WO2019111880A1 - 長尺位相差フィルム、長尺積層体、画像表示装置 - Google Patents
長尺位相差フィルム、長尺積層体、画像表示装置 Download PDFInfo
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- WO2019111880A1 WO2019111880A1 PCT/JP2018/044529 JP2018044529W WO2019111880A1 WO 2019111880 A1 WO2019111880 A1 WO 2019111880A1 JP 2018044529 W JP2018044529 W JP 2018044529W WO 2019111880 A1 WO2019111880 A1 WO 2019111880A1
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
Definitions
- the present invention relates to a long retardation film, a long laminate, and an image display device.
- a polarizing plate having a retardation film and a polarizer has been used in liquid crystal display devices, organic electroluminescent devices and the like for the purpose of optical compensation, reflection prevention and the like. These are generally manufactured by a roll-to-roll process in order to achieve high productivity and stable quality.
- a polarizing plate (so-called broadband polarizing plate) capable of giving the same effect corresponding to light beams of all wavelengths with respect to white light which is a synthetic wave in which light beams in the visible light range are mixed
- the thickness reduction is also required for the retardation film contained in the polarizing plate.
- Patent Documents 1 and 2 propose the use of a reverse-wavelength dispersible polymerizable liquid crystal compound as a polymerizable compound used to form a retardation film.
- the retardation film formed using the reverse wavelength dispersible polymerizable liquid crystal (polymerizable liquid crystal compound) described in Patent Documents 1 and 2 can provide an excellent broadband polarizing plate with a small number of layers.
- a plate is prepared, and this polarizing plate is sandwiched by glass from both sides according to a practical mode (for example, a mode used as a circularly polarizing plate for the purpose of preventing reflection of an organic electroluminescent type smartphone), under high temperature
- a practical mode for example, a mode used as a circularly polarizing plate for the purpose of preventing reflection of an organic electroluminescent type smartphone
- An object of the present invention is to provide a long retardation film, a long laminate, and an image display device capable of solving the above-mentioned problems of the prior art and capable of suppressing the occurrence of reddish unevenness over time.
- the present invention has the following configuration.
- a long retardation film comprising a support made of a resin film and a long optically anisotropic layer disposed on one side of the long support, wherein the long support is , 10 ⁇ m to 50 ⁇ m in thickness, 4.3 GPa to 6.0 GPa in transverse direction, and 20 ⁇ 10 ⁇ 6 / ° C. to 40 ⁇ 10 ⁇ 6 / in linear thermal expansion coefficient in the transverse direction.
- the optically anisotropic layer is composed of a polymerizable liquid crystal composition containing a reverse-dispersive polymerizable liquid crystal compound, and the section of the long retardation film is treated at a temperature of 85 ° C. for 500 hours.
- the long support has a thickness of 10 ⁇ m to 50 ⁇ m, a transverse elastic modulus of 4.3 GPa to 6.0 GPa, and a linear thermal expansion coefficient of 10 ppm / ° C. to 35 ppm / in the transverse direction. ° C, The manufacturing method of the elongate retardation film which hardens while heating a coating film at 80 degreeC or more and 140 degrees C or less in a hardening process.
- the elongate retardation film which can suppress that reddish-colored unevenness generate
- a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
- “orthogonal” and “parallel” in terms of angles shall mean the range of strict angles ⁇ 10 °, and “identical” and “different” in angles may be whether the difference is less than 5 ° It can be judged on the basis of
- “visible light” refers to 380 to 780 nm.
- the measurement wavelength is 550 nm unless otherwise specified.
- the “slow axis” means the direction in which the refractive index is maximum in the plane.
- the slow axis of retardation film the slow axis of the whole retardation film is intended.
- the long retardation film of the present invention includes a long optically anisotropic layer formed by using at least a polymerizable liquid crystal composition on a long support.
- the long support has a thickness of 10 ⁇ m to 50 ⁇ m, a transverse elastic modulus of 4.3 GPa to 6.0 GPa, and a linear thermal expansion coefficient of 10 ppm / ° C. to 35 ppm / ° C. It is.
- the optically anisotropic layer is composed of a polymerizable liquid crystal composition containing a reverse polymerizable liquid crystal compound.
- the in-plane retardation change ⁇ Re is 0.94 to 1.02 when the section of the long retardation film is treated at a temperature of 85 ° C. for 500 hours.
- a sheet-like retardation film can be obtained by cutting out the film from the long retardation film of the present invention to a desired size. Therefore, in the present specification, when referred to simply as a retardation film or an optically anisotropic layer, it is not distinguished whether it is long or sheet-like.
- the various physical properties and characteristics of the retardation film and optical anisotropy described below do not have to be completely uniform over the entire region of the long retardation film, and unless otherwise specified, such a long film Should be applied to the part that can be used in line with the original purpose and / or function.
- the long retardation film of the present invention is applicable to various image display devices, but is preferably used particularly for organic EL display devices.
- the retardation film formed using the reverse wavelength dispersible polymerizable liquid crystal compound can provide an excellent broadband polarizing plate with a small number of layers.
- a retardation film in which an optically anisotropic layer is formed on a thin resin film (support) having a thickness of 50 ⁇ m or less using a polymerizable liquid crystal compound of reverse wavelength dispersion is used for an image display, It has been found that the problem of redness unevenness occurs due to
- the retardation (Re) of the retardation film largely fluctuates in the region where the redness unevenness occurs, and this causes a tint change.
- the reason why the retardation (Re) of the retardation film largely fluctuates is because the polymerization reaction rate of the polymerizable liquid crystal compound in the liquid crystal layer in the optically anisotropic layer is low. It was found that the optically anisotropic layer was deteriorated due to humidity or aging.
- the inventors of the present invention perform the curing treatment to fix the orientation of the polymerizable liquid crystal compound at a high temperature to increase the polymerization reaction rate of the polymerizable liquid crystal compound. It has been found that the durability of the formed optically anisotropic layer can be improved. However, in the case of using a thin resin film as a support, the resin film may be stretched by heating and wrinkles may be generated, so it is difficult to heat sufficiently to increase the polymerization reaction rate.
- the long support is thermally expanded by heating, and as a result of combining the stress and various stresses related to the conveyance of the long support, the stress applied in the lateral direction of the long support causes the rigidity of the long support to be If exceeded, it is estimated that the long support will buckle and cause deflection.
- the elastic modulus in the lateral direction of the elongate support is 4.3 GPa to 6.0 GPa
- the linear thermal expansion coefficient in the lateral direction is 10 ppm / ° C. to 35 ppm / ° C.
- the long retardation film of the present invention has a small in-plane retardation change ⁇ Re of 0.94 to 1.02, and even when incorporated in an image display apparatus, the retardation film has retardation due to heat, humidity, aging and the like. Since (Re) does not easily change, it is possible to suppress the occurrence of unevenness in the center of the plane.
- the in-plane retardation change ⁇ Re is the in-plane retardation after processing the in-plane retardation Rea (550) before the section of the long retardation film is treated under the heating condition of 85 ° C. for 500 hours. It is represented by the following formula from Reb (550).
- ⁇ Re
- Rea (550) and Reb (550) are in-plane retardations of the intercept of the retardation film at a measurement wavelength of 550 nm.
- the section of the retardation film is a sample of 140 mm ⁇ 70 mm in size cut out from an arbitrary position of the long retardation film.
- the in-plane retardation change ⁇ Re is 0.96 to 1.01 from the viewpoint of being able to more suitably suppress the unevenness of redness.
- the thickness of the retardation film is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and still more preferably 25 ⁇ m or less, from the viewpoint of thinning the member. From the viewpoint of production suitability, the thickness is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and still more preferably 15 ⁇ m or more. In addition, the film thickness of retardation film points out the film thickness of the whole including this layer, when retardation film has a several layer.
- the length of the long retardation film can be 100 m to 10000 m, preferably 250 m to 7000 m, and more preferably 1000 m to 6000 m.
- the width can be 400 to 3000 mm, preferably 500 to 2500 mm, and more preferably 600 to 1750 mm. Within this range, it is possible to improve the economics of the roll-to-roll process and to manufacture a long retardation film excellent in the uniformity in the longitudinal direction and the lateral direction.
- the long retardation film of the present invention is not limited to the structure including the long support and the optically anisotropic layer, and may have other layers. Further, the present invention is not limited to the configuration in which the optically anisotropic layer is directly formed on the elongated support, and another layer may be provided between the elongated support and the optically anisotropic layer. For example, an alignment layer in contact with the optically anisotropic layer may be provided between the elongated support and the optically anisotropic layer.
- the alignment layer is a layer having a function of defining the alignment direction of the polymerizable liquid crystal compound.
- the polymerizable liquid crystal compound in the coating film to be the optically anisotropic layer is uniformly and efficiently brought into a desirable alignment state. It can lead.
- the long support for the long retardation film of the present invention is long and preferably transparent.
- the linear light transmittance in the visible light region is preferably 80% or more.
- a support for example, a long film of a polymer film can be mentioned.
- the support is preferably a polymer film in that it has both flexibility and strength when handled as a roll-like wound body.
- Examples of the resin constituting such a polymer film include (meth) acrylic resins such as celluloses such as cellulose acylate, polymethyl methacrylate and copolymers of other (meth) acrylates, polystyrene, fumaric acid polymer, cyclopentadiene Examples thereof include olefin polymers, polyolefins such as polyethylene and polypropylene, polyesters represented by polyethylene terephthalate, polycarbonates, and copolymers thereof.
- acrylic resins such as celluloses such as cellulose acylate, polymethyl methacrylate and copolymers of other (meth) acrylates, polystyrene, fumaric acid polymer, cyclopentadiene
- examples thereof include olefin polymers, polyolefins such as polyethylene and polypropylene, polyesters represented by polyethylene terephthalate, polycarbonates, and copolymers thereof.
- the long support has a thickness in the range of 10 ⁇ m to 50 ⁇ m and a width direction elastic modulus in the range of 4.3 GPa to 6.0 GPa.
- the linear thermal expansion coefficient in the lateral direction is 20 ⁇ 10 ⁇ 6 / ° C. to 40 ⁇ 10 ⁇ 6 / ° C.
- the thickness of the long support is preferably 50 ⁇ m or less, more preferably 25 or less, from the viewpoint of thinning of the long retardation film and the like. On the other hand, it is preferably 10 ⁇ m or more, and more preferably 15 ⁇ m or more, from the viewpoint of supportability of the optically anisotropic layer, generation of wrinkles during handling, and the like.
- the transverse direction elastic modulus of the long support can be determined by measuring the elastic modulus in the direction orthogonal to the longitudinal direction of the long support by a strograph.
- the elastic modulus in the lateral direction of the long support is preferably 4.3 GPa or more, and 4.5 GPa or more from the viewpoint of suppressing generation of wrinkles and the like on the long support due to heat when forming the optically anisotropic layer. Is more preferred.
- the lateral elastic modulus of the long support is preferably 6.0 GPa or less, more preferably 5.5 GPa or less.
- the transverse direction elastic modulus of the long support is an elastic modulus at normal temperature (25 ° C.) unless otherwise specified.
- the elastic modulus in width direction at 140 ° C. of the long support is preferably 1.5 GPa to 3.0 GPa, and more preferably 1.7 GPa to 3.0 GPa.
- the linear thermal expansion coefficient of the long support in the lateral direction is 40 ⁇ 10 ⁇ 6 / ° C. or less from the viewpoint of suppressing generation of wrinkles and the like on the long support due to heat when forming the optically anisotropic layer. Is preferable, and 38 ⁇ 10 ⁇ 6 / ° C. or less is more preferable.
- the linear thermal expansion coefficient in the width direction of the long support is preferably 20 ⁇ 10 ⁇ 6 / ° C. or higher, and 30 ⁇ 10 ⁇ 6 / ° C. or higher. More preferable.
- the linear thermal expansion coefficient in the lateral direction of the long support can be measured by TMA (Thermal Mechanical Analysis).
- the optical properties of the support can be variously set as required, and in a preferred embodiment, can be optically isotropic. More specifically, Re (550) can be 0 nm to 10 nm, and a range of 0 nm to 5 nm is more preferable. Also, Rth (550) can be ⁇ 20 nm to 40 nm, and more preferably ⁇ 10 nm to 20 nm. Moreover, as another preferable embodiment, the Re (550) of the long support is 100 nm to 350 nm, the Nz value is 0.1 to 0.9, and the slow axis is in the longitudinal direction of the long support. It can be parallel or orthogonal.
- a cellulose acylate film As a film which satisfy
- a cellulose acylate film can be used as a long support used in the present invention. It is preferably used in that it has both transparency and strength, and can easily control adhesion to each layer to be described later or peelability.
- a film containing a cellulose acylate resin and, if necessary, an additive may be used as the cellulose acylate film.
- the cellulose acylate film can be produced by solution film formation, and may be produced using melt film formation.
- the cellulose acylate resin triacetyl cellulose, diacetyl cellulose, and cellulose in which a part of acetyl group is substituted by higher acyl group, aromatic acyl group, alkoxy group or substituted alkoxy group can be used.
- the degree of substitution of the cellulose to hydroxyl groups is not particularly limited, but in order to provide appropriate moisture permeability and hygroscopicity, the degree of acyl substitution of the cellulose to hydroxyl groups is 2.00 to 3.00 Is preferred. Furthermore, the degree of substitution is preferably 2.30 to 2.98, more preferably 2.70 to 2.96, and still more preferably 2.80 to 2.94.
- JP-A-6439, JP-A-2016-164668, and JP-A-2017-106975 can be used.
- polyester additive which has a repeating unit represented by the following general formula is mentioned.
- X may be an alkylene group having 2 to 20 carbon atoms which may have a substituent, a polyoxyalkylene group, an alkenylene group, a phenylene group, a naphthylene group or a heterocyclic aromatic group.
- the alkylene group in the said alkylene group, an alkenylene group, and a polyoxyalkylene group may have alicyclic structure.
- Y may be an alkylene group having 2 to 20 carbon atoms which may have a substituent, a polyoxyalkylene group, an alkenylene group, a phenylene group, a naphthylene group or a heterocyclic aromatic group.
- alkylene group in the said alkylene group, an alkenylene group, and a polyoxyalkylene group may have alicyclic structure.
- These divalent linking groups may contain molecules other than carbon such as oxygen atom and nitrogen atom. Examples of the substituent mentioned above include an alkyl group, an alkoxy group, a hydroxyl group, an alkoxy substituted alkyl group and a carboxyl group.
- X represents a non-cyclic divalent linking group having 2 to 10 carbon atoms, in that it is excellent in retardation properties and elastic modulus of the film, and Y is 3 It is preferable to represent a C3-C12 linking group containing an alicyclic structure of a 6-membered ring.
- the alicyclic structure is a 3- to 6-membered ring, preferably a 5- to 6-membered ring, and specifically, a cyclopropylene group, a 1,2-cyclobutylene group, a 1,3-cyclobutylene group, a 1,2- Examples thereof include a cyclopentylene group, a 1,3-cyclopentylene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group.
- the hydrogen atom at the hydroxyl end of the polyester additive having a repeating unit represented by the above general formula (1) is substituted with an acyl group derived from a monocarboxylic acid (hereinafter also referred to as a monocarboxylic acid residue) It is preferable (hereinafter, also referred to as a hydrogen atom at a hydroxyl end is sealed).
- a monocarboxylic acid residue a monocarboxylic acid residue
- both ends of the polyester are monocarboxylic acid residues.
- a residue is a partial structure of the said polyester, and represents the partial structure which has the characteristic of the monomer which has formed the said polyester.
- the monocarboxylic acid residue formed from the monocarboxylic acid R-COOH is R-CO-.
- R an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alicyclic alkyl group and an aromatic group can be mentioned.
- the aliphatic monocarboxylic acid residue is preferably an aliphatic monocarboxylic acid residue, more preferably an aliphatic monocarboxylic acid residue having 2 to 10 carbon atoms, and an aliphatic monocarboxylic acid residue having 2 to 3 carbon atoms It is more preferably a group, and particularly preferably an aliphatic monocarboxylic acid residue having 2 carbon atoms.
- the hydroxyl value of the polyester is 10 mg KOH / g or less from the viewpoint of improving the polarizer durability, more preferably 5 mg KOH / g or less, and particularly preferably 0 mg KOH / g.
- the number average molecular weight (Mw) of the polyester may be 500 to 3,000, and more preferably 700 to 2,000. It is excellent in compatibility as it is this range, and a stable film with little volatilization of additives at the time of film production and use can be obtained.
- a compound (sugar ester) in which at least one substitutable group (for example, a hydroxyl group, a carboxyl group) in the sugar skeleton structure and at least one kind of substituent are esterified Compounds) can be used. More specifically, a hydroxyl group of a compound (M) having 1 to 12 of at least one pyranose structure or furanose structure, or a compound (D) in which at least one furanose structure or pyranose structure is bound A sugar ester compound obtained by alkylating all or part of OH groups simply or preferably is preferably used.
- Examples of the compound (M) include glucose, galactose, mannose, fructose, xylose or arabinose, preferably glucose and fructose, more preferably glucose.
- Examples of the compound (D) include lactose, sucrose, nystose, 1F-fructosyl nistose, stachyose, maltitol, lactitol, lactulose, cellulose, cellulose, cellotriose, maltotriose, raffinose, and kestose.
- genthiobiose genthiotriose
- genthiotetraose genthiotetraose
- xylotriose galactosyl sucrose and the like
- glucose sucrose and lactose are preferred.
- an aliphatic monocarboxylic acid a monocarboxylic acid having an alicyclic structure, or an aromatic monocarboxylic acid for alkylating all or part of OH groups in the compound (M) and the compound (D) .
- monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, benzoic acid and cyclohexanecarboxylic acid. Two or more of these monocarboxylic acids may be used in combination.
- plasticizers As other additives, plasticizers, UV absorbers, crosslinking agents, matting agents (inorganic fine particles), antioxidants, radical scavengers and the like may be added.
- the support of the retardation film of the present invention is also used as a polarizing plate protective film to constitute a polarizing plate as described later, from the viewpoint of imparting an effect of improving the durability of the polarizer, the following general formula It is preferable to contain the compound represented by these.
- each of R 11 , R 13 and R 15 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or 2 to 20 carbon atoms Represents an alkenyl group or an aromatic group having 6 to 20 carbon atoms.
- Such compounds can be used, for example, those described in International Publication WO 2014/112575.
- the cellulose acylate film used in the present invention can be produced using the method described in Japan Institute of Invention and Innovation Technical Publication No. 2001-1745 (Invention Association). These cellulose acylate films can be obtained by uniaxially or biaxially stretching as required, and preferably those stretched in the transverse direction can be used. Moreover, it can also be extended in an oblique direction.
- the draw ratio in one direction can be 1.02 to 1.50 times, preferably 1.05 times to 1.30 times. By performing the stretching treatment, physical property control suitable for the purpose of the present invention can be performed.
- the glass transition temperature can be 140 to 200 ° C., more preferably 160 to 190 ° C., and particularly preferably 170 to 185 ° C. Within this range, the resistance to thermal deflection, which is an object of the present invention, is further improved, and physical property control by stretching treatment is easy.
- the glass transition temperature can be determined as a peak value of tan ⁇ by a dynamic viscoelasticity measuring apparatus.
- the long retardation film of the present invention may include an alignment film (alignment layer) having a function of defining the alignment direction of the polymerizable liquid crystal composition forming the optically anisotropic layer.
- an alignment film alignment layer
- the polymerizable liquid crystal composition can be uniformly and efficiently introduced into a desired alignment state.
- the alignment film As an example of the alignment film, a rubbing-treated film of a layer containing an organic compound such as a polymer or the like, an oblique deposition film of an inorganic compound, a film having microgrooves, or ⁇ -trichosanic acid, dioctadecyl methyl ammonium chloride or methyl stearylate And films obtained by accumulating LB (Langmuir-Blodgett) films by the Langmuir-Blodgett method of such organic compounds. Furthermore, the alignment film etc. which an alignment function produces by irradiation of light are mentioned.
- the alignment film one formed by rubbing the surface of a layer (polymer layer) containing an organic compound such as a polymer can be preferably used.
- the rubbing treatment is carried out by rubbing the surface of the polymer layer with paper or cloth several times in a certain direction (preferably the longitudinal direction of the support).
- a polymer used for formation of alignment film polyimide, polyvinyl alcohol, modified polyvinyl alcohol described in paragraph No. [0071] to [0095] of Japanese Patent No. 3907735, polymerization described in JP-A-9-152509 It is preferable to use a polymer having a functional group.
- photo alignment film photo alignment layer
- an alignment material is irradiated with polarized light or non-polarized light
- an alignment film it is preferable to apply an alignment regulating force to the photo alignment film by the step of irradiating polarized light from the vertical direction or the oblique direction or the step of irradiating non-polarized light from the oblique direction.
- Examples of the photoalignment material used for the photoalignment film include, for example, JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071, and JP-2007-. No. 121721, JP-A-2007-140465, JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, Patent Nos. 3883848, and No.
- Patent Document 1 JP-A-10-506420, JP-A-2003-505561, WO 2010/150748, JP-A 2013-177561, JP-A 2014-12823, and compounds capable of photodimerization
- cinnamate compounds, chalcone compounds and coumarin compounds can be mentioned.
- Particularly preferred examples include azo compounds, photocrosslinkable polyimides, polyamides, esters, cinnamate compounds and chalcone compounds.
- the thickness of the alignment film is not particularly limited as long as the alignment function can be exhibited, but is preferably 0.01 to 5 ⁇ m, and more preferably 0.05 to 2 ⁇ m. Within this range, an excellent alignment regulation force can be exhibited, and the effect of suppressing foreign matter defects is high.
- the support and the alignment film may be separately provided as layers that perform their respective functions, or the support may double as an alignment film, that is, the surface of the support may have an alignment regulating force. .
- the support and the alignment film may be provided in contact with each other, or the functional layer may be interposed between the support and the alignment film.
- the above-described treatment such as rubbing or polarized light irradiation is applied to the surface of the support, and the polymer constituting the support by stretching the support It is possible to take a method of orienting in a certain direction.
- the above-mentioned functional layer which can be interposed between the support and the alignment film include a barrier layer, an impact relaxation layer, an easy peeling layer, and an easy adhesion layer.
- the long retardation film of the present invention includes a long optically anisotropic layer formed by using at least a polymerizable liquid crystal composition on a long support.
- the optically anisotropic layer has a surface measured at a wavelength of 650 nm, Re (450) which is an in-plane retardation value measured at a wavelength of 450 nm, and Re (550) which is an in-plane retardation value measured at a wavelength of 550 nm.
- the value of the internal retardation, Re (650) has a relationship of Re (450) ⁇ Re (550) ⁇ Re (650). That is, this relationship can be said to be a relationship representing the above-mentioned inverse wavelength dispersion.
- the optically anisotropic layer having such characteristics can be suitably used as a ⁇ / 4 plate described later, various optical functional layers, and an optical compensation layer in order to provide uniform polarization conversion characteristics at each wavelength.
- the in-plane retardation Re (550) can be 100 nm to 350 nm, and more preferably 100 nm to 250 nm.
- the method of measuring the in-plane retardation value at each wavelength is as described above.
- the thickness of the optically anisotropic layer can be appropriately set in consideration of the refractive index anisotropy of the polymerizable liquid crystal composition used with respect to the target retardation, and the thickness is, for example, 0.5 ⁇ m to The thickness is preferably 5 ⁇ m, more preferably 0.7 ⁇ m to 4 ⁇ m, and still more preferably 1 ⁇ m to 3 ⁇ m. Within this range, defects such as foreign matter and orientation abnormality are suppressed, the in-plane uniformity is high, and an optically anisotropic layer which is robust and excellent in durability can be obtained.
- the polymerizable liquid crystal composition to be the optically anisotropic layer contains a reverse polymerizable liquid crystal compound having a wavelength dispersive property. Furthermore, other polymerizable compounds, leveling agents, solvents, and other components can be included as required.
- the “inverse wavelength dispersive” polymerizable liquid crystal compound means a retardation at a specific wavelength (visible light range) of a retardation layer produced using this, typically, an in-plane retardation ( When the Re) value is measured, it means that the Re value becomes equal or higher as the measurement wavelength becomes larger, and one that satisfies the relationship of Re (450) ⁇ Re (550) ⁇ Re (650) as described later. Say. It also includes the case where the same relationship is satisfied by Rth ( ⁇ ) instead of Re ( ⁇ ).
- the polymerizable liquid crystal compound in the present specification refers to a liquid crystal compound having a polymerizable group.
- the type of the polymerizable group of the specific polymerizable liquid crystal compound is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, styryl group and allyl group.
- the type of the specific liquid crystal compound is not particularly limited, it can be classified into a rod-like type (rod-like liquid crystal compound) and a disk-like type (disk-like liquid crystal compound.
- Discotic liquid crystal compound according to its shape. Furthermore, there are low molecular type and high molecular type respectively.
- a polymer refers to one having a degree of polymerization of 100 or more (Polymer physics / phase transition dynamics, Masao Doi, page 2, Iwanami Shoten, 1992). Any liquid crystal compound can also be used in the present invention. Two or more types of rod-like liquid crystal compounds, two or more types of discotic liquid crystal compounds, or a mixture of a rod-like liquid crystal compound and a discotic liquid crystal compound may be used.
- a rod-like liquid crystal compound By homogeneously (horizontally) orienting the rod-like liquid crystal compound, there is an advantage that it becomes easy to function the formed retardation film as a positive A plate as described later.
- the liquid crystal compound having reverse wavelength dispersion is not particularly limited as long as it can form a film having reverse wavelength dispersion as described above, and, for example, it can be represented by the general formula (I) described in JP-A-2008-297210.
- Compounds in particular, compounds described in paragraphs [0034] to [0039]), compounds represented by the general formula (1) described in JP-A-2010-84032 (especially, paragraphs [0067] to The compound described in [0073], a liquid crystal compound represented by the general formula (II) described later, and the like can be used.
- the specific liquid crystal compound mentioned above contains the liquid crystal compound represented by the following general formula (II) from a viewpoint that it is excellent by reverse wavelength dispersion.
- Each of R 1 , R 2 , R 3 and R 4 independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
- plural R 1 's , plural R 2' s , plural R 3 's and plural R 4' s may be the same or different from each other.
- G 1 and G 2 each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and the methylene group contained in the above alicyclic hydrocarbon group is —O—, —S—, It may be substituted by -NH-.
- L 1 and L 2 each independently represent a monovalent organic group, and at least one selected from the group consisting of L 1 and L 2 represents a monovalent group having a polymerizable group.
- Ar represents a divalent aromatic ring group represented by the following general formula (II-1), (II-2), (II-3) or (II-4).
- Q 1 is, -S -, - O-, or -NR 11 - it represents, R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Y 1 represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms (note that the above-mentioned aromatic hydrocarbon group and the above-mentioned aromatic heterocyclic group are substituents May have), Z 1 , Z 2 and Z 3 are each independently a hydrogen atom or a C 1-20 aliphatic hydrocarbon group, a C 3-20 alicyclic hydrocarbon group, or a monovalent C 6-20 carbon atom Represents an aromatic hydrocarbon group, a halogen atom, a cyano group, a nitro group, -NR 12 R 13 or -SR 12 , Z 1 and Z 2 may be bonded to each other to form an aromatic ring or heteroaromatic ring,
- Ax represents an organic group having 2 to 30 carbon atoms, having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, preferably an aromatic hydrocarbon ring group; aromatic Heterocyclic group; alkyl group having 3 to 20 carbon atoms, having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon ring and aromatic heterocyclic ring; group consisting of aromatic hydrocarbon ring and aromatic heterocyclic ring An alkenyl group of 3 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of: 3 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring Alkenyl groups, Ay is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, preferably an aromatic hydrocarbon ring group
- a halogen atom an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, a cyano group, an amino group, a nitro group, a nitro group, a carboxy group, an alkylsulfinyl group having 1 to 6 carbon atoms, carbon An alkylsulfonyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 6 carbon atoms, N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms, or a combination
- L 1 , L 2 , R 4 , R 5 , R 6 , R 7 , X 1 , Y 1 , Q 1 and Q 2 are respectively D 1 , D 2 , G 1 , G 2 , L 1 and L 2 , R 1 , R 2 , R 3 , R 4 , Q 1 , Y 1 , Z 1 and Z 2
- the compound represented by the general formula (I) described in JP-A-2008-107767 a 1, a 2, and the description of X respectively a 1, a 2, and X can refer for, Ax of the compound represented by the general formula described in WO 2013/018526 (I), Ay of , respectively, the description with respect to Q 1 x, Ay, it can be referred for Q 2.
- the organic group represented by L 1 and L 2 is preferably a group represented by -D 3 -G 3 -Sp-P 3 in particular.
- D 3 is synonymous with D 1 .
- G 3 represents a single bond, a divalent aromatic ring group or heterocyclic group having 6 to 12 carbon atoms, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and the above alicyclic hydrocarbon group a methylene group contained in the, -O -, - S -, - NR 7 - may be substituted with, where R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- n represents an integer of 2 to 12
- m represents an integer of 2 to 6
- R 8 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- a hydrogen atom of —CH 2 — in each of the above groups may be substituted by a methyl group.
- P 3 represents a polymerizable group.
- the polymerizable group is not particularly limited, but is preferably a polymerizable group capable of radical polymerization or cationic polymerization.
- a radically polymerizable group a generally known radically polymerizable group can be used, and an acryloyl group or a methacryloyl group can be mentioned as a suitable one.
- the acryloyl group is generally fast in polymerization rate, and acryloyl group is preferable from the viewpoint of productivity improvement, but methacryloyl group is also used similarly as the polymerizable group of high birefringence liquid crystal. Can.
- cationically polymerizable group generally known cationic polymerizability can be used, and specifically, alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiroorthoester group, vinyloxy Groups can be mentioned. Among them, alicyclic ether group and vinyloxy group are preferable, and epoxy group, oxetanyl group and vinyloxy group are particularly preferable. Examples of particularly preferred polymerizable groups include the following.
- the “alkyl group” may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group, Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, A cyclohexyl group etc. are mentioned.
- liquid crystal compound represented by the general formula (II) are shown below, but are not limited to these liquid crystal compounds.
- the content of the liquid crystal compound represented by the general formula (II) in the specific liquid crystal compound is preferably 60 to 100% by mass, 70
- the content is more preferably 100% by mass, and still more preferably 70% by mass to 90% by mass.
- 70 mass% or more it is excellent by reverse wavelength dispersion. A plurality of these may be used in combination.
- a polymerizable rod-like compound can be added to the polymerizable composition in addition to the above-mentioned reverse wavelength dispersible polymerizable liquid crystal compound.
- the polymerizable rod-like compound may or may not be liquid crystalline.
- the addition of the polymerizable rod-like compound can improve the phase transition temperature and the orientation of the polymerizable composition, and the orientation stability at the time of orientation fixation by polymerization.
- any material having high compatibility with the specific liquid crystal compound can be preferably used.
- those having the structure of formula (I) described in JP-A-2015-163596 can be preferably used.
- the addition amount is preferably from 0 to 30%, more preferably from 0 to 20%, to the above-mentioned reverse wavelength dispersive liquid crystal compound.
- the polymerizable liquid crystal composition forming the optically anisotropic layer can contain a polymerization initiator.
- the polymerization initiator to be used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation.
- the photopolymerization initiator for example, ⁇ -carbonyl compounds (described in each specification of US Pat. Nos. 2,367,661 and 2367670), acyloin ether (described in US Patent No. 2448828), ⁇ -hydrocarbon-substituted aroma Acyloin compounds (as described in US Pat. No. 2,722,512), polynuclear quinone compounds (as described in US Pat.
- the polymerization initiator is preferably an oxime type polymerization initiator (as described in US Pat. No. 5,496,482), because the durability of the optically anisotropic layer is further improved. It is more preferable that it is a polymerization initiator represented by the following formula (III).
- X represents a hydrogen atom or a halogen atom
- Y represents a monovalent organic group
- Ar 3 represents a divalent aromatic group
- L 6 represents a divalent organic group having 1 to 12 carbon atoms
- R 10 represents an alkyl group having 1 to 12 carbon atoms.
- the divalent aromatic group represented by Ar 3 is selected from the group consisting of the aromatic hydrocarbon ring and the aromatic heterocycle exemplified as Ar 2 in the above formula (II) Examples thereof include divalent groups having at least one aromatic ring.
- the divalent organic group having 1 to 12 carbon atoms L 6 indicates, for example, include a linear or branched alkylene group of 1 to 12 carbon atoms, specifically Are preferably a methylene group, an ethylene group, a propylene group and the like.
- the alkyl group having 1 to 12 carbon atoms represented by R 10 in the above formula (III) specifically, for example, a methyl group, an ethyl group, a propyl group and the like are preferably mentioned.
- the monovalent organic group represented Y is, for example, a functional group containing a benzophenone skeleton ((C 6 H 5) 2 CO).
- a functional group containing a benzophenone skeleton in which the terminal benzene ring is unsubstituted or monosubstituted is preferable.
- * represents a bonding position, that is, a bonding position to a carbon atom of the carbonyl group in the above formula (III).
- Examples of the oxime type polymerization initiator represented by the above formula (III) include a compound represented by the following formula S-1, a compound represented by the following formula S-2, and the like.
- the content of the polymerization initiator is not particularly limited, but the content of the polymerization initiator is 0.5 with respect to 100 parts by mass of the specific liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention.
- the amount is preferably 10 parts by mass, and more preferably 1 to 5 parts by mass.
- the polymerizable liquid crystal composition can contain an alignment control agent, if necessary.
- an alignment control agent for example, a low molecular alignment control agent or a high molecular alignment control agent can be used.
- low-molecular alignment control agents include, for example, paragraphs 0009 to 0083 of JP-A-2002-20363, paragraphs 0111-0120 of JP-A-2006-106662, and 0021-0029 of JP-A-2012-211306. The description can be referred to, the contents of which are incorporated herein.
- the alignment control agent of a polymer for example, the description in paragraphs 0021 to 0057 of JP-A 2004-198511 and paragraphs 0121 to 0167 in JP-A 2006-106662 can be referred to, and the contents thereof are described. Are incorporated herein by reference.
- the amount of use of the alignment control agent is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass of the solid content of the liquid crystal composition in the polymerizable liquid crystal composition.
- the liquid crystal compound can be brought into a homogeneous alignment state in which the liquid crystal compound is aligned in parallel with the surface of the layer.
- the polymerizable liquid crystal composition may contain a polymerizable compound other than the specific liquid crystal compound described above.
- the polymerizable group contained in the polymerizable compound is not particularly limited, and examples thereof include (meth) acryloyl group, vinyl group, styryl group, allyl group and the like. Among them, it is preferable to have a (meth) acryloyl group.
- a polymerizable compound having two or more polymerizable groups for the reason that the durability of the retardation film is improved, etc., it is preferable to use a polymerizable compound having two or more polymerizable groups, and a polymerizable compound having 2 to 6 polymerizable groups. Is more preferred.
- polymerizable compound for example, compounds represented by the formulas (M1), (M2) and (M3) described in paragraphs [0030] to [0033] of JP-A-2014-077068 may be mentioned. More specifically, specific examples described in paragraphs [0046] to [0055] of the same publication can be mentioned.
- the polymerizable compounds may be used alone or in combination of two or more.
- the content in the case of containing the above-mentioned polymerizable compound is not particularly limited, but it is preferably 1 to 40 parts by mass in a total of 100 parts by mass of the specific liquid crystal compound and the above-mentioned polymerizable compound. More preferably, it is 5 to 30 parts by mass.
- the polymerizable liquid crystal composition preferably contains an organic solvent from the viewpoint of workability for forming a retardation film, and the like.
- organic solvent include, for example, ketones (eg, acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone etc.), ethers (eg, dioxane, tetrahydrofuran etc.), aliphatic Hydrocarbons (eg, hexane etc.), alicyclic hydrocarbons (eg, cyclohexane etc.), aromatic hydrocarbons (eg, toluene, xylene, trimethylbenzene etc.), halogenated carbons (eg, dichloromethane, dichloroethane etc.) , Dichlorobenzene, chlorotoluene, etc., esters (eg methyl acetate, ethyl ketone, methyl
- the polymerizable liquid crystal composition may contain other components other than the above, for example, liquid crystal compounds other than the above, leveling agents, surfactants, alignment assistants, plasticizers, crosslinking agents, wet heat durability improver Sensitizers, UV absorbers, dyes, radical quenchers and the like.
- optical properties of the optically anisotropic layer, orientation state can be provided with various optical properties according to the purpose. These optical properties can be obtained by controlling the alignment state and thickness of the polymerizable liquid crystal composition described above.
- One embodiment of the present invention can be a ⁇ / 4 plate which is a positive A plate.
- a positive C plate can be used as another aspect of the present invention.
- the optically anisotropic layer contained in the retardation film of the present invention can be a positive A plate.
- a positive A plate can be obtained by horizontally aligning (homogeneous alignment) this with a rod-like polymerizable liquid crystal compound.
- a positive A plate is defined as follows.
- the positive A plate (positive A plate) has the refractive index nx in the slow axis direction (the direction in which the refractive index in the plane is maximum) in the film plane, and is orthogonal to the in-plane slow axis in the plane
- nx in the slow axis direction
- nz the refractive index in the thickness direction
- the relationship of formula (A1) is satisfied.
- the positive A plate shows a positive value of Rth.
- Formula (A1) nx> ny ⁇ nz The term “ ⁇ ” includes not only the case where both are completely identical but also the case where both are substantially identical.
- substantially the same means, for example, (ny-nz) x d (where d is the thickness of the film), but in the case of -10 nm to 10 nm, preferably -5 nm to 5 nm, "ny nz nz" include.
- JP-A-2008-225281, JP-A-2008-026730, and the like The details of the method for producing the positive A plate can be referred to, for example, the descriptions of JP-A-2008-225281, JP-A-2008-026730, and the like.
- the optically anisotropic layer contained in the retardation film of the present invention preferably has the characteristics of a ⁇ / 4 plate.
- Such a wide band ⁇ / 4 plate is a circularly polarizing plate obtained by arranging and laminating, for example, the slow axis of the optically anisotropic layer at 30 ° to 50 °, preferably 45 ° with the transmission axis of the linear polarizing plate (linear Incident light from the polarizing plate side contributes to forming a suitable broadband circularly polarizing plate in the case where it is emitted as circularly polarized light from the ⁇ / 4 plate side, and as described later, for example, for preventing internal reflection in an image display device It can be suitably used as a film.
- the in-plane slow axis of the optically anisotropic layer forms an angle of 30 ° to 50 ° with the longitudinal direction of the long support. Is preferred.
- the optically anisotropic layer contained in the retardation film of the present invention can be a positive C plate.
- a positive C plate can be obtained by using a rod-like polymerizable liquid crystal compound to vertically align it (homeotropic alignment).
- the positive C plate is defined as follows.
- the refractive index in one direction in the film plane is nx
- the refractive index is ny in the direction orthogonal to the direction of nx
- the refractive index in the thickness direction is nz. It satisfies the relationship of C1).
- the positive C plate exhibits a negative value of Rth.
- Formula (C1) nx ny ny ⁇ nz
- ⁇ includes not only the case where both are completely identical but also the case where both are substantially identical.
- substantially the same means, for example, (nx-ny) x d (where d is the thickness of the film), but in the case of -10 nm to 10 nm, preferably -5 nm to 5 nm, "nx ny ny” include.
- the optically anisotropic layer of the long retardation film of the present invention has an alignment order degree of optical anisotropy at a maximum absorption wavelength in the range of 320 nm to 400 nm of the polymerizable liquid crystal compound measured using the solution (a) S0 can be ⁇ 0.50 ⁇ S0 ⁇ 0.15.
- the solution (a) is a solution in which the reverse wavelength dispersible polymerizable liquid crystal compound to be used is dissolved in chloroform so as to have a concentration of 10 ⁇ 4 mol / l.
- the degree of orientational order S ( ⁇ ) of the optically anisotropic layer is a value represented by the formula (S1).
- the degree of orientational order S ( ⁇ ) of the optical film can be determined by polarization absorption measurement at that wavelength, where ⁇ is the absorption maximum peak value at 320 nm to 400 nm of the reverse wavelength dispersible polymerizable liquid crystal compound.
- the degree of orientational order S0 can be ⁇ 0.50 ⁇ S0 ⁇ 0.15 as described above, preferably ⁇ 0.48 ⁇ S0 ⁇ 0.20. Within this range, it is possible to obtain an optically anisotropic layer excellent in the orientation, the refractive index anisotropy and the reverse wavelength dispersion while suppressing the crystallization of the liquid crystal compound.
- the liquid crystal compound In the state immediately before curing treatment of the optically anisotropic layer of the long retardation film of the present invention (also referred to as “liquid crystal layer (uncured)”), the liquid crystal compound exhibits a nematic phase or a smectic phase. Can be. In order to increase the above-mentioned degree of orientational order S0 to obtain the effect, it is preferable to exhibit a smectic phase.
- the polymerizable liquid crystal composition used in the present invention is preferably a polymerizable liquid crystal composition having a smectic phase, and its nematic phase
- the phase transition temperature from the smectic phase to the smectic phase can be 20 to 120 ° C., preferably 60 ° C. or more, and more preferably 80 ° C. or more.
- the degree of orientational order can be controlled in a temperature range that a general film forming apparatus can cope with, and the orientation is unlikely to be broken even under the heat curing conditions described later, and the durability of the optically anisotropic layer is It is possible to make the property and the orientation order degree of the liquid crystal compound contained be compatible.
- the thickness direction retardation change ⁇ Rth of the following equation can be used instead of the in-plane retardation change ⁇ Re.
- ⁇ Rth
- ⁇ Rth can be 0.94 to 1.02, and more preferably 0.96 to 1.01.
- Such a retardation film can be achieved by achieving both high orientational order and the polymerization reaction rate of the polymerizable liquid crystal composition, and can be specifically realized by the method for producing a retardation film described below.
- the method for forming the long retardation film of the present invention is not particularly limited, and examples thereof include known methods.
- the above-mentioned polymerizable liquid crystal composition is continuously applied on a long support to form a long coating, and the resulting coating is cured (the active energy ray is Irradiation (light irradiation treatment) and / or heat treatment can be performed to produce a retardation film including a cured coating (optically anisotropic layer).
- the orientation layer mentioned above, an orientation process, etc. as needed.
- a preferred method for producing the long retardation film of the present invention is While conveying a long support made of a resin film in the longitudinal direction, Applying a polymerizable liquid crystal composition containing a reverse polymerizable liquid crystal compound to the one surface of a long support to form a coating film; And a curing step of curing the coating film to form an optically anisotropic layer.
- the long support has a thickness of 10 ⁇ m to 50 ⁇ m, a transverse elastic modulus of 4.3 GPa to 6.0 GPa, and a linear thermal expansion coefficient of 10 ppm / ° C. to 35 ppm / ° C.
- a hardening process it is a manufacturing method of the elongate retardation film which hardens while heating a coating film at 80 ° C or more and 140 ° C or less.
- a hardening process is what hardens a coating film by irradiation (light irradiation) of an active energy ray.
- the active energy ray is preferably ultraviolet light.
- the irradiation of the active energy ray is performed at a position where the long support is in contact with the backup roll.
- RtoR roll to roll
- the application of the polymerizable liquid crystal composition can be carried out by a known method (for example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).
- a known method for example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method.
- the solvent contained in the composition can be removed by appropriately heating or depressurizing as necessary. Drying may be performed simultaneously with the orientation treatment described later.
- the alignment treatment of the coating layer of the polymerizable liquid crystal composition can be performed by heating.
- the liquid crystal phase formed by the alignment treatment can generally be transferred by a change in temperature.
- the temperature range in which the nematic phase is developed is generally higher than the temperature range in which the smectic phase is developed. Therefore, the specific liquid crystal compound is changed from the nematic phase to the smectic phase by heating the specific liquid crystal compound to the temperature range in which the nematic phase appears and then reducing the heating temperature to the temperature range in which the specific liquid crystal compound develops the smectic phase. It can be transferred.
- the polymerizable liquid crystalline composition When it is desired to form a nematic layer, and when the polymerizable liquid crystalline composition does not have a smectic phase, it is heated once at a temperature showing the nematic phase or above the temperature at which the nematic phase is transferred to the isotropic layer.
- the orientation treatment can be performed by keeping the temperature within the range shown.
- the reverse wavelength dispersible polymerizable liquid crystal compound used in the present invention is a rod-like liquid crystal
- the heating time (heating aging time) is preferably 10 seconds to 5 minutes, more preferably 10 seconds to 3 minutes, and most preferably 10 seconds to 2 minutes.
- the curing treatment irradiation with active energy rays (light irradiation treatment) and / or heat treatment) to the coating film subjected to the alignment treatment as described above is referred to as immobilization treatment for fixing the orientation of the polymerizable liquid crystal compound. It can also be done.
- the immobilization treatment is preferably performed by irradiation with active energy rays (preferably ultraviolet rays), and the liquid crystal is immobilized by polymerization of the specific liquid crystal compound. Under the present circumstances, by raising the temperature of a coating film, a polymerization reaction can be accelerated
- the heating condition is preferably in the range of 80 ° C.
- the irradiation amount of the active energy ray may be appropriately set according to the type of the polymerizable liquid crystal compound, the type of the polymerization initiator, the type of the active energy ray, and the like. For example, in the case of irradiation with ultraviolet rays as active energy rays, 100 to 500 mJ / cm 2 is preferable.
- the heating means and the curing treatment means are preferably performed continuously or almost simultaneously.
- the heating means include heating by raising the temperature to a high temperature, heating by contacting with a heat source, heating performed by radiation such as infrared rays, and the like, but from the point of being excellent in heating rate and heating uniformity of coating film. Contact heating with a heat roll or the like is preferable.
- the backup roll facing an irradiation apparatus is a heat roll (heating means). Further, it is preferable to carry out preheating before heating to effect processing within a range that does not affect the orientation state.
- the long retardation film including the optically anisotropic layer in which the alignment of the polymerizable liquid crystal composition is fixed is subjected to a post-heating treatment, a liner film or a surface protective film, if necessary, on the core. It can be a wound body.
- a long retardation film having a total length of more than 500 m knurling can be provided at both ends of the film for the purpose of preventing the wound film from rubbing.
- the long laminate (long polarizing plate) of the present invention has the above-mentioned long retardation film and a long linear polarizing film.
- the description of the retardation film is the same as described above, and thus is omitted.
- the long linear polarizing film may be a so-called linear polarizer having a function of converting light into specific linear polarization.
- the polarizer is not particularly limited, but an absorptive polarizer can be used.
- the type of polarizer is not particularly limited, and commonly used polarizers can be used.
- iodine polarizers dye polarizers using dichroic dyes, polyene polarizers, and Any polarizer using a wire grid can be used.
- the iodine-based polarizer and the dye-based polarizer are generally produced by adsorbing iodine or a dichroic dye to polyvinyl alcohol and drawing.
- a thermotropic liquid crystalline dichroic dye for example, a thermotropic liquid crystalline dichroic dye used for a light absorbing anisotropic film described in JP-A-2011-237513 is used and coated.
- the thickness of the polarizer is not particularly limited, but in the case of a typical polyvinyl alcohol polarizer, it is preferably 1 ⁇ m to 40 ⁇ m, more preferably 2 ⁇ m to 30 ⁇ m, and still more preferably 3 ⁇ m to 20 ⁇ m. If it is the said thickness, it will respond to thickness reduction of a display apparatus. If it is a coating type polarizer, it can be in the range of 0.5 ⁇ m to 3 ⁇ m.
- an ideal circularly polarizing plate can be obtained by using the retardation film of the present invention as a ⁇ / 4 plate and setting its slow axis to 45 ° or 135 ° with the transmission axis of the polarizer.
- the in-plane retardation Re of the retardation film of the present invention to 100 to 150 nm and setting the slow axis thereof parallel or perpendicular to the transmission axis of the polarizer, as an optical compensation layer of a liquid crystal display panel of IPS system It can be used.
- various optical anisotropic layers are applied and a polarizer and the retardation film of the present invention are combined to construct various polarizing plates with an optically anisotropic layer, circularly polarizing plates, and elliptically polarizing plates.
- a polarizer and the retardation film of the present invention are combined to construct various polarizing plates with an optically anisotropic layer, circularly polarizing plates, and elliptically polarizing plates.
- the long laminate (long polarizing plate) is generally produced so that the longitudinal direction of the long retardation film (long support) and the absorption axis of the long linearly polarizing film coincide with each other. That is, the width direction of the long retardation film (long support) and the absorption axis of the long linearly polarizing film are orthogonal to each other. Therefore, if the absorption axis of the linearly polarizing film is known from the polarizing plate (section) used for the image display apparatus etc., the width direction of the long support can also be known.
- a polarizer protective film may be disposed on the surface of the polarizer.
- the polarizer protective film may be disposed only on one side of the polarizer (on the surface opposite to the retardation film side) or may be disposed on both sides of the polarizer.
- the configuration of the polarizer protective film is not particularly limited, and may be, for example, a so-called transparent support or a hard coat layer, or a laminate of a transparent support and a hard coat layer.
- the support layer of the retardation film of the present invention may double as a polarizer protective film.
- a well-known layer can be used as a hard-coat layer, for example, the layer obtained by polymerizing and curing a polyfunctional monomer may be sufficient. If necessary, the hard coat layer may be provided with antiglare properties and antistatic properties.
- a known transparent support can be used as the transparent support.
- a cellulose-based polymer represented by triacetyl cellulose (hereinafter referred to as cellulose acylate) And thermoplastic norbornene resin (ZEONEX manufactured by Nippon Zeon Co., Ltd., Zeonor manufactured by JSR Co., Ltd., Arton etc.), acrylic resin and polyester resin can be used.
- the thickness of the polarizer protective film is not particularly limited, but is preferably 40 ⁇ m or less, and more preferably 25 ⁇ m or less because the thickness of the polarizing plate can be reduced. From the viewpoint of film handling, 5 ⁇ m or more is preferable, and 12 ⁇ m or more is more preferable.
- An adhesive layer or an adhesive layer may be disposed between the layers in order to ensure adhesion between the layers.
- a fine pattern of a transparent conductive layer or a metal layer may be provided in contact with any of the layers.
- the polarizing plate which is 1 type of the said long laminated body can be preferably used for image display apparatuses, such as an organic electroluminescent apparatus (preferably organic electroluminescent (EL) display apparatus), a LED display, a liquid crystal display apparatus.
- image display apparatuses such as an organic electroluminescent apparatus (preferably organic electroluminescent (EL) display apparatus), a LED display, a liquid crystal display apparatus.
- EL organic electroluminescent
- a polarizing plate When cutting out from the long laminate, the longitudinal direction of the polarizing plate to be cut out may be aligned with the longitudinal direction of the long laminate, or the width direction of the polarizing plate to be cut out and the width of the long laminate may be cut out.
- the hand direction may be matched and cut out, or it may be cut out so that the longitudinal direction of the cut out polarizing plate is oblique to the longitudinal direction of the long laminate.
- the liquid crystal display device is an example of an image display device, and includes a polarizing plate cut out from the above-described long laminate of the present invention and a liquid crystal cell.
- the polarizing plate of the present invention among the polarizing plates provided on both sides of the liquid crystal cell, it is preferable to use the polarizing plate of the present invention as a polarizing plate on the front side, and the polarizing plate of the present invention as polarizing plates on the front side and rear side. It is more preferable to use Moreover, it is preferable that the said retardation film contained in a polarizing plate is arrange
- the liquid crystal cell constituting the liquid crystal display device will be described in detail.
- the liquid crystal cell used for the liquid crystal display device is preferably a VA (Vertical Alignment) mode, an OCB (Optical Compensated Bend) mode, an IPS (In-Place-Switching) mode, or a TN (Twisted Nematic) mode. It is not limited to In the TN mode liquid crystal cell, rod-like liquid crystalline molecules are substantially horizontally aligned at the time of no voltage application, and are further twisted at 60 to 120 °. The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents. In the VA mode liquid crystal cell, rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied.
- VA mode liquid crystal cell In a VA mode liquid crystal cell, (1) a narrow definition VA mode liquid crystal cell in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and substantially horizontally aligned when a voltage is applied (2) A liquid crystal cell (in the form of MVA mode) in which VA mode is multi-domained (in the form of Digest 97 of Digest of tech. Papers (preprints) 28 (1997) 845) in order to expand the viewing angle.
- liquid crystal cells in a mode in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multidomain oriented when voltage is applied (Japanese Liquid Crystal Discussion Paper 58 to 59) (1998) and (4) SURVIVAL mode liquid crystal cells (presented at LCD International 98) are included.
- any of PVA (Pattered Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA (Polymer-Sustained Alignment) may be used. The details of these modes are described in detail in JP-A-2006-215326 and JP-A-2008-538819.
- an organic EL display device which is an example of the organic electroluminescent device, for example, an embodiment having a circularly polarizing plate cut out from the long laminate of the present invention from the viewing side and an organic EL display panel in this order is preferable. It can be mentioned.
- the retardation film contained in the circularly polarizing plate is preferably disposed on the organic EL display panel side. That is, the circularly polarizing plate containing the retardation film of the present invention is used as a so-called antireflective film which prevents light incident from the outside from being reflected by a panel electrode or the like to lower the contrast of display light.
- the organic EL display panel is a display panel configured using an organic EL element in which an organic light emitting layer (organic electroluminescent layer) is held between electrodes (between a cathode and an anode).
- the configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.
- the long retardation film of the present invention peeling is possible between the support and the optically anisotropic layer, between the orientation layer and the optically anisotropic layer, and / or between the support and the orientation layer.
- a laminate including only the optically anisotropic layer or the optically anisotropic layer and another layer other than the support is transferred to another support or an adherend such as a polarizing plate to achieve high performance.
- a polarizing plate and an image display including the same can be configured. That is, the elongate retardation film of this invention can be utilized as an elongate transfer film which made the support body a temporary support body as another one aspect
- the core layer cellulose acylate dope and the outer layer cellulose acylate dope are filtered with a filter paper having an average pore diameter of 34 ⁇ m and a sintered metal filter having an average pore diameter of 10 ⁇ m, and then the core layer cellulose acylate dope and outer layer cellulose acylate dope on both sides thereof And 3 layers were cast simultaneously from a casting port on a 20 ° C. metal band (band casting machine).
- the film was peeled off in a state of a solvent content of about 20% by mass, and both ends in the width direction of the film were fixed with a tenter clip, and the film was dried while being drawn in the transverse direction at a draw ratio of 1.1.
- a long cellulose acylate film 1 having a thickness of 40 ⁇ m.
- the core layer of the film had a thickness of 36 ⁇ m, and the outer layers disposed on both sides of the core layer had a thickness of 2 ⁇ m.
- the in-plane retardation of the obtained cellulose acylate film 1 was 0 nm.
- the lateral direction elastic modulus, the lateral direction elastic modulus at 140 ° C., and the linear thermal expansion coefficient in the lateral direction measured by the evaluation direction described later were as shown in Table 1.
- the cellulose acylate film 1 is prepared in the same manner as the cellulose acylate film 1 except that the thickness is 20 ⁇ m (the thickness of the core layer is 15 ⁇ m, and the thickness of the outer layer disposed on both sides of the core layer is 2.5 ⁇ m).
- a cellulose acylate film 2 was produced.
- the transverse direction elastic modulus, the transverse direction elastic modulus at 140 ° C., and the linear thermal expansion coefficient in the transverse direction are as shown in Table 1.
- Cellulose acylate films 3 and 4 As the cellulose acylate film 3, a long body of a commercially available cellulose acetate film (ZRD40SL, manufactured by FUJIFILM Corporation) was used. Further, as the cellulose acylate film 4, a long body of a commercially available cellulose acetate film (ZRD60SL, manufactured by Fujifilm Corp.) was used.
- the transverse direction elastic modulus, the transverse direction elastic modulus at 140 ° C., and the linear thermal expansion coefficient in the transverse direction are as shown in Table 1.
- the weight average molecular weight Mw of the obtained epoxy-containing polymethacrylate was 25,000.
- 286 parts by mass of the solution containing the epoxy-containing polymethacrylate obtained above (100 parts by mass in terms of polymethacrylate), obtained by the method of Synthesis Example 1 of JP-A-2015-26050 120 parts by mass of the cinnamic acid derivative, 20 parts by mass of tetrabutylammonium bromide as a catalyst, and 150 parts by mass of propylene glycol monomethyl ether acetate as a dilution solvent are charged, and the reaction is stirred for 12 hours at 90.degree. went.
- Example 1 [Preparation of Long Retardation Film]
- the following composition 1 for photo alignment film was continuously applied by a bar coater. After application, the solvent was removed by drying for 1 minute in a heating zone at 120 ° C. to form a 0.3 ⁇ m thick photoisomerization composition layer. Subsequently, while being wound on the mirror-treated back-up roll, elongated ultraviolet light (10 mJ / cm 2 , using a super high pressure mercury lamp) is applied so that the polarization axis forms an angle of 45 ° in the longitudinal direction. An alignment film was formed.
- composition 1 for forming an optically anisotropic layer described below was applied by a die coater on the photoalignment film formed in a long shape to form a liquid crystal layer (uncured). Thereafter, the film is maintained at 120 ° C., the orientation is fixed by ultraviolet irradiation (using an ultra-high pressure mercury lamp) in a nitrogen atmosphere (oxygen concentration 100 ppm), and an optical anisotropic layer having a thickness of 2.3 ⁇ m is formed.
- ultraviolet irradiation using an ultra-high pressure mercury lamp
- nitrogen atmosphere oxygen concentration 100 ppm
- the average in-plane retardation Re (550) of the obtained retardation film satisfies Re (450) / Re (550) ⁇ 1.0 and 1.0 ⁇ Re (650) / Re (550) at 140 nm.
- the mean slow axis was 45 ° to the longitudinal direction. Moreover, it was 0.87 when wavelength dispersion (Re (450) / Re (550)) was measured by AxoScan.
- Example 2 Comparative Example 1 and Comparative Example 3
- Example 2 Comparative Example 1 and Comparative Example 3
- Table 1 The results are shown in Table 1.
- Example 3 A long retardation film of Example 3 was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition was changed to the following liquid crystal 2 in Example 1. The results are shown in Table 1.
- Example 4 A long retardation film of Example 4 was produced in the same manner as in Example 2 except that the ultraviolet ray irradiation amount at the time of curing the liquid crystal layer by ultraviolet ray irradiation was 150 mJ / cm 2 . The results are shown in Table 1.
- Example 5 The same procedure as in Example 1 was carried out in the same manner as in Example 1 except that the coating liquid for the optically anisotropic layer was replaced with the liquid crystal 3 shown below, and the ultraviolet ray irradiation amount was 150 mJ / cm 2 when curing the liquid crystal layer by ultraviolet ray irradiation. A long retardation film was produced. The results are shown in Table 1.
- Example 6 A long retardation film of Example 6 was produced in the same manner as in Example 5 except that the long cellulose acylate film 2 was used. The results are shown in Table 1.
- Example 7 Example 8 and Example 9
- the polymerizable compound B-1 in the polymerizable liquid crystal composition was changed to B-2, B-3, and B-4, long retardation films of Examples 7 to 9 were produced. did.
- the results are shown in Table 1.
- Example 10 A cellulose acetate film having a thickness of 15 ⁇ m was used as the cellulose acylate film, and the ultraviolet ray irradiation amount at the time of curing the liquid crystal layer by ultraviolet ray irradiation was 100 mJ / cm 2 in the same manner as in Example 2. A long retardation film was produced. The results are shown in Table 1.
- Comparative example 2 A long retardation film was produced in the same manner as in Comparative Example 1 except that the temperature at the time of curing the liquid crystal layer by ultraviolet irradiation was set to 75 ° C. in Comparative Example 1. The results are shown in Table 1.
- the transverse direction elastic modulus of the long support was measured according to ISO 1184 1983 using a Tensilon tensile tester (trade name: RTA-100; manufactured by Orientec Co., Ltd.). Specifically, the modulus of elasticity was calculated from the slope of the load-distortion curve obtained by measurement in an atmosphere of 25 ° C. and 60% RH. The extension direction of the film sample was made to coincide with the width direction of the long support.
- the film sample 5 mm ⁇ 30 mm (the sample longitudinal direction coincides with the lateral direction of the elongated support) cut out from the elongated support film is conditioned at 25 ° C. and 60% relative humidity for 2 hours or more, Dynamic measurement with an elasticity measuring device (Vibron: DVA-225 (manufactured by IT Measurement & Control Co., Ltd.)) with a grip distance of 20 mm, a temperature rise rate of 2 ° C / min, a measurement temperature range of 30 ° C to 250 ° C and a frequency of 1 Hz.
- the elasticity was measured and the storage elastic modulus value at 140 ° C. was taken as the transverse elastic modulus at 140 ° C. of the long support.
- A: ⁇ Re 0.98 or more and 1.01 or less
- B: ⁇ Re 0.96 or more and less than 0.98, more than 1.01 and 1.02 or less
- C: ⁇ Re 0.94 or more and less than 0.96
- D: ⁇ Re Less than 0.94 or greater than 1.02
- the cellulose acylate film side of the retardation film is the polarizing plate side, and the cellulose acylate film 1 doubles as a polarizing plate protective film by a roll-to-roll process.
- the film was wound up once to prepare a long laminate of the present invention.
- the long laminate was further rolled up and cut into a predetermined shape to obtain a circularly polarizing plate 1.
- the GALAXY SII manufactured by SAMSUNG Co., Ltd. mounted with an organic EL panel is disassembled, the circularly polarizing plate is peeled off, and the same shape and the same transmission axis direction as the circularly polarizing plate taken out from the laminate 1 produced above
- the cut out laminate pieces were pasted via a pressure-sensitive adhesive so that the positive C plate side became the panel side, and the OLED display device 1 was produced.
- the obtained OLED display device was observed under natural light in a black display state. As a result, the black display performance was good with no unevenness both in the front and in the oblique direction (Evaluation: A).
- a laminate is produced in the same manner as described above for each of the retardation films 2 to 10 obtained in Examples 2 to 10 and the retardation films 12 to 13 obtained in Comparative Examples 2 to 3, respectively, and cut out from the laminate
- the laminated piece was attached to the organic EL panel.
- a glass plate is pasted on the organic EL panel mounted above via an adhesive and treated with a constant temperature and humidity layer kept at 85 ° C. and 0% RH for 500 hours, and then under an environment of 25 ° C. and 60% RH The humidity was controlled for 3 hours or more, and the appearance was observed under natural light in a black display state.
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Abstract
Description
近年、可視光域の光線が混在している合成波である白色光に対して、全ての波長の光線に対応して同様の効果を与えることができる偏光板(いわゆる広帯域偏光板)の開発が進められており、特に、偏光板が適用される装置の薄型化の要求から、偏光板に含まれる位相差フィルムについても薄型化が求められている。
上記の要求に対して、例えば特許文献1および2においては、位相差フィルムの形成に使用する重合性化合物として、逆波長分散性の重合性液晶化合物の利用が提案されている。
しかしながら、厚み50μm以下の薄い樹脂フィルム(支持体)の上に逆波長分散性の重合性液晶(重合性液晶化合物)を用いて形成した位相差フィルム(光学異方性層に該当)を有する偏光板を作製し、実用上の態様(例えば、有機電界発光方式のスマートフォンの反射防止を目的とした円偏光板として用いる態様)に合わせて、この偏光板を両側からガラスに挟みこみ、高温下の条件に長時間曝した場合、面内の中央部に赤みムラが生じることが分かった。
[2] 長尺支持体の140℃における幅手方向弾性率が1.5GPa~3.0GPaである、[1]に記載の長尺位相差フィルム。
[3] 長尺支持体のRe(550)が0nm~10nm、Rth(550)が-20nm~40nmである、[1]または[2]に記載の長尺位相差フィルム。
[4] 長尺支持体と、長尺光学異方性層との間に、光学異方性層に接して配向層を有する、[1]~[3]のいずれかに記載の長尺位相差フィルム。
[5] 光学異方性層のRe(550)が100nm~250nmである、[1]~[4]のいずれかに記載の長尺位相差フィルム。
[6] 光学異方性層のRe(550)が100nm~160nmであり、光学異方性層の面内遅相軸が長尺支持体の長手方向に対して30°~50°の角度を成している、[5]に記載の長尺位相差フィルム。
[7] 光学異方性層が、長尺支持体と接しているか、
長尺支持体と、光学異方性層との間に、光学異方性層に接して配向層を有しており、
かつ、光学異方性層が、剥離可能に設けられている、[1]~[6]に記載の長尺位相差フィルム。
[8] [1]~[7]のいずれかに記載の長尺位相差フィルムと、長尺直線偏光フィルムとを積層してなる、長尺積層体。
[9] [8]に記載の長尺積層体から切り出された偏光板を含む、画像表示装置。
[10]樹脂フィルムからなる長尺支持体を長手方向に搬送しつつ、
逆波長分散性の重合性液晶化合物を含む重合性液晶組成物を長尺支持体の一方の面に塗布し塗膜を形成する塗布工程と、
塗膜を硬化させて光学異方性層を形成する硬化工程と、を行う長尺位相差フィルムの製造方法であって、
前記長尺支持体は、厚みが10μm~50μmであり、かつ、幅手方向弾性率が4.3GPa~6.0GPaであり、かつ、幅手方向の線熱膨張率が10ppm/℃~35ppm/℃であり、
硬化工程において、塗膜を80℃以上140℃以下に加熱しつつ硬化を行う長尺位相差フィルムの製造方法。
なお、本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
また、角度について「直交」および「平行」とは、厳密な角度±10°の範囲を意味するものとし、角度について「同一」および「異なる」は、その差が5°未満であるか否かを基準に判断できる。
また、本明細書では、「可視光」とは、380~780nmのことをいう。また、本明細書では、測定波長について特に付記がない場合は、測定波長は550nmである。
次に、本明細書で用いられる用語について説明する。
本明細書において、「遅相軸」とは、面内において屈折率が最大となる方向を意味する。なお、位相差フィルムの遅相軸という場合は、位相差フィルム全体の遅相軸を意図する。
面内レターデーションおよび厚み方向のレターデーションの値は、AxoScan OPMF-1(オプトサイエンス社製)を用い、測定波長の光を用いて測定した値をいう。
具体的には、AxoScan OPMF-1にて、平均屈折率((Nx+Ny+Nz)/3)と膜厚(d(μm))を入力することにより、
遅相軸方向(°)
Re(λ)=R0(λ)
Rth(λ)=((nx+ny)/2-nz)×d
が算出される。
なお、R0(λ)は、AxoScan OPMF-1で算出される数値として表示されるものであるが、Re(λ)を意味している。
本発明の長尺位相差フィルムは、長尺支持体上に、少なくとも重合性液晶組成物を用いて形成された長尺状の光学異方性層を含む。
長尺支持体は、厚みが10μm~50μmであり、かつ、幅手方向弾性率が4.3GPa~6.0GPaであり、かつ、幅手方向の線熱膨張率が10ppm/℃~35ppm/℃である。
光学異方性層は逆波長分散性の重合性液晶化合物を含む重合性液晶組成物からなるものである。
長尺位相差フィルムの切片を85℃、500時間の加熱条件で処理した際の面内位相差変化ΔReが0.94~1.02である。
本発明の長尺位相差フィルムは、各種画像表示装置に適用可能であるが、特に有機EL表示装置用途に用いることが好ましい。
しかしながら、薄い樹脂フィルムを支持体として用いる場合には、加熱によって樹脂フィルムが伸びてシワが発生してしまうおそれがあるため、重合反応率を高くするのに十分な加熱をすることが難しい。
長尺支持体は加熱により熱膨張し、その応力と長尺支持体の搬送に係る種々の応力とが複合した結果、長尺支持体の幅手方向にかかる応力が長尺支持体の剛性を上回ると長尺支持体が座屈してたわみを生じると推定される。
また、光学異方性層の耐久性が向上する加熱および硬化条件にした場合でも、長尺支持体が幅手方向にたわむことを抑制できるため、重合性液晶化合物の重合反応率を高くして耐久性を向上できる。具体的には、長尺位相差フィルムの切片を85℃、500時間の加熱条件で処理した際の面内位相差変化ΔReを0.94~1.02と小さくすることができる。
すなわち、このような本発明の長尺位相差フィルムは耐久試験条件下でもその位相差値変化や寸法変化が少ない優れた位相差フィルムである。
ΔRe = |Rea(550)-Reb(550)|÷|Rea(550)|
ここで、Rea(550)およびReb(550)は、測定波長550nmにおける位相差フィルムの切片の面内位相差である。
また、位相差フィルムの切片は、長尺位相差フィルムの任意の位置から切り出した140mm×70mmの大きさのサンプルである。
配向層(配向膜)は、重合性液晶化合物の配向方向を規定する機能を有する層である。光学異方性層に接して配向層を有することで、光学異方性層を形成する際に、光学異方性層となる塗膜中の重合性液晶化合物を均一かつ効率よく望ましい配向状態へ導くことができる。
本発明の長尺位相差フィルムの長尺支持体は長尺状であり、透明であるのが好ましい。具体的には可視光領域の直線光透過率が80%以上であるのが好ましい。このような支持体としては、例えば、ポリマーフィルムの長尺体が挙げられる。ロール状の巻回体として取り扱うに際し柔軟性と強度を兼ね備えた点で、支持体はポリマーフィルムであることが好ましい。
なお、長尺支持体の幅手方向弾性率は、特に記載がない限り、常温(25℃)における弾性率である。
本発明に用いる長尺支持体として、セルロースアシレートフィルムを用いることができる。透明性と強度を兼ね備え、後述する各層との密着性あるいは易剥離性を容易に制御できる点で好ましく用いられる。セルロースアシレートフィルムとしては、セルロースアシレート樹脂を含み、さらに必要に応じて添加剤を含むフィルムを用いることができる。セルロースアシレートフィルムは、溶液製膜により作製することができ、また、溶融製膜を用いて作製してもよい。
Yとしては、置換基を有していてもよい炭素数2~20のアルキレン基、ポリオキシアルキレン基、アルケニレン基、フェニレン基、ナフチレン基、複素環芳香族基であることができる。なお、上記アルキレン基、アルケニレン基、および、ポリオキシアルキレン基中のアルキレン基は、脂環構造を有していてもよい。
これらの2価の連結基中に酸素原子、窒素原子などの炭素以外の分子を含んでもよい。上述した置換基としては、アルキル基、アルコキシ基、水酸基、アルコキシ置換アルキル基、カルボキシル基などが挙げられる。
こうした化合物は、例えば国際公開公報WO2014/112575号公報に記載のものを使用することができる。
これらのセルロースアシレートフィルムは、必要に応じ一軸、または二軸に延伸処理して得ることができ、好ましくは幅手方向に延伸したものを用いることができる。また、斜め方向に延伸したものであることもできる。一方向への延伸倍率としては1.02~1.50倍であることができ、1.05倍~1.30倍であることが好ましい。延伸処理を行うことにより、本発明の趣旨に適した物性制御を行うことができる。
本発明の長尺位相差フィルムには、光学異方性層を形成する重合性液晶組成物の配向方向を規定する機能を有する配向膜(配向層)が含まれていてもよい。これにより、重合性液晶組成物を均一かつ効率よく望ましい配向状態へ導くことができる。
配向膜として、ポリマーなどの有機化合物を含む層(ポリマー層)の表面をラビング処理して形成されたものを好ましく用いることができる。ラビング処理は、ポリマー層の表面を紙や布で一定方向(好ましくは支持体の長手方向)に数回こすることにより実施される。配向膜の形成に使用するポリマーとしては、ポリイミド、ポリビニルアルコール、特許第3907735号公報の段落番号[0071]~[0095]に記載の変性ポリビニルアルコール、特開平9-152509号公報に記載された重合性基を有するポリマー等を用いることが好ましい。
本発明の長尺位相差フィルムは、長尺支持体上に、少なくとも重合性液晶組成物を用いて形成された長尺状の光学異方性層を含む。
上記光学異方性層は、波長450nmで測定した面内レターデーション値であるRe(450)と、波長550nmで測定した面内レターデーション値であるRe(550)と、波長650nmで測定した面内レターデーションの値であるRe(650)とが、Re(450)<Re(550)<Re(650)の関係にある。すなわち、この関係は、上述した逆波長分散性を表す関係といえる。このような特性を有する光学異方性層は、各波長で均一な偏光変換特性を与えるために、後述するλ/4板や、種々の光学機能層、光学補償層として好適に用いることができる。面内レターデーションRe(550)は、100nm~350nmであることができ、100nm~250nmがより好ましい。
各波長における面内レターデーション値の測定方法は、上述した通りである。
本明細書において「逆波長分散性」の重合性液晶化合物とは、これを用いて作製された位相差層の特定波長(可視光範囲)における位相差、典型的には面内のレターデーション(Re)値を測定した際に、測定波長が大きくなるにつれてRe値が同等または高くなるものをいい、後述するようにRe(450)<Re(550)<Re(650)の関係を満たすものをいう。Re(λ)に代えてRth(λ)で同様の関係を満たす場合も含まれる。
これらの中でも、棒状液晶化合物を用いることが好ましい。棒状液晶化合物をホモジニアス(水平)配向させることで、形成される位相差フィルムを後述するようなポジティブAプレートとして機能させることが容易になるという利点がある。
R1、R2、R3およびR4はそれぞれ独立に、水素原子、フッ素原子または炭素数1~4のアルキル基を表す。R1、R2、R3およびR4のそれぞれが複数存在する場合には、複数のR1、複数のR2、複数のR3および複数のR4はそれぞれ、互いに同一でも異なっていてもよい。
G1およびG2はそれぞれ独立に、炭素数5~8の2価の脂環式炭化水素基を表し、上記脂環式炭化水素基に含まれるメチレン基は、-O-、-S-、-NH-で置換されていてもよい。
L1およびL2はそれぞれ独立に、1価の有機基を表し、L1およびL2からなる群から選ばれる少なくとも1種が、重合性基を有する1価の基を表す。
Arは、下記一般式(II-1)、(II-2)、(II-3)または(II-4)で表される2価の芳香環基を表す。
R11は、水素原子または炭素数1~6のアルキル基を表し、
Y1は、炭素数6~12の芳香族炭化水素基、または、炭素数3~12の芳香族複素環基を表し(なお、上記芳香族炭化水素基および上記芳香族複素環基は置換基を有していてもよい)、
Z1、Z2およびZ3はそれぞれ独立に、水素原子または炭素数1~20の脂肪族炭化水素基、炭素数3~20の脂環式炭化水素基、1価の炭素数6~20の芳香族炭化水素基、ハロゲン原子、シアノ基、ニトロ基、-NR12R13または-SR12を表し、
Z1およびZ2は、互いに結合して芳香環または芳香族複素環を形成してもよく、R12およびR13はそれぞれ独立に、水素原子または炭素数1~6のアルキル基を表し、
A1およびA2はそれぞれ独立に、-O-、-NR21-、-S-および-CO-からなる群から選ばれる基であって、R21は、水素原子または置換基を表し、Xは、水素原子または置換基が結合していてもよい第14族~第16族の非金属原子(好ましくは、=O、=S、=NR’、=C(R’)R’が挙げられる(ここでR’は置換基を表す))を表し、
Axは、芳香族炭化水素環および芳香族複素環からなる群から選ばれる少なくとも一つの芳香環を有する、炭素数2~30の有機基を表し、好ましくは、芳香族炭化水素環基;芳香族複素環基;芳香族炭化水素環および芳香族複素環からなる群から選ばれる少なくとも一つの芳香環を有する、炭素数3~20のアルキル基;芳香族炭化水素環および芳香族複素環からなる群から選ばれる少なくとも一つの芳香環を有する、炭素数3~20のアルケニル基;芳香族炭化水素環および芳香族複素環からなる群から選ばれる少なくとも一つの芳香環を有する、炭素数3~20のアルケニル基が挙げられ、
Ayは、水素原子、置換基を有していてもよい炭素数1~6のアルキル基、または、芳香族炭化水素環および芳香族複素環からなる群から選ばれる少なくとも一つの芳香環を有する炭素数2~30の有機基を表し、この有機基の好適態様は、上記Axの有機基の好適態様と同じであり、
AxおよびAyにおける芳香環はそれぞれ、置換基を有していてもよく、AxとAyは結合して、環を形成していてもよく、
Q2は、水素原子、または、置換基を有していてもよい炭素数1~6のアルキル基を表す。
なお、置換基としては、ハロゲン原子、アルキル基、ハロゲン化アルキル基、アルケニル基、アリール基、シアノ基、アミノ基、ニトロ基、ニトロソ基、カルボキシ基、炭素数1~6のアルキルスルフィニル基、炭素数1~6のアルキルスルホニル基、炭素数1~6のフルオロアルキル基、炭素数1~6のアルコキシ基、炭素数1~6のアルキルスルファニル基、炭素数1~6のN-アルキルアミノ基、炭素数2~12のN,N-ジアルキルアミノ基、炭素数1~6のN-アルキルスルファモイル基、炭素数2~12のN,N-ジアルキルスルファモイル基、またはこれらを組み合わせた基等が挙げられる。
D3は、D1と同義である。
G3は、単結合、炭素数6~12の2価の芳香環基もしくは複素環基、または炭素数5~8の2価の脂環式炭化水素基を表し、上記脂環式炭化水素基に含まれるメチレン基は、-O-、-S-、-NR7-で置換されていてもよく、ここでR7は水素原子または炭素数1~6のアルキル基を表す。
Spは、単結合、-(CH2)n-、-(CH2)n-O-、-(CH2-O-)n-、-(CH2CH2-O-)m、-O-(CH2)n-、-O-(CH2)n-O-、-O-(CH2-O-)n-、-O-(CH2CH2-O-)m、-C(=O)-O-(CH2)n-、-C(=O)-O-(CH2)n-O-、-C(=O)-O-(CH2-O-)n-、-C(=O)-O-(CH2CH2-O-)m、-C(=O)-N(R8)-(CH2)n-、-C(=O)-N(R8)-(CH2)n-O-、-C(=O)-N(R8)-(CH2-O-)n-、-C(=O)-N(R8)-(CH2CH2-O-)m、-(CH2)n-O-(C=O)-(CH2)n-C(=O)-O-(CH2)n-で表されるスペーサー基を表す。ここで、nは2~12の整数を表し、mは2~6の整数を表し、R8は水素原子または炭素数1~6のアルキル基を表す。また、上記各基における-CH2-の水素原子は、メチル基で置換されていてもよい。
P3は重合性基を示す。
ラジカル重合性基としては、一般に知られているラジカル重合性基を用いることができ、好適なものとして、アクリロイル基またはメタクリロイル基を挙げることができる。この場合、重合速度はアクリロイル基が一般的に速いことが知られており、生産性向上の観点からアクリロイル基が好ましいが、メタクリロイル基も高複屈折性液晶の重合性基として同様に使用することができる。
カチオン重合性基としては、一般に知られているカチオン重合性を用いることができ、具体的には、脂環式エーテル基、環状アセタール基、環状ラクトン基、環状チオエーテル基、スピロオルソエステル基、ビニルオキシ基などを挙げることができる。中でも、脂環式エーテル基、ビニルオキシ基が好適であり、エポキシ基、オキセタニル基、ビニルオキシ基が特に好ましい。
特に好ましい重合性基の例としては下記が挙げられる。
重合性組成物には、上述の逆波長分散性の重合性液晶化合物以外に、重合性棒状化合物を加えることができる。この重合性棒状化合物は液晶性の有無を問わない。重合性棒状化合物の添加により、重合性組成物の相転移温度や配向性、重合による配向固定時の配向安定性を改善することができる。
特定液晶化合物と混合して重合性組成物として扱うため、特定液晶化合物と相溶性が高いものであれば好ましく用いることができる。特に、特開2015-163596に記載の式(I)の構造のものを好ましく用いることができる。
添加量は、上述の逆波長分散性の液晶化合物に対して0~30%が好ましく、0~20%がさらに好ましい。
光学異方性層を形成する重合性液晶組成物は、重合開始剤を含むことができる。
使用する重合開始剤は、紫外線照射によって重合反応を開始可能な光重合開始剤であるのが好ましい。
光重合開始剤としては、例えば、α-カルボニル化合物(米国特許第2367661号、同2367670号の各明細書記載)、アシロインエーテル(米国特許第2448828号明細書記載)、α-炭化水素置換芳香族アシロイン化合物(米国特許第2722512号明細書記載)、多核キノン化合物(米国特許第3046127号、同2951758号の各明細書記載)、トリアリールイミダゾールダイマーとp-アミノフェニルケトンとの組み合わせ(米国特許第3549367号明細書記載)、アクリジンおよびフェナジン化合物(特開昭60-105667号公報、米国特許第4239850号明細書記載)およびオキサジアゾール化合物(米国特許第4212970号明細書記載)、アシルフォスフィンオキシド化合物(特公昭63-40799号公報、特公平5-29234号公報、特開平10-95788号公報、特開平10-29997号公報記載)等が挙げられる。
また、Ar3は、2価の芳香族基を表し、L6は、炭素数1~12の2価の有機基を表し、R10は、炭素数1~12のアルキル基を表す。
また、上記式(III)中、Ar3が示す2価の芳香族基としては、上記式(II)中のAr2として例示した芳香族炭化水素環および芳香族複素環からなる群から選ばれる少なくとも1つの芳香環を有する2価の基などが挙げられる。
また、上記式(III)中、L6が示す炭素数1~12の2価の有機基としては、例えば、炭素数1~12の直鎖状もしくは分岐状のアルキレン基が挙げられ、具体的には、メチレン基、エチレン基、プロピレン基等が好適に挙げられる。
また、上記式(III)中、R10が示す炭素数1~12のアルキル基としては、具体的には、例えば、メチル基、エチル基、プロピル基等が好適に挙げられる。
また、上記式(III)中、Yが示す1価の有機基としては、例えば、ベンゾフェノン骨格((C6H5)2CO)を含む官能基が挙げられる。具体的には、下記式(2a)および下記式(2b)で表される基のように、末端のベンゼン環が無置換または1置換であるベンゾフェノン骨格を含む官能基が好ましい。
重合性液晶組成物には、必要に応じて、配向制御剤を含有することができる。配向制御剤としては、例えば、低分子の配向制御剤や高分子の配向制御剤を用いることができる。低分子の配向制御剤としては、例えば、特開2002-20363号公報の段落0009~0083、特開2006-106662号公報の段落0111~0120や、特開2012-211306公報の段落0021-0029の記載を参酌することができ、この内容は本願明細書に組み込まれる。また、高分子の配向制御剤としては、例えば、特開2004-198511号公報の段落0021~0057の記載や、特開2006-106662号公報の段落0121~0167を参酌することができ、この内容は本願明細書に組み込まれる。
配向制御剤の使用量は、重合性液晶組成物中における液晶組成物の固形分の0.01~10質量%であることが好ましく、0.05~5質量%であることがさらに好ましい。配向制御剤を用いることにより、例えば、液晶化合物を層の表面と並行に配向したホモジニアス配向状態とすることができる。
重合性液晶組成物は、上記の特定液晶化合物以外の重合性化合物を含有してもよい。
ここで、重合性化合物が有する重合性基は特に限定されず、例えば、(メタ)アクリロイル基、ビニル基、スチリル基、アリル基等が挙げられる。なかでも、(メタ)アクリロイル基を有しているのが好ましい。
重合性化合物は、1種単独で用いてもよいし、2種以上併用してもよい。
重合性液晶組成物は、位相差フィルムを形成する作業性等の観点から、有機溶媒を含有するのが好ましい。
有機溶媒としては、具体的には、例えば、ケトン類(例えば、アセトン、2-ブタノン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、シクロペンタノンなど)、エーテル類(例えば、ジオキサン、テトラヒドロフランなど)、脂肪族炭化水素類(例えば、ヘキサンなど)、脂環式炭化水素類(例えば、シクロヘキサンなど)、芳香族炭化水素類(例えば、トルエン、キシレン、トリメチルベンゼンなど)、ハロゲン化炭素類(例えば、ジクロロメタン、ジクロロエタン、ジクロロベンゼン、クロロトルエンなど)、エステル類(例えば、酢酸メチル、酢酸エチル、酢酸ブチルなど)、水、アルコール類(例えば、エタノール、イソプロパノール、ブタノール、シクロヘキサノールなど)、セロソルブ類(例えば、メチルセロソルブ、エチルセロソルブなど)、セロソルブアセテート類、スルホキシド類(例えば、ジメチルスルホキシドなど)、アミド類(例えば、ジメチルホルムアミド、ジメチルアセトアミドなど)等が挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。
重合性液晶組成物は、上記以外の他の成分を含有してもよく、例えば、上記以外の液晶化合物、レベリング剤、界面活性剤、配向助剤、可塑剤、架橋剤、湿熱耐久性改良剤、増感剤、紫外線吸収剤、色素、ラジカルクエンチャーなどが挙げられる。
本発明の長尺位相差フィルムにおける光学異方性層は、目的に応じ種々の光学特性を付与することができる。これらの光学特性は、上述した重合性液晶組成物の配向状態や厚みを制御することにより得ることができる。本発明の一態様として、ポジティブAプレートであるλ/4板であることができる。また、本発明の別の一態様として、ポジティブCプレートであることができる。
本発明の位相差フィルムに含まれる光学異方性層は、ポジティブAプレートであることができる。上述した重合性組成物において、棒状の重合性液晶化合物を用いてこれを水平配向(ホモジニアス配向)させることにより、ポジティブAプレートを得ることができる。
式(A1) nx>ny≒nz
なお、上記「≒」とは、両者が完全に同一である場合だけでなく、両者が実質的に同一である場合も包含する。「実質的に同一」とは、例えば、(ny-nz)×d(ただし、dはフィルムの厚みである)が、-10nm~10nm、好ましくは-5nm~5nmの場合も「ny≒nz」に含まれる。
本発明の位相差フィルムに含まれる光学異方性層は、λ/4板の特性を持つことが好ましい。λ/4板とは、特定の波長λnmにおける面内レターデーションRe(λ)がRe(λ)=λ/4を満たすかそれに近い位相差板(位相差フィルム)のことをいう。
この式は、可視光域のいずれかの波長(例えば、λ=550nm)において達成されていればよいが、波長550nmにおける面内レターデーションRe(550)が、100nm≦Re(550)≦160nmの関係を満たすことが好ましく、110nm≦Re(550)≦150nmを満たすことがより好ましい。
このように長尺位相差フィルムを広帯域円偏光板として用いる場合には、光学異方性層の面内遅相軸が長尺支持体の長手方向に対して30°~50°の角度を成していることが好ましい。
本発明の位相差フィルムに含まれる光学異方性層は、ポジティブCプレートとすることができる。上述した重合性組成物において、棒状の重合性液晶化合物を用いてこれを垂直配向(ホメオトロピック配向)させることにより、ポジティブCプレートを得ることができる。
式(C1) nx≒ny<nz
なお、上記「≒」とは、両者が完全に同一である場合だけでなく、両者が実質的に同一である場合も包含する。「実質的に同一」とは、例えば、(nx-ny)×d(ただし、dはフィルムの厚みである)が、-10nm~10nm、好ましくは-5nm~5nmの場合も「nx≒ny」に含まれる。
本発明の長尺位相差フィルムが有する光学異方性層は、溶液(a)を用いて測定される重合性液晶化合物の320nm~400nmの範囲の極大吸収波長における光学異方性の配向秩序度S0が、-0.50<S0<-0.15であることができる。ここで、溶液(a)とは、使用する逆波長分散性の重合性液晶化合物を10-4mol/lの濃度になるようにクロロホルムに溶解させた溶液である。
光学異方性層の配向秩序度S(λ)は、式(S1)で表される値である。
S(λ)=(Ap-Av)/(Ap+2Av) ・・・式(S1)
[式(1)中、Apは、光学異方性層に含まれる逆波長分散性の重合性液晶化合物の配向方向(例えば、上記のポジティブAプレートであれば、面内遅相軸方向)に対して平行方向に偏光した光に対する吸光度を表す。Avは、光学フィルムに含まれる重合性液晶化合物の配向方向に対して垂直方向に偏光した光に対する吸光度を示す。]
光学フィルムの配向秩序度S(λ)は、λを逆波長分散性の重合性液晶化合物の320nm~400nmにある吸収極大ピーク値として、その波長における偏光吸収測定により求めることができる。配向秩序度S0は、上述のように-0.50<S0<-0.15であることができ、好ましくは-0.48<S0<-0.20である。この範囲であると液晶化合物の結晶化を抑制しつつ、配向性、屈折率異方性、逆波長分散性に優れた光学異方性層を得ることができる。
ΔRth =|Rtha(550)-Rthb(550)|÷|Rtha(550)|
[ここで、Rtha(550)は測定波長550nmにおける、加熱前の位相差フィルム切片の厚み方向位相差を表し、Rthb(550)は85℃、500時間の加熱条件で処理した後の位相差フィルム切片の厚み方向位相差値を表す。]
本発明の光学異方層がポジティブCプレートである実施様態においては、ΔRthは0.94~1.02であることができ、0.96~1.01であるとより好ましい。
本発明の長尺位相差フィルムの形成方法は特に制限されず、公知の方法が挙げられる。
典型的には、長尺支持体上に、上記重合性液晶組成物を連続的に塗布して長尺状の塗膜を形成し、得られた塗膜に対して硬化処理(活性エネルギー線の照射(光照射処理)および/または加熱処理)を施すことにより、硬化させた塗膜(光学異方性層)を含む位相差フィルムを製造できる。なお、必要に応じて、前述した配向層、配向処理等を用いてもよい。
樹脂フィルムからなる長尺支持体を長手方向に搬送しつつ、
逆波長分散性の重合性液晶化合物を含む重合性液晶組成物を長尺支持体の一方の面に塗布し塗膜を形成する塗布工程と、
塗膜を硬化させて光学異方性層を形成する硬化工程と、を行う長尺位相差フィルムの製造方法であって、
長尺支持体は、厚みが10μm~50μmであり、かつ、幅手方向弾性率が4.3GPa~6.0GPaであり、かつ、幅手方向の線熱膨張率が10ppm/℃~35ppm/℃であり、
硬化工程において、塗膜を80℃以上140℃以下に加熱しつつ硬化を行う長尺位相差フィルムの製造方法である。
また、活性エネルギー線の照射は長尺支持体がバックアップロールに接している位置で行われるのが好ましい。
用いる重合性液晶組成物がサーモトロピック性でスメクチック相を発現する場合、ネマチック相を発現する温度領域の方が、スメクチック相を発現する温度領域よりも高いことが一般的である。したがって、ネマチック相が発現する温度領域まで特定液晶化合物を加熱し、次に、特定液晶化合物がスメクチック相を発現する温度領域まで加熱温度を低下させることにより、特定液晶化合物をネマチック相からスメクチック相に転移させることができる。ネマチック層としたい場合、ならびに、重合性液晶性組成物はスメクチック相を有さない場合は、ネマチック相を示す温度あるいはネマチック相から等方層へ転移する温度以上に一旦加熱した後、ネマチック相を示す温度内に保つことで配向処理を行うことができる。
固定化処理は、活性エネルギー線(好ましくは紫外線)の照射により行われることが好ましく、特定液晶化合物の重合により液晶が固定化される。この際、塗膜の温度を高くすることにより、重合反応を促進して耐久性に優れた光学異方性層を形成することができる。加熱条件としては、80℃~140℃の範囲が好ましく、90℃~140℃の範囲がより好ましい。この範囲であると、光学異方性層に優れた耐久性を付与しつつ、各素材の熱分解を抑えて高品質な長尺位相差フィルムを製造することができる。
また、活性エネルギー線の照射量は、重合性液晶化合物の種類、重合開始剤の種類、活性エネルギー線の種類等に応じて適宜設定すればよい。例えば、活性エネルギー線として紫外線を照射する場合には、100~500mJ/cm2が好ましい。
本発明の長尺積層体(長尺偏光板)は、上記長尺位相差フィルムと、長尺直線偏光フィルムと、を有する。位相差フィルムの説明については、上述した通りであるので省略する。
長尺直線偏光フィルムは、光を特定の直線偏光に変換する機能を有するいわゆる直線偏光子であればよい。偏光子としては、特に限定されないが、吸収型偏光子を利用することができる。
また、偏光子として、サーモトロピック液晶性二色性色素(例えば、特開2011-237513号公報に記載の光吸収性異方性膜に用いられるサーモトロピック液晶性二色性色素)を用い、塗布等により作製した塗布型偏光子を用いることも好ましい。塗布型偏光子を用いることにより、ポリビニルアルコールを延伸した偏光子に対して、さらなる薄膜化が実現できる。また、曲げ等の外力が付加された場合においても、光学特性の変化が少ない偏光板を提供できる。
偏光子の厚みは特に制限されないが、典型的なポリビニルアルコール偏光子であれば1μm~40μmであることが好ましく、2μm~30μmであることがより好ましく、3μm~20μmがさらに好ましい。上記厚みであれば、表示装置の薄型化に対応可能となる。塗布型偏光子であれば、0.5μm~3μmの範囲であることができる。
(偏光子保護フィルム)
偏光子の表面上には、偏光子保護フィルムが配置されていてもよい。偏光子保護フィルムは、偏光子の片面上(位相差フィルム側とは反対側の表面上)にのみ配置されていてもよいし、偏光子の両面上に配置されていてもよい。
偏光子保護フィルムの構成は特に制限されず、例えば、いわゆる透明支持体やハードコート層であっても、透明支持体とハードコート層との積層体であってもよい。また、本発明の位相差フィルムの支持体層が偏光子保護フィルムを兼ねてもよい。
ハードコート層としては、公知の層を使用することができ、例えば、多官能モノマーを重合硬化して得られる層であってもよい。必要に応じ、ハードコート層にアンチグレア性や帯電防止性を付与してもよい。
また、透明支持体としては、公知の透明支持体を使用することができ、例えば、透明支持体を形成する材料としては、トリアセチルセルロースに代表される、セルロース系ポリマー(以下、セルロースアシレートという)や、熱可塑性ノルボルネン系樹脂(日本ゼオン(株)製のゼオネックス、ゼオノア、JSR(株)製のアートン等)、アクリル系樹脂、ポリエステル系樹脂を使用することができる。
偏光子保護フィルムの厚みは特に限定されないが、偏光板の厚みを薄くできることから40μm以下が好ましく、25μm以下がより好ましい。フィルムハンドリングの観点から5μm以上が好ましく、12μm以上であるとより好ましい。
上記長尺積層体の一種である偏光板は、有機電界発光装置(好ましくは、有機EL(エレクトロルミネッセンス)表示装置)やLEDディスプレイ、液晶表示装置などの画像表示装置に好ましく用いることができる。
その際、長尺積層体から所望の大きさ(画像表示装置の表示領域の大きさ)に切り出しで偏光板として用いればよい。また、長尺積層体から切り出す際には、切り出す偏光板の長手方向と長尺積層体の長手方向とを一致させて切り出してもよいし、切り出す偏光板の長手方向と長尺積層体の幅手方向とを一致させて切り出してもよいし、切り出す偏光板の長手方向が長尺積層体の長手方向に対して斜め方向になるように切り出してもよい。
液晶表示装置は、画像表示装置の一例であり、上述した本発明の長尺積層体から切り出した偏光板と、液晶セルとを有する。
なお、本発明においては、液晶セルの両側に設けられる偏光板のうち、フロント側の偏光板として本発明の偏光板を用いるのが好ましく、フロント側およびリア側の偏光板として本発明の偏光板を用いるのがより好ましい。また、偏光板に含まれる上記位相差フィルムは、液晶セル側に配置されることが好ましい。
すなわち、本発明の位相差フィルムは、光学補償フィルムとして好適に使用できる。
以下に、液晶表示装置を構成する液晶セルについて詳述する。
液晶表示装置に利用される液晶セルは、VA(Virtical Alignment)モード、OCB(Optical Compensated Bend)モード、IPS(In-Place-Switching)モード、又はTN(Twisted Nematic)であることが好ましいが、これらに限定されるものではない。
TNモードの液晶セルでは、電圧無印加時に棒状液晶性分子が実質的に水平配向し、更に60~120゜にねじれ配向している。TNモードの液晶セルは、カラーTFT液晶表示装置として最も多く利用されており、多数の文献に記載がある。
VAモードの液晶セルでは、電圧無印加時に棒状液晶性分子が実質的に垂直に配向している。VAモードの液晶セルには、(1)棒状液晶性分子を電圧無印加時に実質的に垂直に配向させ、電圧印加時に実質的に水平に配向させる狭義のVAモードの液晶セル(特開平2-176625号公報記載)に加えて、(2)視野角拡大のため、VAモードをマルチドメイン化した(MVAモードの)液晶セル(SID97、Digest of tech.Papers(予稿集)28(1997)845記載)、(3)棒状液晶性分子を電圧無印加時に実質的に垂直配向させ、電圧印加時にねじれマルチドメイン配向させるモード(n-ASMモード)の液晶セル(日本液晶討論会の予稿集58~59(1998)記載)及び(4)SURVIVALモードの液晶セル(LCDインターナショナル98で発表)が含まれる。また、PVA(Patterned Vertical Alignment)型、光配向型(Optical Alignment)、及びPSA(Polymer-Sustained Alignment)のいずれであってもよい。これらのモードの詳細については、特開2006-215326号公報、及び特表2008-538819号公報に詳細な記載がある。
IPSモードの液晶セルは、棒状液晶分子が基板に対して実質的に平行に配向しており、基板面に平行な電界が印加することで液晶分子が平面的に応答する。IPSモードは電界無印加状態で黒表示となり、上下一対の偏光板の吸収軸は直交している。光学補償シート(光学補償フィルム)を用いて、斜め方向での黒表示時の漏れ光を低減させ、視野角を改良する方法が、特開平10-54982号公報、特開平11-202323号公報、特開平9-292522号公報、特開平11-133408号公報、特開平11-305217号公報、特開平10-307291号公報などに開示されている。
有機電界発光装置の一例である有機EL表示装置としては、例えば、視認側から、本発明の長尺積層体から切り出した円偏光板と、有機EL表示パネルとをこの順で有する態様が好適に挙げられる。円偏光板に含まれる位相差フィルムは、有機EL表示パネル側に配置されることが好ましい。
すなわち、本発明の位相差フィルムを含む円偏光板は、外部から入射する光がパネル電極等で反射されて表示光のコントラストを下げることを防ぐ、いわゆる反射防止フィルムとして使用される。また、有機EL表示パネルは、電極間(陰極および陽極間)に有機発光層(有機エレクトロルミネッセンス層)を挟持してなる有機EL素子を用いて構成された表示パネルである。有機EL表示パネルの構成は特に制限されず、公知の構成が採用される。
本発明の長尺位相差フィルムにおいて、支持体と光学異方性層との間、配向層と光学異方性層との間、支持体と配向層との間の少なくともいずれかで剥離可能に製造することによって、光学異方性層のみあるいは光学異方性層と支持体以外のその他の層とを含む積層体を、別の支持体あるいは偏光板等の被着体に転写し、高機能偏光板やそれを含む画像表示装置を構成することができる。すなわち、本発明の長尺位相差フィルムは、別の一態様として、支持体を仮支持体とした長尺転写フィルムとして利用することができる。
〔セルロースアシレートフィルム1の作製〕
(コア層セルロースアシレートドープの作製)
下記の組成物をミキシングタンクに投入し、攪拌して、各成分を溶解し、コア層セルロースアシレートドープとして用いるセルロースアセテート溶液を調製した。
─────────────────────────────────
コア層セルロースアシレートドープ
─────────────────────────────────
アセチル置換度2.88のセルロースアセテート 100質量部
特開2015-227955号公報の実施例に
記載されたポリエステル化合物B 12質量部
下記の化合物F 2質量部
メチレンクロライド(第1溶媒) 430質量部
メタノール(第2溶剤) 64質量部
─────────────────────────────────
上記のコア層セルロースアシレートドープ90質量部に下記のマット剤溶液を10質量部加え、外層セルロースアシレートドープとして用いるセルロースアセテート溶液を調製した。
─────────────────────────────────
マット剤溶液
─────────────────────────────────
平均粒子サイズ20nmのシリカ粒子
(AEROSIL R972、日本アエロジル(株)製) 2質量部
メチレンクロライド(第1溶媒) 76質量部
メタノール(第2溶剤) 11質量部
上記のコア層セルロースアシレートドープ 1質量部
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上記コア層セルロースアシレートドープと上記外層セルロースアシレートドープを平均孔径34μmのろ紙および平均孔径10μmの焼結金属フィルターでろ過した後、上記コア層セルロースアシレートドープとその両側に外層セルロースアシレートドープとを3層同時に流延口から20℃の金属バンド上に流延した(バンド流延機)。溶剤含有率略20質量%の状態で剥ぎ取り、フィルムの幅方向の両端をテンタークリップで固定し、横方向に延伸倍率1.1倍で延伸しつつ乾燥した。その後、熱処理装置のロール間を搬送することによりさらに乾燥し、これを巻き取って厚み40μmの長尺状のセルロースアシレートフィルム1を作製した。フィルムのコア層は厚み36μm、コア層の両側に配置された外層はそれぞれ厚み2μmであった。得られたセルロースアシレートフィルム1の面内レターデーションは0nmであった。後述する評価方向によって測定した幅手方向弾性率、140℃における幅手方向弾性率、幅手方向の線熱膨張率は、表1の通りであった。
セルロースアシレートフィルム1の製膜において、厚みを20μm(コア層の厚み15μm、コア層の両側に配置された外層の厚みはそれぞれ2.5μm)とした以外はセルロースアシレートフィルム1と同様にしてセルロースアシレートフィルム2を作製した。幅手方向弾性率、140℃における幅手方向弾性率、幅手方向の線熱膨張率は、表1の通りであった。
セルロースアシレートフィルム3として市販のセルロースアセテートフィルム(ZRD40SL、富士フイルム(株)製)の長尺体を用いた。また、セルロースアシレートフィルム4として市販のセルロースアセテートフィルム(ZRD60SL、富士フイルム(株)製)の長尺体を用いた。幅手方向弾性率、140℃における幅手方向弾性率、幅手方向の線熱膨張率は、表1の通りであった。
冷却管および攪拌機を備えたフラスコに、重合開始剤として2,2’-アゾビス(イソブチロニトリル)1質量部、および、溶媒としてジエチレングリコールメチルエチルエーテル180質量部を仕込んだ。ここに、3,4-エポキシシクロヘキシルメチルメタアクリレート100質量部を加え、フラスコ内を窒素置換した後、緩やかに攪拌をした。溶液温度を80℃に上昇させ、この温度を5時間維持することにより、エポキシ基を有するポリメタクリレートを約35重量%含有する重合体溶液を得た。得られたエポキシ含有ポリメタクリレートの重量平均分子量Mwは25,000であった。
次いで、別の反応容器中に、上記で得たエポキシ含有ポリメタクリレートを含む溶液286質量部(ポリメタクリレートに換算して100質量部)、特開2015-26050号公報の合成例1の方法で得られた桂皮酸誘導体120質量部、触媒としてテトラブチルアンモニウムブロミド20質量部、および、希釈溶媒としてプロピレングリコールモノメチルエーテルアセテート150質量部を仕込み、窒素雰囲気下、90℃において12時間、撹拌下に反応を行った。反応終了後、反応混合物にプロピレングリコールモノメチルエーテルアセテート100質量部を加えて希釈し、これを3回水洗した。水洗後の有機相を大過剰のメタノール中に投入して重合体を沈殿させ、回収した沈殿物を40℃において12時間真空乾燥することにより、光配向性基を有する下記重合体A1を得た。
〔長尺位相差フィルムの作製〕
作製したセルロースアシレートフィルム1の片側の面に、下記の光配向膜用組成物1をバーコーターで連続的に塗布した。塗布後、120℃の加熱ゾーンにて1分間乾燥して溶剤を除去し、厚さ0.3μmの光異性化組成物層を形成した。続けて、鏡面処理バックアプロールに巻きかけながら、長手方向に偏光軸が45°の角度を成すように偏光紫外線照射(10mJ/cm2、超高圧水銀ランプ使用)することで、長尺状の光配向膜を形成した。
光学配向膜用組成物1
─────────────────────────────────
上記の光配向性基を有する重合体A1 10質量部
ノムコートTAB(日清オイリオ(株)製) 1.52質量部
多官能エポキシ化合物(エポリードGT401、ダイセル社製)
12.2質量部
熱酸発生剤(サンエイドSI-60、三新化学工業(株)製)
0.55質量部
酢酸ブチル 300質量部
―――――――――――――――――――――――――――――――――
光学異方性層用塗布液(液晶1)
―――――――――――――――――――――――――――――――――
・下記液晶性化合物L-3 42.00質量部
・下記液晶性化合物L-4 42.00質量部
・下記重合性化合物A-1 16.00質量部
・下記重合開始剤S-1(オキシム型) 0.50質量部
・レベリング剤(下記化合物G-1) 0.20質量部
・ハイソルブMTEM(東邦化学工業社製) 2.00質量部
・NKエステルA-200(新中村化学工業社製) 1.00質量部
・メチルエチルケトン 424.8質量部
―――――――――――――――――――――――――――――――――
なお、下記液晶性化合物L-3およびL-4のアクリロイルオキシ基に隣接する基は、プロピレン基(メチル基がエチレン基に置換した基)を表し、下記液晶性化合物L-3およびL-4は、メチル基の位置が異なる位置異性体の混合物を表す。
実施例1において、長尺セルロースアシレートフィルム2~4を用いた以外は同様にして、実施例2、比較例1、および、比較例3の長尺位相差フィルムを作製した。結果を表1に示す。
実施例1において、重合性液晶組成物を以下の液晶2に代えた以外は実施例1と同様にして、実施例3の長尺位相差フィルムを作製した。結果を表1に示す。
光学異方性層用塗布液(液晶2)
―――――――――――――――――――――――――――――――――
・下記液晶性化合物4 100.0質量部
・上記重合開始剤S-1 1.0質量部
・レベリング剤(上記化合物G-1) 0.40質量部
・シクロペンタノン 259質量部
―――――――――――――――――――――――――――――――――
液晶層を紫外線照射によって硬化させる際の紫外線照射量を150mJ/cm2とした以外は実施例2と同様にして、実施例4の長尺位相差フィルムを作製した。結果を表1に示す。
光学異方性層用塗布液を以下に示す液晶3に代え、液晶層を紫外線照射によって硬化させる際の紫外線照射量を150mJ/cm2とした以外は実施例1と同様にして実施例5の長尺位相差フィルムを作製した。結果を表1に示す。
光学異方性層用塗布液(液晶3)
―――――――――――――――――――――――――――――――――
・下記液晶性化合物L-3 42.00質量部
・下記液晶性化合物L-4 42.00質量部
・下記重合性化合物A-1 16.00質量部
・下記重合性化合物B-1 6.00質量部
・下記重合開始剤S-1(オキシム型) 0.50質量部
・レベリング剤(下記化合物G-1) 0.20質量部
・ハイソルブMTEM(東邦化学工業社製) 2.00質量部
・NKエステルA-200(新中村化学工業社製) 1.00質量部
・メチルエチルケトン 424.8質量部
―――――――――――――――――――――――――――――――――
長尺セルロースアシレートフィルム2を用いた以外は実施例5と同様にして実施例6の長尺位相差フィルムを作製した。結果を表1に示す。
重合性液晶組成物中の重合性化合物B-1をB-2,B-3,B-4に代えた以外は実施例6と同様にして実施例7~9の長尺位相差フィルムを作製した。結果を表1に示す。
セルロースアシレートフィルムとして、厚みが15μmのセルロースアセテートフィルムを用い、液晶層を紫外線照射によって硬化させる際の紫外線照射量を100mJ/cm2とした以外は実施例2と同様にして、実施例10の長尺位相差フィルムを作製した。結果を表1に示す。
比較例1において、液晶層を紫外線照射によって硬化させる際の温度を75℃とした以外は比較例1と同様にして長尺位相差フィルムを作製した。結果を表1に示す。
(幅手方向弾性率)
長尺支持体の幅手方向弾性率は、テンシロン引張試験機(商品名:RTA-100;オリエンテック(株)製)を用い、ISO1184 1983に従い測定した。具体的には、25℃、60RH%雰囲気中で測定し、得られた荷重-歪曲線の傾きから弾性率を算出した。フィルムサンプルの伸長方向は、長尺支持体の幅手方向と一致するようにした。
長尺支持体フィルムから切り出したフィルム試料5mm×30mm(サンプル長手方向が長尺支持体の幅手方向と一致)を、25℃、相対湿度60%で2時間以上調湿した後に、動的粘弾性測定装置(バイブロン:DVA-225(アイティー計測制御(株)製))で、つかみ間距離20mm、昇温速度2℃/分、測定温度範囲30℃~250℃、周波数1Hzで動的粘弾性を測定し、140℃における貯蔵弾性率値を以って長尺支持体の140℃における幅手方向弾性率とした。
サンプル長手方向が長尺支持体の幅手方向と一致するように幅3mm、長さ35mmのフィルムを切り出した。試料を、25℃60%RHの環境下で3時間以上調湿した後、TMA(Tharmal Mechanical Analyzer:TA instruments社製)を用いて、チャック間距離25.4mm、昇温条件30~100℃(20℃/min)、張力0.04Nで測定を行い、試料の80℃におけるチャック間寸法から、40℃におけるチャック間寸法を差し引いた値ΔL(mm)を求め、ΔL/(25.4×10)を計算することによって長尺支持体の幅手方向の線熱膨張率を得た。
得られた長尺位相差フィルムから幅40mm、長さ40mmのフィルムを切り出した。試料をクロスニコル下の偏光顕微鏡(10倍の対物レンズ使用)で観察し液晶配向を確認した。
A:観察視野内で光漏れなし。クロスニコルから検光子を4°ずらして観察したときの光学模様が観察視野内で均一であった。
B:観察視野内で光漏れあり。クロスニコルから検光子を4°ずらして観察したときに光学模様が観察視野内で不均一であった(配向不良が観察された)。
得られた長尺位相差フィルムを巻きだして水平な定板上に静置し、目視でシワや折れ痕およびウェブのゆがみ等の面状を確認した。ゆがみは、棒状の蛍光灯を反射させてその反射像を観察することにより確認した。
A:シワ、折れ痕もゆがみも見られず、均一で平坦なフィルムであった
B:シワ、折れ痕は見られないが、フィルムにわずかにゆがみが見られた
C:明らかなシワや折れ痕が観察できた
7×14cm角に切り出した各位相差フィルムを25℃60%RHの環境下で3時間以上調湿した後、両側から粘着剤(特開2017-134414号公報、実施例1)を用いて同サイズのガラス板に挟み込み、Axo Scan(OPMF-1、Axometrics社製)を用いて、波長550nmにおけるレターデーション値(Rea)を測定した。その後、上記サンプルを85℃0%RHに保った恒温恒湿層にて500時間処理した後、25℃60%RHの環境下で3時間以上調湿してからAxo Scanにて面内位相差Reb(550)を測定し、その変化率から面内位相差変化ΔRe=Reb/Reaを定量した。
A:ΔRe=0.98以上1.01以下
B:ΔRe=0.96以上0.98未満、1.01より大きく1.02以下
C:ΔRe=0.94以上0.96未満
D:ΔRe=0.94未満、もしくは1.02より大きい
得られた実施例1の位相差フィルム1を、位相差フィルムのセルロースアシレートフィルム側を偏光板側とし、セルロースアシレートフィルム1が偏光板保護フィルムを兼ねる形でロールトゥロールプロセスにより長尺状の直線偏光板(吸収軸が長手方向にある)と貼合した後、一旦巻き取り、本発明の長尺積層体を作製した。さらに長尺積層体を巻きだして所定の形状に裁断して円偏光板1を得た。得られた円偏光板1の位相差フィルム側の表面に、特開2015-200861号公報実施例0124段落~0127段落に記載のポジティブCプレート(ただし、550nmにおけるRthが-65nmとなるように、ポジティブCプレートの厚さは制御している)を転写貼合し、積層体1を得た。位相差フィルムの面内遅相軸と、直線偏光板の透過軸の成す角度は45°であった。
実施例2~10で得られた位相差フィルム2~10および比較例2~3で得られた位相差フィルム12~13についてもそれぞれ、上記と同様にして積層体を作製し、積層体から切り出した積層体片を有機ELパネルに装着した。
上記で実装した有機ELパネル上に、粘着剤を介してガラス板を貼り合わせ、85℃0%RHに保った恒温恒湿層にて500時間処理した後、25℃60%RHの環境下で3時間以上調湿して、黒表示状態にて自然光下で外観観察を実施した。
A:赤みムラは観察されず、良好な黒表示性能を示した
B:パネル端部に強度の弱いムラが観察された
C:パネル端部に強度の強いムラが観察された
D:全面に赤みムラが観察された
結果を表1および表2に示す。
また、実施例1、実施例2、および、実施例10の対比から、支持体の厚みは15μm以上であるのが好ましいことがわかる。
また、実施例2、実施例4、および、実施例6~9の対比から、面内位相差変化ΔReは、0.96以上1.02以下が好ましく、0.98以上1.01以下がより好ましいことがわかる。
以上より本発明の効果は明らかである。
Claims (9)
- 樹脂フィルムからなる長尺支持体と、前記長尺支持体の一方の面側に配置される長尺状の光学異方性層とを含む長尺位相差フィルムであって、
前記長尺支持体は、厚みが10μm~50μmであり、かつ、幅手方向弾性率が4.3GPa~6.0GPaであり、かつ、幅手方向の線熱膨張率が20×10-6/℃~40×10-6/℃であり、
前記光学異方性層は逆波長分散性の重合性液晶化合物を含む重合性液晶組成物からなるものであり、
前記長尺位相差フィルムを85℃、500時間の加熱条件で処理した際の面内位相差変化ΔReが0.94~1.02である、長尺位相差フィルム。 - 前記長尺支持体の140℃における幅手方向弾性率が1.5GPa~3.0GPaである、請求項1に記載の長尺位相差フィルム。
- 前記長尺支持体のRe(550)が0nm~10nm、Rth(550)が-20nm~40nmである、請求項1または2に記載の長尺位相差フィルム。
- 前記長尺支持体と、前記光学異方性層との間に、前記光学異方性層に接して配向層を有する、請求項1~3のいずれか一項に記載の長尺位相差フィルム。
- 前記光学異方性層のRe(550)が100nm~250nmである、請求項1~4のいずれか一項に記載の長尺位相差フィルム。
- 前記光学異方性層のRe(550)が100nm~160nmであり、前記光学異方性層の面内遅相軸が前記長尺支持体の長手方向に対して30°~50°の角度を成している、請求項5に記載の長尺位相差フィルム。
- 前記光学異方性層が、前記長尺支持体と接しているか、
前記長尺支持体と、前記光学異方性層との間に、前記光学異方性層に接して配向層を有しており、
かつ、前記光学異方性層が、剥離可能に設けられている、請求項1~6のいずれか一項に記載の長尺位相差フィルム。 - 請求項1~7のいずれか一項に記載の長尺位相差フィルムと、長尺直線偏光フィルムとを積層してなる、長尺積層体。
- 請求項8に記載の長尺積層体から切り出された偏光板を含む、画像表示装置。
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