Retardation film, polarizing plate, and liquid crystal display device

Abstract

The present invention addresses the problem of providing: a phase difference film with which it is possible to produce a liquid crystal display device having an excellent planar shape and good slant contrast; and a polarizing plate and a liquid crystal display device using the phase difference film. The phase difference film according to the present invention has a support body that exhibits reverse wavelength dispersibility in an in-plane retardation, and a liquid crystal layer that is directly laminated on the support body, and is characterized in that: the support body is a polymer film that has been stretched in at least one direction in the plane; the liquid crystal layer is a positive C plate obtained by immobilizing the alignment state of a liquid crystal composition containing a liquid crystal compound, and in the surface energy of the surface of the support on the side on which the liquid crystal layer is laminated, the non-polar component is less than 45 mN / m and the polar component is 2 mN / m or more. The half width of the peak of the power spectrum obtained by fast Fourier transform of the reflectance spectrum of the retardation film is 400 nm or less, and the haze value of the retardation film is 1.0% or less.

Description

Technical Field

[0001] This invention relates to a phase retardation film, a polarizer, and a liquid crystal display device. Background Technology

[0002] For a long time, polarizers with phase difference films and polarizers have been used in liquid crystal display devices, organic electroluminescent devices and other devices for purposes such as optical compensation and anti-reflection.

[0003] As a phase retardation film in such a polarizer, for example, Patent Document 1 describes "a phase retardation film comprising: a support; and a liquid crystal layer, formed by contacting the support with a liquid crystal composition containing a liquid crystal compound, wherein the surface energy of the surface of the support forming the liquid crystal layer is 45 mN / m or more and the non-polar dispersive force component contained in the surface energy is 45 mN / m or more, and the liquid crystal compound is immobilized in an oriented state, and the contrast ratio exceeds 10000." ([Claim 1]).

[0004] Previous technical documents Patent documents Patent Document 1: International Publication No. 2020 / 045224 Summary of the Invention

[0005] The technical problem to be solved by the invention

[0006] Based on their research on the phase retardation film described in Patent Document 1, the inventors have determined that when a liquid crystal display device made using this phase retardation film is set to black and viewed from an oblique direction, inhomogeneity and surface aberration sometimes occur within the plane.

[0007] Furthermore, the inventors have clarified that when a liquid crystal display device is manufactured using a positive C-plate formed by fixing the orientation state of a liquid crystal composition as the liquid crystal layer of the retardation film described in Patent Document 1, depending on the forming materials and forming conditions of the support and the liquid crystal layer, when observing the brightness of the black and white displays from an oblique direction, the contrast ratio (brightness of the white display / brightness of the black display) [hereinafter referred to as "oblique contrast ratio"] is sometimes poor.

[0008] Therefore, the objective of this invention is to provide a phase retardation film capable of producing a liquid crystal display device with excellent planar shape and good oblique contrast, as well as a polarizer and a liquid crystal display device using the phase retardation film.

[0009] means for solving technical problems

[0010] The inventors conducted in-depth research on the above-mentioned issues and discovered that by using the following phase retardation film, it is possible to fabricate a liquid crystal display device with excellent planar shape and good oblique contrast. The present invention was thus completed. The phase retardation film has a support having in-plane retardation display of reverse wavelength dispersion and a specified surface energy, and a specified liquid crystal layer directly stacked on the support, and satisfies the specified power spectrum peak width at half maximum and haze value.

[0011] That is, the inventors discovered that the above-mentioned problems can be solved by the following structure.

[0012] [1] A phase retardation film having a support exhibiting in-plane retardation with inverse wavelength dispersion and a liquid crystal layer directly stacked on the support, wherein... The support is a polymer film that has been stretched in at least one direction within its plane. A liquid crystal layer is a positive C-plate formed by fixing the orientation state of a liquid crystal composition containing a liquid crystal compound. In the surface energy of one side of the stacked liquid crystal layer of the support, the non-polar component is less than 45 mN / m and the polar component is greater than 2 mN / m. The power spectrum obtained by performing a fast Fourier transform on the reflectance spectrum of the phase retardation film has a peak width of less than 400 nm. The haze value of the phase retardation film is below 1.0%.

[0013] [2] According to the phase difference film described in [1], wherein, The surface energy of one side of the stacked liquid crystal layer of the support is above 45 mN / m.

[0014] [3] According to the phase difference film described in [1] or [2], wherein, The material constituting the support is polycarbonate or polyester.

[0015] [4] The phase difference film according to any one of [1] to [3], wherein, The supporting structure is the A-plate.

[0016] [5] The phase difference film according to any one of [1] to [4], wherein, The thickness retardation of the liquid crystal layer exhibits reverse wavelength dispersion.

[0017] [6] The phase difference film according to any one of [1] to [5], wherein, The liquid crystal composition also contains a boric acid monomer having polymerizable groups and boric acid groups represented by formula (B) described later.

[0018] [7] A polarizer having a phase difference film and a polarizer as described in any one of [1] to [6].

[0019] [8] According to the polarizer described in [7], wherein, The absorption axis of the polarizer is orthogonal or parallel to the slow axis of the support structure of the phase difference film.

[0020] [9] According to the polarizer described in [7], wherein, The absorption axis of the polarizer is parallel to the slow axis of the support structure of the phase difference film.

[0021]

[10] A liquid crystal display device having a polarizer as described in any one of [7] to [9].

[0022] Invention Effects

[0023] As shown below, according to the present invention, a phase retardation film capable of producing a liquid crystal display device with excellent planar shape and good oblique contrast can be provided, as well as a polarizer and a liquid crystal display device using the phase retardation film. Detailed Implementation

[0024] The following description of the constituent elements is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0025] In addition, in this specification, the numerical range represented by “~” indicates the range included by the values ​​recorded before and after “~” as the lower limit and upper limit values.

[0026] Furthermore, in this specification, the upper or lower limit of a numerical range recorded in a certain numerical range can be replaced with the upper or lower limit of another numerical range recorded in a certain period. Also, the upper or lower limit of a numerical range recorded in this specification can be replaced with the values ​​shown in the embodiments.

[0027] Furthermore, in this specification, regarding angles, "orthogonal" and "parallel" refer to a strict range of ±10°. Regarding angles, "same" and "different" can be determined based on whether their difference is less than 5°.

[0028] Furthermore, in this specification, "visible light" refers to 380–780 nm. Also, in this specification, unless otherwise specified, the measurement wavelength is 550 nm.

[0029] Furthermore, the bonding direction of divalent groups (e.g., -O-CO-) described in this specification is not particularly limited, for example, in "L 1 -L 2 -L 3 In the bonding of "L" 2 In the case of -O-CO-, if it is combined with L1 The side bond position is set to 1 and will be with L 3 The side bond position is set to 2, then L 2 It can be 1-O-CO- 2, or it could be 1-CO-O- 2.

[0030] Next, the terminology used in this specification will be explained.

[0031] [Slow axis]

[0032] In this specification, "slow axis" refers to the direction in which the in-plane refractive index is at its maximum. Additionally, in the case of a slow axis referred to as a retardation film, it refers to the slow axis of the entire retardation film.

[0033] [Re(λ), Rth(λ)]

[0034] In this specification, Re(λ) and Rth(λ) represent the in-plane retardation and the thickness-direction retardation at wavelength λ, respectively. Unless otherwise specified, wavelength λ is set to 550 nm.

[0035] Here, the values ​​of in-plane delay and thickness direction delay refer to the values ​​measured using AxoScan OPMF-1 (manufactured by Opto Science, Inc.) and light of the measurement wavelength.

[0036] Specifically, by inputting the average refractive index ((Nx+Ny+Nz) / 3) and film thickness (d (μm)) into AxoScan OPMF-1, the following can be calculated: Slow axis direction (°) Re(λ) = R0(λ) Rth(λ)=((nx+ny) / 2-nz)×d.

[0037] Additionally, R0(λ) is shown as the value calculated in AxoScan OPMF-1, but refers to Re(λ).

[0038] [Substituents]

[0039] In this specification, the substituents (monovalent substituents) described in substituent group A below can be cited as examples.

[0040] Furthermore, in this specification, the phrase "may have substituents" includes, of course, a mode without substituents, as well as a mode with one or more substituents.

[0041] <Substituent group A>

[0042] As substituents, examples include the following, and more than two of them can be combined: Halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, preferably chlorine atom, fluorine atom, more preferably fluorine atom); Alkyl groups (preferably straight-chain, branched, or cyclic alkyl groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and especially preferably 1 to 8 carbon atoms, for example, straight-chain alkyl groups having 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl), branched alkyl groups having 3 to 6 carbon atoms (e.g., isopropyl, isobutyl, tert-butyl, sec-butyl, neopentyl, isohexyl, 3-methylpentyl), and cyclic alkyl groups having 3 to 12 carbon atoms (e.g., cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl)). Alkenyl (preferably alkenyl with 2 to 48 carbon atoms, more preferably alkenyl with 2 to 18 carbon atoms, for example, vinyl, allyl, 1-butenyl, 2-butenyl); Alkynyl (preferably an alkynyl group with 2 to 6 carbon atoms, more preferably an alkynyl group with 2 to 4 carbon atoms, for example, ethynyl, 1-propynyl, propynyl, 1-butynyl, 2-butynyl); Aryl (preferably aryl with 6 to 48 carbon atoms, more preferably aryl with 6 to 24 carbon atoms, for example, phenyl, oligoaryl (naphthyl, anthracene), phenanthrene, fluorenyl, pyrene, triphenylene, biphenyl); Heteroaryl groups (preferably heterocyclic groups with 1 to 32 carbon atoms, more preferably heterocyclic groups with 1 to 18 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2-furanyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl); Aryl alkyl group (preferably an aryl alkyl group having 7 to 15 carbon atoms, for example, benzyl, phenethyl, methylbenzyl, phenylpropyl, 1-methylphenylethyl, phenylbutyl, 2-methylphenylpropyl, tetrahydronaphthyl, naphthylmethyl, naphthylethyl, indene, fluorenyl, anthrylmethyl, phenanthrylmethyl)); Silyl group (preferably silyl group with 3 to 38 carbon atoms, more preferably silyl group with 3 to 18 carbon atoms, for example, trimethylsilyl, triethylsilyl, tributylsilyl, tert-butyldimethylsilyl, tert-hexyldimethylsilyl); Hydroxyl; cyano; nitro; morpholino; Alkoxy groups (preferably alkoxy groups with 1 to 48 carbon atoms, more preferably alkoxy groups with 1 to 24 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, tert-butoxy, dodecyloxy, cycloalkoxy (e.g., cyclopentoxy, cyclohexyloxy)). Aryloxy group (preferably an aryloxy group with 6 to 48 carbon atoms, more preferably an aryloxy group with 6 to 24 carbon atoms, for example, phenoxy group, 1-naphthoxy group); Alkenyloxy group (preferably an alkenyloxy group having 2 to 6 carbon atoms, for example, ethyleneoxy, 1-propenoxy, 2-n-propenoxy (allyloxy), 1-n-butenoxy, isopreneoxy). Heterocyclic groups (preferably heterocyclic groups with 1 to 32 carbon atoms, more preferably heterocyclic groups with 1 to 18 carbon atoms, for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranoxy); Silyoxy group (preferably siloxy group with 1 to 32 carbon atoms, more preferably siloxy group with 1 to 18 carbon atoms, for example, trimethylsiloxy group, tert-butyldimethylsiloxy group, diphenylmethylsiloxy group). Acyloxy group (preferably an acyloxy group with 2 to 48 carbon atoms, more preferably an acyloxy group with 2 to 24 carbon atoms, for example, acetoxy, neopentyloxy, benzoyloxy, dodecyloxy, acryloyloxy, methacryloyloxy). Hydroxyalkoxide (preferably a hydroxyalkoxide with 2 to 10 carbon atoms, for example, hydroxyethoxy); Alkoxycarbonyloxy (preferably alkoxycarbonyloxy with 2 to 48 carbon atoms, more preferably alkoxycarbonyloxy with 2 to 24 carbon atoms, such as ethoxycarbonyloxy, tert-butoxycarbonyloxy, cycloalkoxycarbonyloxy (e.g., cyclohexyloxycarbonyloxy)); Aryloxycarbonyloxy (preferably aryloxycarbonyloxy with 7 to 32 carbon atoms, more preferably aryloxycarbonyloxy with 7 to 24 carbon atoms, for example, phenoxycarbonyloxy); Carbamoyloxy (preferably carbamoyloxy with 1 to 48 carbon atoms, more preferably with 1 to 24 carbon atoms, for example, N,N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy). Aminosulfonyloxy (preferably an aminosulfonyloxy with 1 to 32 carbon atoms, more preferably an aminosulfonyloxy with 1 to 24 carbon atoms, for example, N,N-diethylaminosulfonyloxy, N-propylaminosulfonyloxy). Alkylsulfonyloxy (preferably alkylsulfonyloxy with 1 to 38 carbon atoms, more preferably alkylsulfonyloxy with 1 to 24 carbon atoms, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy); Arylsulfonyloxy group (preferably arylsulfonyloxy group with 6 to 32 carbon atoms, more preferably arylsulfonyloxy group with 6 to 24 carbon atoms, for example, phenylsulfonyloxy group); Acyl group (preferably an acyl group with 1 to 48 carbon atoms, more preferably an acyl group with 1 to 24 carbon atoms, for example, formyl, acetyl, acryloyl, methacryloyl, neopentyl, benzoyl, tetradecanoyl, cyclohexyl); Alkoxycarbonyl (preferably an alkoxycarbonyl with 2 to 48 carbon atoms, more preferably an alkoxycarbonyl with 2 to 24 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl); Aryloxycarbonyl (preferably an aryloxycarbonyl with 7 to 32 carbon atoms, more preferably an aryloxycarbonyl with 7 to 24 carbon atoms, for example, phenoxycarbonyl); Carbamoyl group (preferably a carbamoyl group with 1 to 48 carbon atoms, more preferably a carbamoyl group with 1 to 24 carbon atoms, for example, carbamoyl group, N,N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N,N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N,N-dicyclohexylcarbamoyl group); Amino group (preferably an amino group with 32 or fewer carbon atoms, more preferably an amino group with 24 or fewer carbon atoms, for example, amino, methylamino, N,N-dimethylamino, N,N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino); Aniline (preferably aniline with 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, aniline or N-methylaniline); Heterocyclic amino group (preferably a heterocyclic amino group with 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 4-pyridylamino group); Carboxylamide group (preferably a carboxylamide group with 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetamide group, benzamide group, tetradecanoamide group, neopentanoylamide group, cyclohexaneamide group); Urea group (preferably a urea group with 1 to 32 carbon atoms, more preferably a urea group with 1 to 24 carbon atoms, for example, urea group, N,N-dimethylurea group, N-phenylurea group); Imide group (preferably an imide group with 36 or fewer carbon atoms, more preferably an imide group with 24 or fewer carbon atoms, for example, N-succinimide group, N-phthalimide group); Alkoxycarbonylamino (preferably alkoxycarbonylamino with 2 to 48 carbon atoms, more preferably alkoxycarbonylamino with 2 to 24 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino). Aryloxycarbonylamino (preferably aryloxycarbonylamino with 7 to 32 carbon atoms, more preferably aryloxycarbonylamino with 7 to 24 carbon atoms, for example, phenoxycarbonylamino); Sulfonamide group (preferably a sulfonamide group with 1 to 48 carbon atoms, more preferably a sulfonamide group with 1 to 24 carbon atoms, for example, methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group); Aminosulfonylamino (preferably an aminosulfonylamino with 1 to 48 carbon atoms, more preferably an aminosulfonylamino with 1 to 24 carbon atoms, for example, N,N-dipropylaminosulfonylamino, N-ethyl-N-dodecylaminosulfonylamino). Azo group (preferably an azo group with 1 to 32 carbon atoms, more preferably an azo group with 1 to 24 carbon atoms, for example, phenyl azo group, 3-pyrazolyl azo group); Alkylthio (preferably alkylthio with 1 to 48 carbon atoms, more preferably alkylthio with 1 to 24 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexylthio); Arylthio (preferably arylthio with 6 to 48 carbon atoms, more preferably arylthio with 6 to 24 carbon atoms, for example, phenylthio); Heterocyclic thio groups (preferably heterocyclic thio groups with 1 to 32 carbon atoms, more preferably heterocyclic thio groups with 1 to 18 carbon atoms, for example, 2-benzothiazolyl thio group, 2-pyridyl thio group, 1-phenyltetrazole thio group); Alkyl sulfinyl group (preferably an alkyl sulfinyl group with 1 to 32 carbon atoms, more preferably an alkyl sulfinyl group with 1 to 24 carbon atoms, for example, dodecane sulfinyl group); Arylsulfinyl group (preferably arylsulfinyl group with 6 to 32 carbon atoms, more preferably arylsulfinyl group with 6 to 24 carbon atoms, for example, phenylsulfinyl group); Alkyl sulfonyl group (preferably an alkyl sulfonyl group with 1 to 48 carbon atoms, more preferably an alkyl sulfonyl group with 1 to 24 carbon atoms, for example, methyl sulfonyl, ethyl sulfonyl, propyl sulfonyl, butyl sulfonyl, isopropyl sulfonyl, 2-ethylhexyl sulfonyl, hexadecyl sulfonyl, octyl sulfonyl, cyclohexyl sulfonyl). Arylsulfonyl group (preferably arylsulfonyl group with 6 to 48 carbon atoms, more preferably arylsulfonyl group with 6 to 24 carbon atoms, for example, phenylsulfonyl group, 1-naphthylsulfonyl group); Aminosulfonyl group (preferably an aminosulfonyl group with 32 or fewer carbon atoms, more preferably an aminosulfonyl group with 24 or fewer carbon atoms, for example, aminosulfonyl group, N,N-dipropylaminosulfonyl group, N-ethyl-N-dodecylaminosulfonyl group, N-ethyl-N-phenylaminosulfonyl group, N-cyclohexylaminosulfonyl group, N-(2-ethylhexyl)aminosulfonyl group); Phosphonoyl group (preferably a phosphonoyl group with 1 to 32 carbon atoms, more preferably a phosphonoyl group with 1 to 24 carbon atoms, for example, phenoxyphosphonoyl group, octoxyphosphonoyl group, phenylphosphonoyl group); Oxyphosphinoamino (preferably oxyphosphinoamino with 1 to 32 carbon atoms, more preferably oxyphosphinoamino with 1 to 24 carbon atoms, for example, ethoxyphosphinoamino, dioctyloxyphosphinoamino). Epoxy groups; -NHCOCH3; -SO2NHC2H4OCH3; -NHSO2CH3, etc.

[0043] These substituents can be further replaced by these substituents. Furthermore, in the case of two or more substituents, they can be identical or different. And, where possible, they can bond together to form a ring.

[0044] [Phase difference film]

[0045] The phase retardation film of the present invention is a phase retardation film having a support exhibiting in-plane retardation and reverse wavelength dispersion, and a liquid crystal layer directly stacked on the support.

[0046] Furthermore, the support of the phase retardation film of the present invention is a polymer film that has been stretched in at least one direction in the plane.

[0047] Furthermore, the liquid crystal layer of the phase retardation film of the present invention is a positive C-plate formed by fixing the orientation state of a liquid crystal composition containing a liquid crystal compound.

[0048] Furthermore, in the phase retardation film of the present invention, the surface energy of the surface of the side of the support on which the liquid crystal layer is stacked has a non-polar component of less than 45 mN / m and a polar component of more than 2 mN / m.

[0049] Furthermore, in the phase difference film of the present invention, the full width at half maximum (FWHM) of the power spectrum obtained by performing a fast Fourier transform on the reflectance spectrum is less than 400 nm.

[0050] Furthermore, the haze value of the phase retardation film of the present invention is 1.0% or less.

[0051] [The full width at half maximum (FWHM) of the power spectrum peaks]

[0052] The full width at half maximum (FWHM) of a power spectrum peak is a value calculated using the following steps.

[0053] First, a sample with a blackened polyethylene terephthalate (PET) film is attached to the surface of the support of the phase retardation film on the side without a liquid crystal layer.

[0054] The prepared sample was placed in a reflectance spectrophotometer (FE-3000, manufactured by Otsuka Electronics Co., Ltd.) and a D2 lamp light source was used to measure the reflectance spectrum of the side of the phase retardation film not bonded to the black PET.

[0055] Next, a fast Fourier transform is performed on the measured spectrum to obtain the power spectrum relative to the film thickness.

[0056] Next, the full width at half maximum (FWHM) is calculated for the peaks in the obtained power spectrum originating from the interface between the support and the liquid crystal layer.

[0057] In addition, the measurement conditions for reflectance spectra using the FE-3000, as well as the calculation method and wavelength range of the fast Fourier transform, are described below. Measurement method: Absolute reflectance Calculation method: FFT (Fast Fourier Transform) The computational wavelength range for FFT analysis is 310.00–760.00 nm.

[0058] [Haze value]

[0059] The haze value refers to the haze measured in accordance with JIS K7136:2000 "Method for determining haze of plastics-transparent materials", and refers to the value measured using a haze meter (e.g., NDH4000 (manufactured by NIPPON DENSHOKUINDUSTRIES Co.,LTD.)) in an environment of 25°C and 55% relative humidity.

[0060] In this invention, the surface energy of the surface of one side of the liquid crystal layer stacked on the support is such that the non-polar component is less than 45 mN / m and the polar component is more than 2 mN / m, and the half-width of the peak of the power spectrum obtained by fast Fourier transform of the reflectance spectrum of the phase difference film is less than 400 nm, etc., which enables the fabrication of a liquid crystal display device with excellent planar shape and good oblique contrast.

[0061] The details of the mechanism are still unclear, but we can make some general speculations as follows.

[0062] That is, it is believed that the surface energy of one side of the liquid crystal layer through the stacking of the above-mentioned support, especially the polar component, is 2mN / m or more, and the interface state between the support and the liquid crystal layer becomes uniform in the thin film surface and the surface appearance becomes good.

[0063] Furthermore, it is believed that when the full width at half maximum (FWHM) of the power spectrum obtained by performing a fast Fourier transform on the reflectance spectrum of the phase retardation film is below 400 nm, the boundary region between the support and the liquid crystal layer is clear, which suppresses the presence of components of the support intruding into the mixing region of the liquid crystal layer. Therefore, the orientation of the liquid crystal layer (a positive C-plate formed by fixing the orientation state of a liquid crystal composition containing a liquid crystal compound) is not disordered, and the oblique contrast becomes good.

[0064] As described above, in the phase difference film of the present invention, the full width at half maximum (FWHM) of the power spectrum obtained by performing a fast Fourier transform on the reflectance spectrum is 400 nm or less, preferably 100 nm or more and less than 400 nm, more preferably 200 nm or more and less than 390 nm, and even more preferably 300 nm or more and less than 380 nm.

[0065] Furthermore, in this invention, the full width at half maximum (FWHM) of the power spectrum peaks can be adjusted based on the type of solvent in the liquid crystal composition used when forming the liquid crystal layer, as can be clearly seen from the results of the examples and comparative examples described later.

[0066] As described above, the haze value of the phase difference film of the present invention is 1.0% or less, preferably 0.1% or more and 0.8% or less, more preferably 0.1% or more and 0.5% or less, and even more preferably 0.1% or more and less than 0.5%.

[0067] Furthermore, in this invention, the haze value of the phase retardation film can be clearly seen from the results of the examples and comparative examples described later, as it can be adjusted according to the type of solvent in the liquid crystal composition used when forming the liquid crystal layer.

[0068] The thickness of the retardation film of the present invention is preferably 2 to 210 μm, more preferably 3 to 110 μm, and even more preferably 5 to 80 μm. Furthermore, the thickness of the retardation film refers to the overall film thickness, including the layers, when the retardation film has multiple layers.

[0069] [Support]

[0070] The phase retardation film of the present invention has a support that exhibits inverse wavelength dispersion with in-plane retardation.

[0071] Here, "in-plane delay exhibits inverse wavelength dispersion" means that when measuring the in-plane delay (Re) value of a layer (film) at a specific wavelength (visible light range), the Re value increases with the increase of the measurement wavelength. In this invention, it means satisfying the relationship Re(450) / Re(550) < 1.00.

[0072] Furthermore, the Re(450) / Re(550) of the support is preferably 0.60 or more and 1.00 or less, more preferably 0.70 or more and 1.00 or less, and even more preferably 0.75 or more and 0.95 or less.

[0073] Furthermore, the in-plane delay of the support preferably satisfies the relationship that Re(650) / Re(550) > 1.00. Moreover, Re(650) / Re(550) is preferably 1.00 or more and 1.30 or less, more preferably 1.00 or more and 1.25 or less, and even more preferably 1.00 or more and 1.20 or less.

[0074] Furthermore, the support of the phase retardation film of the present invention is a polymer film that has been stretched in at least one direction in the plane, preferably a polymer film that has been stretched uniaxially or biaxially.

[0075] Examples of materials that can be used for such polymer films include polycarbonate; polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyarylethers such as polyphenylene sulfide; polyvinyl alcohol; polyarylethers; cellulose ester polymers such as cellulose acylates; polyethersulfone; polysulfone; polyarylethersulfone; polyvinyl chloride; and cyclic olefin polymers such as norbornene polymers.

[0076] Among these, polycarbonate or polyester is preferred because it improves the orientation of the phase retardation film and the adhesion between the support and the liquid crystal layer.

[0077] Furthermore, in the support of the phase retardation film of the present invention, the surface energy (hereinafter also simply referred to as "surface energy") on one side of the surface of the stacked liquid crystal layer of the support has a non-polar component of less than 45 mN / m and a polar component of more than 2 mN / m.

[0078] Here, surface energy (γs) v Unit: mN / m), nonpolar component (γs) d Unit: mN / m) and polar component (γs) h (Unit: mN / m) can be found in DKOwens: J. Appl. Polym. Sci., 13, 1741 (1969), experimentally determined on the surface of the support used as the test object using pure water H2O and diiodomethane CH2I2.

[0079] At this point, the contact angles of pure water and diiodomethane are each set as θ. H2O and θ CH2I2 The following simultaneous equations (SA) and (SB) are used to determine γs. d and γs h , denoted by the sum of their values ​​γs v (=γs) d +γs h Defined by ).

[0080] Furthermore, regarding the contact angle, the value is obtained by adjusting the temperature to 20°C to 27°C and relative humidity to 50% to 65% for more than 2 hours, and then measuring the value at 25°C and relative humidity to 60%. This value can be measured using a contact angle measuring instrument (e.g., Dropmaster (manufactured by Kyowa Interface Science Co., Ltd.)).

[0081] 1+cosθ H2O =2√γs d (√γ) H2O d / γ H2O v )+2√γs h (√γ) H2O h / γ H2O v (SA) 1+cosθ CH2I2 =2√γs d (√γ) CH2I2 d / γ CH2I2 v )+2√γs h (√γ) CH2I2 h / γ CH2I2 v ... (SB) (where is denoted as γ) H2O d =21.8、γ H2O h =51.0、γ H2O v =72.8、γ CH2I2 d =49.5、γ CH2I2 h =1.3、γ CH2I2 v =50.8.

[0082] In this invention, for the purpose of improving the adhesion between the support and the liquid crystal layer and making the oblique contrast of the liquid crystal display device better, the surface energy of the support is preferably 45 mN / m or more, more preferably 45 to 70 mN / m, and even more preferably 48 to 60 mN / m.

[0083] Furthermore, the non-polar component of the surface energy of the support is less than 45 mN / m, but for the purpose of improving the surface properties, it is preferably less than 40 mN / m, more preferably 10 to 40 mN / m, and even more preferably 20 to 40 mN / m.

[0084] Furthermore, the polar component of the surface energy of the support is 2 mN / m or more, but for the purpose of improving the surface properties, it is preferably 2 to 35 mN / m, more preferably 5 to 35 mN / m, and even more preferably 10 to 30 mN / m.

[0085] Furthermore, as can be clearly seen from the results of Embodiments 1 and 2 described later in this invention, the surface energy of the support can be adjusted by performing surface treatments (e.g., corona treatment) on the surface of the support.

[0086] In this invention, the support is preferably a positive A plate because it improves display performance when used in a liquid crystal display device.

[0087] In this specification, the positive A plate is defined as follows.

[0088] That is, when the refractive index in the slow axis direction (the direction where the refractive index is greatest in the plane) is set as nx, the refractive index in the direction orthogonal to the slow axis in the plane is set as ny, and the refractive index in the thickness direction is set as nz, the positive A plate (the positive A plate) satisfies the relationship of equation (A1). In addition, the Rth of the positive A plate shows a positive value.

[0089] Equation (A1) nx>ny≈nz Furthermore, the “≈” above includes not only cases where the two are exactly the same, but also cases where they are substantially the same. “Substantially the same” means, for example, that the case where (ny-nz)×d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm, is also included in “ny≈nz”.

[0090] Furthermore, the Re (550) of the support is preferably 10 nm or more and 300 nm or less, more preferably 50 nm or more and 200 nm or less, and even more preferably 100 nm or more and 160 nm or less.

[0091] Furthermore, the Rth (550) of the support is preferably 10 nm or more and 200 nm or less, more preferably 50 nm or more and 150 nm or less, and even more preferably 60 nm or more and 130 nm or less.

[0092] In this invention, the support is preferably transparent. Furthermore, "transparent" as used in this invention means that the transmittance of visible light is 60% or more, preferably 80% or more, and more preferably 90% or more.

[0093] Furthermore, the thickness of the support is not particularly limited, but it is preferably 1 to 200 μm, more preferably 2 to 100 μm.

[0094] [Liquid Crystal Layer]

[0095] The phase retardation film of the present invention has a liquid crystal layer that is directly stacked on the aforementioned support. That is, there are no other components (e.g., so-called alignment films) between the support and the liquid crystal layer.

[0096] Furthermore, the liquid crystal layer of the phase retardation film of the present invention is a positive C-plate formed by fixing the orientation state of a liquid crystal composition containing a liquid crystal compound.

[0097] Here, as described above, the orientation state of the liquid crystal composition in the liquid crystal layer is fixed, so the liquid crystal compound contained in the liquid crystal layer no longer needs to exhibit liquid crystal properties.

[0098] Furthermore, in this specification, the positive C plate is defined as follows.

[0099] That is, when the refractive index in the slow axis direction (where the refractive index is at its maximum in the plane) of the liquid phase layer is set as nx, the refractive index in the direction orthogonal to the slow axis in the plane is set as ny, and the refractive index in the thickness direction is set as nz, the positive C-plate (positive C-plate) satisfies the relationship of equation (C1). In addition, the Rth of the positive C-plate shows a negative value.

[0100] Equation (C1) nx≈ny<nz Furthermore, the “≈” above includes not only cases where the two are exactly the same, but also cases where they are substantially the same. “Substantially the same” means, for example, that the case where (nx-ny)×d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, is also included in “nx≈ny”.

[0101] Furthermore, the Re (550) of the liquid crystal layer is preferably 0 nm or more and 10 nm or less, more preferably 0 nm or more and 5 nm or less, and even more preferably 0 nm or more and 2 nm or less.

[0102] Furthermore, the Rth (550) of the liquid crystal layer is preferably -200nm or more and -10nm or less, more preferably -180nm or more and -50nm or less, and even more preferably -150nm or more and -80nm or less.

[0103] In this invention, the liquid crystal layer preferably exhibits reverse wavelength dispersion for the purpose of improving display performance when used in a liquid crystal display device. More specifically, it is preferable that the retardation in the thickness direction exhibits reverse wavelength dispersion.

[0104] Here, "the thickness direction delay exhibits reverse wavelength dispersion" means that when measuring the thickness direction delay (Rth) value of the liquid crystal layer at a specific wavelength (visible light range), the absolute value of the Rth value increases as the measurement wavelength increases. In this invention, it means satisfying the relationship Rth(450) / Rth(550) < 1.00.

[0105] Furthermore, in the liquid crystal layer, Rth(450) / Rth(550) is preferably 0.60 or more and 1.10 or less, more preferably 0.70 or more and 1.00 or less, and even more preferably 0.75 or more and 0.95 or less.

[0106] Furthermore, the retardation in the thickness direction of the liquid crystal layer preferably satisfies the relationship that Rth(650) / Rth(550) > 1.00. Moreover, Rth(650) / Rth(550) is preferably 1.00 or more and 1.30 or less, more preferably 1.00 or more and 1.25 or less, and even more preferably 1.00 or more and 1.20 or less.

[0107] In this invention, the thickness of the liquid crystal layer is not particularly limited, but is preferably 0.5 to 5 μm, more preferably 0.5 to 4 μm, and even more preferably 0.5 to 3 μm.

[0108] <Liquid Crystal Composition>

[0109] As described above, the liquid crystal layer of the phase retardation film of the present invention is a positive C-plate formed by fixing the orientation state of a liquid crystal composition containing a liquid crystal compound.

[0110] (Liquid crystal compound)

[0111] The liquid crystal compound contained in the liquid crystal composition is not particularly limited, and conventionally known liquid crystal compounds can be used.

[0112] Liquid crystal compounds are generally classified into rod-shaped and disk-shaped types based on their shape. Furthermore, they are categorized into low-molecular-weight and high-molecular-weight types. High-molecular-weight compounds typically refer to those with a degree of polymerization of 100 or higher (Polymer Physics and Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992).

[0113] In this invention, any liquid crystal compound can be used, but rod-shaped liquid crystal compounds or disc-shaped liquid crystal compounds (disc-shaped liquid crystal compounds) are preferred. Two or more rod-shaped liquid crystal compounds, two or more disc-shaped liquid crystal compounds, or a mixture of rod-shaped and disc-shaped liquid crystal compounds can also be used.

[0114] As a rod-shaped liquid crystal compound, the compound described in claim 1 of Japanese Patent Application Publication No. 11-513019 or in paragraphs

[0026] to

[0098] of Japanese Patent Application Publication No. 2005-289980 is preferred, for example. As a disc-shaped liquid crystal compound, the compound described in paragraphs

[0020] to

[0067] of Japanese Patent Application Publication No. 2007-108732 and paragraphs

[0013] to

[0108] of Japanese Patent Application Publication No. 2010-244038 is preferred, but it is not limited to these.

[0115] In this invention, for the purpose of improving the durability of the liquid crystal layer, the liquid crystal compound preferably has polymerizable groups, and more preferably has two or more polymerizable groups.

[0116] Here, polymerizable groups are not particularly limited, but polymerizable groups capable of free radical polymerization or cationic polymerization are preferred.

[0117] As a free radical polymerizable group, known free radical polymerizable groups can be used. Preferred free radical polymerizable groups include acryloyloxy and methacryloyloxy. In this case, it is known that acryloyloxy generally has a faster polymerization rate, and from the viewpoint of improving productivity, acryloyloxy is preferred. However, methacryloyloxy can also be used as a polymerizable group.

[0118] As the cationic polymerizable group, known cationic polymerizable groups can be used. Specifically, examples include alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spirocyclic orthoester groups, and ethyleneoxy groups. Among these, alicyclic ether groups or ethyleneoxy groups are preferred, and epoxy groups, oxetyl groups, or ethyleneoxy groups are particularly preferred.

[0119] Examples of particularly preferred polymerizable groups include polymerizable groups represented by any one of the following formulas (P-1) to (P-20).

[0120] [Chemical Formula 1]

[0121] In this invention, the liquid crystal compound is preferably a liquid crystal compound with reverse wavelength dispersion, and more preferably a compound represented by the following formula (A), because the orientation of the phase difference film becomes good.

[0122] L 1 -SP 1 -D 5 -(A 1 ) a1 -D 3 -(G 1 ) g1 -D 1 -Ar-D 2 -(G 2 ) g2 -D 4 -(A 2 ) a2 -D 6 -SP 2 -L 2 (A)

[0123] In the above formula (A), a1, a2, g1, and g2 independently represent 0 or 1. Among them, at least one of a1 and g1 represents 1, and at least one of a2 and g2 represents 1.

[0124] Furthermore, D 1 D 2 D 3 D 4 D 5 and D 6 Each can independently represent a single bond or -CO-, -O-, -S-, -C(=S)-, -CR 1 R 2 -、-CR 3 =CR 4 -、-NR 5 - or a divalent linker consisting of two or more of them, R 1 ~R 5 Each can be an alkyl group, representing a hydrogen atom, a fluorine atom, or a carbon atom numbering 1 to 12, respectively.

[0125] Furthermore, G 1 and G 2 Each can independently represent an aromatic ring with 6 to 20 carbon atoms that may have substituents or a divalent alicyclic hydrocarbon group with 5 to 20 carbon atoms that may have substituents, wherein one or more of the -CH2- constituting the alicyclic hydrocarbon group can be substituted by -O-, -S- or -NH-.

[0126] And, A 1 and A 2 Each can independently represent an aromatic ring with 6 to 20 carbon atoms that may have substituents or a divalent alicyclic hydrocarbon group with 5 to 20 carbon atoms that may have substituents, wherein one or more of the -CH2- constituting the alicyclic hydrocarbon group can be substituted by -O-, -S- or -NH-.

[0127] Furthermore, SP 1 and SP 2 Each group independently represents a single bond or a divalent aliphatic hydrocarbon group with 1 to 20 carbon atoms. One or more of the -CH2- groups constituting the aliphatic hydrocarbon group can be substituted by -O-, -S-, -NH-, -N(Q)-, or -CO-. Q represents a substituent.

[0128] Furthermore, L 1 and L 2 Each of the L groups independently represents a monovalent organic group. 1 and L 2 At least one of them represents a polymerizable group. Wherein, when Ar is an aromatic ring represented by the following formula (Ar-3), L 1 and L 2and L in the following formula (Ar-3) 3 and L 4 At least one of them represents a polymerizable group.

[0129] Furthermore, Ar represents any aromatic ring selected from the group consisting of the groups represented by formulas (Ar-1) to (Ar-7) described later.

[0130] In the above formula (A), since the liquid crystal composition easily exhibits a smectic liquid crystal state, a1, a2, g1 and g2 are all preferably 1.

[0131] Furthermore, for the sake of improving the durability of the liquid crystal layer, it is preferable that a1 and a2 are both 0 and g1 and g2 are both 1.

[0132] In the above formula (A), D is used as 1 D 2 D 3 D 4 D 5 and D 6 The divalent linking group represented in one manner can be exemplified by, for example, -CO-, -O-, -S-, -C(=S)-, -CR-. 1 R 2 -、-CR 3 =CR 4 -、-NR 5 - or divalent linking groups composed of two or more of them, etc. Additionally, R 1 ~R 5 Each can be an alkyl group, representing a hydrogen atom, a fluorine atom, or a carbon atom numbering 1 to 12, respectively.

[0133] As divalent linking groups, examples include -CO-, -O-, -CO-O-, -C(=S)O-, and -CR. 1 R 2 -、-CR 1 R 2 -CR 1 R 2 -、-O-CR 1 R 2 -、-CR 1 R 2 -O-CR 1 R 2 -、-CO-O-CR 1 R 2 -、-O-CO-CR 1 R 2 -、-CR 1 R 2 -O-CO-CR 1 R2 -、-CR 1 R 2 -CO-O-CR 1 R 2 -、-NR 5 -CR 1 R 2 -and-CO-NR 5 - etc. Additionally, R 1 R 2 and R 5 Each can be an alkyl group, representing a hydrogen atom, a fluorine atom, or a carbon atom numbering 1 to 12, respectively.

[0134] Among these, the preferred choice is any one of -CO-, -O-, and -CO-O-.

[0135] In the above formula (A), as G 1 and G 2 The aromatic ring represented by one of the methods has 6 to 20 carbon atoms, and examples include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, anthracene rings, and phenanthroline rings; and aromatic heterocycles such as furan rings, pyrrole rings, thiophene rings, pyridine rings, thiazole rings, and benzothiazole rings. Among these, benzene rings (e.g., 1,4-phenyl rings) are preferred.

[0136] In the above formula (A), as G 1 and G 2 The alicyclic hydrocarbon group with 5 to 20 carbon atoms, represented by one of the methods, is preferably a 5-membered or 6-membered ring. Furthermore, the alicyclic hydrocarbon group can be saturated or unsaturated, but a saturated alicyclic hydrocarbon group is preferred. As G 1 and G 2 The divalent alicyclic hydrocarbon group represented can be referred to, for example, in paragraph

[0078] of Japanese Patent Application Publication No. 2012-21068, which is incorporated herein by reference.

[0137] In this invention, because the durability of the manufactured liquid crystal layer becomes good, G in the above formula (A) 1 and G 2 Preferably, it is a cycloalkane ring.

[0138] Examples of cycloalkane rings include cyclohexane, cyclopentane, cyclooctane, cyclododecane, and cyclododecane.

[0139] Among these, cyclohexane ring is preferred, 1,4-cyclohexene ring is more preferred, and trans-1,4-cyclohexene ring is even more preferred.

[0140] Furthermore, in the above equation (A), regarding G... 1 and G 2Substituents that can be present as aromatic rings with 6 to 20 carbon atoms or divalent alicyclic hydrocarbon groups with 5 to 20 carbon atoms include those described in substituent group A above, wherein alkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy or halogen atoms are preferred.

[0141] In the above formula (A), A is... 1 and A 2 Aromatic rings with 6 to 20 or more carbon atoms, as shown in one manner, can be exemplified by G in the above formula (A). 1 and G 2 The aromatic ring described herein is the same aromatic ring.

[0142] Furthermore, in the above formula (A), as A 1 and A 2 One way to show a divalent alicyclic hydrocarbon group with 5 to 20 carbon atoms is to exemplify the G group in formula (A) above. 1 and G 2 The alicyclic hydrocarbon group described herein is the same as the alicyclic hydrocarbon group.

[0143] In addition, regarding A 1 and A 2 Substituents that can be present in an aromatic ring with 6 to 20 carbon atoms or a divalent alicyclic hydrocarbon group with 5 to 20 carbon atoms include those corresponding to G in formula (A) above. 1 and G 2 It can have the same substituents as the substituents.

[0144] In the above formula (A), as SP 1 and SP 2 The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented in one manner can be exemplified by linear or branched alkylene groups having 1 to 20 carbon atoms, alkenyl groups having 1 to 20 carbon atoms, and alkyne groups having 1 to 20 carbon atoms.

[0145] As a straight-chain or branched alkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 12 carbon atoms is preferred, and an alkylene group having 1 to 10 carbon atoms is more preferred. Examples of preferred alkylene groups include methylene, ethylene, propylene, butylene, pentylene, and hexylene.

[0146] As a straight-chain or branched alkenyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 10 carbon atoms is preferred, and an alkenyl group with 2 to 4 carbon atoms is more preferred, for example, vinylidene.

[0147] As a straight-chain or branched ynyl group with 1 to 20 carbon atoms, an ynyl group with 2 to 10 carbon atoms is preferred, and an ynyl group with 2 to 4 carbon atoms is more preferred, for example, an ethynyl group.

[0148] Furthermore, as described above, one or more of the -CH2- constituting the aliphatic hydrocarbon group can be replaced by -O-, -S-, -NH-, -N(Q)- or -CO-. As the substituent represented by Q, the substituents described in the substituent group A above can be cited, wherein alkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy or halogen atom are preferred.

[0149] In the above formula (A), L is used as 1 and L 2 The monovalent organic group represented can be, for example, the substituents described in substituent group A above, among which alkyl, aryl, heteroaryl, alkoxy, cyano and carboxyl groups are preferred.

[0150] The alkyl group can be straight-chain, branched, or cyclic, but is preferably straight-chain. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 10.

[0151] Furthermore, the aryl group can be monocyclic or polycyclic, but monocyclic is preferred. The number of carbon atoms in the aryl group is preferably 6 to 25, more preferably 6 to 10.

[0152] Furthermore, the heteroaryl group can be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the heteroaryl group are preferably nitrogen, sulfur, or oxygen atoms. The number of carbon atoms in the heteroaryl group is preferably 6 to 18, more preferably 6 to 12.

[0153] Furthermore, the alkyl, aryl, and heteroaryl groups may be unsubstituted or have substituents. Examples of substituents include those described in substituent group A above, with alkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, or halogen atoms being preferred.

[0154] Furthermore, as L 1 and L 2 The polymeric group represented by at least one of the above formulas (P-1) to (P-20) can preferably be a polymeric group represented by any one of the above formulas.

[0155] In formula (A) above, as mentioned above, Ar represents any aromatic ring selected from the group consisting of the groups represented by formulas (Ar-1) to (Ar-7) below. Furthermore, in formulas (Ar-1) to (Ar-7) below, This indicates that D in equation (A) above... 1 Or D 2 The bonding positions.

[0156] [Chemical Formula 2]

[0157] In the above equation (Ar-1), Q 1 Represents N or CH, Q 2 Indicates -S-, -O-, or -N(R) 6 )-,R 6 Y represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms. 1 It indicates an aromatic hydrocarbon group with 6 to 12 carbon atoms that may have substituents, an aromatic heterocyclic group with 3 to 12 carbon atoms that may have substituents, or an alicyclic hydrocarbon group with 6 to 20 carbon atoms that may have substituents, wherein one or more of the -CH2- constituting the alicyclic hydrocarbon group can be replaced by -O-, -S- or -NH-.

[0158] Here, as R 6 The alkyl group having 1 to 6 carbon atoms is represented in one manner. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0159] As Y 1 The aromatic hydrocarbon group with 6 to 12 carbon atoms can be represented in one way, for example, aryl groups such as phenyl, 2,6-diethylphenyl, and naphthyl.

[0160] As Y 1 An aromatic heterocyclic group with 3 to 12 carbon atoms, represented by a certain method, includes, for example, thienyl, thiazolyl, furanyl, pyridyl, benzofuranyl, and benzothiazolyl heteroaryl groups; groups formed by removing one hydrogen atom from any one of the indole ring, benzofuran ring, benzothiaphene ring, benzimidazole ring, benzothiazolium ring, and benzoxazole ring. Among these, Y... 1 The aromatic heterocyclic group represented by carbon atoms with 3 to 12 is preferably a group formed by removing one hydrogen atom from a benzofuran ring or a benzothiazole ring.

[0161] As Y 1 The alicyclic hydrocarbon group with 6 to 20 carbon atoms can be represented in one way, for example, cyclohexylene, cyclopentylene, norbornylene, adamantylene, etc.

[0162] And, as Y 1 The substituents that may be present include those described in substituent group A above, wherein alkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, nitro, cyano or halogen atoms are preferred.

[0163] Furthermore, in the above equations (Ar-1) to (Ar-7), Z 1 Z2 and Z 3 Each of the following can be independently represented: a hydrogen atom, a monovalent aliphatic hydrocarbon group with 1-20 carbon atoms, a monovalent alicyclic hydrocarbon group with 3-20 carbon atoms, a monovalent aromatic hydrocarbon group with 6-20 carbon atoms, a monovalent aromatic heterocyclic group with 6-20 carbon atoms, a halogen atom, a cyano group, a nitro group, or -OR. 7 -NR 8 R 9 -SR 10 -COOR 11 or -COR 12 R 7 ~R 12 Z represents, independently, either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 1 and Z 2 They can bond with each other to form aromatic rings.

[0164] As a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, and specifically, methyl, ethyl, isopropyl, tert-amyl (1,1-dimethylpropyl), tert-butyl, 1,1-dimethyl-3,3-dimethyl-butyl is even more preferred, and methyl, ethyl, and tert-butyl are particularly preferred.

[0165] Examples of monocyclic alicyclic hydrocarbon groups with 3 to 20 carbon atoms include monocyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, methylcyclohexyl, and ethylcyclohexyl; monocyclic unsaturated hydrocarbon groups such as cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl, and cyclodecadienyl; and bicyclic [2.2.1]heptyl, bicyclic [2.2.2]octyl, and tricyclic [5.2.1.0]heptyl. 2,6 ] decyl, tricyclic [3.3.1.1] 3,7 ] decyl, tetracyclic [6.2.1.1 3,6 .0 2,7 Dodecyl, adamantyl, and other polycyclic saturated hydrocarbon groups, etc.

[0166] As a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms, examples include phenyl, 2,6-diethylphenyl, naphthyl, biphenyl, etc., with aryl groups having 6 to 12 carbon atoms (especially phenyl) being preferred.

[0167] Examples of monovalent aromatic heterocyclic groups with 6 to 20 carbon atoms include 4-pyridyl, 2-furanyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl.

[0168] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine, chlorine, and bromine atoms being preferred.

[0169] On the other hand, as R 7 ~R 10 The alkyl groups having 1 to 6 carbon atoms shown include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0170] As mentioned above, Z 1 and Z 2 They can bond with each other to form aromatic rings, for example, as Z in the above formula (Ar-1). 1 and Z 2 The structure in which groups bond together to form an aromatic ring can be exemplified by groups represented by the following formula (Ar-1a). Furthermore, in the following formula (Ar-1a), This indicates that D in equation (A) above... 1 Or D 2 The bonding positions.

[0171] [Chemical Formula 3]

[0172] Here, in the above equation (Ar-1a), Q 1 Q 2 and Y 1 Groups that are the same as those described in the above formula (Ar-1) can be cited.

[0173] Furthermore, in the above equations (Ar-2) and (Ar-3), A 3 and A 4 Represent the selection independently of -O- and -N(R) 13 The group consisting of -, -S- and -CO-, R 13 It represents a hydrogen atom or a substituent.

[0174] As R 13 The substituents represented in one manner can be exemplified by those described in the substituent group A above, wherein preferably alkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy or halogen atoms.

[0175] Furthermore, in the above formula (Ar-2), X represents a nonmetallic atom from groups 14 to 16. These nonmetallic atoms may be bonded with hydrogen atoms or substituents.

[0176] Furthermore, examples of nonmetallic atoms in groups 14-16 represented by X include oxygen atoms, sulfur atoms, and nitrogen atoms bonded with hydrogen atoms or substituents [=NR]. N1R N1 Represents a hydrogen atom or substituent. A carbon atom bonded with a hydrogen atom or substituent [=C-(R] C1 )2,R C1 This represents a hydrogen atom or a substituent.

[0177] Examples of substituents can be found in substituent group A above, among which alkyl, alkoxy, alkyl-substituted alkoxy, cyclic alkyl, aryl (e.g., phenyl, naphthyl, etc.), cyano, amino, nitro, alkyl carbonyl, sulfonyl, hydroxyl, etc. are preferred.

[0178] Furthermore, in the above equation (Ar-3), D 7 and D 8 Each can independently represent a single bond or -CO-, -O-, -S-, -C(=S)-, -CR 1 R 2 -、-CR 3 =CR 4 -、-NR 5 - or a divalent linker consisting of two or more of them, R 1 ~R 5 Each can be an alkyl group, representing a hydrogen atom, a fluorine atom, or a carbon atom numbering 1 to 12, respectively.

[0179] Here, as a divalent linking group, examples can be given of D in the above formula (A). 1 D 2 D 3 D 4 D 5 and D 6 The divalent linker described herein is the same divalent linker.

[0180] Furthermore, in the above formula (Ar-3), SP 3 and SP 4 Each of these groups independently represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms. One or more of the -CH2- groups constituting the aliphatic hydrocarbon group may be substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-. Q represents a substituent. Examples of substituents listed in substituent group A above can be used as substituents represented by Q, with alkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, or halogen atoms being preferred.

[0181] Here, as a divalent aliphatic hydrocarbon group, examples can be given that it corresponds to SP in the above formula (A). 1 and SP 2 The divalent aliphatic hydrocarbon group described herein is the same as the divalent aliphatic hydrocarbon group.

[0182] Furthermore, in the above equation (Ar-3), L3 and L 4 Each of these represents a monovalent organic group independently.

[0183] Here, as a monovalent organic group, examples that can be cited are those related to L in the above formula (A). 1 and L 2 The monovalent organic group described herein is the same as the monovalent organic group.

[0184] Furthermore, in the above formulas (Ar-4) to (Ar-7), Ax represents an organic group having 2 to 30 carbon atoms in at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles.

[0185] Furthermore, in the above formulas (Ar-4) to (Ar-7), Ay represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms that may have substituents, or an organic group having 2 to 30 carbon atoms of at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles.

[0186] Here, the aromatic rings in Ax and Ay can have substituents, and Ax and Ay can also bond together to form a ring.

[0187] And Q 3 It represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms that may have substituents.

[0188] As for Ax and Ay, examples can be found in paragraphs

[0039] to

[0095] of International Publication No. 2014 / 010325.

[0189] And, as Q 3 The alkyl group representing 1 to 6 carbon atoms can specifically include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl. As a substituent, the substituents described in the substituent group A above can be included, wherein alkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, or halogen atoms are preferred.

[0190] Examples of liquid crystal compounds include compounds represented by general formula (1) as described in Japanese Patent Application Publication No. 2010-084032 (especially compounds described in paragraphs

[0067] to

[0073] ), compounds represented by general formula (II) as described in Japanese Patent Application Publication No. 2016-053709 (especially compounds described in paragraphs

[0036] to

[0043] ), compounds represented by general formula (1) as described in Japanese Patent Application Publication No. 2016-081035 (especially compounds described in paragraphs

[0043] to

[0055] ), and compounds described in paragraphs

[0025] to

[0056] of International Publication No. 2021 / 060427.

[0191] The content of the liquid crystal compound is preferably 50 to 99% by mass, more preferably 60 to 99% by mass, relative to the total solid content of the liquid crystal composition.

[0192] The total solid content of a liquid crystal composition refers to the total mass of the components excluding the solvent.

[0193] (Other polymeric compounds)

[0194] The liquid crystal composition may contain other polymeric compounds besides the liquid crystal compounds described above. These other polymeric compounds may be used regardless of whether they exhibit liquid crystal properties. Therefore, among these other polymeric compounds, those exhibiting liquid crystal properties can be classified as the liquid crystal compounds described above.

[0195] Here, the polymeric groups of other polymeric compounds are not particularly limited, and the polymeric groups represented by any one of the above formulas (P-1) to (P-20) can be preferred.

[0196] As for other polymeric compounds, in order to further improve the durability of the formed liquid crystal layer, other polymeric compounds having 2 to 4 polymeric groups are preferred, and other polymeric compounds having 2 polymeric groups are more preferred.

[0197] As specific examples of other polymerizable compounds, compounds with liquid crystal properties represented by formulas (M1), (M2), and (M3) described in paragraphs

[0030] to

[0033] of Japanese Patent Application Publication No. 2014-077068 can be cited. More specifically, specific examples described in paragraphs

[0046] to

[0055] of the same publication can be cited.

[0198] Furthermore, examples of compounds that do not exhibit liquid crystal properties include polyfunctional acrylates such as polyethylene glycol diacrylate.

[0199] The content of other polymeric compounds is preferably 0 to 80 parts by mass relative to 100 parts by mass of the liquid crystal compound, and more preferably 0 to 70 parts by mass.

[0200] Other polymeric compounds can be used alone or in combination with two or more.

[0201] (Borate monomer)

[0202] For the purpose of improving the adhesion between the support and the liquid crystal layer and making the oblique contrast of the liquid crystal display device better, the liquid crystal composition preferably contains a boric acid monomer having polymerizable groups and boric acid groups represented by the following formula (B).

[0203] Here, the polymerizable groups of the boric acid monomer are not particularly limited, and any polymerizable group represented by any one of the above formulas (P-1) to (P-20) can be preferred.

[0204] In addition, the number of borate groups represented by the following formula (B) in the borate monomer is not particularly limited, and can be one or more (two or more).

[0205] [Chemical Formula 4]

[0206] In the above formula (B), Indicates the bonding location.

[0207] R 1 and R 2 Each can independently represent a hydrogen atom, an aliphatic hydrocarbon group that may have substituents, an aryl group that may have substituents, or a heterocyclic group that may have substituents, R 1 and R 2 They can be connected to form a ring.

[0208] As R 1 and R 2 Aliphatic hydrocarbon groups represented in one manner may include, for example, substituted or unsubstituted straight-chain or branched alkyl groups (e.g., methyl, ethyl, isopropyl, etc.) having 1 to 20 carbon atoms, substituted or unsubstituted cyclic alkyl groups (e.g., cyclohexyl, etc.) having 3 to 20 carbon atoms, and alkenyl groups (e.g., vinyl, etc.) having 2 to 20 carbon atoms.

[0209] As R 1 and R 2 The aryl group represented by a certain method can be substituted or unsubstituted phenyl groups (e.g., phenyl, tolyl, etc.) with 6 to 20 carbon atoms, or substituted or unsubstituted naphthyl groups with 10 to 20 carbon atoms.

[0210] As R 1 and R2 The heterocyclic group represented in one manner is, for example, a substituted or unsubstituted 5- or 6-membered ring group containing at least one heteroatom (e.g., nitrogen, oxygen, sulfur, etc.), such as pyridyl, imidazolyl, furanyl, piperidinyl, morpholinyl, etc. 1 and R 2 They can be connected to form a loop, for example, R 1 and R 2 It forms a 4,4,5,5-tetramethyl-1,3,2-dioxaborane ring by linking isopropyl groups.

[0211] In addition, as substituents that these aliphatic hydrocarbon groups, aryl groups and heterocyclic groups can have, the substituents described in the above substituent group A can be cited.

[0212] In the above formula (B), R is... 1 and R 2 Preferably, it is a straight-chain or branched alkyl group with 1 to 3 carbon atoms, or R 1 and R 2 The way in which they are connected to form a ring is more preferably hydrogen atoms.

[0213] The molecular weight of boric acid monomers is not particularly limited, but from the viewpoint of excellent compatibility with multifunctional monomers, 120 to 1200 is preferred, and 180 to 800 is more preferred.

[0214] As a preferred option for boric acid monomers, from the viewpoint of achieving better adhesion between the polarizer and the resin layer, the boric acid monomer represented by the following formula (B-1) can be cited.

[0215] [Chemical Formula 5]

[0216] R in equation (B-1) 1 and R 2 The definition is as described above.

[0217] Z represents a polymerizable group. The definition of a polymerizable group is as described above.

[0218] X 1 This indicates a single bond or a divalent linking group. Examples of divalent linking groups include those selected from -O-, -CO-, -NH-, -CO-NH-, -COO-, -O-COO-, alkylene, arylene, heterocyclic (heteroaryl), and combinations thereof.

[0219] In addition, as combinations, examples include -arylene-COO-arylene-O-alkylene-, -arylene-COO-alkylene-, etc.

[0220] The following examples of boric acid monomers are shown, but the present invention is not limited thereto.

[0221] [Chemical Formula 6]

[0222] [Chemical Formula 7]

[0223] [Chemical Formula 8] [Chemical Formula 9]

[0224] When the liquid crystal composition contains boric acid monomer, the content of boric acid monomer is preferably 1 to 10% by mass, more preferably 1 to 9% by mass, and even more preferably 2 to 8% by mass, relative to the total solid content of the liquid crystal composition.

[0225] (solvent)

[0226] From the viewpoint of operability in forming a phase retardation film, the liquid crystal composition preferably contains a solvent.

[0227] As a solvent, organic solvents are preferred. Specifically, examples include ketones (e.g., acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (e.g., dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., toluene, xylene, trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), and esters (e.g., ... Examples of solvents include methyl acetate, ethyl acetate, butyl acetate, etc., water, alcohols (e.g., methanol, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosols (e.g., methyl cellosol, ethyl cellosol, propylene glycol monomethyl ether, etc.), cellosol acetates (e.g., propylene glycol monomethyl ether acetate, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), and amides (e.g., dimethylformamide, dimethylacetamide, etc.). They can be used alone or in combination with two or more.

[0228] From the viewpoint of improving the coatability of the liquid crystal composition, the solvent content is preferably 55-85% by mass, more preferably 60-80% by mass, relative to the total mass of the liquid crystal composition.

[0229] When the solvent contains two or more solvents, the total amount is preferably within the above range.

[0230] (Other ingredients)

[0231] The liquid crystal composition may contain other components besides those mentioned above, such as polymerization initiators, leveling agents, surfactants, tilt angle control agents, orientation aids, plasticizers, and crosslinking agents.

[0232] [Polarizing filter]

[0233] The polarizer of the present invention is a polarizer having the phase difference film and polarizer of the present invention described above.

[0234] Furthermore, in the polarizer of the present invention, the polarizer, the liquid crystal layer of the retardation film, and the support of the retardation film are preferably arranged in sequence.

[0235] [Polarizer]

[0236] The polarizer of the polarizer of the present invention is not particularly limited as long as it is a component that has the function of converting light into specific linearly polarized light, and conventionally known absorption polarizers and reflection polarizers can be used.

[0237] As an absorption-type polarizer, iodine-based polarizers, dye-based polarizers utilizing dichroic dyes, and polyene-based polarizers can be used. Iodine-based polarizers and dye-based polarizers include coated polarizers and stretched polarizers, both of which are applicable, but polarizers made by adsorbing iodine or dichroic dyes onto polyvinyl alcohol and then stretching it are preferred.

[0238] Furthermore, as a method for obtaining a polarizer by stretching and dyeing a laminated film in which a polyvinyl alcohol layer is formed on a substrate, examples include Japanese Patent No. 5048120, Japanese Patent No. 5143918, Japanese Patent No. 4691205, Japanese Patent No. 4751481, and Japanese Patent No. 4751486, and these known technologies related to polarizers can be preferably utilized.

[0239] As a reflective polarizer, polarizers can be made by stacking different birefringent thin films, wire grid polarizers, polarizers that combine cholesteric liquid crystal with a selective reflection region with a 1 / 4 wavelength plate, etc.

[0240] From the viewpoint of superior adhesion, a polarizer comprising a polyvinyl alcohol-based resin (a polymer containing -CH2-CHOH- as a repeating unit, especially at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers) is preferred.

[0241] In this invention, the thickness of the polarizer is not particularly limited, but is preferably 5 to 40 μm, more preferably 5 to 30 μm, and even more preferably 5 to 20 μm. Such a thickness allows for the miniaturization of display devices.

[0242] In the polarizer of the present invention, it is preferable that the slow axis of the support of the phase difference film is configured to be orthogonal or parallel to the absorption axis of the polarizer, and more preferably parallel.

[0243] [Polarizer protective film]

[0244] The polarizer of the present invention can have a polarizer protective film disposed on the surface of the polarizer. The polarizer protective film can be disposed on only one surface of the polarizer (the surface opposite to the phase difference film side), or it can be disposed on both surfaces of the polarizer.

[0245] The structure of the polarizer protective film is not particularly limited; for example, it can be a so-called transparent support or a hard coating, or a laminate of a transparent support and a hard coating.

[0246] As a hard coating, a known layer can be used, such as a layer obtained by polymerizing and curing multifunctional monomers.

[0247] Furthermore, as a transparent support, known transparent supports can be used, and the materials used to form the transparent support can be, for example, cellulose polymers represented by triacetyl cellulose (hereinafter referred to as cellulose acylates), thermoplastic norbornene resins (ZEONEX and ZEONOR manufactured by Zeon Corporation and ARTON manufactured by JSR CORPORATION, etc.), acrylic resins, and polyester resins.

[0248] The thickness of the polarizer protective film is not particularly limited, but it is preferably less than 50 μm for reasons such as enabling the polarizer to be thinner.

[0249] [Adhesive layer]

[0250] The polarizer of the present invention may have an adhesive layer disposed between the phase retardation film (especially the liquid crystal layer) and the polarizer.

[0251] As an adhesive layer used for the lamination of the retardation film and the polarizer, it includes, for example, a substance that represents a ratio (tanδ=G” / G’) of 0.001 to 1.5 of the storage elastic modulus G’ and the loss elastic modulus G” as measured by a dynamic viscoelasticity measuring device, such as an adhesive and a substance prone to creep. Examples of adhesives that can be used in this invention include polyvinyl alcohol-based adhesives, but are not limited thereto.

[0252] Liquid crystal display device

[0253] The liquid crystal display device of the present invention is a liquid crystal display device having the polarizer of the present invention described above.

[0254] Specifically, the liquid crystal display device of the present invention is preferably a liquid crystal display device having the polarizer and the liquid crystal cell of the present invention described above, and having a polarizer, a liquid crystal layer, a support, and a liquid crystal cell arranged sequentially from the visual recognition side.

[0255] The liquid crystal unit that constitutes a liquid crystal display device will be described in detail below.

[0256] [Liquid Crystal Unit]

[0257] The liquid crystal cells used in the liquid crystal display device of the present invention are preferably of the lateral electric field mode (IPS: In-Plane-Switching).

[0258] The liquid crystal cells used in the liquid crystal display device are preferably in VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, FFS (Fringe-Field-Switching) mode or TN (Twisted Nematic) mode, but are not limited to these.

[0259] In TN mode liquid crystal cells, the rod-shaped liquid crystal molecules are substantially horizontally oriented when no voltage is applied, and their twisted orientation is 60–120°. TN mode liquid crystal cells are most commonly used in color TFT liquid crystal display devices and are documented in numerous publications.

[0260] In a VA-mode liquid crystal cell, the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied. In a VA-mode liquid crystal cell, in addition to (1) a narrow VA-mode liquid crystal cell in which the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and substantially horizontally oriented when a voltage is applied (described in Japanese Patent Application Publication No. 2-176625), there are also (2) a liquid crystal cell in which the VA mode is multi-domainized (MVA mode) in order to expand the viewing angle (described in SID97, Digest of tech. Papers (preprint) 28 (1997) 845), (3) a liquid crystal cell in which the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and twisted into multi-domain orientation when a voltage is applied (n-ASM mode) (described in preprints 58-59 (1998) of the Japan Liquid Crystal Conference), and (4) a SURVIVAL mode liquid crystal cell (published in LCD International 98). Furthermore, the liquid crystal cell in VA mode can be any of PVA (Patterned Vertical Alignment), Optical Alignment, or PSA (Polymer-Sustained Alignment). Detailed information about these modes can be found in Japanese Patent Application Publication Nos. 2006-215326 and 2008-538819.

[0261] In IPS-mode liquid crystal cells, rod-shaped liquid crystal molecules are substantially parallel to the substrate, and by applying an electric field parallel to the substrate surface, the liquid crystal molecules respond planarly. In IPS mode, black is displayed when no electric field is applied, and the absorption axes of the upper and lower polarizers are orthogonal. Methods for reducing light leakage and improving viewing angles when displaying black in the tilt direction using optical compensation sheets are disclosed in Japanese Patent Application Publications Nos. 10-54982, 11-202323, 9-292522, 11-133408, 11-305217, and 10-307291.

[0262] Example

[0263] The present invention will now be described in further detail with reference to embodiments. Regarding the materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments, appropriate modifications can be made without departing from the spirit of the invention. Therefore, the scope of the present invention should not be limited by the embodiments shown below.

[0264] [Example 1]

[0265] [Fabrication of the phase retardation film]

[0266] As a support for the phase retardation film, a commercially available polycarbonate film (Pure Ace RM-147, Re(550) = 146 nm, Rth(550) = 111 nm, manufactured by Teijin Limited) was prepared and subjected to biaxial stretching treatment.

[0267] Without performing surface treatment on the support, a liquid crystal composition 1 prepared according to the following composition is applied to one side of the support using a die coating machine.

[0268] Next, to dry the solvent of liquid crystal composition 1 and to ripen the orientation of the liquid crystal compound, it was heated with warm air at 60°C for 60 seconds. Then, it was subjected to ultraviolet irradiation (300 mJ / cm²) at 25°C with an oxygen concentration of 100 ppm under nitrogen purging. 2 The liquid crystal compound was oriented and immobilized to form a liquid crystal layer, thereby producing the phase retardation film of Example 1.

[0269] The optical properties of the liquid crystal layer were estimated based on the changes in optical properties before and after coating. The optical properties of the liquid crystal layer are Re(550) = 0 nm, Rth(550) = -120 nm, and Rth(450) / Rth(550) = 0.93. ─────────────────────────────── Liquid crystal composition 1 ─────────────────────────────── • 28.0 parts by weight of the following liquid crystal compound R1 • 10.0 parts by weight of the following liquid crystal compound R2 • 54.0 parts by weight of the following liquid crystal compound R3 • 8.0 parts by weight of the following liquid crystal compound R4 • 4.5 parts by weight of the following boric acid monomer B1 ·NK ESTER A-600 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 8.0 parts by weight • 1.5 parts by weight of the following photopolymerization initiator S1 • 0.4 parts by weight of the following surfactant P1 • 0.5 parts by weight of the following surfactant P2 · 200.0 parts by weight of acetone 69.0 parts by weight of propylene glycol monomethyl ether acetate ·Methanol 8.0 parts by weight ─────────────────────────────── Liquid crystal compound R1 [a mixture of liquid crystal compounds (RA), (RB), and (RC) in a mass ratio of 83:15:2. In the liquid crystal compounds (RB) and (RC), Me represents a methyl group.] [Chemical Formula 10] • Liquid crystal compound R2 [In the following formula, the group adjacent to the acryloyloxy group represents a propylene group (a group formed by replacing a methyl group with an ethyl group), therefore liquid crystal compound R2 represents a mixture of positional isomers of the methyl group at different positions.] [Chemical Formula 11] • Liquid crystal compound R3 [In the following formula, the group adjacent to the acryloyloxy group represents a propylene group (a group formed by replacing a methyl group with a vinyl group), therefore liquid crystal compound R3 represents a mixture of positional isomers of the methyl group at different positions.] [Chemical Formula 12] Liquid crystal compound R4 [Chemical Formula 13] Boric acid monomer B1 [Chemical Formula 14] Polymerization initiator S1 [Chemical Formula 15] Surfactant P1 [weight-average molecular weight: 15,000; in the following formulas, the values ​​in parentheses next to repeating units refer to mass percentages.] [Chemical Formula 16] Surfactant P2 [weight-average molecular weight: 11,200; in the following formulas, the values ​​in parentheses above repeating units refer to mass percentages.] [Chemical Formula 17]

[0270] [Making of Protective Film 1] The following composition was added to a mixing tank and stirred to prepare core layer cellulose acylated paste 1. ─────────────────────────────── Core layer cellulose acylated gel 1 ─────────────────────────────── 100 parts by weight of cellulose acetate with a degree of acetyl substitution of 2.88 • 10 parts by weight of the following ester oligomer A • 4 parts by weight of the following polarizer durability improver • 2 parts by weight of the following ultraviolet absorber • Dichloromethane (primary solvent) 430 parts by weight • Methanol (second solvent) 64 parts by weight ─────────────────────────────── Ester oligomer A (weight average molecular weight: 750) [Chemical Formula 18] Polarizer durability improver [Chemical Formula 19] UV absorber [Chemical Formula 20]

[0271] The outer cellulose acylated paste 1 was prepared by adding 10 parts by mass of the following matting agent solution to 90 parts by mass of the above-mentioned core layer cellulose acylated paste 1. ─────────────────────────────── Outer cellulose acylated gel 1 ─────────────────────────────── • Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by NIPPON AEROSIL CO.,LTD.) 2 parts by weight • Dichloromethane (primary solvent) 76 parts by mass • Methanol (second solvent) 11 parts by weight · Core layer cellulose acylated gel 1 1 parts by weight ───────────────────────────────

[0272] The three layers—the core cellulose acylated paste 1 and the outer cellulose acylated paste 1 on both sides—were simultaneously cast from the casting port onto a roller at 20°C. The film was peeled off with a solvent content of approximately 20% by mass, and the two ends of the film in the width direction were fixed using a tenter frame. It was then dried while being stretched 1.1 times laterally with a residual solvent content of 3–15%. The obtained film was then further dried by conveying it between the rollers of a heat treatment apparatus to produce a cellulose acylated film 1 with a thickness of 40 μm, which was used as a protective film 1. The phase difference of the protective film 1 was measured, and Re(550) = 2 nm, Rth(550) = 7 nm.

[0273] [Making of Protective Film 2]

[0274] The following composition was added to a mixing tank and stirred to prepare core layer cellulose acylated paste 2. ──────────────────────────────── Core layer cellulose acylated gel 2 ──────────────────────────────── 100 parts by weight of cellulose acetate with a degree of acetyl substitution of 2.88 • 12 parts by weight of the following polyester • 4 parts by weight of the above-mentioned polarizer durability improver • Dichloromethane (primary solvent) 430 parts by weight • Methanol (second solvent) 64 parts by weight ──────────────────────────────── • Polyester (number average molecular weight: 800) [Chemical Formula 21]

[0275] The outer cellulose acylated paste 2 was prepared by adding 10 parts by mass of the following matting agent solution to 90 parts by mass of the above-mentioned core layer cellulose acylated paste 2. ──────────────────────────────── Matting solution ──────────────────────────────── • Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by NIPPON AEROSIL CO.,LTD.) 2 parts by weight • Dichloromethane (primary solvent) 76 parts by mass • Methanol (second solvent) 11 parts by weight ·1 part by weight of core layer cellulose acylate paste ────────────────────────────────

[0276] After filtering the core cellulose acylated paste 2 and the outer cellulose acylated paste 2 with filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm, the three layers of the core cellulose acylated paste 2 and the outer cellulose acylated paste 2 on both sides are simultaneously cast from the casting port onto a roller at 20°C (belt casting machine).

[0277] Next, the film was peeled off with a solvent content of approximately 20% by mass, and the two ends of the film in the width direction were fixed with a tenter frame clamp. The film was then stretched in the transverse direction at a stretch ratio of 1.1 times while being dried.

[0278] The obtained film was then further dried by conveying it between the rollers of the heat treatment apparatus to produce a cellulose acylated film 2 with a thickness of 40 μm, which was used as a protective film 2. The phase difference of the protective film 2 was measured, with Re(550) = 1 nm and Rth(550) = -5 nm.

[0279] [Saponification treatment of the protective film]

[0280] The protective films 1 and 2 prepared above were immersed in a 2.3 mol / L sodium hydroxide aqueous solution for 3 minutes at 55°C. Then, they were washed in a water bath at room temperature and neutralized with 0.05 mol / L sulfuric acid at 30°C. They were then washed again in a water bath at room temperature and further dried with warm air at 100°C to perform saponification treatment on the surface of the protective films.

[0281] [Making of Polarizing Filters]

[0282] The saponified protective film 1, the polyvinyl alcohol-based polarizer, and the retardation film prepared above were bonded together using an adhesive to make the absorption axis of the polarizer parallel to the slow axis of the retardation film, with the liquid crystal layer side of the retardation film becoming the polarizer side, thereby fabricating the first polarizer of Example 1. A 3% aqueous solution of PVA (manufactured by KURARAY CO.,LTD., PVA-117H) was used as the adhesive. At this point, the adhesion between the polarizer and the retardation film in the first polarizer is practically sufficient.

[0283] Furthermore, a second polarizer was fabricated by similarly bonding a saponified protective film 1, a polyvinyl alcohol polarizer, and a saponified protective film 2.

[0284] [Manufacturing of Liquid Crystal Display Devices]

[0285] A commercially available liquid crystal display device (iPad (registered trademark), manufactured by Apple Inc.) was disassembled, and the polarizers on the two bonded sides were peeled off. Using an adhesive (SK2057 manufactured by Soken Science Co., Ltd.), the first polarizer was bonded to the visual recognition side, and the second polarizer was bonded to the backlight side, thus fabricating the liquid crystal display device of Example 1. In this case, the first polarizer is bonded to form a phase retardation film to become the liquid crystal cell side, and the second polarizer is bonded to form a protective film 2 to become the liquid crystal cell side. Furthermore, the slow axis of the liquid crystal within the bonded cell is orthogonal to the absorption axis of the first polarizer, and the slow axis of the liquid crystal within the bonded cell is parallel to the absorption axis of the second polarizer.

[0286] [Example 2]

[0287] Before coating the liquid crystal composition 1, a discharge rate of 100 W·min / m is applied to the surface of the support on one side of the liquid crystal composition 1. 2 Corona treatment was performed, and the phase retardation film of Example 2 was fabricated using the same method as in Example 1. Furthermore, the optical properties of the liquid crystal layer were Re(550) = 0 nm, Rth(550) = -122 nm, and Rth(450) / Rth(550) = 0.93.

[0288] Next, the phase retardation film prepared in Example 2 was used, and a polarizer and a liquid crystal display device were prepared by the same method as in Example 1.

[0289] [Example 3]

[0290] Liquid crystal composition 2 was used instead of liquid crystal composition 1. Otherwise, the phase retardation film of Example 3 was prepared by the same method as in Example 2. In addition, the optical properties of the liquid crystal layer were Re(550) = 0 nm, Rth(550) = -118 nm, and Rth(450) / Rth(550) = 0.93.

[0291] Next, the phase retardation film prepared in Example 3 was used, and a polarizer and a liquid crystal display device were prepared by the same method as in Example 1. ─────────────────────────────── Liquid crystal composition 2 ─────────────────────────────── • 28.0 parts by weight of the above liquid crystal compound R1 • 10.0 parts by weight of the above-mentioned liquid crystal compound R2 • 54.0 parts by weight of the above-mentioned liquid crystal compound R3 • 8.0 parts by weight of the above-mentioned liquid crystal compound R4 ·NK ESTER A-600 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 8.0 parts by weight • 1.5 parts by weight of the above polymerization initiator S1 • 0.4 parts by weight of the above surfactant P1 • 0.5 parts by weight of the above surfactant P2 · 200.0 parts by weight of acetone 69.0 parts by weight of propylene glycol monomethyl ether acetate ·Methanol 8.0 parts by weight ───────────────────────────────

[0292] [Example 4]

[0293] A polycarbonate film RM-147 was dissolved in dichloromethane to prepare a paste with a solid content of 19% by weight. A cast film was then prepared from this paste solution using a known method. The obtained film was uniaxially stretched at 160°C to produce a stretched film 1 with a thickness of 55 μm. Stretched film 1 was a positive A-plate with Re(550) = 134 nm and Rth(550) = 67 nm.

[0294] The stretched film 1 was used as a support. In addition, the phase retardation film of Example 4 was fabricated by the same method as in Example 2. Furthermore, the optical properties of the liquid crystal layer were Re(550) = 0 nm, Rth(550) = -104 nm, and Rth(450) / Rth(550) = 0.93.

[0295] Next, the phase retardation film prepared in Example 4 was used, and a polarizer and a liquid crystal display device were prepared by the same method as in Example 1.

[0296] [Example 5]

[0297] The liquid crystal composition 3 described below was used instead of liquid crystal composition 1. Otherwise, the phase retardation film of Example 5 was prepared by the same method as in Example 4. In addition, the optical properties of the liquid crystal layer are Re(550) = 0 nm, Rth(550) = -105 nm, and Rth(450) / Rth(550) = 1.07.

[0298] Next, the phase retardation film prepared in Example 5 was used, and a polarizer and a liquid crystal display device were prepared by the same method as in Example 1. ─────────────────────────────── Liquid crystal composition 3 ─────────────────────────────── • 100.0 parts by weight of the above-mentioned liquid crystal compound R1 • 4.5 parts by weight of the above boric acid monomer B1 • 2.0 parts by weight of the following orientation aid A1 • A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 8.0 parts by weight • 5.0 parts by weight of the following photopolymerization initiator S2 • 2.0 parts by weight of the following photopolymerization initiator S3 • 0.4 parts by weight of the above surfactant P1 • 0.5 parts by weight of the above surfactant P2 ·Acetone 353.0 parts by weight ·Propylene glycol monomethyl ether acetate 122.0 parts by weight ·Methanol 15.0 parts by weight ─────────────────────────────── Orientation aid A1 [Chemical Formula 22] Photopolymerization initiator S2 [Chemical Formula 23] Photopolymerization initiator S3 [Chemical Formula 24]

[0299] [Comparative Example 1]

[0300] The optical film of Comparative Example 1 was prepared using the method described in Example 1 of Japanese Patent Application Publication No. 2016-206236. Furthermore, the optical properties of the liquid crystal layer were Re(550) = 0 nm and Rth(550) = -119 nm.

[0301] Next, the phase retardation film prepared in Comparative Example 1 was used, and a polarizer and a liquid crystal display device were prepared by the same method as in Example 1.

[0302] [Comparative Example 2]

[0303] The liquid crystal composition 4 described below was used instead of liquid crystal composition 1. Otherwise, the phase retardation film of Comparative Example 2 was prepared by the same method as in Example 1. In addition, the optical properties of the liquid crystal layer were Re(550) = 0 nm and Rth(550) = -120 nm.

[0304] Next, the phase retardation film prepared in Comparative Example 2 was used, and a polarizer and a liquid crystal display device were prepared by the same method as in Example 1. ─────────────────────────────── Liquid crystal composition 4 ─────────────────────────────── • 28.0 parts by weight of the above liquid crystal compound R1 • 10.0 parts by weight of the above-mentioned liquid crystal compound R2 • 54.0 parts by weight of the above-mentioned liquid crystal compound R3 • 8.0 parts by weight of the above-mentioned liquid crystal compound R4 • 4.5 parts by weight of the above boric acid monomer B1 ·NK ESTER A-600 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 8.0 parts by weight • 1.5 parts by weight of the above polymerization initiator S1 • 0.4 parts by weight of the above surfactant P1 • 0.5 parts by weight of the above surfactant P2 277.0 parts by weight of methyl isobutyl ketone ───────────────────────────────

[0305] [Comparative Example 3]

[0306] As the support for the retardation film, a polycarbonate film as described in Example 1 of Patent Document 1 (International Publication No. 2020 / 045224) was used. Otherwise, the retardation film of Comparative Example 3 was fabricated using the same method as in Example 1. In addition, the optical properties of the liquid crystal layer were Re(550) = 0 nm and Rth(550) = -107 nm.

[0307] Surface energy

[0308] Regarding the support of the phase retardation film produced in the embodiments and comparative examples, the surface energy of the surface in which the liquid crystal layer is formed, as well as the non-polar and polar components contained in the surface energy, were measured using the method described above. The results are shown in Table 1 below.

[0309] [The full width at half maximum (FWHM) of the power spectrum peaks]

[0310] The full width at half maximum (FWHM) of the power spectrum peaks of the phase difference films prepared in the examples and comparative examples were determined using the methods described above. The results are shown in Table 1 below.

[0311] [Haze value]

[0312] The haze values ​​of the phase retardation films prepared in the examples and comparative examples were measured using the methods described above. The results are shown in Table 1 below.

[0313] [Orientation]

[0314] In the orientation evaluation, two second polarizers were orthogonally arranged on an observation lamp (LED Viewer Pro HR-2, manufactured by FUJICOLOR) with the two sides of the protective film facing inwards. The phase retardation film was arranged between the polarizers parallel to the absorption axis of either second polarizer. The evaluation was performed visually from the front (normal direction of the film) according to the following criteria. The results are shown in Table 1 below. A: There is no light leakage before and after the phase retardation film is installed. B: There is light leakage before and after the phase retardation film is installed.

[0315] [Seamless]

[0316] Regarding the adhesion between the liquid crystal layer and the support in the retardation film, a cross-cut test as specified in JIS K 5600-5-6 was performed, and the peelability from the support was evaluated using the following criteria. The results are shown in Table 1 below. A: The area of ​​the liquid crystal layer that was peeled off is less than 1%. B: The area of ​​the liquid crystal layer that has been peeled off is more than 1% and less than 50%. C: The area where the liquid crystal layer is peeled off is more than 50%.

[0317] [Face]

[0318] The fabricated liquid crystal display device was placed on a diffused light source, and its surroundings were covered with black paper to allow visual identification of a 15cm square area. Within this 15cm square area, the in-plane non-uniformity when displaying black was observed and confirmed from an oblique direction. The non-uniformity was evaluated using the following evaluation criteria. The results are shown in Table 1 below. A: Unevenness within the surface cannot be detected, so there is no problem. B: The inhomogeneity within the surface can be identified, which is unacceptable.

[0319] [Oblique contrast]

[0320] The fabricated liquid crystal display device was placed on a diffuse light source, and the brightness and hue of the black and white displays were measured using an EZ-Contrast XL88 measuring machine (manufactured by ELDIM) in 1° increments from 0° (horizontal direction) to 359° counterclockwise and from 0° (front direction) to 88° polar angle in 1° increments.

[0321] At a polar angle of 60°, the contrast ratios at four azimuth angles (0°, 90°, 180°, and 270°) along the absorption and transmission axes of the polarizer were compared, and the oblique contrast ratio was evaluated using the following criteria. Contrast ratio is the brightness of the white display divided by the brightness of the black display. The results are shown in Table 1 below. A: Compared to liquid crystal displays without a phase retardation film, the contrast ratio in all four directions is the same. B: Compared to liquid crystal displays without a phase retardation film, the contrast ratio in the four directions is slightly lower, but this is not a problem in practical use. C: Compared to liquid crystal displays without retardation films, the contrast ratio in all four directions is significantly lower, which is unacceptable.

[0322] [Display performance]

[0323] Regarding display performance, light leakage or tonal variation at a polar angle of 60° was evaluated using the following evaluation criteria. The results are shown in Table 1 below. A: Very little light leakage or color variation, excellent. B: Minimal light leakage or color variation, excellent. C: There are slightly more light leaks or color variations, but it's not a problem in practical use. D: Light leakage or significant color variations are unacceptable.

[0324]

[0325] As shown in Table 1 above, it can be seen that if the full width at half maximum (FWHM) of the power spectrum obtained by performing a fast Fourier transform on the reflectance spectrum of the phase difference film exceeds 400 nm, then the oblique contrast difference is significant (Comparative Example 1 and Comparative Example 2).

[0326] Furthermore, regarding the surface energy of the support, it is known that if the nonpolar component is 45 mN / m or more, the surface quality is poor (Comparative Example 3).

[0327] In contrast, it can be seen that if the half-width of the peak of the power spectrum obtained by performing a fast Fourier transform on the reflectance spectrum of the phase difference film is less than 400 nm, and the non-polar component of the surface energy of the support is less than 45 mN / m and the polar component is more than 2 mN / m, then the surface appearance of the liquid crystal display device becomes better and the oblique contrast also becomes better (Examples 1 to 5).

[0328] In particular, a comparison between Example 1 and Example 2 shows that if the surface energy of the support is 45mN / m or more, the adhesion between the support and the liquid crystal layer is improved, and the oblique contrast of the liquid crystal display device becomes better.

[0329] Furthermore, a comparison between Embodiment 2 and Embodiment 4 shows that if the support is a positive A plate, the display performance becomes good when used in a liquid crystal display device.

[0330] Furthermore, a comparison between Example 2 and Example 3 shows that if the liquid crystal composition contains a boric acid monomer having polymerizable groups and boric acid groups represented by formula (B), the adhesion between the support and the liquid crystal layer is improved, and the oblique contrast of the liquid crystal display device becomes better.

[0331] Furthermore, a comparison between Example 4 and Example 5 shows that if the retardation in the thickness direction of the liquid crystal layer exhibits reverse wavelength dispersion, the display performance becomes good.

Claims

1. A retardation film comprising a support exhibiting in-plane retardation with inverse wavelength dispersion and a liquid crystal layer directly stacked on the support, wherein, The support is a polymer film that has been stretched in at least one direction within a plane. The liquid crystal layer is a positive C-plate formed by fixing the orientation state of a liquid crystal composition containing a liquid crystal compound. In the surface energy of one side of the support on which the liquid crystal layer is stacked, the non-polar component is less than 45 mN / m and the polar component is greater than 2 mN / m. The power spectrum obtained by performing a fast Fourier transform on the reflectance spectrum of the phase difference film has a peak width of less than 400 nm. The haze value of the phase retardation film is below 1.0%.

2. The phase retardation film according to claim 1, wherein, The surface energy of the surface of the support on one side of the stacked liquid crystal layer is above 45 mN / m.

3. The phase retardation film according to claim 1 or 2, wherein, The material constituting the support is polycarbonate or polyester.

4. The phase retardation film according to claim 1 or 2, wherein, The support is a positive A plate.

5. The phase retardation film according to claim 1 or 2, wherein, The thickness-direction delay of the liquid crystal layer exhibits reverse wavelength dispersion.

6. The phase retardation film according to claim 1 or 2, wherein, The liquid crystal composition further contains a boric acid monomer having polymerizable groups and boric acid groups represented by the following formula (B). [Chemical Formula 1] In the above formula (B), Indicates the bonding location, R 1 and R 2 Each can independently represent a hydrogen atom, an aliphatic hydrocarbon group that may have substituents, an aryl group that may have substituents, or a heterocyclic group that may have substituents, R 1 and R 2 They can be connected to form a ring.

7. A polarizer having the phase difference film and polarizer as described in claim 1 or 2.

8. The polarizer according to claim 7, wherein, The absorption axis of the polarizer is orthogonal to or parallel to the slow axis of the support of the phase difference film.

9. The polarizer according to claim 7, wherein, The absorption axis of the polarizer is parallel to the slow axis of the support of the phase difference film.

10. A liquid crystal display device having the polarizer of claim 7.

Images