WO2013065587A1 - Plaque de polarisation circulaire permettant une électroluminescence organique et pourvue d'une couche adhésive, et dispositif d'affichage à électroluminescence organique équipé d'une telle plaque - Google Patents

Plaque de polarisation circulaire permettant une électroluminescence organique et pourvue d'une couche adhésive, et dispositif d'affichage à électroluminescence organique équipé d'une telle plaque Download PDF

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WO2013065587A1
WO2013065587A1 PCT/JP2012/077678 JP2012077678W WO2013065587A1 WO 2013065587 A1 WO2013065587 A1 WO 2013065587A1 JP 2012077678 W JP2012077678 W JP 2012077678W WO 2013065587 A1 WO2013065587 A1 WO 2013065587A1
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Prior art keywords
film
polarizing plate
acid
adhesive layer
organic electroluminescence
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PCT/JP2012/077678
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English (en)
Japanese (ja)
Inventor
田坂　公志
理英子 れん
賢治 三島
幸仁 中澤
翠 木暮
範江 谷原
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コニカミノルタアドバンストレイヤー株式会社
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Priority to JP2013541746A priority Critical patent/JP6123676B2/ja
Priority to KR1020147011125A priority patent/KR101630101B1/ko
Publication of WO2013065587A1 publication Critical patent/WO2013065587A1/fr

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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
    • G02B5/3025—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
    • 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

Definitions

  • the present invention relates to a circularly polarizing plate for organic electroluminescence with an adhesive layer, and an organic electroluminescence display device comprising the same.
  • An organic electroluminescence element that emits light by applying a voltage to the light-emitting layer between the electrodes is a variety of light sources such as flat illumination, optical fiber light source, liquid crystal display backlight, liquid crystal projector backlight, and display device. As a result, research and development are underway.
  • Organic electroluminescent elements are excellent in terms of light emission efficiency, low voltage driving, light weight, and low cost, and have attracted considerable attention in recent years.
  • An organic electroluminescence element emits visible light corresponding to the light emission characteristics of a light emitting layer by injecting electrons from a cathode and holes from an anode and recombining them in the light emitting layer.
  • ITO indium tin oxide
  • a metal electrode is usually used for the cathode, but materials such as Mg, MgAg, MgIn, Al, and LiAl are used from the viewpoint of work function in consideration of electron injection efficiency.
  • These metal materials have high light reflectivity, and in addition to the function as an electrode (cathode), they also have a function of reflecting light emitted from the light emitting layer and increasing the amount of emitted light (light emission luminance). That is, the light emitted in the cathode direction is mirror-reflected on the surface of the metal material that is the cathode, and is extracted as emitted light from the transparent ITO electrode (anode).
  • the organic electroluminescence device having such a structure has a problem that the display quality deteriorates due to the reflection of external light in the state where no light is emitted (during black display) because the cathode has a mirror surface with high light reflectivity.
  • black light cannot be expressed in a bright place such as reflection of indoor lighting, and there is a problem that the bright room contrast is extremely low when used as a light source for a display device.
  • Patent Document 1 a circularly polarizing plate is used for preventing reflection of external light on a mirror surface.
  • a typical circularly polarizing plate with an adhesive layer for preventing reflection of external light has a configuration in which a polarizing plate protective film, a polarizer, a ⁇ / 4 retardation film and an adhesive layer are laminated, and the absorption axis of the polarizer and ⁇ / 4.
  • the function of suppressing reflection of external light is exhibited by setting the angle formed with the slow axis of the retardation film to 45 °.
  • the adhesive layer serves for adhesion to the organic electroluminescence device, and the polarizing plate protective film serves to protect the polarizer.
  • the ⁇ / 4 retardation film As a material for the ⁇ / 4 retardation film, having reverse wavelength dispersion characteristics is important from the viewpoint of preventing external light reflection in the entire visible light region, and special polycarbonate materials having reverse wavelength dispersion characteristics are also used. Yes.
  • the polycarbonate resin has a problem in adhesion to a polarizer, and a ⁇ / 4 retardation film made of a cellulose ester having reverse wavelength dispersion characteristics has been demanded from the viewpoint of adhesion with a simple water paste.
  • cellulose ester is used as a ⁇ / 4 retardation film, the dimensional change over time is inferior to that of polycarbonate, resulting in a problem of degrading the display quality of the organic electroluminescence display device. was there.
  • the adhesive component disclosed in Patent Document 2 as a measure for preventing white spots for liquid crystal display devices has an absorption axis of a polarizer and a slow axis of a ⁇ / 4 retardation film made of cellulose ester of 45 °.
  • a circularly polarizing plate with an angle of 5 is used in an organic electroluminescence display device, the display quality deteriorates over time, which is different from the problem caused by liquid crystal display devices. It was not enough for the problem of unevenness of rate.
  • Patent Document 2 does not present any means for solving this unique problem of uneven reflectance that occurs in organic electroluminescence elements.
  • the present invention has been made in view of the above-mentioned problems and situations, and the problem to be solved is an organic electroluminescence with an adhesive layer that is excellent in preventing uneven reflectance and film peeling over time of an organic electroluminescence display device. It is to provide a circularly polarizing plate. Moreover, it is providing the organic electroluminescent display apparatus which comprised this organic electroluminescent circularly-polarizing plate with an adhesion layer.
  • the present inventor examined the cause of the above problems by focusing on the shrinkage force in the slow axis direction of the ⁇ / 4 retardation film, and as a result, the storage elastic modulus of the adhesive layer was optimized. The inventors have found that the above-mentioned problems can be solved by controlling the value, thereby reaching the present invention.
  • a polarizing plate protective film, a polarizer, a ⁇ / 4 retardation film, and an adhesive layer are laminated in this order, and the angle formed by the slow axis of the ⁇ / 4 retardation film and the absorption axis of the polarizer is 45 °.
  • a circular polarizing plate for organic electroluminescence with a featured adhesive layer is provided.
  • Critical angle ( ⁇ ) arcsin (1 / n) 3.
  • the absolute value of the photoelastic coefficient in the slow axis direction of the ⁇ / 4 retardation film is 10 ⁇ 10 ⁇ 11 / Pa or less, 4.
  • An organic electroluminescence display device comprising the circularly polarizing plate for organic electroluminescence with an adhesive layer according to any one of items 1 to 4.
  • the ⁇ / 4 retardation film is produced by stretching, a shrinkage force in the slow axis direction works over time. Because it is fixed by the adhesive, when the slow axis direction is taken as a reference, a strong portion and a weak portion are generated in the plane, and the ⁇ / 4 retardation film is partially deformed over time, This has been a cause of uneven reflectance.
  • the storage elastic modulus of the adhesive layer By controlling the storage elastic modulus of the adhesive layer to an optimal value, it is considered that deformation is suppressed and unevenness in reflectance is reduced.
  • Schematic diagram of a ⁇ / 4 retardation film and a polarizer constituting a circularly polarizing plate Schematic diagram showing direction of shrinkage force over time of ⁇ / 4 retardation film
  • Schematic diagram showing areas with large and small stresses Schematic diagram of light emission from organic electroluminescent light emitting layer
  • Schematic diagram of light emission from organic electroluminescent light emitting layer Schematic diagram of oblique stretching equipment
  • Schematic diagram of oblique stretching equipment Schematic diagram showing an example of a cross section of the configuration of an organic electroluminescence display device
  • the circularly polarizing plate for organic electroluminescence with an adhesive layer of the present invention has a polarizing plate protective film, a polarizer, a ⁇ / 4 retardation film, and an adhesive layer laminated in this order, and the retardation of the ⁇ / 4 retardation film.
  • the storage elastic modulus is in the range of 0.1 to 10 MPa.
  • the polarizing plate protective film according to the present invention has the above polarizing plate protection against light traveling in the polarizing plate protective film at a critical angle ( ⁇ ) defined by the following formula (1) when the refractive index is n.
  • ⁇ critical angle
  • the ⁇ / 4 retardation film of the present invention has a dimensional change rate in the slow axis direction after treatment at 90 ° C. for 500 hours of 0.5% or less.
  • the effect of the present invention is that the absolute value of the photoelastic coefficient in the slow axis direction of the ⁇ / 4 retardation film in the present invention is 10 ⁇ 10 ⁇ 11 / Pa or less (especially the improvement in uneven reflection over time). This is a preferred embodiment from the viewpoint of expression.
  • Nonuniformity in reflectance and film peeling of organic electroluminescence display devices resulting from stress generation described in the background art can be improved by reducing the photoelastic coefficient in the slow axis direction where stress is generated. . Since the photoelastic coefficient is the degree of expression of the phase difference with respect to stress, it can be reduced by increasing the elastic modulus in the slow axis direction instead of decreasing the elastic modulus in the fast axis direction.
  • the circularly polarizing plate for organic electroluminescence with an adhesive layer of the present invention can be suitably provided in an organic electroluminescence display device.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • FIG. 1A is a diagram illustrating only the ⁇ / 4 retardation film 1a and the polarizer 2a extracted from the configuration of the circularly polarizing plate.
  • the absorption axis 3a of the polarizer is installed in the horizontal or vertical direction from the viewpoint of keeping the upper, lower, left, and right reflectances low (in FIG. 1A). , Described schematically vertically).
  • the slow axis 4a of the ⁇ / 4 retardation film is disposed so as to be inclined by 45 ° with respect to the in-plane vertical direction of the display device. Since the ⁇ / 4 retardation film 1a is produced by stretching, the shrinkage force 5a in the slow axis direction works with time (see FIG. 1B). Since the ⁇ / 4 retardation film is fixed by the adhesive, when the slow axis direction is taken as a reference, there are a long portion and a short portion in this direction in the plane.
  • the adhesive force cannot withstand the shrinkage force of the ⁇ / 4 retardation film, and the film over time Causes peeling.
  • the storage elastic modulus of the pressure-sensitive adhesive layer in the range of 0.1 to 10 MPa, it was possible to simultaneously achieve the prevention of uneven reflectance and film peeling over time.
  • the ⁇ / 4 retardation film described in the present invention contains a cellulose ester resin.
  • cellulose acylate which satisfy
  • the “ ⁇ / 4 retardation film” refers to linearly polarized light having a specific wavelength (here, the angle formed by the electric field vibration surface of the linearly polarized light and the slow axis of the ⁇ / 4 retardation film is 45 °). It has a function of converting circularly polarized light (or circularly polarized light into linearly polarized light).
  • the ⁇ / 4 retardation film has an in-plane retardation value Ro of about 1 ⁇ 4 for a predetermined wavelength of light (usually in the visible light region).
  • Ro (550) measured at a wavelength of 550 nm is in the range of 105 to 175 nm, and Ro (550) is 120 to 160 nm from the viewpoint of reducing the front reflectance.
  • Ro (550) is more preferably 130 to 150 nm.
  • the ⁇ / 4 retardation film according to the present invention has a retardation plate having a retardation of approximately 1 ⁇ 4 of the wavelength in the visible light wavelength range in order to obtain almost perfect circularly polarized light in the visible light wavelength range ( Film).
  • “Retardation is approximately 1/4 in the wavelength range of visible light” means that the longer the wavelength is from 400 to 700 nm, the larger the retardation, and the retardation expressed by the following formula (4-1) measured at a wavelength of 450 nm.
  • the ratio Ro (450) / Ro (550) between the value Ro (450) and the retardation value Ro (550) measured at a wavelength of 550 nm is 0.72 to 0.92. It is preferable for reproduction, and is particularly preferably 0.77 to 0.87.
  • the ratio Ro (550) / Ro (650) of Ro (550), which is a retardation value measured at a wavelength of 550 nm, and Ro (650), which is a retardation value measured at a wavelength of 650 nm, is 0.84 to 0.97 is preferable for red reproduction, and 0.84 to 0.92 is particularly preferable.
  • Formula (4-1): Ro (n x ⁇ n y ) ⁇ d
  • Formula (4-2): Rt ⁇ (n x + n y ) / 2 ⁇ n z ⁇ ⁇ d
  • n x, n y and n z is, 23 °C ⁇ 55% RH, say 450 nm
  • Ny reffractive index in the direction perpendicular to the slow axis in the film plane
  • nz reffractive index in the thickness direction of the film
  • d is the thickness (nm) of the film.
  • the thickness direction retardation value Rt is the spectral reflectance of the reflective electrode of the organic electroluminescence display device, the thickness direction retardation value of the electroluminescence element, the wavelength dispersion characteristic, and the value of Ro of the ⁇ / 4 retardation film. However, it can be appropriately set in consideration of the wavelength dispersion characteristics and the like, but is preferably in the range of about 70 to 120 nm from the viewpoint of the color of reflection.
  • the in-plane retardation value Ro and the thickness direction retardation value Rt can be measured using an automatic birefringence meter.
  • Ro and Rt can be calculated by measuring the birefringence at each wavelength in an environment of 23 ° C. and 55% RH. .
  • a circularly polarizing plate is obtained by laminating so that the angle between the slow axis of the ⁇ / 4 retardation film and the absorption axis of the polarizer described later is 45 °.
  • the angle formed by the slow axis of the ⁇ / 4 retardation film and the absorption axis of the polarizer is 45 °, which means 40 ⁇ 5 °.
  • the angle between the in-plane slow axis of the ⁇ / 4 retardation film and the absorption axis of the polarizer is preferably 41 to 49 °, more preferably 42 to 48 °, and more preferably 43 to 47 °. More preferably, it is most preferably 44 to 46 ° from the viewpoint of reducing the reflectance.
  • the ⁇ / 4 retardation film described in the present invention contains a plasticizer in the resin, and other additives such as a UV agent and a matting agent can be appropriately added.
  • the dimensional change rate in the slow axis direction of the ⁇ / 4 retardation film in the present invention after treatment at 90 ° C. for 500 hours is preferably 0.5% or less.
  • the treatment at 90 ° C. for 500 hours means heat treatment and can be carried out using a high-temperature thermostatic bath.
  • the thermostat is commercially available and does not require humidity adjustment.
  • Dimensional change rate (%) 100 ⁇ ((dimension after treatment) ⁇ (dimension before treatment)) / (dimension before treatment)
  • the dimensional change rate can be measured by a known method.
  • the absolute value of the photoelastic coefficient in the slow axis direction of the ⁇ / 4 retardation film in the present invention is in the range of 10 ⁇ 10 ⁇ 11 / Pa or less. This value is preferably close to 0, but the absolute value of the lower limit is about 1 ⁇ 10 ⁇ 11 / Pa from the viewpoint of obtaining materials.
  • the unevenness in reflectance and film peeling of the organic electroluminescence display device due to the stress generation described above can be improved by reducing the photoelastic coefficient in the slow axis direction where stress is generated. Since the photoelastic coefficient is the degree of expression of the phase difference with respect to stress, it can be reduced by increasing the elastic modulus in the slow axis direction instead of decreasing the elastic modulus in the fast axis direction.
  • the photoelastic coefficient is 23 ° C., relative humidity 55%, the slow axis is in the tensile direction, a weight F is applied to the test piece, and the birefringence ⁇ n generated when the test piece is stretched at a wavelength of 550 nm. From this, it can be obtained by ⁇ n / F.
  • the photoelastic coefficient represents the degree of occurrence of birefringence with respect to stress
  • the photoelastic coefficient can be reduced by increasing the elastic modulus. Specifically, it can be achieved by increasing the draw ratio, reducing the amount of plasticizer, decreasing the total substitution degree of the cellulose ester and increasing the hydrogen bonding property, reducing the proportion of long-chain acyl groups of the cellulose ester, etc. it can.
  • the plasticizer is generally an additive having an effect of improving brittleness or imparting flexibility by adding it to a polymer.
  • the ⁇ / 4 retardation film in the present invention there is an effect of lowering the glass transition temperature of the resin containing the plasticizer than the glass transition temperature of the resin alone, and the intermolecular force during stretching is adjusted, and ⁇ / 4 after stretching.
  • the elastic modulus of the retardation film can be adjusted.
  • the ⁇ / 4 retardation film according to the present invention is preferably a polyester resin shown below, a compound represented by the general formula (PEI), a compound represented by the general formula (PEII), or a carboxylic acid sugar ester compound as a plasticizer. Can be contained.
  • the polyester resin that can be used in the present invention is obtained by polymerizing a dicarboxylic acid and a diol, and 70% or more of dicarboxylic acid structural units (constituent units derived from dicarboxylic acid) are derived from aromatic dicarboxylic acid, and 70% or more of the diol constituent units (constituent units derived from the diol) are derived from the aliphatic diol.
  • the proportion of the structural unit derived from the aromatic dicarboxylic acid is 70% or more, preferably 80% or more, and more preferably 90% or more.
  • the proportion of the structural unit derived from the aliphatic diol is 70% or more, preferably 80% or more, and more preferably 90% or more. Two or more polyester resins may be used in combination.
  • aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid such as 2,7-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid. 3,4'-biphenyldicarboxylic acid and the like, and ester-forming derivatives thereof.
  • polyester resin aliphatic dicarboxylic acids such as adipic acid, azelaic acid and sebacic acid, and monocarboxylic acids such as benzoic acid, propionic acid and butyric acid can be used.
  • Examples of the aliphatic diol include ethylene glycol, 1,3-propylene diol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, and ester-forming derivatives thereof.
  • polyester resin monoalcohols such as butyl alcohol, hexyl alcohol and octyl alcohol, and polyhydric alcohols such as trimethylolpropane, glycerin and pentaerythritol can be used.
  • a known esterification method or transesterification method can be applied to the production of the polyester resin.
  • the polycondensation catalyst used in the production of the polyester resin include known antimony compounds such as antimony trioxide and antimony pentoxide, germanium compounds such as germanium oxide, titanium compounds such as titanium acetate, and aluminum compounds such as aluminum chloride. Although it can, it is not limited to these.
  • Preferred polyester resins include polyethylene terephthalate resin, polyethylene terephthalate-isophthalate copolymer resin, polyethylene-1,4-cyclohexanedimethylene-terephthalate copolymer resin, polyethylene-2,6-naphthalene dicarboxylate resin, polyethylene-2, 6-naphthalene dicarboxylate-terephthalate copolymer resin, polyethylene-terephthalate-4,4'-biphenyldicarboxylate resin, poly-1,3-propylene-terephthalate resin, polybutylene terephthalate resin, polybutylene-2,6-naphthalene There are dicarboxylate resins and the like.
  • polyester resins include polyethylene terephthalate resin, polyethylene terephthalate-isophthalate copolymer resin, polyethylene-1,4-cyclohexanedimethylene-terephthalate copolymer resin, polybutylene terephthalate resin, and polyethylene-2,6-naphthalene dicarboxylate. Resin.
  • the ⁇ / 4 retardation film according to the present invention preferably contains a compound represented by the following general formula (PEI) (hereinafter also referred to as “aromatic group-terminated polyester compound”) and a cellulose ester resin.
  • PEI general formula
  • the phase difference can be freely controlled, and the control to the target ⁇ / 4 phase difference is easy.
  • B- (GA) n -GB B represents an aryl monocarboxylic acid residue.
  • G represents an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms.
  • A represents an alkylenedicarboxylic acid residue having 4 to 12 carbon atoms or an arylene dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.
  • aryl monocarboxylic acid component of the aromatic group-terminated polyester compound used examples include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, and normalpropyl benzoic acid.
  • acid aminobenzoic acid, acetoxybenzoic acid and the like, and these can be used as one kind or a mixture of two or more kinds, respectively.
  • alkylene glycol component having 2 to 12 carbon atoms of the aromatic group-terminated polyester compound examples 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 1,6-hexanediol, 2,2,4-trimethyl-1, -Pentaned
  • alkylene glycols having 2 to 12 carbon atoms are particularly preferable because of excellent compatibility with cellulose esters.
  • Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the aromatic group-terminated polyester-based compound include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. , One or a mixture of two or more.
  • alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic group-terminated polyester compound examples include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These are used as one kind or a mixture of two or more kinds.
  • arylene dicarboxylic acid component having 6 to 12 carbon atoms examples include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and the like.
  • n is preferably 1 or more and 100 or less, and the number average molecular weight is preferably in the range of 300 to 1500, more preferably 400 to 1000. .
  • the acid value is 0.5 mgKOH / g or less, the hydroxy (hydroxyl group) value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxy (hydroxyl group) value is 15 mgKOH / g or less. is there.
  • the aromatic group-terminated polyester compound represented by the general formula (PEI) used is preferably contained in an amount of 0.5 to 30% by mass with respect to the cellulose ester resin.
  • aromatic group-terminated polyester compounds that can be used in the present invention are shown below, but the present invention is not limited thereto.
  • the ⁇ / 4 retardation film according to the present invention contains a sugar ester compound in an amount of 0.5 to 30% by mass of the ⁇ / 4 retardation film in order to suppress the fluctuation of the retardation value and stabilize the display quality. Preferably, it is contained preferably 5 to 30% by mass.
  • the content of the aromatic group-terminated polyester compound represented by the general formula (PEI) and the sugar ester compound can be selected in a mass ratio ranging from 99: 1 to 1:99, and the total amount of both compounds is The content is preferably 1 to 40% by mass relative to the cellulose ester resin.
  • polyester compound represented by formula (PEII) Hydroxyl-terminated polyester>
  • various polyester compounds conventionally contained in a ⁇ / 4 retardation film can be used.
  • the polyester compound a polyester having a hydroxy group at the terminal portion of the chemical structural formula as represented by the following general formula (PEII) (referred to as “hydroxy group-terminated polyester”) can also be used.
  • B represents a linear or branched alkylene or cycloalkylene group having 2 to 6 carbon atoms.
  • A represents an aromatic ring having 6 to 14 carbon atoms.
  • N represents one or more. Represents a natural number.
  • the compound represented by the above formula is obtained from a dicarboxylic acid having an aromatic ring (also referred to as “aromatic dicarboxylic acid”) and a linear or branched alkylene or cycloalkylene diol having 2 to 6 carbon atoms. The terminal is not sealed with a monocarboxylic acid.
  • aromatic dicarboxylic acid having 6 to 16 carbon atoms examples include phthalic acid, isophthalic acid, terephthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3- And naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,8-naphthalenedicarboxylic acid, 2,2′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and the like.
  • 2,6-naphthalenedicarboxylic acid and 4,4′-biphenyldicarboxylic acid are preferable.
  • linear or branched alkylene or cycloalkylene diol having 2 to 6 carbon atoms examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, and 1,3-butanediol. 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol 1,4-cyclohexanedimethanol and the like. Of these, ethanediol, 1,2-propanediol, 1,3-propanediol, and 1,3-butanediol are preferable.
  • A is preferably a naphthalene ring or a biphenyl ring which may have a substituent, from the viewpoint of obtaining the effects of the present invention.
  • the substituent is an alkyl group having 1 to 6 carbon atoms, an alkenyl group, or an alkoxyl group.
  • the hydroxy (hydroxyl) value (OH value) of the polyester compound is preferably from 100 mgKOH / g to 500 mgKOH / g, and more preferably from 170 to 400 mgKOH / g. Whether the hydroxy (hydroxyl group) value is larger or smaller than this range, the compatibility with cellulose acetate having a low acetyl substitution degree is lowered.
  • acetic anhydride method described in Japanese Industrial Standard JIS K1557-1: 2007 can be applied to the measurement of hydroxy (hydroxyl group) value.
  • the number average molecular weight (Mn) of the polyester compound can be calculated from the following formula.
  • Polyester compounds can be easily obtained by a conventional method, either a hot melt condensation method using a polyesterification reaction or a transesterification reaction between the dicarboxylic acid and a diol, or an interfacial condensation method between an acid chloride of these acids and a glycol. Can be synthesized.
  • polyester compounds that can be preferably used in the present invention are shown below.
  • the compound represented by the general formula (PEII) is preferably added in an amount of 1% by mass to less than 5% by mass with respect to cellulose acetate.
  • the ⁇ / 4 retardation film according to the present invention preferably contains a carboxylic acid sugar ester compound as a plasticizer.
  • a carboxylic acid sugar ester compound as a plasticizer.
  • the “carboxylic acid sugar ester compound” refers to a compound having an ester bond derived from a hydroxy group (hydroxyl group) of a saccharide and a carboxy group of a carboxylic acid.
  • carboxylic acid structural unit constituting the carboxylic acid sugar ester compound examples include aromatic carboxylic acids such as methylbenzoic acid (toluic acid), aromatic substituted aliphatic carboxylic acids such as phenylacetic acid, and fatty acids such as stearic acid. These carboxylic acids may be substituted with an alkoxy group, an alkylthio group, a halogen atom, a cyano group or a nitro group.
  • aromatic carboxylic acids examples include aromatic monocarboxylic acids, cinnamic acid, benzylic acid, biphenylcarboxylic acid, naphthalenecarboxylic acid having an alkyl group or alkoxy group introduced into the benzene ring of benzoic acid such as benzoic acid or toluic acid.
  • aromatic monocarboxylic acids having two or more benzene rings such as acid and tetralincarboxylic acid, or derivatives thereof.
  • Preferred aliphatic carboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, Tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, mellicic acid, laccellic acid, etc., undecylen Examples thereof include unsaturated fatty acids such as acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid and octenoic acid.
  • the saccharides constituting the carboxylic acid sugar ester compound usually include monosaccharides, disaccharides, and oligosaccharides in which 3 to 6 monosaccharides are bonded, and of these, the number of carbon atoms is 6 ⁇ 48 saccharides are preferred, and monosaccharides and disaccharides are more preferred.
  • Specific examples of monosaccharides include glucose, fructose, arabinose, mannose, and sorbitol
  • examples of disaccharides include sucrose and maltose. From the viewpoint of supplying raw materials, glucose, fructose and sucrose are particularly preferable, and sucrose is most preferable.
  • These saccharides have a plurality of hydroxy groups (hydroxyl groups) in the molecule, and can form ester bonds with the aforementioned carboxylic acid structural units.
  • sucrose when sucrose is used as the saccharide, there are 8 hydroxy groups (hydroxyl groups) in the sucrose molecule, but the average number of ester bonds (also referred to as “average ester substitution degree”) is 1. 0.0 or more, preferably 3.0 to 7.5, and more preferably 3.0 to 6.0.
  • R 1 to R 8 represent a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group, and R 1 to R 8 are the same. It may or may not be.
  • R represents any one of R 1 to R 8 .
  • substituents such as a phenyl group and an alkoxy group included in the alkylcarbonyl group and the arylcarbonyl group shown in the following table are preferable.
  • a four-headed colben equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube was mixed with 34.2 g (0.1 mol) of sucrose, 180.8 g (0.8 mol) of benzoic anhydride, 379. 7 g (4.8 mol) was charged, the temperature was raised while bubbling nitrogen gas from a nitrogen gas introduction tube with stirring, and an esterification reaction was carried out at 70 ° C. for 5 hours.
  • the inside of the Kolben was depressurized to 4 ⁇ 10 2 Pa or less, and after excess pyridine was distilled off at 60 ° C., the inside of the Kolben was depressurized to 1.3 ⁇ 10 Pa or less and the temperature was raised to 120 ° C. Most of the acid and benzoic acid formed were distilled off. Then, 1 L of toluene and 300 g of a 0.5% by mass aqueous sodium carbonate solution were added, and the mixture was stirred at 50 ° C. for 30 minutes and then allowed to stand to separate a toluene layer.
  • the average substitution degree of the compound represented by the general formula (1) added to the ⁇ / 4 retardation film in the present invention is preferably 3.0 to 7.5, and the range of the substitution degree is 3 More preferably, it is 0.0 to 6.0.
  • the substitution degree distribution may be adjusted to the desired substitution degree by adjusting the esterification reaction time or mixing compounds having different substitution degrees.
  • the ⁇ / 4 retardation film and polarizing plate protective film according to the present invention can contain various compounds as additives in addition to the plasticizer.
  • a retardation developing agent, an antioxidant, an acid scavenger, a light stabilizer, an ultraviolet absorber, an optical anisotropy control agent, a matting agent, a wavelength dispersion adjusting agent, an antistatic agent, a release agent, etc. can.
  • a retardation (also referred to as “retardation”) developing agent may be included.
  • the retardation developing agent can be contained, for example, in a proportion of 0.5 to 10% by mass, and more preferably in a proportion of 2 to 6% by mass.
  • the type of retardation developing agent is not particularly defined, but examples thereof include those made of rod-like or discotic compounds.
  • the rod-like or discotic compound a compound having at least two aromatic rings can be preferably used as a retardation developing agent.
  • the addition amount of the retardation developing agent composed of a rod-shaped compound is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer component containing the cellulose ester, and 2 to 6 parts by mass. Is more preferable.
  • the discotic retardation developing agent is preferably used in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer component containing the cellulose ester, and in the range of 1 to 8 parts by mass. It is more preferable to use in the range of 2 to 6 parts by mass.
  • Two or more kinds of retardation developing agents may be used in combination.
  • the retardation developing agent preferably has maximum absorption in the wavelength region of 250 to 400 nm, and preferably has substantially no absorption in the visible region.
  • the discotic compound will be described.
  • As the discotic compound a compound having at least two aromatic rings can be used.
  • aromatic ring includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring.
  • the aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring).
  • the aromatic heterocycle is generally an unsaturated heterocycle.
  • the aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring.
  • Aromatic heterocycles generally have the most double bonds.
  • a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable.
  • aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring , Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring.
  • aromatic ring a benzene ring, a condensed benzene ring and biphenyls are preferable.
  • 1,3,5-triazine ring is preferably used.
  • compounds disclosed in JP-A No. 2001-166144 are preferably used.
  • the number of carbon atoms of the aromatic ring contained in the retardation developing agent is preferably 2-20, more preferably 2-12, and further preferably 2-8. Most preferably.
  • the ⁇ / 4 retardation film and the polarizing plate protective film according to the present invention can also contain an ultraviolet absorber.
  • the ultraviolet absorber is intended to improve durability by absorbing ultraviolet light having a wavelength of 400 nm or less, and the transmittance at a wavelength of 370 nm is particularly preferably 10% or less, more preferably 5% or less. Preferably it is 2% or less.
  • the ultraviolet absorber is contained in the ⁇ / 4 retardation film according to the present invention, the dimensional change caused by the cellulose ester molecule cutting due to the ultraviolet property can be suppressed.
  • permeability in wavelength 370nm of the polarizing plate protective film of this invention is used preferably from a viewpoint of reducing the dimensional change of (lambda) / 4 phase difference film at the time of outdoor use.
  • the ultraviolet absorber is not particularly limited, and examples thereof include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders, and the like. It is done.
  • the UV absorbers preferably used in the present invention are benzotriazole UV absorbers, benzophenone UV absorbers, and triazine UV absorbers, particularly preferably benzotriazole UV absorbers and benzophenone UV absorbers. .
  • a discotic compound such as a compound having a 1,3,5-triazine ring is also preferably used as the ultraviolet absorber.
  • the cellulose ester solution used preferably contains two or more ultraviolet absorbers.
  • a polymer UV absorber can also be preferably used, and in particular, a polymer type UV absorber described in JP-A-6-148430 is preferably used.
  • the method of adding the UV absorber can be added to the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol or butanol, an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane or a mixed solvent thereof. Or you may add directly in dope composition.
  • an alcohol such as methanol, ethanol or butanol
  • an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane or a mixed solvent thereof.
  • inorganic powders that do not dissolve in organic solvents use a dissolver or sand mill in the organic solvent and cellulose ester to disperse them before adding them to the dope.
  • the amount of UV absorber used is not uniform depending on the type of UV absorber, usage conditions, etc., but when the dry film thickness of the ⁇ / 4 retardation film and the polarizing plate protective film is 30 to 200 ⁇ m, ⁇ / 4 0.5-10 mass% is preferable with respect to retardation film and polarizing plate protective film, and 0.6-4 mass% is still more preferable.
  • Antioxidants for example, delay or prevent decomposition of the ⁇ / 4 retardation film by the residual solvent amount of halogen in the ⁇ / 4 retardation film, phosphoric acid of a phosphoric acid plasticizer, or the like. Since it has a role of suppressing dimensional change over time, it is preferably contained in the ⁇ / 4 retardation film.
  • a hindered phenol compound is preferably used.
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oct Decyl-3- (3,5-di-t-butyl-4-hydroxyphenyl
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred.
  • hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.
  • the addition amount of these compounds is preferably 1 ppm to 1.0%, more preferably 10 to 1000 ppm in terms of mass ratio with respect to the total mass of the polymer (A) and the cellulose ester.
  • thermoplastic resin substrate according to the present invention may be added with fine particles as a matting agent in order to prevent scratching or deterioration of transportability when the produced film is handled. preferable.
  • examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Examples thereof include magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.
  • the average primary particle size of the fine particles is preferably 5 to 400 nm, and more preferably 10 to 300 nm. These may be mainly contained as secondary aggregates having a particle size of 0.05 to 0.3 ⁇ m, and may be contained as primary particles without being aggregated if the particles have an average particle size of 80 to 400 nm. preferable.
  • the content of these fine particles in the film is preferably 0.01 to 1% by mass, particularly preferably 0.05 to 0.5% by mass.
  • Silicon dioxide fine particles are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). it can.
  • Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.
  • the resin examples include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.
  • Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the haze of the ⁇ / 4 retardation film low.
  • the dynamic friction coefficient of at least one surface is preferably 0.2 to 1.0.
  • the polarizing plate protective film in this invention means the film which suppresses the fall of the polarizing function of a polarizer by arrange
  • a commonly used polarizer is an absorptive polarizer in which a stretched polyvinyl alcohol film is dyed with iodine. Its properties are weak as a single film, and it has weak mechanical properties such as dimensional shrinkage due to wet heat conditions, and it lacks stability over time such as fading and decreasing polarization degree due to light. have.
  • a polarizing plate protective film for example, cellulose ester film such as cellulose diacetate film, cellulose triacetate film, cellulose acetate petitate film, cellulose acetate propionate film, polyester film, polycarbonate film, polyarylate film, Polysulfone (including polyethersulfone) film, Polyester film such as polyethylene terephthalate and polyethylene naphthalate, Polyethylene film, Polypropylene film, Cellophane, Polyvinylidene chloride film, Polyvinyl alcohol film, Ethylene vinyl alcohol film, Syndiotactic polystyrene Film, polycarbonate film, cycloolefin Polymer film (Arton (manufactured by JSR), ZEONEX, ZEONOR (manufactured by ZEON CORPORATION)), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, poly Examples thereof include a methyl methacrylate
  • a cellulose ester film, a cycloolefin polymer film, a polycarbonate film, and a polysulfone (including polyethersulfone) film are preferable.
  • a cellulose ester film and a cycloolefin polymer film are produced. It is preferably used from the viewpoints of cost, transparency and the like.
  • a cellulose ester film is preferable from the viewpoint of adhesiveness.
  • These films may be films produced by melt casting film production or films produced by solution casting film production.
  • the film thickness of the base film is 10 to 200 ⁇ m, preferably 20 to 100 ⁇ m.
  • the refractive index of the polarizing plate protective film according to the present invention is n, one side of the polarizing plate protective film against light traveling through the polarizing plate protective film at a critical angle ( ⁇ ) defined by the following formula (1) It is preferable to give a phase difference of ⁇ / 4 in at least one optical path when reaching the other surface from.
  • FIG. 2 is a schematic view relating to light emission from the organic electroluminescence light emitting layer.
  • light emission occurs in a light-emitting layer having a high refractive index, and the traveling direction of the light is not limited.
  • FIG. 2A schematically shows how light emitted from the light emitting point 22 in the light emitting layer 21 enters the polarizing plate protective film 23 and travels at the interface 24 between the organic electroluminescence display device and air. (However, in FIG.
  • the light totally reflected at the critical angle ( ⁇ ) 25 returns to the organic electroluminescence element again, is guided through the element, and does not exit the display surface.
  • ⁇ critical angle
  • the polarizer Since the polarizer is provided under the polarizing plate protective film, the light in the above path is considered to be linearly polarized light. For this reason, if a phase difference of ⁇ / 4 is given to the light when passing through this path, total reflection occurs at the air interface and when it enters the polarizer again, it becomes linearly polarized light whose polarization axis is rotated by 90 ° and is absorbed by the polarizer. Is done. As a result, the waveguide is effectively suppressed, and the display quality (particularly the contrast) of the organic electroluminescence display element can be greatly improved.
  • the path of light traveling through the polarizing plate protective film at a critical angle ( ⁇ ) is a set of paths that are parallel to the side surface of the cone in three dimensions. It is preferable to give a phase difference.
  • the polarizing plate protective film have the above characteristics, it is possible to obtain an effect of making the reflectance unevenness with time, particularly the boundary of the region shown in FIG. 1C inconspicuous. This effect is obtained by suppressing light traveling at an angle close to the critical angle ( ⁇ ) from becoming stray light traveling on an optical path larger than the critical angle ( ⁇ ) due to scattering and being emitted again by changing the optical path due to scattering or the like. It is estimated that That is, it is estimated that the effect of making the boundary of the region inconspicuous can be obtained by reducing the difference in the stray light generation region due to the increase in the reflectance unevenness with time.
  • ⁇ / 4 of the polarizing plate protective film is a reference value of 1/4 with respect to the wavelength (550 nm), but in the present invention, the phase difference in a range of ⁇ 25% (105 to 175 nm) with respect to this reference value. A sufficient effect can be obtained.
  • phase difference along the path through the critical angle of the polarizing plate protective film can be obtained by calculation by measuring the incident angle dependency of an ellipsometer (for example, KOBRA-WRP (manufactured by Oji Scientific Instruments)). it can.
  • an ellipsometer for example, KOBRA-WRP (manufactured by Oji Scientific Instruments)
  • the retardation value R ( ⁇ ) observed by changing the incident angle of light to the polarizing plate protective film and the three-dimensional refractive index of the refractive index ellipsoid of the polarizing plate protective film are expressed by the following equations (6) and (7). ).
  • R ( ⁇ ) ⁇ n ( ⁇ ) ⁇ d / [1-sin 2 ⁇ / n 2 ] 1/2
  • ⁇ angle of incidence of measurement light on the film (normal direction is 0 ° with respect to the film surface)
  • nx Maximum refractive index in the film plane (refractive index in the slow axis direction)
  • ny Minimum refractive index in the film plane (refractive index in the fast axis direction)
  • n z refractive index in the film thickness direction
  • n average refractive index of the film
  • d film thickness The average refractive index n of the film is measured using an Abbe refractometer.
  • the film thickness is measured using a contact-type film thickness meter. Measure the three-dimensional refractive index (n x , n y , nz ) of the film by changing the incident angle with the ellipsometer as the reference axis (for example, in increments of 10 ° from 0 ° to 40 °). calculate.
  • the adhesive layer according to the present invention is at least one adhesive layer disposed between the polarizing plate of the liquid crystal display device and the organic electroluminescence element.
  • the storage elastic modulus at 23 ° C. of the adhesive layer is in the range of 0.1 to 10 MPa.
  • the adhesive force cannot withstand the shrinkage force of the ⁇ / 4 retardation film, and the film over time Causes peeling.
  • the storage elastic modulus of the pressure-sensitive adhesive layer to be in the range of 0.1 to 10 MPa, it is possible to simultaneously prevent uneven reflectance and film peeling over time.
  • the storage elastic modulus When the storage elastic modulus is 0.1 MPa or more, film peeling does not occur. Further, when the storage elastic modulus is set to 10 MPa or less, the unevenness in preventing reflection of external light is eliminated.
  • the thickness of the adhesive layer after curing is preferably 0.005 to 50 ⁇ m, more preferably 0.01 to 10 ⁇ m. When the thickness is 0.005 ⁇ m or more, sufficient adhesive strength can be obtained, and when the thickness is 50 ⁇ m or less, the polarizing plate does not fade during the moisture resistance test.
  • the formation of the adhesive layer may be performed directly on the organic electroluminescence element or may be performed on the polarizing plate.
  • the method for forming the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include a method of applying a pressure-sensitive adhesive solution by a general method, but a pressure-sensitive adhesive on a release film such as a polyethylene terephthalate film whose surface is coated with a release agent such as a silicone resin. After applying the liquid and forming the adhesive layer, it is preferable to attach a polarizing plate to the adhesive layer.
  • a curable pressure-sensitive adhesive that forms a high molecular weight body or a crosslinked structure by various chemical reactions after the pressure-sensitive adhesive is applied and bonded together is suitably used.
  • urethane adhesives examples include, for example, urethane adhesives, epoxy adhesives, aqueous polymer-isocyanate adhesives, curable adhesives such as thermosetting acrylic adhesives, moisture-curing urethane adhesives, polyether methacrylate types
  • curable adhesives such as thermosetting acrylic adhesives, moisture-curing urethane adhesives, polyether methacrylate types
  • anaerobic pressure-sensitive adhesives such as ester-based methacrylate type and oxidized polyether methacrylate, cyanoacrylate-based instantaneous pressure-sensitive adhesives, and acrylate-peroxide-based two-component instantaneous pressure-sensitive adhesives.
  • the above-mentioned pressure-sensitive adhesive may be a one-component type or a type in which two or more components are mixed before use.
  • the pressure-sensitive adhesive may be a solvent system using an organic solvent as a medium, or an aqueous system such as an emulsion type, a colloidal dispersion type, or an aqueous solution type that is a medium containing water as a main component. It may be a solvent type.
  • the concentration of the pressure-sensitive adhesive liquid may be appropriately determined depending on the film thickness after adhesion, the coating method, the coating conditions, and the like, and is usually 0.1 to 50% by mass.
  • the storage elastic modulus at 23 ° C. of the pressure-sensitive adhesive is a value obtained by dynamic viscoelasticity measurement, specifically, a value measured by the method described in the following storage elastic modulus measurement method.
  • the ⁇ / 4 retardation film according to the present invention is preferably a long stretched film manufactured by oblique stretching.
  • An in-plane slow axis can be provided at an arbitrary angle with respect to the extending direction of the film by obliquely stretching the long original film.
  • the “long” means a film having a length of at least about 5 times the width of the film, preferably a length of 10 times or more, and specifically wound in a roll shape. It is possible to have a length (film roll) that can be stored or transported.
  • a film can be manufactured to desired arbitrary length by manufacturing a film continuously.
  • the manufacturing method of a elongate stretched film may be made to wind up around a core once after forming a elongate film raw material, and to make it a wound body, and to supply it to the diagonally stretching process, or after film formation You may supply to the diagonal stretch process continuously from a film forming process, without winding up the long film original fabric of this. It is preferable to perform the film forming step and the oblique stretching step continuously, because the film forming conditions can be changed by feeding back the film thickness after stretching and the optical value result, and a desired long stretched film can be obtained.
  • a long stretched film having a slow axis at an angle of more than 0 ° and less than 90 ° with respect to the width direction of the film can be produced.
  • the angle with respect to the width direction of the film is an angle in the film plane. Since the slow axis is usually expressed in the stretching direction, a long stretched film having such a slow axis can be produced by stretching at an angle of more than 0 ° and less than 90 ° with respect to the film transport direction. .
  • the angle formed by the transport direction of the long stretched film and the slow axis can be arbitrarily set to a desired angle within a range of more than 0 ° and less than 90 °, more preferably 40 °. It can be set to 45 ° as a specific example.
  • the long film original fabric used for producing the long stretched film can be obtained by a known method such as a solution cast molding method, an extrusion molding method, an inflation molding method and the like.
  • the solution cast molding method is excellent in the flatness and transparency of the film, and the extrusion molding method makes it easy to reduce the retardation Rt in the thickness direction after oblique stretching, and the amount of residual volatile components is small and the film dimensions are small. It is preferable because it is excellent in stability.
  • This long film original fabric may be a single layer or a laminated film of two or more layers.
  • the laminated film can be obtained by a known method such as a coextrusion molding method, a co-casting molding method, a film lamination method, or a coating method. Of these, the coextrusion molding method and the co-casting molding method are preferable.
  • the thickness unevenness ⁇ m in the flow direction of the long film source supplied for stretching maintains the film take-up tension at the entrance of the oblique stretching tenter, which will be described later, and has optical characteristics such as orientation angle and retardation. From the viewpoint of stabilization, it is necessary to be less than 0.30 ⁇ m, preferably less than 0.25 ⁇ m, more preferably less than 0.20 ⁇ m. If the thickness unevenness ⁇ m in the flow direction of the long film original is within 0.30 ⁇ m, variations in optical properties such as retardation and orientation angle of the long stretched film will not be significant.
  • a film having a thickness gradient in the width direction may be supplied as the long film original.
  • the film thickness gradient of the long film so that the film thickness can be made the most uniform at the position where stretching has been completed can be experienced by stretching films with varying thickness gradients experimentally. Can be obtained.
  • the gradient of the thickness of the original film is adjusted so that, for example, the thickness of the end on the thick side is about 0.5 to 3% thicker than the end on the thin side. Can do.
  • the width of the long film original fabric is not particularly limited, but may be 500 to 4000 mm, preferably 1000 to 2000 mm. Further, the film thickness of the long original film is not particularly limited, but is preferably in the range of 20 to 400 ⁇ m, preferably 20 to 200 ⁇ m.
  • a film obtained by a solution cast molding method or an extrusion molding method may be stretched horizontally in the width direction or vertically stretched in the transport direction.
  • the preferable elastic modulus at the stretching temperature during oblique stretching is expressed in terms of Young's modulus and is from 0.01 MPa to 5000 MPa, more preferably from 0.1 MPa to 500 MPa. If the elastic modulus is high, the shrinkage rate during stretching and after stretching will be high, and wrinkles will be easy to disappear. If it is low, the tension applied during stretching will be small, and the strength of the part holding both side edges of the film must be increased. And the load on the tenter in the subsequent process does not increase.
  • An obliquely stretched tenter is used in order to impart an oblique orientation to an elongated long film original fabric subjected to stretching in the production method according to the present embodiment.
  • the obliquely stretched tenter used in this embodiment can freely set the orientation angle of the film by variously changing the rail pattern and the conveyance speed of the film gripper, and further, the orientation axis of the film can be set to the left and right in the film width direction. It is preferable that the film stretching apparatus be capable of uniformly orienting with high precision and controlling the film thickness and retardation with high precision.
  • FIG. 3A and FIG. 3B are schematic views of a tenter that can be stretched obliquely and is used in the method for producing a long stretched film according to the present embodiment.
  • this is an example, and the present invention is not limited to this.
  • the long film original 4 whose direction is controlled by the guide roller 12-1 on the tenter entrance side has a gripping tool (clip gripper) at the position of the outer film holding start point 8-1 and the inner film holding start point 8-2. Part).
  • a gripping tool clip gripper
  • the pair of left and right film grippers are transported and stretched at the same speed in the diagonal direction indicated by the outer film gripping means trajectory 7-1 and the inner film gripping means trajectory 7-2 by the oblique stretching tenter 6.
  • the gripping is released by the outer film gripping end point 9-1 and the inner film gripping end point 9-2, and the conveyance is controlled by the guide roller 12-2 on the tenter outlet side, whereby the obliquely stretched film 5 is formed.
  • the long film original is obliquely stretched at an angle (feeding angle ⁇ i) in the film stretching direction 14-2 with respect to the film feeding direction 14-1.
  • the traveling speed of the gripping tool can be selected as appropriate, but is usually 1 to 100 m / min.
  • the pair of left and right film grippers having the same speed means that the travel speed of the pair of left and right grippers is substantially 1% or less of the travel speed.
  • the manufacturing method of the elongate stretched film which concerns on embodiment of this invention is performed using the tenter which can be diagonally stretched.
  • This tenter is an apparatus that widens a long film original fabric in an oblique direction with respect to its traveling direction (moving direction of the middle point in the film width direction) in an environment heated by an oven.
  • the tenter includes an oven, a pair of rails on the left and right on which a gripping tool for transporting the film travels, and a number of gripping tools that travel on the rails. Both ends of the film fed out from the film roll and sequentially supplied to the entrance portion of the tenter are gripped by a gripping tool, the film is guided into the oven, and the film is released from the gripping tool at the exit portion of the tenter.
  • the film released from the gripping tool is wound around the core.
  • Each of the pair of rails has an endless continuous track, and the gripping tool which has released the grip of the film at the exit portion of the tenter travels outside and is sequentially returned
  • the rail shape of the tenter becomes an asymmetrical shape or a left-right symmetric shape depending on the orientation angle ⁇ , the stretching ratio, etc. given to the long stretched film to be manufactured. It can be fine-tuned manually or automatically.
  • a long thermoplastic resin film is stretched, and the orientation angle ⁇ can be set to an arbitrary angle within a range of preferably 10 ° to 80 ° with respect to the winding direction after stretching. ing.
  • the traveling speed difference between the left and right gripping tools is appropriately selected according to the tenter stretching method.
  • the positions of the rail portions and the rail connecting portions can be set freely. Accordingly, the oblique stretch tenter can be set to a draw ratio according to an arbitrary entrance width and exit width (the circled portion in FIG. 3 below is an example of a connecting portion).
  • the draw ratio means the tenter relative to the distance between both ends of the unstretched film fixed by the gripping tool at the entrance of the tenter stretching machine (distance between 8-1 and 8-2 in FIG. 3A or FIG. 3B, respectively). This is the ratio value of the distance between both ends of the stretched film fixed by the gripping tool at the exit of the stretching machine (distance between 11-1 and 11-2 in FIG. 3A or FIG. 3B).
  • the traveling direction 14-1 at the tenter entrance of the long film original is different from the traveling direction at the tenter exit side of the stretched film.
  • the feeding angle ⁇ i is an angle formed by the traveling direction 14-1 at the tenter inlet and the stretching direction 14-2 of the stretched film.
  • the traveling direction 14-1 at the tenter entrance of the long film is changed to a direction different from the traveling direction at the entrance of the tenter at the feeding angle ⁇ i. Is done. Thereafter, the transport direction is further changed, and finally, a trajectory that matches the traveling direction on the tenter exit side of the stretched film is taken.
  • the feeding angle ⁇ i is 10 ° ⁇ i ⁇ 60 °, preferably 15 ° ⁇ i ⁇ 50 °. Set by. By setting the feeding angle ⁇ i in the above range, the variation in the optical characteristics in the width direction of the obtained film becomes good (smaller).
  • the left and right gripping tools of the tenter are configured to travel at a constant speed while maintaining a certain distance from the front and rear gripping tools.
  • the film traveling in the oblique stretching tenter passes through an oven divided into a preheating zone, a lateral stretching zone, an oblique stretching zone, a holding zone, a cooling zone and the like in the tenter according to the rail pattern on which the film travels.
  • only a part of the above zones is used, or any zone among the above zones is used several times. Or you may.
  • Preheating zone / oblique stretching zone / holding zone / cooling zone Preheating zone / lateral stretching zone / oblique stretching zone / holding zone / cooling zone
  • Preheating zone / oblique stretching zone / lateral stretching zone / holding zone / cooling zone Preheating zone / lateral stretching zone 1 / oblique stretching zone / transverse stretching zone 2 / holding zone / cooling zone preheating zone / transverse stretching zone 1 / oblique stretching zone 1 / transverse stretching zone 2 / oblique stretching zone 2 / holding zone / cooling zone
  • In the entrance it refers to a section where the gripping tool that grips both ends of the film travels while maintaining a constant spacing.
  • the transverse stretching zone refers to a section where the gap between the gripping tools that grip both ends of the film starts to reach a predetermined interval.
  • the opening angle of the rail on which the gripping tools at both ends run may be opened at the same angle for both rails, or may be opened at different angles.
  • the diagonally stretched zone refers to a gripping tool that grips both ends of the film, while the gripping tool spacing is kept constant or spreads, and then both gripping tools travel on the straight rail again after starting to run on the bending rail. Refers to the section until the beginning.
  • the holding zone refers to a section in which the gripping tools at both ends travel while being parallel to each other during a period in which the interval between the gripping tools after the transverse stretching zone or the oblique stretching zone becomes constant again.
  • the cooling zone refers to a section where the temperature in the zone is set to the glass transition temperature Tg ° C. or lower of the thermoplastic resin constituting the film in the section after the holding zone.
  • a rail pattern that narrows the gap between the opposing grippers in advance may be used.
  • the temperature of each zone is set to Tg to Tg + 30 ° C in the preheating zone, Tg to Tg + 30 ° C in the preheating zone, and Tg-30 to Tg ° C in the cooling zone with respect to the glass transition temperature Tg of the thermoplastic resin. It is preferable to do.
  • a temperature difference may be given in the width direction in the stretching zone.
  • a method of adjusting the opening degree of the nozzle for sending warm air into the temperature-controlled room so as to make a difference in the width direction, or controlling the heating by arranging the heaters in the width direction is known. Can be used.
  • ⁇ Circularly polarizing plate> In the circularly polarizing plate of the present invention, a polarizing plate protective film, a polarizer, a ⁇ / 4 retardation film, and an adhesive layer are laminated in this order.
  • the slow axis of the ⁇ / 4 retardation film and the absorption of the polarizer The angle formed with the axis is 45 °.
  • a long polarizing plate protective film, a long polarizer, and a long ⁇ / 4 retardation film (stretched film) are preferably laminated in this order.
  • the circularly polarizing plate according to the present invention is manufactured by using a stretched polyvinyl alcohol doped with iodine or a dichroic dye as a polarizer, and laminating with a configuration of ⁇ / 4 retardation film / polarizer. be able to.
  • the film thickness of the polarizer is 5 to 40 ⁇ m, preferably 5 to 30 ⁇ m, and particularly preferably 5 to 20 ⁇ m.
  • the circularly polarizing plate can be produced by a general method similar to the polarizing plate.
  • the ⁇ / 4 retardation film subjected to the alkali saponification treatment is preferably bonded to one surface of a polarizer prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution.
  • the circularly polarizing plate can be configured by further bonding a release film on the opposite surface of the polarizing plate protective film of the circularly polarizing plate.
  • the protective film and the release film are used for the purpose of protecting the circularly polarizing plate at the time of shipping the circularly polarizing plate and at the time of product inspection.
  • FIG. 4 is a schematic view showing an example of a cross-sectional view of the configuration of the organic electroluminescence display device of the present invention, but is not limited thereto.
  • a polarizer is formed on an organic electroluminescent element having a metal electrode 102, a light emitting layer 103, a transparent electrode (ITO) 104, and a sealing layer 105 in this order on a substrate 101 made of glass, polyimide, or the like, with an adhesive layer 106 interposed therebetween.
  • An organic electroluminescence display device is configured by providing a circularly polarizing plate in which 108 is sandwiched between a ⁇ / 4 retardation film 107 and a polarizing plate protective film 109.
  • the polarizing plate protective film 109 is preferably laminated with a cured layer.
  • the cured layer not only prevents scratches on the surface of the organic electroluminescence display device but also has an effect of preventing warpage due to the circularly polarizing plate. Further, an antireflection layer may be provided on the cured layer.
  • the thickness of the organic electroluminescence element itself is about 1 ⁇ m.
  • the light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative and the like and a light emitting layer made of a fluorescent organic solid such as anthracene, or Structures with various combinations, such as a laminate of such a light-emitting layer and an electron injection layer composed of a perylene derivative, and / or a laminate of these hole injection layer, light-emitting layer, and electron injection layer, are known. ing.
  • holes and electrons are injected into the light-emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by recombination of these holes and electrons excites the fluorescent material. Then, light is emitted on the principle that the excited fluorescent material emits light when returning to the ground state.
  • the mechanism of recombination in the middle is the same as that of a general diode, and as can be predicted from this, the current and the emission intensity show strong nonlinearity with rectification with respect to the applied voltage.
  • an organic electroluminescence display device in order to extract light emitted from the light emitting layer, at least one of the electrodes must be transparent, and a transparent electrode usually formed of a transparent conductor such as indium tin oxide (ITO) is used as an anode. It is used as.
  • ITO indium tin oxide
  • metal electrodes such as Mg—Ag and Al—Li are used.
  • the light emitting layer is formed of a very thin film having a thickness of about 10 nm. For this reason, the light emitting layer transmits light almost completely like the transparent electrode. As a result, the light that is incident from the surface of the transparent substrate when not emitting light, passes through the transparent electrode and the light emitting layer, and is reflected by the metal electrode again exits to the surface side of the transparent substrate.
  • the display surface of the electroluminescence display device looks like a mirror surface.
  • the circularly polarizing plate for an organic electroluminescence display device of the present invention is suitable for a display device for organic electroluminescence in which such external light reflection is particularly problematic.
  • Example 1> ⁇ Production of ⁇ / 4 retardation film> (Preparation of long film stock) A dope having the following ⁇ dope composition> was prepared as a cellulose ester resin.
  • Fine particles (Aerosil R812 manufactured by Nippon Aerosil Co., Ltd.) 11 parts by mass Ethanol 89 parts by mass The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.
  • Fine particle additive liquid 1 The fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.
  • the inside of the Kolben was depressurized to 4 ⁇ 10 2 Pa or less, and after excess pyridine was distilled off at 60 ° C., the inside of the Kolben was depressurized to 1.3 ⁇ 10 Pa or less and the temperature was raised to 120 ° C. Most of the acid and benzoic acid formed were distilled off. Finally, 100 g of water was added to the collected toluene layer, and after washing with water at room temperature for 30 minutes, the toluene layer was collected, and toluene was distilled off under reduced pressure (4 ⁇ 10 2 Pa or less) at 60 ° C. An ester compound A was obtained. The average degree of substitution was 7.3, and the octanol / water partition coefficient (log P value) was 12.43.
  • Polyester B used was prepared by the following method.
  • polyester B (Preparation of polyester B) In a nitrogen atmosphere, 4.85 g of dimethyl terephthalate, 4.4 g of 1,2-propylene glycol, 6.8 g of p-toluic acid, and 10 mg of tetraisopropyl titanate were mixed and stirred at 140 ° C. for 2 hours. Stirring was carried out at ° C for 16 hours. Next, the temperature was lowered to 170 ° C., and unreacted 1,2-propylene glycol was distilled off under reduced pressure to obtain polyester B.
  • Polyester B has a toluic acid ester at the end because monocarboxylic acid is used in an amount twice as much as that of dicarboxylic acid.
  • the above was put into a sealed container and dissolved with stirring to prepare a dope.
  • the dope was cast uniformly on a stainless steel belt support at a temperature of 33 ° C. and a width of 2000 mm.
  • the temperature of the stainless steel belt was controlled at 30 ° C.
  • the solvent was evaporated until the amount of residual solvent in the cast (cast) film reached 75%, and then peeled off from the stainless steel belt support with a peeling tension of 110 N / m.
  • the peeled cellulose ester film was stretched 1.01 times in the width direction using a tenter while applying heat at 160 ° C.
  • the residual solvent at the start of stretching was 15%.
  • drying was completed while the drying zone was conveyed by a number of rollers.
  • the drying temperature was 130 ° C. and the transport tension was 100 N / m.
  • a zone combination of the oblique stretching tenter at this time a combination including a preheating zone, a lateral stretching zone, an oblique stretching zone, a holding zone, and a cooling zone was used.
  • the distance between the main shaft of the guide roller 12-1 on the tenter entrance side closest to the entrance of the obliquely stretched tenter and the grip start points (clip gripping portions) 8-1 and 8-2 of the obliquely stretched tenter is 1500 mm.
  • the long film original fabric was cut into this width and used.
  • a clip with a length of 2 inches in the conveyance direction was used, and a guide roller with a diameter of 10 cm was used.
  • the preheating zone temperature was 190 ° C
  • the transverse stretching zone temperature was 180 ° C
  • the oblique stretching zone temperature was 175 ° C
  • the holding zone temperature was 175 ° C
  • the cooling zone temperature was 110 ° C.
  • the take-up tension at the tenter outlet was 200 N / m.
  • the stretching ratio R at this time was stretched to 1.95 times.
  • the film was stretched to 1.3 times in the transverse stretching zone and 1.5 times in the oblique stretching zone.
  • the film was stretched in an oblique direction so that the orientation angle ⁇ was 45 °.
  • the stretched film is controlled so that the fluctuation in the take-up tension is less than 3% by performing feedback control that reflects the change in the tension measured by the guide roller 12-2 on the outlet side of the oblique stretch tenter on the take-up motor rotation speed. did.
  • the film is trimmed at both ends, the transport direction is changed by a transport direction change device composed of an airflow roller, the roll is wound by a slidable winding device, and a roll-like long stretched film having a thickness of 80 ⁇ m and a width of 2000 mm is obtained. Obtained.
  • the film moving speed during heating and stretching was 5 m / min.
  • the film was stretched using a heating device for controlling the temperature in the width direction of the film.
  • the heating device controlled the temperature so that the thickness of the film in the film width direction after stretching was approximately the same as the thickness direction film thickness distribution before stretching.
  • the obtained long ⁇ / 4 retardation film was uniform in the longitudinal direction of the film.
  • the slow axis of the ⁇ / 4 retardation film was an angle of 45 ° with respect to the longitudinal direction of the film.
  • copolymer solutions 2 and 3 were obtained with the monomer compositions shown in Table 1.
  • Mw weight average molecular weight
  • GPC GEL Permeation
  • the coating film obtained by drying the copolymer at room temperature was dissolved in tetrahydrofuran and measured with a high performance liquid chromatograph (manufactured by Shimadzu Corporation, LC-10ADvp, column KF-G + KF-806 ⁇ 2).
  • the weight average molecular weight (Mw) in terms of polystyrene was determined.
  • a polarizing plate protective film (KC4UY, manufactured by Konica Minolta Advanced Layer Co., Ltd.) was bonded to the surface of the polarizing film where the circularly polarizing plate was not adhered, and then a polyethylene terephthalate film (thickness: 38 ⁇ m) subjected to a release treatment With a pressure-sensitive adhesive layer comprising a polarizing plate protective film, a polarizer, a ⁇ / 4 retardation film, and a pressure-sensitive adhesive layer after curing for 7 days in an atmosphere of 23 ° C. and 50% RH with the pressure-sensitive adhesive layer protected. A circularly polarizing plate 1 was produced.
  • Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd.
  • Polyisocyanate aluminum chelate A manufactured by Kawaken Fine Chemical Co., Ltd.
  • Aluminum trisacetylacetonate aluminum chelate D aluminum monoacetylacetate bis (ethylacetoacetate)
  • JERRY4000 biphenyl type epoxy resin (epoxy equivalent 186, Mw354)
  • JER806 Bisphenol F type epoxy resin (epoxy equivalent 165, Mw 350)
  • KBM-803 Shin-Etsu Chemical Co., Ltd.
  • ⁇ -mercaptopropylmethyldimethoxysilane X-41-1810 Shin-Etsu Chemical Co., Ltd.
  • methyl mercapto-based alkoxy oligomer KBM-403 Shin-Etsu Chemical Co., Ltd. 3-gly Sidoxypropyltriethoxysilane ⁇ Preparation of circularly polarizing plate 4 with adhesive layer> (Preparation of acrylic polymer)
  • 100 parts by mass of butyl acrylate, 5 parts by mass of acrylic acid and 0.075 parts by mass of 2-hydroxyethyl acrylate, 2 as a polymerization initiator , 2'-Azobisisobutyronitrile (0.2 parts by mass) and ethyl acetate (200 parts by mass) as a polymerization solvent were charged.
  • the liquid temperature in the flask was kept at around 55 ° C while stirring under a nitrogen stream.
  • the acrylic polymer solution was prepared by carrying out the polymerization reaction for 10 hours.
  • the acrylic polymer had a weight average molecular weight of 2,200,000.
  • the acrylic pressure-sensitive adhesive solution is applied onto a separator of a polyethylene terephthalate film (thickness: 38 ⁇ m) that has been subjected to a release treatment, and heated at 155 ° C. for 1 minute to form a pressure-sensitive adhesive layer having a thickness of 22 ⁇ m after drying. Formed.
  • a circularly polarizing plate comprising a polarizing plate protective film (KC4UY, manufactured by Konica Minolta Advanced Layer), a polarizer, and a ⁇ / 4 retardation film was produced,
  • a circularly polarizing plate 4 with an adhesive layer was prepared using the above adhesive layer on the ⁇ / 4 retardation film side of the polarizing plate.
  • ⁇ Preparation of circularly polarizing plate 5 with adhesive layer> (Preparation of adhesive layer)
  • a circularly polarizing plate comprising a polarizing plate protective film (KC4UY, manufactured by Konica Minolta Advanced Layer), a polarizer, and a ⁇ / 4 retardation film was produced, Using the above adhesive layer on the ⁇ / 4 retardation film side of the polarizing plate, a circularly polarizing plate 5 with an adhesive layer was produced.
  • a polarizing plate protective film (KC4UY, manufactured by Konica Minolta Advanced Layer)
  • a polarizer a ⁇ / 4 retardation film
  • the acrylic pressure-sensitive adhesive solution is applied onto a separator of a polyethylene terephthalate film (thickness: 38 ⁇ m) that has been subjected to a release treatment, and heated at 155 ° C. for 1 minute to form a pressure-sensitive adhesive layer having a thickness of 22 ⁇ m after drying. Formed.
  • the acrylic pressure-sensitive adhesive solution is applied onto a separator of a polyethylene terephthalate film (thickness: 38 ⁇ m) that has been subjected to a release treatment, and heated at 155 ° C. for 1 minute to form a pressure-sensitive adhesive layer having a thickness of 22 ⁇ m after drying. Formed.
  • a reflective electrode made of chromium having a thickness of 80 nm is formed on a glass substrate by sputtering, ITO is formed on the reflective electrode as an anode by sputtering to a thickness of 40 nm, and a poly (3,4-layer) is formed on the anode as a hole transport layer.
  • a light-emitting layer for each of RGB was formed to a thickness of 100 nm using ethylenedioxythiophene) -polystyrene sulfonate (PEDOT: PSS) with a thickness of 80 nm by a sputtering method and a shadow mask on the hole transport layer.
  • red light emitting layer tris (8-hydroxyquinolinate) aluminum (Alq 3 ) as a host and a light emitting compound [4- (dicyanomethylene) -2-methyl-6 (p-dimethylaminostyryl) -4H-pyran] (DCM ) Were co-evaporated (mass ratio 99: 1) to form a thickness of 100 nm.
  • Alq 3 as a host and the light emitting compound coumarin 6 were co-deposited (mass ratio 99: 1) to form a thickness of 100 nm.
  • the blue light-emitting layer was formed with a thickness of 100 nm by co-evaporating BAlq and a light-emitting compound Perylene as a host (mass ratio 90:10).
  • calcium is deposited to a thickness of 4 nm by vacuum deposition as a first cathode having a low work function so that electrons can be efficiently injected onto the light emitting layer, and a second cathode is formed on the first cathode.
  • Aluminum was deposited to a thickness of 2 nm.
  • the aluminum used as the second cathode has a role to prevent calcium as the first cathode from being chemically altered when the transparent electrode formed thereon is formed by sputtering.
  • an organic light emitting layer was obtained.
  • a transparent conductive film was formed to a thickness of 80 nm on the cathode by sputtering.
  • ITO was used as the transparent conductive film.
  • an insulating film was formed by depositing 200 nm of silicon nitride on the transparent conductive film by a CVD method.
  • the organic electroluminescence display device was prepared by fixing the circularly polarizing plates 1 to 7 with the adhesive layer to the insulating film of the organic electroluminescence display device obtained above.
  • Table 4 summarizes the evaluation results of the circularly polarizing plates 1 to 7 with the adhesive layer and the organic electroluminescence display device using these (hereinafter referred to as the organic EL display device).
  • the storage elastic modulus was measured by peeling the separator of each circularly polarizing plate with an adhesive layer, and measuring the adhesive layer with ARES (viscoelastic spectrometer, manufactured by Rheometallic Scientific).
  • Deformation mode Torsion measurement frequency: Constant frequency 1 Hz
  • Temperature increase rate 5 ° C / min
  • Measurement temperature From near the glass transition temperature (Tg) of the polymer to 200 ° C.
  • Measurement shape Parallel plate 7.9 mm ⁇ Sample thickness: about 1.8mm (initial stage)
  • the storage elastic modulus (G ′) at 23 ° C. was read.
  • the manufactured organic electroluminescence display device with a circularly polarizing plate was subjected to a durability test of 300 h and 500 h in a high-temperature and high-humidity bath at 90 ° C.
  • the organic electroluminescence display device is placed in an environment where no voltage is applied and no light is emitted, and is placed in an environment of 23 ° C. and 55% RH, and an illuminance of about 100 lx.
  • the unevenness was evaluated. (Double-circle): It does not generate
  • ⁇ Not generated by treatment at 90 ° C. for 300 hours.
  • X Occurs during treatment at 90 ° C for 300 hours.
  • the sample of the present invention is more excellent in the occurrence of unevenness in reflectance over time than the comparative sample, and at the same time, the organic electroluminescence display device is excellent in display quality with no film peeling. Met.
  • the above acetic acid-containing pulp was put into a reactor, and further 500 parts by mass of acetic anhydride and 12 parts by mass of sulfuric acid were added to the reactor, the temperature was gradually increased from room temperature to 40 ° C., and kept at 40 ° C. for 1 hour, The esterification reaction was allowed to proceed.
  • hydrophilic silica particles having an average particle size of 30 ⁇ m having a hydrophilic group were added to the dope and stirred for 5 minutes, and then the acetic acid dope was filtered with a glass filter in a filtration step.
  • the cellulose acylate precipitated in the precipitation step is separated by filtration, washed 5 times with hot water at 50 ° C., and the remaining acetic acid aqueous solution is eluted, followed by drying at 70 ° C. for 3 hours.
  • 89 triacetyl cellulose having a total acyl group substitution degree of 2.89 was obtained.
  • the weight average molecular weight (Mw) was 190000 as a result of measurement using the following measurement method.
  • the number average molecular weight (Mn) was 76000.
  • polarizing plate protective film (Silicon dioxide dispersion) Aerosil R812 (Nippon Aerosil Co., Ltd.) 10 parts by mass Ethanol 90 parts by mass The above was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion with stirring, and the mixture was stirred and mixed with a dissolver for 30 minutes to prepare a silicon dioxide dispersion dilution. The mixture was filtered with a fine particle dispersion dilution filter (Advantech Toyo Co., Ltd .: polypropylene wind cartridge filter TCW-PPS-1N).
  • a fine particle dispersion dilution filter Advancedtech Toyo Co., Ltd .: polypropylene wind cartridge filter TCW-PPS-1N).
  • PEI general formula
  • the dope B was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. in the film production line.
  • In-line additive solution line was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd.
  • the peeled cellulose ester web was evaporated at 35 ° C., slit to 1950 mm width, and then dried at a drying temperature of 135 ° C. while stretching 1.05 times in the width direction with a tenter. At this time, the residual solvent amount when starting stretching with a tenter was 20%.
  • drying is completed while transporting the drying zone at 120 ° C. and 110 ° C. with a large number of rollers, slitting to a width of 2000 mm, a knurling process with a width of 15 mm and an average height of 10 ⁇ m is applied to both ends of the film, and an initial winding tension of 220 N / M and a final tension of 110 N / m were wound around a 6-inch inner diameter core to obtain a polarizing plate protective film 12.
  • the draw ratio in the conveying direction immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.07.
  • the residual solvent amount of the polarizing plate protective film 12 was 0.02%, the dry film thickness was 40 ⁇ m, the width was 2000 mm, and the winding length was 4000 m.
  • drying was completed while the drying zone was conveyed by a number of rollers.
  • the drying temperature was 130 ° C. and the transport tension was 100 N / m.
  • a polarizing plate protective film 13 having a residual solvent of 0.02%, a dry film thickness of 40 ⁇ m, a width of 2000 mm, and a winding length of 6000 m was obtained.
  • ⁇ Preparation of Polarizing Plate Protective Film 14: Ro, Rt 160, 40)> Using the dope of composition A of Example 1, a cellulose ester film was produced in the same manner as the production of the long film original fabric (cellulose ester film). Preparation of polarizing plate protective film 13 except that the peeled cellulose ester film was stretched 1.80 times in the width direction using a biaxial tenter while applying heat at 180 ° C., and the transport direction was contracted 0.90 times. In the same manner as above, a polarizing plate protective film 14 having a residual solvent of 0.01%, a dry film thickness of 40 ⁇ m, a width of 2000 mm, and a winding length of 6000 m was obtained.
  • a cellulose ester film was produced in the same manner as the production of the long film original fabric (cellulose ester film).
  • Preparation of polarizing plate protective film except that the peeled cellulose ester film was stretched 1.65 times in the width direction using a biaxial tenter while applying heat at 180 ° C., and the conveying direction was contracted 0.92 times.
  • a polarizing plate protective film 15 having a residual solvent of 0.02%, a dry film thickness of 40 ⁇ m, a width of 2000 mm, and a winding length of 6000 m was obtained.
  • the peeled cellulose ester film was subjected to a residual solvent of 0.02% in the same manner as in the production of the polarizing plate protective film 13 except that it was stretched 1.01 times in the width direction using a biaxial tenter while applying heat at 160 ° C.
  • a polarizing plate protective film 16 having a dry film thickness of 40 ⁇ m, a width of 2000 mm, and a winding length of 6000 m was obtained.
  • Regions A region and B region divided into left and right were set with the organic electroluminescence display device as a boundary line in the vertical direction. With one of the divided areas (A area) turned on with white 200 cd (waveguide is generated), the contrast of the central part of the B area was measured with CS-2000 (manufactured by Konica Minolta Sensing). The organic electroluminescence display device using the polarizing plate protective film 11 was used as a reference, and the evaluation was performed using the contrast increase rate.
  • Table 5 summarizes the results.
  • an organic electroluminescence display device is abbreviated as an organic EL display device.
  • R (90 °) represents a phase difference value when incident at a critical angle obtained by calculation from the angular dependence of retardation.
  • the vertical tilt with respect to the slow axis and the vertical tilt with respect to the fast axis mean that the slow axis is tilted about the rotation axis and the fast axis is tilted about the fast axis.
  • the polarizing plate protective films 13 to 16 that give a phase difference of ⁇ / 4 with respect to the light traveling at the critical angle even in the sample of the present invention have a low external light reflectance.
  • the organic electroluminescence display device was excellent in contrast and display quality.
  • Whether or not to give a phase difference of ⁇ / 4 to light traveling at a critical angle depends on whether or not the polarizing plate protective film is 90 ° with the in-plane fast axis and slow axis as the rotation axis. This can be determined based on the two phase difference values R (90 °) given to the light when tilted. Specifically, it can be determined whether or not ⁇ / 4 is included in the range where the numerical values of the two phase difference values R (90 °) are the upper limit and the lower limit. When it did not enter, it was shown by x.
  • an upper limit and a lower limit of 0.0 are defined from two phase difference values R (90 °), and the phase difference value that the sample gives to light traveling at a critical angle is 0. Since the value is any value from 0 to 0.0, a phase difference of ⁇ / 4 (wavelength 137.5 nm corresponding to ⁇ / 4 of 550 nm) is given to light traveling at any critical angle. do not do.
  • Sample 12 is similar to sample 11.
  • the phase difference value given to the light traveling at the critical angle is any one of the range of 139.2 to ⁇ 32.4. A phase difference of ⁇ / 4 is achieved.
  • Samples 14 and 15 are similar to sample 13.
  • the visual evaluation with respect to the boundary of the unevenness observed after the 500 h treatment was in the same order as the contrast evaluation.
  • Example 3 After the roll-like long stretched film described in Example 1 was prepared, it was annealed under the conditions shown in Table 6 by passing through a tenter device, and long stretched films ( ⁇ / 4 retardation films) 21 to 23 Got.
  • the draw ratio is a draw ratio when the winding roll width is used as a reference, the temperature represents the set temperature of the tenter, and the time represents the time for passing through the tenter.
  • the dimensional change of the circularly polarizing plate is 100 ⁇ ((size after treatment) ⁇ (size before treatment)) / (size before treatment), and is expressed as a dimensional change rate (%).
  • the dimensional change rate was measured with respect to the slow axis direction by treating at 90 ° C. for 300 hours (hours) and 500 hours using a high-temperature thermostatic chamber and then allowing to cool.
  • Example 4 Production of (Long Stretched Film)
  • the overall stretch ratio R is 1.95 times without changing the ratio of the stretch ratio of the transverse stretch and the oblique stretch.
  • the film was stretched while being changed to 2.0 times and 2.1 times to obtain precursors of roll-shaped long stretched films 31, 32, and 33 having a width of 2000 mm.
  • the long stretched film precursors 31, 31, 33 were annealed under the same conditions as the samples 21, 22, 23 described in Example 3 to obtain long stretched films 31, 32, 33.
  • the long film original for producing the long stretched films 31 to 33 those having different thicknesses were used so that the film thickness of the roll-like long stretched film was 80 ⁇ m.
  • a circularly polarizing plate with an adhesive layer corresponding to each of the long stretched films 31 to 33 and an organic electroluminescence display device using the same were prepared in the same manner as in Example 3.
  • the circularly polarizing plate with the pressure-sensitive adhesive layer of the present invention is excellent in preventing uneven reflectance and film peeling over time of an organic electroluminescence display device, and is an organic electroluminescent display device having the circularly polarizing plate with the pressure-sensitive adhesive layer. Preferably used.

Abstract

La présente invention a pour objet une plaque de polarisation circulaire permettant une électroluminescence organique et pourvue d'une couche adhésive. Ladite plaque prévient nettement mieux une séparation d'un film et une irrégularité de la réflectance au fil du temps dans un dispositif d'affichage à électroluminescence organique. La présente invention a également pour objet un dispositif d'affichage à électroluminescence organique équipé de la plaque de polarisation circulaire permettant une électroluminescence organique et pourvue d'une couche adhésive. Une telle plaque est d'un type dans lequel un film de protection de plaque de polarisation, un polariseur, un film à différence de phase de λ/4 et une couche adhésive sont stratifiés dans cet ordre. L'angle entre l'axe lent du film à différence de phase de λ/4 et l'axe d'absorption du polariseur est de 45°. La plaque de polarisation d'après la présente invention est caractérisée en ce que le film à différence de phase de λ/4 contient une résine d'ester de cellulose et en ce que le module de conservation de la couche adhésive se situe dans la plage de 0,1 à 10 MPa.
PCT/JP2012/077678 2011-10-31 2012-10-26 Plaque de polarisation circulaire permettant une électroluminescence organique et pourvue d'une couche adhésive, et dispositif d'affichage à électroluminescence organique équipé d'une telle plaque WO2013065587A1 (fr)

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JP2013541746A JP6123676B2 (ja) 2011-10-31 2012-10-26 円偏光板を具備する有機エレクトロルミネッセンス表示装置
KR1020147011125A KR101630101B1 (ko) 2011-10-31 2012-10-26 점착층 부착 유기 일렉트로루미네센스용 원편광판, 그것을 구비하는 유기 일렉트로루미네센스 표시 장치

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014029787A (ja) * 2012-07-31 2014-02-13 Nitto Denko Corp 表示装置およびその製造方法
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
JP2016218482A (ja) * 2016-09-20 2016-12-22 三菱樹脂株式会社 光学部材
WO2017104308A1 (fr) * 2015-12-14 2017-06-22 コニカミノルタ株式会社 Plaque polarisante et dispositif d'affichage d'image comprenant ladite plaque polarisante
JP2018159929A (ja) * 2018-05-08 2018-10-11 三菱ケミカル株式会社 光学部材
CN110959307A (zh) * 2017-07-26 2020-04-03 富士胶片株式会社 有机电致发光显示装置
JPWO2021124803A1 (fr) * 2019-12-17 2021-06-24
WO2022153785A1 (fr) * 2021-01-15 2022-07-21 コニカミノルタ株式会社 Rouleau de film et procédé de fabrication de rouleau de film
JP7361849B1 (ja) * 2022-07-29 2023-10-16 住友化学株式会社 偏光板及び画像表示装置
WO2024019176A1 (fr) * 2022-07-22 2024-01-25 ダイキン工業株式会社 Film fluoropolymère long, stratifié revêtu de métal et carte de circuit imprimé

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CN110959307A (zh) * 2017-07-26 2020-04-03 富士胶片株式会社 有机电致发光显示装置
JP2018159929A (ja) * 2018-05-08 2018-10-11 三菱ケミカル株式会社 光学部材
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JP7271721B2 (ja) 2019-12-17 2023-05-11 富士フイルム株式会社 有機エレクトロルミネッセンス表示装置
WO2022153785A1 (fr) * 2021-01-15 2022-07-21 コニカミノルタ株式会社 Rouleau de film et procédé de fabrication de rouleau de film
WO2024019176A1 (fr) * 2022-07-22 2024-01-25 ダイキン工業株式会社 Film fluoropolymère long, stratifié revêtu de métal et carte de circuit imprimé
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JP7361849B1 (ja) * 2022-07-29 2023-10-16 住友化学株式会社 偏光板及び画像表示装置

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