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WO2013031356A1 - Dispositif d'affichage à éléments organiques à électroluminescence, plaque de polarisation circulaire, et plaque allongée λ/4 - Google Patents

Dispositif d'affichage à éléments organiques à électroluminescence, plaque de polarisation circulaire, et plaque allongée λ/4 Download PDF

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Publication number
WO2013031356A1
WO2013031356A1 PCT/JP2012/066202 JP2012066202W WO2013031356A1 WO 2013031356 A1 WO2013031356 A1 WO 2013031356A1 JP 2012066202 W JP2012066202 W JP 2012066202W WO 2013031356 A1 WO2013031356 A1 WO 2013031356A1
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group
acid
formula
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substituent
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Japanese (ja)
Inventor
幸仁 中澤
範江 谷原
理英子 れん
田坂　公志
賢治 三島
田代　耕二
理枝 藤澤
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Konica Minolta Advanced Layers Inc
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8793—Arrangements for polarized light emission
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/10—Esters of organic acids
    • C08J2301/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/14—Mixed esters
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations

Definitions

  • the present invention relates to an organic electroluminescence display device, a circularly polarizing plate, and a long ⁇ / 4 plate.
  • organic electroluminescence element that emits light by applying a voltage to the light-emitting layer between the electrodes is a flat illumination, a light source for an optical fiber, a backlight for a liquid crystal display, and a liquid crystal projector.
  • organic EL organic electroluminescence element
  • the organic EL element is a light emitting element that has attracted much attention in recent years because it exhibits excellent characteristics in terms of luminous efficiency, low voltage driving, light weight, and low cost.
  • the organic EL element emits visible light corresponding to the light emission characteristics of the light emitting layer by injecting electrons from the cathode and holes from the anode and recombining them in the light emitting layer.
  • the anode is mainly composed of an indium-tin composite oxide (hereinafter referred to as “indium-tin composite oxide”) because it has the highest electrical conductivity among the transparent conductive materials, a relatively large work function, and high hole injection efficiency. Abbreviated as ITO).
  • 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).
  • the light emitted in the cathode direction is specularly reflected on the surface of the metal material constituting the cathode, and is taken out as emitted light from the transparent ITO electrode (anode).
  • the cathode since the cathode has a mirror surface with high light reflectivity, external light reflection is noticeable in a state where no light is emitted.
  • the reflection of indoor lighting is intense, and black color cannot be expressed in a bright place, 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 discloses that a circularly polarizing element is used to prevent reflection of external light from a mirror surface.
  • a circularly polarizing element includes an absorption linearly polarizing plate and a ⁇ / 4 wavelength plate (hereinafter also referred to as a 1 ⁇ 4 wavelength plate) so that their optical axes intersect at 45 degrees or 135 degrees. It is configured by laminating.
  • the refractive index of the stretched film is caused by wavelength dispersion that differs for each wavelength, so that the phase difference is for a certain wavelength. Although it can be exactly 1 ⁇ 4 wavelength, the phase difference is shifted from 1 ⁇ 4 wavelength at other wavelengths, so that it does not function as a ⁇ / 4 plate.
  • Patent Document 2 a retardation film in which a vertically aligned liquid crystal layer is provided on an obliquely stretched cellulose acylate film has a retardation of ⁇ / 4 in a wide wavelength range, and the organic film provided with this retardation film
  • An electroluminescence display device hereinafter abbreviated as an organic EL display device
  • the organic EL display device provided with the retardation film has a problem that the image has bleeding and a high-definition image cannot be obtained. This is because light that enters the retardation film from the light emitting layer is reflected at the interface between the retardation film and the adjacent layer, and is further diffusely reflected by the additive that is phase-separated in the retardation film, resulting in image blurring. Presumed to be the cause.
  • Patent Document 3 discloses a retardation plate composed of a single layer having a reverse wavelength dispersion having a retardation value of ⁇ / 4 in the entire wavelength region by containing a specific compound. According to the method proposed in Patent Document 3, there is no bleedout of additives, and the liquid crystal display device using the retardation plate can display neutral black regardless of the viewing angle. However, there is no description suggesting improvement in image bleeding of the organic EL display device.
  • the present invention has been made in view of the above-described problems and circumstances, and the problem to be solved is excellent image blur resistance, and improved visibility (black reproducibility in a bright place) and durability (image degradation resistance). And providing an organic electroluminescence display device excellent in blue display stability during storage over time, a circularly polarizing plate and a long ⁇ / 4 plate used therefor.
  • a ⁇ / 4 film having a specific compound having retardation and reverse wavelength dispersion and cellulose acylate By using it, it is possible to improve image bleeding resistance, visibility (reproducibility of black in a bright place), durability (image deterioration resistance), and blue display stability during storage over time of an organic EL display device. As a result, the inventors have found out that the present invention can be achieved.
  • an organic electroluminescence display device having at least a protective film, a polarizer, a ⁇ / 4 plate and an organic electroluminescence element in this order,
  • the ⁇ / 4 plate contains a cellulose acylate having an average acyl group substitution degree of 2.0 or more and a compound represented by the following general formula (A), an organic electroluminescence display device.
  • L 1 and L 2 each independently represent a single bond or a divalent linking group.
  • R 1 , R 2 and R 3 each independently represent a substituent.
  • n represents an integer of 0 to 2.
  • Wa and Wb each represent a hydrogen atom or a substituent, (I) Wa and Wb may combine with each other to form a ring; (II) At least one of Wa and Wb may have a ring structure, or (III) At least one of Wa and Wb may be an alkenyl group or an alkynyl group. ] 2.
  • the cellulose acylate is a cellulose acylate that simultaneously satisfies the conditions defined by the following formulas (1) and (2).
  • Formula (1) 2.0 ⁇ Z1 ⁇ 3.0
  • Formula (2) 0.5 ⁇ X
  • Z1 represents the average acyl group substitution degree of a cellulose acylate.
  • X represents the total of the propionyl group substitution degree and the butyryl group substitution degree of cellulose acylate.
  • 3. The organic electroluminescence display device according to item 1, wherein the cellulose acylate is cellulose acetate satisfying a condition defined by the following formula (3).
  • a 1 and A 2 each independently represents an oxygen atom, a sulfur atom, NRx or CO.
  • Rx represents a hydrogen atom or a substituent.
  • X represents a nonmetallic atom belonging to Groups 14-16.
  • L 1, L 2, R 1 , R 2, R 3 and n are L 1, L 2, R 1 , same meanings as R 2, R 3 and n in each Formula (A).
  • Q 3 represents a nitrogen atom or CRz.
  • Rz represents a hydrogen atom or a substituent.
  • Q 4 represents a nonmetallic atom belonging to Groups 14-16.
  • Z represents a nonmetallic atom group that forms a ring with Q 3 and Q 4 .
  • L 1, L 2, R 1 , R 2, R 3 and n are L 1, L 2, R 1 , same meanings as R 2, R 3 and n in each Formula (A).
  • the ⁇ / 4 plate has a ratio (Ro (450) / Ro (550)) of the in-plane retardation value Ro (450) of light having a wavelength of 450 nm to the in-plane retardation value Ro (550) of light having a wavelength of 550 nm.
  • Item 7 The organic electroluminescence display device according to any one of Items 1 to 6, wherein the value is in a range of 0.72 to 0.92.
  • the ⁇ / 4 plate has a ratio (Ro (550) / Ro (650)) of the in-plane retardation value Ro (550) due to light having a wavelength of 550 nm to the in-plane retardation value Ro (650) due to light having a wavelength of 650 nm.
  • the organic electroluminescence display device according to any one of items 1 to 7, wherein the value is in a range of 0.84 to 0.97.
  • the organic electroluminescence element includes a glass plate, and the thickness of the glass plate is in a range of 0.1 to 10 mm.
  • the ⁇ / 4 plate contains a cellulose acylate having an average acyl group substitution degree of 2.0 or more and a compound represented by the following general formula (A).
  • L 1 and L 2 each independently represent a single bond or a divalent linking group.
  • R 1 , R 2 and R 3 each independently represent a substituent.
  • n represents an integer of 0 to 2.
  • Wa and Wb each represent a hydrogen atom or a substituent, (I) Wa and Wb may combine with each other to form a ring; (II) At least one of Wa and Wb may have a ring structure, or (III) At least one of Wa and Wb may be an alkenyl group or an alkynyl group. ] 12 Item 12.
  • Formula (1) 2.0 ⁇ Z1 ⁇ 3.0
  • Formula (2) 0.5 ⁇ X
  • Z1 represents the average acyl group substitution degree of a cellulose acylate.
  • X represents the total of the propionyl group substitution degree and the butyryl group substitution degree of cellulose acylate.
  • Item 12 The circularly polarizing plate according to Item 11, wherein the cellulose acylate is cellulose acetate that satisfies a condition defined by the following formula (3).
  • a 1 and A 2 each independently represents an oxygen atom, a sulfur atom, NRx or CO.
  • Rx represents a hydrogen atom or a substituent.
  • X represents a nonmetallic atom belonging to Groups 14-16.
  • L 1, L 2, R 1 , R 2, R 3 and n are L 1, L 2, R 1 , same meanings as R 2, R 3 and n in each Formula (A).
  • Item 14 The circularly polarizing plate according to any one of Items 11 to 13, wherein the compound represented by the general formula (A) is a compound represented by the following general formula (2): .
  • Q 3 represents a nitrogen atom or CRz.
  • Rz represents a hydrogen atom or a substituent.
  • Q 4 represents a nonmetallic atom belonging to Groups 14-16.
  • Z represents a nonmetallic atom group that forms a ring with Q 3 and Q 4 .
  • L 1, L 2, R 1 , R 2, R 3 and n are L 1, L 2, R 1 , same meanings as R 2, R 3 and n in each Formula (A). ] 17.
  • the angle between the longitudinal direction of the ⁇ / 4 plate and the in-plane slow axis is in the range of 40 to 50 °, and the cellulose acylate having an average acyl group substitution degree of 2.0 or more and the following general formula (A) A long ⁇ / 4 plate characterized by containing the compound represented.
  • L 1 and L 2 each independently represent a single bond or a divalent linking group.
  • R 1 , R 2 and R 3 each independently represent a substituent.
  • n represents an integer of 0 to 2.
  • Wa and Wb each represent a hydrogen atom or a substituent, (I) Wa and Wb may combine with each other to form a ring; (II) At least one of Wa and Wb may have a ring structure, or (III) At least one of Wa and Wb may be an alkenyl group or an alkynyl group. ] 18. 18. The long ⁇ / 4 plate according to item 17, wherein the cellulose acylate is a cellulose acylate that simultaneously satisfies the conditions defined by the following formulas (1) and (2).
  • Formula (1) 2.0 ⁇ Z1 ⁇ 3.0
  • Formula (2) 0.5 ⁇ X
  • Z1 represents the average acyl group substitution degree of a cellulose acylate.
  • X represents the total of the propionyl group substitution degree and the butyryl group substitution degree of cellulose acylate.
  • 19. The long ⁇ / 4 plate according to Item 17, wherein the cellulose acylate is cellulose acetate satisfying a condition defined by the following formula (3).
  • a 1 and A 2 each independently represents an oxygen atom, a sulfur atom, NRx or CO.
  • Rx represents a hydrogen atom or a substituent.
  • X represents a nonmetallic atom belonging to Groups 14-16.
  • L 1, L 2, R 1 , R 2, R 3 and n are L 1, L 2, R 1 , same meanings as R 2, R 3 and n in each Formula (A).
  • 21 The long form according to any one of items 17 to 19, wherein the compound represented by the general formula (A) is a compound represented by the following general formula (2): ⁇ / 4 plate.
  • Q 3 represents a nitrogen atom or CRz.
  • Rz represents a hydrogen atom or a substituent.
  • Q 4 represents a nonmetallic atom belonging to Groups 14-16.
  • Z represents a nonmetallic atom group that forms a ring with Q 3 and Q 4 .
  • L 1, L 2, R 1 , R 2, R 3 and n are L 1, L 2, R 1 , same meanings as R 2, R 3 and n in each Formula (A).
  • an organic material having excellent image bleeding resistance, improved visibility (black reproducibility in a bright place) and durability (image deterioration resistance), and excellent blue display stability during storage over time.
  • An electroluminescent display device, a circularly polarizing plate and a long ⁇ / 4 plate used therefor can be provided.
  • the ⁇ / 4 plate provided on the viewing side of the organic EL element causes image blurring due to multiple reflection of light emitted from the organic EL element, and an incompatible additive for the ⁇ / 4 plate. It is considered that image blur occurs due to irregular reflection due to the presence of cellulose, and the cellulose acylate that is a matrix resin and a specific structure represented by the general formula (A) that has excellent compatibility with the cellulose acylate By coexisting a compound having a color, it is possible to effectively prevent image blur, which is the target effect of the present invention, and in addition, excellent visibility (reproducibility of black in a bright place) and durability (image) It is presumed that the blue display stability during storage over time and deterioration over time could be realized.
  • the compound represented by the general formula (A) according to the present invention has an asymmetric structure such as Wa and Wb as a substituent on the benzene ring, and the unsaturated group is a linking group L.
  • the bond axes of 1 and L 2 With respect to the bond axes of 1 and L 2, the number of electrons in the orthogonal direction increases, and as a result, the refractive index increases. In general, as the refractive index increases, the refractive index change with respect to wavelength tends to increase.
  • the main axis represented by L 1 -benzene ring-L 2 is In the case where the cellulose acylate film is oriented in the same direction as the stretching direction, the refractive index change with respect to the wavelength increases in the stretching direction and the stretching orthogonal direction. .
  • simply increasing the number of electrons in the orthogonal direction cannot ensure compatibility with the cellulose acylate, and therefore it is necessary to adjust polarity and interaction.
  • a linking group having polarity in the vicinity of the benzene ring such as L 1 and L 2 , the free electrons on the benzene ring are biased.
  • linking groups L 1 and L 2 are electron donating linking groups that push out electrons in the direction of the benzene ring, the free electrons are present in a higher density in the orthogonal direction. It is speculated that the broadband performance has been improved.
  • the schematic diagram which shows an example of a structure of the organic electroluminescent image display apparatus of this invention.
  • the organic electroluminescence display device of the present invention is an organic electroluminescence display device having at least a protective film, a polarizer, a ⁇ / 4 plate, and an organic electroluminescence element in this order from the viewing side, and the ⁇ / 4 plate
  • the cellulose acylate having an average acyl group substitution degree of 2.0 or more and a compound represented by the general formula (A) are contained. This feature is a technical feature common to the inventions according to claims 1 to 22.
  • the average acyl group substitution degree in the present invention is synonymous with the total acyl group substitution degree, and is esterified (acylated) among the three hydroxy groups (hydroxyl groups) of each anhydroglucose constituting cellulose.
  • the average value of the number of hydroxy groups (hydroxyl groups) is represented by a value within the range of 0 to 3.0, and is characterized by 2.0 or more in the present invention.
  • the cellulose acylate having an average acyl group substitution degree of 2.0 or more satisfies the conditions defined by the preceding formulas (1) and (2) at the same time. It is a preferred embodiment that it is a cellulose acylate or a cellulose acetate that satisfies the conditions defined by the above formula (3).
  • the compound represented by the said general formula (A) is a compound represented by the said general formula (1), (2) or (3).
  • the ⁇ / 4 plate has reverse wavelength dispersion because an effect of preventing reflection can be obtained in all visible light wavelength ranges.
  • the protective film preferably has a cured layer laminated on the viewing surface side. Therefore, the effect which prevents the curvature of an organic electroluminescent display apparatus is acquired.
  • the long ⁇ / 4 plate of the present invention and the circularly polarizing plate of the present invention incorporating the same can be suitably used for the organic electroluminescence display device of the present invention.
  • ⁇ 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. 1 shows an example of the configuration of the organic EL image display device of the present invention, but the present invention is not limited to this.
  • a display device A is configured.
  • a cured layer 12 is preferably laminated on the viewing surface side of the protective film 11.
  • the hardened layer 12 not only prevents scratches on the surface of the organic EL image display device but also has an effect of preventing warpage due to the circularly polarizing plate. Further, an antireflection layer 13 may be provided on the cured layer.
  • the thickness of the organic EL element itself is about 1 ⁇ m.
  • an organic EL image display device has an organic EL element that is a light emitting body in which a metal electrode, an organic functional layer, and a transparent electrode are laminated in this order on a transparent substrate.
  • the organic functional layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Or a structure having various combinations such as a laminate of such a light-emitting layer and an electron injection layer made of a perylene derivative, or a laminate of these hole injection layer, light-emitting layer, and electron injection layer.
  • a laminate of such organic thin films for example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Or a structure having various combinations such as a laminate of such a light-emitting layer and an electron injection
  • an organic EL image display device by applying a voltage to the transparent electrode and the metal electrode of the organic EL element, holes and electrons are injected into the light emitting layer constituting the organic functional layer.
  • the energy generated by the binding excites the fluorescent compound or phosphorescent compound, and emits light on the principle that light is emitted when the excited fluorescent compound or phosphorescent compound returns to the ground state.
  • the mechanism of recombination in the middle is the same as that of a general diode, and as can be predicted from this, the current and the emission intensity show strong nonlinearity with rectification with respect to the applied voltage.
  • an organic EL element used in an organic EL image display device in order to extract light emitted from the light emitting layer, at least one of the electrodes must be transparent.
  • an indium-tin composite oxide (ITO) or the like is used.
  • a transparent electrode formed of a transparent conductor is used as the anode.
  • 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.
  • the organic functional layer including the light emitting layer transmits light almost completely like the transparent electrode.
  • the light incident from the surface of the transparent substrate at the time of non-light emission, transmitted through the transparent electrode and the organic functional layer, and reflected by the metal electrode again comes out to the surface side of the transparent substrate.
  • the display surface of the organic EL image display device looks like a mirror surface.
  • an organic EL image display device including an organic EL element having a transparent electrode on the surface side of a light emitting layer that emits light by applying a voltage and a metal electrode on the back surface side of the light emitting layer, the surface side (viewing side) of the transparent electrode ), And a retardation plate between the transparent electrode and the polarizing plate.
  • the retardation plate and the polarizing plate have a function of polarizing light incident from the outside and reflected by the metal electrode, there is an effect that the mirror surface of the metal electrode is not visually recognized by the polarization action.
  • the retardation plate is composed of a ⁇ / 4 plate and the angle formed by the polarization direction of the polarizing plate and the retardation plate is adjusted to ⁇ / 4, the mirror surface of the metal electrode can be completely shielded.
  • the external light incident on the organic EL image display device transmits only the linearly polarized light component by the polarizing plate, and this linearly polarized light is generally elliptically polarized light by the retardation plate, but the retardation plate is particularly a ⁇ / 4 plate.
  • the angle between the polarization directions of the polarizing plate and the retardation plate is ⁇ / 4, circular polarization is obtained.
  • This circularly polarized light is transmitted through the transparent substrate, the transparent electrode, and the organic functional layer, reflected by the metal electrode, again transmitted through the organic functional layer, the transparent electrode, and the transparent substrate, and becomes linearly polarized light again on the retardation plate. And since this linearly polarized light is orthogonal to the polarization direction of a polarizing plate, it cannot permeate
  • the ⁇ / 4 plate according to the present invention has a cellulose acylate having an angle between the longitudinal direction and the in-plane slow axis in the range of 40 to 50 ° and a substitution degree of 2.0 or more, and the general formula (A It is characterized by containing the compound represented by this.
  • the ⁇ / 4 plate according to the present invention means a plate having a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light).
  • the ⁇ / 4 plate has an in-plane retardation value Ro of about 1 ⁇ 4 for a predetermined wavelength of light (usually in the visible light region).
  • the ⁇ / 4 plate according to the present invention has a retardation value Ro (550) measured at a wavelength of 550 nm in an environment of 23 ° C. and 55% RH in the range of 110 to 170 nm, preferably in the range of 120 to 160 nm. More preferably, it is in the range of 130 to 150 nm.
  • the ⁇ / 4 plate according to the present invention is a retardation plate (film) having a retardation value 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. ) Is preferable.
  • the retardation of approximately 1 ⁇ 4 of the wavelength in the range of visible light means that the longer wavelength has a characteristic that the retardation becomes larger in the wavelength range of 400 to 700 nm. Specifically, it is a ratio between Ro (450), which is a retardation value Ro represented by the following formula (i) measured at a wavelength of 450 nm, and Ro (550), which is a retardation value Ro measured at a wavelength of 550 nm.
  • the value of Ro (450) / Ro (550) is in the range of 0.72 to 0.92
  • Ro (550) is the retardation value Ro measured at a wavelength of 550 nm
  • the retarder is measured at a wavelength of 650 nm.
  • Providing the characteristic that the value of Ro (550) / Ro (650), which is the ratio of Ro (650) being the foundation value Ro, is in the range of 0.84 to 0.97. Door is preferable.
  • the Ro (450) / Ro (550) is preferably in the above range for blue reproduction, more preferably 0.76 to 0.88, and most preferably 0.79 to 0.85. preferable. Further, the value of the ratio Ro (550) / Ro (650) is preferably in the above range for red reproduction, more preferably 0.84 to 0.95, and 0.84 to 0.93. Most preferably.
  • nx and ny are refractive indices at wavelengths of 450 nm, 550 nm, and 650 nm, respectively measured in an environment of 23 ° C. and 55% RH
  • nx is the maximum refractive index in the plane of the film (in the direction of the slow axis).
  • Ny is the refractive index in the direction perpendicular to the slow axis in the film plane.
  • d is the thickness (nm) of the film.
  • Ro can be measured using an automatic birefringence meter.
  • an automatic birefringence meter for example, using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments) or Axoscan manufactured by Axometric, each wavelength in an environment of 23 ° C. and 55% RH Ro is calculated by birefringence measurement at (450 nm, 550 nm and 650 nm).
  • the circularly polarizing plate of the present invention is obtained by laminating so that the angle between the slow axis of the ⁇ / 4 plate and the transmission axis of the polarizer described later is substantially 45 °.
  • substantially 45 ° means that the angle is in the range of 40 to 50 °.
  • the angle between the slow axis in the plane of the ⁇ / 4 plate and the transmission axis of the polarizer is preferably 41 to 49 °, more preferably 42 to 48 °, and more preferably 43 to 47 °. Is more preferably 44 to 46 °.
  • the ⁇ / 4 plate according to the present invention contains a compound represented by the following general formula (A) together with cellulose acylate having an average acyl group substitution degree of 2.0 or more. .
  • L 1 and L 2 each independently represent a single bond or a divalent linking group.
  • L 1 and L 2 include the following structures.
  • R represents a hydrogen atom or a substituent.
  • L 1 and L 2 are preferably an oxygen atom, COO, or OCO.
  • R 1 , R 2 and R 3 each independently represent a substituent.
  • R 1 , R 2 and R 3 include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl group (for example, cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), alkenyl group ( For example, vinyl group, allyl group, etc.), cycloalkenyl group (eg, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aryl
  • halogen atom
  • R 1 and R 2 are preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted cyclohexyl group.
  • a phenyl group having a substituent and a cyclohexyl group having a substituent are more preferable, and a phenyl group having a substituent at the 4-position and a cyclohexyl group having a substituent at the 4-position are more preferable.
  • R 3 is preferably a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxy group, carboxy group, alkoxy group, aryloxy group, acyloxy group, cyano group, amino group, More preferably, they are a hydrogen atom, a halogen atom, an alkyl group, a cyano group, and an alkoxy group.
  • Wa and Wb each represent a hydrogen atom or a substituent, (I) Wa and Wb may combine with each other to form a ring; (II) At least one of Wa and Wb may have a ring structure, or (III) At least one of Wa and Wb may be an alkenyl group or an alkynyl group.
  • substituent represented by Wa and Wb include halogen atoms (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl groups (eg, methyl group, ethyl group, n-propyl group, Isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl group (for example, cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), alkenyl group (for example, vinyl group, Allyl group), cycloalkenyl group (eg 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.), alkynyl group (eg ethynyl group, propargyl group etc.), aryl group (eg phenyl group) ,
  • R 4 , R 5 and R 6 each represent a hydrogen atom or a substituent.
  • Wa and Wb are bonded to each other to form a ring, it is preferably a nitrogen-containing 5-membered ring or a sulfur-containing 5-membered ring, particularly preferably represented by the following general formula (1) or general formula (2). It is a compound.
  • a 1 and A 2 each independently represent an oxygen atom, a sulfur atom, NRx, or CO.
  • Rx represents a hydrogen atom or a substituent. Examples of the substituent represented by Rx include the same groups as the specific examples of the substituent represented by Wa and Wb.
  • Rx is preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • X represents a nonmetallic atom belonging to Groups 14-16.
  • X is preferably an oxygen atom, a sulfur atom, NRc, or C (Rd) Re.
  • Rc, Rd and Re each represent a substituent, and examples thereof include the same groups as the specific examples of the substituents represented by Wa and Wb.
  • L 1, L 2, R 1 , R 2, R 3 and n are L 1, L 2, R 1 , same meanings as R 2, R 3 and n each in the general formula (A).
  • Q 1 represents an oxygen atom, a sulfur atom, NRy, the CRaRb or CO.
  • Ry represents a hydrogen atom or a substituent
  • Ra and Rb each represents a hydrogen atom or a substituent.
  • examples of the substituent represented by Ry, Ra and Rb include the same groups as exemplified as the substituent represented by Wa and Wb.
  • Y represents a substituent.
  • substituent represented by Y include the same groups exemplified as the substituents represented by Wa and Wb.
  • Y is preferably an aryl group, a heterocyclic group, an alkenyl group, or an alkynyl group.
  • Examples of the aryl group represented by Y include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. Among them, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
  • heterocyclic group examples include heterocyclic groups containing at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, etc., such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group.
  • a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, and a thiazolyl group are preferable.
  • aryl groups or heterocyclic groups may have at least one substituent.
  • substituents include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, and a carbon number.
  • alkylsulfinyl group having 1 to 6 carbon atoms an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, carbon N-alkylamino group having 1 to 6 carbon atoms, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 6 carbon atoms, N, N-dialkyl having 2 to 12 carbon atoms Examples thereof include a sulfamoyl group.
  • L 1, L 2, R 1 , R 2, R 3 and n have the same meanings as defined L 1, L 2, R 1 , R 2, R 3 and n in the general formula (A).
  • R 7 and R 8 each represent a hydrogen atom or a substituent.
  • substituent represented by R 7 and R 8 include the same groups as the substituents represented by Wa and Wb.
  • a compound represented by the following general formula (3) is particularly preferable.
  • Q 3 represents a nitrogen atom or CRz.
  • Rz represents a hydrogen atom or a substituent.
  • Q 4 represents a nonmetallic atom belonging to Groups 14-16.
  • Z represents a nonmetallic atom group that forms a ring with Q 3 and Q 4 .
  • the ring formed from Q 3 , Q 4 and Z may be condensed with another ring.
  • the ring formed from Q 3 , Q 4 and Z is preferably a nitrogen-containing 5-membered ring or 6-membered ring condensed with a benzene ring.
  • L 1, L 2, R 1 , R 2, R 3 and n have the same meanings as defined L 1, L 2, R 1 , R 2, R 3 and n in the general formula (A).
  • Wa and Wb is an alkenyl group or an alkynyl group
  • a vinyl group having a substituent and an ethynyl group are preferable.
  • the compound represented by general formula (3) is particularly preferable.
  • the compound represented by the general formula (3) is superior in heat resistance and light resistance to the compound represented by the general formula (1), and is an organic solvent compared to the compound represented by the general formula (2).
  • the solubility with respect to and the compatibility with a polymer are favorable.
  • the compounds represented by the general formula (A) and the general formulas (1) to (3) according to the present invention are contained by adjusting the optimum amount for imparting desired wavelength dispersion and bleeding prevention properties. be able to.
  • the addition amount is preferably within a range of 1 to 15% by mass, and particularly preferably within a range of 2 to 10% by mass with respect to the cellulose derivative. If it is in this range, sufficient wavelength dispersibility and bleeding prevention performance can be imparted to the cellulose derivative according to the present invention.
  • the ⁇ / 4 plate according to the present invention contains, as a main component, cellulose acylate having an average acyl group substitution degree of 2.0 or more together with the compound represented by the general formula (A) described above.
  • the cellulose acylate according to the present invention is preferably contained in the range of 60 to 100% by mass with respect to the total mass of 100% by mass of the ⁇ / 4 plate according to the present invention.
  • cellulose acylate examples include esters of cellulose and aliphatic carboxylic acids and / or aromatic carboxylic acids having about 2 to 22 carbon atoms, particularly esters of cellulose and lower fatty acids having 6 or less carbon atoms. Preferably there is.
  • the acyl group bonded to the hydroxy group of cellulose may be linear or branched, and may form a ring. Furthermore, another substituent may be substituted. When the substitution degree is the same, the birefringence decreases when the number of carbon atoms described above is large. Therefore, the carbon number is preferably selected from acyl groups having 2 to 6 carbon atoms.
  • the total X of the propionyl group substitution degree and the butyryl group substitution degree is 0.5 or more.
  • the cellulose acylate preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
  • cellulose acylate includes propionate group, butyrate group or phthalyl group in addition to acetyl group such as cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate or cellulose acetate phthalate.
  • Bound cellulose mixed fatty acid esters can be used.
  • the butyryl group forming butyrate may be linear or branched.
  • cellulose acetate, cellulose acetate butyrate, or cellulose acetate propionate is particularly preferably used as the cellulose acylate.
  • One cellulose acylate having an average acyl group substitution degree of 2.0 or more according to the present invention is preferably a cellulose acylate that simultaneously satisfies the conditions defined by the following formulas (1) and (2).
  • Formula (1) 2.0 ⁇ Z1 ⁇ 3.0
  • Formula (2) 0.5 ⁇ X
  • Z1 represents the average acyl group substitution degree of cellulose acylate.
  • X represents the total of the propionyl group substitution degree and the butyryl group substitution degree of cellulose acylate.
  • the mixing ratio is preferably in the range of 1:99 to 99: 1 (mass ratio).
  • cellulose acetate propionate is particularly preferably used as the cellulose acylate.
  • cellulose acetate propionate 0 ⁇ Y ⁇ 2.5 and 0.5 ⁇ X ⁇ 3.0 (where 2.0 ⁇ X + Y ⁇ 3.0) are preferable, It is more preferable that 0.5 ⁇ Y ⁇ 2.0 and 1.0 ⁇ X ⁇ 2.0 (where 2.0 ⁇ X + Y ⁇ 3.0).
  • the substitution degree of the acyl group can be measured according to ASTM-D817-96.
  • the other cellulose acylate having an average acyl group substitution degree of 2.0 or more according to the present invention is preferably a cellulose acetate that satisfies the condition defined by the following formula (3).
  • Formula (3) 2.0 ⁇ X 1 ⁇ 3.0
  • X 1 represents an average degree of acetyl group substitution.
  • the cellulose acetate according to the present invention is characterized in that the average degree of acetyl group substitution is 2.0 or more, preferably in the range of 2.0 to 2.7, more preferably 2.2 to 2.
  • the range is 6.
  • the average degree of acetyl group substitution here means the average value of the number of esterified (acetylated) hydroxy groups (hydroxyl groups) among the three hydroxy groups (hydroxyl groups) of each anhydroglucose constituting cellulose. And a value within the range of 2.0 or more and less than 3.0.
  • the average acetyl group substitution degree of cellulose acetate is 2.0 or more, it is possible to prevent deterioration of film surface quality due to an increase in dope viscosity and haze increase due to an increase in stretching tension. Obtainable.
  • the portion not substituted with an acetyl group usually exists as a hydroxy group (hydroxyl group).
  • the cellulose acetate according to the present invention can be synthesized by a known method.
  • the degree of substitution of the acetyl group was determined by the method prescribed in ASTM-D817-96 (test method for cellulose acetate etc.).
  • the number average molecular weight of the cellulose acylate according to the present invention is preferably in the range of 30,000 to 300,000, since the mechanical strength of the resulting film becomes strong. More preferred is cellulose acylate having a number average molecular weight in the range of 50,000 to 200,000.
  • the ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cellulose acylate is preferably in the range of 1.4 to 3.0.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of cellulose acylate are measured using gel permeation chromatography (GPC).
  • the measurement conditions are as follows.
  • this measuring method can be used also as a measuring method of the other polymer in this invention.
  • the cellulose that is the raw material of the cellulose acylate according to the present invention is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively.
  • the cellulose acetate according to the present invention can be produced by a known method.
  • cellulose is mixed with raw material cellulose, a predetermined organic acid (such as acetic acid), acid anhydride (such as acetic anhydride), and a catalyst (such as sulfuric acid) to esterify (acetylate) cellulose, The reaction proceeds until ester (acetylation) is formed.
  • ester acetylation
  • triester acetylation
  • the three hydroxy groups (hydroxyl groups) of the glucose unit are substituted with acetyl groups of organic acids.
  • cellulose acetate having a desired degree of acetyl group substitution is synthesized by hydrolyzing the cellulose triester. Thereafter, cellulose acetate can be obtained through steps such as filtration, precipitation, washing with water, dehydration, and drying.
  • the residual sulfuric acid content in the cellulose acylate is preferably in the range of 0.1 to 45 ppm by mass in terms of sulfur atoms. These are considered to be contained in the form of salts. If the residual sulfuric acid content is 45 mass ppm or less, there is a tendency that it is difficult to break during hot stretching or slitting after hot stretching. The residual sulfuric acid content is more preferably in the range of 1 to 30 ppm by mass. The residual sulfuric acid content can be measured by the method prescribed in ASTM D817-96.
  • the free acid content in the cellulose acylate is preferably 1 to 500 ppm by mass.
  • the above range is preferable because it is difficult to break as described above.
  • the free acid content is preferably in the range of 1 to 100 ppm by mass, and is more difficult to break.
  • the range of 1 to 70 ppm by mass is particularly preferable.
  • the free acid content can be measured by the method prescribed in ASTM D817-96.
  • the residual alkaline earth metal content, residual sulfuric acid content, and residual acid content are The range can be preferable.
  • a cellulose acylate has few bright spot foreign materials when it is made into a film.
  • Bright spot foreign matter means that when two polarizing plates are placed in a crossed Nicol state, an optical film or the like is placed between them, light is applied from one polarizing plate side, and observation is performed from the other polarizing plate side. It means a point (bright spot foreign material) where light from the opposite side appears to leak.
  • the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm 2 or less, more preferably 100 / cm 2 or less, and 50 / cm 2 or less. Is more preferably 30 pieces / cm 2 or less, particularly preferably 10 pieces / cm 2 or less, and most preferably none.
  • the bright spot having a diameter of 0.005 to 0.01 mm or less is also preferably 200 pieces / cm 2 or less, more preferably 100 pieces / cm 2 or less, and 50 pieces / cm 2 or less. Is more preferably 30 pieces / cm 2 or less, particularly preferably 10 pieces / cm 2 or less, and most preferably none.
  • the raw material cellulose used for the production of cellulose acylate is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Moreover, the cellulose acylate obtained from them can be mixed and used in arbitrary ratios, respectively.
  • Cellulose acylate can be produced by a known method. Specifically, for example, it can be synthesized with reference to the method described in JP-A-10-45804.
  • cellulose acylate is affected by the above-mentioned characteristics also by a trace metal component in cellulose acylate.
  • trace metal components are thought to be related to the water used in the production process, but it is preferable that there are few components that can become insoluble nuclei, in particular, metal ions such as iron, calcium, magnesium,
  • An insoluble matter may be formed by salt formation with a polymer degradation product or the like that may contain an organic acidic group, and it is preferable that the amount is small.
  • the calcium (Ca) component easily forms a coordination compound (that is, a complex) with an acidic component such as a carboxylic acid or a sulfonic acid, and many ligands. Insoluble starch, turbidity) may be formed.
  • the content in cellulose acylate is preferably 1 mass ppm or less.
  • the content in the cellulose acylate is preferably 60 ppm by mass or less, more preferably in the range of 0 to 30 ppm by mass.
  • the magnesium (Mg) component too much content will cause insoluble matter, so the content in the cellulose acylate is preferably in the range of 0 to 70 mass ppm, particularly in the range of 0 to 20 mass ppm. It is preferable to be within.
  • each metal component such as iron (Fe) component, calcium (Ca) component, magnesium (Mg) component, etc.
  • a micro digest wet cracking device sulfuric acid decomposition
  • analysis can be performed using ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometer).
  • the ⁇ / 4 plate according to the present invention preferably contains a plasticizer.
  • the ⁇ / 4 plate according to the present invention preferably contains a polyester plasticizer having a number average molecular weight (Mn) in the range of 300 to 10,000.
  • Mn number average molecular weight
  • a range of 1000 to 10,000 is preferably used in order to suppress volatilization of the polyester-based compound.
  • polyester plasticizer applicable to the present invention is not particularly limited, and a polyester plasticizer having an aromatic ring or a cycloalkyl ring in the molecule can be used.
  • polyester plasticizer represented by the following general formula (a) is mentioned, for example.
  • B represents a benzene monocarboxylic acid residue or an aliphatic 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 alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.
  • the polyester plasticizer represented by the general formula (a) can be obtained by the same reaction as a normal polyester plasticizer.
  • benzene monocarboxylic acid component of the polyester plasticizer examples include benzoic acid, para-tert-butyl benzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethyl benzoic acid, ethyl benzoic acid, normal propyl benzoic acid, and aminobenzoic acid. , Acetoxybenzoic acid and the like, each of which can be used alone or as a mixture of two or more.
  • the aliphatic monocarboxylic acid component of the polyester plasticizer is preferably an aliphatic monocarboxylic acid having 3 or less carbon atoms, more preferably acetic acid, propionic acid, or butanoic acid, and most preferably acetic acid.
  • the number of carbon atoms of the monocarboxylic acids used at both ends of the polycondensed ester is 3 or less, the heat loss of the compound does not increase, and no surface failure occurs.
  • a monocarboxylic acid having a cycloaliphatic having 3 to 8 carbon atoms is preferred, a monocarboxylic acid having a cycloaliphatic having 6 carbons is more preferred, cyclohexanecarboxylic acid, 4-methyl-cyclohexane Carboxylic acid is most preferred. If the number of carbon atoms of the cycloaliphatic monocarboxylic acids used at both ends of the polycondensed ester is in the range of 3 to 8, the loss on heating of the compound will not increase, and no surface failure will occur.
  • alkylene glycol component having 2 to 12 carbon atoms in the polyester plasticizer 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-dimethylol) Heptane), 3-methyl-1,5-pentanediol-1,6-hexanediol, 2,2,4-trimethyl-1,3- Nthanediol, 2-ethyl
  • alkylene glycol having 2 to 12 carbon atoms is preferable because of its excellent compatibility with the cellulose ester, and more preferable is an alkylene glycol having 2 to 6 carbon atoms. Particularly preferred are alkylene glycols having 2, 3 or 4 carbon atoms.
  • Examples of the oxyalkylene glycol component having a polyester plasticizer having a carbon number in the range of 4 to 12 include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. Can be used singly or as a mixture of two or more.
  • alkylene dicarboxylic acid component in which the polyester plasticizer has 4 to 12 carbon atoms examples include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These can be used singly or as a mixture of two or more.
  • examples of the arylenedicarboxylic acid component having 6 to 12 carbon atoms include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and the like. .
  • the polyester plasticizer preferably used for the ⁇ / 4 plate according to the present invention preferably has a number average molecular weight in the range of 300 to 10,000. More preferably, it is within the range of 1000 to 10,000. More preferably, it is in the range of 6000 to 8000.
  • the acid value of the polyester plasticizer is preferably 0.5 mgKOH / g or less, and more preferably 0.3 mgKOH / g or less.
  • the hydroxy group value of the polyester plasticizer is preferably 25 mgKOH / g or less, more preferably 15 mgKOH / g or less.
  • an acid value means the milligram number of potassium hydroxide required in order to neutralize the acid (carboxy group which exists in a sample) contained in 1g of samples. The acid value is measured according to JIS K0070.
  • the ⁇ / 4 plate according to the present invention preferably contains a plasticizer other than the above-described “polyester plasticizer having a number average molecular weight (Mn) in the range of 1000 to 10,000”.
  • the dispersion ratio Mw / Mn of the polyester plasticizer (Mw represents a weight average molecular weight and Mn represents a number average molecular weight) is preferably in the range of 1.5 to 10, more preferably in the range of 2 to 8. And particularly preferably in the range of 3-7. It is preferable that the dispersion ratio of the polyester plasticizer is a value within the range specified above from the viewpoint of obtaining a ⁇ / 4 plate excellent in balance of various performances. For example, if the value of the dispersion ratio is 1.5 or more, the compatibility between the cellulose ester and various additives can be sufficiently ensured, and the production of the polyester plasticizer is easy.
  • the value of the dispersion ratio is 10 or less, mixing of low molecular weight components can be prevented, and problems such as additive bleed out and contamination of the process due to volatilization of low molecular weight components, and reduction in film flexibility are caused. Occurrence can be prevented.
  • the content of the low molecular weight component in the polyester plasticizer is preferably small, but if this is expressed quantitatively, the component having a number average molecular weight of 200 or less occupies 100% by mass of the polyester plasticizer.
  • the ratio is preferably 10% by mass or less, more preferably 5.0% by mass or less, and particularly preferably 1.0% by mass or less.
  • the content of the high molecular weight component in the polyester plasticizer is small, but if this is quantitatively expressed, a component having a number average molecular weight of more than 10,000 with respect to 100% by mass of the polyester plasticizer.
  • the proportion occupied by is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • plasticizers can be applied to the ⁇ / 4 plate according to the present invention.
  • plasticizers include polyhydric alcohol ester plasticizers, glycolate plasticizers, phthalate ester plasticizers, citrate ester plasticizers, fatty acid ester plasticizers, and phosphate ester plasticizers. , Polycarboxylic acid ester plasticizers, acrylic plasticizers, and the like.
  • the polyhydric alcohol ester plasticizer is a plasticizer comprising an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
  • the polyhydric alcohol ester plasticizer preferably comprises an ester of a divalent to 20-valent aliphatic polyhydric alcohol.
  • Preferably used polyhydric alcohol is a compound represented by the following general formula (b).
  • R 1 represents an n-valent organic group
  • n represents an integer of 2 or more
  • OH represents an alcoholic or phenolic hydroxy group
  • Preferred examples of the polyhydric alcohol include the following, but the present invention is not limited to these.
  • polyhydric alcohol examples include adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2 -Butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol Mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol and the like.
  • monocarboxylic acid used for polyhydric alcohol ester there is no restriction
  • Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.
  • aliphatic monocarboxylic acid a straight-chain fatty acid having 1 to 32 carbon atoms or a fatty acid having a side chain is preferably used.
  • the number of carbon atoms is more preferably in the range of 1 to 20, and particularly preferably 1 to 10.
  • acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.
  • Preferred aliphatic monocarboxylic acids include, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecyl Acids, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, undecylenic acid And unsaturated fatty acids such as oleic acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid.
  • unsaturated fatty acids such as oleic acid, sorbic
  • Examples of preferable alicyclic monocarboxylic acid include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include those in which 1 to 3 alkoxy groups such as an alkyl group, a methoxy group or an ethoxy group are introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, biphenylcarboxylic acid, Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as naphthalenecarboxylic acid and tetralincarboxylic acid, or derivatives thereof. Benzoic acid is particularly preferable.
  • the molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably in the range of 300 to 1500, and more preferably in the range of 350 to 750. A higher molecular weight is preferable because it is less likely to volatilize, and a lower molecular weight is preferable in terms of moisture permeability and compatibility with cellulose ester.
  • the carboxylic acid used in the polyhydric alcohol ester may be one kind alone or a mixture of two or more kinds. Moreover, all the hydroxyl groups in the polyhydric alcohol may be esterified, or a part of them may be left as they are.
  • the glycolate plasticizer is not particularly limited, but, for example, alkylphthalylalkyl glycolates can be preferably used.
  • alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl Ethyl glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl Glycolate, butyl phthalyl propyl glycolate, methyl phthalyl o
  • phthalate ester plasticizer examples include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.
  • citrate ester plasticizer examples include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.
  • fatty acid ester plasticizer examples include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate and the like.
  • phosphate ester plasticizer examples include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.
  • polycarboxylic acid ester plasticizer examples include a plasticizer made of an ester of a polyvalent carboxylic acid and an alcohol having a valence of 2 or more, preferably in the range of 2 to 20.
  • the aliphatic polyvalent carboxylic acid is preferably in the range of 2 to 20 valences, and in the case of aromatic polyvalent carboxylic acid and alicyclic polyvalent carboxylic acid, it is preferably in the range of 3 to 20 valences. .
  • the polyvalent carboxylic acid is represented by the following general formula (c).
  • R 2 (COOH) m (OH) n
  • R 2 represents an (m + n) -valent organic group
  • m represents an integer of 2 or more
  • n represents an integer of 0 or more
  • COOH represents a carboxy group
  • OH is alcoholic.
  • Or represents a phenolic hydroxy group.
  • Preferred examples of the polyvalent carboxylic acid include the following compounds, but the present invention is not limited to these.
  • Trivalent or higher aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof, succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid, fumaric acid, maleic acid, tetrahydrophthal
  • An aliphatic polyvalent carboxylic acid such as an acid, an oxypolyvalent carboxylic acid such as tartaric acid, tartronic acid, malic acid and citric acid can be preferably used.
  • the alcohol constituting the polycarboxylic acid ester plasticizer is not particularly limited, and known alcohols and phenols can be used.
  • linear aliphatic saturated alcohol or aliphatic unsaturated alcohol having 1 to 32 carbon atoms or aliphatic saturated alcohol or aliphatic unsaturated alcohol having a side chain can be preferably used.
  • the number of carbon atoms is more preferably in the range of 1-20, and particularly preferably in the range of 1-10.
  • alicyclic alcohols such as cyclopentanol and cyclohexanol or derivatives thereof
  • aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, or derivatives thereof can be preferably used.
  • the alcoholic or phenolic hydroxy group of the oxypolycarboxylic acid may be esterified with a monocarboxylic acid.
  • monocarboxylic acids include the following, but the present invention is not limited thereto.
  • aliphatic monocarboxylic acid a straight-chain fatty acid having 1 to 32 carbon atoms or a fatty acid having a side chain can be preferably used.
  • the number of carbon atoms is further preferably in the range of 1-20, and particularly preferably in the range of 1-10.
  • Preferred aliphatic monocarboxylic acids include, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, Tridecyl 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, undecylen
  • unsaturated fatty acids such as acid, oleic acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid.
  • Examples of preferable alicyclic monocarboxylic acid include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid. Examples thereof include aromatic monocarboxylic acids or derivatives thereof. In particular, acetic acid, propionic acid, and benzoic acid are preferable.
  • the molecular weight of the polyvalent carboxylic acid ester plasticizer is not particularly limited, but the molecular weight is preferably in the range of 300 or more and less than 1000, and more preferably in the range of 350 to 750. From the standpoint of improving retention, a larger molecular weight is preferred, and from the viewpoint of moisture permeability and compatibility with cellulose ester, a smaller molecular weight is preferred.
  • the alcohols used in the polyvalent carboxylic acid ester plasticizer may be a single kind or a mixture of two or more kinds.
  • the acid value of the polyvalent carboxylic acid ester plasticizer is preferably 1 mgKOH / g or less, more preferably 0.2 mgKOH / g or less. Setting the acid value within the above range is preferable because the environmental fluctuation of retardation is suppressed.
  • tributyl trimellitic acid and tetrabutyl pyromellitic acid.
  • the ⁇ / 4 plate according to the present invention includes an ester compound having at least one pyranose structure or furanose structure in the range of 1 to 12, and all or part of the hydroxy groups of the structure being esterified. It is preferable. In the present invention, these ester compounds are collectively referred to as “sugar ester compounds”.
  • sugar ester compounds examples include the following, but the present invention is not limited to these.
  • a compound (sugar) having a pyranose structure or a furanose structure glucose, galactose, mannose, fructose, xylose, or arabinose, lactose, sucrose, nystose, 1F-fructosylnystose, stachyose, maltitol, lactitol, lactulose , Cellobiose, maltose, cellotriose, maltotriose, raffinose, and kestose.
  • gentiobiose gentiotriose
  • gentiotetraose gentiotetraose
  • xylotriose galactosyl sucrose
  • sucrose kestose, nystose, 1F-fructosyl nystose, stachyose and the like are preferable, and sucrose is more preferable.
  • the monocarboxylic acid used for esterifying all or part of the hydroxy group of the above-mentioned compound (sugar) having a pyranose structure or furanose structure for the purpose of constituting a sugar ester compound is not particularly limited and is known. Aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid and the like can be used. The carboxylic acid used may be one kind alone or a mixture of two or more kinds.
  • Preferred aliphatic monocarboxylic 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 , Saturated fatty acids such as 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, melicic acid, and laccelic acid; Examples thereof include unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid and o
  • Examples of preferable alicyclic monocarboxylic acids include acetic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include aromatic monocarboxylic acids having an alkyl group or alkoxy group introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, cinnamic acid, benzylic acid, biphenylcarboxylic acid, and naphthalene.
  • aromatic monocarboxylic acids having two or more benzene rings such as carboxylic acid and tetralincarboxylic acid, or derivatives thereof.
  • the sugar ester compound described above is 1 to 100% by mass with respect to 100% by mass of the ⁇ / 4 plate. It is preferably contained in the range of 30% by mass, and more preferably in the range of 5 to 30% by mass. Within this range, the excellent effects of the present invention are exhibited, and the occurrence of bleeding out and the like can be suppressed, which is preferable.
  • the ⁇ / 4 plate according to the present invention preferably contains the following polyester.
  • the ⁇ / 4 plate according to the present invention preferably contains a polyester represented by the following general formula (d) or general formula (e).
  • B 1 represents a monocarboxylic acid
  • G represents a divalent alcohol component
  • A represents a dibasic acid.
  • B 1 , G and A do not contain an aromatic ring.
  • m represents the number of repetitions.
  • B 2 represents a monoalcohol component
  • G represents a divalent alcohol component
  • A represents a dibasic acid.
  • B 2 , G and A do not contain an aromatic ring.
  • n represents the number of repetitions.
  • the monocarboxylic acids represented by B 1 may be known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid.
  • Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.
  • linear fatty acids having 1 to 32 carbon atoms or fatty acids having side chains are preferably used.
  • the number of carbon atoms is more preferably in the range of 1-20, and particularly preferably in the range of 1-12.
  • it is preferable to add acetic acid because the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.
  • Preferred aliphatic monocarboxylic acids include, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, laurin Saturated fatty acids such as 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, melicic acid, and laccelic acid An unsaturated fatty acid such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid;
  • the monoalcohol component represented by B 2 is not particularly limited, and known alcohols can be used.
  • an aliphatic saturated alcohol or an aliphatic unsaturated alcohol having a straight chain or a side chain in the range of 1 to 32 carbon atoms can be preferably used.
  • the carbon number is preferably within the range of 1 to 20, and particularly preferably within the range of 1 to 12.
  • Examples of the divalent alcohol component represented by G include the following, but the present invention is not limited thereto.
  • ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, diethylene glycol, and triethylene glycol are preferable, and 1,3-propylene glycol, 1, - butylene glycol 1,6-hexanediol, diethylene glycol is preferably used.
  • the dibasic acid represented by A is preferably an aliphatic dibasic acid or an alicyclic dibasic acid.
  • the aliphatic dibasic acid include malonic acid, succinic acid, glutaric acid, and adipine. Acids, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid and the like, in particular, aliphatic dicarboxylic acids preferably have 4 to 12 carbon atoms, and at least one selected from these One can be used. In the present invention, two or more dibasic acids may be used in combination.
  • M and n each represents the number of repetitions, preferably in the range of 1 to 170.
  • the ⁇ / 4 plate according to the present invention preferably contains a polyester represented by the following general formula (f) or general formula (g).
  • B 1 represents a monocarboxylic acid having 1 to 12 carbon atoms.
  • G represents a divalent alcohol component having 2 to 12 carbon atoms.
  • A represents a dibasic acid having 2 to 12 carbon atoms.
  • B 1 , G and A do not contain an aromatic ring.
  • m represents the number of repetitions.
  • B 2 represents a monoalcohol component having 1 to 12 carbon atoms.
  • G represents a divalent alcohol component having 2 to 12 carbon atoms.
  • A represents a dibasic acid having 2 to 12 carbon atoms.
  • B 2 , G and A do not contain an aromatic ring.
  • n represents the number of repetitions.
  • the general formula (f) and the general formula (g), B 1 and B 2 are the same meaning as B 1 and B 2 in the above general formula (d) or the general formula (e).
  • G and A correspond to an alcohol component or a dibasic acid component having 2 to 12 carbon atoms in G and A in the general formula (d) or the general formula (e).
  • the number average molecular weight of the preferred polyester is in the range of 1000 to 10,000. If the number average molecular weight is 1000 or more, breakage hardly occurs at high temperature and high magnification stretching, and if it is 10,000 or less, the occurrence of whitening due to phase separation can be suppressed.
  • Polyester polycondensation is carried out by conventional methods.
  • a hot melt condensation method by a direct reaction between the dibasic acid and glycol, a polyesterification reaction or transesterification reaction between the dibasic acid or an alkyl ester thereof, for example, a methyl ester of dibasic acid and a glycol.
  • it can be easily synthesized by any method of dehydrohalogenation reaction between acid chloride of these acids and glycol, but it is preferable to synthesize a polyester having a weight average molecular weight not so large by direct reaction.
  • Polyester having a high molecular weight distribution on the low molecular weight side has a very good compatibility with the cellulose ester, and after formation of the film, a water vapor permeability is small, and a ⁇ / 4 plate rich in transparency can be obtained.
  • the method for adjusting the molecular weight is not particularly limited, and a conventional method can be applied.
  • a method of blocking the molecular ends with a monovalent acid or monovalent alcohol when used, the final amount is adjusted by adjusting the addition amount of these monovalent raw material compounds.
  • the molecular weight can be adjusted. Among these, it is preferable from the viewpoint of the stability of the polymer to adjust the addition amount of the monovalent acid.
  • Examples of monovalent acids include acetic acid, propionic acid, butyric acid, etc., but those that are not distilled out of the system during the polycondensation reaction, but easily distilled off when stopped and removed from the reaction system. Is preferred. For this purpose, a plurality of compounds may be used in combination.
  • the weight average molecular weight can also be adjusted by measuring the timing for stopping the reaction based on the amount of water produced during the reaction.
  • the molecular weight can be adjusted by biasing the number of moles of glycol or dibasic acid to be charged, and the molecular weight can be adjusted by controlling the reaction temperature.
  • the polyester is preferably contained in an amount in the range of 1 to 40% by mass with respect to 100% by mass of the cellulose ester.
  • the polyester represented by the general formula (f) or the general formula (g) is 2 to 30%. It is preferably included in an amount in the range of mass%. In particular, it is preferably contained in the range of 5 to 15% by mass.
  • UV absorber The ⁇ / 4 plate according to the present invention or the protective film described later preferably contains an ultraviolet absorber.
  • ultraviolet absorbers examples include benzotriazole-based, 2-hydroxybenzophenone-based or salicylic acid phenyl ester-based ultraviolet absorbers.
  • 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3 Triazoles such as 5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone And benzophenones.
  • UV absorbers with a molecular weight of 400 or more are less likely to volatilize at high boiling points and are less likely to disperse during high-temperature molding of the film. It is preferable from the viewpoint that can be performed.
  • Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- ( Benzotriazoles such as 1,1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, Hindered amines such as bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl Bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionylo Xyl] ethyl] -4- [3- (3
  • 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylenebis [4- (1,1,3,3- Tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred.
  • TINUVIN series such as TINUVIN 109, TINUVIN 171, TINUVIN 234, TINUVIN 326, TINUVIN 327, TINUVIN 328, and TINUVIN 928 manufactured by BASF Japan can be preferably used. .
  • antioxidants can be added to the ⁇ / 4 plate according to the present invention in order to improve the thermal decomposability and thermal colorability during molding.
  • an antistatic agent can be added to impart an antistatic function to the ⁇ / 4 plate.
  • Phosphorus flame retardant For the ⁇ / 4 plate according to the present invention, a flame retardant acrylic resin composition containing a phosphorus flame retardant may be used.
  • Phosphorus flame retardants used here include red phosphorus, triaryl phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, aryl phosphonate compound, aryl phosphine oxide compound, condensed aryl phosphate ester, halogenated alkyl phosphorus. Examples thereof include one or a mixture of two or more selected from acid esters, halogen-containing condensed phosphates, halogen-containing condensed phosphonates, halogen-containing phosphites, and the like.
  • triphenyl phosphate 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris ( ⁇ -chloroethyl) phosphate, tris (dichloropropyl) Examples thereof include phosphate and tris (tribromoneopentyl) phosphate.
  • the ⁇ / 4 plate according to the present invention includes, for example, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, and hydrated silica from the viewpoint of improving handleability. It is preferable to contain inorganic fine particles such as calcium acid, aluminum silicate, magnesium silicate, and calcium phosphate and organic fine particles such as a crosslinked polymer as a matting agent. Among these, silicon dioxide is preferably used because it can reduce the haze of the film.
  • the primary average particle diameter of the fine particles is preferably 20 nm or less, more preferably in the range of 5 to 16 nm, and particularly preferably in the range of 5 to 12 nm.
  • the ⁇ / 4 plate according to the present invention may be formed by either a solution casting method or a melt casting method.
  • the solution casting method as the casting method from the viewpoints of suppressing coloration of the film, suppressing defects of foreign matters, and suppressing optical defects such as die lines.
  • melt casting method a method of producing by a melt casting method is also preferable.
  • Methods formed by melt casting can be classified into melt extrusion molding methods, press molding methods, inflation methods, injection molding methods, blow molding methods, stretch molding methods, and the like.
  • the melt extrusion method is preferable from the viewpoint of obtaining a film having excellent mechanical strength and surface accuracy.
  • the organic solvent useful for forming the dope is not limited as long as it dissolves cellulose acetate and other additives at the same time. be able to.
  • methylene chloride as a non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, etc.
  • methylene chloride, methyl acetate, ethyl acetate, and acetone can be preferably used.
  • the dope preferably contains a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in the range of 1 to 40% by mass.
  • a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in the range of 1 to 40% by mass.
  • a dope composition prepared by dissolving 15 to 45% by mass is preferable.
  • linear or branched aliphatic alcohols having 1 to 4 carbon atoms examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Can be mentioned. Among these, ethanol is preferable from the viewpoints of excellent dope stability, relatively low boiling point, and good drying properties.
  • the ⁇ / 4 plate according to the present invention can be manufactured by a solution casting method.
  • the solution casting method mainly includes a step of preparing a dope by dissolving a resin and an additive in a solvent, a step of casting the dope on a belt-shaped or drum-shaped metal support, and a web of the cast dope.
  • a drying step a step of peeling a web from a metal support, a step of stretching or maintaining a width, a step of further drying, a step of winding up a finished film, and the like.
  • the concentration of cellulose acetate in the dope is preferably higher because the drying load after casting on a metal support can be reduced. However, if the concentration of cellulose acetate is too high, the load during filtration increases and the filtration accuracy increases. becomes worse.
  • the concentration that achieves both of these is preferably in the range of 10 to 35% by mass, and more preferably in the range of 15 to 25% by mass.
  • the metal support in the casting (casting) step preferably has a mirror-finished surface, and as the metal support, a stainless steel belt or a drum whose surface is plated with a casting is preferably used.
  • the width of the cast is not particularly limited, but can be generally in the range of 1 to 4 m.
  • the surface temperature of the metal support in the casting step is set in a range of ⁇ 50 ° C. to a temperature at which the organic solvent boils and does not foam. A higher temperature is preferable because the drying speed of the web can be increased. However, if the temperature is too high, the web may foam and flatness may deteriorate.
  • a preferable support temperature is appropriately determined within a range of 0 to 100 ° C., and preferably within a range of 5 to 30 ° C. Also preferred is a method in which the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.
  • the method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing warm air or cold air, a method of bringing hot water into contact with the back side of the metal support, and the like.
  • a method using hot water is preferable from the viewpoint of shortening the time until the temperature of the metal support becomes constant because heat is efficiently transferred.
  • the amount of residual solvent when peeling the web from the metal support is preferably in the range of 10 to 150% by mass, more preferably 20 to 40% by mass. %, Or 60 to 130% by mass, particularly preferably 20 to 30% by mass, or 70 to 120% by mass.
  • the residual solvent amount as used in the present invention is defined by the following formula.
  • Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100
  • M is the mass of a sample collected at any time during or after production of the web or film.
  • N is the mass after heating M at 115 ° C. for 1 hour.
  • the web is peeled off from the metal support and further dried to make the residual solvent amount 1.0% by mass or less, more preferably 0.1% by mass.
  • the range is particularly preferably 0 to 0.01% by mass.
  • a roller drying method (a method in which webs are alternately passed through a plurality of upper and lower rollers) and a tenter method for drying while transporting the web are employed.
  • the retardation Ro (550) in the in-plane direction measured at a wavelength of 550 nm is preferably in the range of 100 to 180 nm, but the retardation may be imparted by film stretching. preferable.
  • the stretching method For example, a method in which a circumferential speed difference is applied to a plurality of rollers, and the roller is stretched in the longitudinal direction using the circumferential speed difference between the rollers. Both ends of the web are fixed with clips and pins, and the interval between the clips and pins is widened in the traveling direction. And a method of stretching in the vertical direction, a method of stretching in the horizontal direction and stretching in the horizontal direction, a method of stretching in the vertical and horizontal directions and stretching in both the vertical and horizontal directions, and the like. Of course, you may use combining these methods suitably.
  • the film may be stretched in the transverse direction, in the longitudinal direction, in either the longitudinal direction, or may be stretched in both directions. There may be.
  • driving the clip portion by the linear drive method is preferable because smooth stretching can be performed and the risk of breakage and the like can be reduced.
  • stretching in the transport direction is performed using a difference in peripheral speed of the film transport roller, or the web is stretched in a direction perpendicular to the transport direction (also referred to as the width direction or the TD direction).
  • a tenter system in which both ends are gripped by clips or the like, and it is also preferable to use a tenter that can independently control the web gripping length (distance from gripping start to gripping end) by left and right gripping means.
  • the ⁇ / 4 plate according to the present invention is stretched in a 45 ° direction with respect to the film transport direction in the stretching step, so that the orientation angle ⁇ with respect to the longitudinal direction of the long ⁇ / 4 plate is 35 to 55 °. This is a preferable method.
  • a long polarizing film having a transmission axis in a direction parallel to the longitudinal direction of the slow axis and a long ⁇ / 4 plate having an orientation angle of substantially 45 ° are formed in the longitudinal direction. Since a roll-like long circularly polarizing plate can be easily produced by laminating and roll-to-roll together, there is little cut loss of the film, which is advantageous in production.
  • FIG. 2 is a schematic diagram showing an example of oblique stretching by a tenter.
  • the stretched film is manufactured using a tenter.
  • This tenter is a device that widens a film fed from a film roller (feeding roller) in an oblique direction with respect to its traveling direction (moving direction of the middle point in the film width direction) in an oven heating environment.
  • 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 from the film roller and sequentially supplied to the inlet 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 outlet 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 to the entrance portion.
  • the rail shape of the tenter is asymmetrical on the left and right according to the orientation angle, stretch ratio, etc. given to the stretched film to be manufactured, and can be finely adjusted manually or automatically.
  • a long thermoplastic resin film is stretched, and the orientation angle ⁇ can be set to an arbitrary angle within the range of 10 ° to 80 ° with respect to the winding direction after stretching. Yes.
  • the gripping tool of the tenter is configured to travel at a constant speed with a certain distance from the front and rear gripping tools.
  • FIG. 2 shows the track (rail pattern) of the tenter rail used for oblique stretching.
  • the feeding direction DR1 of the cellulose acylate film is different from the winding direction (MD direction) DR2 of the stretched film, and thus, even in a stretched film having a relatively large orientation angle, a wide and uniform optical characteristic is obtained. It is possible to obtain.
  • the feeding angle ⁇ i is an angle formed by the feeding direction DR1 of the film before stretching and the winding direction DR2 of the film after stretching.
  • the feeding angle ⁇ i is within a range of 10 ° ⁇ i ⁇ 60 °, preferably 15 ° ⁇ i ⁇ 50 °. Is set.
  • the variation in the optical characteristics in the width direction (TD direction) of the obtained film becomes good (becomes small).
  • the cellulose acetate film fed from the film roller is gripped at both ends (both sides) by the left and right gripping tools at the tenter inlet (position a), and travels as the gripping tool travels. .
  • the left and right grips CL and CR that face the direction substantially perpendicular to the film traveling direction (feeding direction DR1) at the tenter entrance (position a) run on a rail that is asymmetrical to the preheating zone. Through an oven having a stretching zone and a heat setting zone.
  • substantially perpendicular indicates that the angle formed by the straight line connecting the aforementioned gripping tools CL and CR and the film feeding direction DR1 is within 90 ⁇ 1 °.
  • the preheating zone refers to a section where the distance between the gripping tools gripping both ends is kept constant at the oven entrance.
  • the stretching zone refers to an interval until the gap between the gripping tools gripping both ends starts to become constant again.
  • the cooling zone refers to a section in which the temperature in the zone is set to be equal to or lower than the glass transition temperature Tg ° C. of the thermoplastic resin constituting the film during a period in which the interval between the gripping tools after the stretching zone becomes constant again. .
  • the temperature of each zone is in the range of Tg + 5 to Tg + 20 ° C. for the preheating zone, Tg to Tg + 20 ° C. for the stretching zone, and Tg-30 to Tg ° C. for the cooling zone with respect to the glass transition temperature Tg of the thermoplastic resin. It is preferable to set to.
  • the draw ratio R (W / Wo) in the drawing step is preferably in the range of 1.3 to 3.0 times, more preferably in the range of 1.5 to 2.8 times.
  • thickness unevenness in the width direction (TD direction) is preferably reduced. If the stretching temperature is differentiated in the width direction in the stretching zone of the tenter stretching machine, the thickness unevenness in the width direction can be further improved.
  • Wo is the width
  • W represents the width
  • the step of stretching in the oblique direction may be performed in the film forming step (online), or may be unwound after being wound up and stretched by the tenter (offline).
  • the means for drying the cellulose acetate film is not particularly limited, and as a general method, hot air, infrared rays, a heating roller, microwaves, or the like can be used, but from the viewpoint of simplicity, a method using hot air is preferable.
  • the drying temperature in the drying process of the cellulose acetate film is preferably a temperature range of ⁇ 5 to + 100 ° C. with respect to the glass transition temperature Tg of the film.
  • the drying temperature is in the range of 100 to 200 ° C, and more preferably in the range of 110 to 160 ° C.
  • the knurling process can be formed by pressing a heated embossing roller.
  • a fine uneven structure is formed on the surface of the embossing roller, and by pressing this, unevenness can be imparted to the film and the end can be made bulky.
  • the height of the knurling at both ends of the width of the cellulose acetate film is preferably 4 to 20 ⁇ m, and the width from the end is preferably in the range of 5 to 20 mm.
  • the knurling process is preferably provided after the drying in the film forming process and before winding.
  • the ⁇ / 4 plate according to the present invention may be formed by a melt film forming method.
  • the melt film-forming method refers to a method in which a composition containing additives such as a resin and a plasticizer is heated and melted to a temperature exhibiting fluidity, and then a melt containing fluid cellulose acetate is cast.
  • the molding method for heating and melting can be classified in detail into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, a stretch molding method, and the like.
  • the melt extrusion method is preferable from the viewpoint of mechanical strength and surface accuracy.
  • the plurality of raw materials used in the melt extrusion method are usually preferably kneaded in advance and pelletized.
  • Pelletization may be performed by a known method. For example, dry cellulose acetate, plasticizer, and other additives are fed to an extruder using a feeder, kneaded using a single or twin screw extruder, and then formed into a strand from a die. It can be carried out by extruding, water cooling or air cooling and cutting.
  • Additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders.
  • a small amount of additives such as particles and antioxidants are preferably mixed in advance in order to mix uniformly.
  • the extruder is preferably processed at as low a temperature as possible so that the shearing force is suppressed and the resin can be pelletized so as not to deteriorate (molecular weight reduction, coloring, gel formation, etc.).
  • a twin screw extruder it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.
  • the raw material powder can be directly fed to the extruder by a feeder without being pelletized to form a film as it is.
  • the melting temperature when extruding the above pellets using a single-screw or twin-screw type extruder is set to a temperature range of 200 to 300 ° C., filtered through a leaf disk type filter, etc.
  • a film is cast from the die, the film is nipped by a cooling roller and an elastic touch roller, and solidified on the cooling roller.
  • a method of preventing oxidative decomposition or the like under vacuum, reduced pressure, or inert gas atmosphere when introducing from the supply hopper to the extruder is also preferable.
  • the extrusion flow rate is preferably carried out stably by introducing a gear pump.
  • a stainless fiber sintered filter is preferably used as a filter used for removing foreign substances.
  • the stainless steel fiber sintered filter is made by compressing the intricately intertwined state of the stainless steel fiber body and sintering and integrating the contact points. The density changes depending on the thickness of the fiber and the amount of compression, and the filtration accuracy Can be adjusted.
  • Additives such as plasticizers and particles may be mixed with the resin in advance, or may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer.
  • the film temperature on the touch roller side is preferably in the temperature range of Tg to Tg + 110 ° C. of the film.
  • a known roller can be used as the roller having an elastic surface used for such a purpose.
  • the elastic touch roller is also called a pinching rotary body.
  • a commercially available elastic touch roller can also be used.
  • the film obtained as described above is stretched by the stretching operation after passing through the step of contacting the cooling roller.
  • the stretching method a known roller stretching machine or tenter can be preferably used.
  • the stretching temperature is usually preferably in the temperature range of Tg to Tg + 60 ° C. of the resin constituting the film.
  • the end Before winding, the end may be slit and cut to the product width, and knurled (embossed) may be applied to both ends to prevent sticking or scratching during winding.
  • the knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing. Note that the clip holding portions at both ends of the film are usually cut out and reused after collection because the film is deformed and cannot be used as a product.
  • the film thickness of the ⁇ / 4 plate according to the present invention is not particularly limited, but is preferably in the range of 10 to 250 ⁇ m, and more preferably in the range of 10 to 100 ⁇ m. Particularly preferably, it is in the range of 30 to 60 ⁇ m.
  • the ⁇ / 4 plate according to the present invention is used in a width range of 1 to 4 m.
  • a width in the range of 1.4 to 4 m is preferably used, and a range of 1.6 to 3 m is particularly preferable. If the width is 4 m or less, stable conveyance can be performed.
  • the arithmetic average roughness Ra of the ⁇ / 4 plate surface according to the present invention is preferably in the range of 2.0 to 4.0 nm, more preferably in the range of 2.5 to 3.5 nm. is there.
  • the ⁇ / 4 plate according to the present invention is required to withstand use in a higher temperature environment, and the ⁇ / 4 plate has a sufficient tension softening point in the temperature range of 105 to 145 ° C. In view of heat resistance, a temperature range of 110 to 130 ° C. is particularly preferable.
  • a Tensilon tester (ORIENTEC Co., Ltd., RTC-1225A) is used to cut out a sample film at 120 mm (length) ⁇ 10 mm (width) and pull it with a tension of 10 N.
  • the temperature can be continuously increased at a temperature increase rate of 30 ° C./min, and the temperature at 9 N can be measured three times, and the average value can be obtained.
  • the dimensional change rate (%) of the ⁇ / 4 plate is preferably less than 0.5%, and more preferably less than 0.3%.
  • the ⁇ / 4 plate according to the present invention preferably has few failures in the film (hereinafter also referred to as defects).
  • defects include voids in the film (foaming defects) generated due to rapid evaporation of the solvent in the drying process of solution casting, foreign substances in the film forming stock solution, and foreign substances mixed in the film forming process. This refers to foreign matter (foreign matter defect) in the film.
  • the number of defects having a diameter of 5 ⁇ m or more in the film plane is 1/10 cm square or less. More preferably, it is 0.5 piece / 10 cm square or less, and particularly preferably 0.1 piece / 10 cm square or less.
  • the diameter of the above defect indicates the diameter when the defect is circular, and when the defect is not circular, the range of the defect is determined by observing with a microscope according to the following method, and the maximum diameter (diameter of circumscribed circle) is determined.
  • the range of the defect is the size of the shadow when the defect is observed with the transmitted light of the differential interference microscope when the defect is a bubble or a foreign object. If the defect is a change in surface shape, such as transfer of a roller flaw or an abrasion, the size of the defect is confirmed by observing the defect with reflected light from a differential interference microscope.
  • the film When the number of defects is more than 1/10 cm square, for example, when a tension is applied to the film during processing in a later process, the film may be broken with the defect as a starting point and productivity may be reduced. Moreover, when the diameter of a defect becomes 5 micrometers or more, it can confirm visually by polarizing plate observation etc., and when used as an optical member, a bright spot may arise.
  • the ⁇ / 4 plate according to the present invention preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more, as measured in accordance with JIS-K7127-1999.
  • the upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming.
  • the ⁇ / 4 plate according to the present invention preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, as a realistic upper limit, it is about 99%. In order to achieve excellent transparency expressed by such total light transmittance, it is necessary not to introduce additives and copolymerization components that absorb visible light, or to remove foreign substances in the polymer by high-precision filtration. It is effective to reduce the diffusion and absorption of light inside the film. Also, reduce the surface roughness of the film surface by reducing the surface roughness of the film contact area (cooling roller, calender roller, drum, belt, coating substrate in solution casting, transport roller, etc.) during film formation. It is effective to reduce the diffusion and reflection of light on the film surface.
  • the circularly polarizing plate of the present invention is prepared by cutting a long roll having a long protective film, a long polarizer and a long ⁇ / 4 plate in this order, and the long ⁇ / 4 plate contains cellulose acylate having a substitution degree of 2.0 or more and the compound represented by the general formula (A), and the circularly polarizing plate of the present invention is an organic EL image.
  • the effect of shielding the specular reflection of the metal electrode of the organic EL light-emitting body is manifested.
  • the ⁇ / 4 plate according to the present invention is obliquely stretched so that the angle of the slow axis (that is, the orientation angle ⁇ ) is “substantially 45 °” with respect to the longitudinal direction
  • the direction of the maximum elastic modulus is also “substantially 45 °” with respect to the longitudinal direction, and the circularly polarizing plate tends to warp in an oblique direction.
  • the circularly polarizing plate of the present invention has an ultraviolet absorbing function in order to prevent deterioration due to ultraviolet rays.
  • the protective film on the viewing side has an ultraviolet absorption function
  • both the polarizer and the organic EL element can be protected from ultraviolet rays, but when the ⁇ / 4 plate on the light emitter side also has an ultraviolet absorption function, The deterioration of the organic EL element can be further suppressed, which is preferable.
  • the polarizer is preferably sandwiched between the ⁇ / 4 plate according to the present invention and a protective film, and a cured layer is preferably laminated on the viewing side of the protective film. Since the amount of warpage and the direction of warpage can be adjusted by the material, thickness and degree of cure of the cured layer, it is preferable because warpage of the circularly polarizing plate can be prevented.
  • the film thickness (dry film thickness) of the hardened layer is in the range of 3 to 30 ⁇ m, preferably in the range of 5 to 15 ⁇ m, from the viewpoint of exhibiting high hardness.
  • the hardness of the hardened layer is desired because it is difficult to be scratched in use on the surface of the display device or in the processing step of the circularly polarizing plate, and is preferably 3H or more, more preferably 4H or more in the pencil hardness test method. .
  • the test pencil specified in JIS S 6006 is used.
  • K is a value measured according to the pencil hardness evaluation method specified in 5400.
  • the hardened layer preferably has a Martens hardness (HMs) in the range of 400 to 800 N / mm 2 .
  • HMs Martens hardness
  • Martens hardness is a microhardness meter using a Vickers indenter and a triangular pyramid indenter whose angle between ridges is 115 degrees.
  • the surface of the cured layer of the film is approximately 1/10 of the thickness of the cured layer.
  • the indentation depth from the 50% value to the 90% value of the maximum load test force (Fmax) obtained from the load test force-indentation depth curve Is a value defined by the following formula from the slope (m) proportional to the square root of the load test force.
  • the resin binder that forms the cured layer will be described.
  • the resin binder is not particularly limited, but an active energy ray curable resin is preferable.
  • the active energy ray-curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with an active energy ray such as an ultraviolet ray or an electron beam.
  • the active energy ray curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam to cure the active energy ray.
  • an active energy ray such as an ultraviolet ray or an electron beam to cure the active energy ray.
  • a functional resin layer is formed.
  • the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin.
  • the ultraviolet curable resin has a mechanical film strength (abrasion resistance, pencil hardness). From the point which is excellent in it.
  • a polyfunctional acrylate is preferable.
  • the polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate.
  • the polyfunctional acrylate is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule. These compounds are used alone or in admixture of two or more.
  • the addition amount of the active energy ray-curable resin is preferably in the range of 15 to 70 mass in the solid content in the cured layer forming composition.
  • the cured layer contains a photopolymerization initiator for promoting the curing of the active energy ray curable resin.
  • photopolymerization initiator examples include acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.
  • a binder such as a thermoplastic resin, a thermosetting resin, or a hydrophilic resin such as gelatin can also be used.
  • the hardened layer may contain inorganic fine particles or organic fine particles in order to adjust slipperiness and refractive index.
  • an antireflection layer described later is further provided on the visible side of the cured layer.
  • the antireflection layer can prevent the contrast of the image from being lowered by reflecting external light on the surface of the protective film or the cured layer.
  • any appropriate polarizer can be adopted depending on the purpose.
  • a dichroic substance such as iodine or a dichroic dye is adsorbed on a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film or an ethylene / vinyl acetate copolymer partially saponified film.
  • a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film or an ethylene / vinyl acetate copolymer partially saponified film.
  • examples include uniaxially stretched films, polyene-based oriented films such as polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
  • a polarizer obtained by adsorbing a dichroic substance such as iodine on a polyvinyl alcohol film and uniaxially stretching is particularly preferable because of its high polarization dichroic ratio.
  • the thickness of these polarizers is not particularly limited, but is generally about 1 to 80 ⁇ m.
  • a polarizer uniaxially stretched by adsorbing iodine to a polyvinyl alcohol film can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. . If necessary, it may contain boric acid, zinc sulfate, zinc chloride, or the like, or may be immersed in an aqueous solution such as potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
  • Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching.
  • the film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.
  • Examples of the protective film according to the present invention include cellulose ester films such as triacetyl cellulose film, cellulose acetate propionate film, cellulose diacetate film, and cellulose acetate butyrate film, and polyester films such as polyethylene terephthalate and polyethylene naphthalate.
  • Film polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film Norbornene resin film, polymethylpentene film, polyester Ether ketone film, polyether ketone imide film, a polyamide film, a fluorine resin film, nylon film, can be used cycloolefin polymer film, a polymethylmethacrylate film, or an acrylic film.
  • a cellulose ester film a polycarbonate film, a cycloolefin polymer film, and a polyester film are preferable.
  • a cellulose ester film is particularly preferable from the viewpoints of optical properties, productivity, and cost.
  • Examples of the cellulose ester film include Konica Minoltack KC8UX, KC4UX, KC4UA, KC6UA, KC4CZ, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, and KC12UR layer. Can be used.
  • the above-mentioned protective film preferably has a maximum in-plane elastic modulus of 4.0 GPa or more in an environment of 23 ° C. and 55 RH% because it can further suppress panel deflection.
  • the protection having a high elastic modulus by controlling the selection of cellulose acetate, the use of the compound represented by the general formula (A), the use of other additives, the stretching conditions, etc. A film can be made.
  • the protective film according to the present invention It is also preferable to use the ⁇ / 4 plate according to the present invention.
  • the direction of the maximum elastic modulus in the plane of the protective film is in the direction of 35 to 55 ° with respect to the longitudinal direction of the screen of the image display device, and the maximum elastic modulus in the plane of the ⁇ / 4 plate is By making it parallel to the direction, a high-quality organic electroluminescence image display device for 3D image display can be obtained.
  • the protective film constituting the circularly polarizing plate of the present invention is preferably provided with an antireflection layer having an external light antireflection function, directly or via the cured layer.
  • the antireflection layer has a structure in which each refractive index layer having a different refractive index is laminated in consideration of the refractive index, the film thickness, the number of constituent layers, the layer order, and the like so that the reflectance is reduced by optical interference.
  • the antireflection layer is preferably composed of a low refractive index layer having a refractive index lower than that of the support, or a combination of a high refractive index layer having a refractive index higher than that of the support and a low refractive index layer.
  • an antireflection layer composed of three or more refractive index layers, and three layers having different refractive indexes from the support side are divided into medium refractive index layers (high refractive index layers having a higher refractive index than the support).
  • medium refractive index layers high refractive index layers having a higher refractive index than the support.
  • Examples of the configuration of the antireflection layer include the following configuration examples, but are not limited thereto.
  • the low refractive index layer essential in the antireflection layer preferably contains silica-based fine particles, and the refractive index is lower than the refractive index of the substrate film as the support, and measured at 23 ° C. and a wavelength of 550 nm. Is preferably in the range of 1.30 to 1.45.
  • the film thickness of the low refractive index layer is preferably in the range of 5 nm to 0.5 ⁇ m, more preferably in the range of 10 to 300 nm, and most preferably in the range of 30 to 200 nm.
  • the silica-based fine particles have a configuration including at least one kind of particles having an outer shell layer and porous or hollow inside.
  • the particles having the outer shell layer and having a porous or hollow inside are preferably hollow silica-based fine particles.
  • composition for forming a low refractive index layer may contain an organosilicon compound represented by the following general formula (OSi-1), a hydrolyzate thereof, or a polycondensate thereof.
  • OSi-1 organosilicon compound represented by the following general formula (OSi-1)
  • hydrolyzate thereof a hydrolyzate thereof
  • polycondensate thereof a polycondensate thereof.
  • organosilicon compound represented by the general formula (OSi-1) R represents an alkyl group having 1 to 4 carbon atoms.
  • Specific examples of the organosilicon compound represented by the general formula (OSi-1) include tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane, which can be preferably used.
  • a solvent In addition to the composition for forming a low refractive index layer, a solvent, and if necessary, a silane coupling agent, a curing agent, a surfactant and the like may be added.
  • the refractive index of the high refractive index layer constituting the antireflection layer is preferably adjusted to a refractive index in the range of 1.4 to 2.2 when measured at 23 ° C. and a wavelength of 550 nm.
  • the thickness of the high refractive index layer is preferably in the range of 5 nm to 1 ⁇ m, more preferably in the range of 10 to 200 nm, and most preferably in the range of 30 to 100 nm.
  • the means for adjusting the refractive index can be achieved by adding metal oxide fine particles and the like.
  • the refractive index of the metal oxide fine particles used is preferably in the range of 1.80 to 2.60, more preferably in the range of 1.85 to 2.50.
  • the kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and It is preferable to use a metal oxide having at least one metal atom selected from S, and these metal oxide fine particles are doped with a small amount of atoms such as Al, In, Sn, Sb, Nb, a halogen element, and Ta. It may be. A mixture of these may also be used.
  • At least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used. It is particularly preferable to use it as the main component. In particular, it is preferable to contain zinc antimonate particles.
  • the average particle diameter of primary particles of these metal oxide fine particles is preferably in the range of 10 to 200 nm, and more preferably in the range of 10 to 150 nm.
  • the average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. Further, it may be measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased.
  • the shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.
  • the metal oxide fine particles may be subjected to a surface treatment with an organic compound.
  • a surface treatment with an organic compound By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the control of the dispersed particle size is facilitated, and aggregation and sedimentation are suppressed during long-term storage. You can also. Therefore, the surface modification amount with the organic compound is preferably in the range of 0.1 to 5.0% by mass, more preferably 0.5 to 3.0% by mass with respect to 100% by mass of the metal oxide particles. Range.
  • the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, a silane coupling agent is preferable.
  • the high refractive index layer may contain a ⁇ -conjugated conductive polymer.
  • the ⁇ -conjugated conductive polymer can be used as long as it is an organic polymer having a main chain composed of a ⁇ -conjugated system. Examples thereof include polythiophenes, polypyrroles, polyanilines, polyphenylenes, polyacetylenes, polyphenylene vinylenes, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of ease of polymerization and stability, polythiophenes, polyanilines, and polyacetylenes are preferable.
  • the ⁇ -conjugated conductive polymer can provide sufficient conductivity and solubility in a binder resin even if it is not substituted, but from the viewpoint of further improving conductivity and solubility, an alkyl group, a carboxy group, a sulfo group, and an alkoxy group.
  • a functional group such as a group, a hydroxy group, or a cyano group may be introduced.
  • the ionic compound include imidazolium-based, pyridium-based, alicyclic amine-based, aliphatic amine-based, aliphatic phosphonium-based cations and inorganic ion-based compounds such as BF 4 ⁇ and PF 6 — , CF 3 SO, and the like.
  • examples thereof include compounds composed of fluorine-based anions such as 2 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , and CF 3 CO 2 — .
  • the ratio of the polymer to the binder is preferably in the range of 10 to 400 parts by weight of the binder with respect to 100 parts by weight of the polymer, particularly preferably 100 to 200 parts by weight of the binder with respect to 100 parts by weight of the polymer. Range.
  • the substrate 1 that can be used in the organic EL element having the configuration shown in FIG. 1 is not particularly limited in kind, such as glass and plastic, and may be transparent or opaque. When light is extracted from the substrate 1 side, the substrate 1 is preferably transparent. Examples of the transparent substrate preferably used include glass, quartz, and a transparent resin film.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, and cellulose acetate propio.
  • Cellulose esters such as nate (CAP), cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone , Polyimide, polyethersulfone (PES), polyphenylene sulfide, polysulfone , Polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, cyclone such as Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Examples include olefin resins.
  • a barrier film composed of an inorganic film, an organic film, or a hybrid film of both may be formed, and the water vapor transmission rate (measured by a method according to JIS K 7129-1992) ( 25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is preferably 0.01 g / (m 2 ⁇ 24 h) or less, and moreover, in accordance with JIS K 7126-1987.
  • any material may be used as long as it has a function of suppressing intrusion of an organic EL element such as moisture or oxygen that deteriorates performance.
  • silicon oxide, silicon dioxide, silicon nitride, or the like is used. it can.
  • the method for forming the barrier film is not particularly limited.
  • the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
  • the opaque substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, ceramic substrates, and the like.
  • the substrate is preferably a glass plate from the viewpoint of preventing warpage of the organic electroluminescence display device.
  • the thickness of the glass plate is preferably in the range of 0.1 to 10 mm. If the thickness is 0.1 mm or more, the durability is good, it will not crack due to a small impact during transportation or use, it will not warp even when heat is applied, and there will be no deterioration in visibility due to cracking. . Moreover, if it is 10 mm or less, an organic electroluminescent display apparatus can be reduced in weight and manufacturing cost can also be suppressed.
  • the transparent sheet 8 shown in FIG. 1 may be used for the organic EL image display device of the present invention, or may be omitted and the sealing layer 7 and the ⁇ / 4 plate according to the present invention may be adjacent to each other. .
  • a transparent sheet is synonymous with the said board
  • 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 at 60 ° C. under reduced pressure (4 ⁇ 10 2 Pa or less). A mixture of compounds A-1, A-2, A-3, A-4 and A-5 was obtained.
  • the obtained mixture was analyzed by the following HPLC and LC-MASS. As a result, A-1 was 1.3% by mass, A-2 was 13.4% by mass, A-3 was 13.1% by mass, A- 4 was 31.7% by mass, and A-5 was 40.5% by mass. The average degree of substitution was 5.5.
  • Fine particle additive solution 1 The fine particle dispersion 1 prepared above was slowly added while sufficiently stirring the following methylene chloride in a dissolution tank. 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.
  • a main dope 1 having the following composition was prepared. First, the following methylene chloride and ethanol were added as a solvent to the pressure dissolution tank. Next, in a pressurized dissolution tank containing a solvent, the following cellulose acetate propionate, exemplified compound (170) which is a compound represented by the general formula (A), sugar ester compound 1, ultraviolet absorber (tinuvin 928), The fine particle addition liquid 1 was sequentially added and dissolved while heating and stirring. Subsequently, this was made into Azumi filter paper No. made by Azumi Filter Paper Co., Ltd. The main dope 1 was prepared by filtration using 244.
  • the main dope 1 prepared above was uniformly cast on a stainless belt support using an endless belt casting apparatus.
  • the solvent was evaporated until the residual solvent amount in the cast (cast) film was 75% by mass, and the film was peeled off from the stainless steel belt support.
  • the peeled cellulose ester film was stretched in the width direction using a tenter while applying heat. Next, drying was terminated while transporting the drying zone with a number of rolls, and the ends sandwiched between tenter clips were slit with a laser cutter, and then wound.
  • the obtained film was obliquely stretched to a stretching ratio of 2.0 times under the condition of 185 ° C. so that the slow axis and the longitudinal direction were 45 °, and a ⁇ / 4 plate 101 (long ⁇ / 4 plate) was obtained.
  • the in-plane retardation Ro (550) at a wavelength of 550 nm of the obtained ⁇ / 4 plate 101 was 138 nm.
  • ⁇ / 4 plates 102 to 130 [Production of ⁇ / 4 plates 102 to 130]
  • the type of cellulose acetate propionate acetyl group substitution degree and propionyl group substitution degree (average acyl group substitution degree)
  • the type of compound represented by the general formula (A) ⁇ / 4 plates 102 to 130 were prepared in the same manner except that the combinations described in Table 1 and Table 2 were changed.
  • the in-plane retardation measured at a wavelength of 550 nm, respectively. The stretching temperature and the stretching ratio were appropriately adjusted so that Ro (550) was 138 nm.
  • the phase difference measurement of each ⁇ / 4 plate was performed using AxoScan made by Axometric, and the above-described average refractive index and film thickness were input into AxoScan.
  • In-plane retardation values Ro (450), Ro (550), and Ro (650) were determined according to the equation. Further, the direction of the slow axis with respect to the width direction of the ⁇ / 4 plate was also measured simultaneously.
  • the in-plane phase difference of wavelength x was defined as Ro (x).
  • nx is the refractive index in the slow axis direction in the ⁇ / 4 plate surface
  • ny is the refractive index in the fast axis direction in the ⁇ / 4 plate surface
  • d is the thickness of the ⁇ / 4 plate. (Nm).
  • chromatic dispersion is obtained by Ro (450) / Ro (550) and Ro (550) / Ro (650), and DSP (Ro (450) / Ro (550)), DSP (Ro ( 550) / Ro (650)).
  • Tables 1 and 2 show the following ranks A to D as guidelines for chromatic dispersion. The ranks shown in Tables 1 and 2 merely indicate the wavelength dispersion characteristics of each ⁇ / 4 plate, and do not determine the superiority or inferiority of the ⁇ / 4 plate in the present invention.
  • the ⁇ / 4 plate 101 produced above was bonded to one side of the long polarizer using a fully saponified polyvinyl alcohol 5% aqueous solution as an adhesive. At that time, the longitudinal direction of the polarizer and the ⁇ / 4 plate 101 was aligned, and the polarizer was bonded so that the transmission axis of the polarizer and the slow axis of the ⁇ / 4 plate 101 were 45 °.
  • Konica Minolta Tack Film KC4UA manufactured by Konica Minolta Advanced Layer Co., Ltd.
  • the bleeding resistance was evaluated according to the following criteria based on the evaluation results by 10 people.
  • the visibility evaluation is performed by 10 people, and if the condition A screen (1000 Lx) has the same quality as the condition B screen (under 500 Lx), the image of the condition A is slightly more visible than the image of the condition B. It was determined as 1 point when it was determined that the image was reduced, and 0 point when the image of Condition A was clearly reduced in visibility relative to the image of Condition B.
  • the total score of 10 monitors was obtained, and visibility evaluation A based on differences in observation environment (illuminance) was performed according to the following criteria.
  • Evaluation B) A sample (condition A) where the organic EL display device was placed in an environment of 23 ° C. and 55% RH for 5 hours and a sample (condition C) placed in an environment of 50 ° C. and 14% RH for 5 hours were prepared.
  • condition C screen (temperature 50 ° C., 14% RH environment) is the same quality as the condition A screen (temperature 23 ° C., 55% RH environment). 1 point when it is determined that the image of the condition C is slightly less visible than the image of the condition A, and 0 when the image of the condition C is clearly less visible than the image of the condition A. Judged as a point.
  • condition D screen (temperature 23 ° C., 80% RH environment) is the same quality as the condition A screen (temperature 23 ° C., 55% RH environment). 1 point when it is determined that the image of the condition D is slightly less visible than the image of the condition A, and 0 when the image of the condition D is clearly less visible than the image of the condition A. Judged as a point.
  • the Konica Minolta Tack Film KC4UA (manufactured by Konica Minolta Advanced Layer Co., Ltd.) used as a protective film in the production of the circularly polarizing plate was KC8UX, KC4UX, KC4UA, KC6UA, KC4CZ, KC5UCR3, KC8UCR4, CC8UCR4, , KC8UY, KC4UY, KC4UE, and KC12UR were produced in the same manner, and circularly polarizing plates were produced in the same manner. As a result of evaluation similar to the above, it was confirmed that all obtained the same results as KC4UA. did it.
  • Example 2 Production of organic EL element >> (Preparation of organic EL elements 2 to 5)
  • the organic EL element was similarly obtained except that the alkali-free glass having a thickness of 5 mm as the substrate was changed to the alkali-free glass having a thickness described in Table 3, respectively. 2 to 5 were produced.
  • Example 3 Preparation of protective film A >> On the Konica Minolta Tack Film KC4UA (manufactured by Konica Minolta Advanced Layer Co., Ltd.) described in Example 1, the following coating solution for cured layer A was die-coated under the condition that the film thickness after curing was 6 ⁇ m, and at 80 ° C. After drying, 120 mJ / cm 2 of ultraviolet light was irradiated with a high-pressure mercury lamp and cured to prepare a protective film A provided with a cured layer A having a thickness of 6 ⁇ m.
  • the following coating solution for the cured layer B is die-coated, dried at 80 ° C., and then irradiated with 120 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp to obtain a thickness after curing. Formed a cured layer B of 110 nm.
  • PGME propylene glycol monomethyl ether
  • Isopropyl alcohol 25 parts by mass Methyl ethyl ketone 25 parts by mass Pentaerythritol triacrylate 0.9 parts by mass Pentaerythritol tetraacrylate 1.0 part by mass Urethane acrylate (trade name: U-4HA Shin-Nakamura Chemical Co., Ltd.) (Made by company) 0.6 parts by mass Particle dispersion
  • tetraethoxysilane hydrolyzate A After mixing 230 g of tetraethoxysilane (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) and 440 g of ethanol, 120 g of 2% aqueous acetic acid solution was added thereto, and the mixture was stirred at room temperature (25 ° C.) for 26 hours. A tetraethoxysilane hydrolyzate A was prepared.
  • organic EL display devices 104A to 108A, 112A to 116A, 120A to 124A, 128A to 132A, 136A to 140A having a cured layer organic EL display devices 104B to 108B, 112B to 116B, 120B to 124B, 128B to 132B, and 136B to 140B were improved by about 1 to 5 mm, thereby reducing image display deterioration.
  • Example 1 the visibility of the organic EL display device when stored in an environment of 23 ° C. and 80% RH is described in Example 1.
  • the organic EL display devices 104 to 108, 112 to 116, 120 to 124, 128 to 132, and 136 to 140 the organic EL display devices 104A to 108A, 112A to 116A, 120A to 124A, and 128A to 132A having a cured layer.
  • 136A to 140A and organic EL display devices 104B to 108B, 112B to 116B, 120B to 124B, 128B to 132B, and 136B to 140B were confirmed to be further improved.
  • Example 4 Production of ⁇ / 4 plate >> [Production of ⁇ / 4 plate 401] (Preparation of main dope) First, the following methylene chloride and the following ethanol were added to the pressure dissolution tank. The following cellulose acetate having an acetyl group substitution degree of 1.90 was added to a pressure dissolution tank containing a solvent while stirring. This was heated and stirred to dissolve completely, and this was dissolved in Azumi Filter Paper No. The main dope was prepared by filtration using 244.
  • the dope solution was prepared by charging into the main dissolution vessel 1 and dissolving with stirring.
  • the main dope prepared above is cast on a stainless steel belt support, the solvent is evaporated until the residual solvent amount in the film reaches 75%, and then the stainless steel belt support with a peeling tension of 130 N / m. It peeled from the top.
  • the peeled film was stretched 1% 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 terminated 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.
  • the roll-shaped raw film A was set in a slidable feeding device and supplied to the oblique stretching tenter device shown in FIG. At that time, the distance between the main shaft of the guide roller (28-1) closest to the entrance portion of the oblique stretching tenter device and the gripping tool (clip gripping portion 22-1 / 22-2) of the oblique stretching device was 80 cm.
  • the clip had a length of 5.08 cm (2 inches) in the conveyance direction, and the guide roller had a diameter of 10 cm.
  • the tenter was stretched in the transverse direction at a stretching temperature of 210 ° C. and a stretching ratio of 80%, and then contracted 0.71 times in the direction perpendicular to the stretching when the rail was bent 45 °.
  • the stretched film is subjected to feedback control that reflects the variation in tension measured by the first roller (28-2) on the outlet side of the obliquely stretched tenter so that the variation in take-up tension is less than 3%. Controlled. Then, both ends of the film are trimmed, the conveyance direction is changed by a conveyance direction changing device composed of an air flow roller, the film is wound by a slidable winding device, and a roll-shaped ⁇ / 4 plate having a film thickness of 20 ⁇ m and a width of 2000 mm 401 was obtained.
  • the orientation angle ⁇ of the ⁇ / 4 plate 401 was measured using KOBRA-21ADH manufactured by Oji Scientific Instruments, and found to be in the range of 45 ° ⁇ 1 ° with respect to the film longitudinal direction.
  • the prepared main dope was uniformly cast on a stainless steel band support using a belt casting apparatus.
  • the solvent was evaporated until the residual solvent amount reached 100%, and the stainless steel band support was peeled off.
  • Cellulose ester film web was evaporated at 35 ° C, slitted to 1.65m width, 30% in TD direction (film width direction) with a tenter while applying heat at 160 ° C, MD draw ratio was Stretched 1%. The residual solvent amount when starting stretching was 20%. Then, after drying for 15 minutes while transporting the inside of a drying device at 120 ° C.
  • the protective film 401 was obtained.
  • the residual solvent amount of the protective film 401 was 0.2%, the film thickness was 40 ⁇ m, and the number of turns was 3900 m.
  • the orientation angle ⁇ of the protective film 401 was measured using KOBRA-21ADH manufactured by Oji Scientific Instruments, and found to be in the range of 90 ° ⁇ 1 ° with respect to the film longitudinal direction.
  • the ⁇ / 4 plates 401 to 430 produced above were bonded to one side of the polarizer using a fully saponified polyvinyl alcohol 5% aqueous solution as an adhesive. At that time, bonding was performed so that the transmission axis of the polarizer and the slow axis of the ⁇ / 4 plate were 45 degrees.
  • the protective film 1 was similarly subjected to alkali saponification treatment and bonded to the other surface of the polarizer to produce circularly polarizing plates 401 to 430.
  • organic EL display devices 401 to 432 were manufactured by pasting on the viewing side of the organic EL cell.
  • Image blur resistance was evaluated in the same manner as in the method described in Example 1.
  • Each organic EL display device is allowed to stand for 5 hours in an environment of 23 ° C. and 55% RH, and then in an environment where the illuminance is 1000 Lx at a position 5 cm higher than the outermost surface of the organic EL display device.
  • Visibility 1 from an angle of 40 ° with respect to the surface normal, and after standing for 5 hours in an environment of 50 ° C and 14% RH, the illuminance at a position 5 cm higher than the outermost surface of the organic EL display device is 1000 Lx
  • visibility 2 from an angle of 40 ° with respect to the surface normal of the organic EL display device was evaluated.
  • Visibility is determined by 10 general monitors, 3 points for “No difference in visibility”, 1 point for “Slight difference in visibility”, and 0 for “Clearly difference in visibility”. Evaluation is made in three stages, the total score is 24 points or more visibility “ ⁇ ”, 21 points or more, less than 24 points visibility “O”, 15 points, less than 21 points “ ⁇ ”, otherwise X.
  • ⁇ No difference is observed in the white display characteristics before and after the temperature shock test.
  • ⁇ Image unevenness is slightly observed in the organic EL display device after the temperature shock test.
  • ⁇ Bright in the organic EL display device after the temperature shock test. Kana image display unevenness is recognized, and some pixels do not light up.
  • the organic EL display device using the ⁇ / 4 plate having the configuration defined in the present invention is superior in image bleeding resistance to the comparative example, in addition to the visibility, It can be seen that the image has excellent effects in image deterioration resistance and blue light quantity stability.
  • Example 5 ⁇ Production of protective film> [Production of Protective Film 402] (Formation of cured layer D) On the protective film 401 produced in Example 4, the following coating solution for a hardened layer D was die-coated with a coating width of 1.4 m, dried at 80 ° C., and then 120 mJ / cm 2 of ultraviolet light was applied with a high-pressure mercury lamp. Irradiation was performed to provide a cured layer A so that the film thickness after curing was 6 ⁇ m, and a protective film 402 was produced.
  • the organic EL display device using the protective film 402 and the protective film 403 provided with a hardened layer is in an environment of 23 ° C. and 80% RH.
  • the reduction in visibility was improved in any configuration of the circularly polarizing plate of the present invention.
  • the amount of warpage of the organic EL display device under a high temperature environment of 50 ° C. was improved by about 0.5 mm to 6 m compared to the organic EL display device using the protective film 401. As a result, it was confirmed that deterioration of image display was reduced.
  • the organic electroluminescence display device of the present invention has excellent image bleeding resistance, improved visibility (reproducibility of black in a bright place) and durability (image degradation resistance), and blue display stability during storage over time. It is excellent and can be suitably used for various light sources such as flat illumination, optical fiber light source, liquid crystal display backlight, liquid crystal projector backlight, and display device.
  • a Organic electroluminescence image display device Organic EL element C Circularly polarizing plate 1 Substrate 2 TFT 3 Metal electrode 4 Organic functional layer 5 Transparent electrode 6 Insulating layer 7 Sealing layer 8 Transparent sheet 9 ⁇ / 4 plate 10 Polarizer 11 Protective film 12 Cured layer 13 Antireflection layer DR1 Feeding direction DR2 Winding direction ⁇ i Feeding angle (feeding) Direction and winding direction) CR, CL Gripping device Wo Width of film before stretching W Width of film after stretching 21 Unstretched film 22-1 Right film holding start point 22-2 Left film holding start point 23-1 Right film holding means Trajectory 23-2 Trajectory of film holding means on left side 24 Tenter 25-1 End point of holding film on right side 25-2 End point of holding film on left side 26 Diagonally stretched film 27-1 Feed direction of film 28-1 Guide on entrance side of tenter Roller 28-2 Guide roller on the tenter exit side 29 Film stretching direction

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Abstract

La présente invention a pour objectif la fourniture d'un dispositif d'affichage à éléments organiques à électroluminescence présentant une excellente stabilité d'affichage du bleu lors d'un entreposage de longue durée et une excellente résistance à l'étalement de l'image et dans lequel la visibilité (aptitude à la reproduction du noir dans des zones claires) ainsi que la durabilité (résistance à la dégradation de l'image) sont améliorées. Le présent dispositif d'affichage à éléments organiques à électroluminescence est au moins pourvu d'un film de protection, d'un polariseur, d'une plaque λ/4, et d'un élément organique à électroluminescence, dans cet ordre depuis le côté visible, la plaque λ/4 contenant un composé représenté par la formule générale (A) et un acylate de cellulose ayant un degré moyen de substitution de groupe acyle supérieur ou égal à 2,0.
PCT/JP2012/066202 2011-09-02 2012-06-26 Dispositif d'affichage à éléments organiques à électroluminescence, plaque de polarisation circulaire, et plaque allongée λ/4 Ceased WO2013031356A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013114768A (ja) * 2011-11-25 2013-06-10 Konica Minolta Advanced Layers Inc 有機エレクトロルミネッセンス立体画像表示システム
WO2014065083A1 (fr) * 2012-10-26 2014-05-01 コニカミノルタ株式会社 Film optique, plaque de polarisation circulaire et dispositif d'affichage d'image
WO2014068893A1 (fr) * 2012-10-29 2014-05-08 コニカミノルタ株式会社 Film à différence de phase, plaque de polarisation circulaire, et dispositif de formation d'image
WO2014141734A1 (fr) * 2013-03-12 2014-09-18 コニカミノルタ株式会社 Dispositif d'affichage électroluminescent organique et procédé permettant de fabriquer ce dernier
US20150323703A1 (en) * 2012-12-13 2015-11-12 Konica Minolta, Inc. Retardation film, polarizing plate and liquid crystal display
KR20160014520A (ko) * 2014-07-29 2016-02-11 스미또모 가가꾸 가부시키가이샤 편광판, 점착제 부착 편광판 및 액정 표시 장치
CN113874765A (zh) * 2019-05-28 2021-12-31 东洋纺株式会社 圆偏振元件转印用层叠体和使用其的光学物品的制造方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006337575A (ja) * 2005-05-31 2006-12-14 Nippon Oil Corp ホメオトロピック配向液晶フィルムおよびそれを用いた装置
JP2007155970A (ja) * 2005-12-02 2007-06-21 Sumitomo Chemical Co Ltd 楕円偏光板及びその製造方法
JP2007322777A (ja) * 2006-06-01 2007-12-13 Nippon Oil Corp 楕円偏光板、楕円偏光板の製造方法、液晶表示装置およびエレクトロルミネッセンス表示装置
JP2008107767A (ja) * 2006-02-07 2008-05-08 Fujifilm Corp 光学フィルムおよび位相差板、並びに液晶化合物
JP2010031223A (ja) * 2007-12-28 2010-02-12 Sumitomo Chemical Co Ltd 化合物、光学フィルム及び光学フィルムの製造方法
JP2010270108A (ja) * 2009-04-21 2010-12-02 Sumitomo Chemical Co Ltd 化合物
JP2011075924A (ja) * 2009-09-30 2011-04-14 Fujifilm Corp 光学フィルム、位相差板、偏光板、ならびに液晶表示装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006337575A (ja) * 2005-05-31 2006-12-14 Nippon Oil Corp ホメオトロピック配向液晶フィルムおよびそれを用いた装置
JP2007155970A (ja) * 2005-12-02 2007-06-21 Sumitomo Chemical Co Ltd 楕円偏光板及びその製造方法
JP2008107767A (ja) * 2006-02-07 2008-05-08 Fujifilm Corp 光学フィルムおよび位相差板、並びに液晶化合物
JP2007322777A (ja) * 2006-06-01 2007-12-13 Nippon Oil Corp 楕円偏光板、楕円偏光板の製造方法、液晶表示装置およびエレクトロルミネッセンス表示装置
JP2010031223A (ja) * 2007-12-28 2010-02-12 Sumitomo Chemical Co Ltd 化合物、光学フィルム及び光学フィルムの製造方法
JP2010270108A (ja) * 2009-04-21 2010-12-02 Sumitomo Chemical Co Ltd 化合物
JP2011075924A (ja) * 2009-09-30 2011-04-14 Fujifilm Corp 光学フィルム、位相差板、偏光板、ならびに液晶表示装置

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013114768A (ja) * 2011-11-25 2013-06-10 Konica Minolta Advanced Layers Inc 有機エレクトロルミネッセンス立体画像表示システム
JPWO2014065083A1 (ja) * 2012-10-26 2016-09-08 コニカミノルタ株式会社 光学フィルム、円偏光板及び画像表示装置
WO2014065083A1 (fr) * 2012-10-26 2014-05-01 コニカミノルタ株式会社 Film optique, plaque de polarisation circulaire et dispositif d'affichage d'image
WO2014068893A1 (fr) * 2012-10-29 2014-05-08 コニカミノルタ株式会社 Film à différence de phase, plaque de polarisation circulaire, et dispositif de formation d'image
JPWO2014068893A1 (ja) * 2012-10-29 2016-09-08 コニカミノルタ株式会社 位相差フィルム、円偏光板、及び画像表示装置
US20150323703A1 (en) * 2012-12-13 2015-11-12 Konica Minolta, Inc. Retardation film, polarizing plate and liquid crystal display
US9581728B2 (en) * 2012-12-13 2017-02-28 Konica Minolta, Inc. Retardation film, polarizing plate and liquid crystal display
WO2014141734A1 (fr) * 2013-03-12 2014-09-18 コニカミノルタ株式会社 Dispositif d'affichage électroluminescent organique et procédé permettant de fabriquer ce dernier
JP2016110159A (ja) * 2014-07-29 2016-06-20 住友化学株式会社 偏光板、粘着剤付き偏光板及び液晶表示装置
KR20160014520A (ko) * 2014-07-29 2016-02-11 스미또모 가가꾸 가부시키가이샤 편광판, 점착제 부착 편광판 및 액정 표시 장치
KR102425120B1 (ko) * 2014-07-29 2022-07-26 스미또모 가가꾸 가부시키가이샤 편광판, 점착제 부착 편광판 및 액정 표시 장치
CN113874765A (zh) * 2019-05-28 2021-12-31 东洋纺株式会社 圆偏振元件转印用层叠体和使用其的光学物品的制造方法
CN113874765B (zh) * 2019-05-28 2024-04-30 东洋纺株式会社 圆偏振元件转印用层叠体和使用其的光学物品的制造方法

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