as Ra is preferably one having 1 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. If the number of carbon atoms is within the above numerical range, the liquid crystal-derived fluidity necessary to achieve good nematic hybrid alignment is maintained, and as a result, good nematic hybrid alignment can be realized. In addition, the temperature range in which the compound exhibits liquid crystallinity tends to be widened. Such an alkyl group may be linear, branched, or cyclic, and is not particularly limited, but it can realize a good nematic hybrid orientation. From a viewpoint, it is more preferable that it is a linear thing.
In addition, the alkoxy group having 1 to 20 carbon atoms that can be selected as Ra is preferably one having 1 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. If such a carbon number is within the above numerical range, the liquidity derived from the liquid crystal of the compound necessary for realizing good nematic hybrid alignment is maintained, and as a result, good nematic hybrid alignment can be realized. In addition, the temperature range in which the compound exhibits liquid crystallinity tends to be widened. The alkoxy group has a structure in which an alkyl group is bonded to an oxygen atom. The structure of the alkyl group portion may be linear, branched, or cyclic. Although it may be sufficient and it does not restrict | limit, From a viewpoint of implement | achieving favorable nematic hybrid orientation, it is more preferable that it is a linear thing.
このように、上記一般式(10)~(12)で表わされる化合物を組み合わせて前記重合性液晶化合物として利用する場合においては、上記一般式(10)で表わされる化合物の含有量は、上記一般式(10)~(12)で表わされる化合物の総量に対して20~60重量%であることが好ましく、30~45重量%であることがより好ましい。このような一般式(10)で表わされる化合物の含有量が上記数値範囲内あれば、ネマチックハイブリッド配向性に関して、配向欠陥が生じるのを抑制することができる。 Further, as the polymerizable liquid crystal compound, it is preferable to use a combination of the compounds represented by the general formulas (10) to (12), and a combination of the compounds represented by the general formulas (110) to (113). It is more preferable to use it.
As described above, when the compounds represented by the general formulas (10) to (12) are used in combination as the polymerizable liquid crystal compound, the content of the compound represented by the general formula (10) It is preferably 20 to 60% by weight, more preferably 30 to 45% by weight, based on the total amount of the compounds represented by formulas (10) to (12). When the content of the compound represented by the general formula (10) is within the above numerical range, it is possible to suppress the occurrence of alignment defects with respect to nematic hybrid alignment.
0.80<Δn・d(500)/Δn・d(550)<1.00 (1)
1.00<Δn・d(600)/Δn・d(550)<1.15 (2)
を満たすことが好ましい。特に、0.80<Δn・d(500)/Δn・d(550)<1.00を満足する方法として、重合性液晶化合物が二種類以上のメソゲン基を有する化合物であり、そのうち少なくとも一つのメソゲン基を液晶層のホモジニアス配向の遅相軸に対して略直交方向に配向させることで、長波長になるほど、位相差が大きくなることが、特開2002-267838号公報や特開2010-31223号公報に記載されている。本発明において、二種以上のメソゲン基を有する液晶化合物の少なくとも一種類のメソゲン基が棒状液晶化合物の光軸方向に対し略直交方向に配向することで、液晶フィルムは重合性二色性色素を添加しない状態でも負の分散特性を有する。
ここで、メソゲン(mesogen)基のメソゲンは、中間相(=液晶相)形成分子(「液晶辞典」、日本学術振興会、情報科学用有機材料第142委員会、液晶部会編、1989年)とも称され、液晶性分子構造とほぼ同義である。本発明では、棒状液晶化合物におけるメソゲン基(棒状液晶化合物の液晶性に関する分子構造)を採用することが好ましい。棒状液晶化合物におけるメソゲン基については、各種文献(例えば、Flussige Kristalle in Tabellen誌、VEB Deutscher Verlag furGrundstoffindustrie, Leipzig(1984年)、第2巻)に記載がある。 In the present invention, the phase difference Δn · d is expressed by the following mathematical formulas (2) and (3):
0.80 <Δn · d (500) / Δn · d (550) <1.00 (1)
1.00 <Δn · d (600) / Δn · d (550) <1.15 (2)
It is preferable to satisfy. In particular, as a method of satisfying 0.80 <Δn · d (500) / Δn · d (550) <1.00, the polymerizable liquid crystal compound is a compound having two or more kinds of mesogenic groups, and at least one of them. By aligning the mesogenic group in a direction substantially orthogonal to the slow axis of the homogeneous alignment of the liquid crystal layer, the longer the wavelength, the greater the phase difference, as disclosed in JP-A-2002-267838 and JP-A-2010-31223. It is described in the gazette. In the present invention, at least one mesogen group of a liquid crystal compound having two or more kinds of mesogenic groups is aligned in a direction substantially orthogonal to the optical axis direction of the rod-shaped liquid crystal compound, whereby the liquid crystal film contains a polymerizable dichroic dye. Even when not added, it has negative dispersion characteristics.
Here, the mesogen of the mesogen group is also an intermediate phase (= liquid crystal phase) forming molecule ("Liquid Crystal Dictionary", Japan Society for the Promotion of Science, 142nd Committee on Organic Materials for Information Science, edited by Liquid Crystal Division, 1989) And is almost synonymous with the liquid crystalline molecular structure. In the present invention, it is preferable to employ a mesogenic group in the rod-like liquid crystal compound (molecular structure relating to liquid crystallinity of the rod-like liquid crystal compound). The mesogenic group in the rod-like liquid crystal compound is described in various documents (for example, Flussige Kristalle in Tabellen, VEB Deutscher Verlag fur Grundstoffindustrie, Leipzig (1984), Volume 2).
カイラルな構造単位としては、例えば光学活性な2-メチル-1,4-ブタンジオール、2,4-ペンタンジオール、1,2-プロパンジオール、2-クロロ-1,4-ブタンジオール、2-フルオロ-1,4-ブタンジオール、2-ブロモ-1,4-ブタンジオール、2-エチル-1,4-ブタンジオール、2-プロピル-1,4-ブタンジオール、3-メチルヘキサンジオール、3-メチルアジピン酸、ナプロキセン誘導体、カンファー酸、ビナフトール、メントールあるいはコレステリル基含有構造単位またはこれらの誘導体(例えばジアセトキシ化合物などの誘導体)から誘導される単位を利用することができる。上記のジオール類はR体、S体のいずれでも良く、またR体およびS体の混合物であっても良い。なおこれら構造単位は、あくまでも例示であって本発明はこれによって何ら制限されるものではない。またオリゴマーや低分子液晶であっても、架橋性基の導入あるいは適宜な架橋剤のブレンドによって、液晶状態あるいは液晶転移温度以下に冷却して配向固定化された状態で、熱架橋あるいは光架橋等の手段により高分子化できるものも液晶高分子に含まれる。 In order to induce twisted nematic alignment of the liquid crystal compound, a chiral agent is added to the liquid crystal composition, or a liquid crystal compound or a non-liquid crystal compound having at least one chiral structural unit is added to the liquid crystal composition. It is particularly desirable to blend.
Examples of the chiral structural unit include optically active 2-methyl-1,4-butanediol, 2,4-pentanediol, 1,2-propanediol, 2-chloro-1,4-butanediol, and 2-fluoro. 1,4-butanediol, 2-bromo-1,4-butanediol, 2-ethyl-1,4-butanediol, 2-propyl-1,4-butanediol, 3-methylhexanediol, 3-methyl Units derived from adipic acid, naproxen derivatives, camphoric acid, binaphthol, menthol or cholesteryl group-containing structural units or derivatives thereof (for example, derivatives such as diacetoxy compounds) can be used. The diols may be either R-form or S-form, and may be a mixture of R-form and S-form. These structural units are merely examples, and the present invention is not limited thereto. In addition, even in the case of oligomers and low-molecular liquid crystals, thermal crosslinking, photocrosslinking, etc. in a state where the alignment is fixed by cooling to below the liquid crystal transition temperature or liquid crystal transition temperature by introducing a crosslinkable group or blending of appropriate crosslinking agents. Those that can be polymerized by the above means are also included in the liquid crystal polymer.
次に、本発明の液晶フィルムからなる位相差板の製造方法について説明する。
位相差板製造の方法としてはこれらに限定されるものではないが、該重合性液晶化合物、該二色性色素および必要に応じて添加される各種の化合物を含む組成物を溶融状態で、あるいは該組成物の溶液を、配向基板上に塗布することにより塗膜を形成し、次に該塗膜を乾燥、熱処理(液晶の配向)することにより、あるいは必要により光照射および/または加熱処理(重合・架橋)等の前述の配向を固定化する手段を用いてネマチックハイブリッド配向を固定化することにより、液晶及び二色性色素の配向が固定化された液晶フィルムが形成される。 <Method for producing retardation plate>
Next, the manufacturing method of the phase difference plate which consists of a liquid crystal film of this invention is demonstrated.
The method of producing the retardation plate is not limited to these, but the composition containing the polymerizable liquid crystal compound, the dichroic dye and various compounds added as necessary is in a molten state, or A solution of the composition is applied onto an alignment substrate to form a coating film, and then the coating film is dried, heat-treated (liquid crystal alignment), or, if necessary, light irradiation and / or heat treatment ( By fixing the nematic hybrid alignment using means for fixing the above-described alignment such as polymerization and crosslinking, a liquid crystal film in which the alignment of the liquid crystal and the dichroic dye is fixed is formed.
また、配向基板上に均一な塗膜を形成するために、反応活性化剤、増感剤、界面活性剤、消泡剤、レベリング剤などを溶液に添加してもよい。 In addition, the content of the solvent used in the present invention is determined by the method of using the composition (for example, when using it to form a liquid crystal film, the method of use including the design of the thickness, the coating method, etc.) It can be adjusted as appropriate. For example, the content of the solvent is preferably 30 to 98% by weight, more preferably 50 to 95% by weight, and still more preferably 70 to 90% by weight. If the content of such a solvent is 30% by mass or more, the amount of the solvent with respect to the mixture of the polymerizable liquid crystal compound and the dichroic dye is ensured, so that the precipitation of the liquid crystal during storage can be suppressed, It is possible to prevent the wettability from being lowered due to an increase in the viscosity of the mixture and to satisfactorily perform coating during the production of the retardation plate. Moreover, if the content of the solvent is 95% by mass or less, the removal time (drying time) does not take long when the solvent is removed, and the production efficiency is reduced when the film is manufactured, Since the fluidity of the surface is suppressed when the mixture is coated on a substrate, a uniform retardation plate can be produced. As described above, in the mixture of the polymerizable liquid crystal compound and the dichroic dye of the present invention, the amount of the mixture of components other than the solvent is preferably 5 to 70% by weight, and 10 to 50% by weight. More preferred is 10 to 30% by weight.
In order to form a uniform coating film on the alignment substrate, a reaction activator, a sensitizer, a surfactant, an antifoaming agent, a leveling agent, and the like may be added to the solution.
配向基板としては、まず平滑な平面を有するものが好ましく、有機高分子材料からなるフィルムやシート、ガラス板、金属板などを挙げることができる。コストや連続生産性の観点からは有機高分子からなる材料を用いることが好ましい。有機高分子材料の例としては、ポリビニルアルコール、ポリイミド、ポリアミド、ポリアミドイミド、ポリフェニレンスルフィド、ポリエーテルスルフォン、ポリフェニレンオキシド、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリスルフォン、環状ないしノルボルネン構造を有するシクロポリオレフィン、ジアセチルセルロース、トリアセチルセルロース、セルロースアセテート、セルロースプロピオネート、セルロースブチレート、エポキシ樹脂、フェノール樹脂等が挙げられる。 Next, the alignment substrate will be described.
As the alignment substrate, a substrate having a smooth plane is preferable, and examples thereof include a film or sheet made of an organic polymer material, a glass plate, and a metal plate. From the viewpoint of cost and continuous productivity, it is preferable to use a material made of an organic polymer. Examples of organic polymer materials include polyvinyl alcohol, polyimide, polyamide, polyamideimide, polyphenylene sulfide, polyether sulfone, polyphenylene oxide, polyether ketone, polyether ether ketone, polyethylene terephthalate, polyethylene naphthalate, polysulfone, cyclic to thru Examples thereof include cyclopolyolefin having a norbornene structure, diacetyl cellulose, triacetyl cellulose, cellulose acetate, cellulose propionate, cellulose butyrate, epoxy resin, and phenol resin.
塗布方法については、塗膜の均一性が確保される方法であれば、特に限定されることはなく公知の方法を採用することができる。例えば、スピンコート法、ダイコート法、カーテンコート法、ディップコート法、ロールコート法などが挙げられる。このような塗膜としては、上記本発明の重合性液晶化合物および二色性色素混合物中の溶媒の含有量等によっても異なるものであり、一概には言えないが、乾燥前の塗膜の厚み(ウエット膜厚)が3~50μmであることが好ましく、5~20μmであることがより好ましい。このような厚み(ウエット膜厚)が3μm以上であれば、所望の光学特性を得るために重合性液晶組成物中の固形分(液晶化合物等)の析出を抑制し、均一な液晶フィルムを得ることができ、また、均一な塗布により液晶フィルムの十分な平滑性が得られる。また、20μm以下であれば、所望の光学特性とするための液晶組成物中の固形分の濃度が薄くなるため、塗布後の乾燥時間が長くなるのを抑制することができる。 Next, the coating method will be described.
The application method is not particularly limited as long as the uniformity of the coating film is ensured, and a known method can be adopted. Examples thereof include spin coating, die coating, curtain coating, dip coating, and roll coating. Such a coating film differs depending on the content of the solvent in the polymerizable liquid crystal compound of the present invention and the dichroic dye mixture, etc., and cannot generally be said, but the thickness of the coating film before drying. The (wet film thickness) is preferably 3 to 50 μm, more preferably 5 to 20 μm. If such a thickness (wet film thickness) is 3 μm or more, in order to obtain desired optical characteristics, precipitation of a solid content (liquid crystal compound or the like) in the polymerizable liquid crystal composition is suppressed, and a uniform liquid crystal film is obtained. Moreover, sufficient smoothness of the liquid crystal film can be obtained by uniform coating. Moreover, since the density | concentration of the solid content in a liquid-crystal composition for setting it as a desired optical characteristic will become thin if it is 20 micrometers or less, it can suppress that the drying time after application | coating becomes long.
塗布された膜の乾燥状態における膜厚は、0.1μm~50μm、好ましくは0.2μm~20μmである。膜厚が上記数値範囲内であれば、得られる液晶フィルムの光学性能を十分に発現でき、重合性液晶化合物及び二色性色素を十分に配向させることができる。 The pressure condition in the drying step is not particularly limited, but is preferably 600 to 1400 hPa, and more preferably 900 to 1100 hPa. If such a pressure condition is 600 hPa or more, drying of the solvent is slow and it is possible to suppress the occurrence of drying unevenness. If the pressure condition is 1400 hPa or less, the time required for drying the solvent can be reduced. The time for the solvent removal step (drying time) is not particularly limited, but is preferably 10 seconds to 60 minutes, and more preferably 1 minute to 30 minutes. If such a drying time is 10 seconds or more, since the solvent is slowly dried, the smoothness of the liquid crystal film can be maintained. Moreover, if it is 60 minutes or less, a manufacturing speed is quick and sufficient productivity can be maintained. When a drying apparatus is used for such a solvent removal step, the relative moving speed between the coating film and the drying apparatus is controlled so that the relative wind speed is 60 m / min to 1200 m / min. Is preferred. Any known method can be employed without particular limitation as long as the uniformity of the coating film is maintained. For example, a method such as a heater (furnace) or hot air blowing may be used.
The thickness of the coated film in the dry state is 0.1 μm to 50 μm, preferably 0.2 μm to 20 μm. If the film thickness is within the above numerical range, the optical performance of the obtained liquid crystal film can be sufficiently exhibited, and the polymerizable liquid crystal compound and the dichroic dye can be sufficiently aligned.
前記重合性液晶化合物を重合して配向状態を固定化する方法としては、用いる前記重合開始剤や前記重合性液晶化合物の種類等に応じて、重合が可能な公知の方法を適宜採用することができる。このような配向状態の固定化(重合・固定化)の方法としては、例えば、重合開始剤の種類等に応じて、光照射及び/又は加熱処理を施すことにより、前記重合性基(反応性官能基)を反応させてホモジニアス配向の配向状態で配向を固定化する方法を採用してもよい。 Next, a method for fixing the orientation will be described.
As a method for polymerizing the polymerizable liquid crystal compound to fix the alignment state, a known method capable of polymerization may be appropriately employed depending on the type of the polymerization initiator used or the type of the polymerizable liquid crystal compound. it can. As a method for fixing such an alignment state (polymerization / fixation), for example, the polymerizable group (reactive property) can be obtained by performing light irradiation and / or heat treatment depending on the kind of the polymerization initiator. A method may be employed in which the orientation is fixed in a homogeneous orientation state by reacting a functional group).
なお、基材が耐熱性の低いものである場合には、前記重合開始剤として光の照射により開始剤の機能を発現するようなものを用い、光照射によりネマチックハイブリッド配向の配向状態を固定化することが好ましい。 In addition, when the polymerization initiator is such that the function of the initiator is manifested by heat (for example, in the case of a so-called thermal cation generator), the alignment is fixed in a nematic hybrid alignment state by heat treatment. It is preferable to do. The conditions for such heat treatment are not particularly limited, and the temperature conditions may be selected so that the orientation state is sufficiently maintained according to the type of the polymerization initiator, and known conditions are appropriately employed. be able to.
If the base material has low heat resistance, the polymerization initiator that exhibits the function of an initiator by light irradiation is used, and the alignment state of the nematic hybrid alignment is fixed by light irradiation. It is preferable to do.
本発明に使用される積層偏光版は、位相差板と偏光子を組み合わせたものである。直線偏光子としては、通常、偏光子の片側または両側に保護フィルムを有するものが使用される。偏光子は、特に制限されず、各種のものを使用でき、例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料等の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等のポリエン系配向フィルム等が挙げられる。これらのなかでもポリビニルアルコール系フィルムを延伸して二色性材料(沃素、染料)を吸着・配向したものが好適に用いられる。偏光子の厚さも特に制限されないが、5~80μm程度が一般的である。 <Laminated polarizing plate>
The laminated polarizing plate used in the present invention is a combination of a retardation plate and a polarizer. As the linear polarizer, one having a protective film on one side or both sides of the polarizer is usually used. The polarizer is not particularly limited, and various types can be used. For example, for a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, an ethylene / vinyl acetate copolymer partially saponified film. And polyene-based oriented films such as those obtained by adsorbing dichroic substances such as iodine and dichroic dyes and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, those obtained by stretching a polyvinyl alcohol film and adsorbing and orienting a dichroic material (iodine, dye) are preferably used. The thickness of the polarizer is not particularly limited, but is generally about 5 to 80 μm.
ハードコート処理は積層偏光板表面の傷付き防止などを目的に施されるものであり、例えばアクリル系、シリコーン系などの適宜な紫外線硬化型樹脂による硬度や滑り特性等に優れる硬化皮膜を保護フィルムの表面に付加する方式などにて形成することができる。反射防止処理は積層偏光板表面での外光の反射防止を目的に施されるものであり、従来に準じた反射防止膜などの形成により達成することができる。また、スティッキング防止処理は隣接層との密着防止を目的に施される。 As the protective film, a hard coat layer, an antireflection treatment, an anti-sticking treatment, or a treatment subjected to diffusion or anti-glare treatment can be used.
The hard coat treatment is applied for the purpose of preventing scratches on the surface of the laminated polarizing plate. For example, a hard film with an excellent UV curable resin such as acrylic or silicone is used to protect the cured film with excellent hardness and sliding properties. It can be formed by a method of adding to the surface of the film. The antireflection treatment is performed for the purpose of preventing reflection of external light on the surface of the laminated polarizing plate, and can be achieved by forming an antireflection film or the like according to the related art. Further, the anti-sticking treatment is performed for the purpose of preventing adhesion with an adjacent layer.
本発明の表示装置は、上記本発明の位相差板及び、該位相差板と偏光子からなる楕円偏光又は円偏光の機能を有する積層偏光板を備えることを特徴とするものである。このような本発明の表示装置としては、上記本発明の位相差板を備えていればよく、表示装置の種類は特に制限されず、画像表示装置、液晶表示装置、有機EL表示装置、プラズマディスプレイ等のような公知の表示装置を適宜利用することができる。また、上記本発明の位相差板を表示装置に配置する方法等も特に制限されず、公知の方法を適宜利用することができる。 <Display device>
The display device of the present invention includes the retardation plate of the present invention and a laminated polarizing plate having a function of elliptically polarized light or circularly polarized light composed of the retardation plate and a polarizer. Such a display device of the present invention only needs to include the retardation plate of the present invention, and the type of the display device is not particularly limited, and is an image display device, a liquid crystal display device, an organic EL display device, a plasma display. A known display device such as can be used as appropriate. Further, the method of arranging the retardation plate of the present invention on the display device is not particularly limited, and a known method can be appropriately used.
本発明の液晶表示装置は、前記位相差板を少なくとも有する。液晶表示装置は一般的に、偏光子、液晶セル、および位相差板、反射層、光拡散層、バックライト、フロントライト、光制御フィルム、導光板、プリズムシート等の部材から構成されるが、本発明においては前記位相差板を使用する点を除いて特に制限は無い。また位相差板の使用位置は特に制限はなく、1カ所でも複数カ所でも良い。また、他の位相差板と組み合わせて使用することもできる。 A liquid crystal display device to which the retardation plate of the present invention is applied will be described.
The liquid crystal display device of the present invention has at least the retardation plate. A liquid crystal display device is generally composed of a polarizer, a liquid crystal cell, and a retardation plate, a reflection layer, a light diffusion layer, a backlight, a front light, a light control film, a light guide plate, a prism sheet, and the like. In the present invention, there is no particular limitation except that the retardation plate is used. The use position of the phase difference plate is not particularly limited, and may be one or a plurality of places. Moreover, it can also be used in combination with another phase difference plate.
液晶セルを構成する前記透明基板としては、液晶層を構成する液晶性を示す材料を特定の配向方向に配向させるものであれば特に制限はない。具体的には、基板自体が液晶を配向させる性質を有している透明基板、基板自体は配向能に欠けるが、液晶を配向させる性質を有する配向膜等をこれに設けた透明基板等がいずれも使用できる。また、液晶セルの電極は、公知のものが使用できる。通常、液晶層が接する透明基板の面上に設けることができ、配向膜を有する基板を使用する場合は、基板と配向膜との間に設けることができる。
前記液晶層を形成する液晶性を示す材料としては、特に制限されず、各種の液晶セルを構成し得る通常の各種低分子液晶物質、高分子液晶物質およびこれらの混合物が挙げられる。また、これらに液晶性を損なわない範囲で色素やカイラル剤、非液晶性物質等を添加することもできる。
前記液晶セルは、前記電極基板および液晶層の他に、後述する各種の方式の液晶セルとするのに必要な各種の構成要素を備えていても良い。 The liquid crystal cell is not particularly limited, and a general liquid crystal cell such as a liquid crystal layer sandwiched between a pair of transparent substrates provided with electrodes can be used.
The transparent substrate constituting the liquid crystal cell is not particularly limited as long as the liquid crystal material constituting the liquid crystal layer is aligned in a specific alignment direction. Specifically, a transparent substrate having the property of aligning the liquid crystal itself, a substrate itself lacking alignment ability, but a transparent substrate provided with an alignment film having the property of aligning liquid crystal, etc. Can also be used. Moreover, a well-known thing can be used for the electrode of a liquid crystal cell. Usually, it can be provided on the surface of the transparent substrate in contact with the liquid crystal layer, and when a substrate having an alignment film is used, it can be provided between the substrate and the alignment film.
The material exhibiting liquid crystallinity for forming the liquid crystal layer is not particularly limited, and examples thereof include various ordinary low-molecular liquid crystal substances, polymer liquid crystal substances, and mixtures thereof that can constitute various liquid crystal cells. In addition, a dye, a chiral agent, a non-liquid crystal substance, or the like can be added to these as long as liquid crystallinity is not impaired.
In addition to the electrode substrate and the liquid crystal layer, the liquid crystal cell may include various components necessary for forming various types of liquid crystal cells described later.
本発明の位相板を備える本発明の液晶表示装置は、位相差板が所望の複屈折波長分散特性を有することから、その特性に応じて、例えば、液晶表示装置の視野角を十分に広げたり、輝度を十分に向上させたりすること等が可能となり、これにより視野角向上や画質向上を十分に図ることができる。 Further, the driving method of the liquid crystal cell is not particularly limited, and a passive matrix method used for STN-LCD and the like, and an active matrix method using active electrodes such as TFT (Thin Film Transistor) electrodes and TFD (Thin Film Diode) electrodes, Any driving method such as a plasma addressing method may be used.
The liquid crystal display device of the present invention including the phase plate of the present invention has a desired birefringence wavelength dispersion characteristic because the phase difference plate has a desired birefringence wavelength dispersion characteristic. Thus, it is possible to sufficiently improve the luminance and the like, and thereby the viewing angle and the image quality can be sufficiently improved.
一般に、有機EL表示装置は、透明基板上に透明電極と有機発光層と金属電極とを順に積層して発光体(有機エレクトロルミネセンス発光体)を形成している。ここで、有機発光層は、種々の有機薄膜の積層体であり、例えばトリフェニルアミン誘導体等からなる正孔注入層と、アントラセン等の蛍光性の有機固体からなる発光層との積層体や、あるいはこのような発光層とペリレン誘導体等からなる電子注入層の積層体や、またあるいはこれらの正孔注入層、発光層、および電子注入層の積層体等、種々の組み合わせをもった構成が知られている。 An organic electroluminescence device (organic EL display device) including the retardation plate of the present invention will be described.
Generally, in an organic EL display device, a transparent electrode, an organic light emitting layer, and a metal electrode are sequentially laminated on a transparent substrate to form a light emitter (organic electroluminescent light emitter). Here, the organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative and the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Alternatively, a structure having various combinations such as a laminate of such a light emitting layer and an electron injection layer composed of a perylene derivative or the like, or a laminate of these hole injection layer, light emitting layer, and electron injection layer is known. It has been.
電圧の印加によって発光する有機発光層の表面側に透明電極を備えるとともに、有機発光層の裏面側に金属電極を備えてなる有機エレクトロルミネセンス発光体を含む有機EL表示装置において、透明電極の表面側に偏光板を設けるとともに、これら透明電極と偏光板との間に位相差板を設けることができる。 In the organic EL display device having such a configuration, the organic light emitting layer is formed of a very thin film having a thickness of about 10 nm. For this reason, the organic light emitting layer transmits light almost completely like the transparent electrode. As a result, light that is incident from the surface of the transparent substrate at the time of non-light emission, passes through the transparent electrode and the organic light emitting layer, and is reflected by the metal electrode is again emitted to the surface side of the transparent substrate. The display surface of the organic EL display device looks like a mirror surface.
In an organic EL display device comprising an organic electroluminescent light emitting device comprising a transparent electrode on the surface side of an organic light emitting layer that emits light upon application of a voltage and a metal electrode on the back side of the organic light emitting layer, the surface of the transparent electrode While providing a polarizing plate on the side, a retardation plate can be provided between the transparent electrode and the polarizing plate.
すなわち、この有機EL表示装置に入射する外部光は、直線偏光子により直線偏光成分のみが透過する。この直線偏光は位相差板により一般に楕円偏光となるが、とくに位相差板が1/4波長板でしかも直線偏光子と位相差板との偏光方向のなす角がπ/4のときには円偏光となる。 Since the retardation plate and the linear polarizer have a function of polarizing light incident from the outside and reflected by the metal electrode, there is an effect that the mirror surface of the metal electrode is not visually recognized by the polarization action. In particular, the mirror surface of the metal electrode is completely shielded by forming a circularly polarizing plate (laminated polarizing plate) in which the retardation plate is a quarter-wave plate and a linear polarizer and a retardation plate are combined. Can do.
That is, only the linearly polarized light component of the external light incident on the organic EL display device is transmitted by the linear polarizer. This linearly polarized light is generally elliptically polarized by the phase difference plate. In particular, when the phase difference plate is a quarter wavelength plate and the angle between the polarization directions of the linear polarizer and the phase difference plate is π / 4, Become.
なお、実施例で用いた各分析方法は以下の通りである。
(1)顕微鏡観察
オリンパス光学社製BH2偏光顕微鏡で液晶の配向状態を観察した。
(2)屈折率
屈折率no、neは、分光エリプソメトリ(堀場製作所社製、製品名「AUTO-SE」)を用い、温度20℃±2℃、相対湿度60±5%の条件下で、波長領域440~1
00nmのスペクトルを測定した。
(3)複屈折測定
Axometrics社製自動複屈折計Axoscanを用いて測定した。
(4)二色性色素の偏光吸収スペクトル
日本分光(株)製分光スペクトル(V-570)を用いて測定した。
(5)反射視野角測定
有機EL表示装置の正面及び斜め方向から見た場合の反射率の視野角特性は、ELDIM社製反射視野角測定装置EZ-CONTRASTを用いて測定した。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In addition, each analysis method used in the Example is as follows.
(1) Microscope observation The alignment state of the liquid crystal was observed with an Olympus BH2 polarizing microscope.
(2) Refractive index Refractive indexes no and ne were measured using a spectroscopic ellipsometry (manufactured by Horiba Ltd., product name “AUTO-SE”) under the conditions of a temperature of 20 ° C. ± 2 ° C. and a relative humidity of 60 ± 5%. Wavelength region 440-1
A spectrum at 00 nm was measured.
(3) Birefringence measurement It measured using the automatic birefringence meter Axoscan by Axometrics.
(4) Polarization absorption spectrum of dichroic dye Measurement was performed using a spectrum (V-570) manufactured by JASCO Corporation.
(5) Reflection viewing angle measurement The viewing angle characteristic of the reflectance when viewed from the front and oblique directions of the organic EL display device was measured using a reflection viewing angle measurement device EZ-CONTRAST manufactured by ELDIM.
〈重合性液晶化合物(A)と二色性色素の混合溶液の調製〉
下記式で表される示される棒状液晶化合物(21)と二種類以上のメソゲン基を有する化合物(22)をそれぞれ準備した。なお、棒状液晶化合物(21)と二種類以上のメソゲン基を有する化合物(22)は、特開2002-267838号公報に記載された方法により製造した。 Example 1
<Preparation of mixed solution of polymerizable liquid crystal compound (A) and dichroic dye>
A rod-shaped liquid crystal compound (21) represented by the following formula and a compound (22) having two or more kinds of mesogenic groups were prepared. The rod-like liquid crystal compound (21) and the compound (22) having two or more kinds of mesogenic groups were produced by the method described in JP-A No. 2002-267838.
次いで、前記第二の混合物を、クロロベンゼン(溶媒)中に溶解させて、孔径0.45μmのポリテトラフルオロエチレン(PTFE)製フィルターで不溶分をろ過して、前記重合性液晶化合物(A)、二色性色素と重合開始剤と溶媒を含む混合溶液(第三の混合物)を得た。なお、このような第三の混合物の製造に際しては、前記第三の混合物中の溶媒の含有量が67重量%となり、前記重合性液晶化合物(B)、二色性色素と前記重合開始剤との総量が33重量%となるようにして溶媒を用いた。 Next, 17.6 parts by weight of the rod-shaped liquid crystal compound (21) and 2 parts by weight of the compound (22) having two or more kinds of mesogenic groups are mixed to obtain a first mixture (polymerizable liquid crystal compound (A)). ) Next, with respect to the first mixture, a dichroic dye (manufactured by Nagase Sangyo Co., Ltd., G-241, trisazo dye, maximum absorption wavelength 560 nm) in a ratio of 0.08 parts by weight with respect to 100 parts by weight as a total. Further, a polymerization initiator (Ciba-Geigy, Irgacure 651, solid at room temperature (25 ° C.)) is added to 100 parts by weight of the total amount of the polymerizable liquid crystal compound (A) and the dichroic dye. Was added at a ratio of 3 parts by weight to obtain a second mixture (solid) obtained by mixing the polymerizable liquid crystal compound (A), the dichroic dye and the polymerization initiator.
Next, the second mixture is dissolved in chlorobenzene (solvent), the insoluble matter is filtered through a polytetrafluoroethylene (PTFE) filter having a pore size of 0.45 μm, and the polymerizable liquid crystal compound (A), A mixed solution (third mixture) containing a dichroic dye, a polymerization initiator, and a solvent was obtained. In producing the third mixture, the content of the solvent in the third mixture is 67% by weight, and the polymerizable liquid crystal compound (B), the dichroic dye, the polymerization initiator, The solvent was used so that the total amount of was 33% by weight.
配向基板は以下のようにして調製した。厚さ38μmのポリエチレンナフタレートフィルム(帝人(株)製、PEN)を15cm角に切り出し、アルキル変性ポリビニルアルコール(PVA:(株)クラレ製、MP-203)の5重量%溶液(溶媒は、水とイソプロピルアルコールの重量比1:1の混合溶媒)をスピンコート法により塗布し、50℃のホットプレートで30分乾燥した後、120℃のオーブンで10分間加熱した。次いで、レーヨンのラビング布でラビングした。得られたPVA層の膜厚は1.2μmであった。ラビング時の周速比(ラビング布の移動速度/基板フィルムの移動速度)は4とした。 <Production of liquid crystal film>
The alignment substrate was prepared as follows. A 38 μm thick polyethylene naphthalate film (manufactured by Teijin Limited, PEN) was cut into a 15 cm square, and a 5 wt% solution of alkyl-modified polyvinyl alcohol (PVA: Kuraray Co., Ltd., MP-203) (the solvent was water) And a mixture solvent of isopropyl alcohol in a weight ratio of 1: 1) was applied by spin coating, dried on a hot plate at 50 ° C. for 30 minutes, and then heated in an oven at 120 ° C. for 10 minutes. Subsequently, it was rubbed with a rayon rubbing cloth. The film thickness of the obtained PVA layer was 1.2 μm. The peripheral speed ratio during rubbing (moving speed of rubbing cloth / moving speed of substrate film) was 4.
次に、前記塗膜と配向基板の積層体を圧力:1013hPa、温度:72℃から10分かけて62℃まで徐冷し、前記塗膜から溶媒を乾燥除去した(溶媒除去工程)後、室温まで急冷した。
次いで、前記溶媒除去工程により乾燥した後の塗膜に対して、照度:15mW/cm2の高圧水銀ランプを用いて、積算照射量が200mJ/cm2となるようにして、紫外光(ただし、365nmの波長の光を測定した光量)を照射することにより、前記液晶化合物を重合(硬化)して配向状態を固定化し、配向基板上に配向状態が固定化された液晶フィルムが積層された積層体(液晶フィルムと配向基板の積層体)を得た。 On the alignment substrate thus obtained, the rod-shaped liquid crystal compound (21) obtained as described above, the compound (22) having two or more kinds of mesogenic groups, a dichroic dye and a polymerization initiator, A mixed solution (third mixture) containing a solvent was applied (coated) by a spin coating method to form a coating film (wet film thickness: 5 μm) to obtain a laminate of the coating film and the alignment substrate.
Next, the laminate of the coating film and the alignment substrate was gradually cooled from pressure: 1013 hPa, temperature: 72 ° C. to 62 ° C. over 10 minutes, and the solvent was removed from the coating film by drying (solvent removal step), followed by room temperature. Quenched until.
Next, with respect to the coating film dried by the solvent removal step, using a high-pressure mercury lamp with an illuminance of 15 mW / cm 2 , the integrated irradiation amount is 200 mJ / cm 2, and ultraviolet light (however, Laminate in which the liquid crystal compound is polymerized (cured) to fix the alignment state, and the alignment state is fixed on the alignment substrate. A body (laminated body of liquid crystal film and alignment substrate) was obtained.
得られた光学フィルム(液晶フィルム/接着剤層/TAC)を偏光顕微鏡下で観察すると、ディスクリネーション(配向欠陥)がなくモノドメインの均一な配向であることがわかった。 Since the PET film used as the substrate has a large birefringence and is not preferable as an optical film, the liquid crystal film on the obtained alignment substrate is converted to a triacetyl cellulose (TAC) film (Fuji Film) via an ultraviolet curable adhesive. And Z-TAC, 40 um). That is, after the adhesive is applied on the cured liquid crystal film layer on the PET film so as to have a thickness of 5 μm, laminated with the TAC film, and the adhesive is cured by irradiating ultraviolet rays from the TAC film side. The alignment substrate was peeled off.
When the obtained optical film (liquid crystal film / adhesive layer / TAC) was observed under a polarizing microscope, it was found that there was no disclination (orientation defect) and the monodomain was uniformly oriented.
また、得られた光学フィルムをラビング方向(液晶分子の配向方向)に傾けたときのレターデーション(Δnd)を「Axoscan」を用いて測定した。測定結果を図17に示す。図17に示す通り、左右非対称な視野角依存性を持っており、傾斜配向していることが分かった。得られた光学フィルムは、特開平11-194325号公報の実施例に記載された方法により、この液晶フィルムが均一チルト配向ではなく、ネマチックハイブリッド配向フィルムであることを確認した。平均チルト角は34度であった。 The wavelength dispersion characteristic of retardation (Δnd) in the in-plane direction of the laminate of the TAC film and the liquid crystal film and the TAC film alone was measured using a trade name “Axoscan” manufactured by Axometrix, and the liquid crystal film layer was subtracted from both. The wavelength dispersion characteristics of the birefringence of was measured. FIG. 16 summarizes the birefringence wavelength dispersion characteristics of the liquid crystal film layer, and Table 2 summarizes the optical characteristics results. Δn · d at 550 nm is 138 nm, Δn · d (500) / Δn · d (550) = 0.96, Δn · d (580) / Δn · d (550) = 1.02, and Δn D (600) / Δn · d (550) = 1.03.
Further, the retardation (Δnd) when the obtained optical film was tilted in the rubbing direction (the alignment direction of liquid crystal molecules) was measured using “Axoscan”. The measurement results are shown in FIG. As shown in FIG. 17, it has a viewing angle dependency that is asymmetrical to the left and right, and is found to be tilted. The obtained optical film was confirmed to be a nematic hybrid alignment film rather than a uniform tilt alignment by the method described in Examples of JP-A-11-194325. The average tilt angle was 34 degrees.
得られた光学フィルムを、市販の偏光板1(住友化学社製、SRW062)と、偏光板1の吸収軸2と光学フィルム3内の液晶層4のチルト方向5が45度になるようにアクリル系粘着剤を介して貼り合わせて円偏光板7を作製した。貼り合わせる際、TACフィルム6側が偏光板1と接するように積層させた。偏光板1と光学フィルム3の液晶層4の積層状態での断面構造の概要図を図18に示す。光学フィルム3内の液晶層は、液晶分子がより立ち上がっている面が偏光板1側になり、液晶分子がより寝ている面が偏光板1と反対側になる。 <Antireflection performance evaluation of organic EL display>
The obtained optical film is made of acrylic resin so that the commercially available polarizing plate 1 (manufactured by Sumitomo Chemical Co., Ltd., SRW062), the
また、外光を入射した際の反射率の視野角特性をELDIM社製反射視野角測定装置EZ-CONTRASTにて測定した結果と正面反射率を図19、表2に示す。
また、この有機EL表示装置の発光スペクトルは図13に示すグラフであり、作製した光学フィルムを貼りあわせても、比較例2で貼り合わせた場合と比較して3%程度の透過率低下に抑えられることが確認できた。 The obtained circularly
In addition, FIG. 19 and Table 2 show the results of measuring the viewing angle characteristics of the reflectance when external light is incident using a reflection viewing angle measuring device EZ-CONTRAST manufactured by ELDIM and the front reflectance.
Moreover, the emission spectrum of this organic EL display device is a graph shown in FIG. 13, and even when the produced optical film is bonded, the transmittance is reduced to about 3% as compared with the case of bonding in Comparative Example 2. It was confirmed that
〈有機ELディスプレイの反射防止性能評価〉
実施例1で作製した光学フィルムを、市販の偏光板1(住友化学社製、SRW062)と、偏光板1の吸収軸2と光学フィルム3内の液晶層4のチルト方向5が45度になるようにアクリル系粘着剤を介して貼り合わせて円偏光板8を作製した。貼り合わせる際、液晶層4側が偏光板1と接するように積層させた。偏光板1と光学フィルム3の液晶層4の積層状態での断面構造の概要図を図20に示す。ネマチックハイブリッド構造は、実施例1の場合と逆になり、光学フィルム3内の液晶層4は、液晶分子がより寝ている面が偏光板1側になり、液晶分子がより立っている面が偏光板1と反対側になる。
得られた円偏光板8を、実施例1と同様に、市販の有機ELディスプレイの有機EL素子の透明ガラス基板上にアクリル系粘着剤を介して貼着し、本発明の有機EL表示装置を作成した。その結果、円偏光板を配置しない場合に比べ、大幅な外光反射防止効果を発揮し、視認性の優れた有機EL表示装置が得られることが分かった。
また、外光を入射した際の反射率の視野角特性をEZ-CONTRASTにて測定した結果と正面反射率を図21、表2に示す。 (Example 2)
<Antireflection performance evaluation of organic EL display>
For the optical film produced in Example 1, the
The obtained circularly
FIG. 21 and Table 2 show the results of measuring the viewing angle characteristics of the reflectance when external light is incident by EZ-CONTRAST and the front reflectance.
〈液晶フィルムの作製〉
実施例1と同様な方法で作製した配向基板上に、実施例1で作製した第三の混合物をスピンコート法により塗布し、塗膜(ウエット膜厚:2.5um)を形成し、塗膜と配向基板との積層体を得た。前記積層体上で使用した基板はポリエチレンナフタレートと大きな複屈折を持つため、液晶フィルム層を実施例1と同様な方法で、TACフィルムに剥離転写し、TAC/接着剤/液晶フィルムからなる積層体を得た。積層体の面内方向のレターデーション(Δn・d)の波長分散特性、斜め方向の位相差測定による平均チルト角の測定を行ったところ、波長500nmでのΔn・dは69nm、平均チルト角は34度であり、複屈折の波長分散特性は実施例1で作製した光学フィルムのグラフ(図16)と一致した。
また、前記積層体の液晶塗膜上に、実施例1と同様な方法で2層目のPVA層を形成し、1層目のPVA層と反平行の方向にラビングによる配向処理を行った。得られたPVA層の膜厚は1.2μmであった。このようにして得られたPVA層上に、実施例1で作製した第三の混合物を同様な方法でスピンコート法により塗布、乾燥による溶媒除去、紫外光照射を行い、液晶フィルム/PVA配向膜/液晶フィルム/PVA配向膜/PEN基板からなる積層体を得た。更に、実施例1と同様な方法で、TACフィルムに転写し、TAC/接着剤/液晶フィルム/PVA配向膜/液晶フィルムからなる積層体を得た。得られた液晶フィルムの積層体とTACフィルム単体の面内方向のリターデーション(Δnd)の波長分散特性をAxoscanを用いて測定し、両者の引き算から、液晶フィルム層の複屈折の波長分散特性を測定した。波長550nmでのΔn・dは138nmであり、波長分散特性は実施例1で作製した光学フィルムのグラフ(図16)と一致した。
得られた光学フィルムをラビング方向(液晶分子の配向方向)に傾けたときのレターデーション(Δnd)の測定結果を図22に示す。図22に示す通り、左右対称であり、視野角依存性もほとんどないことから、図23に示すように2層の液晶層が反平行に傾斜配向して積層していると推定される。 Example 3
<Production of liquid crystal film>
The third mixture prepared in Example 1 was applied by spin coating on an alignment substrate prepared in the same manner as in Example 1, to form a coating film (wet film thickness: 2.5 um). And a laminated body of the alignment substrate was obtained. Since the substrate used on the laminate has a large birefringence with polyethylene naphthalate, the liquid crystal film layer was peeled and transferred to the TAC film in the same manner as in Example 1, and the laminate composed of TAC / adhesive / liquid crystal film. Got the body. When the wavelength dispersion characteristic of retardation (Δn · d) in the in-plane direction of the laminate and the average tilt angle by measuring the phase difference in the oblique direction were measured, Δn · d at a wavelength of 500 nm was 69 nm, and the average tilt angle was It was 34 degrees, and the wavelength dispersion characteristic of birefringence coincided with the graph (FIG. 16) of the optical film produced in Example 1.
Further, a second PVA layer was formed on the liquid crystal coating film of the laminate by the same method as in Example 1, and an alignment treatment was performed by rubbing in a direction antiparallel to the first PVA layer. The film thickness of the obtained PVA layer was 1.2 μm. On the PVA layer thus obtained, the third mixture prepared in Example 1 was applied by the same method by spin coating, solvent removal by drying, and ultraviolet light irradiation were performed to obtain a liquid crystal film / PVA alignment film. A laminate comprising: / liquid crystal film / PVA alignment film / PEN substrate was obtained. Furthermore, it transferred to the TAC film by the same method as in Example 1 to obtain a laminate composed of TAC / adhesive / liquid crystal film / PVA alignment film / liquid crystal film. The wavelength dispersion characteristic of retardation (Δnd) in the in-plane direction of the obtained liquid crystal film laminate and the TAC film alone was measured using Axoscan, and the birefringence wavelength dispersion characteristic of the liquid crystal film layer was subtracted from both. It was measured. Δn · d at a wavelength of 550 nm was 138 nm, and the chromatic dispersion characteristics coincided with the graph of the optical film produced in Example 1 (FIG. 16).
FIG. 22 shows the measurement results of retardation (Δnd) when the obtained optical film is tilted in the rubbing direction (the alignment direction of liquid crystal molecules). As shown in FIG. 22, since it is bilaterally symmetric and has almost no viewing angle dependency, it is presumed that two liquid crystal layers are laminated in a tilted orientation antiparallel as shown in FIG.
実施例3で作製した光学フィルムを、市販の偏光板1(住友化学社製、SRW062)と、偏光板1の吸収軸2と光学フィルム9内の液晶層4のチルト方向5が45度になるようにアクリル系粘着剤を介して貼り合わせて円偏光板10を作製した。貼り合わせる際、光学フィルム9の液晶層4側が偏光板1と接するように積層させた。偏光板1と光学フィルム9の液晶層4の積層状態での断面構造の概要図を図23に示す。ネマチックハイブリッド構造は、実施例1の場合と逆になり、光学フィルム9内の液晶層4は、液晶分子がより寝ている面が偏光板1側になり、液晶分子がより立っている面が偏光板1と反対側になる。
得られた円偏光板10を、実施例1と同様に、市販の有機ELディスプレイの有機EL素子の透明ガラス基板上にアクリル系粘着剤を介して貼着し、本発明の有機EL表示装置を作成した。その結果、円偏光板を配置しない場合に比べ、大幅な外光反射防止効果を発揮し、視認性の優れた有機EL表示装置が得られることが分かった。
また、外光を入射した際の反射率の視野角特性をEZ-CONTRASTにて測定した結果と正面反射率を図24、表2に示す。 <Antireflection performance evaluation of organic EL display>
For the optical film produced in Example 3, the
The obtained circularly
Further, Table 2 and Table 2 show the results of measuring the viewing angle characteristics of the reflectance when external light is incident by EZ-CONTRAST and the front reflectance.
〈重合性液晶化合物(B)と二色性色素の混合溶液の調製〉
実施例1で調製した前記棒状液晶化合物(21)17.6重量部と、前記二種類以上のメソゲン基を有する化合物(22)2重量部とを混合した第一の混合物(重合性液晶化合物(A))に、ツイストドーパントとして重合性液晶化合物(BASF製、Paliocolor LC756)を0.15重量%混合した第四の混合物(重合性液晶化合物(B))とした以外は、実施例1と同様な方法で混合溶液を調製した。 Example 4
<Preparation of mixed solution of polymerizable liquid crystal compound (B) and dichroic dye>
A first mixture (polymerizable liquid crystal compound (1)) obtained by mixing 17.6 parts by weight of the rod-shaped liquid crystal compound (21) prepared in Example 1 and 2 parts by weight of the compound (22) having two or more kinds of mesogenic groups. A)), except that a fourth mixture (polymerizable liquid crystal compound (B)) in which 0.15% by weight of a polymerizable liquid crystal compound (manufactured by BASF, Palicolor LC756) was used as a twist dopant was used. A mixed solution was prepared by various methods.
前記調製した第四の混合物(重合性液晶化合物(B))を実施例1と同様な方法にてTACフィルムに転写し、光学フィルム(液晶フィルム/接着剤層/TAC)を得た。得られた液晶フィルムの積層体とTACフィルム単体の面内方向のリターデーション(Δnd)の波長分散特性をAxoscanを用いて測定し、両者の引き算から、液晶フィルム層の複屈折の波長分散特性を測定した。波長550nmでのΔn・dは209mであり、ねじれ角は55度であった。得られた光学フィルムを全方位に傾けたときのレターデーション(Δnd)を測定し、非対称な視野角依存性を持つことを確認した。液晶層が膜厚方向にツイストしながらネマチックハイブリッド配向していると推定される。なお、チルト角は25度であった。 <Production of liquid crystal film>
The prepared fourth mixture (polymerizable liquid crystal compound (B)) was transferred to a TAC film in the same manner as in Example 1 to obtain an optical film (liquid crystal film / adhesive layer / TAC). The wavelength dispersion characteristic of retardation (Δnd) in the in-plane direction of the obtained liquid crystal film laminate and the TAC film alone was measured using Axoscan, and the birefringence wavelength dispersion characteristic of the liquid crystal film layer was subtracted from both. It was measured. Δn · d at a wavelength of 550 nm was 209 m, and the twist angle was 55 degrees. The retardation (Δnd) when the obtained optical film was tilted in all directions was measured, and it was confirmed that the optical film had an asymmetric viewing angle dependency. It is presumed that the liquid crystal layer is nematic hybrid aligned while being twisted in the film thickness direction. The tilt angle was 25 degrees.
実施例4で作製した光学フィルムを、市販の偏光板1(住友化学社製、SRW062)と、偏光板1の吸収軸2と光学フィルム13内の液晶層4の偏光板1側配向方向11が5度になるようにアクリル系粘着剤を介して貼り合わせて円偏光板14を作製した。この場合、光学フィルム13内の液晶層4の偏光板1と反対側の液晶分子の配向方向12は60度になる。貼り合わせる際、光学フィルム13の液晶層4側が偏光板1と接するように積層させた。偏光板1と光学フィルム13の液晶層の積層状態での断面構造の概要図を図25に示す。ネマチックハイブリッド構造は、実施例1の場合と逆になり、光学フィルム13内の液晶層4は、液晶分子がより寝ている面が偏光板1側になり、液晶分子がより立っている面が偏光板1と反対側になる。
得られた円偏光板14を、実施例1と同様に、市販の有機ELディスプレイの有機EL素子の透明ガラス基板上にアクリル系粘着剤を介して貼着し、本発明の有機EL表示装置を作成した。その結果、円偏光板を配置しない場合に比べ、大幅な外光反射防止効果を発揮し、視認性の優れた有機EL表示装置が得られることが分かった。
また、外光を入射した際の反射率の視野角特性をEZ-CONTRASTにて測定した結果と正面反射率を図26、表2に示す。 <Antireflection performance evaluation of organic EL display>
The optical film produced in Example 4 is obtained by using a commercially available polarizing plate 1 (manufactured by Sumitomo Chemical Co., SRW062), an
The obtained circularly
In addition, FIG. 26 and Table 2 show the results of measuring the viewing angle characteristics of the reflectance when external light is incident by EZ-CONTRAST and the front reflectance.
塗膜を塗布後の乾燥条件を圧力:1013hPa、温度:72℃で2分乾燥後、急冷して室温まで冷却した以外は実施例1と同様に、光学フィルム(液晶フィルム/接着剤層/TAC)を得た。
光学フィルムの正面方向のレターデーション(Δn・d)の波長分散特性、斜め方向の位相差測定による平均チルト角の測定を行ったところ、波長550nmでのΔn・dは138nm、平均チルト角は0度であり、ホモジニアス配向していることがわかった。
また、複屈折の波長分散特性は、Δn・d(500)/Δn・d(550)=0.96であり、Δn・d(580)/Δn・d(550)=1.02であり、Δn・d(600)/Δn・d(550)=1.03であり、実施例1で作製した光学フィルムのグラフ(図16)と一致した。 (Comparative Example 1)
The optical film (liquid crystal film / adhesive layer / TAC) was the same as in Example 1 except that the drying conditions after coating the coating film were dried at a pressure of 1013 hPa and a temperature of 72 ° C. for 2 minutes, and then rapidly cooled to room temperature. )
When measuring the wavelength dispersion characteristic of retardation (Δn · d) in the front direction of the optical film and the average tilt angle by measuring the phase difference in the oblique direction, Δn · d at a wavelength of 550 nm is 138 nm, and the average tilt angle is 0. It was found to be homogeneous and homogeneously oriented.
The wavelength dispersion characteristics of birefringence are Δn · d (500) / Δn · d (550) = 0.96, Δn · d (580) / Δn · d (550) = 1.02, Δn · d (600) / Δn · d (550) = 1.03, which coincided with the graph of the optical film produced in Example 1 (FIG. 16).
比較例1で作製した光学フィルムを、市販の偏光板1(住友化学社製、SRW062)と、偏光板1の吸収軸2と光学フィルム15内の液晶層4の配向方向5が45度になるようにアクリル系粘着剤を介して貼り合わせて円偏光板16を作製した。貼り合わせる際、TAC6側が偏光板1と接するように積層させた。偏光板1と光学フィルム15の液晶層4の積層状態での断面構造の概要図を図27に示す。
得られた円偏光板16を、実施例1と同様に、市販の有機ELディスプレイの有機EL素子の透明ガラス基板上にアクリル系粘着剤を介して貼着し、本発明の有機EL表示装置を作成した。その結果、円偏光板を配置しない場合に比べ、大幅な外光反射防止効果を発揮し、視認性の優れた有機EL表示装置が得られることが分かった。
また、外光を入射した際の反射率の視野角特性をEZ-CONTRASTにて測定した結果と正面反射率を図28、表2に示す。実施例1と比較例1で比較した場合、実施例1の方が反射率の視野角特性が優れることがわかる。複屈折の波長分散特性は同等であることから、この特性の違いは液晶配向がネマチックハイブリッド配向とホモジニアス配向の違いに起因すると考えられ、ネマチックハイブリッド配向が反射防止性能の視野角改良に有効であることを示唆している。
また、実施例2、実施例3、実施例4と比較例1で比較した場合も、3つの実施例とも反射率の視野角特性に優れていることから、ネマチックハイブリッド配向の構造を上下逆にした場合でも、ネマチックハイブリッド配向にねじれ構造を付与した場合でも、あるいはネマチックハイブリッド配向を2層設けることでも同様に視野角改良に有効であることがわかる。 <Antireflection performance evaluation of organic EL display>
For the optical film produced in Comparative Example 1, the
The obtained circularly
In addition, FIG. 28 and Table 2 show the results of measuring the viewing angle characteristics of the reflectance when the external light is incident by EZ-CONTRAST and the front reflectance. When comparing Example 1 and Comparative Example 1, it can be seen that Example 1 is superior in viewing angle characteristics of reflectance. Since the wavelength dispersion characteristics of birefringence are the same, this difference in characteristics is thought to be due to the difference in liquid crystal alignment between nematic hybrid alignment and homogeneous alignment, and nematic hybrid alignment is effective in improving the viewing angle of antireflection performance. Suggests that.
In addition, when compared with Example 2, Example 3, Example 4 and Comparative Example 1, all the three examples are excellent in viewing angle characteristics of reflectance, so the structure of nematic hybrid orientation is turned upside down. It can be seen that even when the twisted structure is added to the nematic hybrid alignment, or when two layers of the nematic hybrid alignment are provided, the viewing angle can be improved.
二色性色素を混合しない以外は、実施例1と同様にして光学フィルム(液晶フィルム/接着剤層/TAC)を得た。図29に液晶フィルム層の複屈折の波長分散特性を、表1に光学特性結果をまとめる。
光学フィルムの正面方向のレターデーション(Δn・d)の波長分散特性、斜め方向の位相差測定による平均チルト角の測定を行ったところ、波長550nmでのΔn・dは138nm、平均チルト角は34度のネマチックハイブリッド配向フィルムであることを確認した。
また、液晶フィルム層の複屈折の波長分散特性を測定した。図29に、液晶フィルム層の複屈折の波長分散特性を、表2に光学特性結果をまとめる。複屈折の波長分散特性は、Δn・d(500)/Δn・d(550)=0.98であり、Δn・d(580)/Δn・d(550)=1.01であり、Δn・d(600)/Δn・d(550)=1.01であり、実施例1で作製した光学フィルムの波長分散特性よりは理想に対し劣ることがわかった。 (Comparative Example 2)
An optical film (liquid crystal film / adhesive layer / TAC) was obtained in the same manner as in Example 1 except that the dichroic dye was not mixed. FIG. 29 summarizes the birefringence wavelength dispersion characteristics of the liquid crystal film layer, and Table 1 summarizes the optical characteristics results.
When measuring the wavelength dispersion characteristics of retardation (Δn · d) in the front direction of the optical film and the average tilt angle by measuring the phase difference in the oblique direction, Δn · d at a wavelength of 550 nm is 138 nm, and the average tilt angle is 34. Of a nematic hybrid alignment film of the same degree.
Further, the birefringence wavelength dispersion characteristic of the liquid crystal film layer was measured. FIG. 29 summarizes the birefringence wavelength dispersion characteristics of the liquid crystal film layer, and Table 2 summarizes the optical characteristics results. The wavelength dispersion characteristics of birefringence are Δn · d (500) / Δn · d (550) = 0.98, Δn · d (580) / Δn · d (550) = 1.01, and Δn · d. It was found that d (600) / Δn · d (550) = 1.01, which was inferior to the ideal wavelength dispersion characteristic of the optical film produced in Example 1.
得られた光学フィルムを、実施例1と同様に市販の偏光板1(住友化学社製、SRW062)と貼り合わせた。偏光板1と光学フィルム3の液晶層4の積層状態での断面構造の概要図は、実施例1と同じ図18であり、光学フィルム3内の液晶層は、液晶分子がより立ち上がっている面が偏光板1側になり、液晶分子がより寝ている面が偏光板1と反対側になる。
得られた円偏光板7を、市販の有機ELディスプレイの有機EL素子の透明ガラス基板上にアクリル系粘着剤を介して貼着し、本発明の有機EL表示装置を作成した。その結果、円偏光板7を配置しない場合に比べ、大幅な外光反射防止効果を発揮し、視認性の優れた有機EL表示装置が得られることが分かった。
また、外光を入射した際の反射率の視野角特性をEZ-CONTRASTにて測定した結果と正面反射率を図30、表2に示す。その結果、円偏光板を配置しない場合に比べると、反射防止効果は確認できたが、実施例1と比較すると、青みがかかっており、反射防止効果は劣ることがわかった。これは、複屈折の波長分散特性が実施例1よりも理想から外れているため反射率が全体的に悪化する結果となった。このことから、ネマチックハイブリッド構造による視野角特性改善の効果は得られるが、正面反射率の改善には二色性色素添加が必須であることがわかる。 <Antireflection performance evaluation of organic EL display>
The obtained optical film was bonded to a commercially available polarizing plate 1 (manufactured by Sumitomo Chemical Co., Ltd., SRW062) in the same manner as in Example 1. The schematic diagram of the cross-sectional structure of the
The obtained circularly
In addition, FIG. 30 and Table 2 show the results of measuring the viewing angle characteristics of the reflectance when the external light is incident by EZ-CONTRAST and the front reflectance. As a result, the antireflection effect could be confirmed as compared with the case where no circularly polarizing plate was arranged, but it was found that the antireflection effect was inferior compared with Example 1 because of being bluish. This is because the birefringence wavelength dispersion characteristic is not ideal as compared with Example 1, and thus the reflectance deteriorates as a whole. From this, it can be seen that the effect of improving the viewing angle characteristics by the nematic hybrid structure can be obtained, but addition of a dichroic dye is essential for improving the front reflectance.
特開平10-186356号公報の実施例1に記載の液晶材料と製造方法により、波長550nmでのΔn・dが138nmであり、平均チルト角が34度のネマチックハイブリッド配向の液晶フィルムを作製した。図31に液晶フィルム層の複屈折の波長分散特性を、表1に光学特性結果をまとめる。Δn・d(500)/Δn・d(550)=1.05であり、Δn・d(580)/Δn・d(550)=0.98であり、Δn・d(600)/Δn・d(550)=0.97であり、可視光領域では「正の分散」特性を有することを確認した。
実施例1と同様に偏光板と貼り合わせを行い、有機ELディスプレイに粘着した。正面から見た場合、強く青みがかかり、反射防止性能としては実施例1と比較しても大きく劣ることがわかった。これは、ネマチックハイブリッド配向構造を有する液晶フィルムの複屈折波長分散特性が不十分であるためと考えられる。
また、外光を入射した際の反射率の視野角特性をEZ-CONTRASTにて測定した結果を図32に示す。ネマチックハイブリッド構造による視野角特性改善の効果は確認できたが、複屈折の波長分散特性が劣ることにより反射率が全体的に悪化する結果となった。
以上のことより、有機ELディスプレイの反射防止性能として、二色性色素を含有するネマチックハイブリッド構造を有する液晶フィルムが、正面および斜め方向において大幅な改善効果があることが確認できた。 (Comparative Example 3)
A nematic hybrid alignment liquid crystal film having a Δn · d at a wavelength of 550 nm of 138 nm and an average tilt angle of 34 degrees was prepared by the liquid crystal material and the manufacturing method described in Example 1 of JP-A-10-186356. FIG. 31 summarizes the birefringence wavelength dispersion characteristics of the liquid crystal film layer, and Table 1 summarizes the optical characteristics results. Δn · d (500) / Δn · d (550) = 1.05, Δn · d (580) / Δn · d (550) = 0.98, and Δn · d (600) / Δn · d. (550) = 0.97, confirming that it has a “positive dispersion” characteristic in the visible light region.
In the same manner as in Example 1, it was bonded to a polarizing plate and adhered to an organic EL display. When viewed from the front, it was strongly bluish, and the antireflection performance was found to be significantly inferior to that of Example 1. This is considered because the birefringence wavelength dispersion characteristic of the liquid crystal film having a nematic hybrid alignment structure is insufficient.
Further, FIG. 32 shows the result of measuring the viewing angle characteristic of the reflectance when external light is incident by EZ-CONTRAST. Although the effect of improving the viewing angle characteristics by the nematic hybrid structure was confirmed, the reflectance was deteriorated as a whole due to the inferior birefringence wavelength dispersion characteristics.
From the above, it was confirmed that the liquid crystal film having a nematic hybrid structure containing a dichroic dye has a significant improvement effect in the front and oblique directions as the antireflection performance of the organic EL display.
Δna・da(580)/Δna・da(550)-Δnb・db(580)/Δnb・db(550)
から算出される値は0.01であり、0よりも大きく、上記数式(1)を満足することがわかった。 Further, based on the above results, the difference in retardation ratio between the system in which the dichroic dye was mixed (Example 1) and the system in which the dichroic dye was not mixed (Comparative Example 2), that is, formula:
Δna · da (580) / Δna · da (550) −Δnb · db (580) / Δnb · db (550)
The value calculated from is 0.01, which is larger than 0, and it was found that the above formula (1) was satisfied.
実施例1で作製した液晶フィルムを1枚偏光板反射型液晶表示装置に組み込み評価した。その構成は観察側から、偏光板/実施例1で作製した液晶フィルム/ガラス基板/ITO透明電極/配向膜/ツイストネマチック液晶/配向膜/金属電極兼反射膜/ガラス基板である。各層間の粘着層は省略してある。電圧オフ時に白表示となるような貼り合わせ角度にして、目視にて色味の評価を実施した。特に電圧オン時の黒表示における着色が少なく、それによりコントラストが高く、視認性に優れることが確認できた。 (Example 5)
The liquid crystal film produced in Example 1 was incorporated into a polarizing plate reflective liquid crystal display device and evaluated. From the observation side, the configuration is polarizing plate / liquid crystal film prepared in Example 1 / glass substrate / ITO transparent electrode / alignment film / twist nematic liquid crystal / alignment film / metal electrode / reflection film / glass substrate. The adhesive layer between each layer is omitted. The color was evaluated visually by setting the bonding angle so as to display white when the voltage was turned off. In particular, it was confirmed that there was little coloration in black display when the voltage was turned on, thereby providing high contrast and excellent visibility.
2:偏光板の吸収軸
3、9、13、15:光学フィルム
4:液晶層
5:チルト方向
6:TACフィルム
7、8、10、14、16:円偏光板
11:液晶配向方向(偏光板側)
12:液晶配向方向(TACフィルム側) 1: Polarizing plate 2:
12: Liquid crystal alignment direction (TAC film side)
Claims (12)
- 複屈折Δnが、可視光領域の少なくとも一部の波長領域において、測定波長が長いほど大きくなる「負の分散」特性を有する位相差板であって、
重合性液晶組成物と、少なくとも1種類以上の二色性色素とを含んでなり、かつ液晶化合物がネマチックハイブリッド配向した液晶フィルムからなる、位相差板。 The birefringence Δn is a phase difference plate having a “negative dispersion” characteristic that increases as the measurement wavelength increases in at least a part of the wavelength region of the visible light region,
A retardation film comprising a polymerizable liquid crystal composition and at least one dichroic dye, and comprising a liquid crystal film in which a liquid crystal compound is nematic hybrid aligned. - 前記位相差板の法線方向でのリターデーションをΔna・da、
前記液晶フィルムから前記二色性色素を除いた液晶フィルムからなる位相差板の法線方向でのリターデーションをΔnb・db、
とした場合に、下記数式(1):
Δna・da(580)/Δna・da(550)-Δnb・db(580)/Δnb・db(550)>0 (1)
(ここで、リターデーションとは、複屈折Δnと位相差板の膜厚dの積で表され、Δna・da(580)、Δna・da(580)は、波長580nmにおける各位相差板のリターデーションであり、Δna・da(550)、Δna・da(550)は、波長550nmにおける各位相差板のリターデーションである。)
を満たす、請求項1に記載の位相差板。 Retardation in the normal direction of the retardation plate is Δna · da,
Retardation in the normal direction of a retardation film composed of a liquid crystal film obtained by removing the dichroic dye from the liquid crystal film is Δnb · db,
When the following formula (1):
Δna · da (580) / Δna · da (550) −Δnb · db (580) / Δnb · db (550)> 0 (1)
(Here, the retardation is represented by the product of birefringence Δn and the thickness d of the retardation plate, and Δna · da (580) and Δna · da (580) are retardations of each retardation plate at a wavelength of 580 nm). Δna · da (550) and Δna · da (550) are retardations of each phase difference plate at a wavelength of 550 nm.)
The retardation plate according to claim 1, wherein - 前記液晶化合物がツイストネマチックハイブリッド配向した液晶フィルムからなる、請求項1または2に記載の位相差板。 The phase difference plate according to claim 1 or 2, wherein the liquid crystal compound comprises a liquid crystal film with twisted nematic hybrid alignment.
- 前記液晶フィルムが、重合性液晶組成物と少なくとも1種類以上の二色性色素とを含む混合物を液晶状態においてネマチックハイブリッド配向させ、光または熱による架橋反応により該配向を固定化したものである、請求項1または2に記載の位相差板。 The liquid crystal film is a nematic hybrid alignment of a mixture containing a polymerizable liquid crystal composition and at least one dichroic dye in a liquid crystal state, and the alignment is fixed by a crosslinking reaction by light or heat. The phase difference plate according to claim 1 or 2.
- 前記液晶フィルムが、重合性液晶組成物と少なくとも1種類以上の二色性色素とを含む混合物を液晶状態においてツイストネマチックハイブリッド配向させ、光または熱による架橋反応により該配向を固定化したものである、請求項3に記載の位相差板。 The liquid crystal film is obtained by twisting nematic hybrid alignment of a mixture containing a polymerizable liquid crystal composition and at least one dichroic dye in a liquid crystal state, and fixing the alignment by light or heat crosslinking reaction. The phase difference plate according to claim 3.
- 特定波長における位相差板の法線方向でのリターデーションの比が、下記数式(2)および(3):
0.80<Δn・d(500)/Δn・d(550)<1.00 (2)
1.00<Δn・d(600)/Δn・d(550)<1.15 (3)
(ここで、リターデーションとは、複屈折Δnと位相差板の膜厚dの積で表され、Δn・d(500)、Δn・d(550)、Δn・d(600)は、それぞれ波長500nm、550nm、600nmにおける位相差板のリターデーションである。)
を満たす、請求項1~5のいずれか一項に記載の位相差板。 The ratio of retardation in the normal direction of the phase difference plate at a specific wavelength is expressed by the following mathematical formulas (2) and (3):
0.80 <Δn · d (500) / Δn · d (550) <1.00 (2)
1.00 <Δn · d (600) / Δn · d (550) <1.15 (3)
(Here, retardation is represented by the product of birefringence Δn and the film thickness d of the retardation plate, and Δn · d (500), Δn · d (550), and Δn · d (600) are respectively wavelengths. Retardation of retardation plate at 500 nm, 550 nm, and 600 nm.)
The retardation film according to any one of claims 1 to 5, which satisfies the following conditions. - 二色性色素の極大吸収波長が測定波長380~780nmの領域にある、請求項1~6のいずれか一項に記載の位相差板。 The phase difference plate according to any one of claims 1 to 6, wherein the maximal absorption wavelength of the dichroic dye is in a measurement wavelength region of 380 to 780 nm.
- 表示装置の発光スペクトルの極大波長と二色性色素の極大吸収波長が異なる、請求項1~7のいずれか一項に記載の位相差板。 The phase difference plate according to any one of claims 1 to 7, wherein the maximum wavelength of the emission spectrum of the display device is different from the maximum absorption wavelength of the dichroic dye.
- 前記液晶フィルムの液晶分子の平均チルト角が5~45度である、請求項1~8のいずれか一項に記載の位相差板。 The phase difference plate according to any one of claims 1 to 8, wherein an average tilt angle of liquid crystal molecules of the liquid crystal film is 5 to 45 degrees.
- 前記液晶フィルムの液晶分子のフィルム面内のツイスト角が0~70度である、請求項1~9のいずれか一項に記載の位相差板。 The retardation plate according to any one of claims 1 to 9, wherein a twist angle in a film plane of liquid crystal molecules of the liquid crystal film is 0 to 70 degrees.
- 請求項1~10のいずれか一項に記載の位相差板と偏光子とを備えた、積層偏光板。 A laminated polarizing plate comprising the retardation plate according to any one of claims 1 to 10 and a polarizer.
- 請求項1~10のいずれか一項に記載の位相差板を備えた、表示装置。 A display device comprising the phase difference plate according to any one of claims 1 to 10.
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JP2015562815A JP6392257B2 (en) | 2014-02-12 | 2015-02-09 | Retardation plate, laminated polarizing plate using retardation plate, and display device using retardation plate |
KR1020167020252A KR101891421B1 (en) | 2014-02-12 | 2015-02-09 | Retardation plate, laminated polarizing plate using retardation plate, and display device using retardation plate |
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JP2016110153A (en) * | 2014-12-08 | 2016-06-20 | 三星電子株式会社Samsung Electronics Co.,Ltd. | Reflection-proof film and organic light emission device comprising the same |
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Also Published As
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KR101891421B1 (en) | 2018-08-24 |
TW201539062A (en) | 2015-10-16 |
JPWO2015122387A1 (en) | 2017-03-30 |
JP6392257B2 (en) | 2018-09-19 |
KR20160121512A (en) | 2016-10-19 |
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