WO2018021312A1 - 光学フィルム、偏光板、及び表示装置 - Google Patents
光学フィルム、偏光板、及び表示装置 Download PDFInfo
- Publication number
- WO2018021312A1 WO2018021312A1 PCT/JP2017/026871 JP2017026871W WO2018021312A1 WO 2018021312 A1 WO2018021312 A1 WO 2018021312A1 JP 2017026871 W JP2017026871 W JP 2017026871W WO 2018021312 A1 WO2018021312 A1 WO 2018021312A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- optical film
- film
- general formula
- present
- polarizing plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Definitions
- the present invention relates to an optical film, a polarizing plate, and a display device, and more particularly to an optically isotropic optical film using a cycloolefin resin.
- liquid crystal display devices such as a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, and an IPS (In-Place-Switching) method have been developed.
- the IPS method is superior in viewing angle performance compared to the TN method and VA method, and is used for various applications.
- the IPS liquid crystal cell is a type in which a nematic liquid crystal is switched by applying a horizontal electric field.
- IDRC Asia Display 1995
- the polarizing film optical film used in the IPS system is required to be an optical film for polarizing film that is optically isotropic (hereinafter also referred to as “zero retardation”) due to the characteristics of the IPS system.
- an optical film for a polarizing plate exhibiting isotropic properties zero retardation
- a cellulose triacetate (TAC) film has been widely used because of its good handleability.
- the cellulose triacetate film is inferior in moisture resistance and has a problem that performance fluctuation due to humidity fluctuation is large. Further, since the phase difference value is not completely zero, an improvement has been demanded.
- optical films using cycloolefin resins have also been used as optical films for polarizing plates having good moisture resistance and zero retardation.
- Patent Document 1 discloses an optical film using a zero-phase-difference cycloolefin resin.
- LCD liquid crystal display devices
- OLED organic electroluminescence display devices
- the optical film using the above-mentioned zero phase difference cycloolefin resin is also required to be thin.
- the film cast by solution casting or melt casting is stretched to reduce the thickness when the optical film is formed.
- the cycloolefin resin for optical films currently used for various display devices has a positive intrinsic birefringence. Therefore, when an optical film is produced by the melt film-forming method, a phase difference derived from positive orientation birefringence is exhibited by elongation in the transport direction or heat stretching. In addition, when producing by the solution casting method, in addition to the above reason, a phase difference is also manifested by the orientation of the resin chain in the drying process after casting from a pressure die slit onto a drum or belt. Furthermore, when the optical film in a state where the solvent remains is held while being held in the width direction by a clip, the optical film contracts due to drying and is pseudo-stretched, resulting in a phase difference. Sometimes.
- Patent Document 2 discloses an optical film suitable for a VA system that is drawn by adding a specific plasticizer to a cycloolefin resin.
- Patent Document 2 has a problem in that a phase difference occurs in the optical film, and visibility deteriorates when the optical film is applied to an IPS liquid crystal display device. Therefore, it is difficult to obtain an isotropic (zero phase difference) optical film suitable for the IPS system while securing productivity by stretching.
- JP 2011-128356 A Korean Published Patent No. 2015-0104886
- the present invention has been made in view of the above-described problems and situations, and a solution to the problem is to provide an optically isotropic (zero retardation) thin film optical film using a cycloolefin-based resin. It is.
- the optical film is produced by stretching with good productivity by a casting film forming method.
- it is providing the polarizing plate and display apparatus which comprised the said optical film.
- the present inventor is an optical film containing a cycloolefin-based resin and a polyester in the process of examining the cause of the above-mentioned problem in order to solve the above-mentioned problems, and the polyester has a different chemical structure or molecular weight. It has been found that a thin film isotropic (zero phase difference) optical film can be provided by being a mixture of two or more kinds of compounds and having a weight average molecular weight (Mw) within the range of 400 to 3800. The present invention has been reached.
- An optical film containing a cycloolefin-based resin and a polyester wherein the polyester is a mixture of two or more kinds of compounds having different chemical structures or weight average molecular weights (Mw), and the weight average molecular weight (Mw) of the polyester Is in the range of 400 to 3800, the film thickness of the optical film is in the range of 5 to 25 ⁇ m, and the position of the optical film in the film plane defined by the following formula (i)
- the retardation value Ro (nm) and the retardation value Rt (nm) in the film thickness direction defined by the following formula (ii) satisfy the conditions defined by the following formulas (iii) and (iv).
- Ro and Rt are phase difference values measured with light having a wavelength of 590 nm in an environment of a temperature of 23 ° C. and a relative humidity of 55%.
- n x is a refractive index in a slow axis direction of the film plane.
- n y is a refractive index in a direction perpendicular to the slow axis direction of the film plane.
- nz is the refractive index in the direction perpendicular to the film surface.
- d is the thickness (nm) of the film.
- the cycloolefin resin is a polymer derived from a cycloolefin monomer having a structure represented by the following general formula (I).
- R 1 to R 4 each independently represents a hydrogen atom, a hydrocarbon group, a halogen atom, or a hydrogen bond accepting group.
- two or more of R 1 to R 4 may be bonded to each other to form an unsaturated bond, a monocycle or a polycycle, and this monocycle or polycycle has a double bond.
- an aromatic ring may be formed.
- At least one of the compounds constituting the polyester mixture is a compound having a structure represented by the following general formula (II) or general formula (III): The optical film as described in any one.
- A represents a divalent group derived from an alkylene dicarboxylic acid, a cycloalkylene dicarboxylic acid, or an aryl dicarboxylic acid.
- G represents a divalent group derived from alkylene glycol, cycloalkylene glycol, or aryl glycol.
- n and m each represents an integer of 0 or more.
- X 1 and X 2 each represent a hydrogen atom or a monovalent group derived from an alkylene monocarboxylic acid, a cycloalkylene monocarboxylic acid, or an aryl monocarboxylic acid.
- Y 1 and Y 2 each represent a hydroxy group or a monovalent group derived from an alkylene monoalcohol, cycloalkylene monoalcohol or aryl monoalcohol.
- a and G may be one type or two or more types may be combined.
- At least one of X 1 and X 2 is derived from an alkylene monocarboxylic acid, a cycloalkylene monocarboxylic acid, or an aryl monocarboxylic acid.
- Item 6 The optical film according to item 4 or 5, wherein
- a polarizing plate comprising the optical film according to any one of items 1 to 8 on at least one surface of a polarizer.
- a display device comprising the polarizing plate according to Item 9.
- an optically isotropic (zero phase difference) thin film optical film using a cycloolefin resin can be provided. Further, the optical film can be produced by stretching with good productivity by a casting film forming method.
- the cycloolefin resin contains polyester, the cycloolefin resin can be easily stretched due to the plastic effect.
- the polyester is a mixture of two or more compounds having different chemical structures or molecular weights, the order in the system is messed up, and the orientation of the polymer chain of the cycloolefin resin is difficult to align in a specific direction. That is, it acts to disturb the orientation of the cycloolefin resin.
- Mw weight average molecular weight
- compatibility with the cycloolefin resin is improved, and the polyester is more widely dispersed uniformly in the film.
- the orientation of the polymer chain of the cycloolefin resin is efficiently disturbed. It is presumed that the phase difference can be reduced by the mechanism as described above.
- the optical film of the present invention is an optical film containing a cycloolefin-based resin and a polyester, wherein the polyester is a mixture of two or more kinds of compounds having different chemical structures or molecular weights, and the weight average molecular weight ( Mw) is in the range of 400 to 3800, the film thickness of the optical film is in the range of 5 to 25 ⁇ m, and the film thickness of the optical film is in the range of 0 to 5 nm.
- the direction retardation value Rt (nm) is in the range of ⁇ 10 to 10 nm.
- the cycloolefin-based resin is a polymer derived from a cycloolefin-based monomer having a structure represented by the following general formula (I) from the viewpoint of manifesting the effects of the present invention. .
- R 1 to R 4 each independently represents a hydrogen atom, a hydrocarbon group, a halogen atom, or a hydrogen bond accepting group.
- two or more of R 1 to R 4 may be bonded to each other to form an unsaturated bond, a monocycle or a polycycle, and this monocycle or polycycle has a double bond.
- an aromatic ring may be formed.
- p is 0, m is 1, R 1 and R 2 are hydrogen atoms, R 3 is a methyl group, and R 4 is A methoxycarbonyl group is more preferable because it can be easily formed into a film by the solution casting method.
- At least one of the compounds constituting the polyester mixture is a compound having a structure represented by the following general formula (II) or general formula (III). preferable.
- A represents a divalent group derived from an alkylene dicarboxylic acid, a cycloalkylene dicarboxylic acid, or an aryl dicarboxylic acid.
- G represents a divalent group derived from alkylene glycol, cycloalkylene glycol, or aryl glycol.
- n and m each represents an integer of 0 or more.
- X 1 and X 2 each represent a hydrogen atom or a monovalent group derived from an alkylene monocarboxylic acid, a cycloalkylene monocarboxylic acid, or an aryl monocarboxylic acid.
- Y 1 and Y 2 each represent a hydroxy group or a monovalent group derived from an alkylene monoalcohol, cycloalkylene monoalcohol or aryl monoalcohol.
- a and G may be one type or two or more types may be combined.
- a or G of the compound having the structure represented by the general formula (II) or the general formula (III) is a combination of two or more groups. preferable.
- n or m of the compound having the structure represented by the general formula (II) or the general formula (III) represents an integer of 1 or 2, from the viewpoint of manifesting the effect of the present invention.
- n or m of the compound having the structure represented by the general formula (II) or the general formula (III) represents an integer of 1.
- At least one of X 1 and X 2 is an alkylene monocarboxylic acid, a cycloalkylene monocarboxylic acid, or an aryl monocarboxylic acid.
- at least one of Y 1 and Y 2 represents a monovalent group derived from an alkylene monoalcohol, cycloalkylene monoalcohol or aryl monoalcohol
- n or m is an integer of 0 It is preferable from the viewpoint of the effect of the present invention.
- a polarizing plate comprising the optical film of the present invention in a polarizer or a display device comprising the polarizing plate has good moisture resistance of the optical film, is a thin film, and has zero phase difference. Is preferable in that a polarizing plate and a display device having a wide and excellent moisture resistance can be obtained.
- the zero phase difference means that the retardation value Ro in the optical film plane is in the range of 0 to 5 nm, and the retardation value Rt in the optical film thickness direction is ⁇ 10 to It is defined as being within a range of 10 nm.
- the optical film of the present invention is an optical film containing a cycloolefin-based resin and a polyester, wherein the polyester is a mixture of two or more kinds of compounds having different chemical structures or molecular weights, and the weight average molecular weight ( Mw) is in the range of 400 to 3800, the film thickness of the optical film is in the range of 5 to 25 ⁇ m, and the in-plane of the optical film defined by the following formula (i)
- the retardation value Ro (nm) of the film and the retardation value Rt (nm) in the film thickness direction defined by the following formula (ii) satisfy the conditions specified by the following formulas (iii) and (iv).
- Ro and Rt are phase difference values measured with light having a wavelength of 590 nm in an environment of a temperature of 23 ° C. and a relative humidity of 55%.
- n x is a refractive index in a slow axis direction of the film plane.
- n y is a refractive index in a direction perpendicular to the slow axis direction of the film plane.
- nz is the refractive index in the direction perpendicular to the film surface.
- d is the thickness (nm) of the film.
- the in-plane retardation value Ro and the thickness direction retardation value Rt were measured under an environment of 23 ° C. and 55% RH using an automatic birefringence meter Axoscan (Axo Scan Mueller Matrix Polarimeter: manufactured by Axometrics). , at a wavelength of 590 nm, subjected to three-dimensional refractive index measured, resulting refractive indices n x, n y, it is calculated using the above formulas n z.
- the optical film of the present invention contains a cycloolefin resin.
- cycloolefin resin means a polymer of a cycloolefin monomer or a polymer of a cycloolefin monomer and another monomer.
- the cycloolefin resin is preferably a polymer derived from a cycloolefin monomer having a structure represented by the general formula (I).
- polymer derived from a cycloolefin monomer having a structure represented by the general formula (I) means a polymer of a cycloolefin monomer having a structure represented by the general formula (I), or a general formula It means a polymer of a cycloolefin monomer having a structure represented by (I) and another monomer.
- R 1 to R 4 are each independently a hydrogen atom, a hydrocarbon group, a halogen atom, or a hydrogen bond accepting group.
- two or more of R 1 to R 4 may be bonded to each other to form an unsaturated bond, a monocycle or a polycycle, and this monocycle or polycycle has a double bond. Alternatively, an aromatic ring may be formed.
- the preferred proportion of hydrogen bond accepting groups in the cycloolefin-based resin is preferably 1 to 2 of R 1 to R 4 having a hydrogen bond accepting group in the general formula (I).
- the possession ratio of the hydrogen bond accepting group of the cycloolefin resin can be identified using, for example, a carbon-13 nuclear magnetic resonance ( 13 CNMR) spectrum method.
- Examples of the hydrogen bond accepting group include an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group, a cyano group, and an amide.
- examples of the alkoxy group include a methoxy group and an ethoxy group
- examples of the acyloxy group include an alkylcarbonyloxy group such as an acetoxy group and a propionyloxy group
- arylcarbonyloxy groups such as benzoyloxy group
- examples of the alkoxycarbonyl group include methoxycarbonyl group and ethoxycarbonyl group
- examples of the aryloxycarbonyl group include, for example, phenoxycarbonyl group and naphthyloxycarbonyl Group, fluorenyloxycarbonyl group, biphenylyloxycarbonyl group and the like
- Examples of the triorganosiloxy group include trimethylsiloxy group and triethylsiloxy group; Trimethylsilyl group Te, triethylsilyl group and the like
- the alkoxysilyl group for example, trimethoxysilyl groups, triethoxysilyl group, and the
- halogen atom examples include a fluorine atom, a chlorine atom and a bromine atom.
- hydrocarbon group having 1 to 30 carbon atoms examples include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group and propenyl group.
- Aromade groups such as phenyl, biphenyl, naphthyl, and anthracenyl groups; These hydrocarbon groups may be substituted, and examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom, phenylsulfonyl group and the like.
- p is 0, m is 1, R 1 and R 2 are hydrogen atoms, R 3 is a methyl group, and R 4 is a methoxycarbonyl group. Since it is easy to form a film by the solution casting method, it is more preferable to reduce the thickness.
- the cycloolefin resin according to the present invention is preferably contained in the optical film within a range of 51 to 99% by mass from the viewpoint of heat resistance.
- the preferred molecular weight of the cycloolefin resin according to the present invention is such that the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is 8000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12000.
- the weight average molecular weight (Mw) is preferably 20,000 to 300,000, more preferably 30,000 to 250,000, and particularly preferably 40,000 to 200,000.
- the preferred intrinsic viscosity [ ⁇ ] inh (measurement temperature 30 ° C.) of the cycloolefin resin according to the present invention is 0.2 to 5 cm 3 / g, more preferably 0.3 to 3 cm 3 / g, and particularly preferably 0.8. 4 to 1.5 cm 3 / g.
- the intrinsic viscosity [ ⁇ ] inh can be measured (measurement temperature: 30 ° C.) using a Ubbelohde viscometer.
- Inherent viscosity [ ⁇ ] inh, number average molecular weight and weight average molecular weight are within the above ranges, so that the heat resistance, water resistance, chemical resistance, mechanical properties of the cycloolefin resin, and molding as the optical film of the present invention Property is improved.
- the glass transition temperature (Tg) of the cycloolefin resin according to the present invention is usually 110 ° C. or higher, preferably 110 to 350 ° C. More preferably, it is 120 to 250 ° C, particularly preferably 150 to 220 ° C.
- Tg of the cycloolefin resin is 110 ° C. or more, it is preferable because deformation under secondary processing such as use under high temperature conditions or coating or printing is suppressed. Moreover, since Tg is 350 degrees C or less, since resin deterioration by the heat
- the optical film of the present invention preferably has a glass transition temperature (Tg) of 130 to 210 ° C. If the glass transition temperature (Tg) of the optical film is 210 ° C. or lower, it is preferable because the increase in internal stress is small and the crack resistance is high.
- Tg is 150 ° C. or more, it is preferable because it can be suitably used for providing functions with heat treatment such as laminating a conductive layer on an optical film and annealing.
- the glass transition temperature Tg referred to here is a midpoint glass transition temperature (Tmg) measured at a rate of temperature increase of 20 ° C./min using a commercially available differential scanning calorimeter and determined according to JIS K7121 (1987). It is. A specific method for measuring the glass transition temperature Tg of an optical film is measured using a differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc. according to JIS K7121 (1987).
- cycloolefin resin Commercially available products can be preferably used as the cycloolefin resin described above.
- Examples of commercially available products include trade names of Arton G, Arton F, Arton R, and Arton RX from JSR Corporation (Arton). Are registered trademarks and can be used.
- the specific products manufactured by JSR Corporation described above include “ARTON G7810” (product name), “ARTON R5000” (product name), and “ARTON GX4500” (product name) as described in Examples below. There is.
- the optical film of the present invention contains polyester, wherein the polyester is a mixture of two or more kinds of compounds having different chemical structures or molecular weights, and the polyester has a weight average molecular weight (Mw) in the range of 400 to 3800. It is characterized by being.
- Mw weight average molecular weight
- Polyester is an esterified product that can be obtained by esterification or transesterification of a dicarboxylic acid compound and a diol compound, and both ends may be sealed or not sealed. Good.
- the optical film of the present invention contains, as polyester, a mixture of two or more compounds having different chemical structures or molecular weights.
- a mixture of two or more kinds of compounds having different chemical structures or molecular weights may be produced by synthesizing a plurality of different kinds of raw materials when synthesizing the polyester, or may have a single structure or molecular weight. After synthesizing a plurality of types of polyesters, a plurality of types of polyesters may be mixed and manufactured.
- the method for adding the “mixture of two or more compounds having different chemical structures or molecular weights” according to the present invention to the optical film is not particularly limited.
- At least one compound of two or more kinds of compounds having different chemical structures or weight average molecular weights constituting the polyester according to the present invention has a structure represented by the following general formula (II) or general formula (III). It is more preferable that it is a compound from a viewpoint that the effect of this invention is large.
- A represents a divalent group derived from an alkylene dicarboxylic acid, a cycloalkylene dicarboxylic acid, or an aryl dicarboxylic acid.
- G represents a divalent group derived from alkylene glycol, cycloalkylene glycol, or aryl glycol.
- n and m each represents an integer of 0 or more.
- X 1 and X 2 each represent a hydrogen atom or a monovalent group derived from an alkylene monocarboxylic acid, a cycloalkylene monocarboxylic acid, or an aryl monocarboxylic acid.
- Y 1 and Y 2 each represent a hydroxy group or a monovalent group derived from an alkylene monoalcohol, cycloalkylene monoalcohol or aryl monoalcohol.
- a and G may be one type or two or more types may be combined.
- the divalent group derived from the alkylene dicarboxylic acid of A is preferably a divalent group derived from an alkylene dicarboxylic acid having 4 to 12 carbon atoms.
- Examples of divalent groups derived from alkylene dicarboxylic acids include divalent groups derived from succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and the like. included.
- a divalent group derived from adipic acid is more preferable from the viewpoint of the effect of the present invention.
- Examples of the divalent group derived from the cycloalkylene dicarboxylic acid of A include 2 derived from hexahydrophthalic anhydride, hexahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and the like. Valent groups are included. Among these, a divalent group derived from 1,4-cyclohexanedicarboxylic acid is more preferable from the viewpoint of manifesting the effects of the present invention.
- the divalent group derived from the aryl dicarboxylic acid of A is preferably a divalent group derived from an aryl dicarboxylic acid having 8 to 14 carbon atoms.
- divalent groups derived from aryl dicarboxylic acids include divalent groups derived from phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and the like. included.
- a divalent group derived from phthalic acid is more preferable from the viewpoint of the effects of the present invention.
- the divalent group derived from the alkylene glycol of G is preferably a divalent group derived from an alkylene glycol having 2 to 12 carbon atoms.
- Examples of divalent groups derived from alkylene glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2- Propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2- Diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1, 5-pentanediol,
- Examples of the divalent group derived from the cycloalkylene glycol of G include 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, bicyclohexyl.
- Divalent groups derived from -4,4'-diol 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, tricyclodecane dimethanol, 1,6-cyclohexanedimethanol and the like are included.
- a divalent group derived from 1,4-cyclohexanedimethanol is more preferable from the viewpoint of manifesting the effects of the present invention.
- the divalent group derived from aryl glycol of G is preferably a divalent group derived from aryl glycol having 6 to 12 carbon atoms.
- divalent groups derived from aryl glycol include 2 derived from 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene (hydroquinone) and the like. Valent groups are included. Among these, a divalent group derived from 1,4-dihydroxybenzene is more preferable from the viewpoint of the effect of the present invention.
- Examples of the monovalent group derived from the alkylene monocarboxylic acid of X 1 and X 2 include a monovalent group derived from an aliphatic monocarboxylic acid such as acetic acid, propionic acid, and butyric acid. . Among these, a monovalent group derived from acetic acid is more preferable from the viewpoint of the effect of the present invention.
- Examples of the monovalent group derived from the cycloalkylene monocarboxylic acid of X 1 and X 2 include a monovalent group derived from cyclohexyl carboxylic acid, 1,1′-bicyclohexane-1-carboxylic acid and the like. Is included.
- Examples of the monovalent group derived from the aryl monocarboxylic acid of X 1 and X 2 include benzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, para-tert-butylbenzoic acid.
- Monovalent groups derived from acids, orthotoluic acid, metatoluic acid, p-toluic acid, dimethyl benzoic acid, ethyl benzoic acid, normal propyl benzoic acid, aminobenzoic acid, acetoxybenzoic acid, and the like are included.
- a monovalent group derived from 4-hydroxybenzoic acid is more preferable from the viewpoint of manifesting the effects of the present invention.
- the cycloolefin resin used in the optical film of the present invention preferably has a polar group, and among them, a methoxycarbonyl group is easy to form a film by a solution casting method and is suitable for thinning. Therefore, it is particularly preferable.
- the monovalent group derived from 4-hydroxybenzoic acid includes a hydroxy group.
- a characteristic of phenol is that it exhibits a stronger acidity than alcohol. From this, it can be said that the hydrogen atom of the hydroxy group of phenol is larger and more positively charged than that of alcohol.
- X 1 and X 2 are derived from 4-hydroxybenzoic acid rather than a hydrogen atom of an alcoholic hydroxy group contained in a monovalent group derived from alkylene monocarboxylic acid or cycloalkylene monocarboxylic acid. The hydrogen atom of the phenolic hydroxy group contained in the monovalent group is expected to be more positively charged.
- the hydrogen atom of the phenolic hydroxy group contained in the monovalent group derived from 4-hydroxybenzoic acid Is expected to act more strongly.
- the polyester according to the present invention is present in the vicinity of the cycloolefin resin according to the present invention, thereby effectively inhibiting the orientation of the cycloolefin resin. It is assumed that the effect of reducing the phase difference is increased.
- Examples of the monovalent group derived from the alkylene monoalcohol of Y 1 and Y 2 include methyl alcohol, ethyl alcohol, 1-propanol, 2-propanol, n-butyl alcohol, t-butyl alcohol, 2-ethylhexyl.
- Monovalent groups derived from alcohol, stearyl alcohol, linoleyl alcohol, benzyl alcohol and the like are included. Of these, a monovalent group derived from 2-propanol is more preferable from the viewpoint of the effects of the present invention.
- Examples of the monovalent group derived from the cycloalkylene monoalcohol of Y 1 and Y 2 include a monovalent group derived from cyclohexanol or the like.
- Examples of the monovalent group derived from the aryl monoalcohol of Y 1 and Y 2 include a monovalent group derived from phenol, 1-naphthol, 2-naphthol and the like. Among these, a monovalent group derived from phenol is more preferable from the viewpoint of the effects of the present invention.
- Examples of combinations of partial structures of compounds having a structure represented by the general formula (II) include those shown in Table 1.
- X 1 and X 2 are monovalent groups derived from arylmonocarboxylic acid
- A is a divalent group derived from alkylenedicarboxylic acid
- G Is preferably a compound having a divalent group structure derived from alkylene glycol (partial combination number 10) from the viewpoint of the effect of the present invention.
- X 1 and X 2 are A monovalent group derived from 4-hydroxybenzoic acid
- A is a divalent group derived from adipic acid
- G is preferably a divalent group derived from 1,2-propylene glycol.
- X 1 and X 2 are a monovalent group derived from an arylmonocarboxylic acid
- A is a divalent group derived from an alkylenedicarboxylic acid
- G Among the compound represented by the combination number 10 of the partial structure, wherein X 1 and X 2 are derived from an aryl monocarboxylic acid , A is a divalent group derived from an aryl dicarboxylic acid, and G is preferably a mixture of compounds having an alkylene glycol structure, from the viewpoint of great effects of the present invention.
- Examples of the compound having the structure represented by the general formula (II) include the compound examples shown in Table 2.
- Examples of the combination of the partial structures of the compound having the structure represented by the general formula (III) include those shown in Table 3.
- Y 1 and Y 2 are monovalent groups derived from aryl monoalcohol
- A is a divalent group derived from alkylenedicarboxylic acid
- G is Use of a compound having a structure of a divalent group (partial combination number 20) derived from alkylene glycol is preferred from the viewpoint of the effect of the present invention.
- Y 1 and Y 2 are a monovalent group derived from an aryl monoalcohol
- A is a divalent group derived from an alkylenedicarboxylic acid
- G is Of the compound having the structure of a divalent group derived from alkylene glycol and the compound represented by the combination number 20 of the partial structure
- Y 1 and Y 2 are monovalent groups derived from an aryl monoalcohol
- A It is preferable from the viewpoint that the effect of the present invention is great that a compound having a divalent group derived from aryldicarboxylic acid and a compound having a divalent group structure derived from alkylene glycol is used.
- Examples of the compound having the structure represented by the general formula (III) include the compound examples shown in Table 4.
- a or G of the compound having the structure represented by the general formula (II) or the general formula (III) is a combination of two or more groups. preferable.
- Examples of the case where two or more groups of A or G are combined include the following cases.
- A is 2 types (A 1 , A 2 ), G is 1 type (G 1 ) A is one type (A 1 ), G is two types (G 1 , G 2 ) A is 2 types (A 1 , A 2 ), G is 2 types (G 1 , G 2 ) A 1 , A 2 , G 1 , and G 2 are the same as the definitions of A and G in the general formula (II) or general formula (III), and A 1 and A 2 are each independently Represents a divalent group derived from alkylenedicarboxylic acid, cycloalkylenedicarboxylic acid, or aryldicarboxylic acid. G 1 and G 2 each independently represent a divalent group derived from alkylene glycol, cycloalkylene glycol, or aryl glycol.
- a compound having a structure represented by the following general formula (IV) and general formula (V) is preferably a compound in which A or G is a combination of two or more groups.
- a 1 and A 2 each independently represents a divalent group derived from an alkylene dicarboxylic acid, a cycloalkylene dicarboxylic acid, or an aryl dicarboxylic acid.
- G 1 and G 2 each independently represent a divalent group derived from alkylene glycol, cycloalkylene glycol, or aryl glycol.
- n, n ′, m, and m ′ each independently represent an integer of 1 or more.
- a 1 and A 2 or G 1 and G 2 represent different groups.
- Examples of the compound having the structure represented by the general formula (IV) include those shown in Table 5. Examples of the compound having the structure represented by the general formula (V) are shown in Table 6. Examples of such compounds are given.
- n or m of the compound having the structure represented by the general formula (II) or the general formula (III) represents an integer of 1 or 2.
- n or m of the compound having the structure represented by the general formula (II) or the general formula (III) represents an integer of 1.
- the polyester synthesis is performed by a conventional method, a dicarboxylic acid compound, a diol compound, and, if necessary, an end-capping monocarboxylic acid or monoalcohol, a hot-melt condensation method using an esterification reaction or an ester exchange reaction, or a dicarboxylic acid system. It can be carried out by any of the interfacial condensation methods between the compound and the acid-blocking monocarboxylic acid chloride and the diol compound.
- the structure of the polyester can be adjusted by the types of the dicarboxylic acid compound and diol compound used as raw materials, the types of monoalcohol compounds and monocarboxylic acid compounds that are end-capping agents, and the amount of the raw material compound added. .
- the weight average molecular weight of the polyester is adjusted by the pressure, temperature, reaction time, addition ratio of dicarboxylic acid compound and diol compound as raw materials, addition time of end capping agent, addition amount, etc. it can.
- the weight average molecular weight (Mw) of the polyester according to the present invention is in the range of 400 to 3800.
- the weight average molecular weight (Mw) number average molecular weight of the polyester according to the present invention is preferably 400 to 2000, more preferably 400 to 1000, from the viewpoint of manifesting the effects of the present invention.
- Mw weight average molecular weight
- the mechanical strength of the optical film is lowered and the productivity is deteriorated.
- cracks and the like are easily generated, and durability against environmental fluctuations such as heat and humidity is deteriorated.
- the weight average molecular weight is larger than 3800, the effect of the present invention is hardly generated. This is presumably because compatibility with the cycloolefin-based resin according to the present invention deteriorates.
- the weight average molecular weight of the polyester according to the present invention can be measured by gel permeation chromatography.
- the measurement conditions are as follows.
- the polyester according to the present invention is a mixture of a compound having a weight average molecular weight in the range of 400 to 3800 and a compound having a weight average molecular weight in the range of 400 to 3800. More preferable from the viewpoint.
- the acid value of the polyester according to the present invention is not particularly limited as long as the effect of the present invention is obtained, but is preferably 0.1 to 200 mgKOH / g, for example. More preferably, it is 1 to 150 mgKOH / g, and still more preferably 15 to 100 mgKOH / g. If it is larger than 200 mgKOH / g, the optical film may become clouded due to the deterioration of compatibility with the cycloolefin-based resin. Moreover, it is preferable from a viewpoint of expression of the phase difference reduction effect of this invention as it is 0.1 mgKOH / g or more.
- the acid value of the polyester is defined as the number of milligrams of potassium hydroxide necessary to neutralize the acid (carboxy group present in the sample) contained in 1 g of the sample.
- the acid value of the polyester plasticizer can be measured according to JIS K0070.
- the content ratio (% by mass) of the compound having the maximum content ratio (mass%) among two or more kinds of compounds having different chemical structures or weight average molecular weights constituting the polyester is from the viewpoint of manifesting the effect of the present invention. 90 to 30% by mass is preferable. More preferably, it is 80 to 50% by mass. Further, the amount of polyester added to the optical film is preferably 1 to 15% by mass with respect to the cycloolefin-based resin from the viewpoint of manifesting the effects of the present invention. Further, it is more preferably 3 to 10% by mass.
- the optical film of the present invention has an in-plane retardation value Ro (nm) defined by the following formula (i) and a retardation value Rt (nm) in the film thickness direction defined by the following formula (ii). The condition defined by the following formulas (iii) and (iv) is satisfied.
- Ro and Rt are phase difference values measured with light having a wavelength of 590 nm in an environment of a temperature of 23 ° C. and a relative humidity of 55%.
- n x is a refractive index in a slow axis direction of the film plane.
- n y is a refractive index in a direction perpendicular to the slow axis direction of the film plane.
- nz is the refractive index in the direction perpendicular to the film surface.
- d is the thickness (nm) of the film.
- the retardation value Ro (nm) in the optical film plane is preferably 0 to +3 nm.
- the retardation value Rt in the optical film thickness direction is preferably ⁇ 5 to +5 nm.
- an optical film of a thin cycloolefin resin can improve the isotropic property (zero phase difference).
- the film thickness of the optical film of the present invention is 5 to 25 ⁇ m.
- the range of 10 to 15 ⁇ m is preferable, and thinning can contribute to thinning for IPS liquid crystal display devices.
- the in-plane retardation value Ro and the thickness direction retardation value Rt were measured using an automatic birefringence meter Axoscan (Axo Scan Mueller Matrix Polarimeter: manufactured by Axometrics) in an environment of 23 ° C. and 55% RH. at a wavelength of 590 nm, subjected to three-dimensional refractive index measured, resulting refractive indices n x, n y, it can be calculated from n z.
- additives examples include the following.
- the optical film of the present invention preferably further contains a matting agent in order to prevent the manufactured optical film from being damaged and the transportability from being deteriorated.
- a matting agent it is particularly preferable to contain silica particles.
- Silica particles are particles mainly composed of silicon dioxide.
- the main component means to contain 50% or more of the components constituting the particles, preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.
- the hydrophobization treatment for the silica particles is preferably an alkylation treatment.
- the surface of the alkylated fine particles has an alkyl group, and the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably The range is from 1 to 8 carbon atoms.
- the silica particles having an alkyl group having 1 to 20 carbon atoms on the surface can be obtained, for example, by treating the silicon dioxide particles with octylsilane.
- octylsilane As an example which has an octyl group on the surface, it is marketed by the brand name of Aerosil R805 (made by Nippon Aerosil Co., Ltd.), and is used preferably.
- the average particle size of the primary particles of the silica particles is preferably within the range of 5 to 400 nm, and more preferably within the range of 10 to 300 nm.
- the average particle size of the secondary particles of the silica particles is preferably in the range of 100 to 400 nm. If the average particle size of the primary particles is in the range of 100 to 400 nm, it is included as the primary particles without agglomeration. It is also preferable.
- silica particles commercially available products can be preferably used.
- Aerosil R805 for example, Aerosil R972, R972V, R974, R976S, R812, R812S, RY300, 300, R202, OX50, TT600 (above, Nippon Aerosil Co., Ltd.) Company name) (Aerosil is a registered trademark) and can be used.
- Aerosil R805, R812, and R976S are preferable because they can improve the handleability during handling and keep the haze of the optical film low.
- plasticizer In addition to polyester, other plasticizers may be used in combination with the optical film of the present invention.
- the content of the plasticizer is preferably in the range of 1 to 15% by mass and more preferably in the range of 3 to 10% by mass with respect to 100 parts by mass of the cycloolefin resin.
- the content of the plasticizer is within the above range, the effect of imparting plasticity can be exhibited, and the decrease in Tg of the optical film is small, which is preferable from the viewpoint of heat resistance.
- the anti-bleeding property of the plasticizer from the optical film is excellent.
- the optical film of the present invention preferably contains an ultraviolet absorber in order to shield unnecessary ultraviolet rays irradiated to the polarizing plate and the liquid crystal display device.
- an ultraviolet absorber By containing the ultraviolet absorber, the deterioration of the liquid crystal molecules in the liquid crystal cell can be prevented, so that the polarizing function can be maintained even when the polarizing plate or the display device is exposed to sunlight or the like for a long time.
- ultraviolet absorbers examples include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like, but less benzotriazole compounds Compounds are preferred. Further, ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574 and polymer ultraviolet absorbers described in JP-A-6-148430 are preferably used.
- the ultraviolet absorber is excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less from the viewpoint of preventing deterioration of a polarizer and liquid crystal.
- the liquid crystal display device has a characteristic that absorbs less visible light having a wavelength of 400 nm or more.
- the addition amount of the ultraviolet absorber is preferably in the range of 0.1 to 5.0% by mass, more preferably in the range of 0.5 to 3.0% by mass with respect to the polymer composition. preferable.
- benzotriazole-based ultraviolet absorber examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t -Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl Phenyl) -5-chlorobenzotriazole, 2- [2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2 -Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2'-hydroxy- '-T-butyl-5'-methylphenyl) -5-
- TINUVIN 109 can be preferably used as commercially available products.
- TINUVIN 171 can be preferably used as commercially available products.
- TINUVIN 326 can be preferably used as commercially available products.
- TINUVIN 328 can be preferably used as commercially available products.
- TINUVIN 928 can be preferably used as commercially available products.
- the method for producing an optical film of the present invention is preferably produced by a solution casting method because it is easy to produce a thin film optical film.
- the dope containing the cycloolefin resin and the organic solvent containing the polyester is prepared within a range of a melting temperature of 15 to 50 ° C. It is preferable.
- the optical film of the present invention includes a step of preparing a dope containing at least a cycloolefin-based resin and polyester (dope preparation step), and a web obtained by casting the dope on a support (also referred to as a cast film).
- Examples of the solvent used in the solution casting method include chlorinated solvents such as chloroform and dichloromethane; aromatic solvents such as toluene, xylene, benzene, and mixed solvents thereof; methanol, ethanol, isopropanol, n-butanol, Examples include alcohol solvents such as 2-butanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone (MEK), ethyl acetate, and diethyl ether. These solvents may be used alone or in combination of two or more.
- chlorinated solvents such as chloroform and dichloromethane
- aromatic solvents such as toluene, xylene, benzene, and mixed solvents thereof
- the solvent according to the present invention is a mixed solvent of a good solvent and a poor solvent
- the good solvent is, for example, dichloromethane as a chlorinated organic solvent, methyl acetate, ethyl acetate, or amyl acetate as a non-chlorine organic solvent.
- an alcohol solvent is preferably used. It is preferable to select from methanol, ethanol, and butanol from the viewpoint of improving peelability and enabling high-speed casting with the effects of the present invention. Of these, ethanol is preferred from the above viewpoint.
- the good solvent is preferably used in an amount of 55% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more based on the total amount of the solvent.
- the dope is fed to a pressure die through a liquid feed pump (for example, a pressurized metering gear pump) and transferred to an endless metal support such as a stainless steel belt or a metal support such as a rotating metal drum.
- a liquid feed pump for example, a pressurized metering gear pump
- an endless metal support such as a stainless steel belt or a metal support such as a rotating metal drum.
- Solvent evaporation process It is a step of heating the web on the metal support for casting and evaporating the solvent, and is a step of controlling the amount of residual solvent at the time of peeling described later.
- the temperature at the peeling position on the metal support is preferably in the range of 10 to 40 ° C, more preferably in the range of 11 to 30 ° C.
- the residual solvent amount of the web on the metal support at the time of peeling is preferably in the range of 15 to 100% by mass.
- the residual solvent amount is preferably controlled by the drying temperature and drying time in the solvent evaporation step.
- the amount of the residual solvent is 15% by mass or more because the silica particles do not have a distribution in the thickness direction and are uniformly dispersed in the optical film in the drying process on the support.
- the optical film has self-supporting properties, can avoid poor peeling of the optical film, and can maintain the mechanical strength of the web, thus improving the flatness at the time of peeling. In addition, it is possible to suppress occurrence of slippage and vertical stripes due to peeling tension.
- a drying process can also be performed by dividing into a preliminary drying process and a main drying process.
- the optical film obtained by peeling the web from the metal support is preliminarily dried.
- the preliminary drying of the optical film may be performed while the optical film is transported by a large number of rollers arranged above and below, or is dried while being transported by fixing both ends of the optical film with clips like a tenter dryer. You may let them.
- the means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roller, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.
- the drying temperature in the web pre-drying step is preferably a glass transition point of the optical film of ⁇ 5 ° C. or lower, and it is effective to perform a heat treatment at a temperature of 30 ° C. or higher for 1 minute or longer and 30 minutes or shorter. Drying is performed at a drying temperature in the range of 40 to 150 ° C, more preferably in the range of 50 to 100 ° C.
- the optical film of the present invention is produced by performing a stretching process under a residual solvent amount with a stretching apparatus, thereby producing a thin optical film, a wide optical film, and improving the flatness of the optical film.
- the retardation values Ro and Rt can be adjusted by controlling the orientation of the molecules in the optical film.
- the residual solvent amount at the start of stretching is preferably 5% by mass or more and less than 30% by mass. More preferably, it is in the range of 10 to 25% by mass. If the residual solvent amount at the start of stretching is 5% or more, the stress generated in the optical film at the time of stretching is lowered, the development of retardation due to the orientation of the resin chain is suppressed, and the retardation value is zero retardation. Easy to adjust to range.
- the stability of the optical film containing the residual solvent for example, the transport direction (also referred to as the longitudinal direction, MD direction, or casting direction), or the width direction It is preferable from the viewpoint of suppressing the talmi (also referred to as the TD direction).
- the stretching operation may be performed in multiple stages.
- simultaneous biaxial stretching may be performed or may be performed stepwise.
- stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible.
- simultaneous biaxial stretching includes stretching in one direction and contracting the other while relaxing the tension.
- the stretched optical film is heated and dried by a drying device.
- a means for preventing the mixing of used hot air by installing a nozzle that can exhaust used hot air is also preferably used.
- the hot air temperature is more preferably in the range of 40 to 350 ° C.
- the drying time is preferably about 5 seconds to 60 minutes, and more preferably 10 seconds to 30 minutes.
- the drying step it is preferable to dry the optical film until the amount of residual solvent is generally 0.5% by mass or less.
- ⁇ Winding process> This is a step of winding as an optical film after the amount of residual solvent in the optical film becomes 2% by mass or less, and obtaining an optical film with good dimensional stability by making the residual solvent amount preferably 1% by mass or less. Can do.
- a winding method As a winding method, a commonly used one may be used, and there are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, etc., and these may be used properly.
- the optical film of the present invention preferably has a haze of less than 1%, more preferably less than 0.5%. By setting the haze to less than 1%, there is an advantage that the transparency of the optical film becomes higher and it becomes easier to use as a film for optical applications.
- the optical film of the present invention when a matting agent is used, it is preferable to disperse silica particles having a uniform particle diameter from the viewpoint of haze. Thereby, the grade of the light scattering by particle
- the haze value is measured at 10 points at equal intervals in the width direction of the optical film with a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) in an environment of 23 ° C. and 50% RH. To haze.
- NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.
- the equilibrium water content at 25 ° C. and 60% relative humidity is preferably 4% or less, more preferably 3% or less.
- the equilibrium moisture content is preferable to easily cope with a change in humidity and to hardly change the optical characteristics and dimensions.
- the equilibrium moisture content is determined by leaving the sample film in a room conditioned at 23 ° C. and 20% RH for 4 hours or more and then leaving it in a room conditioned at 23 ° C. and 80% RH for 24 hours. Using a meter (for example, CA-20 model, manufactured by Mitsubishi Chemical Analytech Co., Ltd.), moisture is dried and vaporized at a temperature of 150 ° C., and then quantified by the Karl Fischer method.
- a meter for example, CA-20 model, manufactured by Mitsubishi Chemical Analytech Co., Ltd.
- the optical film of the present invention is preferably long, specifically, preferably has a length of about 100 to 40,000 m, and is wound into a roll.
- the width of the optical film of the present invention is preferably 1 m or more, more preferably 1.3 m or more, and particularly preferably 1.3 to 4 m.
- the film thickness of the stretched optical film (that is, the optical film of the present invention) is in the range of 5 to 25 ⁇ m. More preferably, it is 10 to 15 ⁇ m. If the film thickness is less than 5 ⁇ m, the productivity may be reduced due to the occurrence of breakage during the production of the optical film. In addition, when a polarizing plate is manufactured using an optical film having a film thickness of less than 5 ⁇ m, cracks are generated due to insufficient strength of the optical film, thereby deteriorating the durability of the polarizing plate. There is a case.
- the film thickness is 5 ⁇ m or more, a certain level or more of optical film strength can be expressed, which is preferable from the viewpoint of the productivity of the optical film and the crack resistance of the polarizing plate using the optical film. If the film thickness is 25 ⁇ m or less, it can be applied to make the polarizing plate and the display device thinner. By adopting the configuration of the present invention, even a thin film has good crack resistance, and an optical form of a cycloolefin resin can be obtained.
- the optical film of the present invention is preferably a functional film used for various display devices such as liquid crystal display devices and organic EL display devices and touch panels.
- the optical film of the present invention includes a polarizing plate protective film, a retardation film, an antireflection film, a brightness enhancement film, a hard coat film, an antiglare film, and an antistatic film for a liquid crystal display device or an organic EL display device.
- the retardation film includes a film in a retardation region having zero retardation.
- optical films for IPS liquid crystal display devices are particularly preferred applications.
- the optical film of the present invention can also be used as a polarizing plate protective film that also serves as the retardation film.
- the polarizing plate of the present invention comprises the optical film of the present invention on at least one surface of a polarizer.
- a polarizer is an element that passes only light having a plane of polarization in a certain direction. Examples thereof include a polyvinyl alcohol polarizing film.
- Polyvinyl alcohol polarizing films include those obtained by dyeing iodine on polyvinyl alcohol films and those obtained by dyeing dichroic dyes.
- the polarizer can be obtained by uniaxially stretching a polyvinyl alcohol film and then dyeing or dying a polyvinyl alcohol film and then uniaxially stretching, preferably by further performing a durability treatment with a boron compound.
- the film thickness of the polarizer is preferably in the range of 5 to 30 ⁇ m, and more preferably in the range of 5 to 15 ⁇ m.
- a coating-type polarizer obtained by stretching polyvinyl alcohol on a support and then stretching is preferable in that it can be made thinner.
- polyvinyl alcohol film examples include an ethylene unit content of 1 to 4 mol%, a degree of polymerization of 2000 to 4000, a degree of saponification of 99.0 to 99 described in JP2003-248123A, JP2003-342322A, and the like. 99 mol% ethylene-modified polyvinyl alcohol is preferably used. Moreover, it is preferable to produce a polarizer by producing a polarizer by the method described in JP2011-1000016A, JP4691205A, and JP4804589A, and attaching the polarizer to the optical film of the present invention.
- the optical film of the present invention is preferably bonded to a polarizer using a completely saponified polyvinyl alcohol aqueous solution (water paste).
- Another polarizing plate protective film can be bonded to the other surface.
- the optical film of the present invention is a liquid crystal display device, it is preferably provided on the liquid crystal cell side of the polarizer.
- the optical film on the side opposite to the liquid crystal cell of the polarizer is the optical film of the present invention and the conventional one. Any of the polarizing plate protective films can be used.
- cellulose ester films for example, Konica Minoltak KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC6UY, KC6UA, KC4UY, KC8UE, KC8UE, KC8UE, KC8UE, KC8UE, RHA, KC8UXW-RHA-C, KC8UXW-RHA-NC, KC4UXW-RHA-NC, manufactured by Konica Minolta Co., Ltd.
- cellulose ester films for example, Konica Minoltak KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC6UY, KC6UA, KC4UY, KC8UE, KC8UE, KC8UE, KC8UE, KC8UE, KC8UE, RHA, KC8UX
- the optical film and polarizer of this invention are bonded by the active energy ray hardening adhesive.
- the active energy ray-curable adhesive is preferably an ultraviolet curable adhesive.
- the film disposed on the opposite side of the optical film of the present invention across the polarizer is preferably a film that functions as a protective film for the polarizer.
- the optical film of the present invention may be used.
- Door can be.
- the optical film of the present invention may be used as a protective film, and the optical film of the present invention may be disposed on both sides of the polarizer.
- resin films such as polyethylene terephthalate, polyethylene naphthalate, and polycarbonate, alicyclic polyolefins (for example, ZEONOR (registered trademark) manufactured by Nippon Zeon Co., Ltd., polyarylate, polyethersulfone, polysulfone, cycloolefin copolymer, polyimide (For example, Mitsubishi Gas Chemical Co., Ltd., Neoprim (registered trademark)), resin films such as fluorene ring-modified polycarbonate, alicyclic modified polycarbonate, acryloyl compound, etc.
- ZEONOR registered trademark
- polyarylate for example, polyethersulfone, polysulfone, cycloolefin copolymer
- polyimide Form example, Mitsubishi Gas Chemical Co., Ltd., Neoprim (registered trademark)
- resin films such as fluorene ring-modified polycarbonate, alicyclic modified polycarbonate, acryloyl compound, etc.
- films such as polyethylene terephthalate (abbreviation: PET), polybutylene terephthalate, polyethylene naphthalate (abbreviation: PEN), polycarbonate (abbreviation: PC), etc. are used as protective films. Used Mashiku.
- the thickness of the protective film is not particularly limited, but can be about 10 to 150 ⁇ m, preferably in the range of 10 to 100 ⁇ m, and more preferably in the range of 10 to 50 ⁇ m.
- FIG. 1 is a schematic cross-sectional view of a polarizing plate according to a preferred embodiment of the present invention.
- the polarizing plate 101 includes a polarizer 10 and an optical film 20 and a protective film 30 disposed on both surfaces of the polarizer 10.
- the polarizer 10, the optical film 20, and the protective film 30 are bonded together via an arbitrary adhesive layer (not shown).
- the display device of the present invention includes the polarizing plate of the present invention.
- liquid crystal display devices having various visibility can be manufactured by using a polarizing plate on which the optical film of the present invention is bonded to a liquid crystal display device.
- the optical film of the present invention is preferably used for a polarizing plate for display applications having a polygon or a curve.
- the polarizing plate of the present invention can be used for liquid crystal display devices of various driving systems such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, OCB.
- An IPS liquid crystal display device is preferable.
- the polarizing plate of the present invention is preferably used as a viewing-side polarizing plate that directly touches the external environment.
- the optical film of the present invention is a protective film
- the viewing-side surface or the optical film of the present invention is an optical compensation film. In some cases, it is preferably disposed on the liquid crystal cell side.
- it is preferably disposed on both sides of the liquid crystal cell.
- a polarizing plate other than the present invention can be used as the polarizing plate on the backlight side.
- a commercially available cellulose ester film for example, Konica Minoltack KC8UX, KC5UX, KC4UX, KC8UCR3
- KC4SR for example, Konica Minoltack KC8UX, KC5UX, KC4UX, KC8UCR3
- KC4SR for example, Konica Minoltack KC8UX, KC5UX, KC4UX, KC8UCR3
- KC4SR for example, Konica Minoltack KC8UX, KC5UX, KC4UX, KC8UCR3
- KC4SR for example, Konica Minoltack KC8UX, KC5UX, KC4UX, KC8UCR3
- KC4SR for example, Konica Minoltack KC8UX,
- the optical film of the present invention is used on the liquid crystal cell side of the polarizer, and the commercially available protective film, retardation film, polyester film, acrylic film, polycarbonate film, or A polarizing plate on which another cycloolefin film is bonded can also be preferably used.
- the polarizing plate of the present invention By using the polarizing plate of the present invention, it is possible to obtain a liquid crystal display device excellent in visibility such as display unevenness, front contrast, and viewing angle even in the case of a large-screen liquid crystal display device having a screen size of 30 or more. .
- Example 1 Each compound shown in Table 2, Table 4, Table 5, and Table 6 was synthesized according to a conventional method as an additive to the cycloolefin resin used in the Examples. In addition, each said compound was mixed suitably and it was used as polyester (mixture of 2 or more types of compounds from which a chemical structure or a weight average molecular weight (Mw) differs) based on this invention.
- ⁇ Production of optical film> ⁇ Preparation of optical film 1> ⁇ Preparation of fine particle dispersion> 11.3 parts by mass of fine particles (Aerosil R812, manufactured by Nippon Aerosil Co., Ltd.) and 84 parts by mass of ethanol were stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.
- a main dope having the following composition was prepared. First, dichloromethane and ethanol were added to the pressure dissolution tank. The cycloolefin-based resin and the fine particle additive solution were added to a pressure dissolution tank containing dichloromethane with stirring. This was heated and completely dissolved with stirring, and this was dissolved in Azumi filter paper No. 1 manufactured by Azumi Filter Paper Co., Ltd. The main dope was prepared by filtration using 244.
- Cycloolefin resin (ARTON G7810, manufactured by JSR Corporation) 90 parts by mass Dichloromethane 200 parts by mass Ethanol 10 parts by mass Fine particle additive solution 7.6 parts by mass ⁇ Preparation of optical film 1> Then, using an endless belt casting apparatus, the main dope was uniformly cast on a stainless steel belt support at a temperature of 31 ° C. and a width of 1800 mm. The temperature of the stainless steel belt was controlled at 28 ° C. The conveyance speed of the stainless steel belt was 20 m / min.
- the solvent was evaporated on the stainless steel belt support until the amount of residual solvent in the cast (cast) optical film was 30%. Subsequently, it peeled from the stainless steel belt support body with the peeling tension of 128 N / m. The peeled optical film was stretched 1.15 times in the width direction under the condition of 160 ° C. The residual solvent at the start of stretching was 5% by mass. Next, drying was completed while transporting the drying zone with a number of rollers, and the end portion sandwiched between tenter clips was slit with a laser cutter, and then wound up to produce an optical film 1 having a thickness of 10 ⁇ m.
- ⁇ Phase difference value> The retardation value Ro in the in-plane direction of the optical film and the retardation value Rt in the thickness direction are 23 ° C. and 55% using an automatic birefringence meter Axoscan (Axo Scan Mueller Matrix Polarimeter: manufactured by Axometrics).
- Axo Scan Mueller Matrix Polarimeter manufactured by Axometrics.
- n x represents a refractive index in the slow axis direction in the in-plane direction of the film.
- n y in-plane direction of the film, the refractive index in the direction y perpendicular to the direction x.
- nz represents the refractive index in the thickness direction z of the film.
- d represents the thickness (nm) of the film.
- the optical film of the present invention had good retardation values and productivity.
- cycloolefin resin P-1 is ARTON G7810 (trade name) manufactured by JSR Corporation
- P-2 is ARTON R5000 (trade name) manufactured by JSR Corporation
- P-3 is ARTON RX4500 (trade name) manufactured by JSR Corporation.
- Example 2 Optical films 36 to 41 were produced in the same manner as the optical film 3 except that the compound 1M of the optical film 3 of Example 1 was changed to the second compound (polyester) shown in Table 8.
- Table 8 shows the results of evaluating the phase difference value and productivity in the same manner as in Example 1.
- the optical film of the present invention had good retardation values and productivity.
- Example 3 ⁇ Preparation of polarizing plate> ⁇ Preparation of stretched laminate 1 having a polarizer> ⁇ Preparation of laminated body 1> The surface of the 120 ⁇ m-thick amorphous polyethylene terephthalate sheet subjected to the antistatic treatment was subjected to corona treatment to obtain a thermoplastic resin layer A.
- Polyvinyl alcohol powder (manufactured by Nippon Vinegar Bipovar Co., Ltd., average polymerization degree 2500, saponification degree 99.0 mol% or more, trade name: JC-25) as a hydrophilic polymer is dissolved in 95 ° C. hot water to obtain a concentration. An 8% by mass aqueous polyvinyl alcohol solution was prepared. The obtained aqueous solution of polyvinyl alcohol is coated on the thermoplastic resin layer A for lamination using a lip coater, dried at 80 ° C. for 20 minutes, and made hydrophilic from the thermoplastic resin layer A and polyvinyl alcohol. The laminated body 1 which laminated
- the laminate 1 was subjected to a 5.3 times free end uniaxial stretching treatment at 160 ° C. in the transport direction (MD direction) to produce a stretched laminate 1.
- the thickness of the hydrophilic resin layer (polarizer 1) in the stretched laminate 1 was 5.6 ⁇ m.
- the stretched laminate 1 is immersed in a warm bath at 60 ° C. for 60 seconds, and immersed in an aqueous solution containing 0.05 parts by mass of iodine and 5 parts by mass of potassium iodide per 100 parts by mass of water at a temperature of 28 ° C. for 60 seconds. did.
- the film washed with water in a tension state, the film was dried at 70 ° C. for 300 seconds to obtain a stretched laminate 1 composed of the thermoplastic resin layer A and the polarizer 1.
- Step 1 The surface of the optical film 1 was subjected to corona discharge treatment.
- the corona discharge treatment was performed at a corona output intensity of 2.0 kW and a line speed of 18 m / min.
- Step 2 A polyvinyl alcohol adhesive having a solid content of 2% by mass was applied to the surface of the stretched laminate 1 having the polarizer 1.
- Process 3 The surface (polarizer 1 formation surface) which apply
- the optical film 1 was bonded so that the absorption axis of the polarizer 1 and the slow axis of the optical film 1 were perpendicular.
- Step 4 The sample superposed in Step 3 was bonded at a pressure of 20 to 30 N / cm 2 and a conveyance speed of about 2 m / min.
- Step 5 The bonded sample prepared in Step 4 was dried for 2 minutes in a dryer at 80 ° C. to obtain a polarizing plate composed of the optical film 1, the polarizer 1, and the thermoplastic resin layer A.
- Step 6 The thermoplastic resin layer A was peeled from the obtained polarizing plate to obtain a polarizing plate PL-A1 ′.
- ⁇ Preparation 2 of polarizing plate> In accordance with the following steps 7 to 11, the prepared PL-1 ′ and the above Konica Minolta 2UAH (trade name) (manufactured by Konica Minolta Co., Ltd.) (hereinafter referred to as “KC2UAH”) are bonded together, and the polarizing plate PL- 1 was produced.
- KC2UAH Konica Minolta 2UAH
- KC2UAH was immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried to saponify the side to be bonded to the polarizer.
- Step 8 A polyvinyl alcohol adhesive having a solid content of 2% by mass was applied to the surface of the polarizer 1 on the side where the PL-1 ′ optical film 1 was not bonded.
- Step 9 The surface where the polyvinyl alcohol adhesive was applied in Step 8 and the surface to which the hard coat layer of KC2UAH treated in Step 7 was not provided were arranged to face each other.
- Step 10 The sample superposed in Step 9 was bonded at a pressure of 20 to 30 N / cm 2 and a conveyance speed of about 2 m / min.
- Step 11 The bonded sample prepared in Step 10 is dried for 2 minutes in a dryer at 80 ° C., and is a polarizing plate composed of PL-1 ′ and KC2UAH, that is, optical film 1, polarizer 1, polarizing plate protective film KC2UAH
- a polarizing plate PL-1 comprising:
- the wet heat durability of the polarizer was measured as follows.
- Example 4 ⁇ Production of liquid crystal display device>
- the polarizing plate attached to the front and back sides of the liquid crystal panel of the Hitachi Ltd. liquid crystal television (Woooo W32-L7000) in IPS mode is peeled off.
- the polarizing plate PL-1 to PL-35 produced in Example 3 is applied to the light source side (rear surface) and the viewing side (front surface) at the peeled location, respectively,
- the same liquid crystal display devices CLD-1 to CLD-35 were bonded by using an acrylic transparent adhesive.
- the contrast of the liquid crystal display device thus produced was evaluated according to the following evaluation criteria, and used as a standard for visibility.
- the liquid crystal display device of the present invention has good visibility, and both the wet heat durability of the polarizing plate used and the productivity of the optical film are good.
- the present invention provides an optically isotropic (zero retardation) thin film optical film using a cycloolefin-based resin, and a polarizing plate and a display device including the optical film. Is suitable.
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Liquid Crystal (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
また、溶液流延法で製造する際は、上記の理由に加え、加圧ダイスリットからドラムやベルト上に流延した後の乾燥過程で樹脂鎖が配向することでも位相差が発現する。さらには、溶剤が残留している状態の光学フィルムをクリップで幅方向に保持しながら搬送する際に、乾燥により光学フィルムが収縮することで疑似的に延伸され、結果的に位相差が発現することもある。
(ii)Rt={(nx+ny)/2-nz)}×d
(iii)0≦Ro≦5
(iv)-10≦Rt≦10
〔式中、Ro及びRtは温度23℃、相対湿度55%の環境下で波長590nmの光で測定した位相差値である。
2.前記シクロオレフィン系樹脂が、下記一般式(I)で表される構造を有するシクロオレフィン系モノマー由来の重合体であることを特徴とする第1項に記載の光学フィルム。
≪本発明の光学フィルムの概要≫
本発明の光学フィルムは、シクロオレフィン系樹脂とポリエステルとを含有する光学フィルムであって、前記ポリエステルが、化学構造又は分子量が異なる2種類以上の化合物の混合物であり、前記ポリエステルの重量平均分子量(Mw)が、400~3800の範囲内であり、前記光学フィルムの膜の厚さが5~25μmの範囲内であり、かつ、前記光学フィルムの、下記式(i)で定義されるフィルム面内の位相差値Ro(nm)及び下記式(ii)で定義されるフィルム膜厚方向の位相差値Rt(nm)が、下記式(iii)及び(iv)で規定する条件を満たすことを特徴とする。
(ii)Rt={(nx+ny)/2-nz)}×d
(iii)0≦Ro≦5
(iv)-10≦Rt≦10
〔式中、Ro及びRtは温度23℃、相対湿度55%の環境下で波長590nmの光で測定した位相差値である。
なお面内位相差値Ro、及び厚さ方向の位相差値Rtは自動複屈折率計アクソスキャン(Axo Scan Mueller Matrix Polarimeter:アクソメトリックス社製)を用いて、23℃・55%RHの環境下、590nmの波長において、三次元屈折率測定を行い、得られた屈折率nx、ny、nzから上記式を用いて算出する。
本発明の光学フィルムは、シクロオレフィン系樹脂を含有することを特徴とする。
本発明において、シクロオレフィン系樹脂の好ましい水素結合受容性基の保有比率は一般式(I)でR1~R4のうち1~2個が水素結合受容性基を有することが好ましい。
本発明の光学フィルムは、ポリエステルを含有し、前記ポリエステルが、化学構造又は分子量が異なる2種類以上の化合物の混合物であり、前記ポリエステルの重量平均分子量(Mw)が、400~3800の範囲内であることを特徴とする。
Aが1種類(A1)、Gが2種類(G1、G2)
Aが2種類(A1、A2)、Gが2種類(G1、G2)
A1、A2、G1、及びG2は、前記の一般式(II)又は一般式(III)におけるA、及びGの定義と同様であり、A1、及びA2は、それぞれ独立に、アルキレンジカルボン酸、シクロアルキレンジカルボン酸、又はアリールジカルボン酸から誘導される2価の基を表す。G1、及びG2は、それぞれ独立に、アルキレングリコール、シクロアルキレングリコール、又はアリールグリコールから誘導される2価の基を表す。
カラム:Shodex K806、K805、K803G(昭和電工(株)製を3本接続して使用した)
カラム温度:25℃
試料濃度:0.1質量%
検出器:RI Model 504(GLサイエンス社製)
ポンプ:L6000(日立製作所(株)製)
流量:1.0ml/min
校正曲線:標準ポリスチレンSTK standard ポリスチレン(東ソー(株)製)Mw=500~2800000迄の13サンプルによる校正曲線を使用した。13サンプルは、ほぼ等間隔に用いることが好ましい。
(ii)Rt=((nx+ny)/2-nz)×d
(iii)0≦Ro≦5
(iv)-10≦Rt≦10
〔式中、Ro及びRtは温度23℃、相対湿度55%の環境下で波長590nmの光で測定した位相差値である。nxは、フィルム平面内の遅相軸方向の屈折率である。nyは、フィルム平面内の遅相軸方向に垂直な方向の屈折率である。nzは、フィルム面に垂直な方向の屈折率である。dは、フィルムの厚さ(nm)である。〕
上記の特性(ゼロ位相差性)を有することで、特にIPS型液晶表示装置用の偏光板として最適な位相差を付与できる。
本発明の光学フィルムは、製造された光学フィルムがハンドリングされる際の、傷つきや、搬送性が悪化することを防止するため、さらにマット剤を含有することが好ましい。マット剤としては特にシリカ粒子を含有することが好ましい。
本発明の光学フィルムには、ポリエステル以外に、他の可塑剤を併用してもよい。
本発明の光学フィルムは、偏光板や液晶表示装置に照射される不要な紫外線を遮蔽するために、紫外線吸収剤を含有することが好ましい。紫外線吸収剤を含有することにより、液晶セル中の液晶分子の劣化を防止できるため偏光板や表示装置が太陽光等に長時間曝されても偏光機能を維持することができる。
本発明の光学フィルムの製造方法は、溶液流延製膜法によって製造することが薄膜の光学フィルムを製造しやすいため好ましい。
溶液流延法に用いられる溶媒としては、例えば、クロロホルム、ジクロロメタンなどの塩素系溶媒;トルエン、キシレン、ベンゼン、及びこれらの混合溶媒などの芳香族系溶媒;メタノール、エタノール、イソプロパノール、n-ブタノール、2-ブタノールなどのアルコール系溶媒;メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、ジメチルホルムアミド、ジメチルスルホキシド、ジオキサン、シクロヘキサノン、テトラヒドロフラン、アセトン、メチルエチルケトン(MEK)、酢酸エチル、ジエチルエーテル;などが挙げられる。これら溶剤は1種のみ用いてもよいし、2種以上を併用してもよい。
ドープを、送液ポンプ(例えば、加圧型定量ギヤポンプ)を通して加圧ダイに送液し、無限に移送する無端の金属支持体、例えば、ステンレスベルト、又は回転する金属ドラム等の金属支持体上の流延位置に、加圧ダイスリットからドープを流延する工程である。
ウェブを流延用金属支持体上で加熱し、溶媒を蒸発させる工程であり、後述する剥離時の残留溶媒量を制御する工程である。
金属支持体上で溶媒が蒸発したウェブを、剥離位置で剥離する工程である。剥離されたウェブは光学フィルムとして次工程に送られる。
乾燥工程は予備乾燥工程、本乾燥工程に分けて行うこともできる。
本発明の光学フィルムは、延伸装置にて残留溶媒量下で延伸処理を行うことで、薄膜の光学フィルムを製造したり、広幅の光学フィルムを製造したり、また光学フィルムの平面性を向上したり、光学フィルム内の分子の配向を制御することで、位相差値Ro及びRtを調整することができる。
・長手方向に延伸→幅手方向に延伸→長手方向に延伸→長手方向に延伸
・幅手方向に延伸→幅手方向に延伸→長手方向に延伸→長手方向に延伸
・幅手方向に延伸→斜め方向に延伸
また、同時二軸延伸には、一方向に延伸し、もう一方を、張力を緩和して収縮させる場合も含まれる。
乾燥工程では、乾燥装置によって延伸後の光学フィルムを加熱して乾燥させる。
光学フィルム中の残留溶媒量が2質量%以下となってから光学フィルムとして巻取る工程であり、残留溶媒量を好ましくは1質量%以下にすることにより寸法安定性の良好な光学フィルムを得ることができる。
<ヘイズ>
本発明の光学フィルムは、ヘイズが1%未満であることが好ましく、0.5%未満であることがより好ましい。ヘイズを1%未満とすることにより、光学フィルムの透明性がより高くなり、光学用途のフィルムとしてより用いやすくなるという利点がある。
本発明の光学フィルムは、25℃、相対湿度60%における平衡含水率が4%以下であることが好ましく、3%以下であることがより好ましい。平衡含水率を4%以下とすることにより、湿度変化に対応しやすく、光学特性や寸法がより変化しにくく好ましい。
本発明の光学フィルムは、長尺であることが好ましく、具体的には、100~40000m程度の長さであることが好ましく、ロール状に巻き取られる。また、本発明の光学フィルムの幅は1m以上であることが好ましく、更に好ましくは1.3m以上であり、特に1.3~4mであることが好ましい。
本発明の光学フィルムは、液晶表示装置、有機EL表示装置等の各種表示装置やタッチパネルに用いられる機能フィルムであることが好ましい。具体的には、本発明の光学フィルムは、液晶表示装置又は有機EL表示装置用の偏光板保護フィルム、位相差フィルム、反射防止フィルム、輝度向上フィルム、ハードコートフィルム、防眩フィルム、帯電防止フィルムなどでありうる。ここで、位相差フィルムとは、ゼロ位相差性の位相差領域のフィルムも含む。
本発明の偏光板は、上記本発明の光学フィルムを偏光子の少なくとも片面に具備する。
<偏光子>
偏光子は、一定方向の偏波面の光だけを通す素子であり、その例には、ポリビニルアルコール系偏光フィルムが含まれる。
<水糊>
本発明の偏光板は、本発明の光学フィルムを完全ケン化型ポリビニルアルコール水溶液(水糊)を用いて偏光子に貼り合わせることが好ましい。もう一方の面には他の偏光板保護フィルムを貼合することができる。本発明の光学フィルムは液晶表示装置とされた際に、偏光子の液晶セル側に設けられることが好ましく、偏光子の液晶セルとは反対側の光学フィルムは、本発明の光学フィルム、及び従来の偏光板保護フィルムのどちらでも用いることができる。
また、本発明の偏光板においては、本発明の光学フィルムと偏光子とが、活性エネルギー線硬化性接着剤により貼合されていることが好ましい。
偏光子を挟んで本発明の光学フィルムとは反対側に配置されるフィルムは、偏光子の保護フィルムとして機能するフィルムであることが好ましい。
図1は、本発明の好ましい実施形態による偏光板の概略断面図である。図1の実施形態においては、偏光板101は、偏光子10と該偏光子10の両方の面に配置された光学フィルム20及び保護フィルム30とを備える。該偏光子10と該光学フィルム20及び保護フィルム30は、任意の接着層(図示せず)を介して、貼り合わせられている。
本発明の表示装置は、上記本発明の偏光板を具備する。
具体的には、上記本発明の光学フィルムを貼合した偏光板を液晶表示装置に用いることによって、種々の視認性に優れた液晶表示装置を作製することができる。
実施例で用いるシクロオレフィン系樹脂への添加剤として、前記表2、表4、表5及び表6に示される各化合物を、定法に従って合成した。なお、前記各化合物を適宜混合して、本発明に係るポリエステル(化学構造又は重量平均分子量(Mw)が異なる2種類以上の化合物の混合物)として使用した。
<光学フィルム1の作製>
<微粒子分散液の調製>
11.3質量部の微粒子(アエロジル R812、日本アエロジル(株)製)と、84質量部のエタノールとを、ディゾルバーで50分間撹拌混合した後、マントンゴーリンで分散した。
下記組成の主ドープを調製した。まず加圧溶解タンクにジクロロメタン及びエタノールを添加した。ジクロロメタンの入った加圧溶解タンクにシクロオレフィン系樹脂と微粒子添加液を撹拌しながら投入した。これを加熱し、撹拌しながら完全に溶解し、これを安積濾紙(株)製の安積濾紙No.244を使用してろ過して、主ドープを調製した。
90質量部
ジクロロメタン 200質量部
エタノール 10質量部
微粒子添加液 7.6質量部
<光学フィルム1の作製>
次いで、無端ベルト流延装置を用い、主ドープを温度31℃、1800mm幅でステンレスベルト支持体上に均一に流延した。ステンレスベルトの温度は28℃に制御した。ステンレスベルトの搬送速度は20m/minとした。
光学フィルム1の作製において、シクロオレフィン系樹脂の種類、化合物(ポリエステル)の種類及び膜厚をそれぞれ表7に記載のように変化させて、光学フィルム2~35を作製した。但し、ポリエステルを添加する場合は、ポリエステルの総量が、シクロオレフィン系樹脂90質量部に対して3質量部となるように添加し、ポリエステルを混合物とする場合の混合比率は、ポリエステル混合物の平均分子量が、表7に記載の平均分子量となるように混合した。
光学フィルムの面内方向の位相差値Ro、及び厚さ方向の位相差値Rtは自動複屈折率計アクソスキャン(Axo Scan Mueller Matrix Polarimeter:アクソメトリックス社製)を用いて、23℃・55%RHの環境下、590nmの波長において、三次元屈折率測定を行い、得られた屈折率nx、ny、nzから下記式を用いて算出する。
式(ii):Rt={(nx+ny)/2-nz}×d(nm)
〔式(i)及び式(ii)において、nxは、フィルムの面内方向において遅相軸方向における屈折率を表す。nyは、フィルムの面内方向において、前記方向xと直交する方向yにおける屈折率を表す。nzは、フィルムの厚さ方向zにおける屈折率を表す。dは、フィルムの厚さ(nm)を表す。〕
<生産性>
光学フィルムの製造時に延伸工程やロール搬送工程で、破断や端部裂けの発生度を下記の評価基準で評価した。
○:光学フィルム1000mを製造したときに、破断や端部裂けが発生しない
×:光学フィルム1000mを製造したときに、破断や端部裂けが1回以上発生する
光学フィルムの構成と、以上の結果をまとめて表7に示した。
実施例1の光学フィルム3の化合物1Mを、表8に示す第2の化合物(ポリエステル)に変えた以外は光学フィルム3と同様にして光学フィルム36~41を作製した。
<偏光板の作製>
<偏光子を有する延伸積層体1の作製>
<積層体1の作製>
帯電防止処理が施された厚さ120μmの非晶性ポリエチレンテレフタレートシートの表面をコロナ処理し、熱可塑性樹脂層Aとした。
上記積層体1を、搬送方向(MD方向)に160℃で5.3倍の自由端一軸延伸処理を施し、延伸積層体1を作製した。なお、延伸積層体1における親水性樹脂層(偏光子1)の厚さは5.6μmであった。
次いで、延伸積層体1を60℃の温浴に60秒浸漬し、水100質量部あたりヨウ素を0.05質量部及びヨウ化カリウムを5質量部それぞれ含有する水溶液に、温度28℃で60秒間浸漬した。次いで、緊張状態に保ったまま、水100質量部あたりホウ酸を7.5質量部及びヨウ化カリウムを6質量部それぞれ含有するホウ酸水溶液に、温度73℃で300秒間浸漬した。その後、15℃の純水で10秒間洗浄した。水洗したフィルムを緊張状態に保ったまま、70℃で300秒間乾燥し、熱可塑性樹脂層Aと偏光子1からなる延伸積層体1を得た。
下記工程1~6に従って、上記作製した延伸積層体1と、実施例1で作成した本発明の光学フィルム1を貼合し、次いで熱可塑性樹脂層Aを剥離して、偏光板PL-1′を作製した。
<偏光板の作製2>
下記工程7~11に従って、上記作製したPL-1′と、前記コニカミノルタタック2UAH(商品名)(コニカミノルタ(株)製)(以下「KC2UAH」という。)を貼合し、偏光板PL-1を作製した。
液晶パネルに搭載された状態を再現するために、本発明の光学フィルムの偏光子とは反対側の面を、粘着層を介してガラスに貼り付けた後、40℃、相対湿度90%の環境下で1000時間保管した際の保管前後での偏光子の退色を目視で観察し下記の評価基準で評価した。
○:退色無し
×:明らかに退色している
評価結果を、下記実施例4の評価とともに、表9に示す。本発明の偏光板はいずれも湿熱耐久性評価で退色が無かった。
<液晶表示装置の作製>
上記作製した偏光板の特性を評価するため、IPSモードである(株)日立製作所製液晶テレビ(Wooo W32-L7000)の液晶パネルの観察者側の前面及び背面に貼付している偏光板を剥がし、この剥がした箇所に、上記実施例3で作製した偏光板PL-1~PL-35を光源側(背面)と視認側(前面)に、それぞれ元々貼合されていた偏光板の透過軸と同一にして、アクリル系透明粘着剤を用いて貼合し、液晶表示装置CLD-1~CLD-35とした。
上記で作製した液晶パネルを暗室に設置し、黒表示で点灯した。その状態で点灯後30分後と24時間後に、次のようにして光漏れの有無を確認した。すなわち、パネル正面および、正面からの倒れ角がパネル長辺方向に45°(左)と-45°(右)の角度、正面からの倒れ角がパネル短辺方向に45°(上)と―45°(下)の角度、以上の5つの方向から目視にて観察し、以下の基準に基づき評価した。
◎:30分後、24時間後のいずれの時点においても、5方向への光漏れがない
○:30分後、24時間後のいずれかの時点で、5方向のうち1方向以上へ、注視すればわかる程度の僅かな光漏れがあるも、実用上問題ないと考えられる
×:30分後、24時間後のいずれかの時点で、5方向のうち1方向以上へ、明らかな光漏れがある
評価結果を、実施例1、実施例3の評価結果とともに、表9に示した。
20 光学フィルム
30 保護フィルム
101 偏光板
Claims (10)
- シクロオレフィン系樹脂とポリエステルとを含有する光学フィルムであって、
前記ポリエステルが、化学構造又は重量平均分子量(Mw)が異なる2種類以上の化合物の混合物であり、
前記ポリエステルの重量平均分子量(Mw)が、400~3800の範囲内であり、
前記光学フィルムの膜の厚さが5~25μmの範囲内であり、かつ、
前記光学フィルムの、下記式(i)で定義されるフィルム面内の位相差値Ro(nm)及び下記式(ii)で定義されるフィルム膜厚方向の位相差値Rt(nm)が、下記式(iii)及び(iv)で規定する条件を満たす光学フィルム。
(i)Ro=(nx-ny)×d
(ii)Rt={(nx+ny)/2-nz)}×d
(iii)0≦Ro≦5
(iv)-10≦Rt≦10
〔式中、Ro及びRtは温度23℃、相対湿度55%の環境下で波長590nmの光で測定した位相差値である。
nxは、フィルム平面内の遅相軸方向の屈折率である。
nyは、フィルム平面内の遅相軸方向に垂直な方向の屈折率である。
nzは、フィルム面に垂直な方向の屈折率である。
dは、フィルムの厚さ(nm)である。〕 - 前記一般式(I)で表される構造を有するシクロオレフィン系モノマーのpが0を表し、R1及びR2が水素原子を表し、R3がメチル基を表し、かつ、R4がメトキシカルボニル基を表す請求項2に記載の光学フィルム。
- 前記ポリエステルの混合物を構成する化合物の少なくとも1種が、下記一般式(II)又は一般式(III)で表される構造を有する化合物である請求項1から請求項3までのいずれか一項に記載の光学フィルム。
前記一般式(II)及び一般式(III)において、Aは、アルキレンジカルボン酸、シクロアルキレンジカルボン酸、又はアリールジカルボン酸から誘導される2価の基を表す。Gは、アルキレングリコール、シクロアルキレングリコール、又はアリールグリコールから誘導される2価の基を表す。n及びmは、それぞれ0以上の整数を表す。X1及びX2は、それぞれ水素原子、又はアルキレンモノカルボン酸、シクロアルキレンモノカルボン酸、若しくはアリールモノカルボン酸から誘導される1価の基を表す。Y1及びY2は、それぞれヒドロキシ基又はアルキレンモノアルコール、シクロアルキレンモノアルコール若しくはアリールモノアルコールから誘導される1価の基を表す。ここで、A及びGは、1種類であっても2種類以上の基が組み合わされていても良い。 - 前記一般式(II)又は一般式(III)で表される構造を有する化合物のA又はGが、2種類以上の基が組み合わされている請求項4に記載の光学フィルム。
- 前記一般式(II)又は一般式(III)で表される構造を有する化合物のn又はmが、1又は2の整数を表す請求項4又は請求項5に記載の光学フィルム。
- 前記一般式(II)又は一般式(III)で表される構造を有する化合物のn又はmが、1の整数を表す請求項4から請求項6までのいずれか一項に記載の光学フィルム。
- 前記一般式(II)又は一般式(III)で表される構造を有する化合物の、X1及びX2の少なくとも一方がアルキレンモノカルボン酸、シクロアルキレンモノカルボン酸、又はアリールモノカルボン酸から誘導される1価の基を表し、Y1及びY2の少なくとも一方がアルキレンモノアルコール、シクロアルキレンモノアルコール、又はアリールモノアルコールから誘導される1価の基を表し、かつ
n又はmが0の整数を表す請求項4又は請求項5に記載の光学フィルム。 - 請求項1から請求項8までのいずれか一項に記載の光学フィルムを偏光子の少なくとも片面に具備する偏光板。
- 請求項9に記載の偏光板を具備する表示装置。
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201780045150.6A CN109661600B (zh) | 2016-07-26 | 2017-07-25 | 光学膜、偏振片及显示装置 |
| KR1020187037202A KR102117187B1 (ko) | 2016-07-26 | 2017-07-25 | 광학 필름, 편광판, 및 표시 장치 |
| JP2018529914A JP6969555B2 (ja) | 2016-07-26 | 2017-07-25 | 光学フィルム、偏光板、及び表示装置 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-145859 | 2016-07-26 | ||
| JP2016145859 | 2016-07-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2018021312A1 true WO2018021312A1 (ja) | 2018-02-01 |
Family
ID=61017076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2017/026871 Ceased WO2018021312A1 (ja) | 2016-07-26 | 2017-07-25 | 光学フィルム、偏光板、及び表示装置 |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6969555B2 (ja) |
| KR (1) | KR102117187B1 (ja) |
| CN (1) | CN109661600B (ja) |
| WO (1) | WO2018021312A1 (ja) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019124096A1 (ja) * | 2017-12-21 | 2019-06-27 | Dic株式会社 | エステル樹脂、可塑化剤、セルロースエステル樹脂組成物、光学フィルム及び液晶表示装置 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008120905A (ja) * | 2006-11-10 | 2008-05-29 | Fujifilm Corp | 環状ポリオレフィンフィルム、それを用いた偏光板および液晶表示装置 |
| KR20090113347A (ko) * | 2007-02-21 | 2009-10-30 | 후지필름 가부시키가이샤 | 투명 폴리머 필름의 제조 방법과 이 방법에 의해 제조되는 투명 폴리머 필름, 위상차 필름, 편광판, 및 액정 표시 장치 |
| JP2013116621A (ja) * | 2011-03-31 | 2013-06-13 | Fujifilm Corp | 積層フィルム、光学補償フィルム、偏光板、及び液晶表示装置 |
| JP2016018021A (ja) * | 2014-07-07 | 2016-02-01 | コニカミノルタ株式会社 | 円偏光板、有機エレクトロルミネッセンス表示装置及び円偏光板の製造方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4145282B2 (ja) | 2004-09-24 | 2008-09-03 | 富士フイルム株式会社 | Ips型液晶表示装置用長尺状偏光板とその製造方法、およびips型液晶表示装置 |
| JP2011128356A (ja) | 2009-12-17 | 2011-06-30 | Nippon Zeon Co Ltd | 偏光板用保護フィルム |
| KR101577105B1 (ko) * | 2012-12-28 | 2015-12-11 | 제일모직주식회사 | 광학필름의 제조방법, 이로부터 제조된 광학필름 및 이를 포함하는 액정 디스플레이 |
| KR101629076B1 (ko) | 2014-03-06 | 2016-06-09 | 주식회사 효성 | 노르보넨계 광학 보상 필름, 및 이를 이용한 편광판 및 표시장치 |
| JP6728651B2 (ja) | 2015-11-27 | 2020-07-22 | コニカミノルタ株式会社 | 光学フィルム及びその製造方法、偏光板及び液晶表示装置 |
-
2017
- 2017-07-25 CN CN201780045150.6A patent/CN109661600B/zh active Active
- 2017-07-25 JP JP2018529914A patent/JP6969555B2/ja active Active
- 2017-07-25 WO PCT/JP2017/026871 patent/WO2018021312A1/ja not_active Ceased
- 2017-07-25 KR KR1020187037202A patent/KR102117187B1/ko active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008120905A (ja) * | 2006-11-10 | 2008-05-29 | Fujifilm Corp | 環状ポリオレフィンフィルム、それを用いた偏光板および液晶表示装置 |
| KR20090113347A (ko) * | 2007-02-21 | 2009-10-30 | 후지필름 가부시키가이샤 | 투명 폴리머 필름의 제조 방법과 이 방법에 의해 제조되는 투명 폴리머 필름, 위상차 필름, 편광판, 및 액정 표시 장치 |
| JP2013116621A (ja) * | 2011-03-31 | 2013-06-13 | Fujifilm Corp | 積層フィルム、光学補償フィルム、偏光板、及び液晶表示装置 |
| JP2016018021A (ja) * | 2014-07-07 | 2016-02-01 | コニカミノルタ株式会社 | 円偏光板、有機エレクトロルミネッセンス表示装置及び円偏光板の製造方法 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019124096A1 (ja) * | 2017-12-21 | 2019-06-27 | Dic株式会社 | エステル樹脂、可塑化剤、セルロースエステル樹脂組成物、光学フィルム及び液晶表示装置 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190008378A (ko) | 2019-01-23 |
| CN109661600B (zh) | 2021-12-03 |
| KR102117187B1 (ko) | 2020-05-29 |
| CN109661600A (zh) | 2019-04-19 |
| JPWO2018021312A1 (ja) | 2019-05-09 |
| JP6969555B2 (ja) | 2021-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI569967B (zh) | A polarizing plate and a liquid crystal display device using the same | |
| JPWO2018070132A1 (ja) | 偏光板および液晶表示装置 | |
| JPWO2007102327A1 (ja) | 偏光板及び液晶表示装置 | |
| JPWO2015076250A1 (ja) | 光学フィルム、偏光板および液晶表示装置 | |
| CN105849599B (zh) | 纤维素酯膜、其制造方法及偏振片 | |
| JP5707811B2 (ja) | 長尺状λ/4板、円偏光板、偏光板、OLED表示装置、及び立体画像表示装置 | |
| WO2015060167A1 (ja) | 位相差フィルム、偏光板及び液晶表示装置 | |
| KR20150115890A (ko) | 광학 필름, 및 이를 포함하는 편광판 및 va형 액정 표시 장치 | |
| TWI405797B (zh) | 醯化纖維素薄膜、偏光板及液晶顯示裝置 | |
| JP5668593B2 (ja) | 偏光板、その製造方法及び垂直配向型液晶表示装置 | |
| JP2017116759A (ja) | 光学フィルム、光学フィルムの製造方法及び偏光板 | |
| JP2017121777A (ja) | プロテクトフィルム積層体 | |
| JP6969555B2 (ja) | 光学フィルム、偏光板、及び表示装置 | |
| JP6737287B2 (ja) | 光学フィルム、偏光板及び表示装置 | |
| CN103314325B (zh) | 垂直取向型液晶显示装置及其制造方法 | |
| JP5626133B2 (ja) | Va型液晶表示装置 | |
| KR102778133B1 (ko) | 광학 필름 및 그 제조 방법, 편광판 그리고 표시 장치 | |
| JP5957818B2 (ja) | 位相差フィルム、偏光板及び液晶表示装置 | |
| JP2017102310A (ja) | 光学フィルム及び表示装置 | |
| JP5626134B2 (ja) | Va型液晶表示装置 | |
| CN120028899A (zh) | 相位差膜、偏振片和液晶显示装置 | |
| JP2012198280A (ja) | 垂直配向型液晶表示装置とその製造方法 | |
| JP2011248042A (ja) | 液晶表示装置とその製造方法 | |
| JP2012003209A (ja) | 光学補償フィルム、並びにそれを用いた偏光板及び液晶表示装置 | |
| JP2017102311A (ja) | 光学フィルムの製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ENP | Entry into the national phase |
Ref document number: 2018529914 Country of ref document: JP Kind code of ref document: A |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17834314 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 20187037202 Country of ref document: KR Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 17834314 Country of ref document: EP Kind code of ref document: A1 |